JP5476741B2 - Diene rubber composition - Google Patents
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- JP5476741B2 JP5476741B2 JP2009045424A JP2009045424A JP5476741B2 JP 5476741 B2 JP5476741 B2 JP 5476741B2 JP 2009045424 A JP2009045424 A JP 2009045424A JP 2009045424 A JP2009045424 A JP 2009045424A JP 5476741 B2 JP5476741 B2 JP 5476741B2
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- 229920003244 diene elastomer Polymers 0.000 title claims description 44
- 239000000203 mixture Substances 0.000 title claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 19
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 description 14
- 239000002174 Styrene-butadiene Substances 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 235000021355 Stearic acid Nutrition 0.000 description 9
- 230000003712 anti-aging effect Effects 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000008117 stearic acid Substances 0.000 description 9
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- 229920000459 Nitrile rubber Polymers 0.000 description 7
- 239000005062 Polybutadiene Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 4
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000010692 aromatic oil Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HUMLQUKVJARKRN-UHFFFAOYSA-M sodium;n,n-dibutylcarbamodithioate Chemical compound [Na+].CCCCN(C([S-])=S)CCCC HUMLQUKVJARKRN-UHFFFAOYSA-M 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960002447 thiram Drugs 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
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- 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
Description
本発明は、ジエン系ゴム組成物に関する。さらに詳しくは、空気入りタイヤのトレッド部形成材料等として好適に用いられるジエン系ゴム組成物に関する。 The present invention relates to a diene rubber composition. More specifically, the present invention relates to a diene rubber composition suitably used as a tread portion forming material for a pneumatic tire.
自動車の空気入りタイヤについては、今迄以上に低燃費化が求められている。タイヤ用ゴム組成物中にシリカを配合することで、タイヤの高性能化が進んでいるが、さらなる物性の向上が望まれている。向上が求められる物性として、耐摩耗性の改善や発熱量を抑え、転がり抵抗が良好であることを示す60℃におけるtanδ値の改善などが挙げられる。 As for pneumatic tires for automobiles, lower fuel consumption is required than ever. By adding silica to the tire rubber composition, the performance of the tire has been improved, but further improvement in physical properties is desired. Physical properties that need to be improved include improved wear resistance, reduced calorific value, and improved tan δ value at 60 ° C. indicating good rolling resistance.
また、近年自動車用空気入りタイヤに求められる性能は、低燃費性に加えて、安定性、操縦安定性などの多岐にわたっており、空気入りタイヤを構成するジエン系ゴム組成物については、これらの要求をみたすために種々の提案がなされている。例えば、低燃費性をみたすために、キャップトレッド用ジエン系ゴム組成物への上記の如きシリカの配合が考えられるが、シリカ配合は加硫ゴムの剛性(モジュラス、硬度)を低下させ、操縦安定性の低下や各部材の走行中の動きを大きくし、結果的にセパレーション等の安全面に悪影響を及ぼすこととなる。剛性を上げるためには、カーボンブラックの増量が考えられるが、これは低燃費性に悪影響を及ぼすようになる。 In recent years, the performance demanded of pneumatic tires for automobiles has varied in terms of stability, handling stability, etc. in addition to low fuel consumption, and these requirements are required for diene rubber compositions constituting pneumatic tires. Various proposals have been made to meet the requirements. For example, in order to achieve low fuel consumption, it is conceivable to add silica as described above to the diene rubber composition for cap treads. Silica compounding reduces the rigidity (modulus, hardness) of the vulcanized rubber and stabilizes handling. As a result, the performance of each member is increased and the movement of each member is increased, resulting in adverse effects on safety such as separation. In order to increase the rigidity, an increase in the amount of carbon black can be considered, but this adversely affects fuel efficiency.
本発明の目的は、空気入りタイヤのトレッド部形成材料等として好適に用いられ、耐摩耗性の改善や発熱量を抑え、転がり抵抗が良好であることを示す60℃におけるtanδ値の改善などを達成せしめ、また加硫ゴムの剛性と低燃費性とのバランスを良好とするジエン系ゴム組成物を提供することにある。 The object of the present invention is to be suitably used as a tread part forming material of a pneumatic tire, etc., to improve wear resistance, suppress calorific value, and improve tan δ value at 60 ° C. indicating good rolling resistance. Another object of the present invention is to provide a diene rubber composition that achieves a good balance between the rigidity and low fuel consumption of vulcanized rubber.
