US20010016629A1 - Rubber composition for tire and method of manufacturing same - Google Patents
Rubber composition for tire and method of manufacturing same Download PDFInfo
- Publication number
- US20010016629A1 US20010016629A1 US09/768,805 US76880501A US2001016629A1 US 20010016629 A1 US20010016629 A1 US 20010016629A1 US 76880501 A US76880501 A US 76880501A US 2001016629 A1 US2001016629 A1 US 2001016629A1
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- US
- United States
- Prior art keywords
- rubber
- weight
- parts
- expandable graphite
- tire
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 59
- 239000005060 rubber Substances 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 45
- 239000010439 graphite Substances 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims description 29
- 229920005992 thermoplastic resin Polymers 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000003094 microcapsule Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims 1
- 238000005299 abrasion Methods 0.000 description 19
- 238000004073 vulcanization Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 230000000977 initiatory effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 230000008016 vaporization Effects 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010692 aromatic oil Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VQZMFJVOYYLAHM-UHFFFAOYSA-N buta-1,2,3-trienylbenzene Chemical class C=C=C=CC1=CC=CC=C1 VQZMFJVOYYLAHM-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- -1 silas balloon Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
Definitions
- the present invention relates to a rubber composition for a tire. More specifically it relates to a rubber composition suitable for use as a tread for a tire, especially a tire for icy and snowy road, having an improved ice traction, while maintaining abrasion resistance, by blending an expandable graphite into a diene rubber, and a manufacturing method of a tire using the same.
- examples of the blending of the above hard substances are disclosed in JP-A-60-258235 (i.e., ceramic fine powder), JP-A-2-274740 (i.e., cracked or divided plants), JP-A-2-281052 (i.e., metals).
- JP-A-60-258235 i.e., ceramic fine powder
- JP-A-2-274740 i.e., cracked or divided plants
- JP-A-2-281052 i.e., metals.
- JP-A-2-281052 i.e., metals
- JP-A-11-35736 discloses the blending of thermoexpandable microcapsule as a hollow particle capable of improving the ice traction of rubber without increasing the rubber hardness and without being broken by a shearing force during mixing.
- the decrease in the abrasion resistance of the rubber vulcanizate with increase in the compounding amount is inevitable.
- the objects of the present invention are to provide a rubber composition for a tire having an improved ice traction, while maintaining abrasion resistance and also to provide a method for manufacturing a tire therefrom.
- a rubber composition for a tire comprising 100 parts by weight of a diene rubber and 1 to 30 parts by weight of an expandable graphite having a particle size of 30 to 600 ⁇ m.
- a method for manufacturing a pneumatic tire from a rubber composition comprising 100 parts by weight of a diene rubber, 1 to 30 parts by weight of an expandable graphite having a particle size of 30 to 600 ⁇ m and curing agents comprising the steps of:
- the expandable graphite is preferably a powdery material containing a substance capable of vaporizing upon heating and having a particle size of 30 to 600 ⁇ m, preferably 100 to 350 ⁇ m, that is, one which expands to become a expanded graphite body under the heat at the time of vulcanization.
- the expandable graphite is composed of sheets formed from graphite structures stacked in layers and can be expanded by vaporization of the substance between the layers to form the expanded graphite. Since the material before the expansion treatment is hard, there is little decrease in the quality thereof due to mixing. Further, since the substance expands irreversibly at a certain temperature, it is possible to easily form foreign substances along with voids inside the rubber matrix during the vulcanization of a tire. This tread portion of the tire using such a rubber acts to form suitable irregularities on the surface at the time of wear so that the water film on the ice surface can be efficiently removed, which results in the improved traction on ice.
- the expandable graphite has a good affinity with the rubber matrix or carbon black due to its inherent structure composed of non-polar carbon atoms.
- the advantage that, even if added to rubber, it does not cause a large decrease in the abrasion resistance of the vulcanized rubber on the tire.
- the diene rubber usable in the present invention may include any diene rubber used for a tire in the past, for example, natural rubber (NR), polyisoprene rubber (IR), various styrene-butadiene copolymer rubbers (SBR), various butadiene rubbers (BR), acrylonitrile-butadiene copolymer rubber, etc. These may be used alone or in any blends thereof.
- natural rubber NR
- IR polyisoprene rubber
- SBR various styrene-butadiene copolymer rubbers
- BR butadiene rubbers
- acrylonitrile-butadiene copolymer rubber etc.
- the present invention preferably it is possible to further include 1 to 20 parts by weight, preferably 5 to 10 parts by weight, based upon 100 parts by weight of the diene rubber, of heat expandable thermoplastic resin particles containing therein a liquid or solid capable of generating a gas upon vaporization, decomposition, or a chemical reaction under heating.
- the heat expandable thermoplastic resin particles contain therein a liquid or solid which vaporizes, decomposes, or chemically reacts under heat to generate a gas in a thermoplastic resin. These heat expandable thermoplastic resin particles are heated to expand at a temperature above the temperature of start of expansion, normally a temperature of 140 to 190° C. The gas is sealed inside a shell comprised of the thermoplastic resin. Therefore, the size of the gas-encompassed thermoplastic resin particles is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m before expansion.
