WO2008145155A1 - Pneu et composition élastomère réticulable - Google Patents

Pneu et composition élastomère réticulable Download PDF

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Publication number
WO2008145155A1
WO2008145155A1 PCT/EP2007/004759 EP2007004759W WO2008145155A1 WO 2008145155 A1 WO2008145155 A1 WO 2008145155A1 EP 2007004759 W EP2007004759 W EP 2007004759W WO 2008145155 A1 WO2008145155 A1 WO 2008145155A1
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WO
WIPO (PCT)
Prior art keywords
phr
group
tire according
elastomeric polymer
elastomeric composition
Prior art date
Application number
PCT/EP2007/004759
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English (en)
Inventor
Maurizio Galimberti
Massimiliano Guglielmone
Luca Napolitano
Original Assignee
Pirelli Tyre S.P.A.
Politecnico Di Milano
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pirelli Tyre S.P.A., Politecnico Di Milano filed Critical Pirelli Tyre S.P.A.
Priority to PCT/EP2007/004759 priority Critical patent/WO2008145155A1/fr
Publication of WO2008145155A1 publication Critical patent/WO2008145155A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • 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

Definitions

  • the present invention relates to a tire, to a tire tread band and to a crosslinkable elastomeric composition.
  • the present invention relates to a tire including at least one structural element obtained by crosslinking a crosslinkable elastomeric composition comprising at least one solid elastomeric polymer, at least one liquid elastomeric polymer, at least one silica reinforcing filler, at least one coupling agent containing at least one mercapto group.
  • the present invention also relates to a tire tread band including a crosslinkable elastomeric composition comprising at least one solid elastomeric polymer, at least one liquid elastomeric polymer, at least one silica reinforcing filler, at least one coupling agent containing at least one mercapto group.
  • the present invention also relates to a crosslinkable elastomeric composition
  • a crosslinkable elastomeric composition comprising at least one solid elastomeric polymer, at least one liquid elastomeric polymer, at least one silica reinforcing filler, at least one coupling agent containing at least one mercapto group, as well as to a crosslinked manufactured article obtained by crosslinking said crosslinkable elastomeric composition.
  • processing oils may show some drawbacks. For example, while increasing the processing oils contents of a tread band elastomeric composition usually increases its dry traction, it also usually reduces its lifetime as evidenced by a reduction of one of more of tensile modulus at 300% elongation (300% Modulus), stress at break, elongation at break, and/or abrasion resistance.
  • United States Patent US 6,242,523 relates to a rubber composition comprised of, based upon its rubber component, (A) 100 parts by weight (phr) of at least one solid, sulfur vulcanizable, diene-based elastomer selected from homopolymers and copolymers of conjugated diene and copolymers of at least one conjugated diene with a vinyl aromatic compound selected from styrene and ⁇ - methylstyrene; wherein said elastomers have a glass transition temperature (T 9 ) of lower than +10 0 C and wherein at least 50% by weight of said elastomers have a glass transition temperature (T 9 ) above -40 0 C; and (B) from about 5 phr to about 50 phr of a liquid polymer of high vinyl polybutadiene, characterized by being a pourable liquid at a temperature in a range of about 20 0 C to about 25°C, having a vinyl (1 ,2-) content in
  • a tire having a tread made of said rubber composition is also disclosed.
  • the abovementioned rubber composition is said to be advantageously used for a tire tread in order to improve dry traction (increased hysteresis) while maintaining durability and treadwear in high performance tires which are intended to be driven at relatively high speeds.
  • Canadian Patent Application CA 2,544,592 relates to a sulfur-vulcanizable rubber mixture, especially for the treads of tires, which comprises at least one diene rubber; liquid polybutadiene having a molecular weight of from 1500 g/mol to 10000 g/mol and a vinyl content of from 15% to 50%; at least one polar filler; at least one high- structure carbon black having a iodine absorption number of from 115 g/kg to 200 g/kg and a DBP number of from 125 ml/100 g to 160 ml/100 g; and at least one glyceride and/or factice.
  • the abovementioned rubber composition is said to give tires having good abrasion characteristics, good wet traction, good traction on ice and snow and good dry braking.
  • the Applicant has noticed that the crosslinked elastomeric compositions including the above disclosed liquid elastomeric polymers, as well as the tires so obtained, may show the following drawbacks: a reduction of one or more of the static mechanical properties, in particular a reduction of the tensile modulus at 300% elongation (300% Modulus) and, consequently, a reduced lifetime of the obtained tires; an increased variation of the dynamic elastic modulus (E') as the temperature increases (namely, an increased "thermoplastic behaviour" of the crosslinked elastomeric compositions, consequently, the crosslinked elastomeric compositions may not be able to maintain essentially constant elastic performance qualities over a wide temperature range which is of fundamental importance when using the compositions in tires manufacturing); - an increase in the Tan delta (loss factor) values (in particular, at 70 0 C) and, consequently, an increased rolling resistance of the obtained tire; a reduction of abrasion resistance and, consequently, a reduced lifetime of the obtained tires.
  • tires e.g., high-performance tires
  • tires showing a good balance between wet grip, rolling resistance and abrasion resistance
  • the Applicant has faced the problem of providing a tire showing a good balance between wet grip, rolling resistance and abrasion resistance.
  • the Applicant has now found that it is possible to obtain a tire having the abovementioned properties, by adding at least one coupling agent containing at least one mercapto group to crosslinkable elastomeric compositions comprising at least one solid elastomeric polymer, at least one liquid elastomeric polymer and at least one silica reinforcing filler.
  • the Applicant has also found that the amount of said at least one solid elastomeric polymer may be reduced.
