WO2017077712A1 - ゴム組成物およびタイヤ - Google Patents
ゴム組成物およびタイヤ Download PDFInfo
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- WO2017077712A1 WO2017077712A1 PCT/JP2016/004803 JP2016004803W WO2017077712A1 WO 2017077712 A1 WO2017077712 A1 WO 2017077712A1 JP 2016004803 W JP2016004803 W JP 2016004803W WO 2017077712 A1 WO2017077712 A1 WO 2017077712A1
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- carbon atoms
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 70
- 239000005060 rubber Substances 0.000 title claims abstract description 70
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- 229920000642 polymer Polymers 0.000 claims abstract description 169
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000945 filler Substances 0.000 claims abstract description 55
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- 230000009477 glass transition Effects 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 66
- -1 dimethylaminoethyl group Chemical group 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 34
- 125000001931 aliphatic group Chemical group 0.000 claims description 33
- 125000002723 alicyclic group Chemical group 0.000 claims description 31
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 31
- 244000043261 Hevea brasiliensis Species 0.000 claims description 9
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- 238000012986 modification Methods 0.000 claims description 8
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- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
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- 125000003118 aryl group Chemical group 0.000 claims 2
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- 125000000524 functional group Chemical group 0.000 description 14
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- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 4
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
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- AWIJRPNMLHPLNC-UHFFFAOYSA-N methanethioic s-acid Chemical compound SC=O AWIJRPNMLHPLNC-UHFFFAOYSA-N 0.000 description 3
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- 239000001993 wax Substances 0.000 description 3
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- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 2
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 2
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 2
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- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- KUCGHDUQOVVQED-UHFFFAOYSA-N ethyl(tripropoxy)silane Chemical compound CCCO[Si](CC)(OCCC)OCCC KUCGHDUQOVVQED-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000004658 ketimines Chemical group 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical class [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- XOXRRQOIDCIGAX-UHFFFAOYSA-N lithium ethyl(propyl)azanide Chemical compound [Li+].CCC[N-]CC XOXRRQOIDCIGAX-UHFFFAOYSA-N 0.000 description 1
- LHPXHKQJYVVXKC-UHFFFAOYSA-N lithium;benzyl(ethyl)azanide Chemical compound [Li+].CC[N-]CC1=CC=CC=C1 LHPXHKQJYVVXKC-UHFFFAOYSA-N 0.000 description 1
- NVMMPHVQFFIBOS-UHFFFAOYSA-N lithium;dibutylazanide Chemical compound [Li+].CCCC[N-]CCCC NVMMPHVQFFIBOS-UHFFFAOYSA-N 0.000 description 1
- FHLMGEQZTIKOBY-UHFFFAOYSA-N lithium;didecylazanide Chemical compound [Li+].CCCCCCCCCC[N-]CCCCCCCCCC FHLMGEQZTIKOBY-UHFFFAOYSA-N 0.000 description 1
- AHNJTQYTRPXLLG-UHFFFAOYSA-N lithium;diethylazanide Chemical compound [Li+].CC[N-]CC AHNJTQYTRPXLLG-UHFFFAOYSA-N 0.000 description 1
- QLEXLQBDIFPTQE-UHFFFAOYSA-N lithium;diheptylazanide Chemical compound [Li+].CCCCCCC[N-]CCCCCCC QLEXLQBDIFPTQE-UHFFFAOYSA-N 0.000 description 1
- HOLCSXZMVPOUQR-UHFFFAOYSA-N lithium;dihexylazanide Chemical compound [Li+].CCCCCC[N-]CCCCCC HOLCSXZMVPOUQR-UHFFFAOYSA-N 0.000 description 1
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 description 1
- VZKVUHUYEOZDIY-UHFFFAOYSA-N lithium;dioctylazanide Chemical compound [Li+].CCCCCCCC[N-]CCCCCCCC VZKVUHUYEOZDIY-UHFFFAOYSA-N 0.000 description 1
- OKMANNMCASEBSW-UHFFFAOYSA-N lithium;methyl(2-phenylethyl)azanide Chemical compound [Li+].C[N-]CCC1=CC=CC=C1 OKMANNMCASEBSW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QSAHYVPJMMYBOB-UHFFFAOYSA-N n,n-dimethyl-2-(3-trimethoxysilylpropoxy)ethanamine Chemical compound CO[Si](OC)(OC)CCCOCCN(C)C QSAHYVPJMMYBOB-UHFFFAOYSA-N 0.000 description 1
- QANFDEXNUDRRPG-UHFFFAOYSA-N n,n-dimethyl-3-(3-trimethoxysilylpropoxy)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCOCCCN(C)C QANFDEXNUDRRPG-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OQTSOKXAWXRIAC-UHFFFAOYSA-N tetrabutan-2-yl silicate Chemical compound CCC(C)O[Si](OC(C)CC)(OC(C)CC)OC(C)CC OQTSOKXAWXRIAC-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- BCLLLHFGVQKVKL-UHFFFAOYSA-N tetratert-butyl silicate Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BCLLLHFGVQKVKL-UHFFFAOYSA-N 0.000 description 1
- 125000005068 thioepoxy group Chemical group S(O*)* 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- MQVCTPXBBSKLFS-UHFFFAOYSA-N tri(propan-2-yloxy)-propylsilane Chemical compound CCC[Si](OC(C)C)(OC(C)C)OC(C)C MQVCTPXBBSKLFS-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
-
- 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
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Definitions
- the present invention relates to a rubber composition and a tire.
- Patent Document 1 when the rubber composition disclosed in Patent Document 1 is used, there is a problem in that the low loss and wear resistance of the rubber composition cannot be achieved at a high level.
- the rubber composition according to the present invention is a rubber composition containing a rubber component containing at least a polymer component P1 and a polymer component P2 and a filler containing at least silica, and the glass transition temperature (Tg) of the polymer component P1. 1 ) and the glass transition temperature (Tg 2 ) of the polymer component P2 satisfy the relationship of 0 ⁇
- the glass transition temperature (Tg) of each polymer component can be measured by differential scanning calorimetry (DSC). For example, using a differential scanning calorimeter manufactured by TA Instruments, 5-10 ° C./min. It can be measured under sweep speed conditions.
- means the absolute value of the difference between Tg 1 and Tg 2 .