- thermoplastic resin particles are commercially available as the current “Expancel 091 DU-80” or “Expancel 092 DU-120” etc. from Sweden's EXPANCEL Co. or “Matsumoto Microsphere F-85” or “Matsumoto Microsphere F-100” from Matsumoto Yushi-Seiyaku Co..
- the preferable thermoplastic resin comprising the outer shell of the gas-encompassed thermoplastic resin particles are, for example, those having a temperature of start of expansion of at least 100° C., preferably at least 120° C., and a maximum temperature of expansion of at least 150° C., preferably at least 160° C.
- a thermoplastic resin are a (meth)acrylonitrile polymer or a copolymer having a high content of (meth)acrylonitrile.
- a halogenated vinyl, halogenated vinylidene, styrene based monomer, (meth)acrylate based monomer, vinyl acetate, butadiene, vinyl pyridine, chloroprene, or other monomer may be used.
- thermoplastic resin may be cross-linked by a cross-linking agent such as divinylbenzene, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, ary(meth)acrylate, triacrylformal, and triarylisocyanulate.
- a cross-linking agent such as divinylbenzene, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, ary(meth)acrylate, triacrylformal, and triarylisocyanulate.
- a cross-linking agent such as divinylbenzene, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acryl
- liquid or solid capable of generating a gas by vaporization, decomposition, or chemical reaction under heat examples include hydrocarbons such as n-pentane, isopentane, neopentane, butane, isobutane, hexane, and petroleum ether, liquids such as a chlorinated hydrocarbon, e.g., methyl chloride, methylene chloride, dichloroethylene, trichloroethane, and trichloroethylene, or solids such as azodicarbonamide, dinitrosopentamethylene-tetramine, azobisisobutyronitrile, toluenesulfonyl hydrazide derivative, or aromatic succinyl hydrazide.
- hydrocarbons such as n-pentane, isopentane, neopentane, butane, isobutane, hexane, and petroleum ether
- liquids such as a chlorinated hydrocarbon,
- the expandable graphite per se is an already known material and produced by a known method.
- graphite particles are immersed in a mixture of a strong acid substance and an oxidizing agent, followed by an intercalation treatment to insert the acid between layers of the graphite particles to provide the expandability on the graphite.
- a strong acid substance for example, conc. sulfuric acid is used as the strong acid substance and nitric acid is used as the oxidizing agent, whereby the expandable graphite having sulfuric acid between the layers of the graphite particle is obtained.
- the expandable graphite is expanded by vaporizing the interlayer compound to thereby open the interlayer to be expanded.
- Typical expandable graphite containing sulfuric acid anhydride as a vaporizable interlayer component has an onset expansion temperature of around 300° C.
- the expandable graphite having an expansion initiating temperature of 300° C. or less is manufactured and sold in the market.
- the processing temperature of the rubber composition containing the diene rubber is typically 200° C. or less, according to the present invention, and the intended effects of the present invention can be obtained by the use of the expandable graphite having an expansion initiating temperature of 190° C. or less.
- Examples of such an expandable graphite having an expansion initiating temperature of 190° C. or less are “GRAFGuard 160-50” or “GRAFGuard 160-80” produced by UCAR Graphtech (USA) and available from Tomoe Engineering Co. (Japan), both of which have an onset expansion temp. of around 160° C.
- the expandable graphite is desirably expanded neither in the mixing nor extrusion steps of the rubber composition, but in the vulcanization step and those having an expansion initiating temperature of 120 to 190° C., preferably 140 to 170° C. If the expansion initiating temperature is less than 120° C., the expandable graphite is unpreferably expanded at the mixing step or extrusion step, whereby the specific density of the rubber is fluctuated during these steps and the processability is seriously impaired.
- the processing temperature in the vulcanization step should be fitted at a temperature of more than 190° C., in which the molecules of the diene rubber, the main component of the rubber composition, tend to be remarkably deteriorated.
- the rubber composition of the present invention may contain therein any carbon black which is usually blended into a rubber composition as a rubber reinforcing filler. Further, it is possible to use carbon black treated on its surface with silica. Further, it is also possible to use unhydrated or precipitated silica per se.
- the amount of the carbon black blended is 20 to 80 parts by weight, preferably 30 to 60 parts by weight, based upon 100 parts by weight of the rubber component. If the amount blended is too small, the rubber cannot be sufficiently reinforced, and therefore, the abrasion resistance is unpreferably decreased, for example. Conversely, if too large, the hardness becomes too high and the processability becomes poorer.
- unhydrated or precipitated silica is blended in an amount of 0 to 50 parts by weight, preferably 0 to 20 parts by weight, based upon 100 parts by weight of the rubber component.
- the silica does not have to be used, but if used, it should be used in a certain amount where the viscoelastic property of the rubber vulcanizate, such as tan ⁇ , is improved. If the amount of silica is too large, the electrical conductivity is unpreferably decreased, the agglomeration of the reinforcing filler becomes larger so that the dispersion during the mixing becomes unpreferably insufficient.