  • the use of a reduced amount of said at least one solid elastomeric polymer may allow to obtain crosslinkable elastomeric compositions having a relatively low viscosity (Mooney viscosity) which, consequently, may be more easily processed in conventional rubber processing apparatus, including internal rubber mixers and various rubber extruders.
  • Mooney viscosity relatively low viscosity
  • the Applicant has also found that, the amount of processing oils which is usually added to crosslinkable elastomeric compositions may be reduced.
  • the use of a reduced amount of said processing oils may allows to avoid a decrease in tensile modulus which often occurs in the crosslinked elastomeric composition so obtained.
  • a reduced amount of said processing oils, which often are aromatic oils have a positive effect on the environment (pollution problems are avoided).
  • the Applicant has also found that the amount of silane coupling agents, in particular the amount of those containing a sequence of sulfur atoms, other than said coupling agent containing at least one mercapto group, which is usually used in crosslinkable elastomeric compositions comprising silica reinforcing fillers, may be reduced or even eliminated.
  • the reduced amount of said silane coupling agents allows to avoid the limitation on the maximum temperature which may be reached during the blending and thermomechanical processing operations of the crosslinkable elastomeric compositions comprising the same, which is usually necessary in order to avoid the penalty of an irreversible thermal degradation of the silane coupling agents.
  • the present invention relates to a tire comprising at least one structural element including a crosslinked elastomeric material obtained by crosslinking a crosslinkable elastomeric composition
  • a crosslinked elastomeric material obtained by crosslinking a crosslinkable elastomeric composition
  • a crosslinkable elastomeric composition comprising:
  • the present invention relates to a tire comprising at least one structural element including a crosslinked elastomeric material obtained by crosslinking a crosslinkable elastomeric composition
  • a crosslinked elastomeric material obtained by crosslinking a crosslinkable elastomeric composition
  • a crosslinkable elastomeric composition comprising: (a) from 75 phr to 95 phr, preferably of from 85 phr to 90 phr, of at least one solid elastomeric polymer having a Mooney viscosity, measured at 100 0 C, of from 30 to 90, preferably of from 40 to 75; (b) from 5 phr to 25 phr, preferably of from 10 phr to 15 phr, of at least one liquid elastomeric polymer having a number average molecular weight (M n ) of from 1000 to 20000, preferably of from 3000 to 15000, and an amount of vinyl unsaturations in the butadiene part,
  • Said number average molecular weight (M n ) may be measured according to techniques known in the art such as, for example, by gel permeation chromatography (GPC).
  • Said vinyl unsaturations may be measured according to techniques known in the art such as, for example, by 1 H-NMR spectroscopy or 13 C-NMR spectroscopy.
  • the term “phr” means the parts by weight of a given component of the crosslinkable elastomeric composition per 100 parts by weight of the elastomeric polymer(s).
  • the present invention relates to a tire tread band including a crosslinkable elastomeric composition
  • a crosslinkable elastomeric composition comprising:
  • the present invention relates to a tire tread band including a crosslinkable elastomeric composition
  • a crosslinkable elastomeric composition comprising:
  • the present invention relates to a crosslinkable elastomeric composition
  • a crosslinkable elastomeric composition comprising:
  • the present invention relates to a crosslinkable elastomeric composition
  • a crosslinkable elastomeric composition comprising:
  • the present invention relates to a crosslinked manufactured article obtained by crosslinking a crosslinkable elastomeric composition above reported.
  • the present invention in at least one of the abovementioned aspects, may show one or more of the preferred characteristics hereinafter described.
  • said crosslinkable elastomeric composition may further comprise (e) at least one silane coupling agent, other than said at least one coupling containing at least one mercapto group (d).
  • said crosslinkable elastomeric composition may further comprise (f) at least one layered material having an individual layer thickness of from 0.01 nm to 30 nm, preferably of from 0.2 nm to 15 nm, more preferably of from 0.5 nm to 2 nm.
  • the addition of said at least one layered material (T) may allow to improve, in particular, the abrasion resistance of the crosslinked elastomeric composition so obtained and, consequently, the lifetime of the tire so obtained,
  • said at least one solid elastomeric polymer (a) may be selected, for example, from Ca 1 ) diene elastomeric polymers which are commonly used in sulfur-crosslinkable elastomeric compositions, that are particularly suitable for producing tires, that is to say from elastomeric polymers or copolymers with an unsaturated chain having a glass transition temperature (T 9 ) generally below 20 0 C, preferably in the range of from 0 0 C to -110°C.
  • T 9 glass transition temperature
  • polymers or copolymers may be of natural origin or may be obtained by solution polymerization, emulsion polymerization or gas-phase polymerization of one or more conjugated diolefins, optionally blended with at least one comonomer selected from monovinylarenes and/or polar comonomers.
  • the obtained polymers or copolymers contain said at least one comonomer selected from monovinylarenes and/or polar comonomers in an amount of not more than 60% by weight.
  • the conjugated diolefins generally contain from 4 to 12, preferably from 4 to 8 carbon atoms, and may be selected, for example, from: 1 ,3-butadiene, isoprene, 2,3-dimethyl-1 ,3-butadiene, 1 ,3-pentadiene, 1 ,3-hexadiene, 3-butyl-1 ,3-octadiene, 2-phenyl-1 ,3-butadiene, or mixtures thereof. 1 ,3-butadiene, or isoprene, are particularly preferred.
  • Monovinylarenes which may optionally be used as comonomers generally contain from 8 to 20, preferably from 8 to 12 carbon atoms, and may be selected, for example, from: styrene; 1-vinylnaphthalene; 2-vinylnaphthalene; various alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl derivatives of styrene such as, for example, ⁇ - methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4- dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4-phenylbutyl)styrene, or mixtures thereof. Styrene is particularly preferred.
  • Polar comonomers which may optionally be used may be selected, for example, from: vinylpyridine, vinylquinoline, acrylic acid and alkylacrylic acid esters, nitriles, or mixtures thereof, such as, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile, or mixtures thereof.