- the abundance ratio of the filler present in the phase of the polymer component P2 is, for example, a measurement range of 2 ⁇ m ⁇ 2 ⁇ m using an atomic force microscope (AFM), for example, MFP-3D manufactured by ASYLUM RESEARCH, on a smooth surface of a sample cut by a microtome. Can be measured.
- AFM atomic force microscope
- the obtained AFM image is obtained by converting the obtained AFM image into a ternary image into two polymer components and a filler portion.
- the filler area contained in the phases of the two types of polymer components is obtained, and the ratio of the filler present in the phase of the polymer component P2 is calculated from the total amount of fillers in the measurement area.
- the filler is on the boundary surface between the two polymer components, the two points where each polymer component and the filler are in contact are connected to divide the area of the filler.
- the domain width (region width) of the phase of the polymer component refers to the diameter of the circle when the image obtained from AFM is ternarized and the portion corresponding to the filler is extracted and the domain is circular.
- the domain has an irregular shape such as a mottled pattern, it means the maximum length of the domain in the direction orthogonal to the longitudinal direction of each domain (the direction in which the linear distance between the ends in one domain is the longest).
- the average aggregate area of the filler is obtained by, for example, obtaining the aggregate area of the filler part from the image obtained in the measurement range 4 ⁇ m ⁇ 4 ⁇ m from FIB / SEM, and calculating the average from the total aggregate surface area of the filler part and the number of aggregates.
- the aggregate area can be calculated by the number average (arithmetic average). In the calculation, particles in contact with the edge (side) of the image are not counted, and particles of 20 pixels or less are regarded as noise and are not counted.
- the submicron order means a range of 100 nm or more and less than 1000 nm.
- the (co) polymer means a polymer or a copolymer.
- Modified polymer means a modified (co) polymer.
- the modification rate in the modified polymer can be measured by the following method. After the modified polymer is dissolved in toluene, the amino group-containing compound not bonded to the modified polymer is separated from the rubber by precipitation in a large amount of methanol, and then dried. Using this treated polymer as a sample, the total amino group content is quantified by the “total amine number test method” described in JIS K7237.
- the contents of the secondary amino group and the tertiary amino group are quantified with respect to the sample by the “acetylacetone blocked method”.
- O-Nitrotoluene is used as a solvent for dissolving the sample, acetylacetone is added, and potentiometric titration is performed with a perchloric acid acetic acid solution.
- the first amino group content bound to the polymer by subtracting the content of the second amino group and the third amino group from the total amino group content to obtain the first amino group content and dividing the polymer mass used in the analysis Ask for.
- the third amino group content is obtained by dissolving the polymer in toluene and then precipitating it in a large amount of methanol to separate the amino group-containing compound not bound to the modified polymer from the rubber and then drying.
- the tertiary amino group content is quantified by the “acetylation method”.
- the tertiary amino group content bound to the polymer is determined by reverting the polymer mass used in the analysis for the tertiary amino group content.
- the weight average molecular weight of the polymer component can be calculated as a standard polystyrene conversion value by, for example, gel permeation chromatography (GPC).
- the hydrolyzable group is, for example, a trialkylsilyl group such as a trimethylsilyl group or a tert-butyldimethylsilyl group; an —O (trialkylsilyl) group; an —S (trialkylsilyl) group; Alkylsilyl) group; -N (trialkylsilyl) group and the like.
- the (thio) isocyanate group means an isocyanate group or a thioisocyanate group.
- the (thio) epoxy group means an epoxy group or a thioepoxy group.
- the (thio) ketone group means a ketone group or a thioketone group.
- the (thio) aldehyde group means an aldehyde group or a thioaldehyde group.
- the (thio) carboxylic acid ester group means a carboxylic acid ester group or a thiocarboxylic acid ester group.
- a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms means “a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or one having 3 to 20 carbon atoms”.
- Valent alicyclic hydrocarbon group ". The same applies to a divalent hydrocarbon group.
- the halogen atom is, for example, fluorine, chlorine, bromine or iodine.
- TMS means a trimethylsilyl group.
- the present invention it is possible to provide a rubber composition that can achieve both low loss and high wear resistance. Further, according to the present invention, it is possible to provide a tire that has both low loss and high wear resistance.
- FIG. 1 is a photograph of FIB / SEM of Example 2.
- the rubber composition according to the present invention includes at least a rubber component including at least a polymer component P1 and a polymer component P2, a filler including at least silica, and further includes other components as necessary.
- the glass transition temperature of the polymer component P1 (Tg 1), the glass transition temperature of the polymer component P2 (Tg 2) is, 0 ⁇
- the low loss property and wear resistance of the composition can be highly compatible.
- the rubber component includes at least a polymer component P1 and a polymer component P2.
- the glass transition temperature of the polymer component P1 (Tg 1), the glass transition temperature of the polymer component P2 (Tg 2) is, 0 ⁇
- the polymer components P1 and P2 may be incompatible with each other on the order of submicrons, and may be compatible with the naked eye. In order to observe the incompatibility on the order of submicron, for example, using FIB / SEM, the region of 4 ⁇ m ⁇ 4 ⁇ m of the rubber composition is observed. The method of judging is mentioned.
- P1, P2, and P3 when blending three polymers of polymer components P1, P2, and P3, in one embodiment, all of P1, P2, and P3 are incompatible with each other, and in another embodiment, for example, P1 and P2 is incompatible and P3 is compatible with either P1 or P2.
- ⁇ Polymer component P1> As the polymer component P1, if the relationship of 0 ⁇
- the polymer component P1 may be, for example, a diene copolymer.
- a copolymer of a diene monomer and an aromatic vinyl compound is preferable, and 50 to 80% by mass of a diene monomer and 20 to 50% by mass with respect to all monomer components of the polymer component P1. It is more preferable that it is a copolymer with an aromatic vinyl compound.
- diene monomer examples include conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene.
- conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene.
- 1,3-butadiene is preferable because the glass transition temperature (Tg 1 ) of the polymer component P1 can be easily adjusted.
- a conjugated diene compound may be used independently and may be used in combination of 2 or more type.
- aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene, and the like. .
- styrene is preferable because it is easy to adjust the glass transition temperature (Tg 1 ) of the polymer component P1.