- the carbon black used in the present invention preferably has a specific area of nitrogen adsorption (N 2 SA) of at least 70 m 2 /g, more preferably 80 to 200 m 2 /g, and a dibutyl phthalate oil absorption (DBP) of preferably at least 95 ml/100 g, more preferably 105 to 140 ml/100 g.
- N 2 SA nitrogen adsorption
- DBP dibutyl phthalate oil absorption
- a pneumatic tire can be manufactured from the above-mentioned rubber composition for a tire containing 100 parts by weight of a diene rubber, 1 to 30 parts by weight, preferably 5 to 15 parts by weight, of an expandable graphite having a particle size of 30 to 600 ⁇ m, preferably 100 to 350 ⁇ m and a curing agents (e.g., sulfur and optionally a cure accelerator).
- a curing agents e.g., sulfur and optionally a cure accelerator
- the diene rubber is mixed with other ingredients generally used in the rubber compounding for a tire, other than the expandable graphite and the curing agents by means of, for example, Banbury mixer, followed by adding, at a separate mixing step called final mixing, thereto the expandable graphite and the curing agents.
- the final mixing must be performed under such a condition that the maximum reaching temperature during the mixing is less than, preferably by 20° C. or more less than, the expansion initiating temperature of the expandable graphite, followed by extrusion processing under the similar temperature condition of the above final mixing.
- the extruded tread part composed of rubber mixture is assembled and then vulcanized in a curing press at a temperature of higher than, preferably by 10° C.
- the expansion initiating temperature of the expandable graphite If the temperature of the mixing steps or the extrusion step reach the expansion initiating temperature or more, the expandability at the vulcanization step unpreferably becomes insufficient or the expandable graphite expanded at the mixing or extrusion step is unpreferably broken or deformed (or distorted) in the extrusion or vulcanization step. Furthermore, if the temperatures at the mixing or extrusion step reaches a temperature of, or higher than, the expansion initiating temperature, the specific gravity of the rubber composition is undesirably changed during the processing by the expansion of the expandable graphite inside the rubber mixture and therefore the processability is unpreferably impaired.
- the rubber composition for a tire according to the present invention may contain therein various additives generally used for rubber compositions such as a vulcanization or cross-linking agent, a vulcanization or cross-linking accelerator, various oils, an antioxidant, a filler, a plasticizer, etc.
- the composition may be mixed and vulcanized to form a composition which has an improved ice traction.
- the amount of these additives added may be the general amounts used in the past so long as the object of the present invention is not impaired.
- Rubber and compounding agents such as carbon black were mixed for five minutes using a 1.7 liter closed Banbury mixer based upon the formulations (parts by weight) shown in Table I, then blended with a vulcanization promoter, sulfur, microcapsules, and expandable graphite by an open roll.
- test pieces i.e., rubber sheets. These vulcanization test pieces were evaluated for physical properties such as the ice traction on ice ( ⁇ 1.5° C. and ⁇ 3° C.) and abrasion resistance. The results are shown in Table II.
- Sheets composed of the various components were attached to a flat columnar shaped rubber base and measured for the coefficient of ice traction by an inside-drum type ice traction tester. The measurements are performed at a temperatures of ⁇ 3.0° C. and ⁇ 1.5° C., the load was 5.5 kg/cm 3 , and the drum rotational speed was 25 km/h.
- a Lambourne abrasion tester manufactured by Iwamoto Seisakusho was used to measure the abrasion resistance under a load of 5 kg, a slip rate of 25%, a time of 4 minutes, and room temperature. The amount of abrasion loss for the test sample obtained from the amount of loss by abrasion was compared with the one for the standard sample (#1) and then the performance of the abrasion resistance was indicated by an index.
- Aromatic oil manufactured by Fuji Kosan
- Microsphere F100D Expandable microcapsule manufactured by Matsumoto Yushi
- Rubber and compounding agents such as carbon black were mixed for five minutes using a 1.7 liter closed Banbury mixer based upon the formulations (parts by weight) shown in Table III, then blended with a vulcanization accelerator, sulfur, nylon fine particles, silas balloon, microcapsules, and expandable graphite by an open roll.
- test pieces i.e., rubber sheets. These test pieces were evaluated for vulcanized physical properties such as the ice traction on ice ( ⁇ 1.5° C. and ⁇ 3° C.) and abrasion resistance.
- Table III The results are shown in Table III, according to the above-mentioned methods.
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Abstract
A rubber composition for a tire comprising 100 parts by weight of diene rubber and 1 to 30 parts by weight of expandable graphite having a particle size of 30 to 600 μm.
Description
- 1. Field of the Invention
- The present invention relates to a rubber composition for a tire. More specifically it relates to a rubber composition suitable for use as a tread for a tire, especially a tire for icy and snowy road, having an improved ice traction, while maintaining abrasion resistance, by blending an expandable graphite into a diene rubber, and a manufacturing method of a tire using the same.
