JP4294070B2 - Rubber composition for tire - Google Patents
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- JP4294070B2 JP4294070B2 JP2007318718A JP2007318718A JP4294070B2 JP 4294070 B2 JP4294070 B2 JP 4294070B2 JP 2007318718 A JP2007318718 A JP 2007318718A JP 2007318718 A JP2007318718 A JP 2007318718A JP 4294070 B2 JP4294070 B2 JP 4294070B2
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- 229920001971 elastomer Polymers 0.000 title claims description 46
- 239000005060 rubber Substances 0.000 title claims description 46
- 239000000203 mixture Substances 0.000 title claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 150000003505 terpenes Chemical class 0.000 claims description 13
- 235000007586 terpenes Nutrition 0.000 claims description 13
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920003244 diene elastomer Polymers 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 3
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 3
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 3
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 3
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 3
- 229930006722 beta-pinene Natural products 0.000 claims description 3
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 3
- 235000001510 limonene Nutrition 0.000 claims description 3
- 229940087305 limonene Drugs 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical class NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 2
- 238000012986 modification Methods 0.000 claims 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 13
- 239000002174 Styrene-butadiene Substances 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 10
- 239000000446 fuel Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 241000985973 Castilla ulei Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 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
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
- 239000011787 zinc oxide 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、タイヤ用ゴム組成物に関し、更に詳細には、低燃費でかつグリップ性能を高めたタイヤ用ゴム組成物に関する。 The present invention relates to a tire rubber composition, and more particularly to a tire rubber composition having low fuel consumption and improved grip performance.
近年、地球環境の悪化を懸念する風潮から、環境に配慮したタイヤが求められている。環境に配慮したタイヤに必要な性能としては、低燃費であることが最も重要であるが、同時に加速性能やブレーキ性能に代表されるグリップ性能も従来品と同等以上にする必要がある。しかしながら、これら二つの性能は相反するものであるため、その両立は、一般的に難しいものとされている。 In recent years, environmentally friendly tires have been demanded due to the trend of concern about deterioration of the global environment. The most important performance required for environmentally friendly tires is low fuel consumption, but at the same time, the grip performance represented by acceleration performance and braking performance must be equal to or higher than that of conventional products. However, since these two performances are contradictory, it is generally considered difficult to achieve both.
従来、タイヤの低燃費性を向上させるために、末端変性ジエン系ゴムを用いることが以下の特許文献１に提案され、また、タイヤのグリップ性能を高めるために、末端変性ＳＢＲや芳香族変性テルペン樹脂などを配合することが以下の特許文献２及び３に提案されている。 Conventionally, use of a terminal-modified diene rubber has been proposed in the following Patent Document 1 in order to improve the fuel efficiency of the tire, and terminal-modified SBR and aromatic-modified terpenes have been proposed to improve the grip performance of the tire. The following patent documents 2 and 3 propose blending a resin or the like.
本発明では、燃費を可能な限り低く抑えながら、同時にウェットグリップ性能を向上させたタイヤ用ゴム組成物を提供することを目的とする。 An object of the present invention is to provide a rubber composition for tires that simultaneously improves wet grip performance while keeping fuel consumption as low as possible.
本発明によれば、末端変性ＳＢＲ２０〜５０重量部と、Ｔｇが−３５℃未満のジエン系ゴムとして選定されるＳＢＲ１０〜４０重量部及び天然ゴム１０〜５０重量部でこれらの合計量５０〜８０重量部とからなるジエン系ブレンドゴム１００重量部に対して、窒素吸着比表面積が７０〜９０ｍ2／ｇのカーボンブラック１０〜５０重量部、ＣＴＡＢ吸着比表面積が９５〜１７５ｍ2／ｇで、ＢＥＴ比表面積が１８０ｍ2／ｇ以下のシリカ１０〜６０重量部、及びα−ピネン、β−ピネン、ジペンテン及びリモネンから選ばれる少なくとも一種のテルペンと芳香族化合物を重合させて得られる芳香族変性テルペン樹脂１〜２５重量部を配合してなるタイヤ用ゴム組成物が提供される。 According to the present invention, 20 to 50 parts by weight of terminal-modified SBR, 10 to 40 parts by weight of SBR selected as a diene rubber having a Tg of less than -35 ° C, and 10 to 50 parts by weight of natural rubber, the total amount of these is 50 to 80. 10 parts by weight of carbon black having a nitrogen adsorption specific surface area of 70 to 90 m 2 / g, CTAB adsorption specific surface area of 95 to 175 m 2 / g, Aromatic modified terpene resin obtained by polymerizing 10 to 60 parts by weight of silica having a specific surface area of 180 m 2 / g or less, and at least one terpene selected from α-pinene, β-pinene, dipentene and limonene and an aromatic compound. There is provided a rubber composition for a tire comprising 1 to 25 parts by weight.