かかる本発明の目的は、ジエン系ゴム100重量部当り、ポリマー主鎖にカルボニル基含有不飽和化合物およびこのカルボニル基と反応し得る官能性基で置換された含窒素複素環化合物としての4H-3-アミノ-1,2,4-トリアゾールを順次反応させて得られた重量平均分子量Mwが50,000以下の水素結合性熱可塑性エラストマー0.1〜25重量部、好ましくは0.2〜10重量部とシリカまたはシリカとカーボンブラックの両者30〜120重量部とを添加してなるジエン系ゴム組成物によって達成される。 The object of the present invention is to provide 4H-3 as a nitrogen-containing heterocyclic compound in which the polymer main chain is substituted with a carbonyl group-containing unsaturated compound and a functional group capable of reacting with the carbonyl group, per 100 parts by weight of the diene rubber. 0.1 to 25 parts by weight, preferably 0.2 to 10 parts by weight of a hydrogen-bonding thermoplastic elastomer having a weight average molecular weight Mw of 50,000 or less obtained by sequentially reacting -amino-1,2,4-triazole and silica or silica This is achieved by a diene rubber composition obtained by adding 30 to 120 parts by weight of both carbon blacks .
本発明に係るジエン系ゴム組成物は、ポリマー主鎖にカルボニル基含有不飽和化合物およびこのカルボニル基と反応し得る官能性基で置換された含窒素複素環化合物を順次反応させて得られた水素結合性熱可塑性エラストマーを、シリカ含有ジエン系ゴム、特にSBRを50重量％以上含有するジエン系ゴムに添加することにより、耐摩耗性の改善や発熱量を抑え、転がり抵抗が良好であることを示す60℃におけるtanδ値の改善などの点ですぐれた加硫物を与え得るので、自動車の空気入りタイヤのトレッド部形成などに有効に用いられる。 The diene rubber composition according to the present invention is obtained by sequentially reacting a polymer main chain with a carbonyl group-containing unsaturated compound and a nitrogen-containing heterocyclic compound substituted with a functional group capable of reacting with the carbonyl group. By adding a binder thermoplastic elastomer to a silica-containing diene rubber, especially a diene rubber containing 50% by weight or more of SBR, it is possible to improve wear resistance, suppress calorific value, and have good rolling resistance. Since it is possible to give a vulcanizate that is excellent in terms of improvement of the tan δ value at 60 ° C. shown, it is effectively used for forming a tread portion of a pneumatic tire of an automobile.
また、ジエン系ゴム、特にSBRを50重量％以上、好ましくは90重量％以上含有するジエン系ゴムをシリカと共に用いた場合には、空気入りタイヤのキャップトレッド部形成に有効であり、空気入りタイヤの剛性(モジュラス、硬度)と低燃費性とのバランス性にすぐれているものを与えることができる。 Further, when a diene rubber, particularly a diene rubber containing SBR of 50% by weight or more, preferably 90% by weight or more is used together with silica, it is effective for forming a cap tread portion of a pneumatic tire. It is possible to provide an excellent balance between rigidity (modulus and hardness) and low fuel consumption.
ジエン系ゴムとしては、タイヤ製造に用いられる任意のジエン系ゴムを用いることができ、好ましくは天然ゴム、スチレンブタジエンゴム(SBR)、ブタジエンゴムが用いられる。特に、SBRを50〜100重量％含むものが用いられた場合には、空気入りタイヤのトレッド部形成材料として、また90〜100重量％含むものが用いられた場合には、空気入りタイヤのキャップトレッド部形成材料として好適に用いることができる。SBRとしては、乳化重合SBR(E-SBR)、溶液重合SBR(S-SBR)のいずれをも用いることができ、SBRが他のジエン系ゴムとブレンドして用いられる場合には、他のジエン系ゴムとして天然ゴム、ブタジエンゴムまたはこれら両者が用いられることが好ましい。 As the diene rubber, any diene rubber used for tire production can be used, and natural rubber, styrene butadiene rubber (SBR), and butadiene rubber are preferably used. In particular, when a material containing 50 to 100% by weight of SBR is used, as a material for forming a tread portion of a pneumatic tire, and when a material containing 90 to 100% by weight is used, a cap for a pneumatic tire It can be suitably used as a tread part forming material. As SBR, either emulsion polymerization SBR (E-SBR) or solution polymerization SBR (S-SBR) can be used. When SBR is blended with other diene rubbers, other diene is used. Natural rubber, butadiene rubber or both are preferably used as the rubber.