  • said diene elastomeric polymer (a ⁇ may be selected, for example, from: cis-1 ,4-polyisoprene (natural or synthetic cis-1 ,4-polyisoprene, preferably natural cis-1,4-polyisoprene, i.e.
  • Styrene/1 , 3-butadiene copolymers, styrene/isoprene/1 , 3-butadiene copolymers, styrene/1 ,3- butadiene/acrylonitrile copolymers, or mixtures thereof, are particualrly preferred.
  • said at least one solid elastomeric polymer (a) may be selected, for example, from (a 2 ) elastomeric polymers of one or more monoolefins with an olefinic comonomer or derivatives thereof.
  • the monoolefins may be selected, for example, from: ethylene and ⁇ -olefins generally containing from 3 to 12 carbon atoms, such as, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or mixtures thereof.
  • copolymers between ethylene and an ⁇ -olefin, optionally with a diene are preferred: copolymers between ethylene and an ⁇ -olefin, optionally with a diene; isobutene homopolymers or copolymers thereof with small amounts of a diene, which are optionally at least partially halogenated.
  • the diene optionally present generally contains from 4 to 20 carbon atoms and is preferably selected from: 1 , 3-butadiene, isoprene, 1 ,4-hexadiene, 1 ,4-cyclohexadiene, 5- ethylidene-2-norbornene, 5-methylene-2-norbornene, vinylnorbornene, or mixtures thereof.
  • EPR ethylene/propylene copolymers
  • EPDM ethylene/propylene/diene copolymers
  • poly-isobutene butyl rubbers
  • halobutyl rubbers in particular chlorobutyl or bromobutyl rubbers; or mixtures thereof.
  • said crosslinkable elastomeric composition may comprise at least 10% by weight, preferably from 20% by weight to 100% by weight, with respect to the total weight of the at least one solid elastomeric polymer (a), of styrene/1 ,3-butadiene copolymers, in particular of styrene/1 ,3-butadiene copolymers having a high amount of vinyl unsaturation (e.g., higher than or equal to 40% in the butadiene part).
  • the above reported solid elastomeric polymers (a) may optionally be functionalized by reaction with suitable terminating agents or coupling agents.
  • the diene elastomeric polymers Ca 1 ) obtained by anionic polymerization in the presence of an organometallic initiator may be functionalized by reacting the residual organometallic groups derived from the initiator with suitable terminating agents or coupling agents such as, for example, imines, carbodiimides, alkyltin halides, substituted benzophenones, alkoxysilanes or aryloxysilanes (see, for example, European Patent EP 451 ,604, or United States Patents US 4,742,124, or US 4,550,142).
  • the above reported solid elastomeric polymers (a) may optionally include at least one functional group which may be selected, for example, from: carboxylic groups, carboxylate groups, anhydride groups, ester groups, epoxy groups, or mixtures thereof.
  • said at least one liquid elastomeric polymer (b) may be selected, for example, from liquid elastomeric polymers having a Brookfield viscosity, measured at 45°C, not higher than 150000 cPs, preferably of from 10000 cPs to 100000 cPs.
  • said at least one liquid elastomeric polymer (b) may be selected, for example, from liquid elastomeric polymers having a glass transition temperature (T 9 ) of from -5°C to -120 0 C, preferably of from -1O 0 C to -8O 0 C.
  • T 9 glass transition temperature
  • said at least one liquid elastomeric polymer may be pourable at a temperature of from 20 0 C to 25°C. Said polymer is preferably administered within such temperature, although it might be used at a temperature above or below such temperature range.
  • said at least one liquid elastomeric polymer (b) may be selected, for example, from homopolymers or copolymers of conjugated diolefins containing from 4 to 12, preferably from 4 to 8, carbon atoms, such as, for example: 1 ,3-butadiene, isoprene, 2,3-dimethyl-1 ,3-butadiene, 1 ,3-pentadiene, 1 ,3- hexadiene, 3-butyl-1 ,3-octadiene, 2-phenyl-1 ,3-butadiene, or mixtures thereof.
  • 1 ,3- Butadiene homopolymers, or 1 ,3-butadiene-isoprene copolymers are particularly preferred.
  • said at least one liquid elastomeric polymer (b) may be selected, for example, from copolymers of 1 ,3-butadiene with at least one monovinylarene containing from 8 to 20, preferably from 8 to 12 carbon atoms, said monovinylarene being selected, for example from: styrene; 1-vinylnaphthalene; 2-vinylnaphthalene; various alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl derivatives of styrene such as, for example, ⁇ -methylstyrene, 3- methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4- benzylstyrene, 4-p-tolylstyrene, 4-(4-phenylbutyl)styrene
  • epoxydized poly(butadienes), maleic poly(butadienes), acrylated poly(butadienes), acrylonitrile/1 ,3-butadiene copolymers may be advantageously used.
  • liquid elastomeric polymers which may be used according to the present invention and are available commercially are the following products: poly(butadienes) (Ricon 130, 131 , 134, 142, 150, 152, 153, 154, 156, 157, P30D) available from Sartomer Company, Inc; styrene/1 ,3-butadiene random copolymers (Ricon 100, 181 , 184) available from Sartomer Company Inc.; maleinized poly(butadienes) (Ricon 130MA8, 130MA13, 130MA20, 131 MA5, 131 MA10, 131 MA17, 131 MA20, 156MA17) available from Sartomer Company, Inc.; acrylated poly(butadienes) (CN302, NTX6513, CN301 , NTX6039, PRO6270, Ricacryl 3100, Ricacryl 3500) available from Sartomer Inc.; epoxydized poly(butadienes) (Polybd 600, 60,
  • said at least one silica reinforcing filler (c) may be selected, for example, from: pyrogenic silica, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), fumed silica, calcium silicate, or mixtures thereof.
  • suitable fillers include aluminum silicate, magnesium silicate, or mixtures thereof.
  • precipitated amorphous wet- process hydrated silicas are preferred. These silicas are so-called because they are produced by a chemical reaction in water, from which they are precipitated as ultrafine, spherical particles. These primary particles strongly associate into aggregates, which in turn combine less strongly into agglomerates.
  • Silica reinforcing fillers which may be advantageously used according to the present invention, preferably have a surface area of from 32 m 2 /g to 400 m 2 /g, more preferably of from 100 m 2 /g to 250 m 2 /g, still more preferably of from 150 m 2 /g to 220 m 2 /g.
  • the pH of said silica reinforcing fillers is, generally, of from 5.5 to 7.0, preferably of from 5.5 to 6.8.
  • silica reinforcing fillers which may be used according to the present invention and are available commercially are the products known by the name of Hi- Sil ® 190, Hi-Sil ® 210, Hi-Sil ® 215, Hi-Sil ® 233, Hi-Sil ® 243, from PPG Industries (Pittsburgh, Pa.); or the products known by the name of Ultrasil ® VN2, Ultrasil ® VN3 from Degussa; or the product known under the name of Zeosil ® 1165MP from Rhodia.
  • said at least one coupling agent containing at least one mercapto group (d) may be selected, for example, from compounds having the following general formula (I): HS (CH) a — (X) b — (CH) c - ⁇ ( D
  • R R wherein: a + c is an integer of from 1 to 36, extremes included;
  • R represents a hydrogen atom; a linear or branched C 1 -C 6 alkyl group; a COOH group;
  • X represents an oxygen atom; a sulfur atom; a NH group; when X represent an oxygen atom or a NH group, b is O or 1 ; when X represents a sulfur atom, b is O, or an integer of from 1 to 4, extremes included;
  • - Y represents a polar group which is selected from: silane groups; acid groups; ester groups; amide groups; imide groups; nitro groups; hydroxy groups; mercapto groups; on condition that, when Y represents a mercapto group, at least one of the R substituents is a COOH group.
  • said at least one coupling agent containing at least one mercapto group (d) may be selected from mercaptosilanes, mercaptans, or mixtures thereof. Mercaptosilanes are particularly preferred.
  • said mercaptosilanes may be selected, for example, from compounds having the following general formula (II):
  • R" represents a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or a Ci-C 10 alkoxy group;
  • R' which may be equal or different from each other, are selected from: C 1 -C 36 alkyl groups; C 6 -C 20 aryl groups; C 7 -C 30 alkylaryl or arylalkyl groups; C 5 -C 30 cycloaliphatic groups; n is an integer of from 1 to 3, extremes included.
  • R" represents a C 1 -C 3 alkoxy group
  • R represents a hydrogen atom
  • b is 0
  • a + c is 3
  • n is 3.
  • mercaptosilanes having general formula (II) which may be advantageously used according to the present invention are: 1-mercapto- methyltriethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltriethoxy- silane, 3-mercaptopropylmethyldiethoxysilane, 2-mercaptoethyltripropoxysilane, 18- mercaptooctadecyldiethoxychlorosilane, or mixture thereof.
  • 3-Mercaptopropyl- triethoxysilane is particularly preferred.
  • said mercaptanes may be selected, for example, from compounds having the following general formula (III):
  • R R wherein: a, b, c, R and X, have the same meanings as above disclosed; - R'" represents: a OR a group, wherein R a represents a hydrogen atom; a metal such as, for example, lithium, sodium, potassium, magnesium, calcium; a linear or branched or cyclic C 1 -C 36 alkyl group; a C 6 -C 20 aryl group; a C 7 -C 30 alkylaryl or arylalkyl group; a C 5 -C 30 cycloaliphatic group; an ammonium ion; a NRiR 2 group, wherein Ri and R 2 , represents a linear or branched or cyclic Ci-C 36 alkyl group; a C 6 -C 20 aryl group; a C 7 -C 30 alkylaryl or arylalkyl group; a C 5 -C 30 cycloaliphatic group.
  • R is a hydrogen atom
  • b is 0
  • a + c is an integer of from 3 to 12, extremes included
  • R'" represent a OR a wherein R a is a hydrogen atom.
  • mercaptans having general formula (III) which may be advantageously used according to the present invention are: thioglycolic acid, 2- mercaptopropionic acid (thiolactic acid), 3-mercaptopropionic acid, 4- mercaptobutyric acid, mercaptoundecanoic acid, mercaptooctadecanoic acid, 2- mercaptosuccinic acid, 3,4-dimercaptosuccinic acid, 3-(3-mercaptopropyl- sulfanyl)propionic acid, 3-(3-mercaptopropyloxy)propionic acid, alkali, alkaline earth or ammonium salts thereof, or mixtures thereof.
  • Mercaptoundecanoic acid is preferred.
  • said crosslinkable elastomeric composition may further comprise (e) at least one silane coupling agent, other than said at least one coupling agent containing at least one mercapto group (d).
  • said at least one silane coupling agent (e) may be selected from those having at least one hydrolizable silane group which may be identified, for example, by the following general formula (IV): (Rs) 3 Si-C n H 2n -R 6 (IV) wherein the groups Rs, which may be equal or different from each other, are selected from: alkyl, alkoxy or aryloxy groups or from halogen atoms, on condition that at least one of the groups R 5 is an alkoxy or aryloxy group; n is an integer of from 1 to 6, extremes included; R 6 is a group selected from: nitroso, amino, epoxide, vinyl, imide, chloro, -(S) 01 C n H 2n -Si-(Rs) 3 , or -S-COR 5 , in which m and n are integers of from 1 to 6, extremes included and the groups R 5 are defined as above.
