CN102947379B - Tire rubber composition and pneumatic tire using same - Google Patents
Tire rubber composition and pneumatic tire using same Download PDFInfo
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- CN102947379B CN102947379B CN201180030068.9A CN201180030068A CN102947379B CN 102947379 B CN102947379 B CN 102947379B CN 201180030068 A CN201180030068 A CN 201180030068A CN 102947379 B CN102947379 B CN 102947379B
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- specific surface
- tire
- 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 146
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 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 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 30
- 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 12
- 235000007586 terpenes Nutrition 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 54
- 229960001866 silicon dioxide Drugs 0.000 claims description 54
- 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
- 239000002253 acid 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
- 150000002632 lipids Chemical class 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 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
- 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 11
- 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
- 239000007788 liquid Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000000126 substance Substances 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
- 230000006866 deterioration Effects 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
- 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
- 238000006424 Flood reaction Methods 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
- IVLBGFRTARNACQ-UHFFFAOYSA-N [3-[3,3-bis(triethoxysilyl)propyltetrasulfanyl]-1-triethoxysilylpropyl]-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)C([Si](OCC)(OCC)OCC)CCSSSSCCC([Si](OCC)(OCC)OCC)[Si](OCC)(OCC)OCC IVLBGFRTARNACQ-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
- 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
- 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
- 238000005304 joining Methods 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
- 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- 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 maintaining 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 tyre surface the pneumatic tyre of this rubber composition for tire.
Background technology
In passenger car tire, much less its rideability is high, and to security be considered as its require one of characteristic also gradually improve.For example, in patent documentation 1～3 grade, disclose in rubber composition for tire, to improve wet grabbing property of road and the low-rolling-resistance technology as object.
But, in recent years, strong request Shi Shi grabbing property of road and low-rolling-resistance more height balance, and improve hardness and make control stability, take sensation improve.In addition, improving hardness is to improve contrary performance with improving wet grabbing property of road and low-rolling-resistance, not yet finds to improve the technology of these performances in the past simultaneously.
On the other hand, in order to make control stability, low-rolling-resistance, antifriction consumption height balance, the known silicon-dioxide that coordinates in rubber composition for tire.
In addition, if use the silicon-dioxide of high-specific surface area, the combination number of silicon-dioxide and rubber increases, and infers that above-mentioned performance improves.But, according to the inventor's etc. research, if by silicon-dioxide high-specific surface area, find that silicon-dioxide interaction each other increases, 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.
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 object 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 maintaining hardness and the pneumatic tyre that has used this rubber composition for tire.
For solving the method for problem
The inventor etc. conduct in-depth research repeatedly, found that, by specified quantitative in diene series rubber, coordinate the mixture of the tenderizer composition, fatty acid metal salt and the fatty acid ester that there is the silicon-dioxide, silane coupling agent of specific specific surface area, formed by terpine resin and oil, above-mentioned problem can be solved, thereby the present invention can be completed.
Be that the present invention is as described below.
1. a rubber composition for tire, it coordinates following compositions to form with respect to 100 mass parts diene series rubbers, and described composition is: the nitrogen adsorption specific surface area (N obtaining according to JIS K6217-2 standard of 60～120 mass parts
2sA) be 170～225m
2the silicon-dioxide of/g; It with respect to above-mentioned silicon-dioxide, is the silane coupling agent of 4～10 quality %; The tenderizer composition (more than wherein coordinating above-mentioned terpine resin 1 mass parts) being formed by terpine resin and oil below 1/2 of the use level of above-mentioned silicon-dioxide; And the mixture of the fatty acid metal salt of 0.5～10 mass parts (wherein except zinc salt) and fatty acid ester.
2. according to the rubber composition for tire described in above-mentioned 1, it is characterized in that, above-mentioned silicon-dioxide meets the full terms of following (1)～(4),
The condition of above-mentioned silicon-dioxide is:
(1) the nitrogen adsorption specific surface area (N obtaining 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)/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 190ml/100g.
3. according to the rubber composition for tire described in above-mentioned 2, it is characterized in that, above-mentioned silicon-dioxide meets the full terms of following (5)～(8),
The condition of above-mentioned silicon-dioxide is:
(5) the nitrogen adsorption specific surface area (N obtaining 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)/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 the rubber composition for tire described in above-mentioned 1～3 any one, it is characterized in that, the softening temperature of above-mentioned terpine resin is more than 100 ℃, and the SP value scope that is 8.4～9.0.
