WO1997035461A2 - Rubber composition and pneumatic tire - Google Patents
Rubber composition and pneumatic tire Download PDFInfo
- Publication number
- WO1997035461A2 WO1997035461A2 PCT/JP1997/002224 JP9702224W WO9735461A2 WO 1997035461 A2 WO1997035461 A2 WO 1997035461A2 JP 9702224 W JP9702224 W JP 9702224W WO 9735461 A2 WO9735461 A2 WO 9735461A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- rubber
- carbon atoms
- weight
- rubber composition
- Prior art date
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 87
- 239000005060 rubber Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 26
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 12
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 8
- 229920001194 natural rubber Polymers 0.000 claims abstract description 8
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 4
- -1 tertiary amine compound Chemical class 0.000 claims description 34
- 239000006229 carbon black Substances 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229950010007 dimantine Drugs 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 150000001993 dienes Chemical class 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 15
- 230000020169 heat generation Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 125000005372 silanol group Chemical group 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FHPUNDSYXHZZNA-UHFFFAOYSA-N 18-aminooctadecan-7-ol Chemical compound CCCCCCC(O)CCCCCCCCCCCN FHPUNDSYXHZZNA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- 241000238558 Eucarida Species 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 101150068326 bro1 gene Proteins 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- ITDIJRBBGVHIQA-UHFFFAOYSA-N n,n-dibenzyloctadecan-1-amine Chemical compound C=1C=CC=CC=1CN(CCCCCCCCCCCCCCCCCC)CC1=CC=CC=C1 ITDIJRBBGVHIQA-UHFFFAOYSA-N 0.000 description 1
- XLQINSOTYAWFOG-UHFFFAOYSA-N n,n-dimethylhexadec-1-en-1-amine Chemical compound CCCCCCCCCCCCCCC=CN(C)C XLQINSOTYAWFOG-UHFFFAOYSA-N 0.000 description 1
- BUHHOHWMNZQMTA-UHFFFAOYSA-N n,n-dioctadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC BUHHOHWMNZQMTA-UHFFFAOYSA-N 0.000 description 1
- WRFZIYBFCULKKO-UHFFFAOYSA-N n-benzyl-n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CC1=CC=CC=C1 WRFZIYBFCULKKO-UHFFFAOYSA-N 0.000 description 1
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
- MPAMXJNEIAPUEL-UHFFFAOYSA-N n-ethenyl-n-methylethenamine Chemical compound C=CN(C)C=C MPAMXJNEIAPUEL-UHFFFAOYSA-N 0.000 description 1
- UNVMOPYJBABOAS-UHFFFAOYSA-N n-ethenyldodecanamide Chemical group CCCCCCCCCCCC(=O)NC=C UNVMOPYJBABOAS-UHFFFAOYSA-N 0.000 description 1
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- 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
Definitions
- the present invention relates to a rubber composition containing silica, in which the dispersibility of silica in rubber is improved, the heat generation and the abrasion resistance are improved, and a pneumatic tire using the rubber composition.
- a rubber composition containing silica in which the dispersibility of silica in rubber is improved, the heat generation and the abrasion resistance are improved, and a pneumatic tire using the rubber composition.
- carbon black has been used as a reinforcing filler for rubber. This is because carbon black has higher reinforcing properties and abrasion resistance than other fillers. Therefore, it has been required at the same time to reduce the heat generation of the rubber composition.
- silica is known as a filler for lowering the heat generation of the rubber composition, and a number of patents have been filed, such as Japanese Patent Application Laid-Open No. Hei 3-252541, to date.
- silica particles tend to agglomerate due to hydrogen bonds of silanol groups, which are surface functional groups, and it is necessary to lengthen the kneading time in order to improve the dispersion of the silica particles in the rubber.
- the rubber composition had a disadvantage that the Mooney viscosity of the rubber composition was high due to insufficient dispersion of the silica particles in the rubber, resulting in poor processability such as extrusion.
- the surface of the silica particles is acidic, it is used as a vulcanization accelerator.
- the rubber composition adsorbs basic substances, and the rubber composition is not sufficiently vulcanized, and the elastic modulus does not increase. .
- Silane coupling agents have been developed to remedy these drawbacks, but the dispersion of silica has not yet reached a sufficient level, and in particular, it is not possible to obtain industrially good silica force dispersion. It was difficult.