  • silane coupling agents (e) that are particularly preferred are bis(3- triethoxysilyl-propyl)tetrasulphide or bis(3-triethoxysilylpropyl)-disulphide.
  • Said silane coupling agents (e) may be used as such or as a suitable mixture with an inert filler (for example carbon black) so as to facilitate their incorporation into the elastomeric polymer(s).
  • said at least one silane coupling agent (e) may be present in the crosslinkable elastomeric composition in an amount of from 0 phr to 10 phr, preferably of from 0.5 phr to 5 phr.
  • said crosslinkable elastomeric composition may further comprise (f) at least one layered material.
  • said at least one layered material (f) may be selected, for example, from: phyllosilicates such as, for example, smectites, for example, montmorillonite, bentonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite; vermiculite; halloisite; sericite; aluminate oxides; hydrotalcite; or mixtures thereof.
  • phyllosilicates such as, for example, smectites, for example, montmorillonite, bentonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite; vermiculite; halloisite; sericite; aluminate oxides; hydrotalcite; or mixtures thereof.
  • Montmorillonite is particularly preferred.
  • These layered material generally contains exchangeable ions such as sodium (Na + ), calcium (Ca 2+ ), potassium (K + ), magnesium (Mg 2+ ), hydroxide (HO " ), or carbonate (CO 3 2' ), present at the interlayer surfaces.
  • exchangeable ions such as sodium (Na + ), calcium (Ca 2+ ), potassium (K + ), magnesium (Mg 2+ ), hydroxide (HO " ), or carbonate (CO 3 2' ), present at the interlayer surfaces.
  • said at least one layered material (f) may be treated with at least one compatibilizing agent.
  • Said compatibilizing agent is capable of undergoing ion exchange reactions with the ions present at the interlayers surfaces of the layered material.
  • said at least one compatibilizing agent may be selected, for example, from the quaternary ammonium or phosphonium salts having the following general formula (V):
  • R 1 , R 2 , R 3 and R 4 which may be equal or different from each other, represent a linear or branched C 1 -C 2O alkyl or hydroxyalkyl group; a linear or branched C 1 -C 20 alkenyl or hydroxyalkenyl group; a group -R 5 -SH or -R 5 -NH wherein R 5 represents a linear or branched C 1 -C 2 O alkylene group; a C 6 -C 18 aryl group; a C 7 -C 20 arylalkyl or alkylaryl group; a C 5 -C 18 cycloalkyl group, said cycloalkyl group possibly containing hetero atom such as oxygen, nitrogen or sulfur; X 1 " " represents an anion such as the chloride ion, the sulphate ion or the phosphate ion; - n represents 1 , 2 or 3.
  • Said layered material (f) may be treated with the compatibilizing agent before adding it to the elastomeric polymer(s).
  • said layered material (f) and the compatibilizing agent may be separately added to the elastomeric polymer(s).
  • the treatment of the layered material (T) with the compatibilizing agent may be carried out according to known methods such as, for example, by an ion exchange reaction between the layered material and the compatibilizing agent: further details about said methods may be found, for example, in United States Patents US 4,136,103, US 5,747,560, or US 5,952,093.
  • said at least one layered material (f) may be present in the crosslinkable elastomeric composition in an amount of from 0 phr to 20 phr, preferably from 2 phr to 10 phr.
  • Examples of layered material (f) which may be used according to the present invention and are available commercially are the products known by the name of Dellite ® 67G, Dellite ® 72T, Dellite ® 43B, from Laviosa Chimica Mineraria S.p.A.; Cloisite ® 25A, Cloisite ® 10A, Cloisite ® 15A, Cloisite ® 2OA, from Southern Clays; Nanofil ® 5, Nanofil ® 8, Nanofil ® 9, from S ⁇ d Chemie; Bentonite ® AG/3 from DaI Cin S.p.A.
  • At least one additional reinforcing filler may be advantageously added to the above reported crosslinkable elastomeric composition, in an amount generally of from 0 phr to 70 phr, preferably of from 20 phr to 50 phr.
  • the reinforcing filler may be selected from those commonly used for crosslinked manufactured articles, in particular for tires, such as, for example, carbon black, calcium carbonate, kaolin, or mixtures thereof.
  • the types of carbon black which may be used according to the present invention may be selected from those conventionally used in tires manufacturing, and generally have a surface area of not less than 20 m 2 /g (determined by CTAB absorption as described in Standard ISO 6810:1995).
  • the crosslinkable elastomeric composition above reported may be vulcanized according to known techniques, in particular with sulfur-based vulcanizing systems commonly used for elastomeric polymer(s).
  • a sulfur-based vulcanizing agent is incorporated together with vulcanization accelerators.
  • the temperature is generally kept below 140°C, so as to avoid any undesired pre-crosslinking phenomena.
  • the vulcanizing agent most advantageously used is sulfur, or molecules containing sulfur (sulfur donors), with accelerators and activators known to those skilled in the art.
  • Activators that are particularly effective are zinc compounds, and in particular ZnO, ZnCO 3 , zinc salts of saturated or unsaturated fatty acids containing from 8 to 18 carbon atoms, such as, for example, zinc stearate, which are preferably formed in situ in the elastomeric composition from ZnO and fatty acid, and also BiO, PbO, Pb 3 O 4 , PbO 2 , or mixtures thereof.
  • Accelerators that are commonly used may be selected from: dithiocarbamates, guanidine, thiourea, thiazoles, sulphenamides, thiurams, amines, xanthates, or mixtures thereof.
  • Said crosslinkable elastomeric composition may comprise other commonly used additives selected on the basis of the specific application for which the composition is intended.
  • the following may be added to said crosslinkable elastomeric composition: antioxidants, anti-ageing agents, plasticizers, adhesives, anti-ozone agents, modifying resins, or mixtures thereof.