5. according to the rubber composition for tire described in above-mentioned 1～4 any one, 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 the rubber composition for tire described in above-mentioned 1～5 any one, it is characterized in that, the SP value of above-mentioned terpine resin is 8.5～8.9.
7. according to the rubber composition for tire described in above-mentioned 1～6 any one, 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 plam oil.
8. according to the rubber composition for tire described in above-mentioned 1～7 any one, 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 the rubber composition for tire described in above-mentioned 1～8 any one, it is characterized in that, in the mixture of above-mentioned fatty acid metal salt and fatty acid ester, ratio for above-mentioned fatty acid metal salt and fatty acid ester is, when the former is made as to 1 (quality), the latter is 0.5～2.0.
10. according to the rubber composition for tire described in above-mentioned 1～9 any one, it is characterized in that, above-mentioned diene series rubber comprises styrene-butadiene copolymer rubber (SBR).
11. according to the rubber composition for tire described in above-mentioned 1～10 any one; 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 3-sulfydryl propyl trimethoxy silicane.
12. 1 kinds of pneumatic tyres, it has used the rubber composition for tire described in above-mentioned 1～11 any one.
13. 1 kinds of pneumatic tyres, have been used the rubber composition for tire described in above-mentioned 1～11 any one in its tyre surface.
The effect of invention
According to the present invention, by specified quantitative in diene series rubber, coordinate the mixture of the tenderizer composition, fatty acid metal salt and the fatty acid ester that there is the silicon-dioxide, silane coupling agent of particular characteristics, formed by terpine resin and oil, thereby can be provided in the pneumatic tyre that further improves the rubber composition for tire of wet grabbing property of road, control stability, low-rolling-resistance, antifriction consumption when maintaining hardness and used this rubber composition for tire.
In addition, according to specified quantitative in diene series rubber, coordinate and there is the silicon-dioxide of particular characteristics and the optimal way of the present invention of terpine resin, even if can provide, use the silicon-dioxide of high-specific surface area also can give good dispersiveness, for low-rolling-resistance, the rubber composition for tire of control stability and antifriction consumption excellence and used the pneumatic tyre of this rubber composition for tire.
Accompanying drawing explanation
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 the partial cross section figure of the airtyred example of car.
In Fig. 1, the tyre surface 3 that pneumatic tyre is connected with sidewall 2 and with two sidewalls 2 by pair of right and left bead part 1 forms, 1,1 of bead part, shelving the body piles 4 that are embedded with fiber cord, turns back laterally and rolls from tire inner side in the end of body piles 4 around bead core 5 and tyre bead filler 6.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 joining with wheel rim, there is wheel rim pad 8.
Illustrated rubber composition for tire of the present invention is particularly useful for tyre surface 3 below.
(diene series rubber)
The diene series rubber composition using in the present invention can be used the diene series rubber arbitrarily that can be engaged in 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, in diene series rubber, specified quantitative cooperation has in the silicon-dioxide of high-specific surface area and the optimal way of the present invention of terpine resin of particular characteristics, from effect of the present invention aspect, more than preferably in 100 mass parts diene series rubbers, SBR accounts for 60 mass parts, further preferably SBR accounts for the above and BR of 60 mass parts and/or NR accounts for other parts.
(silicon-dioxide)
About the silicon-dioxide using in the present invention, the nitrogen adsorption specific surface area (N obtaining according to JIS K6217-2 standard
2sA) be 170～225m
2/ g, according to this nitrogen adsorption specific surface area (N
2sA) scope, rubber composition for tire Shi grabbing property of road and low-rolling-resistance are further improved.
In addition,, in the present invention, preferably use the silicon-dioxide (following, to be sometimes referred to as particular silica) of the high-specific surface area of the full terms that meets following (1)～(4).
(1) the nitrogen adsorption specific surface area (N obtaining 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)/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 190ml/100g.
As the further preferred characteristic of particular silica:
(5) the nitrogen adsorption specific surface area (N obtaining 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)/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 that meets the particular silica of the full terms of above-mentioned (1)～(4) is known, the manufacture method of for example recording in above-mentioned patent documentation 4.That is, silicate is reacted comprising with souring agent, obtains thus silica suspension, then make this suspension separate and the manufacture method of the silicon-dioxide of dry type in, silicate can be undertaken by following series-operation with reacting of souring agent:
(i) form the water-based bottom liquid that has 2～5, is 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 in this bottom liquid simultaneously,
(iii) stop adding this souring agent, in this reaction mixture, continue on the other hand to add silicate 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 in this reaction mixture simultaneously,
(v) stop adding 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 in the present invention also can be utilized commercially available product, can enumerate for example ロ mono-デ イ ア society system, Zeosil Premium 200MP.
In addition, from effect of the present invention aspect, preferably the dimension of object Tile Width Ld ((d84-d16)/d50) of particular silica is at least 0.91, and V (d5-d50)/V (d5-d100) is at least 0.66.
The measuring method of dimension of object Tile Width Ld ((d84-d16)/d50) and V (d5-d50)/V (d5-d100) is known, the measuring method of for example recording in above-mentioned patent documentation 4, also measures above-mentioned physical property according to the method for recording in this patent documentation 4 in the present invention.
Dimension of object Tile Width Ld ((d84-d16)/d50) measures by the XDC grain size analysis method with centrifugal settling.
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 for above-mentioned analyzer as modulated.The deionized water of the silicon-dioxide of 3.2g and 40ml is added in tall form beaker, and modulation suspension, floods the Branson probe (using with 60% of maximum output) of 1500 watts therein, pulverizes this suspension through 20 minutes.
In the register of above-mentioned analyzer, the value of passing through diameter of record 16 % by weight, 50 % by weight (or central value) and 84 % by weight.
By above-mentioned record value, calculate dimension of object Tile Width Ld ((d84-d16)/d50).Here dn is size, the n% (% by weight) of particle have the size less than this size (therefore, this Tile Width Ld by as a whole and obtain accumulation granularity calculate).
V (d5-d50)/V (d5-d100) measures by mercury porosimetry.A corpse or other object for laboratory examination and chemical testing is as modulated.That is, make silicon-dioxide in baking oven 200 ℃ predrying through 2 hours, then it is taken out in latter 5 minutes and is placed in test chamber from this baking oven, then, use and for example rotate wing pump and carry out vacuum outgas.Pore diameter (AUTOPORE III 9420 powder technologies porosity meter) calculates with the contact angle of 140 ° and the surface tension γ of 484 dyne/cm (or N/m) by the equation of Washburn.
V (d5-d50) represents the pore volume being formed by the pore of the diameter of d5～d50, V (d5-d100) represents the pore volume being 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 the (pore (S being formed by 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, dispersed deterioration, can not get the such problem of desired effect, but the particular silica of using in the present invention is by also using with the terpine resin of following explanation, thereby hybrid process improves, and shows good dispersiveness in rubber.The rubber composition for tire of grabbing property of Shi Shi road, control stability, low-rolling-resistance, antifriction consumption height counter-balanced excellence can be provided thus.
(silane coupling agent)
The silane coupling agent using in 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 using in 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,, using in the mode of the present invention of particular silica, from the viewpoint of its effect, in these terpine resins, preferably softening temperature is the terpine resin of 100 ℃ of above and scopes that SP value is 8.4～9.0.By using softening temperature, be 100 ℃ of above terpine resins, thereby under the low state of the mixing temperature while mixing in the early stage, the shearing force of rubber and particular silica uprised, the dispersiveness of particular silica is improved.In addition, by making SP value, be 8.4～9.0 scope, thereby the affinity of rubber and terpine resin uprise, result, the dispersiveness of particular silica is improved.In addition, so-called SP value in the present invention, such as known in the art, be by the molar energy of vaporization Δ E of liquid
vsquare root (the Δ E of the value (cohesive energy density(CED)) obtaining 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 using in the present invention, SP value more preferably 8.5～8.9.
The terpine resin that meets 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 using in 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 salt that forms these lipid acid, can enumerate at least a kind of metal being selected from K, Ca, Na, Mg, Co, Ni, Ba, Fe, Al, Cu and Mn, be particularly preferably K, Ca.In addition, in the present invention, from not reaching the such reason of effect of the present invention, consider, 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 carbonatoms lower alcohol below 10 etc.
Fatty acid metal salt and fatty acid ester can be used separately, also can two kinds be used in combination above.
In addition, about the ratio of fatty acid metal salt and fatty acid ester, preferably, when the former is made as to 1 (quality), the latter uses 0.5～2.0.