- Japanese Patent Application Laid-Open No. 5-51484 discloses that a silylating agent is added in order to improve the dispersibility of silica.
- the reaction efficiency was not sufficient because the reactants had to be reacted, and further, these silylating agents had a drawback that they had a low boiling point, volatilized during kneading, and did not carry out the reaction sufficiently.
- Japanese Patent Publication No. 63-28886 and Japanese Patent Application Laid-Open No. Hei 6-157825 disclose the use of a hydrophobic precipitated keic acid. Since the precipitated gay acid is used, there is no surface silanol group to which the silane coupling agent reacts, so that there is a disadvantage that the rubber cannot be sufficiently reinforced.
- Japanese Unexamined Patent Application Publication No. 3-1975336 discloses that at least one kind of rubber selected from the group consisting of natural rubber and gen-based synthetic rubber is reinforced with carbon black or the like.
- a rubber composition having improved heat build-up which comprises 20 to 150 parts by weight of a functional filler and 0.05 to 20 parts by weight of an alkylamine compound.
- an alkylamine compound is compounded in order to improve heat buildup.
- a rubber composition containing silica the silica dispersibility is improved.
- the heat generation and the abrasion resistance are improved even in a rubber composition containing a sili-con and a sili force.
- An object of the present invention is to solve the above-mentioned conventional problems, and to provide a rubber composition and a pneumatic tire with improved dispersibility of silica in rubber, and improved heat build-up and wear resistance.
- Disclosure of the invention The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a specific amount of silica has been kneaded with a specific dispersion improver to significantly reduce the dispersion of silica into rubber.
- the present invention has succeeded in obtaining a rubber composition having improved and low heat build-up and high abrasion resistance and a pneumatic tire using the rubber composition, thereby completing the present invention.
- composition and a pneumatic tire to the following (1) to lie in (7) c (1) natural rubber and Z or diene-based rubber component 1 0 0 parts by weight of synthetic rubber, silica 1 5-8 5 weight And a tertiary amine compound represented by the following general formula (I): 1 to 15% by weight based on the amount of the silica.
- [In the above general formula (I), represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 36 carbon atoms, a hydroxy substituent thereof, a benzyl group, an alkyl group or an alkenyl group having 4 to 36 carbon atoms.
- C represents a xyl group and these hydroxy substituents.
- R 4 is an alkyl or alkenyl group having 1 to 3 6 carbon atoms
- R 5 represents an ethylene group or propylene group
- X is hydrogen
- carbon number 1 ⁇ represents an alkyl group, an alkenyl group, an alkylyl group or an alkenyl group of 18,
- A represents an alkylene group or a hydroxyalkylene group having 2 to 6 carbon atoms
- m is an integer of 1 to 10
- m is 2 or more.
- each A may be the same or different
- n is an integer from 1 to 10.
- R ! R 2 is a methyl group represented by the general formula (I)
- said R 3 is dimethyl alkylamine 12-3 6 carbon atoms (1) rubber composition.
- the tread is the rubber composition according to any one of the above (1) to (6).
- Pneumatic tires BEST MODE FOR CARRYING OUT THE INVENTION
- NR natural rubber
- synthetic rubber examples include synthetic polyisoprene rubber (IR), polybutadiene rubber (BR), styrene butadiene rubber (SBR), and the like.
- silica used in the present invention for example, synthetic hydrated maleic acid is preferable, but is not particularly limited.
- the amount of silica is 15 to 85 parts by weight based on 100 parts by weight of the rubber component. If the silica is less than 15 parts by weight, the reinforcing properties are not If the amount exceeds 85 parts by weight, workability such as hot extrusion may deteriorate.
- the amount of silica is preferably 20 to 65 parts by weight from the viewpoints of reinforcement, low heat generation and workability.
- the amine compound used as the dispersion improver of the present invention is a tertiary amine compound represented by the following general formula (I). Two
- a benzyl group a group represented by the following general formula (II), wherein R 2 and R 3 each independently represent an alkyl group having 1 to 36 carbon atoms or an alkenyl group, a benzyl group, a cyclohexyl group, C representing these hydroxy substituents
- R 4 represents an alkyl group or an alkenyl group having 1 to 36 carbon atoms
- R 5 represents an ethylene group or a propylene group
- X represents hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an alkylyl group or an alkenyl group
- A represents an alkylene group having 2 to 6 carbon atoms or a hydroxyalkylene group
- m represents an integer of 1 to 10.