- An aromatic vinyl compound may be used independently and may be used in combination of 2 or more type.
- the polymerization method for obtaining the polymer component P1 is not particularly limited, and a known method can be used. Examples of such polymerization methods include anionic polymerization, coordination polymerization, and emulsion polymerization.
- the molecular weight of the polymer component P1 is not particularly limited, and good fracture resistance and wear resistance can be obtained by setting the peak molecular weight to 50,000 or more, and good workability can be obtained by setting it to 700,000 or less. can get. Furthermore, a peak molecular weight of 100,000 to 350,000 is preferable in order to achieve both high fracture resistance and wear resistance and workability.
- Polymer component P2 examples include natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, and modified ones thereof.
- the polymer component P2 is preferably a modified polymer. Thereby, the ratio of the filler which exists in the phase of polymer component P2 can further be raised, and it is advantageous at the point of low exothermic property and abrasion resistance.
- modified functional group for example, a modified functional group having an interaction property with a filler to be described later is preferably exemplified.
- the interaction with the filler can be enhanced, and both low loss and wear resistance can be achieved at a higher level.
- modified functional group having an interaction property with the filler means, for example, a covalent bond between the modified functional group and the filler (for example, silica) surface; intermolecular force (ion-dipole interaction). Functions, dipole-dipole interactions, hydrogen bonds, intermolecular forces such as van der Waals forces).
- a modified functional group with high interaction property with a filler for example, silica
- a filler for example, silica
- a nitrogen-containing functional group, a silicon-containing functional group, an oxygen-containing functional group etc. are mentioned suitably.
- the polymer component P2 is obtained by polymerizing 80 to 100% by mass of a diene monomer and 0 to 20% by mass of an aromatic vinyl compound with respect to the total monomer components of the polymer component P2. It is preferably a coalescence. Furthermore, the polymer component P2 is preferably a modified (co) polymer obtained by modifying a (co) polymer. This is because the low loss and wear resistance of the rubber composition can be further improved.
- Examples of the diene monomer used for the polymerization of the polymer component P2 include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1 Conjugated diene compounds such as 1,3-hexadiene.
- 1,3-butadiene is preferable because the glass transition temperature (Tg 2 ) of the polymer component P2 can be easily adjusted.
- Tg 2 glass transition temperature of the polymer component P2 can be easily adjusted.
- a conjugated diene compound may be used independently and may be used in combination of 2 or more type.
- aromatic vinyl compound used for polymerizing the polymer component P2 examples include styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6- And trimethylstyrene.
- styrene because of easy adjustment of the glass transition temperature of the polymer component P2 (Tg 2), styrene is preferred.
- An aromatic vinyl compound may be used independently and may be used in combination of 2 or more type.
- the polymer component P1 is preferably natural rubber or isoprene rubber
- the polymer component P2 is preferably a modified polymer.
- both low loss and wear resistance can be achieved at a higher level.
- the polymer component P1 is natural rubber or isoprene rubber, so that the rubber composition exhibits high fracture resistance, and further, natural rubber and isoprene rubber This is presumed to be because the polymer skeleton has a low compatibility with silica, and silica tends to exist on the modified polymer side, which is the polymer component P2.
- the polymerization method for obtaining the polymer component P2 is not particularly limited, and a known method can be used. Examples of such polymerization methods include anionic polymerization, coordination polymerization, and emulsion polymerization.
- the modifier for obtaining the modified (co) polymer as the polymer component P2 can be appropriately selected from known modifiers.
- the modifier may be, for example, a modifier that reacts with a polymerization active terminal of anionic polymerization or coordination polymerization, or an amide portion of a lithium amide compound used as a polymerization initiator.
- the modifier for obtaining the modified (co) polymer as the polymer component P2 it can be appropriately selected from the above-mentioned known modifiers having a modified functional group.
- the modifying agent is preferably a modifying agent having at least one atom selected from a silicon atom, a nitrogen atom and an oxygen atom.
- the modifier is preferably at least one selected from the group consisting of an alkoxysilane compound, a hydrocarbyloxysilane compound, and a combination thereof because of high interaction with a filler (for example, silica).
- a filler for example, silica
- the alkoxysilane compound is not particularly limited, but is more preferably an alkoxysilane compound represented by the following general formula (I).
- R 1 a -Si- (OR 2 ) 4-a (I)
- R 1 and R 2 each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, Is an integer of 0 to 2, and when there are a plurality of OR 2 , each OR 2 may be the same as or different from each other, and no active proton is contained in the molecule.
- alkoxysilane compound represented by the general formula (I) include N- (1,3-dimethylbutylidene) -3-triethoxysilyl-1-propanamine, tetramethoxysilane, tetraethoxysilane, tetra -N-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxy Silane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltrime
- N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, tetraethoxysilane, methyltriethoxysilane, and dimethyldiethoxysilane are preferable.
- An alkoxysilane compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- the hydrocarbyloxysilane compound is preferably a hydrocarbyloxysilane compound represented by the following general formula (II).
- n1 + n2 + n3 + n4 4 (where n2 is an integer of 1 to 4, n1, n3 and n4 are integers of 0 to 3), and A 1 is a saturated cyclic tertiary amine compound Residue, unsaturated cyclic tertiary amine compound residue, ketimine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester group, carbonic acid dihydrocarbyl ester group, nitrile group, pyridine Group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid ester group, metal salt of (thio) carboxylic acid ester, carboxylic acid anhydride residue, carboxylic acid halogen compound residue, and It is at least one functional group selected from a primary or secondary amino group having a hydroly
- a 1 may be the same or different, and A 1 may be a divalent group that forms a cyclic structure by bonding to Si, and R 21 is a monovalent fatty acid having 1 to 20 carbon atoms. a group or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having a carbon number of 6 - 18, n1 well be the same or different in the case of 2 or more, R 23 is a C1- 20 monovalent aliphatic or alicyclic hydrocarbon group, monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or halogen atom, and may be the same or different when n3 is 2 or more R 22 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, both of which are nitrogen atoms and / or silicon atoms And when n2 is 2 or more, they are the same or different from each other.
- R 24 may be a divalent alipha
- the hydrolyzable group in the primary or secondary amino group having a hydrolyzable group or the mercapto group having a hydrolyzable group is preferably a trimethylsilyl group or a tert-butyldimethylsilyl group, particularly preferably a trimethylsilyl group.
