US20070249775A1 - Tread compositions with improved dynamic storage modulus - Google Patents
Tread compositions with improved dynamic storage modulus Download PDFInfo
- Publication number
- US20070249775A1 US20070249775A1 US11/406,796 US40679606A US2007249775A1 US 20070249775 A1 US20070249775 A1 US 20070249775A1 US 40679606 A US40679606 A US 40679606A US 2007249775 A1 US2007249775 A1 US 2007249775A1
- Authority
- US
- United States
- Prior art keywords
- carbon black
- tire component
- series
- iodine adsorption
- rubber
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims description 32
- 238000003860 storage Methods 0.000 title description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 133
- 229920001971 elastomer Polymers 0.000 claims abstract description 50
- 239000005060 rubber Substances 0.000 claims abstract description 45
- 125000000524 functional group Chemical group 0.000 claims abstract description 39
- 239000000945 filler Substances 0.000 claims abstract description 35
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 27
- 239000011630 iodine Substances 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- 235000019241 carbon black Nutrition 0.000 claims description 129
- 229920000642 polymer Polymers 0.000 claims description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 16
- 239000004594 Masterbatch (MB) Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 229960002380 dibutyl phthalate Drugs 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- -1 cyclic amine Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001002 functional polymer Polymers 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CXWGKAYMVASWDQ-UHFFFAOYSA-N 1,2-dithiane Chemical group C1CCSSC1 CXWGKAYMVASWDQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical group C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 239000006105 batch ingredient Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000004887 dithianes Chemical class 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- CKVWBMJEETWJTF-UHFFFAOYSA-N lithium;tributyltin Chemical compound CCCC[Sn]([Li])(CCCC)CCCC CKVWBMJEETWJTF-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010061 rubber shaping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical group CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- XMHKTINRBAKEDS-UHFFFAOYSA-N trioctyltin Chemical group CCCCCCCC[Sn](CCCCCCCC)CCCCCCCC XMHKTINRBAKEDS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0025—Modulus or tan delta
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- 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
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2221/00—Indexing scheme relating to security arrangements for protecting computers, components thereof, programs or data against unauthorised activity
- G06F2221/21—Indexing scheme relating to G06F21/00 and subgroups addressing additional information or applications relating to security arrangements for protecting computers, components thereof, programs or data against unauthorised activity
- G06F2221/2101—Auditing as a secondary aspect
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2221/00—Indexing scheme relating to security arrangements for protecting computers, components thereof, programs or data against unauthorised activity
- G06F2221/21—Indexing scheme relating to G06F21/00 and subgroups addressing additional information or applications relating to security arrangements for protecting computers, components thereof, programs or data against unauthorised activity
- G06F2221/2105—Dual mode as a secondary aspect
Definitions
- One or more embodiments of the present invention are directed toward tire components and/or tire compositions, including treads, with improved dynamic storage modulus.
- Hysteresis loss particularly at operating temperatures such as 50° C., is often attributed to rolling resistance. As a result, rolling resistance can be decreased by decreasing hysteresis loss (i.e., tan ⁇ ) at operating temperatures.
- Functional polymers have successfully been employed to reduce rolling resistance. It is believed that certain functional groups, when attached to polymer chain ends, can serve to reduce free ends and/or reduce filler agglomeration, which are believed to be sources of hysteresis loss.
- One or more embodiments of the present invention provide a tire component comprising a rubber vulcanizate including one or more functional groups, where said one or more functional groups reduce the 50° C. hysteresis loss of the vulcanizate when compared to similar vulcanizates without the functional group, and a carbon black filler, where said carbon black filler includes (i) a first carbon black characterized by an iodine adsorption number, per ASTM D1510, that is greater than 60 g/kg, and (ii) a second carbon black characterized by an iodine adsorption number, per ASTM D1510, that is less than 60 g/kg.
- One or more embodiments of the present invention also provide a tire component comprising a rubber vulcanizate including one or more functional groups, where said one or more functional groups reduce the 50° C. hysteresis loss of the vulcanizate when compared to similar vulcanizates without the functional group, a carbon black filler, where said carbon black filler includes (i) a first carbon black selected from N-300 series or lower carbon blacks, and (ii) a second carbon black selected from N-400 series or higher carbon blacks, per ASTM D1765.
- One or more embodiments of the present invention also provide a tire component comprising a rubber vulcanizate; and a carbon black filler, dispersed in said rubber vulcanizate, where said carbon black filler includes (i) a first carbon black characterized by an iodine adsorption number, per ASTM D1510, that is greater than 60 g/kg and less than 110 g/kg, and (ii) a second carbon black characterized by an iodine adsorption number, per ASTM D1510, that is less than 60 g/kg.
- the FIGURE includes a plot of G′ versus tan ⁇ for samples prepared according to the present invention as compared to comparative samples.
- Tire components of one or more embodiments of the present invention include rubber vulcanizates having dispersed therein a carbon black filler, where the carbon black filler includes at least two distinct carbon blacks.
- the first carbon black may be generally characterized by a medium or small particle size
- the second carbon black may be generally characterized by a larger particle size.
- the rubber vulcanizates are prepared from functionalized polymers, and therefore the vulcanizates include one or more functional groups.
- the tire components include tire treads characterized by advantageous G′ and tan ⁇ .
- rubber vulcanizates including one or more functional groups can be prepared by vulcanizing an unsaturated polymer including a functional group.
- the unsaturated polymer may be characterized by a glass transition temperature (T g ) that is less than about 0° C., in other embodiments less than about ⁇ 20° C., and in other embodiments less than about ⁇ 30° C.
- Exemplary unsaturated polymers include polybutadiene, polyisoprene, poly(styrene-co-butadiene), poly(styrene-co-butadiene-co-isoprene), poly(isoprene-co-styrene), and poly(butadiene-co-isoprene).
- the unsaturated polymer may have a number average molecular weight (M n ) of from about 5 to about 1,000 kg/mole, in other embodiments from about 50 to about 500 kg/mole, and in other embodiments 100 to about 300 kg/mole.
- M n number average molecular weight
- the unsaturated polymer may also be characterized by a weight average molecular weight (M w ) of from about 5 to about 3,000 kg/mole, in other embodiments from about 50 to about 2,000 kg/mole, and in other embodiments 100 to about 1,200 kg/mole.
- M w weight average molecular weight
- Molecular weight may be determined using Gel Permeation Chromatography (GPC) calibrated with polystyrene standards and adjusted for the Mark-Houwink constants for the polymer in question.
- the functional group may be tethered or attached to the polymer at the head and/or tail of the polymer, and in certain embodiments may be pendant to the polymer chain.
- Functional polymers may include multiple functional groups including head and tail functionalization. As those skilled in the art appreciate, head functionalization refers to the presence of a functional group at or near the location of initiation of the polymer, and tail functionalization refers to the presence of a functional group at or near the location of termination of the polymer.
- functional groups include those substituents that reduce the 50° C. hysteresis loss of a carbon black-filled vulcanizates as compared to similar carbon black-filled vulcanizates without the functional group. In one or more embodiments, this reduction in hysteresis loss is at least 5%, in other embodiments at least 10%, and in other embodiments at least 15%.
- the functional groups include a hetero atom. These hetero atom-bearing substituents include those that may generally be characterized as an electron rich species or metal-containing species. Functional groups include those substituents that react or interact with rubber or rubber fillers or otherwise have a desirable impact on filled rubber compositions or vulcanizates.
- Exemplary functional groups include tin-containing groups, nitrogen-containing groups, boron-containing groups, oxygen-containing groups, phosphorous-containing groups, and sulfur-containing groups.
- Exemplary tin-containing groups include trialkyltin groups such as tributyl tin and trioctyltin groups.
- Exemplary nitrogen-containing groups include cyclic amine groups such as hexamethyleneimine groups, pyrollidine groups, and aziridine groups.
- Exemplary sulfur-containing groups include sulfur-containing azaheterocycle groups, and dithiane groups.
- Exemplary oxygen-containing groups include carbonyl-containing groups, oxygen-containing and azaheterocycle.