これらのジエン系ゴムに添加される、ポリマー主鎖にカルボニル基含有不飽和化合物および含窒素複素環化合物と順次反応させて得られた水素結合性熱可塑性エラストマーとしては、重量平均分子量Mw(GPC法により測定)が50,000以下、好ましくは10,000〜40,000のものが用いられる。より具体的には、好ましくは特許文献１に記載される如き、主鎖がジエン系ゴム分子からなり、またカルボニル基含有不飽和化合物としては無水マレイン酸が用いられる。 The hydrogen-bonded thermoplastic elastomer added to these diene rubbers by sequentially reacting the polymer main chain with a carbonyl group-containing unsaturated compound and a nitrogen-containing heterocyclic compound includes a weight average molecular weight Mw (GPC method). (Measured by the above) is 50,000 or less, preferably 10,000 to 40,000. More specifically, as described in Patent Document 1, the main chain is composed of a diene rubber molecule, and maleic anhydride is used as the carbonyl group-containing unsaturated compound.
主鎖がジエン系ゴム分子からなる水素結合性熱可塑性エラストマーのジエン系ゴム分子としては、天然ゴム、イソプレンゴム、ブタジエンゴム、クロロプレンゴム、ニトリルゴム、スチレンブタジエンゴム等が用いられ、好ましくはイソプレンゴムが用いられる。 Natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, nitrile rubber, styrene butadiene rubber, etc. are used as the diene rubber molecule of the hydrogen bondable thermoplastic elastomer whose main chain is composed of a diene rubber molecule, preferably isoprene rubber. Is used.
ここで、熱可塑性エラストマーとしてジエン系ゴムに無水マレイン酸を付加反応させ、さらに官能性基置換含窒素複素環化合物を反応させた水素結合性のものが用いられるのは、シリカと親和性のよい水素結合基を形成されることにより、シリカの分散性、補強性が向上し、低発熱化、高物性、高耐摩耗性が発現するようになるためである。この水素結合は、カルボニル基含有不飽和化合物に由来するカルボニル基とこれと反応した含窒素複素環化合物との間で、O-H…O、N-H…O、O-H…N、N-H…Nで示されるようなドナー-H-アクセプターよりなり、自己架橋を可能とし、また加熱時(120℃)には解離して、常温付近では再び水素結合を形成させる。 Here, as a thermoplastic elastomer, a hydrogen-bonded one obtained by adding maleic anhydride to a diene rubber and further reacting with a functional group-substituted nitrogen-containing heterocyclic compound is used because of its good affinity with silica. This is because the formation of a hydrogen bonding group improves the dispersibility and reinforcement of silica, and exhibits low heat generation, high physical properties, and high wear resistance. This hydrogen bond is represented by OH ... O, NH ... O, OH ... N, NH ... N between the carbonyl group derived from the carbonyl group-containing unsaturated compound and the nitrogen-containing heterocyclic compound reacted with the carbonyl group. It consists of a new donor-H-acceptor, and enables self-crosslinking, dissociates when heated (120 ° C.), and forms hydrogen bonds again at around room temperature.
主鎖がこれらのジエン系ゴム分子からなり、そのポリマー主鎖にカルボニル基含有不飽和化合物およびこのカルボニル基と反応し得る官能性基で置換された含窒素複素環化合物と順次反応させて得られた水素結合性熱可塑性エラストマーの合成に際しては、まずジエン系ゴム分子に無水マレイン酸、マレイン酸等のカルボニル基含有不飽和化合物、好ましくは無水マレイン酸を付加反応させる。無水マレイン酸の変性率は、一般に変性されるポリマー分子重量に対して約0.1〜10重量％程度に設定される。 The main chain consists of these diene rubber molecules, and is obtained by sequentially reacting the polymer main chain with a carbonyl group-containing unsaturated compound and a nitrogen-containing heterocyclic compound substituted with a functional group capable of reacting with the carbonyl group. In synthesizing a hydrogen-bonding thermoplastic elastomer, first, a diene rubber molecule is subjected to an addition reaction with a carbonyl group-containing unsaturated compound such as maleic anhydride or maleic anhydride, preferably maleic anhydride. The modification rate of maleic anhydride is generally set to about 0.1 to 10% by weight based on the weight of the polymer molecule to be modified.
このようにして付加された無水マレイン酸基には、含窒素複素環が5員環であり、マレイン酸等と反応し得る官能性基で置換された含窒素複素環化合物である4H-3-アミノ-1,2,4-トリアゾールを少過剰用い、約120〜200℃で加熱することにより、さらに付加反応が行われる。 This way the added maleic acid group, a nitrogen-containing heterocyclic ring is 5-membered ring, 4H-3- nitrogen-containing heterocyclic compounds substituted with a functional group capable of reacting with maleic acid or the like Further addition reaction is carried out by heating at about 120-200 ° C. with a small excess of amino-1,2,4-triazole.