本発明では、低燃費性能と高グリップ性能を同時に満たすタイヤのゴム配合について鋭意探求していたところ、この度、前記配合のゴム組成物とすることにより、その実現が図られたものである。 In the present invention, the tire rubber compounding that simultaneously satisfies the low fuel consumption performance and the high grip performance has been eagerly sought, and this is achieved by making the rubber composition of the above compounding.
即ち、本発明によれば、所定の末端変性スチレン−ブタジエン共重合体ゴム（末端変性ＳＢＲ）と、Ｔｇが−３５℃未満のＳＢＲおよび天然ゴムとからなるジエン系ブレンドゴムに対して、所定の窒素吸着比表面積を有するカーボンブラック、所定のＣＴＡＢ吸着比表面積、ＢＥＴ比表面積を有するシリカ、及び所定の芳香族変性テルペン樹脂をそれぞれ所定量配合してなるタイヤ用ゴム組成物を得ることによって、上記低燃費性と高グリップ性能との両立が図られたタイヤ用ゴム組成物としたものである。 That is, according to the present invention, a predetermined end-modified styrene-butadiene copolymer rubber (terminal-modified SBR), a diene-based blend rubber composed of SBR having a Tg of less than -35 ° C. and natural rubber, By obtaining a rubber composition for a tire comprising carbon black having a nitrogen adsorption specific surface area, a predetermined CTAB adsorption specific surface area, silica having a BET specific surface area, and a predetermined aromatic modified terpene resin, respectively. A rubber composition for tires that achieves both low fuel consumption and high grip performance.
本発明のタイヤ用ゴム組成物のゴム成分に用いられるＴｇが−３５℃未満のＳＢＲ及び天然ゴムとしては、ＳＢＲ１０〜４０重量部と天然ゴム１０〜５０重量部の配合量でかつこれらのゴムが全ゴム成分中５０〜８０重量部、好ましくは５０〜７５重量部の配合量で使用される。天然ゴムは、これを前記所定量の範囲内で配合使用するとゴム組成物の耐摩耗性が向上し、また樹脂とポリマーの相溶性が向上することによりウェットグリップ性能の向上が図られる。 The SBR and natural rubber having a Tg of less than -35 ° C. used for the rubber component of the rubber composition for tires of the present invention includes 10 to 40 parts by weight of SBR and 10 to 50 parts by weight of natural rubber. The total rubber component is used in an amount of 50 to 80 parts by weight, preferably 50 to 75 parts by weight. When natural rubber is blended and used within the predetermined range, the abrasion resistance of the rubber composition is improved, and the compatibility between the resin and the polymer is improved, thereby improving the wet grip performance.
また、本発明のタイヤ用ゴム組成物の上記ゴム成分に用いられる末端変性ＳＢＲとしては、ＳＢＲの分子末端部分に水酸基、Ｎ−アルキル置換アミノケトン基、又はＮ−アルキル置換アミノチオケトン基を導入した末端変性ＳＢＲが有効に使用される。かかる末端変性ＳＢＲをジエン系ゴムに配合することによって、カーボンブラックやシリカの分散性が良好となり、ゴム組成物のウェットグリップ性能が向上する。当該末端変性ＳＢＲは、全ゴム成分中２０〜５０重量部、好ましくは２５〜５０重量部の配合量で使用される。これらの配合量が２０重量部未満では、所望のウェットグリップ性能が得られないので好ましくなく、逆に５０重量部を超えると、転がり抵抗を増大させることになるので好ましくない。 Further, as the terminal-modified SBR used for the rubber component of the tire rubber composition of the present invention, a hydroxyl group, an N-alkyl-substituted aminoketone group, or an N-alkyl-substituted aminothioketone group is introduced into the molecular terminal portion of the SBR. Terminally modified SBR is effectively used. By blending such a terminal-modified SBR with a diene rubber, the dispersibility of carbon black and silica is improved, and the wet grip performance of the rubber composition is improved. The terminal-modified SBR is used in an amount of 20 to 50 parts by weight, preferably 25 to 50 parts by weight, based on the total rubber component. If the blending amount is less than 20 parts by weight, the desired wet grip performance cannot be obtained. On the other hand, if it exceeds 50 parts by weight, the rolling resistance is increased, which is not preferable.