- Exemplary phosphorous-containing functionalized polymers are disclosed in U.S. Pat. No. 4,485,833; exemplary oxygen-containing azaheterocycle functionalized polymers are disclosed in U.S. Pat. No. 6,596,798; exemplary oxygen-containing and sulfur-containing heterocycle functionalized polymers are disclosed in International Publication Nos. WO 2004/020475; exemplary trialkyl tin substituent functionalized polymers are disclosed in U.S. Pat. No. 5,268,439; exemplary cyclic amine functionalized polymers are disclosed in U.S. Pat. No. 6,080,853; exemplary aryl or alkyl thio acetal (e.g., dithianes) functionalized polymers are disclosed in International Publication No. WO 2004/041870, all of which are incorporated herein by reference.
- the functionalized polymers may be prepared by initiating the anionic polymerization of conjugated diene monomer (optionally together with vinyl aromatic monomer) with an initiator bearing one or more functional groups (i.e., a functional initiator).
- the functionalized polymer may be prepared by terminating living polymers, prepared from conjugated diene monomers optionally together with vinyl aromatic monomer, with a terminating agent bearing one or more functional groups (i.e., a functional terminator).
- a functional initiator and a functional terminator may be employed.
- Many functional initiators and functional terminators are known in the art. Exemplary functional initiators are disclosed in U.S. Pat. Nos.
- the carbon black filler includes at least two distinct carbon blacks. At least one carbon black may be referred to as a first carbon black, and at least one other carbon black may be referred to as a second carbon black. In these or other embodiments, the first carbon black may be referred to as a medium or small particle size carbon black, and the second carbon black may be referred to as a large particle size carbon black.
- the first carbon black may be defined by an iodine absorption number that is greater than 60 g/kg, in other embodiments greater than 70 g/kg, in other embodiments greater than 80 g/kg, and in other embodiments greater than 90 g/kg, as determined according to ASTM D1510. In these or other embodiments, the first carbon black may be defined by an iodine absorption number that is less than 200 g/kg, in other embodiments less than 175 g/kg, and in other embodiments greater than 161 g/kg, as determined according to ASTM D1510. The first carbon black may also be characterized by a dibutylphthalate absorption number, as determined according to ASTM D2414, that varies over a wide range.
- the dibutylphthalate absorption number may be as low as 70 cc/100 g and increase up to numbers such as 154 cc/100 g.
- the dibutylphthalate absorption number for the first carbon black as determined by ASTM D2414, may be in excess of 115 cc/100 g.
- the first carbon black may be defined by an iodine adsorption number that is greater than 60 g/kg, but less than 110 g/kg, in other embodiments less than 105 g/kg, and in other embodiments less than 100 g/kg, as determined according to ASTM D1510.
- the first carbon black may be characterized as an N-300 series or lower carbon black according to ASTM D1765.
- These carbon blacks may include N-100 series, N-200 series, and N-300 series carbon blacks.
- Exemplary N-100 series carbon blacks include N-100, N-115, N-120, N-121, N-125, N-134, and N-135 carbon blacks.
- Exemplary N-200 series carbon blacks may include N-220, N-231, N-294 and N-299.
- Exemplary N-300 series carbon blacks may include N-326, N-330, N-335, N-343, N-347, N-351, N-356, N-358, and N-375.
- the second carbon black may be defined by an iodine absorption number that is less than 60 g/kg, in other embodiments less than 55 g/kg, in other embodiments greater than 40 g/kg, and in other embodiments less than 30 g/kg, as determined according to ASTM D1510. In these or other embodiments, the second carbon black may be defined by an iodine absorption number that is greater than 8 g/kg, in other embodiments greater than 10 g/kg, and in other embodiments greater than 20 g/kg, as determined according to ASTM D1510. The second carbon black may also be characterized by a dibutylphthalate absorption number that varies over a wide range.
- the dibutylphthalate absorption number may be as low as 34 cc/100 g and increase up to numbers such as 180 cc/100 g.
- the dibutylphthalate absorption number for the second carbon black may be less than 115 cc/100 g, and in other embodiments less than 100 cc/100 g.
- the second carbon black may be characterized as an N-400 series or higher carbon black according to ASTM D1765.
- These carbon blacks may include those selected from the group consisting of N-400 series, N-500 series, N-600 series, N-700 series, N-800 series, and N-900 series carbon blacks.
- Exemplary N-500 series carbon blacks include N-539, N-550, and N-582 carbon blacks.
- Exemplary N-600 series carbon blacks may include N-630, N-642, N-650, N-660, and N-683.
- Exemplary N-700 series carbon blacks may include N-754, N-762, N-765, N-772, N-774, and N-787.
- Exemplary N-600 series carbon blacks may include N-630, N-642, N-650, N-660, and N-683.
- Exemplary N-900 series carbon blacks may include N-907, N-908, N-990, and N-991.
- the iodine absorption number (as determined according to ASTM D1510, of said first carbon black and the iodine absorption number of said second carbon black differ by at least 25 g/kg, in other embodiments by at least 50 g/kg and in other embodiments by at least 75 g/kg.
- the carbon black filler component of the vulcanizates (e.g., treads) of the present invention may include a major amount of the first carbon black (i.e., the medium structure black).
- the carbon black filler component includes greater than 50% by weight of the first carbon black, in other embodiments greater than 60% by weight of the first carbon black, and in other embodiments greater than 75% by weight of the first carbon black based on the total weight of the carbon black component.
- the carbon black component includes less than about 99% by weight, in other embodiments less than about 95% by weight, and in other embodiments less than 90% by weight of the first carbon black based upon the total weight of the carbon black component.
- the carbon black filler component of the vulcanizates may include a minor amount of the second carbon black.
- the carbon black filler component includes less than 50% by weight of the second carbon black, in other embodiments less than 40% by weight of the second carbon black, and in other embodiments less than 25% by weight of the second carbon black based on the total weight of the carbon black component.
- the carbon black component includes greater than about 1% by weight, in other embodiments greater than about 5% by weight, and in other embodiments greater than 10% by weight of the second carbon black based upon the total weight of the carbon black component.
- the vulcanizates of one or more embodiments of the present invention may include from about 1 to about 100 parts by weight carbon black per 100 parts by weight rubber, in other embodiments from about 10 to about 85 parts by weight carbon black per 100 parts by weight rubber, and in other embodiments from about 20 to about 80 parts by weight carbon black per 100 parts by weight rubber.
- the tire components or vulcanizates may be prepared from rubber mixtures (also known as vulcanizable rubber compositions) that include a rubber component, a filler component, a curative system, and other ingredients that are conventionally employed in the preparation of tire components and/or vulcanizates.
- the rubber component may include both functionalized and non-functionalized polymers.
- the rubber component includes at least 5%, in other embodiments at least 10%, in other embodiments at least 20%, in other embodiments at least 40%, and in other embodiments at least 60% by weight functionalized polymer based on the total weight of the rubber component.
- the rubber component includes at least 1%, in other embodiments at least 5%, in other embodiments at least 10%, and in other embodiments at least 50% non-functionalized polymer based on the total weight of the rubber component.
- the rubber component may include both functionalized polymers and unfunctionalized polymers.
- the vulcanizates may be prepared by vulcanizing both unsaturated functionalized polymers and unsaturated non-functionalized polymers.
- the non-functionalized unsaturated polymers which may also be referred to as elastomers or rubbery elastomers, may include natural and synthetic elastomers.
- the synthetic elastomers may derive from the polymerization of conjugated diene monomers. These conjugated diene monomers may be copolymerized with other monomers such as vinyl aromatic monomers.
- Other rubbery elastomers may derive from the polymerization of ethylene together with one or more ⁇ -olefins and optionally one or more diene monomers.
- Exemplary rubbery elastomers include natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), and poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof. These elastomers can have a myriad of macromolecular structures including linear, branched and star shaped.
- the filler component includes a carbon black filler component, which itself includes a first carbon black and a second carbon black as discussed above.