- 2. Description of the Related Art
- Numerous studies have been conducted on the technique of blending hard substances, foaming agents, and hollow particulates into rubber to form microirregularities on the surface of the rubber so as to remove the water film formed on the surface of ice and improve the ice traction. However, there is the problem that these methods sometimes cannot result in the desired effects since the additives are brittle by nature and therefore part of the additives is made extremely fine or destroyed after mixing. Further, when mixing powders of these foreign substances to the rubber composition, generally the abrasion resistance of the rubber vulcanizate is remarkably decreased.
- For example, examples of the blending of the above hard substances are disclosed in JP-A-60-258235 (i.e., ceramic fine powder), JP-A-2-274740 (i.e., cracked or divided plants), JP-A-2-281052 (i.e., metals). However, according to these methods, there are problems that the hardness of rubber is increased and the flexibilities of the rubber are spoiled, whereby the follow-up property of the tire to road becomes poor. In addition, examples of the above-mentioned hollow particulates are disclosed in JP-A-2-170840, JP-A-2-208336 and JP-A-4-5543. However, according to these methods, the hardness of the rubber is similarly increased or the hollow particles are broken during mixing. On the other hand, JP-A-11-35736 discloses the blending of thermoexpandable microcapsule as a hollow particle capable of improving the ice traction of rubber without increasing the rubber hardness and without being broken by a shearing force during mixing. However, the decrease in the abrasion resistance of the rubber vulcanizate with increase in the compounding amount is inevitable.
- Accordingly, the objects of the present invention are to provide a rubber composition for a tire having an improved ice traction, while maintaining abrasion resistance and also to provide a method for manufacturing a tire therefrom.
- In accordance with the present invention, there is provided a rubber composition for a tire comprising 100 parts by weight of a diene rubber and 1 to 30 parts by weight of an expandable graphite having a particle size of 30 to 600 μm.
- In accordance with the present invention, there is also provided a method for manufacturing a pneumatic tire from a rubber composition comprising 100 parts by weight of a diene rubber, 1 to 30 parts by weight of an expandable graphite having a particle size of 30 to 600 μm and curing agents comprising the steps of:
- mixing the diene rubber with other ingredients except for the expandable graphite and the curing agents;
- adding thereto the expandable graphite and the curing agents in the separate mixing step (i.e., final mixing) under such a condition that the maximum reaching temperature is below the expansion onset temperature of the expandable graphite, followed by extrusion processing under the substantially same temperature condition as in the final mixing; and then
- assembling a green tire with the extrude of the rubber mixture, and then, vulcanizing the green tire having the extruded rubber mixture as a tire tread at a temperature of more than the expansion onset temperature of the expandable graphite.
- The present invention will now be explained in more detail. In this specification and in the claims the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise.
- The expandable graphite is preferably a powdery material containing a substance capable of vaporizing upon heating and having a particle size of 30 to 600 μm, preferably 100 to 350 μm, that is, one which expands to become a expanded graphite body under the heat at the time of vulcanization.
- The expandable graphite is composed of sheets formed from graphite structures stacked in layers and can be expanded by vaporization of the substance between the layers to form the expanded graphite. Since the material before the expansion treatment is hard, there is little decrease in the quality thereof due to mixing. Further, since the substance expands irreversibly at a certain temperature, it is possible to easily form foreign substances along with voids inside the rubber matrix during the vulcanization of a tire. This tread portion of the tire using such a rubber acts to form suitable irregularities on the surface at the time of wear so that the water film on the ice surface can be efficiently removed, which results in the improved traction on ice.
- On the other hand, the expandable graphite has a good affinity with the rubber matrix or carbon black due to its inherent structure composed of non-polar carbon atoms. There is the advantage that, even if added to rubber, it does not cause a large decrease in the abrasion resistance of the vulcanized rubber on the tire.
- The diene rubber usable in the present invention may include any diene rubber used for a tire in the past, for example, natural rubber (NR), polyisoprene rubber (IR), various styrene-butadiene copolymer rubbers (SBR), various butadiene rubbers (BR), acrylonitrile-butadiene copolymer rubber, etc. These may be used alone or in any blends thereof.
- In the present invention, 1 to 30 parts by weight, preferably 5 to 15 parts by weight, of expandable graphite are blended into 100 parts by weight of a diene rubber. If the amount blended is too small, the desired effect cannot be obtained, while conversely if it is too large, the ice traction is unpreferably decreased due to the decrease in the micro-level contact between the rubber surface and the iced surface of the road, and also the mechanical strength and the abrasion resistance of the rubber vulcanizate is unpreferably decreased.
- In the present invention, preferably it is possible to further include 1 to 20 parts by weight, preferably 5 to 10 parts by weight, based upon 100 parts by weight of the diene rubber, of heat expandable thermoplastic resin particles containing therein a liquid or solid capable of generating a gas upon vaporization, decomposition, or a chemical reaction under heating.
- The heat expandable thermoplastic resin particles contain therein a liquid or solid which vaporizes, decomposes, or chemically reacts under heat to generate a gas in a thermoplastic resin. These heat expandable thermoplastic resin particles are heated to expand at a temperature above the temperature of start of expansion, normally a temperature of 140 to 190° C. The gas is sealed inside a shell comprised of the thermoplastic resin. Therefore, the size of the gas-encompassed thermoplastic resin particles is preferably 5 to 300 μm, more preferably 10 to 200 μm before expansion.