このような一連の反応によって得られるポリマー主鎖にカルボニル基含有不飽和化合物およびこの基と反応し得る官能性基で置換された含窒素複素環化合物としての4H-3-アミノ-1,2,4-トリアゾールを順次反応させた水素結合性熱可塑性エラストマーは、ジエン系ゴム100重量部当り0.1〜25重量部、好ましくは0.2〜10重量部の割合で用いられる。これよりも少ない割合で用いられると、耐摩耗性およびtanδ(60℃)の値などの改善が達成されず、一方これよりも多い割合で用いられると、モジュラス、破断強度などが低下するようになる。 As a nitrogen-containing heterocyclic compound substituted with a carbonyl group-containing unsaturated compound and a functional group capable of reacting with this group in the polymer main chain obtained by such a series of reactions , 4H-3-amino-1,2, The hydrogen-bonding thermoplastic elastomer obtained by sequentially reacting 4-triazole is used in a ratio of 0.1 to 25 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the diene rubber. If it is used at a lower ratio, improvement in wear resistance and tan δ (60 ° C) value will not be achieved, while if it is used at a higher ratio, the modulus, breaking strength, etc. will decrease. Become.
ジエン系ゴム組成物中には、ジエン系ゴム100重量部当り30〜120重量部のシリカまたはシリカとカーボンブラックの両者が添加して用いられる。これら充填剤、特にシリカの添加は、転がり抵抗などを低減させるが、これ以上の割合で用いられると、逆に転がり抵抗などを悪化させる。 In the diene rubber composition, 30 to 120 parts by weight of silica or both silica and carbon black is added per 100 parts by weight of the diene rubber . Addition of these fillers, particularly silica, reduces rolling resistance and the like, but when used in a proportion higher than this, the rolling resistance and the like are worsened.
シリカとしては、BET比表面積(ASTM D1993-03準拠)が70〜200m2/g、好ましくは70〜190m2/gのものが用いられる。これらは、ハロゲン化けい素または有機けい素化合物の熱分解法などで製造される乾式法シリカやけい酸ナトリウムの酸による分解法などで製造される湿式法シリカなどであり、コストおよび性能の面から、湿式法シリカが好んで用いられる。実際には、ゴム工業用として上市されている市販品をそのまま用いることができる。 Silica having a BET specific surface area (according to ASTM D1993-03) of 70 to 200 m 2 / g, preferably 70 to 190 m 2 / g is used. These include dry process silica manufactured by pyrolysis of silicon halides or organosilicon compounds, and wet process silica manufactured by decomposition of sodium silicate with acid. Therefore, wet method silica is preferably used. Actually, a commercial product marketed for the rubber industry can be used as it is.
シリカに求められる特性およびジエン系ゴムとの分散性(シリカはゴムポリマーとの親和性に乏しく、またゴム中でシリカ同士がシラノール基を通して水素結合を生成し、シリカのゴム中への分散性を低下させる性質を有する)を高めるために、シランカップリング剤がシリカ100重量部当り0.5〜15重量部程度配合される。シランカップリング剤としては、シリカ表面のシラノール基と反応するアルコキシシリル基とポリマーと反応するイオウ連鎖を有するポリスルフィド系シランカップリング剤、例えばビス(3-トリエトキシシリルプロピル)テトラスルフィド、ビス(2-トリエトキシシリルエチル)テトラスルフィド、ビス(3-トリメトキシシリルプロピル)テトラスルフィド、ビス(3-トリエトキシシリルプロピル)ジスルフィド等が好んで用いられる。 Properties required for silica and dispersibility with diene rubbers (silica has poor affinity with rubber polymers, and silica in the rubber generates hydrogen bonds through silanol groups, thereby improving the dispersibility of silica in rubber. In order to improve (having a lowering property), about 0.5 to 15 parts by weight of a silane coupling agent is blended per 100 parts by weight of silica. Examples of the silane coupling agent include polysulfide silane coupling agents having an alkoxysilyl group that reacts with a silanol group on a silica surface and a sulfur chain that reacts with a polymer, such as bis (3-triethoxysilylpropyl) tetrasulfide, bis (2 -Triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide and the like are preferably used.
カーボンブラックとしては、一般にSAF、ISAF、HAF、FEF、GPF、SRF等のファーネスブラックが用いられる。空気入りタイヤのトレッド部、特にキャップトレッド部の形成の際の有効な成分であるこれらのカーボンブラックは、特にジエン系ゴムとしてSBRを90重量％以上含有するジエン系ゴムが用いられた場合には、シリカと共に、ジエン系ゴム100重量部当り30〜120重量部の割合で用いられる。 As the carbon black, furnace black such as SAF, ISAF, HAF, FEF, GPF, and SRF is generally used. These carbon blacks, which are effective components when forming the tread part of a pneumatic tire, particularly the cap tread part, are particularly used when a diene rubber containing 90% by weight or more of SBR is used as a diene rubber. The silica is used together with silica at a ratio of 30 to 120 parts by weight per 100 parts by weight of the diene rubber.