- each A may be the same or different
- n is an integer of 1-10.
- Specific examples include a methyl group, an ethyl group, a propyl group, a lauryl group, a stearyl group, a lauroylaminoethylene group, a stearoyloquinethylene group, an acrylolyoquinpropylene group, and a methylacryloyloxypropylene group.
- R 2 and R 3 include a methyl group, an ethyl group, a lauryl group, a stearyl group, a vinyl group, an aryl group, a 3-aryloxy-2-hydroxypropyl group, a benzyl group, and a hydroxyloxy group. Is mentioned.
- R 4 examples include a methyl group, an ethyl group, a lauryl group, a stearyl group, a vinyl group, and an aryl group.
- X include hydrogen, ethyl group, lauryl group, stearyl group, vinyl group, acryl group, lauroyl group, stearoyl group, acryloyl group, methacryloyl group and the like.
- tertiary amine compound used in the present invention include trioctylamine, trilaurylamine, dimethylstearylamine, dimethyldenamine, dimethylmyristylamine, dilaurylmonomethylamine, dimethyloctadecenyl.
- R! With R 2 is a methyl group, R 3 is dimethyl al Kiruamin 1 2-3 6 carbon atoms, more preferably, the flash point and a low heat build-up, dispersion improving surface Karaji methyl stearyl ⁇ Min.
- the amount of the tertiary amine compound should be 1 to 15% by weight, preferably 3 to 10% by weight, based on the amount of silica. If the amount of the tertiary amine compound is less than 1% by weight, the intended improvement in dispersibility, low heat build-up and abrasion resistance cannot be sufficiently exhibited. The effect of improving the dispersion of silica saturates, and conversely, the tertiary amine compound acts as a plasticizer, so that the abrasion resistance decreases (this point will be described in more detail in Examples).
- the tertiary amine compound used in the present invention preferably has a molecular weight of 180 or more. If the molecular weight of the tertiary amine compound is lower than 180, the flash point is lowered, and there is a risk of ignition in the heating step, which is not preferable.
- the silane coupling agent used in the present invention is not particularly limited as long as it is generally used in the rubber industry. Specifically, bis (3-triethoxysilylpropyl) polysulfide and y-mercaptopropyl trisulfide are used. Examples thereof include ethoxysilane, aminopropyltriethoxysilane, N-phenyl y-aminopropyltrimethoxysilane, and N- (aminoethyl) -aminopropyltrimethoxysilane.
- the amount of the silane coupling agent is 1 to 15% by weight based on the weight of silica. Preferably, it is more preferably 5 to 12% by weight. When the amount of the silane coupling agent is less than 1% by weight, the coupling effect is small, and when the amount exceeds 15% by weight, gelation of the polymer is caused, which is not preferable.
- the carbon black used in the present invention SAF, ISAF, and HAF can be preferably used, but are not particularly limited.
- the compounding amount of carbon black is preferably 20 to 80 parts by weight based on 100 parts by weight of the rubber component from the viewpoint of reinforcing properties and low heat generation. If the amount of carbon black exceeds 80 parts by weight, the heat build-up will be significantly deteriorated. The effect is remarkable at 25 to 60 parts by weight.
- silica in addition to the above rubber component, silica, tertiary amine compound, silane coupling agent, and carbon black, if necessary, a curing agent, an antioxidant, a vulcanizing agent, a vulcanization accelerator.
- a compounding agent usually used in the rubber industry, such as a vulcanization accelerator, can be appropriately compounded.
- the rubber composition and the pneumatic tire of the present invention include the above rubber component, silica, a tertiary amine compound, a silane coupling agent, carbon black, and the above rubber compounding agent that is combined with E as necessary, such as a Banbury mixer. It is manufactured by mixing with.
- silica particles aggregate due to hydrogen bonds of silanol groups, which are surface functional groups, causing poor dispersion in rubber.
- a silane coupling agent generally used in the rubber industry is used to convert a silanol group generated by hydrolysis of an alkoxy group into a silanol group on the surface of silica particles by a dehydration condensation reaction of the silanol group on the surface of the silica. Reduces and improves dispersion in rubber. However, this reaction is unlikely to occur at low temperatures, and is thought to react at temperatures above 140 ° C. On the other hand, at a high temperature of 170 ° C. or more, the silane coupling agent causes a three-dimensional crosslinking reaction of rubber, and the viscosity sharply increases. Real rubber In the kneading process, the temperature of the kneaded rubber rises quickly, so that the reaction time between silica and the silane coupling agent cannot be sufficiently long.