本発明のタイヤ用ゴム組成物に使用されるカーボンブラックとしては、ＪＩＳ Ｋ６２１７−２に準じて測定した窒素吸着比表面積（Ｎ2ＳＡ）が７０〜９０ｍ2／ｇであるカーボンブラックが、１０〜５０重量部、好ましくは２０〜４５重量部の配合量で用いられる。Ｎ2ＳＡがこの範囲にあるカーボンブラックを用いると、本発明のタイヤ用ゴム組成物における転がり抵抗の低減が可能となるので好ましい。これらの配合量が１０重量部未満であると、ゴムの補強性が不十分となり、逆に５０重量部を超えると、転がり抵抗の悪化を招くので好ましくない。 As carbon black used for the rubber composition for tires of the present invention, carbon black having a nitrogen adsorption specific surface area (N 2 SA) measured according to JIS K6217-2 of 70 to 90 m 2 / g is 10 to 10%. It is used in an amount of 50 parts by weight, preferably 20 to 45 parts by weight. It is preferable to use carbon black having N 2 SA in this range because the rolling resistance in the tire rubber composition of the present invention can be reduced. If the blending amount is less than 10 parts by weight, the reinforcing property of the rubber becomes insufficient. Conversely, if it exceeds 50 parts by weight, the rolling resistance is deteriorated, which is not preferable.
また、本発明のタイヤ用ゴム組成物に使用されるシリカとしては、ＪＩＳ Ｋ６２１７−３に準じて測定したＣＴＡＢ吸着比表面積が９５〜１７５ｍ2／ｇであり、ＡＳＴＭ Ｄ１９９３−０３に準じて測定したＢＥＴ比表面積が１８０ｍ2／ｇ以下、好ましくは２０〜１８０ｍ2／ｇであるシリカが、１０〜６０重量部、好ましくは１０〜４５重量部の配合量で用いられる。ＣＴＡＢ吸着比表面積及びＢＥＴ比表面積がこの範囲にあるシリカを用いると、本発明のタイヤ用ゴム組成物における転がり抵抗の低減が可能となるので好ましい。シリカの配合量が６０重量部を超えると、転がり抵抗が増大するため好ましくない。 Moreover, as a silica used for the rubber composition for tires of this invention, the CTAB adsorption specific surface area measured according to JIS K6217-3 is 95-175 m < 2 > / g, and measured according to ASTM D1993-03. BET specific surface area of 180 m 2 / g or less, preferably silica is 20~180m 2 / g is 10 to 60 parts by weight, preferably in an amount of 10 to 45 parts by weight. It is preferable to use silica having a CTAB adsorption specific surface area and a BET specific surface area in this range since rolling resistance in the tire rubber composition of the present invention can be reduced. If the amount of silica exceeds 60 parts by weight, rolling resistance increases, which is not preferable.
前記したシリカに求められる特性及びジエン系ブレンドゴムとの分散性（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、シリカ重量に対して２〜１５重量％、好ましくは５〜１０重量％の割合で用いるのがよい。かか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ゴムポリマーと反応する硫黄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。シランカップリング剤の使用割合が２重量％よりも少ないと、シリカに求められる特性やジエン系ブレンドゴムとの分散性が十分に発揮されず、逆に１５重量％よりも多いと、加工性が悪化するので好ましくない。 Characteristics required for silica and dispersibility with diene blend rubber (Silica has poor affinity with rubber polymer, and silica in the rubber forms hydrogen bonds through silanol groups and enters silica rubber. The silane coupling agent is preferably used in a proportion of 2 to 15% by weight, preferably 5 to 10% by weight, based on the silica weight. Examples of the silane coupling agent include polysulfide silane coupling agents having an alkoxysilyl group that reacts with a silanol group on the silica surface and a sulfur chain that reacts with a rubber 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. When the proportion of the silane coupling agent used is less than 2% by weight, the characteristics required of silica and dispersibility with the diene blend rubber are not sufficiently exhibited. Since it deteriorates, it is not preferable.