以上の各成分を必須成分とするゴム組成物中には、加硫剤としての硫黄およびチアゾール系(MBT、MBTS、ZnMBT等)、スルフェンアミド系(CBS、DCBS、BBS等)、グアニジン系(DPG、DOTG、OTBG等)、チウラム系(TMTD、TMTM、TBzTD、TETD、TBTD等)、ジチオカルバミン酸塩系(ZTC、NaBDC等)、キサントゲン酸塩系(ZnBX等)等の加硫促進剤のいずれか一種類以上が配合されて用いられる。さらに、ゴムの配合剤として一般的に用いられている他の配合剤、例えばタルク、クレー、グラファイト、珪酸カルシウム等の補強剤または充填剤、ステアリン酸等の加工助剤、酸化亜鉛、軟化剤、可塑剤、老化防止剤などが必要に応じて適宜配合されて用いられる。 In the rubber composition containing the above components as essential components, sulfur and thiazole (MBT, MBTS, ZnMBT, etc.), sulfenamide (CBS, DCBS, BBS, etc.), guanidine ( DPG, DOTG, OTBG, etc.), thiuram (TMTD, TMTM, TBzTD, TETD, TBTD, etc.), dithiocarbamate (ZTC, NaBDC, etc.), xanthate (ZnBX, etc.), etc. One or more types are blended and used. Furthermore, other compounding agents generally used as rubber compounding agents, such as reinforcing agents or fillers such as talc, clay, graphite, calcium silicate, processing aids such as stearic acid, zinc oxide, softeners, A plasticizer, an antiaging agent, and the like are appropriately blended and used as necessary.
組成物の調製は、ニーダ、バンバリーミキサ等の混練機または混合機およびオープンロール等を用いる一般的な方法で混練することによって行われ、得られた組成物は、所定形状に成形された後、用いられたジエン系ゴム、加硫剤、加硫促進剤の種類およびその配合割合に応じた加硫温度で加硫され、空気入りタイヤのトレッド部等を形成させる。 Preparation of the composition is carried out by kneading by a general method using a kneader such as a kneader, a Banbury mixer or a mixer and an open roll, and the obtained composition is molded into a predetermined shape, The rubber is vulcanized at a vulcanization temperature corresponding to the type of diene rubber, vulcanizing agent and vulcanization accelerator used and the blending ratio thereof to form a tread portion of a pneumatic tire.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
参考例
無水マレイン酸変性液状イソプレンゴム(クラレ製品LIR-410A；Mw 25,000、無水マレイン酸変性率3.9重量％)200.00g(無水マレイン酸骨格換算で79.6ミリモル)に、4H-3-アミノ-1,2,4-トリアゾール6.97g(82.9ミリモル)を加え、160℃で3時間攪拌した。均一溶液になったことを確認した後、一昼夜放置することにより、ゲル状の水素結合性熱可塑性エラストマー202.8g(収率98％)を得た。
Reference Example Maleic anhydride-modified liquid isoprene rubber (Kuraray product LIR-410A; Mw 25,000, maleic anhydride modification rate 3.9% by weight) 200.00 g (79.6 mmol in terms of maleic anhydride skeleton) was added 4H-3-amino-1, 6.97 g (82.9 mmol) of 2,4-triazole was added and stirred at 160 ° C. for 3 hours. After confirming that the solution was uniform, the solution was allowed to stand overnight to obtain 202.8 g of a gel-like hydrogen-bonding thermoplastic elastomer (yield 98%).