- the hydrocarbyloxysilane compound represented by the general formula (II) is preferably a hydrocarbyloxysilane compound represented by the following general formula (III).
- p1 + p2 + p3 2 (wherein p2 is an integer of 1 to 2 and p1 and p3 are integers of 0 to 1),
- a 2 is NRa (Ra is a monovalent A hydrocarbon group, a hydrolyzable group or a nitrogen-containing organic group), or sulfur
- R 25 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or 6 to 6 carbon atoms.
- R 18 is a monovalent aromatic hydrocarbon group
- R 27 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 26 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a nitrogen-containing organic group. Any of them may contain a nitrogen atom and / or a silicon atom, and p2 is 2.
- R 28 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a carbon It is a divalent aromatic hydrocarbon group of formula 6-18.
- the hydrolyzable group a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable.
- the hydrocarbyloxysilane compound represented by the general formula (II) is preferably a hydrocarbyloxysilane compound represented by the following general formula (IV) or (V).
- R 34 is an aliphatic or alicyclic hydrocarbon group or a carbon number of monovalent 1-20 carbon atoms
- R 35 is a monovalent aliphatic or alicyclic hydrocarbon having 1 to 20 carbon atoms Group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the same when q2 is 2 or more It may be different also.
- R 36 is a divalent aliphatic having 1 to 20 carbon atoms.
- R 37 is a dimethylaminomethyl group, dimethylaminoethyl group, diethylaminomethyl group, diethylaminoethyl group, methylsilyl (methyl) Aminomethyl group, methylsilyl (methyl) aminoethyl group, methylsilyl (ethyl) aminomethyl group, methylsilyl (ethyl) aminoethyl group, dimethylsilylaminomethyl group, dimethylsilylaminoethyl group, monovalent fat having 1 to 20 carbon atoms
- R 38 is a hydrocarbyloxy group having 1 to 20 carbon atoms, monovalent 1-20 carbon atoms aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon having 6 to 18 carbon atoms And when r2 is 2, they may be the same or different.
- the hydrocarbyloxysilane compound represented by the general formula (II) is preferably a hydrocarbyloxysilane compound having two or more nitrogen atoms represented by the following general formula (VI) or (VII). Thereby, both low loss and wear resistance can be achieved at a higher level.
- R 40 represents a trimethylsilyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; 41 is a hydrocarbyloxy group, a monovalent aromatic hydrocarbon group of monovalent aliphatic or cycloaliphatic hydrocarbon group or a C 6-18 having 1 to 20 carbon atoms having 1 to 20 carbon atoms, R 42 Is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 43 and R 44 are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 45 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and each R 45 is the same or different. It may be.
- the hydrocarbyloxysilane compound represented by the general formula (II) is preferably a hydrocarbyloxysilane compound represented by the following general formula (VIII).
- R 47 and R 48 are each independently a monovalent aliphatic or alicyclic group having 1 to 20 carbon atoms. It is a hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- a plurality of R 47 or R 48 may be the same or different.
- the hydrocarbyloxysilane compound represented by the general formula (II) is preferably a hydrocarbyloxysilane compound represented by the following general formula (IX).
- X is a halogen atom
- R 49 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms
- R 50 and R 51 are each independently a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 50 and R 51 are bonded to form a divalent organic group, and R 52 and R 53 are each independently a halogen atom, a hydrocarbyloxy group, or a group having 1 to 20 carbon atoms.
- R 50 and R 51 are preferably hydrolyzable groups, and the hydrolyzable group is preferably a trimethylsilyl group or a tert-butyldimethylsilyl group, and particularly preferably a trimethylsilyl group.
- the hydrocarbyloxysilane compound represented by the general formula (II) is preferably a hydrocarbyloxysilane compound having a structure represented by the following general formulas (X) to (XIII).
- R 54 to 92 in the general formulas (X) to (XIII) may be the same or different and are each a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aliphatic group having 6 to 18 carbon atoms. Valent aromatic hydrocarbon group.
- ⁇ and ⁇ are integers of 0 to 5.
- N1, N1, N7-tetramethyl-4-((trimethoxysilyl) methyl) -1,7heptane 2-((hexyl-dimethoxysilyl) methyl ) -N1, N1, N3, N3-2-pentamethylpropane-1,3-diamine, N1- (3- (dimethylamino) propyl-N3, N3-dimethyl-N1- (3- (trimethoxysilyl) propyl ) Propane-1,3-diamine, 4- (3- (dimethylamino) propyl) -N1, N1, N7, N7-tetramethyl-4-((trimethoxysilyl) methyl) heptane-1,7-diamine Is preferred.
- hydrocarbyloxysilane compounds represented by the general formulas (II) to (XIII) are preferably used as a modifier for the polymer component P2, but may be used as a modifier for the polymer component P1 and any other polymer component. Good.
- hydrocarbyloxysilane compounds represented by the general formulas (II) to (XIII) are preferably alkoxysilane compounds.
- Suitable modifiers for obtaining a modified polymer as the polymer component P2 by anionic polymerization include, for example, 3,4-bis (trimethylsilyloxy) -1-vinylbenzene, 3,4-bis (trimethylsilyloxy) benzaldehyde, And at least one compound selected from 3,4-bis (tert-butyldimethylsilyloxy) benzaldehyde, 2-cyanopyridine, 1,3-dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidone. .
- the modifier is preferably an amide portion of a lithium amide compound used as a polymerization initiator in anionic polymerization.
- lithium amide compounds include lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethylamide, lithium diethylamide, lithium dibutylamide, and lithium dipropyl.
- the modifying agent that becomes the amide portion of lithium hexamethyleneimide is hexamethyleneimine
- the modifying agent that becomes the amide portion of lithium pyrrolidide is pyrrolidine
- the modifying agent that becomes the amide portion of lithium piperidide is piperidine.
- Suitable modifiers for obtaining a modified polymer as the polymer component P2 by coordination polymerization include, for example, at least one compound selected from 2-cyanopyridine and 3,4-ditrimethylsilyloxybenzaldehyde.