- Examples of such heat expandable thermoplastic resin particles (unexpanded particles) are commercially available as the current “Expancel 091 DU-80” or “Expancel 092 DU-120” etc. from Sweden's EXPANCEL Co. or “Matsumoto Microsphere F-85” or “Matsumoto Microsphere F-100” from Matsumoto Yushi-Seiyaku Co..
- The preferable thermoplastic resin comprising the outer shell of the gas-encompassed thermoplastic resin particles are, for example, those having a temperature of start of expansion of at least 100° C., preferably at least 120° C., and a maximum temperature of expansion of at least 150° C., preferably at least 160° C. Examples of such a thermoplastic resin are a (meth)acrylonitrile polymer or a copolymer having a high content of (meth)acrylonitrile. As the other monomer (i.e., comonomer) in the case of a copolymer, a halogenated vinyl, halogenated vinylidene, styrene based monomer, (meth)acrylate based monomer, vinyl acetate, butadiene, vinyl pyridine, chloroprene, or other monomer may be used. Note that the above-mentioned thermoplastic resin may be cross-linked by a cross-linking agent such as divinylbenzene, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, ary(meth)acrylate, triacrylformal, and triarylisocyanulate. For the cross-linking mode, noncross-linking condition is preferable, but partial cross-linking to an extent not detracting from the properties as the thermoplastic resin is also possible.
- Examples of the liquid or solid capable of generating a gas by vaporization, decomposition, or chemical reaction under heat are hydrocarbons such as n-pentane, isopentane, neopentane, butane, isobutane, hexane, and petroleum ether, liquids such as a chlorinated hydrocarbon, e.g., methyl chloride, methylene chloride, dichloroethylene, trichloroethane, and trichloroethylene, or solids such as azodicarbonamide, dinitrosopentamethylene-tetramine, azobisisobutyronitrile, toluenesulfonyl hydrazide derivative, or aromatic succinyl hydrazide.
- The expandable graphite per se is an already known material and produced by a known method. Generally speaking, graphite particles are immersed in a mixture of a strong acid substance and an oxidizing agent, followed by an intercalation treatment to insert the acid between layers of the graphite particles to provide the expandability on the graphite. For example, conc. sulfuric acid is used as the strong acid substance and nitric acid is used as the oxidizing agent, whereby the expandable graphite having sulfuric acid between the layers of the graphite particle is obtained. The expandable graphite is expanded by vaporizing the interlayer compound to thereby open the interlayer to be expanded. Typical expandable graphite containing sulfuric acid anhydride as a vaporizable interlayer component has an onset expansion temperature of around 300° C. By the modification of the interlayer component and by the use of, or the combined use with, other low boiling point acidic substance (e.g., nitric acid), the expandable graphite having an expansion initiating temperature of 300° C. or less is manufactured and sold in the market. The processing temperature of the rubber composition containing the diene rubber is typically 200° C. or less, according to the present invention, and the intended effects of the present invention can be obtained by the use of the expandable graphite having an expansion initiating temperature of 190° C. or less.
- Examples of such an expandable graphite having an expansion initiating temperature of 190° C. or less are “GRAFGuard 160-50” or “GRAFGuard 160-80” produced by UCAR Graphtech (USA) and available from Tomoe Engineering Co. (Japan), both of which have an onset expansion temp. of around 160° C.
- In the present invention, the expandable graphite is desirably expanded neither in the mixing nor extrusion steps of the rubber composition, but in the vulcanization step and those having an expansion initiating temperature of 120 to 190° C., preferably 140 to 170° C. If the expansion initiating temperature is less than 120° C., the expandable graphite is unpreferably expanded at the mixing step or extrusion step, whereby the specific density of the rubber is fluctuated during these steps and the processability is seriously impaired.
- Contrary to this, if the expansion initiating temperature is more than 190° C., the processing temperature in the vulcanization step should be fitted at a temperature of more than 190° C., in which the molecules of the diene rubber, the main component of the rubber composition, tend to be remarkably deteriorated.
- The rubber composition of the present invention may contain therein any carbon black which is usually blended into a rubber composition as a rubber reinforcing filler. Further, it is possible to use carbon black treated on its surface with silica. Further, it is also possible to use unhydrated or precipitated silica per se. The amount of the carbon black blended is 20 to 80 parts by weight, preferably 30 to 60 parts by weight, based upon 100 parts by weight of the rubber component. If the amount blended is too small, the rubber cannot be sufficiently reinforced, and therefore, the abrasion resistance is unpreferably decreased, for example. Conversely, if too large, the hardness becomes too high and the processability becomes poorer. Further, unhydrated or precipitated silica is blended in an amount of 0 to 50 parts by weight, preferably 0 to 20 parts by weight, based upon 100 parts by weight of the rubber component. The silica does not have to be used, but if used, it should be used in a certain amount where the viscoelastic property of the rubber vulcanizate, such as tan δ, is improved. If the amount of silica is too large, the electrical conductivity is unpreferably decreased, the agglomeration of the reinforcing filler becomes larger so that the dispersion during the mixing becomes unpreferably insufficient.