(weighting agent)
Rubber composition for tire of the present invention, except above-mentioned silicon-dioxide, can coordinate various weighting agents.As weighting agent, be not particularly limited, as long as carry out suitably selecting 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) (note: measure according to JIS K6217-2) is 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 coordinates following compositions to form with respect to 100 mass parts diene series rubbers, and described composition is: the nitrogen adsorption specific surface area (N obtaining according to JIS K6217-2 standard of 60～120 mass parts
2sA) be 170～225m
2the silicon-dioxide of/g; It with respect to above-mentioned silicon-dioxide, is the silane coupling agent of 4～10 quality %; The tenderizer composition (more than wherein coordinating above-mentioned terpine resin 1 mass parts) being formed by terpine resin and oil below 1/2 of the use level of above-mentioned silicon-dioxide; And the mixture of the fatty acid metal salt of 0.5～10 mass parts (wherein except zinc salt) and fatty acid ester.
If the use level of silicon-dioxide is lower than 60 mass parts, Ze Shi road performance reduces, therefore not preferred.If exceed on the contrary 120 mass parts, antifriction consumption reduces, therefore not preferred.In addition, using particular silica in the situation that, if the mixing ratio of particular silica lower than 60 mass parts, addition is very few, can not realize effect of the present invention.If exceed on the contrary 120 mass parts, fuel consumption performance worsens.
If the use level of silane coupling agent is lower than 4 quality %, antifriction consumption reduces, therefore not preferred.If exceed on the contrary 10 quality %, silane coupling agent polymerization each other, can not obtain desired effect.
If by terpine resin and the tenderizer composition that forms of oil, exceeded above-mentioned silicon-dioxide use level 1/2, 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, 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, use level is very few, can not realize effect of the present invention.If exceed on the contrary 10 mass parts, antifriction consumption reduces, therefore not preferred.
In rubber composition for tire of the present invention, the nitrogen adsorption specific surface area (N obtaining 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.In the situation that using particular silica, preferred use level is to be 65～115 mass parts with respect to 100 mass parts diene series rubbers in addition.
The further preferred use level of silane coupling agent is to be 5～9 quality % with respect to silicon-dioxide.
The further preferred use level of the tenderizer composition consisting of terpine resin and oil is to be 10～40 quality % with respect to the use level of silicon-dioxide.
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 the present invention relates to, except mentioned component, can coordinate general coordinated various additives 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, for sulfuration or crosslinked.The use level of these additives, as long as without prejudice to object of the present invention, can be also just general use level in the past.In addition rubber combination of the present invention can be according to airtyred manufacture method in the past and for the manufacture of pneumatic tyre.
Embodiment
Below, by embodiment and comparative example, further illustrate the present invention, but the invention is not restricted to following example.
Embodiment 1～7 and comparative example 1～14
The modulation of sample
In the cooperation shown in table 1 and 2 (mass parts), by mixing 5 minutes of the hermetic type mixing tank of 1.8L for composition except sulphur, vulcanization accelerator, in the masterbatch of emitting, add sulphur, vulcanization accelerator, with open roller, carry out mixing, thereby modulation.Next by the rubber combination of gained in the mould of regulation 160 ℃ of press vulcanizations 20 minutes, obtain vulcanized rubber test film, adopt test method determination physical property shown below.
Rolling resistance: according to JIS K6394, use (strain) Japan essence mechanism to make made visco-elasticity spectrometer, under the condition of strain=10%, amplitude=± 2%, frequency=20Hz, measure in the early stage tan δ (60 ℃), adopt this value to evaluate rolling resistance.Result is made as 100 with exponential representation by comparative example 1 or 9.Index is higher, represents that rolling resistance is better.
Wet road performance: according to JIS K6394, use (strain) Japan essence mechanism to make made visco-elasticity spectrometer, under the condition of strain=10%, amplitude=± 2%, frequency=20Hz, measure in the early stage tan δ (0 ℃), adopt this value to evaluate wet road performance (grabbing property of wet road).Result is made as 100 with exponential representation by comparative example 1.Index is higher, represents that rolling resistance is better.
Hardness: according to JIS K6253, measure 20 ℃ of temperature by scleroscopic type A.This value is higher, can say that hardness is higher, is good result.