- the filler component may also include other fillers including those conventionally employed in the preparation of tire components and/or vulcanizates.
- These fillers may include inorganic and organic fillers.
- the organic fillers include carbon black (including those not classified as medium or low structure blacks as defined herein) and starch.
- the inorganic fillers may include silica, aluminum hydroxide, magnesium hydroxide, clays (hydrated aluminum silicates), and mixtures thereof.
- Rubber curing agents may be employed, including sulfur or peroxide-based curing systems. Curing agents are described in 20 Kirk - Othmer, Encyclopedia of Chemical Technology, 365-468, (3 rd Ed. 1982), particularly Vulcanization Agents and Auxiliary Materials, 390-402, and A. Y. Coran, Vulcanization in Encyclopedia of Polymer Science and Engineering, (2 nd Ed. 1989), which are incorporated herein by reference. Vulcanizing agents may be used alone or in combination.
- ingredients that may be employed include accelerators, oils, waxes, scorch inhibiting agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, peptizers, and one or more additional rubbers.
- the preparation of vulcanizable compositions and the construction and curing of the tire is not affected by the practice of this invention.
- the rubber mixture may be prepared by forming an initial masterbatch that includes the rubber component and filler.
- the initial masterbatch may include the functional polymer, the medium structure black, and the low structure black.
- one or more of the functionalized polymer, the medium structure black, and the low structure black may be added in subsequent mixing stages.
- This initial masterbatch may be mixed at a starting temperature of from about 25° C. to about 125° C. with a discharge temperature of about 135° C. to about 180° C.
- this initial masterbatch may exclude vulcanizing agents.
- the vulcanizing agents may be introduced and blended into the initial masterbatch at low temperatures in a final mix stage, which preferably does not initiate the vulcanization process.
- additional mixing stages sometimes called remills, can be employed between the masterbatch mix stage and the final mix stage.
- Various ingredients including the functionalized polymer, medium structure black, or low structure black can be added during these remills. Rubber compounding techniques and the additives employed therein are generally known as disclosed in Stephens, The Compounding and Vulcanization of Rubber, in Rubber Technology (2 nd Ed. 1973).
- vulcanizable rubber compositions which may also be referred to as stocks, are useful for forming tire components such as treads, subtreads, black sidewalls, body ply skins, bead filler, and the like.
- these compositions can be processed into tire components according to ordinary tire manufacturing techniques including standard rubber shaping, molding and curing techniques.
- vulcanization is effected by heating the vulcanizable composition in a mold; e.g., it may be heated to about 140 to about 180° C.
- Cured or crosslinked rubber compositions may be referred to as vulcanizates, which generally contain three-dimensional polymeric networks that are thermoset.
- the other ingredients may be evenly dispersed throughout the vulcanized network.
- Pneumatic tires can be made as discussed in U.S. Pat. Nos. 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.
- tire treads can be prepared that exhibit both advantageous dynamic storage modulus and advantageous tan ⁇ (i.e., hysteresis loss) at 50° C.
- the present invention provides tire treads characterized by a dynamic storage modulus (G′) of at least 1 MPa, in other embodiments at least 1.5 MPa, and in other embodiments at least 2 MPa, while maintaining a tan ⁇ of less than 0.3, in other embodiments less than 0.25, and in other embodiments less than 0.2, as determined at 50° C. by employing a Rheometrics Dynamic Analyzer at a frequency of 1.0 Hz for a strain sweep from 1 to 10% strain.
- G′ dynamic storage modulus
- 50° C. hysteresis loss refers to tan ⁇ at these conditions.
- one or more embodiments of the present invention include a method for increasing the dynamic storage modulus of tire treads while minimizing any increase in hysteresis loss.
- the functionalized polymer was a di-functionalized polymer (i.e., head and tail functionalized polymer) that was prepared by employing a tributyl tin lithium initiator and was terminated and/or coupled with tin tetrachloride and tributyl tin chloride.
- the polymer was a random styrene-butadiene copolymer including about 35% styrene and about 18% vinyl content and was characterized by a weight average molecular weight of about 295 kg/mole and a number average molecular weight of about 235 kg/mole.
- the functionalized polymer was oil extended with 15 parts by weight oil per 100 parts by weight rubber.
- the medium structure carbon black was an N-343 carbon black, which was characterized by an iodine absorption number (per ASTM D1510) of 92 g/kg and a dibutylphthalate absorption number (per ASTM D2414) of 130 cc/100 g.
- the low structure carbon black was an N-660 carbon black, which was characterized by an iodine absorption number per ASTM D1510 of 36 g/kg and a dibutylphthalate absorption number per ASTM D2414 of 90 cc/100 g.
- the accelerators included a blend of diphenylguanadine and N-cyclohexyl-2-benzothiazolesulfenamide accelerators.
- Each rubber composition was prepared in three mixing segments.
- a 300 g Brabender mixer was used for the mixing.
- the first mix which may be referred to as the masterbatch, employed a mixer speed of 60 r.p.m. with an initial temperature of 130° C.
- a total mixing time of 6 minutes was used, and the drop temperature ranged from about 170° C. to about 176° C.
- the mixture was transferred to a two-roll mill operating at a temperature of about 60° C., where the composition was sheeted and subsequently cooled to room temperature.
- the masterbatch stock was then further mixed in a remill stage using similar conditions to those employed in the masterbatch.
- the mixture was transferred to a two-roll mill operating at 60° C., where the composition was sheeted and subsequently cooled to room temperature.
- the composition was then transferred back to the Brabender mixer and the final-batch ingredients (e.g., curatives) were added.
- the initial mixer temperature was 70° C., and the mixing speed was about 40 r.p.m.
- the composition was removed from the mixer after 2.5 minutes, and the temperature of the composition was about 100° C. This composition was then milled and sheeted using a two-roll mill at 60° C.
- the green samples were then cured at 171° C. for 15 minutes in standard molds placed in a hot press.
- the line drawn between data points for the samples of the present invention is steeper than that of the comparative samples. This indicates that practice of the present invention allows for increased G′ by higher carbon black loading with less deleterious impact on tan ⁇ .
- the green stock Mooney viscosity measurements were taken at 130° C. The sample was preheated for 1 minute, a large rotor was started, and the torque was measured after 4 minutes of rotation. Mooney scorch measurements, specifically the time required for an increase of 5 Mooney units (T5) can indicate how fast the compound viscosity will increase during extrusion processes. Curing characteristics were measured using a Monsanto Rheometer MD2000, at a frequency of 1.67 Hz, 160° C., and a strain of 7%. MH and ML are the measured maximum and minimum torques, respectively. TS2 is the time required for the torque to reach 2% of the total torque increase during the curing process. T90 is the time required for the torque to reach 90% of the total torque increase during the curing process. Likewise, T10 is the time required for the torque to reach 10% of the total torque increase during the curing process.
- the Zwick Rebound Test is a dynamic test that measures rebound resilience. Rebound resilience is typically defined as the ratio of mechanical energies before and after impact. Samples were tested according to ASTM D1054-91(2000). Sample specimens were milled and cured according to ASTM D1054, using the mold specified. The cured sample was coated with talc and conditioned in an oven for about one hour at the recommended temperature. The conditioned sample was placed into a Zwick type rebound tester, a pendulum was swung against the sample, and the angle at which the pendulum bounced back was measured. Percent rebound is calculated according to the equation specified in ASTM D1054.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A tire component comprising a rubber vulcanizate including one or more functional groups, where said one or more functional groups reduce the 50° C. hysteresis loss of the vulcanizate when compared to similar vulcanizates without the functional group, and a carbon black filler, where said carbon black filler includes (i) a first carbon black characterized by an iodine adsorption number, per ASTM D1510, that is greater than 60 g/kg, and (ii) a second carbon black characterized by an iodine adsorption number, per ASTM D1510, that is less than 60 g/kg.
Description
- One or more embodiments of the present invention are directed toward tire components and/or tire compositions, including treads, with improved dynamic storage modulus.
- Hysteresis loss, particularly at operating temperatures such as 50° C., is often attributed to rolling resistance. As a result, rolling resistance can be decreased by decreasing hysteresis loss (i.e., tan δ) at operating temperatures.
