CN102947379A - Tire rubber composition and pneumatic tire using same - Google Patents
Tire rubber composition and pneumatic tire using same Download PDFInfo
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- CN102947379A CN102947379A CN2011800300689A CN201180030068A CN102947379A CN 102947379 A CN102947379 A CN 102947379A CN 2011800300689 A CN2011800300689 A CN 2011800300689A CN 201180030068 A CN201180030068 A CN 201180030068A CN 102947379 A CN102947379 A CN 102947379A
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- tire
- rubber composition
- surface area
- specific surface
- fatty acid
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- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 229920001971 elastomer Polymers 0.000 title claims abstract description 88
- 239000005060 rubber Substances 0.000 title claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 148
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 55
- 229920005989 resin Polymers 0.000 claims abstract description 55
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 44
- 239000000194 fatty acid Substances 0.000 claims abstract description 44
- 229930195729 fatty acid Natural products 0.000 claims abstract description 44
- -1 zinc salts Chemical class 0.000 claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 150000003505 terpenes Chemical class 0.000 claims abstract description 11
- 235000007586 terpenes Nutrition 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 55
- 229960001866 silicon dioxide Drugs 0.000 claims description 55
- 239000003921 oil Substances 0.000 claims description 30
- 150000001993 dienes Chemical class 0.000 claims description 21
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- 231100000987 absorbed dose Toxicity 0.000 claims description 8
- 239000002174 Styrene-butadiene Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 239000010729 system oil Substances 0.000 claims description 6
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000002632 lipids Chemical class 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 244000068988 Glycine max Species 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 150000003097 polyterpenes Chemical class 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 3
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 239000002304 perfume Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 9
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 239000011701 zinc Substances 0.000 abstract description 6
- 238000005299 abrasion Methods 0.000 abstract description 3
- 239000004902 Softening Agent Substances 0.000 abstract description 2
- 229920003244 diene elastomer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 9
- 239000011324 bead Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 241000863032 Trieres Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000013098 chemical test method Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 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
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 102200090666 rs1556026984 Human genes 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011787 zinc oxide 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Provided are a tire rubber composition wherein wet traction, steering stability, low rolling resistance, and abrasion resistance have been improved while hardness has been maintained, and a pneumatic tire using same. The disclosed tire rubber composition is produced by blending, in 100 parts by mass of diene rubber, 60-120 parts by mass of silica with a nitrogen adsorption specific surface area of 170-225 m<2>/g, 4-10 mass% of silane coupling agent with respect to said silica, softening agent components comprising terpene resin and oil in an amount that is 1/2 of the amount of said silica blended or less (provided that 1 part by mass or more of said terpene resin is blended), and 0.5-10 parts by mass of a mixture of fatty acid metal salt (excluding zinc salts) and fatty acid ester. The disclosed pneumatic tire uses said tire rubber composition.
Description
Technical field
The present invention relates to rubber composition for tire and used the pneumatic tyre of this rubber composition for tire, in detail, the present invention relates to when keeping hardness to have used in rubber composition for tire that grabbing property of wet road, control stability, low-rolling-resistance, antifriction consumption further improved and the tyre surface pneumatic tyre of this rubber composition for tire.
Background technology
In passenger car tire, much less its rideability is high, and being considered as it and requiring one of characteristic also to improve gradually security.For example, disclose in rubber composition for tire in patent documentation 1～3 grade, to improve wet grabbing property of road and low-rolling-resistance as the technology of purpose.
Yet in recent years, strong request makes more height balance of wet grabbing property of road and low-rolling-resistance, and improves hardness and make control stability, take sensation and improve.In addition, improving hardness is to improve opposite performance with improving wet grabbing property of road and low-rolling-resistance, not yet finds to improve simultaneously the technology of these performances in the past.
On the other hand, in order to make control stability, low-rolling-resistance, antifriction consumption height balance, the known silicon-dioxide that in rubber composition for tire, cooperates.
In addition, if use the silicon-dioxide of high-specific surface area, then increasing in conjunction with number of silicon-dioxide and rubber infers that above-mentioned performance improves.Yet, according to the inventor's etc. research, if with the silicon-dioxide high-specific surface area, find that silicon-dioxide interaction each other increases, the dispersed deterioration can not obtain the such problem of desired effect fully.In addition, as the silicon-dioxide of high-specific surface area, in following patent documentation 4, disclose.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-37998 communique
Patent documentation 2: TOHKEMY 2006-213747 communique
Patent documentation 3: TOHKEMY 2004-175993 communique
Patent documentation 4: Japanese Unexamined Patent Application Publication 2005-500238 communique
Summary of the invention
Invent problem to be solved
The purpose of this invention is to provide the rubber composition for tire that grabbing property of wet road, control stability, low-rolling-resistance, antifriction consumption are further improved when keeping hardness and the pneumatic tyre that has used this rubber composition for tire.
Be used for solving the method for problem
The inventor etc. conduct in-depth research repeatedly, found that, by specified quantitative in diene series rubber cooperate silicon-dioxide with specific specific surface area, silane coupling agent, the mixture of the tenderizer composition, fatty acid metal salt and the fatty acid ester that are consisted of by terpine resin and oil, above-mentioned problem can be solved, thereby the present invention can be finished.
Be that the present invention is as described below.