- Suitable modifiers for obtaining the modified polymer as the polymer component P2 by emulsion polymerization include, for example, at least one compound selected from 3,4-ditrimethylsilyloxybenzaldehyde and 4-hexamethyleneiminoalkylstyrene. It is done. These modifiers preferably used in emulsion polymerization are preferably copolymerized at the time of emulsion polymerization as monomers containing nitrogen atoms and / or silicon atoms.
- the modification rate is preferably 30% or more, more preferably 35% or more, and particularly preferably 70% or more.
- the filler containing silica is selectively present in the phase of the polymer component P2, and both low loss and wear resistance can be achieved at a higher level.
- modified polymer as the polymer component P2 will be described.
- a copolymer of styrene and 1,3-butadiene (microstructure: 10% by mass of styrene / 40% by mass of vinyl bonds derived from 1,3-butadiene, base molecular weight (polystyrene conversion): 180,000).
- a polymer was prepared, and modified with N, N-bis (trimethylsilyl) -3- [diethoxy (methyl) silyl] propylamine in a state where the terminal was an anion, and a modified polymer (modified rate: 70%, weight) Average molecular weight (Mw): 200,000) is obtained.
- the polymer components P1 and P2 satisfy the above-described relationship of 0 ⁇
- the SP value (SP 1 ) of P2 and the SP value (SP 2 ) of P2 are preferably different and 0.15 ⁇
- the content of the polymer components P1 and P2 in the rubber component is not particularly limited and may be appropriately selected depending on the intended purpose.
- the ratio of the polymer component P2 to the total amount of the rubber component is 5 to 60%.
- it is 10 to 60%.
- the domain width of the phase of the polymer component P2 is not particularly limited, but is preferably 200 nm or less.
- the rubber component can contain other polymer components such as natural rubber and ethylene-propylene copolymer, if necessary, in addition to the polymer components P1 and P2.
- a polymer other than the polymer components P1 and P2 may be selected from the polymer components P1 and P2 described above.
- the filler contains at least silica, and 80% or more of the total amount of the filler is present in the phase of the polymer component P2.
- the low loss property and abrasion resistance of a rubber composition can be highly compatible.
- 90% or more of the total amount of filler is present in the phase of the polymer component P2.
- both low loss and wear resistance can be achieved at a higher level.
- the filler may include at least silica, and may be appropriately selected from known fillers used for tire rubber compositions and the like according to the purpose.
- Examples of the filler include silica alone, a mixture of silica and carbon black, and the like.
- the average aggregate area of the filler is not particularly limited, is preferably 2100 nm 2 or less, and more preferably 1800 nm 2 or less. As a result, both low loss and wear resistance can be achieved at a higher level.
- the content rate of the silica in a filler is not specifically limited, It can adjust suitably according to the objective.
- the ratio of silica in the filler is preferably 60% by mass or more, and more preferably 90% by mass or more. Thereby, the ratio of the filler which exists selectively in the phase of the polymer component P2 can be increased, the reinforcing effect of the rubber composition can be increased, and the fracture characteristics and wear resistance can be improved.
- the ratio of silica in the filler is preferably 40% by mass or less.
- silica is not particularly limited, and can be used according to applications such as general grade silica, special silica surface-treated with a silane coupling agent, and the like.
- silica for example, wet silica is preferably used, and thereby processability, mechanical strength, and wear resistance can be further improved.
- Carbon black is not particularly limited and can be appropriately selected depending on the purpose.
- the carbon black is preferably, for example, FEF, SRF, HAF, ISAF, or SAF grade, and more preferably HAF, ISAF, or SAF grade.
- the content of carbon black in the filler is not particularly limited as long as silica is contained in the filler, and can be appropriately adjusted according to the purpose. For example, it may be 0 to 40% by mass of the total amount of filler.
- the rubber composition according to the present invention can be blended by appropriately selecting a compounding agent usually used in the rubber industry.
- a compounding agent usually used in the rubber industry.
- examples of such a compounding agent include an antioxidant, a silane coupling agent, a thermoplastic resin, a vulcanization accelerator (for example, stearic acid), a vulcanization acceleration auxiliary (for example, zinc white), and a vulcanizing agent ( For example, sulfur), softener (for example, oil), wax, and the like can be mentioned.
- a compounding agent usually used in the rubber industry.
- a compounding agent include an antioxidant, a silane coupling agent, a thermoplastic resin, a vulcanization accelerator (for example, stearic acid), a vulcanization acceleration auxiliary (for example, zinc white), and a vulcanizing agent ( For example, sulfur), softener (for example, oil), wax, and the like can be mentioned.
- a commercial item can be used conveniently for a compounding agent.
- Thermoplastic resins C 5 resins, C 5 ⁇ C 9 resins, C 9 resins, terpene resins, terpene - aromatics-based resin, rosin resin, from the dicyclopentadiene resin and alkylphenol resin At least one selected.
- the rubber composition contains a certain amount of thermoplastic resin, the Tg of the rubber is increased and the loss tangent (tan ⁇ ) at 0 ° C. is improved, so that the wet grip property of the tire can be improved.
- thermoplastic resin is highly compatible with natural rubber, when natural rubber is used as the rubber component, it is advantageous in that the compatibility of the thermoplastic resin is increased.
- the blending amount of the thermoplastic resin is not particularly limited and can be appropriately adjusted.
- the blending amount of the thermoplastic resin is, for example, preferably 5 to 50 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the rubber component.
- the blending amount of the thermoplastic resin is 5 to 50 parts by mass, both low loss and wet grip properties can be achieved at a higher level.
- the preparation method of a rubber composition is not specifically limited, The well-known preparation method of a rubber composition can be used. For example, it can be produced by blending a rubber component with a filler and various compounding agents appropriately selected as necessary, kneading, heating, extruding and the like.
- the tire according to the present invention is characterized in that the rubber composition is used for a tread member.
- the tread member include, but are not limited to, a tread rubber.
- the tire according to the present invention is not particularly limited except that the rubber composition is used in any of the tread members, and can be produced according to a conventional method.
- Modifier 1 N, N-bis (trimethylsilyl) -3- [diethoxy (methyl) silyl] propylamine, equivalent to hydrocarbyloxysilane compound of general formula (IV) 2: Modifier 2: N- (1,3-dimethylbutyrate Riden) -3-triethoxysilyl-1-propanamine, equivalent to hydrocarbyloxysilane compound of general formula (V)
- Silica Trade name NIPSIL AQ manufactured by Tosoh Silica Co., Ltd. Carbon black: Product name # 80 manufactured by Asahi Carbon Co., Ltd.