- Functional polymers have successfully been employed to reduce rolling resistance. It is believed that certain functional groups, when attached to polymer chain ends, can serve to reduce free ends and/or reduce filler agglomeration, which are believed to be sources of hysteresis loss.
- While functionalized polymers can be used to reduce hysteresis loss, there is also a desire to increase dynamic storage modulus, which often correlates to vulcanizate stiffness. While vulcanizate stiffness can be increased by employing larger amounts of filler materials, the increase in dynamic storage modulus often coincides with a large increase in hysteresis loss.
- There is therefore a desire to increase dynamic storage modulus while minimizing the corresponding increase in hysteresis loss. In other words, it would be advantageous to increase dynamic storage modulus without observing any (or even a proportional) increase in hysteresis loss.
- One or more embodiments of the present invention provide a tire component comprising a rubber vulcanizate including one or more functional groups, where said one or more functional groups reduce the 50° C. hysteresis loss of the vulcanizate when compared to similar vulcanizates without the functional group, and a carbon black filler, where said carbon black filler includes (i) a first carbon black characterized by an iodine adsorption number, per ASTM D1510, that is greater than 60 g/kg, and (ii) a second carbon black characterized by an iodine adsorption number, per ASTM D1510, that is less than 60 g/kg.
- One or more embodiments of the present invention also provide a tire component comprising a rubber vulcanizate including one or more functional groups, where said one or more functional groups reduce the 50° C. hysteresis loss of the vulcanizate when compared to similar vulcanizates without the functional group, a carbon black filler, where said carbon black filler includes (i) a first carbon black selected from N-300 series or lower carbon blacks, and (ii) a second carbon black selected from N-400 series or higher carbon blacks, per ASTM D1765.
- One or more embodiments of the present invention also provide a tire component comprising a rubber vulcanizate; and a carbon black filler, dispersed in said rubber vulcanizate, where said carbon black filler includes (i) a first carbon black characterized by an iodine adsorption number, per ASTM D1510, that is greater than 60 g/kg and less than 110 g/kg, and (ii) a second carbon black characterized by an iodine adsorption number, per ASTM D1510, that is less than 60 g/kg.
- The FIGURE includes a plot of G′ versus tan δ for samples prepared according to the present invention as compared to comparative samples.
- Tire components of one or more embodiments of the present invention include rubber vulcanizates having dispersed therein a carbon black filler, where the carbon black filler includes at least two distinct carbon blacks. In one or more embodiments, the first carbon black may be generally characterized by a medium or small particle size, and the second carbon black may be generally characterized by a larger particle size. In one or more embodiments, the rubber vulcanizates are prepared from functionalized polymers, and therefore the vulcanizates include one or more functional groups. In certain embodiments, the tire components include tire treads characterized by advantageous G′ and tan δ.
- In one or more embodiments, rubber vulcanizates including one or more functional groups can be prepared by vulcanizing an unsaturated polymer including a functional group. In one or more embodiments, the unsaturated polymer may be characterized by a glass transition temperature (Tg) that is less than about 0° C., in other embodiments less than about −20° C., and in other embodiments less than about −30° C.
- Exemplary unsaturated polymers include polybutadiene, polyisoprene, poly(styrene-co-butadiene), poly(styrene-co-butadiene-co-isoprene), poly(isoprene-co-styrene), and poly(butadiene-co-isoprene).
- In one or more embodiments, the unsaturated polymer may have a number average molecular weight (Mn) of from about 5 to about 1,000 kg/mole, in other embodiments from about 50 to about 500 kg/mole, and in other embodiments 100 to about 300 kg/mole. In these or other embodiments, the unsaturated polymer may also be characterized by a weight average molecular weight (Mw) of from about 5 to about 3,000 kg/mole, in other embodiments from about 50 to about 2,000 kg/mole, and in other embodiments 100 to about 1,200 kg/mole. Molecular weight may be determined using Gel Permeation Chromatography (GPC) calibrated with polystyrene standards and adjusted for the Mark-Houwink constants for the polymer in question.
- The functional group may be tethered or attached to the polymer at the head and/or tail of the polymer, and in certain embodiments may be pendant to the polymer chain. Functional polymers may include multiple functional groups including head and tail functionalization. As those skilled in the art appreciate, head functionalization refers to the presence of a functional group at or near the location of initiation of the polymer, and tail functionalization refers to the presence of a functional group at or near the location of termination of the polymer.
- In one or more embodiments, functional groups include those substituents that reduce the 50° C. hysteresis loss of a carbon black-filled vulcanizates as compared to similar carbon black-filled vulcanizates without the functional group. In one or more embodiments, this reduction in hysteresis loss is at least 5%, in other embodiments at least 10%, and in other embodiments at least 15%. In one or more embodiments, the functional groups include a hetero atom. These hetero atom-bearing substituents include those that may generally be characterized as an electron rich species or metal-containing species. Functional groups include those substituents that react or interact with rubber or rubber fillers or otherwise have a desirable impact on filled rubber compositions or vulcanizates.
- Numerous functional groups are known in the art. Exemplary functional groups include tin-containing groups, nitrogen-containing groups, boron-containing groups, oxygen-containing groups, phosphorous-containing groups, and sulfur-containing groups. Exemplary tin-containing groups include trialkyltin groups such as tributyl tin and trioctyltin groups. Exemplary nitrogen-containing groups include cyclic amine groups such as hexamethyleneimine groups, pyrollidine groups, and aziridine groups. Exemplary sulfur-containing groups include sulfur-containing azaheterocycle groups, and dithiane groups. Exemplary oxygen-containing groups include carbonyl-containing groups, oxygen-containing and azaheterocycle.
- Exemplary phosphorous-containing functionalized polymers are disclosed in U.S. Pat. No. 4,485,833; exemplary oxygen-containing azaheterocycle functionalized polymers are disclosed in U.S. Pat. No. 6,596,798; exemplary oxygen-containing and sulfur-containing heterocycle functionalized polymers are disclosed in International Publication Nos. WO 2004/020475; exemplary trialkyl tin substituent functionalized polymers are disclosed in U.S. Pat. No. 5,268,439; exemplary cyclic amine functionalized polymers are disclosed in U.S. Pat. No. 6,080,853; exemplary aryl or alkyl thio acetal (e.g., dithianes) functionalized polymers are disclosed in International Publication No. WO 2004/041870, all of which are incorporated herein by reference.
- In one or more embodiments, the functionalized polymers may be prepared by initiating the anionic polymerization of conjugated diene monomer (optionally together with vinyl aromatic monomer) with an initiator bearing one or more functional groups (i.e., a functional initiator). In these or other embodiments, the functionalized polymer may be prepared by terminating living polymers, prepared from conjugated diene monomers optionally together with vinyl aromatic monomer, with a terminating agent bearing one or more functional groups (i.e., a functional terminator). In one or more embodiments, both a functional initiator and a functional terminator may be employed. Many functional initiators and functional terminators are known in the art. Exemplary functional initiators are disclosed in U.S. Pat. Nos. 5,332,810, 5,329,005, 5,578,542, 5,393,721, 5,698,646, 5,491,230, 5,521,309, 5,496,940, 5,574,109, 5,786,441, U.S. Patent Application Nos. 60/683,231, 60/683,152, and Ser. No. 10/533,408, and International Publication Nos. WO 2004/020475 and WO 2004/041870, which are incorporated herein by reference. Exemplary functional terminators are disclosed in U.S. Pat. Nos. 3,109,871, 3,135,716, 5,332,810, 5,109,907, 5,210,145, 5,227,431, 5,329,005, 5,935,893, 4,519,431, 4,540,744, 4,603,722, 5,248,722, 5,349,024, 5,502,129, 5,877,336, 5,786,441, 5,916,976 5,552,473, 5,916,976 5,552,473, 4,677,165, 5,219,942, 5,902,856, 4,616,069, 4,929,679, 5,115,035, 6,359,167, 6,596,798, International Publication No. WO 2004/020475, and U.S. Ser. Nos. 60/644,164, 60/591,065, 60/622,188, 60/624,347 and 60/643,653, which are incorporated herein by reference.