反応生成物であるゲル状水素結合性熱可塑性エラストマーは、アミック酸結合を有するもの〔I〕、イミド結合を有するもの〔II〕またはこれら両者を有するものと思われ、その主生成物は〔II〕と考えられる。
＜実施例１〜７、比較例１〜５＞
比較例１(標準例１)
SBR(日本ゼオン製品Nipol 1502) 100重量部
シリカ(ローディア社製品ZEOSIL 1165MP) 75 〃
亜鉛華(正同化学工業製品酸化亜鉛3種) 3 〃
ステアリン酸(日油製品ビーズステアリン酸) 2 〃
老化防止剤6C(フレキシス社製品サントフレックス6PPD) 3 〃
老化防止剤RD(大内新興化学工業製品ノクラック224) 2 〃
シランカップリング剤(エボニックデグッサジャパン製品Si69) 8 〃
アロマ系オイル(昭和シェル石油製品エキストラクト4号S) 30 〃
硫黄(細井化学工業製品油処理硫黄) 2.10 〃
加硫促進剤(大内新興化学工業製品ノクセラーNS) 2.30 〃
ジフェニルグアニジン(フレキシス社製品PERKACIT DPG GRS) 0.50 〃
以上の各成分の内、硫黄および加硫促進剤を除く各成分をバンバリーミキサで混練した後、硫黄および加硫促進剤を加えてオープンロールで混合し、得られたゴム組成物を160℃で20分間加硫した。
<Examples 1-7, Comparative Examples 1-5>
Comparative example 1 (standard example 1)
SBR (Nippon ZEON product Nipol 1502) 100 parts by weight Silica (Rhodia ZEOSIL 1165MP) 75 〃
Zinc Hana (Zinc Oxide Industrial Products, 3 types of zinc oxide) 3 〃
Stearic acid (NOF product beads stearic acid) 2 〃
Anti-aging agent 6C (Santoflex 6PPD manufactured by Flexis) 3 〃
Anti-aging agent RD (Ouchi Emerging Chemical Industry Product Nocrack 224) 2 〃
Silane coupling agent (Evonik Degussa Japan product Si69) 8 〃
Aroma oil (Showa Shell Petroleum Product Extract No. 4 S) 30 〃
Sulfur (sulfur treated with Hosoi Chemical Industry products) 2.10
Vulcanization accelerator (Ouchi Emerging Chemical Industry Noxeller NS) 2.30 〃
Diphenylguanidine (Flexis product PERKACIT DPG GRS) 0.50 〃
Among the above components, after kneading each component excluding sulfur and vulcanization accelerator with a Banbury mixer, adding sulfur and vulcanization accelerator and mixing with an open roll, the resulting rubber composition at 160 ° C Vulcanized for 20 minutes.
得られた加硫物について、次の各項目の測定を行った。
JIS A硬度：JIS K6253に準拠、0℃、20℃、60℃のデュロメータ硬度試験(タイプA)を
実施
引張試験：JIS K6251に準拠し、20℃の100％モジュラス、300％モジュラス、引張強
度、切断時伸びを測定
tanδ(60℃)：JIS K6394準拠、東洋精機製作所製粘弾性スペクトロメーターを用
い、初期歪10％、振幅±2％、周波数20Hzの条件で、60℃でのtanδを
測定
(この値が小さい程、発熱量が抑えられ、また転がり抵抗が良好である
ことを示している)
耐摩耗性：JIS K6264準拠、ランボーン摩耗試験機を用いて、荷重4.0kg(39N)、スリ
ップ率30％の条件下で摩耗量を測定してその逆数を求め、各標準例を100
とする指数で表示
(この値が大きい程、耐摩耗性が良好であることを示している)
The obtained vulcanizate was measured for the following items.
JIS A hardness: Compliant with JIS K6253, Durometer hardness test (Type A) at 0 ℃, 20 ℃, 60 ℃
Tensile test: 100% modulus at 300C, 300% modulus, tensile strength according to JIS K6251
Measures elongation at break
tanδ (60 ℃): JIS K6394 compliant, Toyo Seiki Seisakusho viscoelastic spectrometer is used
Tanδ at 60 ℃ under conditions of initial strain 10%, amplitude ± 2%, frequency 20Hz
Measurement
(The smaller this value, the lower the amount of heat generated and the better the rolling resistance.
It is shown that)
Abrasion resistance: JIS K6264 compliant, using a Lambourn abrasion tester, load 4.0 kg (39 N),
Measure the amount of wear under the condition of a 30% wear rate and determine its reciprocal.
Displayed as an index
(The higher this value, the better the wear resistance)
比較例２
比較例１において、アロマ系オイル量が33重量部に変更された。
Comparative Example 2
In Comparative Example 1, the amount of the aroma oil was changed to 33 parts by weight.
実施例１
比較例１において、参考例で得られたゲル状水素結合性熱可塑性エラストマー3重量部がさらに追加して用いられた。
Example 1
In Comparative Example 1, 3 parts by weight of the gel-like hydrogen-bonding thermoplastic elastomer obtained in Reference Example was additionally used.
実施例２
比較例１において、参考例で得られたゲル状水素結合性熱可塑性エラストマー10重量部がさらに追加して用いられた。
Example 2
In Comparative Example 1, 10 parts by weight of the gel-like hydrogen-bonding thermoplastic elastomer obtained in Reference Example was additionally used.
比較例３(標準例２)
比較例１において、下記各成分が用いられた。
天然ゴム(RSS#3) 20重量部
SBR(Nipol 1502) 70 〃
ブタジエンゴム(日本ゼオン製品NIPOL BR 1220) 10 〃
HAFカーボンブラック(キャボットジャパン製品ショウブラックN339) 8 〃
シリカ(ZEOSIL 1165MP) 70 〃
亜鉛華(酸化亜鉛3種) 3 〃
ステアリン酸(ビーズステアリン酸) 1 〃
老化防止剤6C(サントフレックス6PPD) 2 〃
老化防止剤RD(ノクラック224) 2 〃
シランカップリング剤(Si69) 7 〃
アロマ系オイル(エキストラクト4号S) 28 〃
硫黄(油処理硫黄) 1.85 〃
加硫促進剤(ノクセラーNS) 2.30 〃
ジフェニルグアニジン(PERKACIT DPG GRS) 0.50 〃
Comparative example 3 (standard example 2)
In Comparative Example 1, the following components were used.
Natural rubber (RSS # 3) 20 parts by weight
SBR (Nipol 1502) 70 〃
Butadiene rubber (Nippon Zeon product NIPOL BR 1220) 10 〃
HAF Carbon Black (Cabot Japan Product Show Black N339) 8 〃
Silica (ZEOSIL 1165MP) 70 〃
Zinc flower (3 types of zinc oxide) 3 〃
Stearic acid (bead stearic acid) 1 〃
Anti-aging agent 6C (Santoflex 6PPD) 2 〃
Anti-aging agent RD (NOCRACK 224) 2 〃
Silane coupling agent (Si69) 7 〃
Aromatic oil (Extract No. 4 S) 28 〃
Sulfur (oil-treated sulfur) 1.85〃
Vulcanization accelerator (Noxeller NS) 2.30 〃
Diphenylguanidine (PERKACIT DPG GRS) 0.50 〃
実施例３
比較例３において、参考例で得られたゲル状水素結合性熱可塑性エラストマー3重量部がさらに追加して用いられた。
Example 3
In Comparative Example 3, 3 parts by weight of the gel-like hydrogen-bonding thermoplastic elastomer obtained in Reference Example was additionally used.
比較例４(標準例３)
比較例１において、下記各成分が用いられた。
SBR(Nipol 1502) 100重量部
カーボンブラック(ショウブラックN339) 10 〃
シリカ(ZEOSIL 1165MP) 40 〃
亜鉛華(酸化亜鉛3種) 3 〃
ステアリン酸(ビーズステアリン酸) 2 〃
老化防止剤6C(サントフレックス6PPD) 3 〃
老化防止剤RD(ノクラック224) 2 〃
シランカップリング剤(Si69) 8 〃
アロマ系オイル(エキストラクト4号S) 20 〃
硫黄(油処理硫黄) 2.20 〃
加硫促進剤(ノクセラーNS) 2.30 〃
ジフェニルグアニジン(PERKACIT DPG GRS) 0.50 〃
Comparative example 4 (standard example 3)
In Comparative Example 1, the following components were used.
SBR (Nipol 1502) 100 parts by weight Carbon black (show black N339) 10 〃
Silica (ZEOSIL 1165MP) 40 〃
Zinc flower (3 types of zinc oxide) 3 〃
Stearic acid (bead stearic acid) 2 〃
Anti-aging agent 6C (Santoflex 6PPD) 3 〃
Anti-aging agent RD (NOCRACK 224) 2 〃
Silane coupling agent (Si69) 8 〃
Aromatic oil (Extract No. 4 S) 20 〃
Sulfur (oil-treated sulfur) 2.20〃
Vulcanization accelerator (Noxeller NS) 2.30 〃
Diphenylguanidine (PERKACIT DPG GRS) 0.50 〃
実施例４
比較例４において、参考例で得られたゲル状水素結合性熱可塑性エラストマー5重量部がさらに追加して用いられた。
Example 4
In Comparative Example 4, 5 parts by weight of the gel-like hydrogen-bonding thermoplastic elastomer obtained in Reference Example was additionally used.
実施例５
比較例４において、参考例で得られたゲル状水素結合性熱可塑性エラストマー10重量部がさらに追加して用いられた。
Example 5
In Comparative Example 4, 10 parts by weight of the gel-like hydrogen-bonding thermoplastic elastomer obtained in the reference example was further used.
実施例６
比較例４において、参考例で得られたゲル状水素結合性熱可塑性エラストマー25重量部がさらに追加して用いられた。
Example 6
In Comparative Example 4, 25 parts by weight of the gel-like hydrogen-bonding thermoplastic elastomer obtained in the reference example was additionally used.
比較例５(標準例４)
比較例１において、下記各成分が用いられた。
天然ゴム(RSS#3) 20重量部
SBR(Nipol 1502) 60 〃
ブタジエンゴム(NIPOL BR 1220) 20 〃
HAFカーボンブラック(ショウブラックN339) 3 〃
シリカ(ZEOSIL 1165MP) 90 〃
亜鉛華(酸化亜鉛3種) 3 〃
ステアリン酸(ビーズステアリン酸) 1 〃
老化防止剤6C(サントフレックス6PPD) 2 〃
老化防止剤RD(ノクラック224) 2 〃
シランカップリング剤(Si69) 9 〃
アロマ系オイル(エキストラクト4号S) 35 〃
硫黄(油処理硫黄) 1.70 〃
加硫促進剤(ノクセラーNS) 2.30 〃
ジフェニルグアニジン(PERKACIT DPG GRS) 0.50 〃
Comparative Example 5 (Standard Example 4)
In Comparative Example 1, the following components were used.
Natural rubber (RSS # 3) 20 parts by weight
SBR (Nipol 1502) 60 〃
Butadiene rubber (NIPOL BR 1220) 20 〃
HAF carbon black (show black N339) 3 〃
Silica (ZEOSIL 1165MP) 90 〃
Zinc flower (3 types of zinc oxide) 3 〃
Stearic acid (bead stearic acid) 1 〃
Anti-aging agent 6C (Santoflex 6PPD) 2 〃
Anti-aging agent RD (NOCRACK 224) 2 〃
Silane coupling agent (Si69) 9 〃
Aroma-based oil (Extract No. 4 S) 35 〃
Sulfur (oil treated sulfur) 1.70 〃
Vulcanization accelerator (Noxeller NS) 2.30 〃
Diphenylguanidine (PERKACIT DPG GRS) 0.50 〃
実施例７
比較例５において、参考例で得られたゲル状水素結合性熱可塑性エラストマー5重量部がさらに追加して用いられた。
Example 7
In Comparative Example 5, 5 parts by weight of the gel-like hydrogen-bonding thermoplastic elastomer obtained in the reference example was additionally used.
以上の各実施例および比較例における測定結果は、次の表に示される。
表
引張試験
切断時
JIS A硬度 100％モジュ 300％モジュ 引張強 伸び tanδ 耐摩
例 0℃ 20℃ 60℃ ラス(MPa) ラス(MPa) 度(MPa) (％) 60℃ 耗性
比較例１ 75 71 67 2.8 10.7 19.5 524 0.254 100
〃 ２ 75 72 67 2.6 9.9 19.3 544 0.264 93
実施例１ 77 72 68 3.3 12.1 19.3 505 0.238 107
〃 ２ 79 73 69 3.6 13.0 19.3 479 0.212 108
比較例３ 71 66 63 2.9 10.5 20.7 523 0.161 100
実施例３ 71 67 63 3.0 10.8 20.9 541 0.151 104
比較例４ 66 62 58 1.8 8.5 20.1 531 0.152 100
実施例４ 68 64 61 1.9 8.7 20.0 518 0.143 103
〃 ５ 71 67 63 2.1 9.3 20.4 497 0.135 111
〃 ６ 78 74 71 2.4 9.9 20.3 481 0.130 115
比較例５ 75 73 68 2.8 10.9 21.2 465 0.168 100
実施例７ 76 74 70 3.0 12.5 20.8 453 0.154 106
The measurement results in the above examples and comparative examples are shown in the following table.
table
Tensile test
When cutting
JIS A Hardness 100% Mod 300% Mod Tensile Strength Elongation tanδ Abrasion Resistance
Example 0 ℃ 20 ℃ 60 ℃ Las (MPa) Las (MPa) Degree (MPa) (%) 60 ℃ Abrasion
Comparative Example 1 75 71 67 2.8 10.7 19.5 524 0.254 100
〃 2 75 72 67 2.6 9.9 19.3 544 0.264 93
Example 1 77 72 68 3.3 12.1 19.3 505 0.238 107
〃 2 79 73 69 3.6 13.0 19.3 479 0.212 108
Comparative Example 3 71 66 63 2.9 10.5 20.7 523 0.161 100
Example 3 71 67 63 3.0 10.8 20.9 541 0.151 104
Comparative Example 4 66 62 58 1.8 8.5 20.1 531 0.152 100
Example 4 68 64 61 1.9 8.7 20.0 518 0.143 103
５ 5 71 67 63 2.1 9.3 20.4 497 0.135 111
６ 6 78 74 71 2.4 9.9 20.3 481 0.130 115
Comparative Example 5 75 73 68 2.8 10.9 21.2 465 0.168 100
Example 7 76 74 70 3.0 12.5 20.8 453 0.154 106
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| JP6780325B2 (en) * | 2016-06-30 | 2020-11-04 | 日本ゼオン株式会社 | Modified Hydrocarbon Resins and Elastomer Compositions for Tires |
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