- Process oil Trade name A / O mix silane coupling agent manufactured by Sankyo Oil Chemical Co., Ltd .: Bis (3-triethoxysilylpropyl) noitrasulfide, trade name Si69 manufactured by Evonik Degussa
- Thermoplastic resin Product name Nisseki Neopolymer 140 manufactured by JX Nippon Mining & Energy Corporation
- Anti-aging agent N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, trade name NOCRACK 6C manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
- Wax Microcrystalline wax, trade name Ozoace 0701 manufactured by Nippon Seiwa Co., Ltd.
- Vulcanization accelerator 1 bis (2-benzothiazolyl) persulfide, trade name Noxeller DM-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
- Vulcanization accelerator 2 1,3-diphenylguanidine, trade name Noxeller D manufactured by Ouchi Shinsei Chemical Co., Ltd.
- Vulcanization accelerator 3 N- (tert-butyl) -2-benzothiazolesulfenamide, trade name Sunseller NS-G manufactured by Sanshin Chemical Industry Co., Ltd.
- Unmodified polymer B In the polymerization of the unmodified polymer A, a polymerization reaction was carried out in the same manner as the polymerization of the unmodified polymer A, except that the amount of 1,3-butadiene was changed to 50 g and that of styrene to 25 g.
- Modified polymer C To an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, a cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene are added to 67.5 g of 1,3-butadiene and 7.5 g of styrene, and 2,2 After adding 0.6 mmol of -ditetrahydrofurylpropane and 0.8 mmol of n-butyllithium, polymerization was carried out at 50 ° C. for 1.5 hours.
- modifier 1 0.72 mmol of modifier 1 was added as a modifier to the polymerization reaction system in which the polymerization conversion rate was almost 100%, and a modification reaction was performed at 50 ° C. for 30 minutes. Thereafter, 2 mL of a 5 mass% solution of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol was added to stop the reaction, followed by drying according to a conventional method to obtain a modified polymer C. As a result of measuring the microstructure of the obtained modified polymer C, the amount of bonded styrene was 10% by mass, the amount of vinyl bond in the butadiene portion was 40%, and the peak molecular weight was 200,000.
- BHT 2,6-di-t-butyl-p-cresol
- Modified polymer D A modified polymer D was obtained by conducting a polymerization reaction and a modification reaction in the same manner as the modified polymer C, except that the modifier 2 was used instead of the modifier 1 as a modifier. As a result of measuring the microstructure of the resulting modified polymer D, the amount of bound styrene was 10% by mass, the amount of vinyl bond in the butadiene portion was 40%, and the peak molecular weight was 200,000.
- Modified polymer E In the polymerization of the modified polymer C, the polymerization of the modified polymer C was performed except that the amount of 1,3-butadiene was changed to 57 g and the amount of styrene was changed to 19 g, and the addition amount of the modifier 1 was changed to 0.4 mmol. Similarly, a polymerization reaction and a modification reaction were performed. As a result of measuring the microstructure of the obtained modified polymer E, the amount of bonded styrene was 10% by mass, the amount of vinyl bond in the butadiene portion was 40%, and the peak molecular weight was 200,000.