  • a plasticizer generally selected from mineral oils, vegetable oils, synthetic oils, or mixtures thereof, such as, for example, aromatic oil, naphthenic oil, phthalates, soybean oil, or mixtures thereof, may be added to said crosslinkable elastomeric composition.
  • the amount of plasticizer generally ranges from O phr to 50 phr, preferably from of 5 phr to 30 phr.
  • the above reported crosslinkable elastomeric composition may be prepared by mixing together the solid elastomeric polymer(s), the liquid elastomeric polymer(s), and the coupling agent(s) containg at least one mercapto group, with the silica reinforcing filler and the other compounds optionally present, according to techniques known in the art.
  • the mixing may be carried out, for example, using an open mixer of open-mill type, or an internal mixer of the type with tangential rotors (Banbury) or with interlocking rotors (Intermix), or in continuous mixers of Ko- Kneader type (Buss), or of co-rotating or counter-rotating twin-screw type.
  • FIG. 1 is a view in cross-section of a portion of a tire made according to the present invention.
  • Fig. 1 shows only a portion of the tire, the remaining portion not represented being identical and symmetrically arranged with respect to the radial direction "r".
  • the tire (100) comprises at least one carcass ply (101), the opposite lateral edges of which are associated with respective bead structures comprising at least one bead core (102) and at least one bead filler (104).
  • the association between the carcass ply (101 ) and the bead core (102) is achieved here by turning back the opposite lateral edges of the carcass ply (101 ) around the bead core (102) so as to form the so-called carcass turn-up (101a) as shown in Fig. 1.
  • the conventional bead core (102) may be replaced with at least one annular insert formed from rubberized wires arranged in concentric coils (not represented in Fig. 1 ) (see, for example, European Patent Applications EP 928,680 or EP 928,702).
  • the carcass ply (101) is not tumed-up around said annular inserts, the coupling being provided by a second carcass ply (not represented in Fig. 1 ) applied externally over the first.
  • the carcass ply (101) usually comprises a plurality of reinforcing cords arranged parallel to each other and at least partially coated with a layer of a crosslinked elastomeric composition.
  • These reinforcing cords are usually made of textile fibres, for example rayon, nylon or polyethylene terephthalate, or of steel wires stranded together, coated with a metal alloy (for example copper/zinc, zinc/manganese, zinc/molybdenum/cobalt alloys, and the like).
  • the carcass ply (101) is usually of radial type, i.e. it incorporates reinforcing cords arranged in a substantially perpendicular direction relative to a circumferential direction.
  • the core (102) is enclosed in a bead (103), defined along an inner circumferential edge of the tire (100), with which the tire engages on a rim (not represented in Fig. 1 ) forming part of a vehicle wheel.
  • the space defined by each carcass turn-up (101a) contains a bead filler (104) usually made of a crosslinked elastomeric composition.
  • An antiabrasive strip (105) is usually placed in an axially external position relative to the carcass turn-up (101a).
  • a belt structure (106) is applied along the circumference of the carcass ply (101).
  • the belt structure (106) comprises two belt strips (106a, 106b) which incorporate a plurality of reinforcing cords, typically metal cords, which are parallel to each other in each strip and intersecting with respect to the adjacent strip, oriented so as to form a predetermined angle relative to a circumferential direction.
  • At least one zero-degree reinforcing layer (106c) may optionally be applied, commonly known as a "0° belt", which generally incorporates a plurality of reinforcing cords, typically textile cords, arranged at an angle of a few degrees relative to a circumferential direction, usually coated with a crosslinked elastomeric composition.
  • the tread band (109) has a rolling surface (109a) designed to come into contact with the ground.
  • Circumferential grooves which are connected by transverse notches (not represented in Fig. 1 ) so as to define a plurality of blocks of various shapes and sizes distributed over the rolling surface (109a) are generally made in this surface (109a), which is represented for simplicity in Fig. 1 as being smooth.
  • a sidewall (108) is also applied externally onto the carcass ply (101 ), this sidewall extending, in an axially external position, from the bead (103) to the end of the belt structure (106).
  • a tread underlayer (111) is placed between the belt structure (106) and the tread band (109).
  • the tread underlayer (111) may have uniform thickness.
  • the tread underlayer (111) may have a variable thickness in the transversal direction.
  • the thickness may be greater near its outer edges than at a central zone.
  • said tread underlayer (111 ) extends over a surface substantially corresponding to the surface of development of said belt structure (106).
  • said tread underlayer (111) extends only along at least one portion of the development of said belt structure (106), for instance at opposite side portions of said belt structure (106) (not represented in Fig. 1).
  • the end portion of the side wall (108) directly covers the lateral edge of the tread band (109).
  • the process for producing the tire according to the present invention may be carried out according to techniques and using apparatus that are known in the art, said process including manufacturing a green tire, and subsequently moulding and vulcanizing the green tire.
  • the tire according to the present invention may be suitable for running at high speeds.
  • said tire may be a high performance tire commonly referred to as "HP" ("High Performance"), i.e. a tire capable of sustaining a maximum speed of at least 210 Km/h, preferably of from 210 Km/h and 240 Km/h.
  • HP High Performance
  • Examples of said tires are those belonging to the classes "H” and "V”.
  • the elastomeric compositions given in Table 1 were prepared as follows (the amounts of the various components are given in phr).