- the nitrogen atom of the tertiary amine has a high ability to form a hydrogen bond with the silanol group on the silica surface, and it is considered that the masking effect of the silanol group on the silica surface prevents aggregation of the silica particles. Since this reaction is not a primary bond but a chemical adsorption, it exhibits this effect even in a low temperature range around room temperature.
- the silica composition has an effect of preventing the silica particles from agglomerating from a low temperature region at the initial stage of rubber kneading.
- the dispersion of silica into the rubber is significantly improved, It is assumed that the properties and abrasion resistance are improved.
- Rubber compositions were prepared with the basic blending ratios shown in Table 1 below and the blending contents shown in Tables 2 and 3 below.
- the unit of weight in the table is part by weight.
- a slab sheet having a thickness of 2 and a width of 5 mm was used as a test piece, and the distance between sample sandwiches was 2 cm (the initial load was 100 g.
- the Payne effect is considered to indicate the degree of dispersion of the filler in the rubber.
- the rubber composition is applied to the tread of a 195Z65R15 size passenger car tire, and the inner pressure of 2.0 kg, the load of 440 kg, and the rim 6JJ tire are brought into contact with the outer diameter of 1.7 drum and the drum is rotated. After ascending to a certain speed, the drum was coasted and the speed was 80 km, and the value calculated from the inertial moment at the time was evaluated by the following equation. The larger the value, the better. ⁇ moment of the tire of Comparative Example 1
- Examples 1 to 13 which are within the scope of the present invention have higher silica than Comparative Examples 1 to 8 which are outside the IBffl of the present invention. It was found that the dispersibility of the rubber in the rubber was high, the heat build-up was low, and the abrasion resistance was excellent.
- a rubber composition and a pneumatic tire containing a component, silica, a silane coupling agent and a tertiary amine compound, and the composition of Examples 1 to 3 is Comparative Example 1 in which only a tertiary amine compound is not added. Compared with (control), it was found that silica had higher dispersibility in rubber, lower heat generation, and better abrasion resistance.
- Comparative Example 2 is out of the scope of the present invention, in which the tertiary amine compound was blended at 20% by weight (> 15% by weight) with respect to silica, but the effect of improving the dispersion of silica was saturated. On the contrary, wear resistance deteriorates.
- Examples 4 to 12 are a rubber composition containing a rubber component, silica, a silane coupling agent and various tertiary amine compounds, and a pneumatic tire using the same, which fall within the scope of the present invention.
- the composition of 4 to 13 means that silica has higher dispersibility in rubber, lower heat build-up, and lower abrasion resistance than the control (Comparative Example 1 and Comparative Example 4) in which only a tertiary amine compound is not added. It turned out to be excellent.
- Comparative Example 3 is out of the range of the present invention, in which 90 parts by weight (> 85 parts by weight) of silica was blended with 100 parts by weight of the rubber component. It was found that the dispersibility of the silica in the rubber was rather deteriorated, but the heat build-up was also worsened.
- Comparative Examples 4 and 5 and Examples 11 and 12 are a combination system of silica and carbon black, and Comparative Example 4 is used as a control.
- Comparative Example 5 is out of the scope of the present invention, in which the amount of silica is less than the lower limit of 15 parts by weight, the low heat build-up of the rubber composition is poor, and the rolling of the pneumatic tire is poor. Poor resistance.
- the rubber composition and the pneumatic tire of the present invention 15 to 85 parts by weight of silica based on 100 parts by weight of the rubber and / or gen-based synthetic rubber and represented by the above general formula (I). 1 to 15% by weight of tertiary amine compound to silica
- the dispersibility of silica in rubber and the heat build-up and abrasion resistance were improved.
- the rubber composition and the pneumatic tire of the present invention can be suitably used for applications requiring low heat generation and high abrasion resistance, and are particularly suitably applied to rubber products such as tires, conveyor belts, and hoses. can do.