また、本発明のタイヤ用ゴム組成物に配合して用いられる芳香族変性テルペン樹脂としては、α−ピネン、β−ピネン、ジペンテン、リモネンなどのテルペンと、スチレン、α−メチルスチレン、ビニルトルエン、インデンなどの芳香族化合物とを重合させて得られる芳香族変性テルペン樹脂が有効に使用される。当該芳香族化合物の芳香族変性テルペン樹脂中での含有量は、１０〜５０重量％であることが好ましい。かかる芳香族変性テルペン樹脂を前記所定のジエン系ブレンドゴムに配合することによって、当該樹脂とジエン系ブレンドゴムとの相溶性が一層良好となるため、ゴム組成物のウェットグリップ性能が向上する。当該芳香族変性テルペン樹脂は、１〜２５重量部、好ましくは３〜２５重量部の配合量で使用される。この配合量が１重量部未満では、所望のウェットグリップ性能が得られないので好ましくなく、逆に２５重量部を超えると、転がり抵抗が増加するため好ましくない。 The aromatic modified terpene resin used by blending in the tire rubber composition of the present invention includes terpenes such as α-pinene, β-pinene, dipentene, limonene, styrene, α-methylstyrene, vinyltoluene, An aromatic modified terpene resin obtained by polymerizing an aromatic compound such as indene is effectively used. The content of the aromatic compound in the aromatic modified terpene resin is preferably 10 to 50% by weight. By blending such an aromatic modified terpene resin into the predetermined diene blend rubber, the compatibility between the resin and the diene blend rubber is further improved, so that the wet grip performance of the rubber composition is improved. The aromatic modified terpene resin is used in an amount of 1 to 25 parts by weight, preferably 3 to 25 parts by weight. If the blending amount is less than 1 part by weight, the desired wet grip performance cannot be obtained. On the contrary, if it exceeds 25 parts by weight, the rolling resistance increases, which is not preferable.
本発明のタイヤ用ゴム組成物には、更に、加硫又は架橋剤、加硫又は架橋促進剤、老化防止剤、プロセスオイルなどのタイヤ用ゴム組成物に配合されている各種配合剤を配合することができ、かかる配合剤は、一般的な方法で混練してゴム組成物とし、加硫または架橋することができる。これら配合剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 The tire rubber composition of the present invention is further blended with various compounding agents blended in the tire rubber composition such as a vulcanization or crosslinking agent, a vulcanization or crosslinking accelerator, an antioxidant, and a process oil. Such a compounding agent can be kneaded by a general method to obtain a rubber composition, which can be vulcanized or crosslinked. The compounding amounts of these compounding agents can be set to conventional general compounding amounts as long as the object of the present invention is not adversely affected.
以下、実施例及び比較例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことは言うまでもない。 Hereinafter, although an example and a comparative example explain the present invention further, it cannot be overemphasized that the scope of the present invention is not limited to these examples.
サンプルの調製
表１に示す配合（重量部）に従って、硫黄及び加硫促進剤を除くゴム、カーボンブラックなどの各配合成分を１.７ＬのＢ型バンバリーミキサーに装填して５分間混合し、得られたマスターバッチに対し、硫黄と加硫促進剤を配合してオープンロールにて混練することでゴム組成物を得た。次いで、このゴム組成物を所定の金型中で、１６０℃、２０分間プレス加硫して試験サンプル（ゴムシート）を作製し、以下の試験に供した。
Sample preparation According to the formulation (parts by weight) shown in Table 1, each component such as rubber and carbon black excluding sulfur and vulcanization accelerator was loaded into a 1.7 L B-type Banbury mixer and mixed for 5 minutes. The rubber composition was obtained by mix | blending sulfur and a vulcanization accelerator with respect to the obtained masterbatch, and knead | mixing with an open roll. Next, this rubber composition was press vulcanized at 160 ° C. for 20 minutes in a predetermined mold to prepare a test sample (rubber sheet), which was subjected to the following test.
試験方法
１）ウェットグリップ性能： ＪＩＳ Ｋ６３９４に準拠して、（株）東洋精機製作所製の粘弾性スペクトロメーターを用いて、初期歪＝１０％、振幅＝±２％、周波数＝２０Ｈｚの条件下でｔａｎδ（０℃）を測定し、この値をもってウェットグリップ性能を評価した。結果は、比較例１を１００として指数で示した。指数が大きい程、ウェットグリップ性能が良好であることを示す。
２）転がり抵抗性： ＪＩＳ Ｋ６３９４に準拠して、（株）東洋精機製作所製の粘弾性スペクトロメーターを用いて、初期歪＝１０％、振幅＝±２％、周波数＝２０Ｈｚの条件下でｔａｎδ（６０℃）を測定し、この値をもって転がり抵抗性を評価した。結果は、比較例１を１００として指数で示した。指数が小さい程、転がり抵抗性が良好、即ち低燃費性能が良好であることを示す。
Test Method 1) Wet Grip Performance: In accordance with JIS K6394, using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd. under the conditions of initial strain = 10%, amplitude = ± 2%, frequency = 20 Hz. Tan δ (0 ° C.) was measured, and wet grip performance was evaluated with this value. The results are shown as an index with Comparative Example 1 as 100. The larger the index, the better the wet grip performance.
2) Rolling resistance: In accordance with JIS K6394, using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd., under the conditions of initial strain = 10%, amplitude = ± 2%, frequency = 20 Hz, 60 ° C) was measured, and the rolling resistance was evaluated with this value. The results are shown as an index with Comparative Example 1 as 100. The smaller the index, the better the rolling resistance, that is, the better the fuel efficiency.
３）３００％モジュラス： ＪＩＳ Ｋ６２５１に準拠して、３号ダンベルにて２ｍｍのゴムシートを打ち抜き、５００ｍｍ／分の引張速度にて３００％モジュラスを測定した。結果は、比較例１を１００として指数で示した。指数が大きい程、補強性能に優れていることを示す。
４）カーボン分散： ＡＳＴＭ Ｄ２６６３に準拠して、ＯＰＴＩ ＧＲＡＤＥ社製ＤＩＳＰＥＲＧＲＡＤＥＲ １０００を用いて測定した。結果は、比較例１を１００として指数で示した。指数が大きい程、カーボンブラックの分散性に優れていることを示す。
3) 300% modulus: Based on JIS K6251, a 2 mm rubber sheet was punched out with a No. 3 dumbbell, and the 300% modulus was measured at a tensile speed of 500 mm / min. The results are shown as an index with Comparative Example 1 as 100. The larger the index, the better the reinforcing performance.
4) Carbon dispersion: Measured using DISPERGRADE 1000 manufactured by OPTI GRADE in accordance with ASTM D2663. The results are shown as an index with Comparative Example 1 as 100. It shows that it is excellent in the dispersibility of carbon black, so that an index | exponent is large.
実施例１〜４及び比較例１〜９
本発明の結果を、以下の表１に示す。
The results of the present invention are shown in Table 1 below.
１）：Nipol NS116 (日本ゼオン製）
２）：Nipol 1502（日本ゼオン製）
３）：ＴＳＲ ２０
４）：シ−スト N（東海カーボン製）
５）：シースト 7HM（東海カーボン製）
６）：Ultrasil VN3G(デグッサ製)
７）：Nipsil AQ（東ソー・シリカ製）
８）：YSレジン TO125 （ヤスハラケミカル製）
９）：YSレジン PX200（ヤスハラケミカル製）
１０）：酸化亜鉛３種（正同化学工業製）
１１）：ビーズステアリン酸（日本油脂製）
１２）：サントフレックス 6PPD（フレキシス製）
１３）：サンノック（大内新興化学工業製）
１４）：エキストラクト４号Ｓ（昭和シェル石油製）
１５）：Si69（デグッサ製）
１６）：金華印油入微粉硫黄（鶴見化学工業製）
１７）：ノクセラー CZ-G（大内新興化学工業製）
1): Nipol NS116 (Nippon Zeon)
2): Nipol 1502 (Nippon Zeon)
3): TSR 20
4): Crust N (Tokai Carbon)
5): Seast 7HM (Tokai Carbon)
6): Ultrasil VN3G (Degussa)
7): Nipsil AQ (Tosoh Silica)
8): YS Resin TO125 (Yasuhara Chemical)
9): YS resin PX200 (manufactured by Yasuhara Chemical)
10): 3 types of zinc oxide (manufactured by Shodo Chemical Industry)
11): Bead stearic acid (manufactured by NOF Corporation)
12): Santoflex 6PPD (made by Flexis)
13): Sunnock (Ouchi Shinsei Chemical Co., Ltd.)
14): Extract No. 4 S (made by Showa Shell Sekiyu)
15): Si69 (Degussa)
16): Fine powder sulfur with Jinhua seal oil (manufactured by Tsurumi Chemical Co., Ltd.)
17): Noxeller CZ-G (Ouchi Shinsei Chemical Co., Ltd.)
表１の結果によれば、本発明によるゴム組成物では、ウェットグリップ性能及び転がり抵抗（低燃費性能）が共に向上し、これらの両立が図られていることが判る。 According to the results in Table 1, it can be seen that the rubber composition according to the present invention improves both wet grip performance and rolling resistance (low fuel consumption performance), and achieves both of them.
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| JP4883172B2 (en) | 2009-12-10 | 2012-02-22 | 横浜ゴム株式会社 | Rubber composition for tire |
| JP4849176B2 (en) * | 2010-02-26 | 2012-01-11 | 横浜ゴム株式会社 | Rubber composition for tire tread and pneumatic tire using the same |
| JP4788843B1 (en) * | 2010-05-27 | 2011-10-05 | 横浜ゴム株式会社 | Rubber composition for tire |
| JP5633230B2 (en) * | 2010-08-04 | 2014-12-03 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire using the same |
| US10072138B2 (en) * | 2010-12-03 | 2018-09-11 | The Yokohama Rubber Co., Ltd | Rubber composition for use in tire treads |
| JP5234203B2 (en) * | 2011-07-14 | 2013-07-10 | 横浜ゴム株式会社 | Rubber composition for tire |
| CN106146690B (en) | 2012-02-10 | 2018-10-02 | 东洋橡胶工业株式会社 | Polymer-modified manufacturing method and diolefinic polymer, rubber composition and pneumatic tire |
| JP5316660B2 (en) * | 2012-02-15 | 2013-10-16 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP5644838B2 (en) * | 2012-03-08 | 2014-12-24 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP5569655B2 (en) * | 2012-04-16 | 2014-08-13 | 横浜ゴム株式会社 | Rubber composition for tire, pneumatic tire |
| JP5376008B2 (en) | 2012-04-24 | 2013-12-25 | 横浜ゴム株式会社 | Rubber composition for tire |
| JP6193577B2 (en) * | 2013-02-01 | 2017-09-06 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| DE102014003164B4 (en) | 2013-03-12 | 2023-12-14 | Sumitomo Chemical Company, Limited | Conjugated diene-based polymer and polymer composition containing the polymer |
| JP5999014B2 (en) * | 2013-04-15 | 2016-09-28 | 横浜ゴム株式会社 | Rubber composition for conveyor belt and conveyor belt |
| WO2015093316A1 (en) | 2013-12-18 | 2015-06-25 | 横浜ゴム株式会社 | Rubber composition for tires |
| JP7140179B2 (en) | 2020-12-14 | 2022-09-21 | 横浜ゴム株式会社 | rubber composition |
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| JPH05287126A (en) * | 1992-04-13 | 1993-11-02 | Bridgestone Corp | Tread rubber composition for high performance tire |
| JP2002097308A (en) * | 2000-09-22 | 2002-04-02 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2004002584A (en) * | 2002-06-03 | 2004-01-08 | Sumitomo Rubber Ind Ltd | Tire rubber composition |
| JP2005126604A (en) * | 2003-10-24 | 2005-05-19 | Sumitomo Rubber Ind Ltd | Rubber composition and tire obtained by using the same |
| JP2005336303A (en) * | 2004-05-26 | 2005-12-08 | Bridgestone Corp | Pneumatic tire |
| JP4372171B2 (en) * | 2007-02-28 | 2009-11-25 | 横浜ゴム株式会社 | Rubber composition for tire tread |
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