  • S-SBR solution-prepared styrene/1 ,3-butadiene copolymer having a styrene content of 25% by weight and an amount of vinyl unsaturations in the butadiene part of 67%; and having a Mooney viscosity, measured at 100 0 C, of
  • Silquest ® A-1891 Silane 3-mercaptopropyltriethoxysilane (GE Silicones); TESPD: bis(3-triethoxysilylpropyl)disulphide (Degussa-H ⁇ ls); Antioxidant: phenyl-p-phenylenediamine (6-PPD - Akzo Nobel); Silica: Zeosil ® 1165 MP (Rhodia);
  • DPG80 diphenyl guanidine (Rhenogran ® DPG80 - Rhein Chemie); CBS (accelerator): N-cyclohexyl ⁇ -benzothiazyl-sulphenamide (Vulkacit ® CZ/C - Lanxess).
  • the modulus (100% Modulus and 300% Modulus), the stress at break, as well as the elongation at break, were measured according to Standard ISO 37:2005 on samples of the abovementioned elastomeric compositions vulcanized at 17O 0 C, for 10 min. The results obtained are given in Table 2.
  • Table 2 also shows the dynamic mechanical properties, measured using an lnstron dynamic device in the traction-compression mode according to the following methods.
  • the dynamic mechanical properties are expressed in terms of dynamic elastic modulus (E') and Tan delta (loss factor) values.
  • the Tan delta value is calculated as a ratio between viscous modulus (E") and elastic modulus (E').
  • Table 2 also show the DIN abrasion: the data (expressed in mm 3 ) correspond to the amount of elastomeric composition removed by operating under the standard conditions given in Standard DIN 53516. TABLE 2
  • the elastomeric compositions given in Table 3 were prepared as follows (the amounts of the various components are given in phr).
  • S-SBR solution-prepared styrene/1 ,3-butadiene copolymer having a styrene content of 25% by weight and an amount of vinyl unsaturations in the butadiene part of 67%; and having a Mooney viscosity, measured at 100°C, of 48 (Europrene ® SOL R 76612 - Polimeri Europa);
  • NR cis-1 ,4-polyisoprene having a Mooney viscosity, measured at 100 0 C, of 72
  • T 9 glass transition temperature
  • Silquest ® A-1891 Silane 3-mercaptopropyltriethoxysilane (GE Silicones); TESPD: bis(3-triethoxysilylpropyl)disulphide (Degussa-H ⁇ ls);
  • Antioxidant phenyl-p-phenylenediamine (6-PPD - Akzo Nobel); Silica: Zeosil ® 1165 MP (Rhodia);
  • DPG80 diphenyl guanidine (Rhenogran ® DPG80 - Rhein Chemie); CBS (accelerator): N-cyclohexyl ⁇ -benzothiazyl-sulphenamide (Vulkacit ® CZ/C - Lanxess).
  • the elastomeric compositions given in Table 5 were prepared as follows (the amounts of the various components are given in phr).
  • S-SBR solution-prepared styrene/1 ,3-butadiene copolymer having a styrene content of 25% by weight and an amount of vinyl unsaturations in the butadiene part of 67%; and having a Mooney viscosity, measured at 100 0 C, of
  • NR cis-1 ,4-polyisoprene having a Mooney viscosity, measured at 100 0 C, of 60
  • TESPD bis(3-triethoxysilylpropyl)disulphide (Degussa-H ⁇ ls);
  • Dellite ® 67G montmorillonite belonging to the smectite family modified with quaternary ammonium salt (Laviosa Chimica Mineraria S.p.A.); Antioxidant: phenyl-p-phenylenediamine (6-PPD - Akzo Nobel); Silica: Zeosil ® 1165 MP (Rhodia);

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Abstract

L'invention concerne un pneu qui comporte au moins un élément structurel comprenant une matière élastomère réticulée obtenue par la réticulation d'une composition élastomère pouvant être réticulée comportant : (a) 100 phr d'au moins un polymère élastomère solide ayant une viscosité de Mooney, mesurée à 100°C, de 30 à 90, de préférence de 40 à 75 ; (b) de 3 phr à 33 phr, de préférence de 5 phr à 15 phr, d'au moins un polymère élastomère liquide ayant un poids moléculaire moyen en nombre (Mn) de 1000 à 20000, de préférence de 3000 à 15000, et une quantité de non saturations vinyliques dans la partie butadiène de 15 % à 100 %, de préférence de 30 % à 90 % ; (c) de 5 phr à 120 phr, de préférence de 20 phr à 90 phr, d'au moins une charge de renforcement à silice ; (d) de 0,1 phr à 10 phr, de préférence de 0,5 phr à 8 phr, d'au moins un agent de couplage contenant au moins un groupe mercaptobenzothiazole. De préférence, ledit ou lesdits éléments structuraux sont une bande de roulement.
PCT/EP2007/004759 2007-05-30 2007-05-30 Pneu et composition élastomère réticulable WO2008145155A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2250218A1 (fr) * 2008-02-25 2010-11-17 Pirelli Tyre S.P.A. Pneu et composition élastomère réticulable
ITTO20100476A1 (it) * 2010-06-07 2011-12-08 Bridgestone Corp Mescola per battistrada per pneumatici invernali
EP2424737A1 (fr) * 2009-04-29 2012-03-07 Societe de Technologie Michelin Bande de roulement pour pneus de poids lourd
ITTO20120954A1 (it) * 2012-10-29 2014-04-30 Bridgestone Corp Metodo per la preparazione di una mescola per battistrada
WO2014105813A1 (fr) * 2012-12-27 2014-07-03 Compagnie Generale Des Etablissements Michelin Support de flanc pour pneu pouvant rouler à plat
US9296840B2 (en) 2013-10-25 2016-03-29 China Petroleum & Chemical Corporation Functional diene polymer, preparation method thereof, and rubber composition comprising the same
WO2017046766A1 (fr) * 2015-09-18 2017-03-23 Pirelli Tyre S.P.A. Compositions d'élastomères pour des élémemts de pneu et pneus mettant en œuvre ces dernières
WO2017046771A1 (fr) * 2015-09-18 2017-03-23 Pirelli Tyre S.P.A. Pneumatiques d'hiver
EP3176208A1 (fr) * 2015-12-03 2017-06-07 Sumitomo Rubber Industries, Ltd. Procédé de production de composition de caoutchouc pour pneumatiques
EP3176209A1 (fr) * 2015-12-03 2017-06-07 Sumitomo Rubber Industries, Ltd. Procédé de production de composition de caoutchouc pour pneumatiques
CN108892816A (zh) * 2018-05-12 2018-11-27 南京工程学院 一种浅色耐溶剂天然橡胶硫化胶及其制备方法
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread
CN109642054A (zh) * 2016-09-02 2019-04-16 株式会社可乐丽 橡胶组合物
CN109642055A (zh) * 2016-09-02 2019-04-16 株式会社可乐丽 橡胶组合物

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EP1529806A1 (fr) * 2003-11-04 2005-05-11 Continental Aktiengesellschaft Composition de caoutchouc et pneus
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EP1788020A1 (fr) * 2004-09-10 2007-05-23 The Yokohama Rubber Co., Ltd. Formulation de caoutchouc pour pneumatiques

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US4840988A (en) * 1987-02-17 1989-06-20 Toyo Tire & Rubber Co., Ltd. Rubber composition for tire tread
EP0708137A1 (fr) * 1994-10-21 1996-04-24 Uniroyal Englebert Reifen GmbH Composition de caoutchouc vulcanizable et pneumatique fabriqué à partir de cette composition
US6204320B1 (en) * 1999-02-12 2001-03-20 The Goodyear Tire & Rubber Company Liquid isoprene-butadiene rubber
EP1035164A1 (fr) * 1999-03-08 2000-09-13 The Goodyear Tire & Rubber Company Composition de caoutchouc contenant un polymère liquide à haute Tg et pneu avec bande de roulement à base de ce mélange
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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2250218B1 (fr) * 2008-02-25 2017-04-05 Pirelli Tyre S.p.A. Pneu et composition élastomère réticulable
EP2250218A1 (fr) * 2008-02-25 2010-11-17 Pirelli Tyre S.P.A. Pneu et composition élastomère réticulable
EP2424737A1 (fr) * 2009-04-29 2012-03-07 Societe de Technologie Michelin Bande de roulement pour pneus de poids lourd
EP2424737A4 (fr) * 2009-04-29 2012-12-05 Michelin & Cie Bande de roulement pour pneus de poids lourd
ITTO20100476A1 (it) * 2010-06-07 2011-12-08 Bridgestone Corp Mescola per battistrada per pneumatici invernali
ITTO20120954A1 (it) * 2012-10-29 2014-04-30 Bridgestone Corp Metodo per la preparazione di una mescola per battistrada
WO2014105813A1 (fr) * 2012-12-27 2014-07-03 Compagnie Generale Des Etablissements Michelin Support de flanc pour pneu pouvant rouler à plat
US9296840B2 (en) 2013-10-25 2016-03-29 China Petroleum & Chemical Corporation Functional diene polymer, preparation method thereof, and rubber composition comprising the same
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread
RU2731927C2 (ru) * 2015-09-18 2020-09-09 Пирелли Тайр С.П.А. Зимние шины
CN108137866A (zh) * 2015-09-18 2018-06-08 倍耐力轮胎股份公司 轮胎组件用弹性体组合物和包含它们的轮胎
CN108137867A (zh) * 2015-09-18 2018-06-08 倍耐力轮胎股份公司 冬季轮胎
RU2735686C2 (ru) * 2015-09-18 2020-11-05 Пирелли Тайр С.П.А. Эластомерные композиции для компонентов шины и содержащие их шины
WO2017046771A1 (fr) * 2015-09-18 2017-03-23 Pirelli Tyre S.P.A. Pneumatiques d'hiver
WO2017046766A1 (fr) * 2015-09-18 2017-03-23 Pirelli Tyre S.P.A. Compositions d'élastomères pour des élémemts de pneu et pneus mettant en œuvre ces dernières
CN108137866B (zh) * 2015-09-18 2020-08-25 倍耐力轮胎股份公司 轮胎组件用弹性体组合物和包含它们的轮胎
EP3176208A1 (fr) * 2015-12-03 2017-06-07 Sumitomo Rubber Industries, Ltd. Procédé de production de composition de caoutchouc pour pneumatiques
EP3176209A1 (fr) * 2015-12-03 2017-06-07 Sumitomo Rubber Industries, Ltd. Procédé de production de composition de caoutchouc pour pneumatiques
EP3508527A4 (fr) * 2016-09-02 2020-01-15 Kuraray Co., Ltd. Composition de caoutchouc
EP3508526A4 (fr) * 2016-09-02 2020-01-15 Kuraray Co., Ltd. Composition de caoutchouc
CN109642055A (zh) * 2016-09-02 2019-04-16 株式会社可乐丽 橡胶组合物
CN109642054A (zh) * 2016-09-02 2019-04-16 株式会社可乐丽 橡胶组合物
CN109642054B (zh) * 2016-09-02 2021-05-18 株式会社可乐丽 橡胶组合物
US11034821B2 (en) 2016-09-02 2021-06-15 Kuraray Co., Ltd. Rubber compositions
CN109642055B (zh) * 2016-09-02 2021-07-02 株式会社可乐丽 橡胶组合物
US11124631B2 (en) 2016-09-02 2021-09-21 Kuraray Co., Ltd. Rubber compositions
CN108892816A (zh) * 2018-05-12 2018-11-27 南京工程学院 一种浅色耐溶剂天然橡胶硫化胶及其制备方法
CN108892816B (zh) * 2018-05-12 2020-11-10 南京工程学院 一种浅色耐溶剂天然橡胶硫化胶及其制备方法

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