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP53426497A JP3451094B2 (ja) | 1997-06-26 | 1997-06-26 | ゴム組成物及び空気入りタイヤ |
EP97928488A EP0846724B1 (en) | 1996-06-26 | 1997-06-26 | Rubber composition and pneumatic tire |
US08/930,817 US6559209B1 (en) | 1996-06-26 | 1997-06-26 | Rubber composition and pneumatic tire |
DE69724221T DE69724221T2 (de) | 1996-06-26 | 1997-06-26 | Gummimischung und pneumatischer reifen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16605296A JP4157608B2 (ja) | 1996-06-26 | 1996-06-26 | ゴム組成物 |
JP8/166052 | 1996-06-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1997035461A2 true WO1997035461A2 (en) | 1997-10-02 |
WO1997035461A3 WO1997035461A3 (fr) | 1997-11-20 |
Family
ID=15824078
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1997/002224 WO1997035461A2 (en) | 1996-06-26 | 1997-06-26 | Rubber composition and pneumatic tire |
Country Status (8)
Country | Link |
---|---|
US (1) | US6559209B1 (ja) |
EP (1) | EP0846724B1 (ja) |
JP (1) | JP4157608B2 (ja) |
KR (1) | KR100450989B1 (ja) |
CN (1) | CN1154687C (ja) |
DE (1) | DE69724221T2 (ja) |
ES (1) | ES2202626T3 (ja) |
WO (1) | WO1997035461A2 (ja) |
Cited By (10)
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JP2001106830A (ja) * | 1999-07-30 | 2001-04-17 | Jsr Corp | ゴム組成物およびタイヤ |
JP2001131344A (ja) * | 1999-11-08 | 2001-05-15 | Bridgestone Corp | ゴム組成物及びそれを用いた空気入りタイヤ |
JP2001158835A (ja) * | 1999-12-02 | 2001-06-12 | Bridgestone Corp | ゴム組成物及びそれを用いた空気入りタイヤ |
US6559209B1 (en) | 1996-06-26 | 2003-05-06 | Bridgestone Corporation | Rubber composition and pneumatic tire |
JP2009263536A (ja) * | 2008-04-25 | 2009-11-12 | Bridgestone Corp | 空気入りタイヤ |
JP2013087185A (ja) * | 2011-10-18 | 2013-05-13 | Bridgestone Corp | ゴム組成物及びそれを用いたタイヤ |
WO2013094693A1 (ja) * | 2011-12-20 | 2013-06-27 | 株式会社ブリヂストン | タイヤ用ゴム組成物及びそれを用いたタイヤ |
WO2014098155A1 (ja) | 2012-12-19 | 2014-06-26 | 株式会社ブリヂストン | ゴム組成物及びそれを用いたタイヤ |
JP2019189732A (ja) * | 2018-04-24 | 2019-10-31 | 横浜ゴム株式会社 | タイヤ用ゴム組成物の製造方法 |
US10662318B2 (en) | 2014-04-30 | 2020-05-26 | Bridgestone Corporation | Rubber composition for tire, production process for same, and tire |
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KR20010072010A (ko) * | 1998-07-22 | 2001-07-31 | 미첼 롤리에르 | 폴리설파이드 알콕시실란, 엔아민 및 구아니딘 유도체를기본으로 하는 커플링 시스템(백색 충전제/디엔엘라스토머) |
DE60018649T2 (de) * | 1999-07-30 | 2006-05-04 | Jsr Corp. | Kautschukzusammensetzung und Reifen daraus |
KR100375656B1 (ko) * | 2000-11-30 | 2003-03-10 | 금호산업 주식회사 | 실리카를 보강 충진제로 사용하는 타이어용 고무조성물 |
DE602005017622D1 (de) * | 2004-04-27 | 2009-12-24 | Bridgestone Corp | Verfahren zur herstellung einer reifenzusammensetzung mit verbesserter kieselsäureverstärkung |
US20060173118A1 (en) * | 2005-01-28 | 2006-08-03 | Sumitomo Rubber Industries, Ltd. | Rubber composition and tire having tread comprising thereof |
US7714051B2 (en) * | 2006-08-07 | 2010-05-11 | The Goodyear Tire & Rubber Company | Rubber compounds containing polyoxyalkylene amines |
US8034316B2 (en) | 2006-11-07 | 2011-10-11 | Cabot Corporation | Carbon blacks having low PAH amounts and methods of making same |
KR100803319B1 (ko) * | 2007-02-23 | 2008-02-13 | 금호타이어 주식회사 | 변성 이소프렌 고무, 3급 아민, 실리카, 실란커플링제를포함하는 마스터배치 및 상기 마스터배치를 포함하는타이어용 고무조성물 |