1. rubber composition for tire, it cooperates following compositions to form with respect to 100 mass parts diene series rubbers, and described composition is: the nitrogen adsorption specific surface area (N that obtains according to JIS K6217-2 standard of 60～120 mass parts
2SA) be 170～225m
2The silicon-dioxide of/g; Be the silane coupling agent of 4～10 quality % with respect to above-mentioned silicon-dioxide; The use level of above-mentioned silicon-dioxide below 1/2 by terpine resin and the tenderizer composition (wherein cooperating more than above-mentioned terpine resin 1 mass parts) that consists of of oil; And the mixture of the fatty acid metal salt of 0.5～10 mass parts (wherein except the zinc salt) and fatty acid ester.
2. according to above-mentioned 1 described rubber composition for tire, it is characterized in that above-mentioned silicon-dioxide satisfies the full terms of following (1)～(4),
The condition of above-mentioned silicon-dioxide is:
(1) the nitrogen adsorption specific surface area (N that obtains according to JIS K6217-2 standard
2SA) be 194～225m
2/ g,
(2) the CTAB specific surface area of obtaining according to JIS K6217-3 standard is 170～210m
2/ g,
(3) above-mentioned nitrogen adsorption specific surface area (N
2SA) and the relation of above-mentioned CTAB specific surface area be nitrogen adsorption specific surface area (N
2SA)/the CTAB specific surface area is 0.9～1.4,
(4) the DBP absorbed dose of obtaining according to JIS K6217-4 oil number A method is more than the 190ml/100g.
3. according to above-mentioned 2 described rubber composition for tire, it is characterized in that above-mentioned silicon-dioxide satisfies the full terms of following (5)～(8),
The condition of above-mentioned silicon-dioxide is:
(5) the nitrogen adsorption specific surface area (N that obtains according to JIS K6217-2 standard
2SA) be 200～225m
2/ g,
(6) the CTAB specific surface area of obtaining according to JIS K6217-3 standard is 180～210m
2/ g,
(7) above-mentioned nitrogen adsorption specific surface area (N
2SA) and the relation of above-mentioned CTAB specific surface area be nitrogen adsorption specific surface area (N
2SA)/the CTAB specific surface area is 1.0～1.3,
(8) the DBP absorbed dose of obtaining according to JIS K6217-4 oil number A method is 195～230ml/100g.
4. according to each described rubber composition for tire of above-mentioned 1～3, it is characterized in that the softening temperature of above-mentioned terpine resin is more than 100 ℃, and the SP value is 8.4～9.0 scope.
5. according to each described rubber composition for tire of above-mentioned 1～4, it is characterized in that, above-mentioned terpine resin be selected from polyterpene resin, aromatic series modified terpene resin, phenol modified terpene resin and hydrogenated terpene resin that these terpine resin hydrogenations are formed at least a kind.
6. according to each described rubber composition for tire of above-mentioned 1～5, it is characterized in that the SP value of above-mentioned terpine resin is 8.5～8.9.
7. according to each described rubber composition for tire of above-mentioned 1～6, it is characterized in that above-mentioned oil is at least a kind that is selected from alkane hydrocarbon system oil, cycloalkanes hydrocarbon system oil, perfume oil, soya-bean oil and the plam oil.
8. according to each described rubber composition for tire of above-mentioned 1～7, it is characterized in that the lipid acid in the mixture of above-mentioned fatty acid metal salt and fatty acid ester is the saturated or unsaturated fatty acids of carbonatoms 3～30.
9. according to each described rubber composition for tire of above-mentioned 1～8, it is characterized in that, in the mixture of above-mentioned fatty acid metal salt and fatty acid ester, for the ratio of above-mentioned fatty acid metal salt and fatty acid ester be, when the former was made as 1 (quality), the latter was 0.5～2.0.
10. according to each described rubber composition for tire of above-mentioned 1～9, it is characterized in that above-mentioned diene series rubber comprises styrene-butadiene copolymer rubber (SBR).
11. each described rubber composition for tire according to above-mentioned 1～10; it is characterized in that above-mentioned silane coupling agent is for being selected from least a kind in 3-capryloyl thiopropyl triethoxyl silane, 3-propionyl thiopropyl Trimethoxy silane, two-(the two triethoxysilylpropyltetrasulfide of 3-)-tetrasulfide, two-(the two triethoxysilylpropyltetrasulfide of 3-)-disulphide and the 3-sulfydryl propyl trimethoxy silicane.
12. a pneumatic tyre, it has used each described rubber composition for tire of above-mentioned 1～11.
13. a pneumatic tyre has used each described rubber composition for tire of above-mentioned 1～11 in its tyre surface.
The effect of invention
According to the present invention, by specified quantitative in diene series rubber cooperate silicon-dioxide with particular characteristics, silane coupling agent, the mixture of the tenderizer composition, fatty acid metal salt and the fatty acid ester that are consisted of by terpine resin and oil, further improve wet grabbing property of road, control stability, low-rolling-resistance, the rubber composition for tire of antifriction consumption and the pneumatic tyre that has used this rubber composition for tire when keeping hardness thereby can be provided in.