- The carbon black used in the present invention preferably has a specific area of nitrogen adsorption (N2SA) of at least 70 m2/g, more preferably 80 to 200 m2/g, and a dibutyl phthalate oil absorption (DBP) of preferably at least 95 ml/100 g, more preferably 105 to 140 ml/100 g.
- According to the present invention, a pneumatic tire can be manufactured from the above-mentioned rubber composition for a tire containing 100 parts by weight of a diene rubber, 1 to 30 parts by weight, preferably 5 to 15 parts by weight, of an expandable graphite having a particle size of 30 to 600 μm, preferably 100 to 350 μm and a curing agents (e.g., sulfur and optionally a cure accelerator).
- First, the diene rubber is mixed with other ingredients generally used in the rubber compounding for a tire, other than the expandable graphite and the curing agents by means of, for example, Banbury mixer, followed by adding, at a separate mixing step called final mixing, thereto the expandable graphite and the curing agents. The final mixing must be performed under such a condition that the maximum reaching temperature during the mixing is less than, preferably by 20° C. or more less than, the expansion initiating temperature of the expandable graphite, followed by extrusion processing under the similar temperature condition of the above final mixing. Thereafter, the extruded tread part composed of rubber mixture is assembled and then vulcanized in a curing press at a temperature of higher than, preferably by 10° C. or more higher than, the expansion initiating temperature of the expandable graphite. If the temperature of the mixing steps or the extrusion step reach the expansion initiating temperature or more, the expandability at the vulcanization step unpreferably becomes insufficient or the expandable graphite expanded at the mixing or extrusion step is unpreferably broken or deformed (or distorted) in the extrusion or vulcanization step. Furthermore, if the temperatures at the mixing or extrusion step reaches a temperature of, or higher than, the expansion initiating temperature, the specific gravity of the rubber composition is undesirably changed during the processing by the expansion of the expandable graphite inside the rubber mixture and therefore the processability is unpreferably impaired.
- The rubber composition for a tire according to the present invention may contain therein various additives generally used for rubber compositions such as a vulcanization or cross-linking agent, a vulcanization or cross-linking accelerator, various oils, an antioxidant, a filler, a plasticizer, etc. The composition may be mixed and vulcanized to form a composition which has an improved ice traction. The amount of these additives added may be the general amounts used in the past so long as the object of the present invention is not impaired.
- The present invention will now be further explained with reference to Examples and Comparative Examples, but the present invention is of course not limited in scope by these Examples.
- Rubber and compounding agents such as carbon black were mixed for five minutes using a 1.7 liter closed Banbury mixer based upon the formulations (parts by weight) shown in Table I, then blended with a vulcanization promoter, sulfur, microcapsules, and expandable graphite by an open roll.
- Next, the composition was press vulcanized in a 15×15×0.2 cm mold at 175° C. for 10 minutes to prepare test pieces (i.e., rubber sheets). These vulcanization test pieces were evaluated for physical properties such as the ice traction on ice (−1.5° C. and −3° C.) and abrasion resistance. The results are shown in Table II.
- Sheets composed of the various components were attached to a flat columnar shaped rubber base and measured for the coefficient of ice traction by an inside-drum type ice traction tester. The measurements are performed at a temperatures of −3.0° C. and −1.5° C., the load was 5.5 kg/cm3, and the drum rotational speed was 25 km/h.
- A Lambourne abrasion tester (manufactured by Iwamoto Seisakusho) was used to measure the abrasion resistance under a load of 5 kg, a slip rate of 25%, a time of 4 minutes, and room temperature. The amount of abrasion loss for the test sample obtained from the amount of loss by abrasion was compared with the one for the standard sample (#1) and then the performance of the abrasion resistance was indicated by an index.
TABLE I Comparative Example Example 1 2 1 2 3 4 Natural rubber 50 50 50 50 50 50 RSS#3 Nipol 1220*1 50 50 50 50 50 50 Shoblack N220*2 55 55 55 55 55 55 Santoflex 6PPD*3 1 1 1 1 1 1 Zinc oxide # 3*4 3 3 3 3 3 3 Stearic acid*5 1 1 1 1 1 1 Aromatic oil*6 30 30 30 30 30 30 Santocure NS*7 1.5 1.5 1.5 1.5 1.5 1.5 Sulfur*8 2 2 2 2 2 2 Microsphere- — 10 — 10 — 10 F100D*9 GRAFGuard 160- — — 10 10 — — 50N*10 GRAFGuard 160- — — — — 10 10 80N*11 - 2: Shoblack N220: Carbon black manufactured by Showa Cabot (N2SA: 111 m2/g, DBP oil absorption: 111 ml/100 g)
- 3: Santoflex 6PPD: Antioxidant manufactured by Flexsis
- 4: Zinc oxide # 3: manufactured by Seido Chemical Industry
- 5: Stearic acid: manufactured by NOC
- 6: Aromatic oil: manufactured by Fuji Kosan
- 7: Santocure NS: Vulcanization accelerator manufactured by Flexsis
- 8: Sulfur: manufactured by Karuizawa Refinery
- 9: Microsphere F100D: Expandable microcapsule manufactured by Matsumoto Yushi
- 10: GRAFGuard 160-50N: Expandable graphite manufactured by UCAR (marketed by Tomoe Kogyo), Ave. particle size=300 μm, expansion onset temperature=160° C.