Tensile strength: according to JIS K6251,300% modulus (M300) while measuring 23 ℃.Comparative example 9 is made as to 100 with exponential representation.This numerical value is larger, represents that tensile strength is higher.
Antifriction consumption (1): use the blue Berne abrasion trier of rock this making institute (strain) system, measure under the condition of loading 5kg (49N), sliding ratio 25%, 4 minutes time, room temperature.Comparative example 1 is made as to 100 with exponential representation.This numerical value is larger, represents that antifriction consumption is more excellent.
Antifriction consumption (2): according to JIS K6264, measure antifriction consumption with FERRY MACHINE CO. pik abrasion processed trier.Comparative example 9 is made as to 100 with exponential representation.This numerical value is larger, represents that antifriction consumption is more excellent.
Control stability: make the test tire that has used the 195/R15 size of vulcanized rubber test film in tyre surface.Then, on the test vehicle of free air delivery 2L, 4 take turns the test tire that same size is all installed, and the grabbing level of feeling evaluation in dry road surface pavement and operating the rudder property, be made as 100 with index assessment by comparative example 9.This numerical value is larger, represents that 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 mono-ボ Application シ mono-ス ト 9 processed, nitrogen adsorption specific surface area (N
2sA)=142m
2/ g)
* 3: silicon-dioxide (eastern ソ mono-シ リ カ (strain) NipsilAQ processed, N
2sA=200m
2/ g)
* 4: relatively silicon-dioxide (the ロ mono-デ イ ア 1165MP processed of society, nitrogen adsorption specific surface area (N
2sA)=163m
2/ g, CTAB specific surface area 159m
2/ g, DBP absorbed dose=202ml/100g)
* 5: particular silica (the ロ mono-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=bis--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 trade(brand)name ス ト processed ラ of ス ト ラ クトYiル society Network ト mono-Le A50P.Zinc content 10.5%)
* 12: mixture B (the ス ト processed ラ of ス ト ラ クトYiル society Network ト mono-Le HT207.Zinc content=do not contain)
* 13: zinc oxide (sub-plumbous 3 kinds of just same chemical industry (strain) oxygenerating)
* 14: stearic acid (day oil (strain) PVC one ズ ス テ ア リ Application acid processed)
* 15: anti-aging agent (FLEXSYS SANTOFLEX 6PPD processed)
* 16: vulcanization accelerator (the emerging chemical industry of imperial palace (strain) ノ Network processed セ ラ mono-CZ)
* 17: sulphur (crane sees that chemical industry (strain) Jinhua processed stamp-pad ink enters micro mist Sulfur)
Clear and definite by above-mentioned table 1, about the rubber composition for tire by embodiment 1～3 modulation, the mixture of tenderizer composition, fatty acid metal salt and the fatty acid ester that there is the silicon-dioxide, silane coupling agent of specific specific surface area because specified quantitative in diene series rubber coordinates, formed by terpine resin and oil, therefore the rubber composition for tire forming with respect to the cooperation of the representational comparative example 1 by the past further improves grabbing property of Liao Shi road, low-rolling-resistance, antifriction consumption when maintaining hardness.
On the other hand, in comparative example 2, owing to not coordinating terpine resin, in addition, use fatty acid zinc as mixture A, therefore can not get low-rolling-resistance.
In comparative example 3, owing to not coordinating terpine resin, therefore the improvement of wet grabbing property of road and low-rolling-resistance is few.
In comparative example 4, owing to not coordinating mixture B (mixture of fatty acid metal salt and fatty acid ester), therefore the improvement of wet grabbing property of road and low-rolling-resistance is few, in addition, also has no antifriction consumption and improves.
In comparative example 5, due to by the use level of terpine resin and the tenderizer composition that forms of oil, exceeded silicon-dioxide use level 1/2, therefore can not have hardness and low-rolling-resistance (if compared with embodiment 3, rolling resistance (60 ℃ of tan δ) and hardness start to worsen) concurrently.In addition, also having no antifriction consumption improves.
In comparative example 6, because the use level of silicon-dioxide exceedes the upper limit given to this invention, therefore antifriction consumption worsens.In addition, rolling resistance also worsens.
In comparative example 7, because the use level of mixture B (mixture of fatty acid metal salt and fatty acid ester) exceedes the upper limit given to this invention, therefore antifriction consumption worsens.