- Unmodified polymer F An unmodified polymer F was obtained in the same manner as the polymerization reaction of the modified polymer C, except that the polymerization reaction was performed and the modification reaction was not performed. As a result of measuring the microstructure of the resulting unmodified polymer F, the amount of bound styrene was 10% by mass, the amount of vinyl bond in the butadiene portion was 40%, and the peak molecular weight was 200,000.
- the present invention it is possible to provide a rubber composition that can achieve both low loss and high wear resistance. Further, according to the present invention, it is possible to provide a tire that has both low loss and high wear resistance.
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Abstract
Description
本発明に係るゴム組成物は、少なくとも、ポリマー成分P1とポリマー成分P2を少なくとも含むゴム成分と、少なくともシリカを含むフィラーとを含み、さらに必要に応じて、その他の成分を含む。ここで、ポリマー成分P1のガラス転移温度(Tg1)と、ポリマー成分P2のガラス転移温度(Tg2)が、0<|Tg1-Tg2|≦20の関係を満たし、ポリマー成分P1とP2が互いにサブミクロンオーダーで非相溶であることにより、ゴム組成物のモルフォロジーが微細化し、シリカを含むフィラーがその微細化したポリマー成分P2の相に一定割合以上選択的に存在することにより、ゴム組成物の低ロス性および耐摩耗性を高度に両立することができる。
ゴム成分は、ポリマー成分P1とポリマー成分P2とを少なくとも含む。ポリマー成分P1のガラス転移温度(Tg1)と、ポリマー成分P2のガラス転移温度(Tg2)は、0<|Tg1-Tg2|≦20の関係を満たし、ポリマー成分P1とP2は、互いにサブミクロンオーダーで非相溶である。したがって、各ポリマー成分を配合した後には、ガラス転移温度(Tg)が異なる2つ以上のポリマー相に相分離する。ポリマー成分P1とP2は、互いにサブミクロンオーダーで非相溶であればよく、肉眼での観察で相溶していてもよい。サブミクロンオーダーで非相溶であることを観察するためには、例えば、FIB/SEMを用いて、ゴム組成物の4μm×4μmの領域を観察し、染色具合の違いがあれば非相溶と判断する方法が挙げられる。
ポリマー成分P1としては、上述した0<|Tg1-Tg2|≦20の関係を満たし、ポリマー成分P1とP2が互いにサブミクロンオーダーで非相溶であれば、公知のポリマー成分を適宜選択して用いることができる。ポリマー成分P1としては、例えば、天然ゴム、イソプレンゴム、スチレン-ブタジエンゴム、ブタジエンゴムなどが挙げられる。
ポリマー成分P2としては、例えば、天然ゴム、イソプレンゴム、スチレン-ブタジエンゴム、ブタジエンゴムおよびこれらを変性したものなどが挙げられる。ポリマー成分P2は、変性ポリマーであることが好ましい。これにより、ポリマー成分P2の相に存在するフィラーの割合をさらに高めることができ、低発熱性と耐摩耗性という点で有利である。
R1 a-Si-(OR2)4-a ・・・ (I)
一般式(I)中、R1およびR2は、それぞれ独立に炭素数1~20の一価の脂肪族炭化水素基または炭素数6~18の一価の芳香族炭化水素基を示し、aは0~2の整数であり、OR2が複数ある場合、各OR2は互いに同一でも異なっていてもよく、また分子中には活性プロトンは含まれない。
ゴム成分は、上記ポリマー成分P1およびP2の他に、必要に応じて、天然ゴム、エチレン-プロピレン共重合体などのその他のポリマー成分を含有することができる。その他のポリマー成分は、上述したポリマー成分P1およびP2から、当該ポリマー成分P1およびP2以外のポリマーを選択してもよい。
本発明において、フィラーは、少なくともシリカを含み、フィラーの総量の80%以上が、ポリマー成分P2の相に存在している。これにより、ゴム組成物の低ロス性および耐摩耗性を高度に両立することができる。フィラーの総量の90%以上が、ポリマー成分P2の相に存在していることがより好ましい。これにより、低ロス性および耐摩耗性をより高度に両立することができる。
フィラー中のシリカの含有率は、特に限定されず、目的に応じて適宜調整することができる。フィラー中のシリカの割合は、一実施形態では、60質量%以上であることが好ましく、90質量%以上であることがより好ましい。これにより、ポリマー成分P2の相に選択的に存在するフィラーの割合を増やし、ゴム組成物の補強効果を高め、破壊特性および耐摩耗性を向上させることができる。カーボンブラックなどの他のフィラーを併用するためには、フィラー中のシリカの割合は、40質量%以下であることが好ましい。
カーボンブラックは、特に限定されず、目的に応じて適宜選択することができる。カーボンブラックは、例えば、FEF、SRF、HAF、ISAF、SAFグレードのものが好ましく、HAF、ISAF、SAFグレードのものがより好ましい。
本発明に係るゴム組成物は、上述したゴム成分およびフィラーの他に、ゴム工業界で通常使用される配合剤を適宜選択して配合することができる。このような配合剤としては、例えば、老化防止剤、シランカップリング剤、熱可塑性樹脂、加硫促進剤(例えば、ステアリン酸)、加硫促進助剤(例えば、亜鉛華)、加硫剤(例えば、硫黄)、軟化剤(例えば、オイル)、ワックスなどが挙げられる。配合剤は、市販品を好適に使用することができる。
熱可塑性樹脂は、C5系樹脂、C5~C9系樹脂、C9系樹脂、テルペン系樹脂、テルペン-芳香族化合物系樹脂、ロジン系樹脂、ジシクロペンタジエン樹脂およびアルキルフェノール系樹脂の中から選ばれる少なくとも1種である。ゴム組成物が一定量の熱可塑性樹脂を含むことで、ゴムのTgが高くなり、0℃での損失正接(tanδ)が向上するため、タイヤのウェットグリップ性を向上させることができる。
ゴム組成物の調製方法は、特に限定されず、公知のゴム組成物の調製方法を用いることができる。例えば、ゴム成分に、フィラーと、必要に応じて適宜選択した各種配合剤とを配合して、混練り、熱入れ、押出等することにより製造することができる。
本発明に係るタイヤは、上記ゴム組成物をトレッド部材に用いたことを特徴とする。これにより、低ロス性および耐摩耗性を高度に両立させたタイヤを提供することができる。トレッド部材としては、例えば、トレッドゴムが挙げられるがこれに限定されない。
変性剤1:N,N-ビス(トリメチルシリル)-3-[ジエトキシ(メチル)シリル]プロピルアミン、一般式(IV)のヒドロカルビルオキシシラン化合物に相当
変性剤2:N-(1,3-ジメチルブチリデン)-3-トリエトキシシリル-1-プロパンアミン、一般式(V)のヒドロカルビルオキシシラン化合物に相当
シリカ:東ソー・シリカ株式会社製の商品名NipSil AQ
カーボンブラック:旭カーボン株式会社製の商品名#80
プロセスオイル:三共油化工業株式会社製の商品名A/Oミックス
シランカップリング剤:ビス(3-トリエトキシシリルプロピル)ペルテトラスルフィド、エボニックデグッサ社製の商品名Si69
熱可塑性樹脂:JX日鉱日石エネルギー株式会社製の商品名日石ネオポリマー140
老化防止剤:N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン、大内新興化学工業株式会社製の商品名ノクラック 6C
ワックス:マイクロクリスタリンワックス、日本精蝋株式会社製の商品名オゾエース0701
加硫促進剤1:ビス(2-ベンゾチアゾリル)ペルスルフィド、大内新興化学工業株式会社製の商品名ノクセラーDM-P
加硫促進剤2:1,3-ジフェニルグアニジン、大内新興化学工業株式会社製の商品名ノクセラーD
加硫促進剤3:N-(tert-ブチル)-2-ベンゾチアゾールスルフェンアミド、三新化学工業株式会社製の商品名サンセラーNS-G
以下の手順にしたがって、ポリマー成分P1として、未変性重合体Aおよび未変性重合体Bを調製した。各ポリマー成分P1の変性官能基の位置、変性剤の種類、変性率(%)およびTg(℃)を、表1に示す。変性率、Tgおよびピーク分子量の測定方法は上述した方法により測定した。
乾燥し、窒素置換した800mLの耐圧ガラス容器に、1,3-ブタジエンのシクロヘキサン溶液、およびスチレンのシクロヘキサン溶液を、1,3-ブタジエン45gおよびスチレン30gになるように加え、2,2-ジテトラヒドロフリルプロパン0.6mmolを加え、0.6mmolのn-ブチルリチウムを加えた後、50℃で3.0時間重合を行った。
未変性重合体Aの重合において、1,3-ブタジエンが50g、スチレンが25gになるように変更したこと以外は未変性重合体Aの重合と同様に重合反応を行った。
以下の手順にしたがって、ポリマー成分P2として、変性重合体C~E、未変性重合体Fを調製した。各ポリマー成分P2の変性官能基の位置、変性剤の種類、変性率(%)およびTg(℃)を、表1に示す。変性率、Tgおよびピーク分子量の測定方法は上述した方法により測定した。
乾燥し、窒素置換した800mLの耐圧ガラス容器に、1,3-ブタジエンのシクロヘキサン溶液およびスチレンのシクロヘキサン溶液を、1,3-ブタジエン67.5gおよびスチレン7.5gになるように加え、2,2-ジテトラヒドロフリルプロパン0.6mmolを加え、0.8mmolのn-ブチルリチウムを加えた後、50℃で1.5時間重合を行った。この際の重合転化率がほぼ100%となった重合反応系に対し、変性剤として変性剤1を0.72mmol添加し、50℃で30分間変性反応を行った。その後、2,6-ジ-t-ブチル-p-クレゾール(BHT)のイソプロパノール5質量%溶液2mLを加えて反応を停止させ、常法に従い乾燥して変性重合体Cを得た。得られた変性重合体Cのミクロ構造を測定した結果、結合スチレン量が10質量%、ブタジエン部分のビニル結合量が40%、ピーク分子量が200,000であった。
変性剤として変性剤1に代えて変性剤2を用いたこと以外は、変性重合体Cと同様に重合反応および変性反応を行い、変性重合体Dを得た。得られた変性重合体Dのミクロ構造を測定した結果、結合スチレン量が10質量%、ブタジエン部分のビニル結合量が40%、ピーク分子量が200,000であった。
変性重合体Cの重合において、1,3-ブタジエンが57g、スチレンが19gになるように変更し、さらに変性剤1の添加量を0.4mmolに変更したこと以外は変性重合体Cの重合と同様に重合反応と変性反応を行った。得られた変性重合体Eのミクロ構造を測定した結果、結合スチレン量が10質量%、ブタジエン部分のビニル結合量が40%、ピーク分子量が200,000であった。
重合反応までを行い、変性反応を行わなかったこと以外は、変性重合体Cの重合反応と同様にして、未変性重合体Fを得た。得られた未変性重合体Fのミクロ構造を測定した結果、結合スチレン量が10質量%、ブタジエン部分のビニル結合量が40%、ピーク分子量が200,000であった。
表2に示すゴム成分に、以下のフィラーなどを配合してゴム組成物を調製した。
シリカ:55質量部
カーボンブラック:3.8質量部
プロセスオイル:1.0質量部
シランカップリング剤:4.4質量部
熱可塑性樹脂:15質量部
ステアリン酸:2質量部
老化防止剤:1質量部
ワックス:2質量部
亜鉛華:2.5質量部
加硫促進剤1:1.2質量部
加硫促進剤2:1.2質量部
加硫促進剤3:1質量部
硫黄:1.8質量部
(1)ポリマー成分P2の相のフィラー存在率(%)
(2)ドメイン幅(nm)
(3)フィラーの平均凝集塊面積(nm2)
(4)低ロス性(tanδ)
(5)耐摩耗性
(6)耐破壊特性
各ゴム組成物について、損失正接(tanδ)を、粘弾性測定装置(レオメトリックス社製)を用いて、温度50℃、歪み5%、周波数15Hzの条件で測定した。得られたtanδの値は、比較例1の値を100として、指数表示した。結果を表2に示す。指数値が大きいほど低ロス性に優れる。
各ゴム組成物について、ランボーン式摩耗試験機を用い、室温におけるスリップ率60%での摩耗量を測定した。得られた摩耗量の値は、その逆数をとり、比較例1の値を100として、指数表示した。結果を表2に示す。指数値が大きいほど摩耗量が少なく、耐摩耗性に優れる。
各ゴム組成物について、JIS K 6251に準拠して室温で引張試験を行い、加硫したゴム組成物の引張強さを測定し、比較例1の値を100として、指数表示した。結果を表2に示す。指数値が大きいほど耐破壊特性に優れる。
Claims (9)
- ポリマー成分P1とポリマー成分P2とを少なくとも含むゴム成分と、
少なくともシリカを含むフィラーと、
を含むゴム組成物であって、
前記ポリマー成分P1のガラス転移温度(Tg1)と、前記ポリマー成分P2のガラス転移温度(Tg2)は、0<|Tg1-Tg2|≦20の関係を満たし、
前記ポリマー成分P1とP2は、互いにサブミクロンオーダーで非相溶であり、
前記フィラーの総量の80%以上が、前記ポリマー成分P2の相に存在していることを特徴とする、ゴム組成物。 - 前記ポリマー成分P2の相のドメイン幅が、200nm以下であることを特徴とする、請求項1に記載のゴム組成物。
- 前記ポリマー成分P2の相に存在するフィラーの平均凝集塊面積が、2100nm2以下であることを特徴とする、請求項1または2に記載のゴム組成物。
- 前記ポリマー成分P1が、天然ゴムまたはイソプレンゴムであり、
前記ポリマー成分P2が、変性ポリマーであることを特徴とする、請求項1~3のいずれか1項に記載のゴム組成物。 - 前記変性ポリマーの変性率が、70%以上であることを特徴とする、請求項4に記載のゴム組成物。
- 前記変性ポリマーが、下記一般式(IV):
下記一般式(V):
- 前記ゴム成分の総量に対する前記ポリマー成分P2の割合が、5~60%であることを特徴とする、請求項1~6のいずれか1項に記載のゴム組成物。
- 前記フィラー中のシリカの割合が、60質量%以上であることを特徴とする、請求項1~7のいずれか1項に記載のゴム組成物。
- 請求項1~8のいずれか1項に記載のゴム組成物をトレッド部材に用いたことを特徴とする、タイヤ。
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JP2022174896A (ja) * | 2021-05-12 | 2022-11-25 | 横浜ゴム株式会社 | タイヤ用ゴム組成物 |
WO2022239491A1 (ja) * | 2021-05-12 | 2022-11-17 | 横浜ゴム株式会社 | タイヤ用ゴム組成物 |
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JP2021050340A (ja) | 2021-04-01 |
JP7055857B2 (ja) | 2022-04-18 |
EP3372638A1 (en) | 2018-09-12 |
JP6802178B2 (ja) | 2020-12-16 |
CN108350232A (zh) | 2018-07-31 |
EP3372638A4 (en) | 2018-12-05 |
US20180319960A1 (en) | 2018-11-08 |
JPWO2017077712A1 (ja) | 2018-08-23 |
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