In addition, cooperation has the silicon-dioxide of particular characteristics and the optimal way of the present invention of terpine resin according to specified quantitative in diene series rubber, use the silicon-dioxide of high-specific surface area also can give good dispersiveness even can provide, be low-rolling-resistance, the rubber composition for tire of control stability and antifriction consumption excellence and the pneumatic tyre that has used this rubber composition for tire.
Description of drawings
Fig. 1 is the partial cross section figure of an airtyred example.
Embodiment
Below, the present invention is described in further detail.
Fig. 1 is car with the partial cross section figure of an airtyred example.
In Fig. 1, pneumatic tyre is made of pair of right and left bead part 1 and sidewall 2 and the tyre surface 3 that links to each other with two sidewalls 2, shelving the body piles 4 that are embedded with fiber cord bead part 1,1, turning back laterally from the tire inboard around bead core 5 and tyre bead filler 6 and rolling in the end of body piles 4.In tyre surface 3, in the outside of body piles 4, spread all over tire 1 week and dispose belt 7.In addition, in bead part 1, at the partial configuration that joins with wheel rim wheel rim pad 8 is arranged.
Below illustrated rubber composition for tire of the present invention particularly useful for tyre surface 3.
(diene series rubber)
The diene series rubber composition that uses among the present invention can use the arbitrarily diene series rubber that can be engaged in the rubber composition for tire, for example can enumerate natural rubber (NR), synthetic polyisoprene (IR), divinyl rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene copolymer rubber (NBR) etc.They can use separately, and also two or more kinds may be used.In addition, its molecular weight, microstructure are not particularly limited, and can carry out with amine, acid amides, silyl, alkoxysilyl, carboxyl, hydroxyl etc. terminal-modifiedly, also can carry out epoxidation.
In these diene series rubbers, from effect of the present invention aspect, diene series rubber preferably comprises SBR.
In addition, specified quantitative cooperates in the optimal way of the present invention of the silicon-dioxide of the high-specific surface area with particular characteristics and terpine resin in diene series rubber, from effect of the present invention aspect, preferably SBR accounts for more than 60 mass parts in 100 mass parts diene series rubbers, and further preferred SBR accounts for the above and BR of 60 mass parts and/or NR accounts for other parts.
(silicon-dioxide)
About the silicon-dioxide that uses among the present invention, the nitrogen adsorption specific surface area (N that obtains according to JIS K6217-2 standard
2SA) be 170～225m
2/ g is according to this nitrogen adsorption specific surface area (N
2SA) scope, grabbing property of wet road and the low-rolling-resistance of rubber composition for tire are further improved.
In addition, among the present invention, the silicon-dioxide of the high-specific surface area of the full terms of (1)～(4) below preferred use is satisfied (below, be sometimes referred to as particular silica).
(1) the nitrogen adsorption specific surface area (N that obtains according to JIS K6217-2 standard
2SA) be 194～225m
2/ g.
(2) the CTAB specific surface area of obtaining according to JIS K6217-3 standard is 170～210m
2/ g.
(3) above-mentioned nitrogen adsorption specific surface area (N
2SA) and the relation of above-mentioned CTAB specific surface area be nitrogen adsorption specific surface area (N
2SA)/the CTAB specific surface area is 0.9～1.4.
(4) the DBP absorbed dose of obtaining according to JIS K6217-4 oil number A method is more than the 190ml/100g.
Further preferred characteristic as particular silica:
(5) the nitrogen adsorption specific surface area (N that obtains according to JIS K6217-2 standard
2SA) be 200～225m
2/ g.
(6) the CTAB specific surface area of obtaining according to JIS K6217-3 standard is 180～210m
2/ g.
(7) above-mentioned nitrogen adsorption specific surface area (N
2SA) and the relation of above-mentioned CTAB specific surface area be nitrogen adsorption specific surface area (N
2SA)/the CTAB specific surface area is 1.0～1.3.
(8) the DBP absorbed dose of obtaining according to JIS K6217-4 oil number A method is 195～230ml/100g.
The manufacture method of particular silica that satisfies the full terms of above-mentioned (1)～(4) is known, the manufacture method of for example putting down in writing in the above-mentioned patent documentation 4.That is, silicate and souring agent are reacted comprising, obtain thus silica suspension, this suspension is separated and the manufacture method of the silicon-dioxide of dry type in, the reaction of silicate and souring agent can be undertaken by following series-operation:
(i) form the water-based bottom liquid have 2～5, to be preferably 2.5～5 pH,
(ii) adopt make the pH of reaction mixture remain 2～5,2.5～5 such methods that are preferably add silicate and souring agent simultaneously in this bottom liquid,
(iii) stop to add this souring agent, in this reaction mixture, continue to add silicate on the other hand until obtain 7～10, be preferably the pH value of this reaction mixture of 7.5～9.5,
(iv) adopt make the pH of this reaction mixture remain 7～10,7.5～9.5 such methods that are preferably add silicate and souring agent simultaneously in this reaction mixture,
(v) stop to add silicate, in this reaction mixture, continue on the other hand to add this souring agent until obtain the pH value of this reaction mixture below 6.
The particular silica of using among the present invention also can be utilized commercially available product, can enumerate for example ロ one デ イ ア society system, Zeosil Premium 200MP.
In addition, from effect of the present invention aspect, the dimension of object Tile Width Ld of preferred particular silica ((d84-d16)/d50) be at least 0.91, and V (d5-d50)/V (d5-d100) is at least 0.66.