RU2569854C2 (ru) | 2010-11-24 | 2015-11-27 | Бриджстоун Корпорейшн | Резиновая смесь и шина, произведенная с использованием этой смеси |
EP2770020B1 (en) * | 2011-10-18 | 2017-09-06 | Bridgestone Corporation | Rubber composition and tire using same |
JP5798899B2 (ja) * | 2011-12-02 | 2015-10-21 | 株式会社ブリヂストン | ゴム組成物の製造方法 |
FR2984899B1 (fr) * | 2011-12-21 | 2014-08-15 | Michelin Soc Tech | Pneumatique comprenant une composition essentiellement depourvue de derive guanidique et comprenant une diamine hydroxylee |
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FR3022261B1 (fr) * | 2014-06-12 | 2016-06-03 | Michelin & Cie | Cable gomme in situ comprenant une composition de gommage comprenant un inhibiteur de corrosion |
CN113166480B (zh) | 2018-11-30 | 2023-09-05 | 花王株式会社 | 橡胶组合物 |
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-
1996
- 1996-06-26 JP JP16605296A patent/JP4157608B2/ja not_active Expired - Lifetime
-
1997
- 1997-06-26 CN CNB971907803A patent/CN1154687C/zh not_active Expired - Lifetime
- 1997-06-26 WO PCT/JP1997/002224 patent/WO1997035461A2/ja active IP Right Grant
- 1997-06-26 ES ES97928488T patent/ES2202626T3/es not_active Expired - Lifetime
- 1997-06-26 EP EP97928488A patent/EP0846724B1/en not_active Expired - Lifetime
- 1997-06-26 US US08/930,817 patent/US6559209B1/en not_active Expired - Lifetime
- 1997-06-26 KR KR1019970708405A patent/KR100450989B1/ko not_active Expired - Lifetime
- 1997-06-26 DE DE69724221T patent/DE69724221T2/de not_active Expired - Lifetime
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6559209B1 (en) | 1996-06-26 | 2003-05-06 | Bridgestone Corporation | Rubber composition and pneumatic tire |
JP2001106830A (ja) * | 1999-07-30 | 2001-04-17 | Jsr Corp | ゴム組成物およびタイヤ |
JP2001131344A (ja) * | 1999-11-08 | 2001-05-15 | Bridgestone Corp | ゴム組成物及びそれを用いた空気入りタイヤ |
JP2001158835A (ja) * | 1999-12-02 | 2001-06-12 | Bridgestone Corp | ゴム組成物及びそれを用いた空気入りタイヤ |
JP2009263536A (ja) * | 2008-04-25 | 2009-11-12 | Bridgestone Corp | 空気入りタイヤ |
JP2013087185A (ja) * | 2011-10-18 | 2013-05-13 | Bridgestone Corp | ゴム組成物及びそれを用いたタイヤ |
WO2013094693A1 (ja) * | 2011-12-20 | 2013-06-27 | 株式会社ブリヂストン | タイヤ用ゴム組成物及びそれを用いたタイヤ |
WO2014098155A1 (ja) | 2012-12-19 | 2014-06-26 | 株式会社ブリヂストン | ゴム組成物及びそれを用いたタイヤ |
US9765202B2 (en) | 2012-12-19 | 2017-09-19 | Bridgestone Corporation | Rubber composition and tire produced by using the same |
US10662318B2 (en) | 2014-04-30 | 2020-05-26 | Bridgestone Corporation | Rubber composition for tire, production process for same, and tire |
JP2019189732A (ja) * | 2018-04-24 | 2019-10-31 | 横浜ゴム株式会社 | タイヤ用ゴム組成物の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
DE69724221D1 (de) | 2003-09-25 |
ES2202626T3 (es) | 2004-04-01 |
DE69724221T2 (de) | 2004-06-24 |
CN1196745A (zh) | 1998-10-21 |
CN1154687C (zh) | 2004-06-23 |
KR100450989B1 (ko) | 2005-01-17 |
JP2001316522A (ja) | 2001-11-16 |
JP4157608B2 (ja) | 2008-10-01 |
EP0846724B1 (en) | 2003-08-20 |
EP0846724A2 (en) | 1998-06-10 |
KR19990021930A (ko) | 1999-03-25 |
EP0846724A4 (en) | 2000-12-06 |
WO1997035461A3 (fr) | 1997-11-20 |
US6559209B1 (en) | 2003-05-06 |
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