- The carbon black filler includes at least two distinct carbon blacks. At least one carbon black may be referred to as a first carbon black, and at least one other carbon black may be referred to as a second carbon black. In these or other embodiments, the first carbon black may be referred to as a medium or small particle size carbon black, and the second carbon black may be referred to as a large particle size carbon black.
- In one or more embodiments, the first carbon black may be defined by an iodine absorption number that is greater than 60 g/kg, in other embodiments greater than 70 g/kg, in other embodiments greater than 80 g/kg, and in other embodiments greater than 90 g/kg, as determined according to ASTM D1510. In these or other embodiments, the first carbon black may be defined by an iodine absorption number that is less than 200 g/kg, in other embodiments less than 175 g/kg, and in other embodiments greater than 161 g/kg, as determined according to ASTM D1510. The first carbon black may also be characterized by a dibutylphthalate absorption number, as determined according to ASTM D2414, that varies over a wide range. For example, the dibutylphthalate absorption number may be as low as 70 cc/100 g and increase up to numbers such as 154 cc/100 g. In certain embodiments, the dibutylphthalate absorption number for the first carbon black, as determined by ASTM D2414, may be in excess of 115 cc/100 g. In certain embodiments, the first carbon black may be defined by an iodine adsorption number that is greater than 60 g/kg, but less than 110 g/kg, in other embodiments less than 105 g/kg, and in other embodiments less than 100 g/kg, as determined according to ASTM D1510.
- In one or more embodiments, the first carbon black may be characterized as an N-300 series or lower carbon black according to ASTM D1765. These carbon blacks may include N-100 series, N-200 series, and N-300 series carbon blacks. Exemplary N-100 series carbon blacks include N-100, N-115, N-120, N-121, N-125, N-134, and N-135 carbon blacks. Exemplary N-200 series carbon blacks may include N-220, N-231, N-294 and N-299. Exemplary N-300 series carbon blacks may include N-326, N-330, N-335, N-343, N-347, N-351, N-356, N-358, and N-375.
- In one or more embodiments, the second carbon black may be defined by an iodine absorption number that is less than 60 g/kg, in other embodiments less than 55 g/kg, in other embodiments greater than 40 g/kg, and in other embodiments less than 30 g/kg, as determined according to ASTM D1510. In these or other embodiments, the second carbon black may be defined by an iodine absorption number that is greater than 8 g/kg, in other embodiments greater than 10 g/kg, and in other embodiments greater than 20 g/kg, as determined according to ASTM D1510. The second carbon black may also be characterized by a dibutylphthalate absorption number that varies over a wide range. For example, the dibutylphthalate absorption number may be as low as 34 cc/100 g and increase up to numbers such as 180 cc/100 g. In certain embodiments, the dibutylphthalate absorption number for the second carbon black may be less than 115 cc/100 g, and in other embodiments less than 100 cc/100 g.
- In one or more embodiments, the second carbon black may be characterized as an N-400 series or higher carbon black according to ASTM D1765. These carbon blacks may include those selected from the group consisting of N-400 series, N-500 series, N-600 series, N-700 series, N-800 series, and N-900 series carbon blacks. Exemplary N-500 series carbon blacks include N-539, N-550, and N-582 carbon blacks. Exemplary N-600 series carbon blacks may include N-630, N-642, N-650, N-660, and N-683. Exemplary N-700 series carbon blacks may include N-754, N-762, N-765, N-772, N-774, and N-787. Exemplary N-600 series carbon blacks may include N-630, N-642, N-650, N-660, and N-683. Exemplary N-900 series carbon blacks may include N-907, N-908, N-990, and N-991.
- In one or more embodiments, the iodine absorption number (as determined according to ASTM D1510, of said first carbon black and the iodine absorption number of said second carbon black differ by at least 25 g/kg, in other embodiments by at least 50 g/kg and in other embodiments by at least 75 g/kg.
- The carbon black filler component of the vulcanizates (e.g., treads) of the present invention may include a major amount of the first carbon black (i.e., the medium structure black). In one or more embodiments, the carbon black filler component includes greater than 50% by weight of the first carbon black, in other embodiments greater than 60% by weight of the first carbon black, and in other embodiments greater than 75% by weight of the first carbon black based on the total weight of the carbon black component. In these or other embodiments, the carbon black component includes less than about 99% by weight, in other embodiments less than about 95% by weight, and in other embodiments less than 90% by weight of the first carbon black based upon the total weight of the carbon black component.
- With respect to the second carbon black (i.e., the low structure black), the carbon black filler component of the vulcanizates may include a minor amount of the second carbon black. In one or more embodiments, the carbon black filler component includes less than 50% by weight of the second carbon black, in other embodiments less than 40% by weight of the second carbon black, and in other embodiments less than 25% by weight of the second carbon black based on the total weight of the carbon black component. In these or other embodiments, the carbon black component includes greater than about 1% by weight, in other embodiments greater than about 5% by weight, and in other embodiments greater than 10% by weight of the second carbon black based upon the total weight of the carbon black component.
- With respect to the carbon black filler component as a whole, the vulcanizates of one or more embodiments of the present invention may include from about 1 to about 100 parts by weight carbon black per 100 parts by weight rubber, in other embodiments from about 10 to about 85 parts by weight carbon black per 100 parts by weight rubber, and in other embodiments from about 20 to about 80 parts by weight carbon black per 100 parts by weight rubber.
- The tire components or vulcanizates may be prepared from rubber mixtures (also known as vulcanizable rubber compositions) that include a rubber component, a filler component, a curative system, and other ingredients that are conventionally employed in the preparation of tire components and/or vulcanizates. The rubber component may include both functionalized and non-functionalized polymers. In one or more embodiments, the rubber component includes at least 5%, in other embodiments at least 10%, in other embodiments at least 20%, in other embodiments at least 40%, and in other embodiments at least 60% by weight functionalized polymer based on the total weight of the rubber component. In these or other embodiments, the rubber component includes at least 1%, in other embodiments at least 5%, in other embodiments at least 10%, and in other embodiments at least 50% non-functionalized polymer based on the total weight of the rubber component.
- The rubber component may include both functionalized polymers and unfunctionalized polymers. In other words, the vulcanizates may be prepared by vulcanizing both unsaturated functionalized polymers and unsaturated non-functionalized polymers. The non-functionalized unsaturated polymers, which may also be referred to as elastomers or rubbery elastomers, may include natural and synthetic elastomers. The synthetic elastomers may derive from the polymerization of conjugated diene monomers. These conjugated diene monomers may be copolymerized with other monomers such as vinyl aromatic monomers. Other rubbery elastomers may derive from the polymerization of ethylene together with one or more α-olefins and optionally one or more diene monomers.
- Exemplary rubbery elastomers include natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), and poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof. These elastomers can have a myriad of macromolecular structures including linear, branched and star shaped.
- As discussed above, the filler component includes a carbon black filler component, which itself includes a first carbon black and a second carbon black as discussed above. The filler component may also include other fillers including those conventionally employed in the preparation of tire components and/or vulcanizates. These fillers may include inorganic and organic fillers. The organic fillers include carbon black (including those not classified as medium or low structure blacks as defined herein) and starch. The inorganic fillers may include silica, aluminum hydroxide, magnesium hydroxide, clays (hydrated aluminum silicates), and mixtures thereof.
- A multitude of rubber curing agents may be employed, including sulfur or peroxide-based curing systems. Curing agents are described in 20 Kirk-Othmer, Encyclopedia of Chemical Technology, 365-468, (3rd Ed. 1982), particularly Vulcanization Agents and Auxiliary Materials, 390-402, and A. Y. Coran, Vulcanization in Encyclopedia of Polymer Science and Engineering, (2nd Ed. 1989), which are incorporated herein by reference. Vulcanizing agents may be used alone or in combination.
- Other ingredients that may be employed include accelerators, oils, waxes, scorch inhibiting agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, peptizers, and one or more additional rubbers.
- In one or more embodiments, the preparation of vulcanizable compositions and the construction and curing of the tire is not affected by the practice of this invention. In one or more embodiments, the rubber mixture may be prepared by forming an initial masterbatch that includes the rubber component and filler. The initial masterbatch may include the functional polymer, the medium structure black, and the low structure black. In other embodiments, one or more of the functionalized polymer, the medium structure black, and the low structure black may be added in subsequent mixing stages. This initial masterbatch may be mixed at a starting temperature of from about 25° C. to about 125° C. with a discharge temperature of about 135° C. to about 180° C. To prevent premature vulcanization (also known as scorch), this initial masterbatch may exclude vulcanizing agents. Once the initial masterbatch is processed, the vulcanizing agents may be introduced and blended into the initial masterbatch at low temperatures in a final mix stage, which preferably does not initiate the vulcanization process. Optionally, additional mixing stages, sometimes called remills, can be employed between the masterbatch mix stage and the final mix stage. Various ingredients including the functionalized polymer, medium structure black, or low structure black can be added during these remills. Rubber compounding techniques and the additives employed therein are generally known as disclosed in Stephens, The Compounding and Vulcanization of Rubber, in Rubber Technology (2nd Ed. 1973).
- Useful coupling and shielding agents are disclosed in U.S. Pat. Nos. 3,842,111, 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,674,932, 5,684,171, 5,684,172 5,696,197, 6,608,145, 6,667,362, 6,579,949, 6,590,017, 6,525,118, 6,342,552, and 6,683,135, which are incorporated herein by reference.
- These vulcanizable rubber compositions, which may also be referred to as stocks, are useful for forming tire components such as treads, subtreads, black sidewalls, body ply skins, bead filler, and the like. Where the vulcanizable rubber compositions are employed in the manufacture of tires, these compositions can be processed into tire components according to ordinary tire manufacturing techniques including standard rubber shaping, molding and curing techniques. Typically, vulcanization is effected by heating the vulcanizable composition in a mold; e.g., it may be heated to about 140 to about 180° C. Cured or crosslinked rubber compositions may be referred to as vulcanizates, which generally contain three-dimensional polymeric networks that are thermoset. The other ingredients, such as processing aides and fillers, may be evenly dispersed throughout the vulcanized network. Pneumatic tires can be made as discussed in U.S. Pat. Nos. 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.
- In one or more embodiments, tire treads can be prepared that exhibit both advantageous dynamic storage modulus and advantageous tan δ (i.e., hysteresis loss) at 50° C. In certain embodiments, the present invention provides tire treads characterized by a dynamic storage modulus (G′) of at least 1 MPa, in other embodiments at least 1.5 MPa, and in other embodiments at least 2 MPa, while maintaining a tan δ of less than 0.3, in other embodiments less than 0.25, and in other embodiments less than 0.2, as determined at 50° C. by employing a Rheometrics Dynamic Analyzer at a frequency of 1.0 Hz for a strain sweep from 1 to 10% strain. For purposes of this specification, 50° C. hysteresis loss refers to tan δ at these conditions. Accordingly, one or more embodiments of the present invention include a method for increasing the dynamic storage modulus of tire treads while minimizing any increase in hysteresis loss.
- In order to demonstrate the practice of the present invention, the following examples have been prepared and tested. The examples should not, however, be viewed as limiting the scope of the invention. The claims will serve to define the invention.
- Samples 1-5
- Five rubber compositions were mixed, prepared into green rubber samples, cured into vulcanizates, and tested for various mechanical and dynamic properties. The recipe for the rubber formulation for each sample is set forth in Table I, which provides the various ingredients in parts by weight.
TABLE I Samples 1 2 3 4 5 Functionalized Polymer 80.5 80.5 80.5 80.5 80.5 and Oil Natural Rubber 30 30 30 30 30 Carbon Black Medium Sized 41 46 51 41 41 Carbon Black (N343) Large Sized 0 0 0 5 10 Carbon Black (N660) Antiozonant 0.95 0.95 0.95 0.95 0.95 Zinc Oxide 2.5 2.5 2.5 2.5 2.5 Stearic Acid 2 2 2 2 2 Wax 1 1 1 1 1 Sulfur 1.3 1.3 1.3 1.3 1.3 Accelerators 1.9 1.9 1.9 1.9 1.9 - The functionalized polymer was a di-functionalized polymer (i.e., head and tail functionalized polymer) that was prepared by employing a tributyl tin lithium initiator and was terminated and/or coupled with tin tetrachloride and tributyl tin chloride. The polymer was a random styrene-butadiene copolymer including about 35% styrene and about 18% vinyl content and was characterized by a weight average molecular weight of about 295 kg/mole and a number average molecular weight of about 235 kg/mole. The functionalized polymer was oil extended with 15 parts by weight oil per 100 parts by weight rubber.
- The medium structure carbon black was an N-343 carbon black, which was characterized by an iodine absorption number (per ASTM D1510) of 92 g/kg and a dibutylphthalate absorption number (per ASTM D2414) of 130 cc/100 g. The low structure carbon black was an N-660 carbon black, which was characterized by an iodine absorption number per ASTM D1510 of 36 g/kg and a dibutylphthalate absorption number per ASTM D2414 of 90 cc/100 g. The accelerators included a blend of diphenylguanadine and N-cyclohexyl-2-benzothiazolesulfenamide accelerators.
- Each rubber composition was prepared in three mixing segments. A 300 g Brabender mixer was used for the mixing. The first mix, which may be referred to as the masterbatch, employed a mixer speed of 60 r.p.m. with an initial temperature of 130° C. A total mixing time of 6 minutes was used, and the drop temperature ranged from about 170° C. to about 176° C. Immediately following the masterbatch, the mixture was transferred to a two-roll mill operating at a temperature of about 60° C., where the composition was sheeted and subsequently cooled to room temperature. The masterbatch stock was then further mixed in a remill stage using similar conditions to those employed in the masterbatch. Immediately following the remill, the mixture was transferred to a two-roll mill operating at 60° C., where the composition was sheeted and subsequently cooled to room temperature. The composition was then transferred back to the Brabender mixer and the final-batch ingredients (e.g., curatives) were added. The initial mixer temperature was 70° C., and the mixing speed was about 40 r.p.m. The composition was removed from the mixer after 2.5 minutes, and the temperature of the composition was about 100° C. This composition was then milled and sheeted using a two-roll mill at 60° C. The composition was fabricated into green test samples including cylindrical buttons (0.79 cm×1.5 cm), sheets (15.24 cm×15.24 cm×0.19 cm or 15.24 cm×15.24 cm×0.52 cm), and donut-shaped Lambourn wear specimens (outer=4.85 cm, inner=2.25 cm, thickness=0.49 cm). The green samples were then cured at 171° C. for 15 minutes in standard molds placed in a hot press.
- Table II sets forth the data obtained from various mechanical and dynamic tests performed on the various samples.
TABLE II Sample 1 2 3 4 5 ML1+4 @ 130° C.: 44.1 52.2 62.5 47.2 53.5 50% Modulus @ 23° C. (MPa): 0.98 1.10 1.78 1.05 1.13 300% Modulus @ 23° C. (MPa): 9.66 11.30 18.60 10.60 11.81 Tensile Break Stress @ 23° C. (MPa): 21 19.3 27.9 18.6 18.5 Elongation at Break @ 23° C. (%): 488 427 398 437 412 50% Modulus @ 100° C. (MPa): 0.8 0.85 1.39 0.87 0.94 200% Modulus @ 100° C. (MPa): 3.96 4.51 7.61 4.48 5.10 Tensile Break Stress @ 100° C. (MPa): 8.25 8.21 10.48 7.13 7.73 Elongation at Break @ 100° C. (%): 307 285 242 265 258 Ring Tear, Tear Strength @ 171° C. (kN/m): 13.1 13.9 13.5 14.2 14.2 Ring Tear, Travel at Tear @ 171° C. (%): 265 257 228 260 242 Lambourn Wear Index [65% slip]: 100 92 88 91 85 Pendulum Rebound @ 23° C.: 55.2 52.0 48.8 54.0 52.8 Pendulum Rebound @ 50° C.: 68.8 65.6 62.8 67.8 66.2 TEMPERATURE SWEEP tan δ [torsion strip; 50° C.; 5 Hz, 2% strain]: 0.108 0.128 0.154 0.123 0.126 G′ (MPa) [torsion strip; 50° C.; 5 Hz, 2% strain]: 2.65 3.42 3.93 2.93 3.89 STRAIN SWEEP ΔG′ (MPa) [torsion button; 50° C.; 1 Hz, 0.03%- 0.47 0.69 0.93 0.56 0.68 14%]: G′ (MPa) [torsion button; 50° C.; 1 Hz, 5%]: 1.62 1.87 2.18 1.80 2.08 tan δ [torsion button; 50° C.; 1 Hz, 5%]: 0.098 0.111 0.122 0.100 0.105 - As can be seen from the FIGURE, the line drawn between data points for the samples of the present invention is steeper than that of the comparative samples. This indicates that practice of the present invention allows for increased G′ by higher carbon black loading with less deleterious impact on tan δ.
- Tensile mechanical properties were measured using ASTM-D 412 at 25° C. Tear mechanical properties were measured using ASTM-D 624 at 171° C. Dynamic properties were determined by using a Rheometrics Dynamic Analyzer (RDA). Tan δ was obtained from temperature sweep experiments conducted with a frequency of 31.4 rad/sec using 0.5% strain for temperatures ranging from −100° C. to −10° C., and with 2% strain for temperatures ranging from −10° C. to 100° C. Strain sweep experiments on an RPA 2000 Rubber Process Analyzer (Alpha Technologies) were used to obtain) G′ data, at a frequency of 1.0 Hz (3.14 rad/sec) and a temperature of 50° C., with strain sweeping from 0.25% to 1000%.
- The green stock Mooney viscosity measurements were taken at 130° C. The sample was preheated for 1 minute, a large rotor was started, and the torque was measured after 4 minutes of rotation. Mooney scorch measurements, specifically the time required for an increase of 5 Mooney units (T5) can indicate how fast the compound viscosity will increase during extrusion processes. Curing characteristics were measured using a Monsanto Rheometer MD2000, at a frequency of 1.67 Hz, 160° C., and a strain of 7%. MH and ML are the measured maximum and minimum torques, respectively. TS2 is the time required for the torque to reach 2% of the total torque increase during the curing process. T90 is the time required for the torque to reach 90% of the total torque increase during the curing process. Likewise, T10 is the time required for the torque to reach 10% of the total torque increase during the curing process.
- The Zwick Rebound Test is a dynamic test that measures rebound resilience. Rebound resilience is typically defined as the ratio of mechanical energies before and after impact. Samples were tested according to ASTM D1054-91(2000). Sample specimens were milled and cured according to ASTM D1054, using the mold specified. The cured sample was coated with talc and conditioned in an oven for about one hour at the recommended temperature. The conditioned sample was placed into a Zwick type rebound tester, a pendulum was swung against the sample, and the angle at which the pendulum bounced back was measured. Percent rebound is calculated according to the equation specified in ASTM D1054.
- Various modifications and alterations that do not depart from the scope and spirit of this invention will become apparent to those skilled in the art. This invention is not to be duly limited to the illustrative embodiments set forth herein.
Claims (20)
1. A tire component comprising:
a rubber vulcanizate including one or more functional groups, where said one or more functional groups reduce the 50° C. hysteresis loss of the vulcanizate when compared to similar vulcanizates without the functional group; and
a carbon black filler, where said carbon black filler includes (i) a first carbon black characterized by an iodine adsorption number, per ASTM D1510, that is greater than 60 g/kg, and (ii) a second carbon black characterized by an iodine adsorption number, per ASTM D1510, that is less than 60 g/kg.
2. The tire component of claim 1 , where the one or more functional groups reduce the 50° C. hysteresis loss by at least 5% when compared to similar vulcanizates without the functional group.
3. The tire component ad of claim 2 , where the one or more functional groups reduce the 50° C. hysteresis loss by at least 10% when compared to similar vulcanizates without the functional group.
4. The tire component of claim 1 , where said functional group includes a heteroatom.
5. The tire component of claim 4 , where said functional group includes a tin-containing, a nitrogen-containing, a carbonyl-containing, a boron-containing, a phosphorous-containing, sulfur-containing, or oxygen-containing group.
6. The tire component of claim 5 , where tire component is a tire tread.
7. The tire component of claim 1 , where said first carbon black is characterized by an iodine adsorption number that is greater than 70 g/kg.
8. The tire component of claim 1 , where said first carbon black is characterized by an iodine adsorption number that is greater than 80 g/kg.
9. The tire component of claim 1 , where said second carbon black is characterized by an iodine adsorption number that is less than 55 g/kg.
10. The tire component of claim 1 , where said second carbon black is characterized by an iodine adsorption number that is less than 40 g/kg.
11. The tire component of claim 1 , where the iodine adsorption number of said first carbon black and the iodine adsorption number of said second carbon black differ by at least 25 g/kg.
12. The tire component of claim 1 , where the iodine adsorption number of said first carbon black and the iodine adsorption number of said second carbon black differ by at least 50 g/kg.
13. The tire component of claim 1 , where the tire includes from about 1 to about 100 parts by weight carbon black per 100 parts by weight rubber.
14. The tire component of claim 17 , where the carbon black includes greater than 50 percent by weight of said first carbon black, with the balance including said second carbon black.
15. The tire component of claim 17 , where the carbon black includes at least 60 parts by weight of said first carbon black and less than 40 parts by weight of said second carbon black, based upon the total weight of the carbon black filler.
16. The tire component of claim 1 , where said vulcanizate includes a cured polymer of butadiene and optionally comonomers.
17. The tire component of claim 1 , where said vulcanizate is formed by vulcanizing a rubber mixture, where the rubber mixture includes an unsaturated polymer bearing said one or more functional groups and optionally unsaturated polymer without a functional group.
18. A tire component comprising:
a rubber vulcanizate including one or more functional groups, where said one or more functional groups reduce the 50° C. hysteresis loss of the vulcanizate when compared to similar vulcnaizates without the functional group;
a carbon black filler, where said carbon black filler includes (i) a first carbon black selected from N-300 series or lower carbon blacks, and (ii) a second carbon black selected from N-400 series or higher carbon blacks, per ASTM D1765.
19. The tire component of claim 18 , where said N-300 series or lower is selected form the group consisting of the group consisting of N-100 series, N-200 series, and N-300 series carbon black, and where said N-400 series or higher is selected from the group consisting of N-400 series or higher, N-500 series, and N-600 series carbon black.