(measuring method of (d84-d16)/d50) and V (d5-d50)/V (d5-d100) is known to dimension of object Tile Width Ld, the measuring method of for example putting down in writing in the above-mentioned patent documentation 4 is also measured above-mentioned physical property according to the method for putting down in writing in this patent documentation 4 in the present invention.
((d84-d16)/d50) measures by the XDC grain size analysis method with centrifugal settling dimension of object Tile Width Ld.
As analyzer, can utilize commercially available BI-XDC (Brookhaven Instrument X disk is centrifugal) the centrifugal settling particle size analyzer by Block Le Star Network ヘ Block Application イ Application ス ト Le メ Application ト society.
Be applicable to a corpse or other object for laboratory examination and chemical testing such as the modulated of above-mentioned analyzer.The silicon-dioxide of 3.2g and the deionized water of 40ml are added in the tall form beaker, and modulation suspension flooded 1500 watts Branson probe (using with 60% of maximum output) therein, pulverized this suspension through 20 minutes.
In the register of above-mentioned analyzer, record the value of passing through diameter of 16 % by weight, 50 % by weight (or central value) and 84 % by weight.
Calculate dimension of object Tile Width Ld ((d84-d16)/d50) by above-mentioned record value.Here dn is size, and the n% of particle (% by weight) has the size less than this size (therefore, this Tile Width Ld is calculated by the accumulation granularity that obtains as a whole).
V (d5-d50)/V (d5-d100) measures by mercury porosimetry.A corpse or other object for laboratory examination and chemical testing such as modulated.That is, make silicon-dioxide in baking oven 200 ℃ predrying through 2 hours, then be placed in the test chamber with interior in rear 5 minutes in that it is taken out from this baking oven, then, use is for example rotated wing pump and is carried out vacuum outgas.Pore diameter (AUTOPORE III 9420 powder technologies porosity meter) is calculated with 140 ° contact angle and the surface tension γ of 484 dyne/cm (or N/m) by the equation of Washburn.
The pore volume that V (d5-d50) expression is formed by the pore of the diameter of d5～d50, the pore volume that V (d5-d100) expression is formed by the pore of the diameter of d5～d100, here, dn is pore diameter, and all the n% of the total surface area of pore is by the formed (pore (S of the pore of the diameter larger than this diameter
0) total surface area can immerse curve by mercury and determine).
Shown as mentioned above, the silicon-dioxide of high-specific surface area has silicon-dioxide interaction each other to increase, the dispersed deterioration, can not get the such problem of desired effect, but the particular silica of using among the present invention is by also using with the terpine resin of following explanation, thereby the hybrid process raising shows good dispersiveness in rubber.Thus, can provide the rubber composition for tire that makes grabbing property of wet road, control stability, low-rolling-resistance, antifriction consumption height counter-balanced excellence.
(silane coupling agent)
The silane coupling agent that uses among the present invention is not particularly limited; be preferably silane coupler containing sulfur, can enumerate such as 3-capryloyl thiopropyl triethoxyl silane, 3-propionyl thiopropyl Trimethoxy silane, two-(the two triethoxysilylpropyltetrasulfide of 3-)-tetrasulfide, two-(the two triethoxysilylpropyltetrasulfide of 3-)-disulphide, 3-sulfydryl propyl trimethoxy silicane etc.
(terpine resin)
As the terpine resin that uses among the present invention, for example can enumerate polyterpene resin, aromatic series modified terpene resin, phenol modified terpene resin and hydrogenated terpene resin that these terpine resin hydrogenations are formed etc.
In addition, in using the mode of the present invention of particular silica, from the viewpoint of its effect, in these terpine resins, preferred softening temperature is more than 100 ℃ and the SP value is the terpine resin of 8.4～9.0 scope.Be terpine resin more than 100 ℃ by using softening temperature, thereby under the low state of the mixing temperature when mixing in the early stage, the shearing force of rubber and particular silica uprised that the dispersiveness of particular silica is improved.In addition, be 8.4～9.0 scope by making the SP value, thereby the affinity of rubber and terpine resin uprise, the result, the dispersiveness of particular silica is improved.In addition, so-called SP value among the present invention, such as known in the art, be the molar energy of vaporization Δ E with liquid
vSquare root (the Δ E of the value (cohesive energy density(CED)) that obtains divided by molecular volume V
v/ V)
1/2Abbreviation.This parameter is with (kcal/mol)
1/2Unit representation.
More preferably 110～130 ℃ of the softening temperatures of the terpine resin that uses among the present invention, SP value more preferably 8.5～8.9.
The terpine resin that satisfies above-mentioned condition is commercially available, for example, by ヤ ス Ha ラ ケ ミ カ Le (strain) as sale such as YS レ ジ Application TO-125, YS レ ジ Application TO-115.
(oil)
As the oil that uses among the present invention, for example can enumerate alkane hydrocarbon system oil, cycloalkanes hydrocarbon system oil, fragrant wet goods mineral oil; Soya-bean oil, palm wet goods vegetables oil; Deng, they can be used alone or two or more kinds may be used.
(mixture of fatty acid metal salt and fatty acid ester)
In the present invention, use the mixture of fatty acid metal salt and fatty acid ester.
As lipid acid, can enumerate the saturated or unsaturated fatty acids of carbonatoms 3～30, can enumerate such as lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid etc.
As the metal of the salt that forms these lipid acid, can enumerate at least a kind of metal that is selected among K, Ca, Na, Mg, Co, Ni, Ba, Fe, Al, Cu and the Mn, be particularly preferably K, Ca.In addition, in the present invention, consider from not reaching the such reason of effect of the present invention, do not use zinc salt as fatty acid metal salt.
In addition, as carboxylate, can enumerate the ester of above-mentioned lipid acid and the lower alcohol of carbonatoms below 10 etc.
Fatty acid metal salt and fatty acid ester can use separately, also can be used in combination more than two kinds.
In addition, about the ratio of fatty acid metal salt and fatty acid ester, preferably when the former was made as 1 (quality), the latter used 0.5～2.0.
(weighting agent)
Rubber composition for tire of the present invention except above-mentioned silicon-dioxide, can cooperate various weighting agents.As weighting agent, be not particularly limited, as long as suitably select according to purposes, can enumerate such as carbon black, inorganic filler etc.As inorganic filler, can enumerate such as clay, talcum, calcium carbonate etc.Wherein be preferably carbon black.
From effect of the present invention aspect, the nitrogen adsorption specific surface area (N of carbon black
2SA) (notes: measure according to JIS K6217-2) are preferably 100～160m
2/ g.
(mixing ratio of rubber composition for tire)
Rubber composition for tire of the present invention is characterised in that, it cooperates following compositions to form with respect to 100 mass parts diene series rubbers, and described composition is: the nitrogen adsorption specific surface area (N that obtains according to JIS K6217-2 standard of 60～120 mass parts
2SA) be 170～225m
2The silicon-dioxide of/g; Be the silane coupling agent of 4～10 quality % with respect to above-mentioned silicon-dioxide; The use level of above-mentioned silicon-dioxide below 1/2 by terpine resin and the tenderizer composition (wherein cooperating more than above-mentioned terpine resin 1 mass parts) that consists of of oil; And the mixture of the fatty acid metal salt of 0.5～10 mass parts (wherein except the zinc salt) and fatty acid ester.
If the use level of silicon-dioxide is lower than 60 mass parts, then wet road performance reduction is therefore not preferred.If surpass on the contrary 120 mass parts, then the antifriction consumption reduces, and is therefore not preferred.In addition, in the situation of using particular silica, if the mixing ratio of particular silica is lower than 60 mass parts, then addition is very few, can not realize effect of the present invention.If surpass on the contrary 120 mass parts, then fuel consumption mis-behave.
If the use level of silane coupling agent is lower than 4 quality %, then the antifriction consumption reduces, and is therefore not preferred.If surpass on the contrary 10 quality %, then each other polymerization of silane coupling agent can not obtain desired effect.
If surpassed by terpine resin and the tenderizer composition that consists of of oil above-mentioned silicon-dioxide use level 1/2, then be difficult to have concurrently rolling resistance and hardness, therefore not preferred.
If the use level of terpine resin is lower than 1 mass parts, then use level is very few, can not realize effect of the present invention.
If the use level of the mixture of fatty acid metal salt and fatty acid ester is lower than 0.5 mass parts, then use level is very few, can not realize effect of the present invention.If surpass on the contrary 10 mass parts, then the antifriction consumption reduces, and is therefore not preferred.
In the rubber composition for tire of the present invention, the nitrogen adsorption specific surface area (N that obtains according to JIS K6217-2 standard
2SA) be 170～225m
2The further preferred use level of the silicon-dioxide of/g is to be 65～115 mass parts with respect to 100 mass parts diene series rubbers.Using in the situation of particular silica in addition, preferred use level is to be 65～115 mass parts with respect to 100 mass parts diene series rubbers.
The further preferred use level of silane coupling agent is to be 5～9 quality % with respect to silicon-dioxide.
That use level with respect to silicon-dioxide is 10～40 quality % by the further preferred use level of terpine resin and the tenderizer composition that consists of of oil.
The further preferred use level of terpine resin is to be 1～59 mass parts with respect to 100 mass parts diene series rubbers, and particularly preferred use level is 3～57 mass parts.
The further preferred use level of the mixture of fatty acid metal salt and fatty acid ester is to be 1～9 mass parts with respect to 100 mass parts diene series rubbers.
In the rubber composition for tire that the present invention relates to, except mentioned component, can cooperate the general various additives that cooperate in the rubber composition for tire such as sulfuration or linking agent, sulfuration or crosslinking accelerator, the weighting agent beyond above-mentioned, anti-aging agent, softening agent, above-mentioned additive can adopt general method to carry out mixing and make composition, is used for sulfuration or crosslinked.As long as the use level of these additives also without prejudice to purpose of the present invention, just can be general use level in the past.Rubber combination of the present invention can be according in the past airtyred manufacture method and for the manufacture of pneumatic tyre in addition.
Embodiment
Below, further specify the present invention by embodiment and comparative example, but the invention is not restricted to following example.
The modulation of sample
In the cooperation shown in table 1 and 2 (mass parts), the composition except sulphur, vulcanization accelerator with mixing 5 minutes of the hermetic type mixing tank of 1.8L, is added sulphur, vulcanization accelerator in the masterbatch of emitting, carry out with open roller mixing, thereby modulate.Next with the rubber combination of gained in the mould of regulation 160 ℃ of press vulcanizations 20 minutes, obtain the vulcanized rubber test film, adopt test method determination physical property shown below.
Rolling resistance: according to JIS K6394, use the smart mechanism of (strain) Japan to make made visco-elasticity spectrometer, measure tan δ (60 ℃) under the condition of in the early stage strain=10%, amplitude=± 2%, frequency=20Hz, adopt this to be worth to estimate rolling resistance.The result is made as 100 with exponential representation with comparative example 1 or 9.Index is higher, represents that then rolling resistance is better.
Wet road performance: according to JIS K6394, use the smart mechanism of (strain) Japan to make made visco-elasticity spectrometer, measure tan δ (0 ℃) under the condition of in the early stage strain=10%, amplitude=± 2%, frequency=20Hz, adopt this to be worth to estimate wet road performance (grabbing property of wet road).The result is made as 100 with exponential representation with comparative example 1.Index is higher, represents that then rolling resistance is better.
Hardness: according to JIS K6253, measure 20 ℃ of temperature by scleroscopic type A.This value is higher, can say that then hardness is higher, is good result.
Tensile strength: according to JIS K6251,300% modulus (M300) when measuring 23 ℃.Comparative example 9 is made as 100 with exponential representation.This numerical value is larger, represents that then tensile strength is higher.
Antifriction consumption (1): use the blue Berne abrasion trier of rock this making institute (strain) system, under the condition of loading 5kg (49N), sliding ratio 25%, 4 minutes time, room temperature, measure.Comparative example 1 is made as 100 with exponential representation.This numerical value is larger, represents that then the antifriction consumption is more excellent.
Antifriction consumption (2): according to JIS K6264, measure the antifriction consumption with FERRY MACHINE CO. pik abrasion processed trier.Comparative example 9 is made as 100 with exponential representation.This numerical value is larger, represents that then the antifriction consumption is more excellent.
Control stability: make the test tire that has used the 195/R15 size of vulcanized rubber test film in the tyre surface.Then, 4 take turns the test tire that same size all is installed on the test vehicle of free air delivery 2L, and the grabbing level of feeling evaluation on the road surface pavement of drying and operating the rudder property are made as 100 with index assessment with comparative example 9.This numerical value is larger, represents that then control stability is more excellent.
[table 1]
[table 2]
* 1:SBR (ラ Application Network セ ス society VSL5025, ST/VN=25/67 processed)
* 2: carbon black SAF (East Sea カ one ボ Application シ one ス ト 9 processed, nitrogen adsorption specific surface area (N
2SA)=142m
2/ g)
* 3: silicon-dioxide (eastern ソ one シ リ カ (strain) NipsilAQ processed, N
2SA=200m
2/ g)
* 4: relatively silicon-dioxide (the ロ one デ イ ア 1165MP processed of society, nitrogen adsorption specific surface area (N
2SA)=163m
2/ g, CTAB specific surface area 159m
2/ g, the DBP absorbed dose=202ml/100g)
* 5: particular silica (the ロ one Zeosil Premium processed 200MP of デ イ ア society.Nitrogen adsorption specific surface area (N
2SA)=205m
2/ g, CTAB specific surface area=197m
2/ g, DBP absorbed dose=203ml/100g, dimension of object Tile Width Ld ((d84-d16)/d50)=1.0, V (d5-d50)/V (d5-d100)=0.71.)
* 6: silane coupling agent (エ ボ ニ Star Network デ グ Star サ ジ ヤ パ Application (strain) Si69 processed, compound name=two-triethoxysilylpropyltetrasulfide tetrasulfide)
* 7: terpine resin A (the ヤ ス Ha ラ ケ ミ カ YS レ processed ジ of Le society Application TO-125, softening temperature=125 ℃, SP value=8.7)
* 8: terpine resin B (the ヤ ス Ha ラ ケ ミ カ YS レ processed ジ of Le society Application TO-85, softening temperature=85 ℃, SP value=8.7)
* 9: terpine resin C (the ヤ ス Ha ラ ケ ミ カ YS レ processed ジ of Le society Application PX1250, softening temperature=125 ℃, SP value=8.3)
* 10: oil (clear and No. 4 S of シ エ Le oil (strain) エ キ processed ス ト ラ Network ト)
* 11: mixture A (the ス ト ラ Network ト trade(brand)name ス ト processed ラ of one Le society Network ト one Le A50P.Zinc content 10.5%)
* 12: mixture B (the ス ト ラ Network ト ス ト processed ラ of one Le society Network ト one Le HT207.Zinc content=do not contain)
* 13: zinc oxide (just with inferior plumbous 3 kinds of chemistry industry (strain) oxygenerating)
* 14: stearic acid (day oil (strain) PVC one ズ ス テ ア リ Application processed is sour)
* 15: anti-aging agent (FLEXSYS SANTOFLEX 6PPD processed)
* 16: vulcanization accelerator (the emerging chemical industry of imperial palace (strain) ノ Network processed セ ラ one CZ)
* 17: sulphur (crane sees that chemical industry (strain) Jinhua processed stamp-pad ink enters the micro mist Sulfur)
Clear and definite by above-mentioned table 1, about the rubber composition for tire by embodiment 1～3 modulation, since in diene series rubber specified quantitative cooperate silicon-dioxide with specific specific surface area, silane coupling agent, the mixture of the tenderizer composition, fatty acid metal salt and the fatty acid ester that are consisted of by terpine resin and oil, therefore the rubber composition for tire that consists of with respect to the cooperation by in the past representational comparative example 1 has further improved grabbing property of wet road, low-rolling-resistance, antifriction consumption when keeping hardness.
Relative therewith, in the comparative example 2, owing to do not cooperate terpine resin, in addition, use fatty acid zinc as mixture A, therefore can not get low-rolling-resistance.
In the comparative example 3, owing to do not cooperate terpine resin, the improvement of therefore wet grabbing property of road and low-rolling-resistance is few.
In the comparative example 4, owing to do not cooperate mixture B (mixture of fatty acid metal salt and fatty acid ester), the improvement of therefore wet grabbing property of road and low-rolling-resistance is few, in addition, also has no the antifriction consumption and improves.
In the comparative example 5, since surpassed by the use level of terpine resin and the tenderizer composition that consists of of oil silicon-dioxide use level 1/2, therefore can not have hardness and low-rolling-resistance (if compare with embodiment 3, then rolling resistance (60 ℃ of tan δ) and hardness begin to worsen) concurrently.In addition, also having no the antifriction consumption improves.
In the comparative example 6, because the use level of silicon-dioxide surpasses the upper limit given to this invention, so the antifriction consumption worsens.In addition, rolling resistance also worsens.
In the comparative example 7, because the use level of mixture B (mixture of fatty acid metal salt and fatty acid ester) surpasses the upper limit given to this invention, so the antifriction consumption worsens.
In the comparative example 8, because the nitrogen adsorption specific surface area (N of silicon-dioxide
2SA) be lower than lower value given to this invention, so the antifriction consumption does not improve.
Clear and definite by above-mentioned table 2, about the rubber composition for tire by embodiment 4～7 modulation, owing to be that specified quantitative cooperates the silicon-dioxide of the high-specific surface area with particular characteristics and the optimal way of the present invention of terpine resin in diene series rubber, therefore compare with the comparative example 9 of conduct representational example in the past, the result is, even use the silicon-dioxide of high-specific surface area also can give good dispersiveness, be low-rolling-resistance, the excellence of control stability and antifriction consumption.In addition, because the favorable dispersity of silicon-dioxide, so tensile strength is also excellent.
Relative therewith, in comparative example 10 and the comparative example 11, owing to do not cooperate terpine resin, so the deterioration of the dispersiveness of silicon-dioxide, rolling resistance or control stability have no improvement, and the antifriction consumption has worsened.
In the comparative example 12, because the nitrogen adsorption specific surface area (N of silicon-dioxide
2SA) be lower than lower limit given to this invention, do not use the particular silica of high-specific surface area, so control stability, antifriction consumption have no improvement.
In the comparative example 13, because the use level of silicon-dioxide is lower than lower limit given to this invention, so control stability has no improvement, and rolling resistance has worsened.
In the comparative example 14, because the use level of silicon-dioxide surpasses the upper limit given to this invention, so control stability and rolling resistance have worsened.
The explanation of symbol
1 bead part
2 sidewalls
3 tyre surfaces
4 body piles
5 bead cores
6 tyre bead fillers
7 belts
8 wheel rim pads.
Claims (13)
1. rubber composition for tire, it cooperates following compositions to form with respect to 100 mass parts diene series rubbers, and described composition is:
The nitrogen adsorption specific surface area N that obtains according to JIS K6217-2 standard of 60～120 mass parts
2SA is 170～225m
2The silicon-dioxide of/g,
Be the silane coupling agent of 4～10 quality % with respect to described silicon-dioxide,
The use level of described silicon-dioxide below 1/2 by terpine resin and the tenderizer composition that consists of of oil, wherein cooperate more than described terpine resin 1 mass parts, and
0.5 the fatty acid metal salt except zinc salt of～10 mass parts and the mixture of fatty acid ester.
2. rubber composition for tire according to claim 1 is characterized in that, described silicon-dioxide satisfies the full terms of following (1)～(4),
The condition of described silicon-dioxide is:
(1) the nitrogen adsorption specific surface area N that obtains according to JIS K6217-2 standard
2SA is 194～225m
2/ g,
(2) the CTAB specific surface area of obtaining according to JIS K6217-3 standard is 170～210m
2/ g,
(3) described nitrogen adsorption specific surface area N
2The relation of SA and described CTAB specific surface area is nitrogen adsorption specific surface area N
2The SA/CTAB specific surface area is 0.9～1.4,
(4) the DBP absorbed dose of obtaining according to JIS K6217-4 oil number A method is more than the 190ml/100g.
3. rubber composition for tire according to claim 2 is characterized in that, described silicon-dioxide satisfies the full terms of following (5)～(8),
The condition of described silicon-dioxide is:
(5) the nitrogen adsorption specific surface area N that obtains according to JIS K6217-2 standard
2SA is 200～225m
2/ g,
(6) the CTAB specific surface area of obtaining according to JIS K6217-3 standard is 180～210m
2/ g,
(7) described nitrogen adsorption specific surface area N
2The relation of SA and described CTAB specific surface area is nitrogen adsorption specific surface area N
2The SA/CTAB specific surface area is 1.0～1.3,
(8) the DBP absorbed dose of obtaining according to JIS K6217-4 oil number A method is 195～230ml/100g.
4. the described rubber composition for tire of according to claim 1～3 each is characterized in that, the softening temperature of described terpine resin is more than 100 ℃, and the SP value is 8.4～9.0 scope.
5. the described rubber composition for tire of according to claim 1～4 each, it is characterized in that, described terpine resin be selected from polyterpene resin, aromatic series modified terpene resin, phenol modified terpene resin and hydrogenated terpene resin that these terpine resin hydrogenations are formed at least a kind.
6. the described rubber composition for tire of according to claim 1～5 each is characterized in that, the SP value of described terpine resin is 8.5～8.9.
7. the described rubber composition for tire of according to claim 1～6 each is characterized in that, described oil is at least a kind that is selected from alkane hydrocarbon system oil, cycloalkanes hydrocarbon system oil, perfume oil, soya-bean oil and the plam oil.
8. the described rubber composition for tire of according to claim 1～7 each is characterized in that, the lipid acid in the mixture of described fatty acid metal salt and fatty acid ester is the saturated or unsaturated fatty acids of carbonatoms 3～30.
9. the described rubber composition for tire of according to claim 1～8 each, it is characterized in that in the mixture of described fatty acid metal salt and fatty acid ester, the ratio of described fatty acid metal salt and fatty acid ester is, when the former was made as 1 in mass, the latter was 0.5～2.0.
10. the described rubber composition for tire of according to claim 1～9 each is characterized in that it is SBR that described diene series rubber comprises styrene-butadiene copolymer rubber.
11. the described rubber composition for tire of according to claim 1～10 each; it is characterized in that described silane coupling agent is for being selected from least a kind in 3-capryloyl thiopropyl triethoxyl silane, 3-propionyl thiopropyl Trimethoxy silane, two-(the two triethoxysilylpropyltetrasulfide of 3-)-tetrasulfide, two-(the two triethoxysilylpropyltetrasulfide of 3-)-disulphide and the 3-sulfydryl propyl trimethoxy silicane.
12. a pneumatic tyre, it has used each described rubber composition for tire of claim 1～11.
13. a pneumatic tyre has used each described rubber composition for tire of claim 1～11 in its tyre surface.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010139601 | 2010-06-18 | ||
| JP139601/2010 | 2010-06-18 | ||
| JP2010150962 | 2010-07-01 | ||
| JP150962/2010 | 2010-07-01 | ||
| PCT/JP2011/003444 WO2011158509A1 (en) | 2010-06-18 | 2011-06-16 | Tire rubber composition and pneumatic tire using same |
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| Publication Number | Publication Date |
|---|---|
| CN102947379A true CN102947379A (en) | 2013-02-27 |
| CN102947379B CN102947379B (en) | 2014-04-30 |
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| CN201180030068.9A Active CN102947379B (en) | 2010-06-18 | 2011-06-16 | Tire rubber composition and pneumatic tire using same |
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|---|---|
| JP (1) | JP4952863B2 (en) |
| CN (1) | CN102947379B (en) |
| DE (1) | DE112011102060B4 (en) |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304858A (en) * | 2012-03-08 | 2013-09-18 | 横滨橡胶株式会社 | Rubber composition for tire tread |
| CN106795337A (en) * | 2014-08-27 | 2017-05-31 | 横滨橡胶株式会社 | Rubber composition for tire and pneumatic tire |
| CN107001713A (en) * | 2014-12-24 | 2017-08-01 | 住友橡胶工业株式会社 | Pneumatic tire |
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| JP2001302847A (en) * | 2000-04-24 | 2001-10-31 | Ohtsu Tire & Rubber Co Ltd :The | Rubber composition for studless tire |
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| JP4067391B2 (en) | 2002-11-28 | 2008-03-26 | 横浜ゴム株式会社 | Rubber composition for tire |
| JP4409971B2 (en) * | 2004-01-21 | 2010-02-03 | 東洋ゴム工業株式会社 | Rubber composition for tire tread |
| JP4635627B2 (en) | 2005-02-01 | 2011-02-23 | 横浜ゴム株式会社 | Rubber composition for tire tread |
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| JP2008280438A (en) * | 2007-05-11 | 2008-11-20 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread |
| JP2008297493A (en) * | 2007-06-01 | 2008-12-11 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
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| JP5597959B2 (en) * | 2009-09-11 | 2014-10-01 | 横浜ゴム株式会社 | Rubber composition for tire |
| JP2011074332A (en) * | 2009-10-02 | 2011-04-14 | Yokohama Rubber Co Ltd:The | Rubber composition for tire sidewall and pneumatic tire using the same |
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- 2011-06-16 DE DE112011102060.0T patent/DE112011102060B4/en active Active
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- 2011-06-16 WO PCT/JP2011/003444 patent/WO2011158509A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011158509A1 (en) | 2013-08-19 |
| DE112011102060B4 (en) | 2020-11-12 |
| JP4952863B2 (en) | 2012-06-13 |
| CN102947379B (en) | 2014-04-30 |
| WO2011158509A1 (en) | 2011-12-22 |
| DE112011102060T5 (en) | 2013-03-28 |
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