In comparative example 8, due to the nitrogen adsorption specific surface area (N of silicon-dioxide
2sA), lower than lower value given to this invention, therefore 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 being the silicon-dioxide of high-specific surface area and the optimal way of the present invention of terpine resin that specified quantitative cooperation has particular characteristics in diene series rubber, therefore compared with the comparative example 9 of the representational example as in the past, result is, even if 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,, due to the favorable dispersity of silicon-dioxide, therefore tensile strength is also excellent.
On the other hand, in comparative example 10 and comparative example 11, owing to not coordinating terpine resin, therefore the dispersiveness of silicon-dioxide worsens, and rolling resistance or control stability have no improvement, and antifriction consumption has worsened.
In comparative example 12, due to the nitrogen adsorption specific surface area (N of silicon-dioxide
2sA) lower than lower limit given to this invention, do not use the particular silica of high-specific surface area, therefore control stability, antifriction consumption have no improvement.
In comparative example 13, because the use level of silicon-dioxide is lower than lower limit given to this invention, therefore control stability has no improvement, and rolling resistance has worsened.
In comparative example 14, because the use level of silicon-dioxide exceedes the upper limit given to this invention, therefore 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. a rubber composition for tire, it coordinates following compositions to form with respect to 100 mass parts diene series rubbers, and described composition is:
The silicon-dioxide of the full terms of meeting of 60～120 mass parts following (1)～(4),
With respect to described silicon-dioxide, be the silane coupling agent of 4～10 quality %,
The tenderizer composition being formed by terpine resin and oil below 1/2 of the use level of described silicon-dioxide, more than wherein coordinating described terpine resin 1 mass parts, and
The fatty acid metal salt except zinc salt of 0.5～10 mass parts and the mixture of fatty acid ester,
The condition of described silicon-dioxide is:
(1) the nitrogen adsorption specific surface area N obtaining 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
2sA/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 190ml/100g.
2. rubber composition for tire according to claim 1, is characterized in that, described silicon-dioxide meets the full terms of following (5)～(8),
The condition of described silicon-dioxide is:
(5) the nitrogen adsorption specific surface area N obtaining 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
2sA/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.
3. rubber composition for tire according to claim 1 and 2, is characterized in that, the softening temperature of described terpine resin is more than 100 ℃, and the SP value scope that is 8.4～9.0.
4. rubber composition for tire according to claim 1 and 2, is characterized in that, described terpine resin be selected from polyterpene resin, aromatic series modified terpene resin and hydrogenated terpene resin that these terpine resin hydrogenations are formed at least a kind.
5. rubber composition for tire according to claim 4, is characterized in that, described aromatic series modified terpene resin is phenol modified terpene resin.
6. rubber composition for tire according to claim 1 and 2, is characterized in that, the SP value of described terpine resin is 8.5～8.9.
7. rubber composition for tire according to claim 1 and 2, 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 plam oil.
8. rubber composition for tire according to claim 1 and 2, 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. rubber composition for tire according to claim 1 and 2, 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 is made as to 1 in mass, the latter is 0.5～2.0.
10. rubber composition for tire according to claim 1 and 2, is characterized in that, it is SBR that described diene series rubber comprises styrene-butadiene copolymer rubber.
11. rubber composition for tire according to claim 1 and 2; 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 3-sulfydryl propyl trimethoxy silicane.
12. 1 kinds of pneumatic tyres, it has used the rubber composition for tire described in any one of claim 1～11.
13. 1 kinds of pneumatic tyres, have been used the rubber composition for tire described in any one of claim 1～11 in its tyre surface.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP139601/2010 | 2010-06-18 | ||
| JP2010139601 | 2010-06-18 | ||
| JP150962/2010 | 2010-07-01 | ||
| JP2010150962 | 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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| CN102947379A CN102947379A (en) | 2013-02-27 |
| CN102947379B true 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) |
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| JP5882074B2 (en) * | 2012-02-06 | 2016-03-09 | 東洋ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP5644838B2 (en) * | 2012-03-08 | 2014-12-24 | 横浜ゴム株式会社 | Rubber composition for tire tread |
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| DE112011102060B4 (en) | 2020-11-12 |
| WO2011158509A1 (en) | 2011-12-22 |
| CN102947379A (en) | 2013-02-27 |
| JP4952863B2 (en) | 2012-06-13 |
| JPWO2011158509A1 (en) | 2013-08-19 |
| DE112011102060T5 (en) | 2013-03-28 |
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