- 11: GRAFGuard 160-80N: Expandable graphite manufactured by UCAR (marketed from Tomoe Kogyo), Ave. particle size=177 μm, expansion onset temperature=160° C.
TABLE II Comparative Example Example 1 2 1 2 3 4 Traction on ice 100 133 138 162 135 155 (index)*12 (−3.0° C.) Traction on ice 100 146 150 181 140 187 (index)*12 (−1.5° C.) Abrasion 100 87 105 90 101 92 performance*12 (index) - The higher the value, the higher the traction on ice or the abrasion resistance exhibited.
- Rubber and compounding agents such as carbon black were mixed for five minutes using a 1.7 liter closed Banbury mixer based upon the formulations (parts by weight) shown in Table III, then blended with a vulcanization accelerator, sulfur, nylon fine particles, silas balloon, microcapsules, and expandable graphite by an open roll.
- Next, the composition was press vulcanized in a 15×15×0.2 cm mold at 175° C. for 10 minutes to prepare test pieces (i.e., rubber sheets). These test pieces were evaluated for vulcanized physical properties such as the ice traction on ice (−1.5° C. and −3° C.) and abrasion resistance. The results are shown in Table III, according to the above-mentioned methods.
- Since the tests in Table II and Table III were not carried out at the same time, the absolute values shown in Tables II and III are not always the same due to the minor differences in the test condition and/or the experimental errors. Especially, a variation in the dielectric constant of the water used for the preparation of ice in the ice traction tester may give the large deviation on the test results. Nevertheless, the relative order of the performance in the same test is always true.
TABLE III Comparative Example Example 1 3 4 5 6 7 5 6 7 8 9 10 11 12 Natural rubber 50 50 50 50 50 50 50 50 50 50 50 50 50 50 RSS #3 Nipol 1220*1 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Shoblack N220*1 55 55 55 55 55 55 55 55 55 55 55 55 55 55 Santoflex 6PPD*1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Zinc oxide #3*1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Stearic acid*1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Aromatic oil*1 30 30 30 30 30 30 30 30 30 30 30 30 30 30 Santocure NS*1 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Sulfur*1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Nylon fine — 5 — — — — — — — — — — — — particle*2 Silas balloon*3 — — 5 — — — — — — — — — — — Microsphere*4 — — — 1 10 20 — — — — — 1 10 20 GG50N*5 — — — — — — 1 5 10 20 30 5 5 5 Traction on ice 100 92 100 104 130 145 104 118 132 148 137 123 141 155 (index)*6 (−3.0° C.) Traction on ice 100 101 103 107 142 164 107 131 150 170 160 135 167 195 (index)*7 (−1.5° C.) Abrasion 100 72 74 98 86 69 100 103 101 92 80 99 95 70 performance*8 (index) - As explained above, according to the present invention, by blending into a diene rubber an expandable graphite and in some cases a heat expandable thermoplastic resin, it is possible to achieve a remarkable balance between the improved ice traction and the adequate abrasion resistance of the vulcanized rubber.
Claims (6)
1. A rubber composition for a tire comprising 100 parts by weight of a diene rubber and 1 to 30 parts by weight of an expandable graphite having a particle size of 30 to 600 μm.
2. A rubber composition as claimed in , further comprising 1 to 20 parts by weight, based upon 100 parts by weight of the diene rubber, of a microcapsule capable of being expanded to form a gas-encompassed thermoplastic resin upon heating.
claim 1
3. A rubber composition as claimed in , wherein an average glass transition temperature of the diene rubber is not more than −55° C.
claim 1
4. A rubber composition as claimed in , wherein 20 to 80 parts by weight of a carbon black having a specific surface area of nitrogen adsorption (N2SA) of not less than 70 m2/g and a dibutyl phthalate (DBP) oil absorption of not less than 105 ml/100 g and 0 to 50 parts by weight of unhydrated or precipitated silica, based upon 100 parts by weight of the rubber, are contained therein.
claim 1
5. A method for manufacturing a pneumatic tire from a rubber composition comprising 100 parts by weight of a diene rubber, 1 to 30 parts by weight of an expandable graphite having a particle size of 30 to 600 μm and curing agents comprising the steps of:
mixing the diene rubber with other components except for the expandable graphite and the curing agents;
adding thereto the expandable graphite and the curing agents in the separate mixing step (i.e., final mixing) under such a condition that the maximum reaching temperature is below the expansion onset temperature of the expandable graphite, followed by extrusion processing under the substantially same temperature condition as in the final mixing; and then
assembling a green tire with the extrude of the rubber mixture, and then, vulcanizing the green tire having the extruded rubber mixture at a temperature of more than the expansion onset temperature of the expandable graphite.
6. A radial tire suitable for icy and snowy road comprising using the rubber composition, as a tire tread, according to .
claim 1
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JPS5481518A (en) * | 1977-12-09 | 1979-06-29 | Togawa Rubber Mfg | Selffblockade rubber hose |
GB8611671D0 (en) * | 1986-05-13 | 1986-06-18 | Dunlop Ltd | Flame-retardent latex foams |
JPH02292344A (en) * | 1989-05-02 | 1990-12-03 | Koa Oil Co Ltd | Elastic graphite-containing rubber composition |
JPH04159341A (en) * | 1990-10-23 | 1992-06-02 | Hitachi Cable Ltd | Conductive composition |
DE4135678A1 (en) * | 1991-10-30 | 1993-05-06 | Chemie Linz (Deutschland) Gmbh, 6200 Wiesbaden, De | Thermally expandable fire protection materials - contain expanded graphite, polymeric binders, substances which form carbon skeleton when exposed to fire, and hollow microspheres, etc. |
JP2590697B2 (en) * | 1993-08-10 | 1997-03-12 | アキレス株式会社 | Rubber composition for foam molding |
US5760115A (en) * | 1995-03-03 | 1998-06-02 | Tosoh Corporation | Fire-retardant polymer composition |
US6410122B1 (en) * | 1997-01-16 | 2002-06-25 | Sekisui Chemical Co., Ltd. | Fire-resistant sheetlike molding, fire-resistant laminate for covering steel, fire-resistant structure for wall, and method for constructing fire-resistant steel and fire-resistant wall |
JP3352627B2 (en) | 1997-05-19 | 2002-12-03 | 横浜ゴム株式会社 | Rubber composition for tire tread with increased frictional force on ice and pneumatic tire |
JPH1143551A (en) * | 1997-05-27 | 1999-02-16 | Toyo Tire & Rubber Co Ltd | Thermoplastic elastomer foam |
-
2001
- 2001-01-25 US US09/768,805 patent/US20010016629A1/en not_active Abandoned
- 2001-01-26 DE DE10103507.1A patent/DE10103507B4/en not_active Expired - Lifetime
-
2003
- 2003-03-27 US US10/397,173 patent/US6892774B2/en not_active Expired - Lifetime
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US20070142547A1 (en) * | 2005-12-16 | 2007-06-21 | Schlumberger Technology Corporation | Polymeric Composites, Oilfield Elements Comprising Same, and Methods of Using Same in Oilfield Applications |
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WO2008021033A3 (en) * | 2006-08-10 | 2008-04-17 | Dow Global Technologies Inc | Polymers filled with highly expanded graphite |
WO2008021033A2 (en) * | 2006-08-10 | 2008-02-21 | Dow Global Technologies, Inc. | Polymers filled with highly expanded graphite |
US20080071028A1 (en) * | 2006-09-15 | 2008-03-20 | Sumitomo Rubber Industries, Ltd. | Conductive roller |
US7728060B2 (en) * | 2006-09-15 | 2010-06-01 | Sumitomo Rubber Industries, Ltd. | Conductive roller of rubber, thermoplastics, EO-PO-glycidyl ether, fluoro and sulfonyl anion salt and microcapsule |
EP2108527A1 (en) * | 2008-04-09 | 2009-10-14 | The Goodyear Tire & Rubber Company | Tire with tread having an intermediate rubber layer containing a microsphere dispersion |
US20090255613A1 (en) * | 2008-04-09 | 2009-10-15 | Ping Zhang | Tire with tread having an intermediate rubber layer containing a microsphere dispersion |
US20170226233A1 (en) * | 2014-09-08 | 2017-08-10 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
US20170233562A1 (en) * | 2014-09-08 | 2017-08-17 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
US20180054105A1 (en) * | 2015-03-26 | 2018-02-22 | Siemens Aktiengesellscyaft | Self-adhesive slot-closing device for an electric machine |
US10218238B2 (en) * | 2015-03-26 | 2019-02-26 | Siemens Aktiengesellschaft | Self-adhesive slot-closing device for an electric machine |
US10526472B2 (en) | 2016-02-18 | 2020-01-07 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire and method for producing pneumatic tire |
US10808082B2 (en) | 2016-10-31 | 2020-10-20 | Sumitomo Rubber Industries, Ltd. | Method for kneading a polymer |
US10472505B2 (en) | 2016-11-22 | 2019-11-12 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
Also Published As
Publication number | Publication date |
---|---|
US6892774B2 (en) | 2005-05-17 |
DE10103507A1 (en) | 2001-08-02 |
US20030191249A1 (en) | 2003-10-09 |
DE10103507B4 (en) | 2017-06-08 |
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Legal Events
Date | Code | Title | Description |
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AS | Assignment |
Owner name: YOKOHAMA RUBBER CO., LTD., THE, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MORI, MAKIO;HOTAKA, TAKESHI;REEL/FRAME:011637/0720 Effective date: 20010126 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |