Patent Application
20150183953
The invention relates to tyres for motor vehicles and to the rubber compositions which can be used for the manufacture of such tyres.
It relates more particularly to tyres comprising, in the vulcanized state, a foam rubber composition intended to reduce the noise emitted by these tyres during the running of the vehicles.
It is known (see, for example, Patent Application WO 2011/051203) that the noise emitted by a tyre when running originates, inter alia, from the vibrations of its structure resulting from the contact of the tyre with the irregularities of the roadway, also bringing about generation of various sound waves. Everything is ultimately manifested in the form of noise, both inside and outside the vehicle. The amplitude of these various manifestations depends on the modes of vibration specific to the tyre and also on the nature of the surface on which the vehicle is moving. The range of frequencies corresponding to the noise generated by the tyres typically extends from 20 to 4000 Hz approximately.
As regards the noise noticed inside the vehicle, two methods of propagation of the sound coexist:
The noise referred to as “road noise” instead describes the overall level of noise noticed in the vehicle and within a frequency range extending up to 2000 Hz. The noise referred to as “cavity noise” describes the nuisance due to the resonance of the inflation cavity of the casing of the tyre.
As regards the noise emitted outside the vehicle, the various interactions between the tyre and the road surface, and the tyre and the air, which will be a nuisance for the occupants of the vehicle when the latter rolls over a roadway, are relevant. In this case, several sources of noise, such as the noise referred to as “indentation noise”, due to the impact of the rough patches of the road in the contact area, the noise referred to as “friction noise”, essentially generated on exiting the contact area, and the noise referred to as “pattern noise”, due to the arrangement of the pattern elements and to the resonance in the various grooves, are distinguished. The range of frequencies concerned typically corresponds here to a range extending from 300 to 3000 Hz approximately.
Numerous solutions have been provided for reducing the running noise of tyres, in particular the use, in their structure, for example in their tread or their inflation cavity, of a foam rubber based on diene elastomer, of a blowing agent and various other additives, such as, in particular, an expansion activator. In a well known way, these blowing agents, such as, for example, nitro, sulphonyl or azo compounds, are capable of releasing, during thermal activation, for example during the vulcanization of the tyre, a large amount of gas, in particular of nitrogen, and of thus resulting in the formation of bubbles within a sufficiently soft material, such as a rubber composition comprising such blowing agents. Such foam rubber formulations for tyres, capable, once expanded (vulcanized), of reducing running noise, have been described, for example, in the documents Patent EP 337 787 or U.S. Pat. No. 5,176,765, EP 885 925 or U.S. Pat. No.6,427,738, EP 1 800 911 or US 2007/0065821, JP 3-167008, WO 2009/003577 or WO 2011/051203.
However, these blowing agents and/or expansion activators can significantly slow down the curing or vulcanization times for these rubber compositions, which is, of course, harmful to the rates of manufacture of the tyres, so much so that it proves to be difficult for a person skilled in the art to find foam rubber formulations which make it possible to reduce the running noise without detrimentally affecting the curing properties.
In point of fact, during their research studies on the above technology relating to the use of foam rubber, the Applicant Companies have discovered a specific formulation based on a high content of a specific blowing agent and of a specific activator in combination which makes it possible to overcome the problem set out above, that is to say which exhibits improved sound barrier properties, in particular in a frequency range located between 200 and 1000 Hz, and which is thus capable of contributing to reducing the noise emitted during the running of the tyres, this being the case without detrimentally affecting the vulcanization properties.
Consequently, the present invention relates to a heat-expandable rubber composition comprising at least:
The invention also relates to a rubber composition in the vulcanized state (thus expanded) obtained after curing (vulcanization) of the composition according to the invention above.
The invention also relates to any tyre, whether in the raw (non-vulcanized) state or in the cured (vulcanized) state, comprising a composition in accordance with the invention, in particular any tyre, the tread of which, at the very least for the portion (radially outermost part) of this tread intended to come directly into contact with the surface of the road, comprises a rubber composition in accordance with the invention.
The tyres of the invention are particularly intended to equip motor vehicles of passenger type, including 4×4 (four-wheel drive) vehicles and SUV (Sport Utility Vehicles) vehicles, two-wheel vehicles (in particular motorcycles), and also industrial vehicles chosen in particular from vans and heavy-duty vehicles (i.e., underground trains, buses and heavy road transport vehicles, such as lorries or tractors).
The invention and its advantages will be readily understood in the light of the description and the implementational examples which follow.
In the present description, unless expressly indicated otherwise, all the percentages (%) shown are percentages by weight.
“Diene” elastomer (or, without distinction, rubber) is understood to mean an elastomer resulting at least in part (that is to say, a homopolymer or a copolymer) from diene monomer(s) (i.e., monomers carrying two conjugated or non-conjugated carbon-carbon double bonds). “Isoprene elastomer” is understood to mean an isoprene homopolymer or copolymer, in other words a diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IRs), various isoprene copolymers and the mixtures of these elastomers.
The abbreviation “phr” means parts by weight per hundred parts of elastomer (of the total of the elastomers, if several elastomers are present).
Furthermore, any interval of values denoted by the expression “between a and b” represents the range of values greater than “a” and lower than “b” (that is to say, limits a and b excluded), whereas any interval of values denoted by the expression “from a to b” means the range of values extending from “a” up to “b” (that is to say, including the strict limits a and b).
The heat-expandable rubber composition (that is to say, in the non-vulcanized state) of the invention thus has the essential characteristic of comprising at least:
The various components above are described in detail below.
4.1. Copolymer Based on Styrene and Butadiene
The first essential characteristic of the heat-expandable rubber composition is to comprise from 50 to 100 phr of a copolymer based on styrene and butadiene, that is to say of a copolymer of at least one styrene monomer and of at least one butadiene monomer; in other words, the said copolymer based on styrene and butadiene comprises, by definition, at least units resulting from styrene and units resulting from butadiene.
Preferably, the content of the said copolymer in the heat-expandable rubber composition is within a range from 50 to 90 phr, more preferably within a range from 60 to 85 phr.
The following are suitable in particular as butadiene monomers: 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C1-C5 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, or an aryl-1,3-butadiene. The following are suitable in particular as styrene monomers: styrene, methylstyrenes, para(tert-butyl)styrene, methoxystyrenes or chlorostyrenes.
The said copolymer based on styrene and butadiene can have any microstructure, which depends on the polymerization conditions used, in particular on the presence or absence of a modifying and/or randomizing agent and on the amounts of modifying and/or randomizing agent employed. It can, for example, be a block, random, sequential or microsequential copolymer and can be prepared in dispersion or in solution; it can be coupled and/or star-branched branched or else functionalized with a coupling and/or star-branching or functionalization agent.
Preferably, the copolymer based on styrene and butadiene is selected from the group consisting of styrene/butadiene copolymers (abbreviated to SBRs), styrene/butadiene/isoprene copolymers (abbreviated to SBIRs) and the mixtures of such copolymers.
Mention may in particular be made, among the SBIR copolymers, of those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60% by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly of between 20% and 40%, a content (mol %) of 1,2-units of the butadiene part of between 4% and 85%, a content (mol %) of trans-1,4-units of the butadiene part of between 6% and 80%, a content (mol %) of 1,2-plus 3,4-units of the isoprene part of between 5% and 70% and a content (mol %) of trans-1,4-units of the isoprene part of between 10% and 50%.
More preferably, an SBR copolymer is used. Mention may in particular be made, among the SBR copolymers, of those having a styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol %) of 1,2-bonds of the butadiene part of between 4% and 75%, and a content (mol %) of trans-1,4-bonds of between 10% and 80%.
The Tg (glass transition temperature) of the copolymer based on styrene and butadiene is preferably greater than −40° C., more preferably greater than −35° C. and in particular between −30° C. and +30° C. (more particularly within a range from −25° C. to +25° C.).
The Tg of the elastomers described here is measured in a conventional way well known to a person skilled in the art on an elastomer in the dry state (i.e., without extending oil) and by DSC (for example according to ASTM D3418-1999).
A person skilled in the art knows how to modify the microstructure of a copolymer based on styrene and butadiene, in particular of an SBR, in order to increase and adjust its Tg, in particular by varying the contents of styrene, of 1,2-bonds or also of trans-1,4-bonds of the butadiene part. Use is more preferably made of an SBR (solution or emulsion) having a styrene content (mol %) which is greater than 35%, more preferably between 35% and 60%, in particular within a range from 38% to 50%. SBRs having a high Tg are well known to a person skilled in the art; they have been used essentially in tyre treads in order to improve some of their wear properties.
The above copolymer based on styrene and butadiene can be combined with at least one other (also referred to as second) diene elastomer, other than the said copolymer (that is to say, not comprising units resulting from styrene and butadiene), the said second diene elastomer being present at a content by weight which is consequently at most equal to 50 phr.
This optional second diene elastomer is preferably selected from the group consisting of natural rubbers (NRs), synthetic polyisoprenes (IRs), polybutadienes (BRs), isoprene copolymers and the blends of these elastomers. Such copolymers are more preferably selected from the group consisting of isoprene/butadiene copolymers (BIRs) and isoprene/styrene copolymers (SIRs).
Among the latter, polybutadiene homopolymers (BRs), in particular those having a content (mol %) of 1,2-units of between 4% and 80% or those having a cis-1,4-content (mol %) of greater than 80%; polyisoprene homopolymers (IRs); butadiene/isoprene copolymers (BIRs), in particular those having an isoprene content of between 5% and 90% by weight and a Tg of from −40° C. to −80° C.; isoprene/styrene copolymers (SIRs), in particular those having a styrene content of between 5% and 50% by weight and a Tg of between −25° C. and −50° C., are suitable in particular.
According to a preferred embodiment, the second diene elastomer is an isoprene elastomer, more preferably natural rubber or a synthetic polyisoprene of the cis-1,4-type; use is preferably made, among these synthetic polyisoprenes, of polyisoprenes having a content (mol %) of cis-1,4-bonds of greater than 90%, more preferably still of greater than 98%.
According to another preferred embodiment, the second diene elastomer is a polybutadiene, preferably a polybutadiene having a content of cis-1,4-bonds of greater than 90%.
According to another preferred embodiment, the second diene elastomer is a mixture of polybutadiene with an isoprene elastomer (natural rubber or synthetic polyisoprene).
More preferably, the content of second diene elastomer, in particular of polybutadiene and/or isoprene elastomer (in particular natural rubber), is within a range from 10 to 50 phr, more preferably still within a range from 15 to 40 phr.
The diene elastomers described above might also be combined, in a predominant amount, with synthetic elastomers other than diene elastomers, indeed even polymers other than elastomers, for example thermoplastic polymers.
4.2. Filler
Use may be made of any filler known for its capabilities in reinforcing a rubber composition, for example an organic filler, such as carbon black, or else an inorganic filler, such as silica, with which is combined, in a known way, a coupling agent.
Such a filler preferably consists of nanoparticles, the (weight-)average size of which is less than a micrometre, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
Preferably, the content of total reinforcing filler (especially silica or carbon black or a mixture of silica and carbon black) is between 50 and 150 phr. A content of greater than 50 phr promotes good mechanical strength; beyond 150 phr, there exists a risk of excessive stiffness of the rubber composition. For these reasons, the content of total reinforcing filler is more preferably within a range from 70 to 120 phr.
Suitable as carbon blacks are, for example, all carbon blacks which are conventionally used in tyres (“tyre-grade” blacks), such as carbon blacks of the 100, 200 or 300 series (ASTM grades), such as, for example, the N115, N134, N234, N326, N330, N339, N347 or N375 blacks. The carbon blacks might, for example, be already incorporated in the diene elastomer, in particular isoprene elastomer, in the form of a masterbatch (see, for example, Application WO 97/36724 or WO 99/16600).
Mention may be made, as examples of organic fillers other than carbon blacks, of functionalized polyvinyl organic fillers, such as described in Applications WO-A-2006/069792, WO-A-2006/069793, WO-A-2008/003434 and WO-A-2008/003435.
“Reinforcing inorganic filler” should be understood here as meaning any inorganic or mineral filler, whatever its colour and its origin (natural or synthetic), also known 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 tyres, in other words capable of replacing, in its reinforcing role, a conventional tyre-grade carbon black; such a filler is generally characterized, in a known way, by the presence of hydroxyl (—OH) groups at its surface.
Mineral fillers of the siliceous type, especially silica (SiO2), are suitable in particular as reinforcing inorganic fillers. The silica used can be any reinforcing silica known to a person skilled in the art, in particular any precipitated or fumed silica exhibiting a BET specific surface and a CTAB specific surface both of less than 450 m2/g, preferably from 30 to 400 m2/g, in particular between 60 and 300 m2/g. Mention will be made, as highly dispersible precipitated silicas (HDSs), for example, of the Ultrasil 7000 and Ultrasil 7005 silicas from Degussa, the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia, the Hi-Sil EZ150G silica from PPG or the Zeopol 8715, 8745 and 8755 silicas from Huber.
According to another particularly preferred embodiment, use is made, as predominant filler, of a reinforcing inorganic filler, in particular silica, at a content within a range from 70 to 120 phr, to which reinforcing inorganic filler can advantageously be added carbon black at a minor content at most equal to 15 phr, in particular within a range from 1 to 10 phr.
In order to couple the reinforcing inorganic filler to the diene elastomer, use is made, in a known way, of an at least bifunctional coupling agent (or bonding agent) intended to provide a satisfactory connection, of chemical and/or physical nature, between the inorganic filler (surface of its particles) and the diene elastomer. Use is made in particular of at least bifunctional organosilanes or polyorganosiloxanes.
Use is made in particular of silane polysulphides, referred to as “symmetrical” or “unsymmetrical” depending on their specific structure, such as described, for example, in Applications WO 03/002648 (or US 2005/016651) and WO 03/002649 (or US 2005/016650).
Particularly suitable, without the definition below being limiting, are silane polysulphides corresponding to the following general formula (I):
Z-A-Sx-A-Z, in which: (I)
In the case of a mixture of alkoxysilane polysulphides corresponding to the above formula (I), in particular normal commercially available mixtures, the mean value of the “x” indices is a fractional number preferably of between 2 and 5, more preferably of approximately 4. However, the invention can also advantageously be carried out, for example, with alkoxysilane disulphides (x =2).
Mention will more particularly be made, as examples of silane polysulphides, of bis((C1-C4)alkoxyl(C1-C4)alkylsilyl(C1-C4)alkyl)polysulphides (in particular disulphides, trisulphides or tetrasulphides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxsilylpropyl triethoxysilylpropyl)polysulphides. Use is made in particular, among these compounds, of bis(3-triethoxysilylpropyl)tetrasulphide, abbreviated to TESPT, of formula [(C2H5O)3Si(CH2)3S2]2, or bis(triethoxysilylpropyl)disulphide, abbreviated to TESPD, of formula [(C2H5O)3Si(CH2)3S]2. Mention will also be made, as preferred examples, of bis(mono(C1-C4)alkoxyldi(C1-C4)alkylsilylpropyl)polysulphides (in particular disulphides, trisulphides or tetrasulphides), more particularly bis(monoethoxydimethylsilylpropyl) tetrasulphide, such as described in the abovementioned Patent Application WO 02/083782 (or U.S. Pat. No. 7,217,751).
Mention will in particular be made, as examples of coupling agents other than an alkoxysilane polysulphide, of bifunctional POSs (polyorganosiloxanes), or else of hydroxysilane polysulphides (R2═OH in the above formula I), such as described, for example, in Patent Applications WO 02/30939 (or U.S. Pat. No. 6,77,255), WO 02/31041 (or US 2004/051210) and WO 2007/061550, or else of silanes or POSs bearing azodicarbonyl functional groups, such as described, for example, in Patent Applications WO 2006/125532, WO 2006/125533 and WO 2006/125534.
Mention will be made, as examples of other silane sulphides, for example, of silanes bearing at least one thiol (—SH) function (referred to as mercaptosilanes) and/or at least one masked thiol function, such as described, for example, in patents or patent applications U.S. Pat. No. 6,849,754, WO 99/09036, WO 2006/023815 and WO 2007/098080.
Of course, use might also be made of mixtures of the coupling agents described above, as described in particular in the abovementioned Application WO 2006/125534.
When they are reinforced with an inorganic filler, such as silica, the rubber compositions preferably comprise between 2 and 15 phr, more preferably between 3 and 12 phr, of coupling agent.
A person skilled in the art will understand that a reinforcing filler of another nature, in particular organic nature, 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.
4.3. Blowing Agent and Associated Activator
The invention has the essential characteristic of using, in combination, at particularly high contents, microparticles of sodium carbonate, sodium hydrogencarbonate, potassium carbonate or potassium hydrogencarbonate, as blowing agent, with which is combined, as expansion activator, a carboxylic acid, the melting point of which is between 60° C. and 220° C.
Microparticles are understood to mean, generally, particles of micrometric size, that is to say the median size of which (expressed by weight) is greater than 1 μm and less than 1 mm, it being possible for these microparticles to be provided in any densified form, for example in the form of a powder, microbeads, granules or beads; a presentation in the powder form is preferred here.
An essential characteristic of the blowing agent according to the invention lies in the median size of its microparticles, which is particularly low, of between 1 and 50 μm (micrometres), preferably between 2 and 30 μm and more preferably still within a range from 5 to 25 μm. By virtue of such conditions, it has been observed that the kinetics of vulcanization of the rubber compositions were not significantly slowed down, furthermore without adversely affecting the noise reduction properties.
In a well-known way, a blowing agent is a compound which can decompose thermally and which is intended to release, during thermal activation, for example during the vulcanization of the tyre, a large amount of gas and to thus result in the formation of bubbles. The release of gas in the rubber composition thus originates from this thermal decomposition of the blowing agent.
The blowing agent used in accordance with the present invention is sodium carbonate, sodium hydrogencarbonate (sometimes also referred to as bicarbonate), potassium carbonate or potassium hydrogencarbonate. In other words, it is selected from the group consisting of sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate and the mixtures of these compounds (including, of course, the hydrated forms).
Such a blowing agent has the advantage of only giving off carbon dioxide and water during its decomposition; it is thus particularly favourable to the environment. Use is made in particular of sodium hydrogencarbonate (NaHCO3).
The content of this blowing agent is between 5 and 25 phr, preferably between 8 and 20 phr.
Another essential characteristic of the invention is to add, to the blowing agent described above, a carboxylic acid, the melting point of which is between 60° C. and 220° C.
The content of this carboxylic acid is between 2 and 20 phr, preferably between 2 and 15 phr. By dispersing homogeneously in the composition, during the melting thereof within the specific temperature range indicated above, this carboxylic acid has the role of chemically activating (i.e., activating by chemical reaction) the blowing agent which, during its thermal decomposition, will thus release many more bubbles of gas (CO2 and H2O) than if it were used alone.
Any carboxylic acid exhibiting a melting point of between 60° C. and 220° C. (thus solid at 23° C.), preferably between 100° C. and 200° C., in particular between 120° C. and 180° C., is capable of being suitable. The melting point is a well-known basic physical constant (available, for example, in “Handbook of Chemistry and Physics”) of organic or inorganic heat-fusible compounds; it can be monitored by any known means, for example by the Thiele method, the Köfler bench method or also by DSC analysis.
The carboxylic acids can be monoacids, diacids or triacids; they can be aliphatic or aromatic; they can also comprise additional functional groups (other than COOH), such as hydroxyl (OH) groups, ketone (C═O) groups or also groups bearing ethylenic unsaturation.
According to a preferred embodiment, the pKa (Ka acidity constant) of the carboxylic acid is greater than 1, more preferably between 2.5 and 12, in particular between 3 and 10.
According to another preferred embodiment, in or not in combination with the preceding embodiment, the carboxylic acid comprises, along its hydrocarbon chain, from 2 to 22 carbon atoms, preferably from 4 to 20 carbon atoms.
The aliphatic monoacids preferably comprise, along their hydrocarbon chain, at least 16 carbon atoms; mention may be made, as examples, of palmitic acid (C16), stearic acid (C18), nonadecanoic acid (C19), behenic acid (C20) and their various mixtures. The aliphatic diacids preferably comprise, along their hydrocarbon chain, from 2 to 10 carbon atoms; mention may be made, as examples, of oxalic acid (C2), malonic acid (C3), succinic acid (C4), glutaric acid (C5), adipic acid (C6), pimelic acid (C7), suberic acid (C8), azelaic acid (C9), sebacic acid (C10) and their various mixtures. Mention may be made, as aromatic monoacid, for example, of benzoic acid. The acids comprising functional groups can be monoacids, diacids or triacids of the aliphatic type and of the aromatic type; mention may be made, as examples, of tartaric acid, malic acid, maleic acid, glycolic acid, a-ketoglutaric acid, salicylic acid, phthalic acid or citric acid.
Preferably, the carboxylic acid is selected from the group consisting of palmitic acid, stearic acid, nonadecanoic acid, behenic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, benzoic acid, tartaric acid, malic acid, maleic acid, glycolic acid, a-ketoglutaric acid, salicylic acid, phthalic acid, citric acid or the mixtures of these acids.
More particularly, the carboxylic acid is selected from the group consisting of malic acid, a-ketoglutaric acid, citric acid, stearic acid and their mixtures. More preferably still, citric acid, stearic acid or a mixture of these two is used.
Another essential characteristic of the invention, for the targeted reduction in the running noise, is that the total amount of blowing agent and of its associated activator is greater than 10 phr, preferably between 10 and 40 phr. This total amount is more preferably greater than 15 phr, in particular between 15 and 40 phr.
Various known methods are applicable for the analysis of the particle size and the calculation of the median size (size distribution by weight) of the microparticles (or median diameter for microparticles assumed to be substantially spherical), for example by laser diffraction (see, for example, Standard ISO-8130-13 or Standard JIS K5600-9-3).
Use may also simply and furthermore preferably be made of an analysis of the particle size by mechanical sieving; the operation consists in sieving a defined amount of sample (for example 200 g) on a vibrating table for 30 min with different sieve diameters and within a range of meshes which are suitable for the sizes of microparticles to be analysed; the oversize collected on each sieve is weighed on a precision balance; the % of oversize for each mesh diameter with respect to the total weight of product is deduced therefrom; the median size (or median diameter) is finally calculated in a known way from the histogram of the particle size distribution. It should be remembered that the median size by weight corresponds to 50% (by weight) of the cumulative distribution of the particles, that is to say that, by weight, half of the particles have a size less than the median size and that the other half of the particles have a size greater than this median size.
4.4. Various Additives
The heat-expandable rubber composition of the invention can also comprise all or some of the usual additives generally used in foam rubber compositions for tyres, such as, for example, protection agents, such as anti-ozone waxes, chemical antiozonants or antioxidants, plasticizing agents, a crosslinking system based either on sulphur or on sulphur donors and/or on peroxide and/or on bismaleimides, vulcanization accelerators or vulcanization activators.
According to a preferred embodiment, the heat-expandable rubber composition also comprises a liquid plasticizing agent (liquid at 20° C.), the role of which is to soften the matrix by diluting the diene elastomer and the reinforcing filler; its Tg is, by definition, less than-20° C., preferably less than 31 40° C.
According to another preferred embodiment, this liquid plasticizer is used at a relatively small content, such that the ratio by weight of reinforcing filler to liquid plasticizing agent is greater than 2.0, more preferably greater than 2.5, in particular greater than 3.0.
Any extending oil, whether of aromatic or non-aromatic nature, any liquid plasticizing agent known for its plasticizing properties with regard to diene elastomers, can be used. At ambient temperature (20° C.), these plasticizers or these oils, which are more or less viscous, are liquids (that is to say, as a reminder, substances which have the ability to eventually assume the shape of their container), in contrast in particular to plasticizing hydrocarbon resins, which are by nature solids at ambient temperature.
Liquid plasticizers selected from the group consisting of naphthenic oils (low- or high-viscosity, in particular hydrogenated or non-hydrogenated), paraffinic oils, MES (Medium Extracted Solvates) oils, DAE (Distillate Aromatic Extracts) oils, TDAE (Treated Distillate Aromatic Extracts) oils, RAE (Residual Aromatic Extracts) oils, TRAE (Treated Residual Aromatic Extracts) oils, SRAE (Safety Residual Aromatic Extracts) oils, mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and the mixtures of these compounds are particularly suitable. According to a more preferred embodiment, the liquid plasticizing agent is selected from the group consisting of MES oils, TDAE oils, naphthenic oils, vegetable oils and the mixtures of these oils.
Mention may be made, as phosphate plasticizers, for example, of those which comprise between 12 and 30 carbon atoms, for example trioctyl phosphate. Mention may in particular be made, as examples of ester plasticizers, of the compounds selected from the group consisting of trimellitates, pyromellitates, phthalates, 1,2-cyclohexanedicarboxylates, adipates, azelates, sebacates, glycerol triesters and the mixtures of these compounds. Mention may in particular be made, among the above triesters, of glycerol triesters, preferably predominantly composed (for more than 50%, more preferably for more than 80% by weight) of an unsaturated C18 fatty acid, that is to say selected from the group consisting of oleic acid, linoleic acid, linolenic acid and the mixtures of these acids. More preferably, whether it is of synthetic origin or natural origin (case, for example, of sunflower or rapeseed vegetable oils), the fatty acid used is composed for more than 50% by weight, more preferably still for more than 80% by weight, of oleic acid. Such triesters (trioleates) having a high content of oleic acid are well known; they have been described, for example in Application WO 02/088238, as plasticizing agents in tyre treads.
According to another preferred embodiment, the rubber composition of the invention can also comprise, as solid plasticizer (solid at 23° C.), a hydrocarbon resin exhibiting a Tg of greater than +20° C., preferably of greater than +30° C., such as described, for example, in Applications WO 2005/087859, WO 2006/061064 or WO 2007/017060.
Hydrocarbon resins are polymers well-known to a person skilled in the art which are essentially based on carbon and hydrogen and which are thus miscible by nature in diene elastomer compositions, when they are additionally described as “plasticizing”. They can be aliphatic, aromatic or also of the aliphatic/aromatic type, that is to say based on aliphatic and/or aromatic monomers. They can be natural or synthetic, based or not based on petroleum (if such is the case, also known under the name of petroleum resins). They are preferably exclusively of hydrocarbon nature, that is to say that they comprise only carbon and hydrogen atoms.
Preferably, the plasticizing hydrocarbon resin exhibits at least one, more preferably all, of the following characteristics:
The Tg of this resin is measured in a known way by DSC (Differential Scanning calorimetry) according to Standard ASTM D3418. The macrostructure (Mw, Mn and PI) of the hydrocarbon resin is determined by steric exclusion chromatography (SEC); solvent tetrahydrofuran; temperature 35° C.; concentration 1 g/1; flow rate 1 ml/min; solution filtered through a filter with a porosity of 0.45 μm before injection; Moore calibration with polystyrene standards; set of 3 Waters columns in series (Styragel HR4E, HR1 and HR0.5); detection by differential refractometer (Waters 2410) and its associated operating software (Waters Empower).
According to a particularly preferred embodiment, the plasticizing hydrocarbon resin is selected from the group consisting of cyclopentadiene (abbreviated to CPD) homopolymer or copolymer resins, dicyclopentadiene (abbreviated to DCPD) homopolymer or copolymer resins, terpene homopolymer or copolymer resins, C5 fraction homopolymer or copolymer resins, C9 fraction homopolymer or copolymer resins, α-methylstyrene homopolymer or copolymer resins and the mixtures of these resins. Use is more preferably made, among the above copolymer resins, of those selected from the group consisting of (D)CPD/vinylaromatic copolymer resins, (D)CPD/terpene copolymer resins, (D)CPD/C5 fraction copolymer resins, (D)CPD/C9 fraction copolymer resins, terpene/vinylaromatic copolymer resins, terpene/phenol copolymer resins, C5 fraction/vinylaromatic copolymer resins, C9 fraction/vinylaromatic copolymer resins and the mixtures of these resins.
The term “terpene” combines here, in a known way, α-pinene, β-pinene and limonene monomers; use is preferably made of a limonene monomer, which compound exists, in a known way, in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer) or else dipentene, a racemate of the dextrorotatory and laevorotatory enantiomers. Suitable as vinylaromatic monomers are, for example: styrene, α-methylstyrene, ortho-, meta- or para-methylstyrene, vinyltoluene, para(tert-butyl)styrene, methoxystyrenes, chlorostyrenes, hydroxystyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene or any vinylaromatic monomer resulting from a C9 fraction (or more generally from a C8 to C10 fraction). Preferably, the vinylaromatic compound is styrene or a vinylaromatic monomer resulting from a C9 fraction (or more generally from a C8 to C10 fraction). Preferably, the vinylaromatic compound is the minor monomer, expressed as molar fraction, in the copolymer under consideration.
The content of hydrocarbon resin is preferably between 3 and 60 phr, more preferably between 3 and 40 phr, in particular between 5 and 30 phr.
In the case where it is desired to increase the stiffness of the composition once blown, without, however, reducing the content of liquid plasticizer above, reinforcing resins (e.g., methylene acceptors and donors), such as described, for example, in WO 02/10269 or U.S. Pat. No. 7,199,175, can advantageously be incorporated.
The heat-expandable rubber composition can also comprise coupling activators, when a coupling agent is used, agents for covering the inorganic filler, when an inorganic filler is used, 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 processability in the raw state; these agents are, for example, hydroxysilanes or hydrolysable silanes, such as alkylalkoxysilanes, polyols, polyethers, amines, or hydroxylated or hydrolysable polyorganosiloxanes.
4.5. Manufacture of the Compositions
The rubber compositions are manufactured in appropriate mixers, for example using two successive phases of preparation according to a general procedure known to a person skilled in the art: a first phase of thermomechanical working or kneading (sometimes referred to as “non-productive” phase) at high temperature, up to a maximum temperature of between 130° C. and 200° C., preferably between 145° C. and 185° C., during which in particular the blowing activator (carboxylic acid) is incorporated, followed by a second phase of mechanical working (sometimes referred to as “productive” phase) at low temperature, typically below 120° C., for example between 60° C. and 100° C., during which finishing phase the blowing agent and the crosslinking or vulcanization system are incorporated.
A process which can be used for the manufacture of such rubber compositions comprises, for example and preferably, the following stages:
By way of example, all the necessary constituents, the optional supplementary covering agents or processing aids and various other additives, with the exception of the blowing agent and the crosslinking system, are introduced, during the first non-productive phase, into an appropriate mixer, such as an ordinary internal mixer. After thermomechanical working, dropping and cooling of the mixture thus obtained, the blowing agent, then the vulcanization retarder (if such a compound is used) and, finally, the remainder of the vulcanization system (sulphur and accelerator), at low temperature, are then incorporated, preferably in this order, generally in an external mixer, such as an open mill; everything is then mixed (productive phase) for a few minutes, for example between 5 and 15 min.
The crosslinking system proper is preferably based on sulphur and on a primary vulcanization accelerator, in particular on an accelerator of the sulphenamide type. Additional to this vulcanization system are various known secondary vulcanization accelerators or vulcanization activators, such as zinc oxide, stearic acid, guanidine derivatives (in particular diphenylguanidine), and the like, incorporated during the first non-productive phase and/or during the productive phase. The sulphur content is preferably between 0.5 and 5 phr and the content of the primary accelerator is preferably between 0.5 and 8 phr.
Use may be made, as (primary or secondary) accelerator, of any compound capable of acting as accelerator for the vulcanization of diene elastomers in the presence of sulphur, in particular accelerators of the thiazole type, and also their derivatives, and accelerators of thiuram and zinc dithiocarbamate types. These accelerators are, for example, selected from the group consisting of 2-mercaptobenzothiazyl disulphide (abbreviated to “MBTS”), tetrabenzylthiuram disulphide (“TBZTD”), N-cyclohexyl-2-benzothiazolesulphenamide (“CBS”), N,N-dicyclohexyl-2-benzothiazolesulphenamide (“DCBS”), N-(tert-butyl)-2-benzothiazolesulphenamide (“TBBS”), N-(tert-butyl)-2-benzothiazolesulphenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ZBEC”) and the mixtures of these compounds.
As the carboxylic acid has, as possible effect, that of reducing the induction period (that is to say, the time necessary at the start of the vulcanization reaction) during the curing of the composition, a retarder of the start of vulcanization, which makes it possible to thwart this phenomenon and to thus provide the rubber composition with the time necessary for complete expansion before the vulcanization thereof, can advantageously be used.
The content of this vulcanization retarder is preferably between 0.5 and 10 phr, more preferably between 1 and 5 phr, in particular between 1 and 3 phr.
Vulcanization retarders are well known to a person skilled in the art. Mention may be made of N-cyclohexylthiophthalimide, sold under the name “Vulkalent G” by Lanxess, N-(trichloromethylthio) benzenesulphonamide, sold under the name “Vulkalent E/C” by Lanxess, or also phthalic anhydride, sold under the name “Vulkalent B/C” by Lanxess. Preferably, N-cyclohexylthiophthalimide (abbreviated to “CTP”) is used.
The final composition thus obtained is subsequently calendered, for example in the form of a sheet or plaque, in particular for laboratory characterization, or else calendered or extruded in the form of a heat-expandable rubber profiled element.
In the raw state (i.e., non-vulcanized state) and thus non-expanded state, the density, denoted D1, of the heat-expandable rubber composition is preferably between 1.100 and 1.400 g/cm3, more preferably within a range from 1.150 to 1.350 g/cm3.
The vulcanization (or curing) is carried out in a known way at a temperature generally of between 130° C. and 200° C., for a sufficient time which can vary, for example, between 5 and 90 min, as a function in particular of the curing temperature, of the vulcanization system adopted and of the kinetics of vulcanization of the composition under consideration.
It is during this vulcanization stage that the blowing agent will release a large amount of gas, to result in the formation of bubbles in the foam rubber composition and finally in its expansion.
In the cured state (i.e., vulcanized state), the density, denoted D2, of the rubber composition once expanded (i.e., in the foam rubber state) is preferably between 0.500 and 1.000 g/cm3, more preferably within a range from 0.600 to 0.850 g/cm3.
Its degree of expansion by volume, denoted TE (expressed as %), is preferaby between 30% and 150%, more preferably within a range from 50% to 120%, this degree of expansion TE being calculated in a known way from the above densities D1 and D2, as follows:
T
E=[(D1/D2)−1]×100.
Preferably, its Shore A hardness (measured in accordance with Standard ASTM D 2240-86) is within a range from 45 to 60.
The heat-expandable rubber composition described above can especially be used in treads, at least for their portion which is intended to come directly into contact with the surface of the road, of tyres for any type of vehicle, in particular in tyres for passenger vehicles, as demonstrated in the tests which follow.
For the requirements of these tests, three rubber compositions (denoted C-0, C-1 and C-2) were prepared, the formulations of which are given in Table 1 (contents of the various products expressed in phr). The composition C-0 is the control composition, it does not comprise a blowing agent; the composition C-1 is a composition not in accordance with the invention, it indeed comprises a blowing agent (sodium hydrogencarbonate) but for which the median size of the microparticles is outside the range of the invention (approximately 100 μm); finally, the composition C-3 is a composition according to the invention, it comprises a blowing agent (sodium hydrogencarbonate) exhibiting a median size of the microparticles of between 1 and 50 μm (in this case, approximately 10 μm). In addition, in the two compositions C-1 and C-2, the blowing agent is combined with a carboxylic acid as expansion activator; in addition, the two compositions C-1 and C-2 comprise a retarder of the start of vulcanization (CTP).
The following procedure was used for the manufacture of these compositions: the reinforcing filler, the diene elastomer (SBR and BR blend), the carboxylic acid for the compositions C-1 and C-2 and the various other ingredients, with the exception of the vulcanization system and the blowing agent, were successively introduced into an internal mixer, the initial vessel temperature of which was approximately 60° C.; the mixer was thus filled to approximately 70% (% by volume). Thermomechanical working (non-productive phase) was then carried out in a stage of approximately 2 to 4 min, until a maximum “dropping” temperature of approximately 150° C. was reached. The mixture thus obtained was recovered and cooled to approximately 50° C. and then the blowing agent (sodium hydrogencarbonate), the vulcanization retarder (CTP), followed by the sulphenamide accelerator and the sulphur were incorporated on an external mixer (homofinisher) at 30° C., everything being mixed (productive phase) for a few minutes.
The compositions C-0, C-1 and C-2 thus prepared were subsequently vulcanized under a press, and their properties were measured before and after curing (see appended Table 2).
First of all, as regards the rheometry (curing) properties of Table 2, the measurements are carried out at 150° C. with an oscillating disc rheometer, according to Standard DIN 53529-part 3 (June 1983). The change in the rheometric torque as a function of time describes the change in the stiffening of the composition as a result of the vulcanization reaction. The measurements are processed according to Standard DIN 53529-part 2 (March 1983): Ti is the induction period, that is to say the time necessary for the start of the vulcanization reaction; Tα (for example T95) is the time necessary to achieve a conversion of α %, that is to say α % (for example 95%) of the difference between the minimum and maximum torques.
The scorch time (denoted T5) is also measured, at 130° C., in accordance with French Standard NF T 43-005 (1991); the change in the consistometric index as a function of time also makes it possible to determine this scorch time of the rubber compositions, assessed in accordance with the abovementioned standard, by the parameter T5 (case of a large rotor), expressed in minutes, and defined as being the time necessary to obtain an increase in the consistometric index (expressed in MU) of 5 units above the minimum value measured for this index.
On reading Table 2, it is found first of all that, in comparison with the control composition C-0, the vulcanization (curing) process is significantly detrimentally effected (slowed down) with regard to the composition C-1 not in accordance with the invention, as illustrated in particular by the significant increase in the parameter T95: it is noted in particular that the total curing time, which can be illustrated by the different (T95-Ti), is increased by 50% (30 min instead of 20 min).
On the other hand, unexpectedly, the composition in accordance with the invention (C-2) incorporating microparticles, the median size of which is greatly reduced in comparison with the composition C-1, exhibits rheometry (T95) properties which not only are not affected by the presence of the blowing agent but are even improved in comparison with the initial values observed with regard to the control composition (C-0) devoid of blowing agent; it is noted in particular that the total curing time (T95-Ti) is significantly reduced (13 min instead of 20 min) in the case of the invention.
As regards now the properties of Table 3, it is furthermore noted that the rubber compositions C-1 and C-2, respectively comparative and in accordance with the invention, exhibit, after curing (once in the foam, that is say expanded, rubber state), a markedly reduced density in both cases, corresponding to a particularly high degree of expansion by volume (of 36% to 48%). Such an expansion capacity confers improved sound barrier properties on them, capable of contributing to reducing the running noise of tyres.
In order to subsequently characterize the noise reduction properties of the treads, a running test was carried out on the tyres in which the sound level emitted by the tyres was evaluated by measuring the acoustic pressure level, during running of the vehicle at a speed of 60 km/h, by virtue of several microphones positioned inside the vehicle (road noise) The vehicle used was a vehicle of “Subaru” make (“R1” model); the surface of the roadway used for this test corresponds to a semi-rough asphalt; during passage through the measurement region, recording of the acoustic pressure is triggered.
The results in Table 4 express the difference in sound level recorded between the tyres according to the invention (composition C-2) or the comparative tyres (composition C-1), with respect to the control tyres (composition C-0), within a frequency range from 200 to 800 Hz. These differences are expressed in acoustic energy (dB(A)), which corresponds to the integration of the acoustic pressure as a function of the frequency over the frequency ranges under consideration, a negative value indicating a reduction in the noise with respect to the reference (composition C-0).
On reading Table 4, it is found that a reduction in noise significant to a person skilled in the art is obtained with regard to the composition in accordance with the invention (C-2), over all the frequency ranges tested, with respect to the reference (composition C-0), this reduction furthermore being close to that observed for the comparative composition C-1.
Finally, during additional running tests, it was unexpectedly observed (see results in Table 5, expressed in relative units) that the use of the microparticles of reduced size (composition C-2 according to the invention) makes it possible, in comparison with the reference microparticles (comparative composition C-1), to significantly reduce the rolling resistance of the tyres (measured on a rolling drum according to the ISO 87-67-1992 method).
| Number | Date | Country | Kind |
|---|---|---|---|
| 1257301 | Jul 2012 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2013/064546 | 7/10/2013 | WO | 00 |