20. A tire component comprising:
a rubber vulcanizate; and
a carbon black filler, dispersed in said rubber vulcanizate, where said carbon black filler includes (i) a first carbon black characterized by an iodine adsorption number, per ASTM D1510, that is greater than 60 g/kg and less than 110 g/kg, and (ii) a second carbon black characterized by an iodine adsorption number, per ASTM D1510, that is less than 60 g/kg.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/406,796 US20070249775A1 (en) | 2006-04-19 | 2006-04-19 | Tread compositions with improved dynamic storage modulus |
US12/260,393 US8071671B2 (en) | 2006-04-19 | 2008-10-29 | Tread compositions with improved dynamic storage modulus |
US13/283,812 US8399550B2 (en) | 2006-04-19 | 2011-10-28 | Tread compositions with improved dynamic storage modulus |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/406,796 US20070249775A1 (en) | 2006-04-19 | 2006-04-19 | Tread compositions with improved dynamic storage modulus |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/260,393 Continuation US8071671B2 (en) | 2006-04-19 | 2008-10-29 | Tread compositions with improved dynamic storage modulus |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070249775A1 true US20070249775A1 (en) | 2007-10-25 |
Family
ID=38620308
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/406,796 Abandoned US20070249775A1 (en) | 2006-04-19 | 2006-04-19 | Tread compositions with improved dynamic storage modulus |
US12/260,393 Expired - Fee Related US8071671B2 (en) | 2006-04-19 | 2008-10-29 | Tread compositions with improved dynamic storage modulus |
US13/283,812 Expired - Fee Related US8399550B2 (en) | 2006-04-19 | 2011-10-28 | Tread compositions with improved dynamic storage modulus |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/260,393 Expired - Fee Related US8071671B2 (en) | 2006-04-19 | 2008-10-29 | Tread compositions with improved dynamic storage modulus |
US13/283,812 Expired - Fee Related US8399550B2 (en) | 2006-04-19 | 2011-10-28 | Tread compositions with improved dynamic storage modulus |
Country Status (1)
Country | Link |
---|---|
US (3) | US20070249775A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009145784A1 (en) * | 2008-05-30 | 2009-12-03 | Societe De Technologie Michelin | Lignin in tire components |
US20140200307A1 (en) * | 2011-07-29 | 2014-07-17 | Michelin Recherche Et Technique S.A. | Method for the production of a rubber composition at high temperature |
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 |
CN113799543A (en) * | 2020-06-12 | 2021-12-17 | 住友橡胶工业株式会社 | Tyre for racing bicycle |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2938504B1 (en) | 2012-12-27 | 2018-05-23 | Compagnie Générale des Etablissements Michelin | Sidewall support for a runflat tire |
FR3005471B1 (en) | 2013-05-13 | 2015-04-24 | Michelin & Cie | RUBBER COMPOSITION HAVING HIGH PROCESSABILITY FOR TIRES SUITABLE FOR FLAT ROLLING |
US20160257167A1 (en) | 2013-10-17 | 2016-09-08 | Bridgestone Americas Tire Operations, Llc | Tire Innerliner With Carbon Black Blend |
KR101582253B1 (en) * | 2014-04-21 | 2016-01-04 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
JP6445916B2 (en) * | 2015-04-01 | 2018-12-26 | 株式会社ブリヂストン | tire |
KR102620929B1 (en) * | 2021-10-05 | 2024-01-05 | 넥센타이어 주식회사 | Rubber composition for tire under tread and tire manufactured from it |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5430087A (en) * | 1993-09-02 | 1995-07-04 | Hydril Company | Carbon black pair with different particle size and improved rubber stock |
US5798405A (en) * | 1997-03-20 | 1998-08-25 | The Goodyear Tire & Rubber Company | Tire with tread of rubber composition containing two different carbon blacks |
US6399692B2 (en) * | 1999-05-06 | 2002-06-04 | Bridgestone Corporation | Electrical conductivity of silica-filled rubber compositions using alkali metal salts dissolved in poly (alkylene oxide) compounds |
US6630535B1 (en) * | 2000-08-18 | 2003-10-07 | Bridgestone Corporation | Rubber compositions & vulcanizates including comb polymers |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7165584B2 (en) | 2002-10-01 | 2007-01-23 | Bridgestone Corporation | Rubber compositions and vulcanizates comprising nylon-containing copolymers |
JP5016924B2 (en) | 2003-06-09 | 2012-09-05 | 株式会社ブリヂストン | Elastomeric composition having improved hysteresis comprising sequentially terminated polymers |
US7230050B2 (en) | 2004-10-02 | 2007-06-12 | Bridgestone Corporation | Tire components including thermoplastic-elastomeric block copolymers |
US7836928B2 (en) | 2004-10-26 | 2010-11-23 | Bridgestone Corporation | Method of producing a tire composition having improved silica reinforcement |
US20060178467A1 (en) | 2005-01-14 | 2006-08-10 | Yasuo Fukushima | Tire treads with reduced hysteresis loss |
CN101107294B (en) | 2005-01-14 | 2011-05-25 | 株式会社普利司通 | Functionalized polymers and improved tires therefrom |
-
2006
- 2006-04-19 US US11/406,796 patent/US20070249775A1/en not_active Abandoned
-
2008
- 2008-10-29 US US12/260,393 patent/US8071671B2/en not_active Expired - Fee Related
-
2011
- 2011-10-28 US US13/283,812 patent/US8399550B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5430087A (en) * | 1993-09-02 | 1995-07-04 | Hydril Company | Carbon black pair with different particle size and improved rubber stock |
US5798405A (en) * | 1997-03-20 | 1998-08-25 | The Goodyear Tire & Rubber Company | Tire with tread of rubber composition containing two different carbon blacks |
US6399692B2 (en) * | 1999-05-06 | 2002-06-04 | Bridgestone Corporation | Electrical conductivity of silica-filled rubber compositions using alkali metal salts dissolved in poly (alkylene oxide) compounds |
US6630535B1 (en) * | 2000-08-18 | 2003-10-07 | Bridgestone Corporation | Rubber compositions & vulcanizates including comb polymers |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009145784A1 (en) * | 2008-05-30 | 2009-12-03 | Societe De Technologie Michelin | Lignin in tire components |
US20110073229A1 (en) * | 2008-05-30 | 2011-03-31 | Claudina Veas | Lignin in tire components |
US20140200307A1 (en) * | 2011-07-29 | 2014-07-17 | Michelin Recherche Et Technique S.A. | Method for the production of a rubber composition at high temperature |
US9023938B2 (en) * | 2011-07-29 | 2015-05-05 | Compagnie Generale Des Etablissements Michelin | Method for the production of a rubber composition at high temperature |
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 |
CN113799543A (en) * | 2020-06-12 | 2021-12-17 | 住友橡胶工业株式会社 | Tyre for racing bicycle |
Also Published As
Publication number | Publication date |
---|---|
US8399550B2 (en) | 2013-03-19 |
US20090054582A1 (en) | 2009-02-26 |
US8071671B2 (en) | 2011-12-06 |
US20120046410A1 (en) | 2012-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8399550B2 (en) | Tread compositions with improved dynamic storage modulus | |
US9206264B2 (en) | Method for producing modified conjugated diene based (co)polymer, modified conjugated diene based (co)polymer, and rubber composition | |
JP6243499B2 (en) | Side wall for tire | |
US10137733B2 (en) | Pneumatic tire | |
CN107849160B (en) | Modified conjugated diene polymer, preparation method thereof and modifier | |
US20070185267A1 (en) | Rubber composition | |
US8772374B2 (en) | Preparation of silica reinforced rubber composition and tire with component thereof | |
EP3086928B1 (en) | Vulcanizates and tire components prepared from compositions including mercapto-functional siloxanes | |
JP4491868B2 (en) | Method for producing diolefin polymer composition, and method for producing rubber composition for vulcanization | |
EP3517570A1 (en) | Rubber composition and tire | |
EP3385091B1 (en) | Rubber composition and tire | |
US20190389995A1 (en) | Rubber composition and tire | |
JP5656869B2 (en) | Rubber composition comprising a polymer component having a multimodal molecular weight distribution | |
US10913840B2 (en) | Rubber composition and tire | |
JP4348795B2 (en) | Diolefin polymer composition, process for producing the same, and rubber composition for vulcanization | |
US10836209B2 (en) | Tire sidewalls including high molecular weight waxes | |
US11697305B2 (en) | Tire for a motorcycle | |
JP2013155308A (en) | Rubber composition for cap tread, base tread, side wall, carcass, clinch or bead apex and pneumatic tire | |
US20160060438A1 (en) | Tire with silica-rich rubber tread | |
EP3517569A1 (en) | Rubber composition, and tire | |
US7875671B2 (en) | Process for preparing filler-dispersed polymeric compositions | |
KR102384180B1 (en) | Diene copolymer and method for preparing the same | |
US20230030838A1 (en) | Rubber compositions prepared with a polar polysulfide crosslinking agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BRIDGESTONE CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HOGAN, TERRENCE E.;ROBERTSON, CHRISTOPHER G.;SCURATI, ALBERTO;REEL/FRAME:017805/0210;SIGNING DATES FROM 20060227 TO 20060228 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |