JP5860684B2 - Method for producing rubber composition for tire tread - Google Patents
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- JP5860684B2 JP5860684B2 JP2011259169A JP2011259169A JP5860684B2 JP 5860684 B2 JP5860684 B2 JP 5860684B2 JP 2011259169 A JP2011259169 A JP 2011259169A JP 2011259169 A JP2011259169 A JP 2011259169A JP 5860684 B2 JP5860684 B2 JP 5860684B2
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- 229920001971 elastomer Polymers 0.000 title claims description 71
- 239000005060 rubber Substances 0.000 title claims description 71
- 239000000203 mixture Substances 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 238000002156 mixing Methods 0.000 claims description 47
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 33
- 239000005062 Polybutadiene Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 16
- 229920002857 polybutadiene Polymers 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229910018540 Si C Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 23
- 238000005096 rolling process Methods 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004073 vulcanization Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000013329 compounding Methods 0.000 description 8
- 244000043261 Hevea brasiliensis Species 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000020169 heat generation Effects 0.000 description 7
- 229920003052 natural elastomer Polymers 0.000 description 7
- 229920001194 natural rubber Polymers 0.000 description 7
- 229910052779 Neodymium Inorganic materials 0.000 description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- AQSMLSJHYWHNRT-UHFFFAOYSA-N s-(3-trimethoxysilylpropyl) propanethioate Chemical compound CCC(=O)SCCC[Si](OC)(OC)OC AQSMLSJHYWHNRT-UHFFFAOYSA-N 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 235000014692 zinc oxide Nutrition 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、空気入りタイヤのトレッド部に用いられるタイヤトレッド用ゴム組成物、及びそれを用いた空気入りタイヤに関するものである。 The present invention relates to a rubber composition for a tire tread used for a tread portion of a pneumatic tire, and a pneumatic tire using the same.
自動車の低燃費化の要求は近年ますます高まり、タイヤについても低燃費化が求められている。タイヤの低燃費化を行う方法の一環として、低発熱性のゴム組成物を使用したり、タイヤを軽量化したりする方策がある。このうち、前者の低発熱性のゴム組成物を使用する方策は、低発熱化によりタイヤの転がり抵抗が低減するので、低燃費化に繋がるというものであり、種々の方策が提案されている。例えば、フィラーとしてシリカを用いるとともに、シリカの分散性を向上させるためにシランカップリング剤を併用することが知られている（例えば、下記特許文献１〜３参照）。 In recent years, the demand for lower fuel consumption of automobiles has been increasing and tires are also required to have lower fuel consumption. As a part of the method for reducing the fuel consumption of a tire, there are measures to use a rubber composition having low heat generation or to reduce the weight of the tire. Among these, the former method using the low heat-generating rubber composition is to reduce the rolling resistance of the tire by reducing the heat generation, which leads to a reduction in fuel consumption, and various measures have been proposed. For example, it is known that silica is used as a filler and a silane coupling agent is used in combination in order to improve the dispersibility of silica (for example, see Patent Documents 1 to 3 below).
また、更なる低発熱化のため、ポリマー末端をヒドロキシル基やアミノ基等の官能基で変性したスチレンブタジエンゴムを用いることにより、シリカの分散性を改良することも知られている（例えば、下記特許文献４〜６参照）。しかしながら、官能基を導入したスチレンブタジエンゴムを用いると、ゴム組成物のガラス転移温度（Ｔｇ）が高くなり、低温性能が悪化するという問題がある。 It is also known to improve the dispersibility of silica by using a styrene butadiene rubber having a polymer terminal modified with a functional group such as a hydroxyl group or an amino group in order to further reduce heat generation (for example, the following) (See Patent Documents 4 to 6). However, when a styrene butadiene rubber having a functional group introduced therein is used, there is a problem that the glass transition temperature (Tg) of the rubber composition increases and the low temperature performance deteriorates.
空気入りタイヤ、とりわけオールシーズンタイヤのトレッドに用いられるゴム組成物においては、冬場でも硬くなりにくくグリップ性能が悪化しないこと、即ち低温性能が求められるが、従来の低発熱性を改良したゴム組成物は低温性能に劣るという問題があり、サマータイヤ用としては好適であったものの、オールシーズンタイヤ用の要求特性を満足しないという問題があった。 In rubber compositions used for pneumatic tires, especially treads for all-season tires, it is difficult to be hard even in winter, and grip performance is not deteriorated, that is, low temperature performance is required. Has a problem that it is inferior in low-temperature performance, and although it is suitable for summer tires, it has a problem that it does not satisfy the required characteristics for all-season tires.
低温性能を改良するために、ガラス転移点の低いブタジエンゴムを配合することが考えられるが、コバルト触媒やニッケル触媒を用いて重合された汎用のブタジエンゴムでは、低温性能は改良するものの、低発熱性が損なわれるという問題がある。 In order to improve low temperature performance, it is conceivable to add butadiene rubber with a low glass transition point. However, general-purpose butadiene rubber polymerized using a cobalt catalyst or nickel catalyst improves low temperature performance but has low heat generation. There is a problem that the sex is impaired.
一方、タイヤトレッド用ゴム組成物において、天然ゴムを主体としたゴム成分に、ネオジウム系触媒を用いて重合されたブタジエンゴムを配合することにより、低発熱性を改善できることが知られている（下記特許文献７参照）。しかしながら、ネオジウム系触媒で重合したブタジエンゴムを用いることにより、低温性能と低発熱性を改良することはできるものの、加工性が悪化するという問題がある。 On the other hand, in rubber compositions for tire treads, it is known that low heat build-up can be improved by blending a rubber component mainly composed of natural rubber with a butadiene rubber polymerized using a neodymium catalyst (described below). (See Patent Document 7). However, the use of butadiene rubber polymerized with a neodymium-based catalyst can improve low temperature performance and low heat build-up, but has a problem that workability deteriorates.
上記のように従来、オールシーズンタイヤ等に要求される低温性能を満足しつつ、また加工性を維持しながら、低発熱性を改良することは困難であり、これらを全て満足したものは得られていなかったのが実情である。 As described above, it is difficult to improve the low heat buildup while satisfying the low temperature performance required for all-season tires and the like, and maintaining the workability, and those satisfying all of these can be obtained. The fact was not.
本発明は、以上の点に鑑みてなされたものであり、低温性能を満足しつつ、また加工性を維持しながら、低発熱性を改良することができるタイヤトレッド用ゴム組成物、及びそれを用いた空気入りタイヤを提供することを目的とする。 The present invention has been made in view of the above points, and a rubber composition for a tire tread capable of improving low heat buildup while satisfying low temperature performance and maintaining workability, and An object is to provide a used pneumatic tire.
本発明に係るタイヤトレッド用ゴム組成物の製造方法は、ヘテロ原子を含む官能基が導入された変性溶液重合スチレンブタジエンゴム６０〜９０質量部と、希土類元素系触媒を用いて合成されたブタジエンゴム１０〜４０質量部と、を含有するゴム成分１００質量部のうち、４０質量部以上の前記変性溶液重合スチレンブタジエンゴムを含む６０〜９０質量部のゴム成分に、シリカ３０〜１１０質量部を含む全フィラー４０〜１１０質量部と、該シリカ配合量の５〜３０質量％の下記一般式（１）で表されるシランカップリング剤とを混練してマスターバッチを作製する第一混合段階と、前記マスターバッチに残部のゴム成分１０〜４０質量部を混合する第二混合段階と、を含むものである。
（ＣnＨ2n+1Ｏ）3Ｓｉ−ＣmＨ2m−Ｓ−ＣＯ−ＣkＨ2k+1 …（１）
式中、ｎは１〜３の整数、ｍは１〜５の整数、ｋは２〜９の整数である。
A method for producing a rubber composition for a tire tread according to the present invention includes a butadiene rubber synthesized using 60 to 90 parts by mass of a modified solution-polymerized styrene butadiene rubber having a heteroatom-containing functional group and a rare earth element-based catalyst. 10 to 40 parts by mass, and 100 to 100 parts by mass of the rubber component containing 60 to 90 parts by mass of the rubber component containing 40 parts by mass or more of the modified solution-polymerized styrene butadiene rubber includes 30 to 110 parts by mass of silica. A first mixing stage in which a master batch is prepared by kneading 40 to 110 parts by mass of all fillers and a silane coupling agent represented by the following general formula (1) of 5 to 30% by mass of the silica content ; A second mixing stage in which 10 to 40 parts by mass of the remaining rubber component is mixed with the master batch .
(C n H 2n + 1 O ) 3 Si-C m H 2m -S-CO-C k H 2k + 1 ... (1)
In the formula, n is an integer of 1 to 3, m is an integer of 1 to 5, and k is an integer of 2 to 9.
また、本発明の好ましい態様に係る空気入りタイヤの製造方法は、該タイヤトレッド用ゴム組成物でトレッド部を作製するものである。 A method of manufacturing a pneumatic tire according to a preferred embodiment of the present invention is to prepare a tread portion with a rubber composition for the tire tread.
本発明によれば、上記のように、変性溶液重合スチレンブタジエンゴムと、希土類元素系触媒で重合されたブタジエンゴムと、シリカと、特定のシランカップリング剤を併用することにより、低温性能を確保しつつ、また加工性を維持しつつ、低発熱性を改良してタイヤの転がり抵抗を低減することができる。 According to the present invention, as described above, low-temperature performance is ensured by using a modified solution-polymerized styrene butadiene rubber, a butadiene rubber polymerized with a rare earth element-based catalyst, silica, and a specific silane coupling agent. In addition, while maintaining the workability, the low heat build-up can be improved and the rolling resistance of the tire can be reduced.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本実施形態に係るゴム組成物において、ゴム成分１００質量部は、（Ａ）ヘテロ原子を含む官能基が導入された変性溶液重合スチレンブタジエンゴム６０〜９０質量部と、（Ｂ）希土類元素系触媒を用いて合成されたブタジエンゴム１０〜４０質量部と、任意成分としての（Ｃ）他のジエン系ゴム０〜３０質量部とからなる。このように、変性溶液重合スチレンブタジエンゴムと希土類元素系触媒のブタジエンゴムを組み合わせることにより、低発熱性と低温性能を改善することができる。 In the rubber composition according to this embodiment, 100 parts by mass of the rubber component includes (A) 60 to 90 parts by mass of a modified solution-polymerized styrene butadiene rubber introduced with a functional group containing a hetero atom, and (B) a rare earth element-based catalyst. 10 to 40 parts by mass of a butadiene rubber synthesized using, and (C) 0 to 30 parts by mass of another diene rubber as an optional component. Thus, by combining the modified solution-polymerized styrene butadiene rubber and the butadiene rubber of the rare earth element-based catalyst, low heat buildup and low temperature performance can be improved.
上記（Ａ）成分は、ヘテロ原子を含む官能基が導入された溶液重合スチレンブタジエンゴム（以下、変性Ｓ−ＳＢＲということがある）である。該官能基は、ポリマー鎖の末端に導入されてもよく、あるいはまたポリマー鎖中に導入されてもよいが、好ましくは末端に導入されることである。該官能基としては、アミノ基、アルコキシル基、ヒドロキシル基、エポキシ基、カルボキシル基、シアノ基、及びハロゲン基等が挙げられ、これらはそれぞれ１種のみ導入されてもよく、あるいはまた２種以上組み合わせて導入されてもよい。上記アミノ基としては、１級アミノ基だけでなく、２級もしくは３級アミノ基でもよい。アルコキシル基（−ＯＲ、但しＲはアルキル基）としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などが挙げられる。ハロゲン基としては、塩素、臭素などが挙げられる。これらの官能基は、シリカのシラノール基（Ｓｉ−ＯＨ）と相互作用があるものとして知られているものである。ここで、相互作用とは、シリカのシラノール基との間で化学反応による化学結合又は水素結合することを意味する。 The component (A) is a solution-polymerized styrene butadiene rubber (hereinafter sometimes referred to as modified S-SBR) into which a functional group containing a hetero atom is introduced. The functional group may be introduced at the end of the polymer chain, or may be introduced into the polymer chain, but is preferably introduced at the end. Examples of the functional group include an amino group, an alkoxyl group, a hydroxyl group, an epoxy group, a carboxyl group, a cyano group, and a halogen group. These may be introduced alone or in combination of two or more. May be introduced. The amino group may be not only a primary amino group but also a secondary or tertiary amino group. Examples of the alkoxyl group (—OR, where R is an alkyl group) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen group include chlorine and bromine. These functional groups are known to interact with silanol groups (Si—OH) of silica. Here, the interaction means a chemical bond or a hydrogen bond with a silanol group of silica by a chemical reaction.
このような官能基を導入した変性Ｓ−ＳＢＲを配合することにより、シリカとの親和性を高くして分散性を改善することができる。なお、かかる官能基を有する変性Ｓ−ＳＢＲ自体は公知であり、その製造方法等は限定されるものではない。例えば、アニオン重合で合成されたＳ−ＳＢＲを変性剤で変性することで、上記官能基を導入することができる。 By blending such modified S-SBR into which a functional group is introduced, the affinity with silica can be increased and the dispersibility can be improved. In addition, modified S-SBR itself having such a functional group is known, and its production method and the like are not limited. For example, the functional group can be introduced by modifying S-SBR synthesized by anionic polymerization with a modifier.
該変性Ｓ−ＳＢＲとしては、特に限定するものではないが、そのガラス転移温度（Ｔｇ）が−７０〜−１０℃であるものが好ましく、より好ましくは−６０〜−２０℃である。また、スチレン含量（Ｓｔ）が５〜５０質量％であることが好ましく、より好ましくは１０〜４０質量％である。なお、ガラス転移温度は、ＪＩＳ Ｋ７１２１に準拠して示差走査熱量測定（ＤＳＣ）法により、昇温速度：２０℃／分にて（測定温度範囲：−１５０℃〜５０℃）測定される値である。スチレン含量は、１ＨＮＭＲスペクトルの積分比により算出される値である。 The modified S-SBR is not particularly limited, but preferably has a glass transition temperature (Tg) of −70 to −10 ° C., more preferably −60 to −20 ° C. Moreover, it is preferable that a styrene content (St) is 5-50 mass%, More preferably, it is 10-40 mass%. The glass transition temperature is a value measured by a differential scanning calorimetry (DSC) method in accordance with JIS K7121 at a rate of temperature increase of 20 ° C./minute (measurement temperature range: −150 ° C. to 50 ° C.). is there. The styrene content is a value calculated by an integration ratio of 1 HNMR spectrum.
上記（Ｂ）成分のブタジエンゴムは、希土類元素系触媒を用いて重合されたブタジエンゴム（以下、希土類元素系触媒ＢＲということがある）である。希土類元素系触媒としては、ネオジウム系触媒が好ましく、例えば、ネオジウム単体、ネオジウムと他の金属類との化合物、及び有機化合物が挙げられ、より詳細には、ＮｄＣｌ３、Ｅｔ−ＮｄＣｌ２等が具体例として挙げられる。 The butadiene rubber as the component (B) is a butadiene rubber polymerized using a rare earth element-based catalyst (hereinafter sometimes referred to as a rare earth element-based catalyst BR). As the rare earth element-based catalyst, a neodymium-based catalyst is preferable, and examples thereof include neodymium alone, a compound of neodymium and other metals, and an organic compound, and more specifically, NdCl 3 , Et-NdCl 2 and the like Take as an example.
希土類元素系触媒で合成したブタジエンゴムは、一般に、高シス含量で、かつ低ビニル含量のミクロ構造を有する。本実施形態において、希土類元素系触媒ＢＲのミクロ構造は特に限定されないが、好ましくは、シス−１，４結合含有量が９５％以上であり、かつビニル基（１，２−ビニル結合）含有量が１．８％以下のものを用いることである。シス−１，４結合含有量は９６％以上であることがより好ましく、ビニル基含有量は１．０％以下であることがより好ましい。ここで、シス−１，４結合含有量及びビニル基含有量は、１ＨＮＭＲスペクトルの積分比により算出される値である。 A butadiene rubber synthesized with a rare earth element-based catalyst generally has a microstructure with a high cis content and a low vinyl content. In the present embodiment, the microstructure of the rare earth element-based catalyst BR is not particularly limited, but preferably the cis-1,4 bond content is 95% or more and the vinyl group (1,2-vinyl bond) content. Is 1.8% or less. The cis-1,4 bond content is more preferably 96% or more, and the vinyl group content is more preferably 1.0% or less. Here, the cis-1,4 bond content and the vinyl group content are values calculated by the integration ratio of the 1 HNMR spectrum.
上記（Ｃ）成分は、上述した変性Ｓ−ＳＢＲ及び希土類元素系触媒ＢＲ以外のジエン系ゴムであるが、これは任意成分であり、従ってゴム成分中に含まれても、含まれなくてもよい。他のジエン系ゴムとしては、例えば、未変性のスチレンブタジエンゴム（ＳＢＲ）、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、スチレン−イソプレン共重合体ゴム、ブタジエン−イソプレン共重合体、またはこれらの２種以上の組み合わせ等が挙げられ、特に限定されない。好ましくは、天然ゴムを用いることである。 The component (C) is a diene rubber other than the modified S-SBR and the rare earth element-based catalyst BR described above, but this is an optional component, and therefore it may or may not be included in the rubber component. Good. Other diene rubbers include, for example, unmodified styrene butadiene rubber (SBR), natural rubber (NR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), and styrene-isoprene. A polymer rubber, a butadiene-isoprene copolymer, or a combination of two or more thereof may be used, and the invention is not particularly limited. Preferably, natural rubber is used.
上記のようにゴム成分は、（Ａ）変性Ｓ−ＳＢＲ：６０〜９０質量％、（Ｂ）希土類元素系触媒ＢＲ：１０〜４０質量％、及び（Ｃ）その他のジエン系ゴム：０〜３０質量％からなる。（Ａ）変性Ｓ−ＳＢＲが６０質量％未満では、低発熱性の改良効果が不十分となる。また、（Ｂ）希土類元素系触媒ＢＲが１０質量％未満では、低温性能が悪化してしまう。（Ａ）変性Ｓ−ＳＢＲのゴム成分中に占める比率は、６５〜８５質量％であることが好ましく、より好ましくは６５〜８０質量％である。（Ｂ）希土類元素系触媒ＢＲのゴム成分中に占める比率は、１５〜３５質量％であることが好ましく、より好ましくは１５〜３０質量％である。（Ｃ）他のジエン系ゴムのゴム成分中に占める比率は、０〜２０質量％であることが好ましく、より好ましくは５〜１５質量％である。 As described above, the rubber component comprises (A) modified S-SBR: 60 to 90% by mass, (B) rare earth element-based catalyst BR: 10 to 40% by mass, and (C) other diene rubbers: 0 to 30. It consists of mass%. (A) If modified S-SBR is less than 60 mass%, the improvement effect of low exothermic property will become inadequate. Further, when the (B) rare earth element-based catalyst BR is less than 10% by mass, the low temperature performance is deteriorated. (A) The ratio of the modified S-SBR in the rubber component is preferably 65 to 85 mass%, more preferably 65 to 80 mass%. (B) The ratio of the rare earth element-based catalyst BR in the rubber component is preferably 15 to 35% by mass, more preferably 15 to 30% by mass. (C) The ratio of the other diene rubber in the rubber component is preferably 0 to 20% by mass, more preferably 5 to 15% by mass.
本実施形態に係るゴム組成物には、上記ゴム成分１００質量部に対して、シリカ３０〜１１０質量部を含むフィラー４０〜１１０質量部が配合される。フィラーとしては、シリカ単独でもよく、シリカとともにカーボンブラック等の他の充填剤を含んでもよい。フィラーの配合量が４０質量部未満では、補強性を確保することが困難となり、逆に１１０質量部を超えると、低発熱性を改善することが困難となる。フィラーの配合量は、より好ましくは５０〜８０質量部である。また、シリカの配合量が３０質量部未満では、低発熱性の改善効果が不十分となる。シリカの配合量は、より好ましくは４０〜８０質量部である。また、フィラー全体のうち、シリカを７０質量％以上含むことが、低発熱性の点から好ましく、より好ましくは８０質量％以上である。なお、フィラーは、基本的には、シリカ単独、又はシリカとカーボンブラックとのブレンドからなるが、本発明の効果を損なわない限り、クレー、タルク、マイカなどの他の充填剤を含んでもよい。カーボンブラックの配合量は、特に限定されないが、２０質量部以下であることが好ましく、より好ましくはタイヤへの色付けのために２〜１０質量部とすることである。 In the rubber composition according to this embodiment, 40 to 110 parts by mass of filler containing 30 to 110 parts by mass of silica is blended with 100 parts by mass of the rubber component. The filler may be silica alone or may contain other fillers such as carbon black together with silica. When the blending amount of the filler is less than 40 parts by mass, it is difficult to ensure the reinforcing property, and when it exceeds 110 parts by mass, it is difficult to improve the low heat build-up. The blending amount of the filler is more preferably 50 to 80 parts by mass. Moreover, if the compounding quantity of a silica is less than 30 mass parts, the improvement effect of low exothermic property will become inadequate. The amount of silica is more preferably 40 to 80 parts by mass. Moreover, it is preferable from the point of low heat build-up to contain 70 mass% or more of silica among the whole filler, More preferably, it is 80 mass% or more. The filler is basically composed of silica alone or a blend of silica and carbon black, but may contain other fillers such as clay, talc and mica as long as the effects of the present invention are not impaired. Although the compounding quantity of carbon black is not specifically limited, It is preferable that it is 20 mass parts or less, More preferably, it is 2-10 mass parts for coloring to a tire.
シリカとしては、特に限定されず、例えば、湿式シリカ（含水ケイ酸），乾式シリカ（無水ケイ酸），ケイ酸カルシウム，ケイ酸アルミニウム等が挙げられるが、中でも湿式シリカが好ましい。シリカのコロイダル特性は特に限定しないが、ＢＥＴ法による窒素吸着比表面積（ＢＥＴ）１５０〜２５０ｍ２／ｇであるものが好ましく用いられ、より好ましくは１８０〜２３０ｍ２／ｇである。なお、シリカのＢＥＴはＩＳＯ ５７９４に記載のＢＥＴ法に準拠し測定される。 The silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. Among them, wet silica is preferable. Colloidal properties of the silica are not particularly limited, those which are nitrogen adsorption specific surface area (BET) 150~250m 2 / g by BET method is preferably used, more preferably 180~230m 2 / g. The BET of silica is measured according to the BET method described in ISO 5794.
本実施形態に係るゴム組成物には、上記一般式（１）で表される保護化メルカプト基を有するシランカップリング剤（保護化メルカプトシランカップリング剤）が配合される。かかる保護化メルカプトシランカップリング剤を配合することにより、未加硫ゴム組成物の粘度上昇を抑えて、加工性を維持することができる。保護化メルカプトシランカップリング剤としては、例えば、３−オクタノイルチオプロピルトリエトキシシラン、３−プロピオニルチオプロピルトリメトキシシランなどが好ましいものとして挙げられる。保護化メルカプトシランカップリング剤の配合量は、シリカ配合量の５〜３０質量％（すなわち、シリカ１００質量部に対して５〜３０質量部）であることが好ましく、より好ましくは５〜２０質量％である。 In the rubber composition according to the present embodiment, a silane coupling agent having a protected mercapto group represented by the general formula (1) (protected mercaptosilane coupling agent) is blended. By blending such a protected mercaptosilane coupling agent, an increase in the viscosity of the unvulcanized rubber composition can be suppressed and processability can be maintained. Preferred examples of the protected mercaptosilane coupling agent include 3-octanoylthiopropyltriethoxysilane, 3-propionylthiopropyltrimethoxysilane, and the like. The compounding amount of the protected mercaptosilane coupling agent is preferably 5 to 30% by mass of the silica compounding amount (that is, 5 to 30 parts by mass with respect to 100 parts by mass of silica), more preferably 5 to 20 masses. %.
本実施形態に係るゴム組成物には、上記の各成分の他に、亜鉛華、ステアリン酸、老化防止剤、軟化剤、加硫剤、加硫促進剤など、タイヤのトレッド用ゴム組成物において一般に使用される各種添加剤を配合することができる。上記加硫剤としては、硫黄、硫黄含有化合物等が挙げられ、特に限定するものではないが、その配合量は上記ゴム成分１００質量部に対して０．１〜１０質量部であることが好ましく、より好ましくは０．５〜５質量部である。また、加硫促進剤の配合量としては、上記ゴム成分１００質量部に対して０．１〜７質量部であることが好ましく、より好ましくは０．５〜５質量部である。 In the rubber composition according to the present embodiment, in addition to the above-described components, in the rubber composition for tire treads such as zinc white, stearic acid, anti-aging agent, softener, vulcanizing agent, vulcanization accelerator, etc. Various commonly used additives can be blended. Examples of the vulcanizing agent include sulfur and sulfur-containing compounds, and are not particularly limited. However, the blending amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, it is 0.5-5 mass parts. Moreover, as a compounding quantity of a vulcanization accelerator, it is preferable that it is 0.1-7 mass parts with respect to 100 mass parts of said rubber components, More preferably, it is 0.5-5 mass parts.
該ゴム組成物は、通常に用いられるバンバリーミキサーやニーダー、ロール等の混合機を用いて、常法に従い混練し作製することができる。すなわち、第一混合段階で、ゴム成分に対し、上記フィラー及びシランカップリング剤とともに、加硫剤及び加硫促進剤を除く他の添加剤を添加混合し、次いで、得られた混合物に、最終混合段階で加硫剤及び加硫促進剤を添加混合してゴム組成物を調製することである。 The rubber composition can be prepared by kneading according to a conventional method using a commonly used Banbury mixer, kneader, roll, or other mixer. That is, in the first mixing stage, the rubber component is added and mixed with the filler and the silane coupling agent, and other additives excluding the vulcanizing agent and the vulcanization accelerator. A rubber composition is prepared by adding and mixing a vulcanizing agent and a vulcanization accelerator in the mixing stage.
本実施形態に係るゴム組成物は、より好ましくは、上記ゴム成分１００質量部のうち、４０質量部以上の変性Ｓ−ＳＢＲを含む６０〜９０質量部のゴム成分に、上記フィラー及びシランカップリング剤を、予め密閉式混合機等で混合してマスターバッチを作製した後（第一混合段階）、該マスターバッチに残部のゴム成分１０〜４０質量部を混合する（第二混合段階）により調製されることである。このように、まず変性Ｓ−ＳＢＲを含むゴム成分にシリカを含むフィラーを混合し、一部のゴム成分を後入れすることにより、シリカを変性Ｓ−ＳＢＲに偏在させることができ、これにより低発熱性と耐摩耗性を改良することができる。変性Ｓ−ＳＢＲへのシリカの偏在化を期待するため、第二混合段階において後入れする残部のゴム成分としては、変性Ｓ−ＳＢＲ以外のジエン系ゴムであることが好ましく、すなわち、上記希土類元素系触媒ＢＲや、天然ゴム等の他のジエン系ゴムであることが好ましい。このように第一混合段階及び第二混合段階を経て得られた混合物は、最終混合段階において加硫剤及び加硫促進剤が添加混合されることで、本実施形態に係るゴム組成物が得られる。 More preferably, in the rubber composition according to the present embodiment, 60 to 90 parts by mass of the rubber component including 40 parts by mass or more of the modified S-SBR in 100 parts by mass of the rubber component is added to the filler and the silane coupling. After the agent is mixed in advance with a closed mixer or the like to prepare a master batch (first mixing stage), the remaining 10 to 40 parts by mass of the remaining rubber component is mixed with the master batch (second mixing stage). It is to be done. Thus, by first mixing a filler containing silica with a rubber component containing modified S-SBR, and adding a part of the rubber component later, silica can be unevenly distributed in the modified S-SBR. The heat generation and wear resistance can be improved. In order to expect the uneven distribution of silica in the modified S-SBR, the remaining rubber component to be added later in the second mixing stage is preferably a diene rubber other than the modified S-SBR. Other diene rubbers such as a system catalyst BR and natural rubber are preferable. As described above, the mixture obtained through the first mixing stage and the second mixing stage is obtained by adding and mixing the vulcanizing agent and the vulcanization accelerator in the final mixing stage, thereby obtaining the rubber composition according to the present embodiment. It is done.
なお、上記第一混合段階で混合するゴム成分の量は６０〜８０質量部であることがより好ましい。また、この第一混合段階で混合するゴム成分中に含まれる上記変性Ｓ−ＳＢＲの量は４０〜９０質量部であることが好ましく、より好ましくは６０〜８０質量部である。上記フィラー及びシランカップリング剤以外の添加剤についての添加時期としては、加硫系配合剤（即ち、加硫剤及び加硫促進剤）を最後に添加することを除けば特に限定されないが、第一混合段階において混合することが好ましい。すなわち、第一混合段階では、フィラー及びシランカップリング剤とともに、加硫系配合剤を除くその他の添加剤が配合されることが好ましい。従って、第二混合段階では、上記残部のゴム成分のみがマスターバッチに添加し混合されることが好ましい。 In addition, it is more preferable that the amount of the rubber component mixed in the first mixing stage is 60 to 80 parts by mass. The amount of the modified S-SBR contained in the rubber component to be mixed in the first mixing stage is preferably 40 to 90 parts by mass, more preferably 60 to 80 parts by mass. The addition timing of additives other than the filler and silane coupling agent is not particularly limited except that the vulcanizing compounding agent (that is, vulcanizing agent and vulcanization accelerator) is added last, It is preferable to mix in one mixing stage. That is, in the first mixing stage, it is preferable that other additives except the vulcanizing compounding agent are blended together with the filler and the silane coupling agent. Therefore, in the second mixing stage, it is preferable that only the remaining rubber component is added to the master batch and mixed.
本実施形態に係るタイヤトレッド用ゴム組成物は、ＪＩＳ Ｋ６２５５のリュプケ式反発弾性試験に準拠して温度６０℃で測定した加硫物の反発弾性率が６０〜８０％であることが好ましい。６０℃での反発弾性率は低発熱性の指標として一般に用いられており、これが６０％未満では、低発熱性に劣り、空気入りタイヤの転がり抵抗性能の改善効果が不十分となる。逆に、８０％を超えると、湿潤路面での制動性能（ウェット制動性）が悪化するおそれがある。６０℃での反発弾性率は、６５〜７５％であることがより好ましい。 The rubber composition for a tire tread according to the present embodiment preferably has a rebound resilience of 60 to 80% of a vulcanizate measured at a temperature of 60 ° C. in accordance with a Lücke rebound resilience test of JIS K6255. The rebound resilience at 60 ° C. is generally used as an index of low heat build-up, and if it is less than 60%, it is inferior in low heat build-up and the effect of improving the rolling resistance performance of a pneumatic tire is insufficient. Conversely, if it exceeds 80%, the braking performance (wet braking performance) on wet road surfaces may be deteriorated. The rebound resilience at 60 ° C. is more preferably 65 to 75%.
本実施形態に係るタイヤトレッド用ゴム組成物は、また、ＪＩＳ Ｋ６２５３に準拠してタイプＡデュロメータにより温度−１０℃で測定した加硫物の硬さが８０以下であることが好ましい。−１０℃での硬さは低温性能の指標として一般に用いられており、これが８０より大きいと、低温性能が悪化する。−１０℃での硬さは、７５以下であることが好ましい。該硬さの下限は特に限定されないが、通常は６５以上であることが好ましい。 In the tire tread rubber composition according to this embodiment, the hardness of the vulcanizate measured at a temperature of −10 ° C. with a type A durometer in accordance with JIS K6253 is preferably 80 or less. Hardness at −10 ° C. is generally used as an index of low temperature performance, and if it is greater than 80, low temperature performance deteriorates. The hardness at −10 ° C. is preferably 75 or less. Although the minimum of this hardness is not specifically limited, Usually, it is preferable that it is 65 or more.
６０℃での反発弾性率と−１０℃での硬さは、上記変性Ｓ−ＳＢＲの配合量、希土類元素系触媒ＢＲの配合量、シリカの種類及び配合量等によって変化するので、上記数値範囲を満足するようにこれらを適宜設定すればよい。例えば、変性Ｓ−ＳＢＲの配合量が多いほど反発弾性率は高くなる傾向があり、また希土類元素系触媒ＢＲの配合量が多いほど−１０℃硬さは低下する傾向がある。また、シリカについては、ＢＥＴが小さく、また配合量が少ないほど、反発弾性率は高くなる傾向があり、また、配合量が少ないと硬さが低下する傾向がある。本実施形態によれば、上記のように変性Ｓ−ＳＢＲと希土類元素系触媒ＢＲとを組み合わせることにより、シリカ配合において、低温性能と低発熱性を従来よりも高度に両立することができるので、６０℃での反発弾性率と−１０℃での硬さを上記数値範囲内に容易に設定することができる。 The rebound elastic modulus at 60 ° C. and the hardness at −10 ° C. vary depending on the blending amount of the modified S-SBR, the blending amount of the rare earth element-based catalyst BR, the type and blending amount of silica, etc. These may be set as appropriate so as to satisfy the above. For example, the rebound resilience tends to increase as the blending amount of the modified S-SBR increases, and the hardness at −10 ° C. tends to decrease as the blending amount of the rare earth element-based catalyst BR increases. As for silica, as the BET is small and the blending amount is small, the resilience elastic modulus tends to increase, and when the blending amount is small, the hardness tends to decrease. According to the present embodiment, by combining the modified S-SBR and the rare earth element-based catalyst BR as described above, the low temperature performance and the low heat build-up can be achieved at a higher level than before in the silica formulation. The rebound resilience at 60 ° C. and the hardness at −10 ° C. can be easily set within the above numerical range.
以上よりなる本実施形態に係るゴム組成物は、空気入りタイヤのトレッド部のためのゴム組成物として好適に用いられ、常法に従い加硫成形することにより、トレッド部を形成することができる。本実施形態に係るゴム組成物は、特に、オールシーズンタイヤのトレッド用に好適であるが、これに限定されるものではなく、各種空気入りタイヤに適用することができる。 The rubber composition according to the present embodiment as described above is suitably used as a rubber composition for a tread portion of a pneumatic tire, and can be formed by vulcanization molding according to a conventional method. The rubber composition according to this embodiment is particularly suitable for treads of all-season tires, but is not limited to this, and can be applied to various pneumatic tires.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
［第１実施例］（参考例）
バンバリーミキサーを使用し、下記表１に示す配合（質量部）に従い、まず、第一混合段階で、硫黄と加硫促進剤を除く成分を添加混合し第１マスターバッチを得た（排出温度＝１６０℃）。次いで、第二混合段階において、得られた第１マスターバッチを再度混合し第２マスターバッチを得た（排出温度＝１６０℃）。次いで、最終混合段階で第２マスターバッチと硫黄と加硫促進剤を添加混合して（排出温度＝９０℃）、タイヤトレッド用ゴム組成物を調製した。表１中の各成分の詳細は以下の通りである。
[First Example] (Reference Example)
Using a Banbury mixer, according to the composition (parts by mass) shown in Table 1 below, first, in the first mixing stage, components other than sulfur and vulcanization accelerator were added and mixed to obtain a first master batch (discharge temperature = 160 ° C.). Next, in the second mixing stage, the obtained first master batch was mixed again to obtain a second master batch (discharge temperature = 160 ° C.). Next, in the final mixing stage, the second masterbatch, sulfur and a vulcanization accelerator were added and mixed (discharge temperature = 90 ° C.) to prepare a tire tread rubber composition. The details of each component in Table 1 are as follows.
・未変性ＳＢＲ：ＪＳＲ株式会社製「ＳＢＲ１５０２」
・変性Ｓ−ＳＢＲ１：アミノ基及びアルコキシル基末端変性溶液重合ＳＢＲ（Ｔｇ＝−３５℃、Ｓｔ＝２０質量％）、ＪＳＲ株式会社製「ＨＰＲ３５０」
・変性Ｓ−ＳＢＲ２：ヒドロキシル基末端変性溶液重合ＳＢＲ（Ｓｔ＝２１質量％、Ｔｇ＝−２５℃）、日本ゼオン（株）製「Ｎｉｐｏｌ ＮＳ６１６」
・Ｃｏ−ＢＲ：宇部興産株式会社製「ＢＲ１５０Ｂ」（コバルト系触媒により重合されたブタジエンゴム）
・Ｎｄ−ＢＲ：ランクセス社製「Ｂｕｎａ ＣＢ２２」（ネオジウム系触媒で重合されたブタジエンゴム、シス−１，４結合含有量＝９６．５％、ビニル基含有量＝０．４％）
・ＮＲ：天然ゴム（ＲＳＳ＃３）、
・カーボンブラック：東海カーボン株式会社製「シーストＫＨ」
・シリカ：東ソー・シリカ株式会社製「ニップシールＡＱ」（ＢＥＴ＝２０５ｍ２／ｇ）
・オイル：ＪＯＭＯ製「プロセスＮＣ１４０」
・Ｓｉ７５：スルフィドシランカップリング剤、デグサ社製「Ｓｉ７５」
・ＮＸＴ：３−オクタノイルチオプロピルトリエトキシシラン（上記式（１）中、ｎ＝２，ｍ＝３，ｋ＝７）、モメンティブ・パフォーマンス・マテリアルズ社製「ＮＸＴ」
・ステアリン酸：花王株式会社製「ルナックＳ２０」
・亜鉛華：三井金属鉱業株式会社製「亜鉛華１種」
・老化防止剤：住友化学工業株式会社製「アンチゲン６Ｃ」
・ワックス：大内新興化学工業（株）製「サンノックＮ」
・加硫促進剤：住友化学工業株式会社製「ソクシールＣＺ」
・硫黄：鶴見化学工業株式会社製「粉末硫黄」
Unmodified SBR: “SBR1502” manufactured by JSR Corporation
Modified S-SBR1: amino group and alkoxyl group terminal modified solution polymerization SBR (Tg = −35 ° C., St = 20 mass%), “HPR350” manufactured by JSR Corporation
Modified S-SBR2: hydroxyl group terminal modified solution polymerization SBR (St = 21% by mass, Tg = −25 ° C.), “Nipol NS616” manufactured by Nippon Zeon Co., Ltd.
Co-BR: “BR150B” manufactured by Ube Industries, Ltd. (butadiene rubber polymerized with a cobalt-based catalyst)
Nd-BR: “Buna CB22” manufactured by LANXESS (butadiene rubber polymerized with a neodymium catalyst, cis-1,4 bond content = 96.5%, vinyl group content = 0.4%)
NR: natural rubber (RSS # 3),
・ Carbon black: “Seast KH” manufactured by Tokai Carbon Co., Ltd.
Silica: “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd. (BET = 205 m 2 / g)
・ Oil: JOMO “Process NC140”
Si75: sulfide silane coupling agent, “Si75” manufactured by Degussa
NXT: 3-octanoylthiopropyltriethoxysilane (in the above formula (1), n = 2, m = 3, k = 7), “NXT” manufactured by Momentive Performance Materials
・ Stearic acid: “Lunac S20” manufactured by Kao Corporation
・ Zinc flower: “Zinc flower 1” manufactured by Mitsui Mining & Smelting Co., Ltd.
Anti-aging agent: “Antigen 6C” manufactured by Sumitomo Chemical Co., Ltd.
・ Wax: “Sunnock N” manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Vulcanization accelerator: “SOC SEAL CZ” manufactured by Sumitomo Chemical Co., Ltd.
・ Sulfur: “Sulfur Powder” manufactured by Tsurumi Chemical Co., Ltd.
各ゴム組成物について、未加硫状態での粘度を測定するとともに、１５０℃で３０分間加硫した所定形状の試験片を用いて、反発弾性率と−１０℃硬さを測定した。更に、各ゴム組成物をトレッド用ゴムとして用いて、２１５／４５ＺＲ１７の空気入りラジアルタイヤを作製し、転がり抵抗性能とスノー制動性能を評価した。各評価・測定方法は以下の通りである。 About each rubber composition, while measuring the viscosity in an unvulcanized state, the impact resilience and -10 degreeC hardness were measured using the test piece of the predetermined shape vulcanized at 150 degreeC for 30 minutes. Furthermore, using each rubber composition as a tread rubber, a 215 / 45ZR17 pneumatic radial tire was produced, and rolling resistance performance and snow braking performance were evaluated. Each evaluation / measurement method is as follows.
・反発弾性率：ＪＩＳ Ｋ６２５５に従い、６０℃におけるリュプケ式反発弾性試験を実施して、反発弾性率を測定した。値が大きいほど、発熱しにくく、即ち低発熱性に優れることを意味する。 -Rebound resilience: According to JIS K6255, a Rupke rebound resilience test at 60 ° C. was performed to measure the resilience resilience. A larger value means less heat generation, that is, better low heat generation.
・−１０℃硬さ：ＪＩＳ Ｋ６２５３に準拠してタイプＡデュロメータを用いて、−１０℃での硬さを測定した（試験片の厚み＝２０ｍｍ）。値が小さいほど、低温性能に優れることを意味する。 --10 degreeC hardness: The hardness in -10 degreeC was measured using the type A durometer based on JISK6253 (thickness of a test piece = 20mm). A smaller value means better low temperature performance.
・粘度：ＪＩＳ Ｋ６３００に準拠して東洋精機（株）製ロータレスムーニー測定機を用い、未加硫ゴムを１００℃で１分間余熱後、４分後のトルク値をムーニー単位で測定し、比較例１の値を１００とした指数で示した。指数が小さいほど、粘度が小さく、加工性に優れることを意味する。 ・ Viscosity: Using a Toyo Seiki Co., Ltd. rotorless Mooney measuring machine in accordance with JIS K6300, after preheating the unvulcanized rubber at 100 ° C for 1 minute, measuring the torque value after 4 minutes in Mooney units and comparing It was shown as an index with the value of Example 1 being 100. The smaller the index, the smaller the viscosity and the better the workability.
・転がり抵抗性能：空気圧２３０ｋＰａ、荷重４．４ｋＮとして、転がり抵抗測定用の１軸ドラム試験機にて、室温を２３℃に設定し、８０Ｋｍ／ｈで走行させたときの転がり抵抗を測定した。結果は、比較例１の値を１００とした指数で示した。指数が小さいほど、転がり抵抗が小さく、従って低燃費性に優れることを示す。 Rolling resistance performance: With a pneumatic pressure of 230 kPa and a load of 4.4 kPa, the rolling resistance was measured when running at 80 Km / h with a single-axis drum tester for measuring rolling resistance at a room temperature of 23 ° C. The results are shown as an index with the value of Comparative Example 1 being 100. The smaller the index is, the smaller the rolling resistance is, and thus the better the fuel efficiency.
・スノー制動性能：上記タイヤを２０００ｃｃの４ＷＤ車に装着し、雪道において６０ｋｍ／ｈ走行からＡＢＳ作動させて２０ｋｍ／ｈまで減速時の制動距離を測定し（ｎ＝１０の平均値）、各測定値の逆数について、比較例１の値を１００として指数で示した。指数が大きいほど制動距離が短く、従ってスノー制動性能（低温性能）に優れることを示す。 Snow braking performance: The above tire is mounted on a 2000 cc 4WD vehicle, and the braking distance at the time of deceleration to 20 km / h is measured by driving the ABS from 60 km / h on a snowy road (n = 10 average value). About the reciprocal number of the measured value, the value of the comparative example 1 was set to 100, and it showed with the index | exponent. The larger the index, the shorter the braking distance, and thus the better the snow braking performance (low temperature performance).
結果は、表１に示す通りであり、変性Ｓ−ＳＢＲを配合した比較例２，８では、比較例１に対し、転がり抵抗性能は改善したものの、スノー制動性能が大幅に悪化した。比較例３では、Ｃｏ−ＢＲを配合したことで、比較例２に対して低温性能は改善されたが、転がり抵抗性能は悪化した。比較例４，９では、Ｎｄ−ＢＲを配合したことにより、比較例２，８に対して、転がり抵抗性能とスノー制動性能を改善することができたが、加工性が大幅に悪化していた。比較例５では、保護化メルカプトシランカップリング剤の配合量が少なすぎて、加工性の改善効果が認められなかった。比較例６では、Ｎｄ−ＢＲの配合量が少なすぎて、スノー制動性能の改善効果に劣っていた。比較例７では、Ｎｄ−ＢＲの配合量が多すぎて、転がり抵抗性能の改善効果が得られなかった。 The results are as shown in Table 1. In Comparative Examples 2 and 8 in which modified S-SBR was blended, although the rolling resistance performance was improved compared to Comparative Example 1, the snow braking performance was greatly deteriorated. In Comparative Example 3, by blending Co-BR, the low-temperature performance was improved compared to Comparative Example 2, but the rolling resistance performance was deteriorated. In Comparative Examples 4 and 9, by adding Nd-BR, rolling resistance performance and snow braking performance could be improved compared to Comparative Examples 2 and 8, but the workability was greatly deteriorated. . In Comparative Example 5, the compounding amount of the protected mercaptosilane coupling agent was too small, and the effect of improving processability was not recognized. In Comparative Example 6, the blending amount of Nd-BR was too small, and the effect of improving snow braking performance was inferior. In Comparative Example 7, the amount of Nd-BR was too large, and the effect of improving rolling resistance performance was not obtained.
これに対し、実施例１〜６であると、反発弾性率を６０〜８０％の範囲内としつつ、−１０℃硬さを８０以下に設定することができ、スノー制動性能の悪化をできるだけ抑えながら、また、加工性を維持しつつ、転がり抵抗性能を大幅に改善することができた。 On the other hand, in Examples 1 to 6, the -10 ° C. hardness can be set to 80 or less while suppressing the deterioration of the snow braking performance as much as possible while keeping the rebound resilience within the range of 60 to 80%. However, the rolling resistance performance could be greatly improved while maintaining the workability.
［第２実施例］
バンバリーミキサーを使用し、下記表２に従い、第一混合段階で同表に記載の成分を混合して第１マスターバッチを得た（排出温度＝１６０℃）。次いで、第二混合段階において、得られた第１マスターバッチに同表に記載の残部のゴム成分を添加し混合して第２マスターバッチを得た（排出温度＝１６０℃）。次いで、最終混合段階において、得られた第２マスターバッチに同表に記載の硫黄と加硫促進剤を添加混合して（排出温度＝９０℃）、タイヤトレッド用ゴム組成物を調製した。表２中の各成分の詳細は、上記表１と同じである。
[Second Embodiment]
Using a Banbury mixer, according to Table 2 below, the components described in the same table were mixed in the first mixing stage to obtain a first master batch (discharge temperature = 160 ° C.). Next, in the second mixing stage, the remaining rubber component described in the same table was added to and mixed with the obtained first master batch to obtain a second master batch (discharge temperature = 160 ° C.). Next, in the final mixing stage, the rubber composition for tire tread was prepared by adding and mixing sulfur and a vulcanization accelerator shown in the same table to the obtained second masterbatch (discharge temperature = 90 ° C.). The details of each component in Table 2 are the same as in Table 1 above.
各ゴム組成物について、未加硫状態での粘度を測定するとともに、１５０℃で３０分間加硫した所定形状の試験片を用いて、反発弾性率と−１０℃硬さと耐摩耗性を評価・測定した。更に、各ゴム組成物をトレッド用ゴムとして用いて、２１５／４５ＺＲ１７の空気入りラジアルタイヤを作製し、転がり抵抗性能とスノー制動性能を評価した。各評価・測定方法は、耐摩耗性を除いて上記第１実施例と同じである（但し、粘度、転がり抵抗性能及びスノー制動性能は例Ａを１００とした指数で示した。）。 For each rubber composition, the viscosity in an unvulcanized state is measured, and a test piece having a predetermined shape vulcanized at 150 ° C. for 30 minutes is used to evaluate the resilience modulus, −10 ° C. hardness and wear resistance. It was measured. Furthermore, using each rubber composition as a tread rubber, a 215 / 45ZR17 pneumatic radial tire was produced, and rolling resistance performance and snow braking performance were evaluated. Each evaluation / measurement method is the same as that of the first example except for wear resistance (however, the viscosity, rolling resistance performance, and snow braking performance are indicated by an index with Example A as 100).
・耐摩耗性：ＪＩＳ Ｋ６２６４に準拠し、岩本製作所（株）製のランボーン摩耗試験機を用いて、荷重４０Ｎ、スリップ率３０％の条件で摩耗減量を測定し、摩耗減量の逆数について例Ａの値を１００とした指数で示した。指数が大きいほど、耐摩耗性に優れることを意味する。 Abrasion resistance: In accordance with JIS K6264, a wear loss tester manufactured by Iwamoto Seisakusho Co., Ltd. was used to measure wear loss under the conditions of a load of 40 N and a slip rate of 30%. It was shown as an index with a value of 100. It means that it is excellent in abrasion resistance, so that an index | exponent is large.
結果は、表２に示す通りであり、第１実施例と同様に通常混合を行った例Ａ及びＤに対し、所定量のゴム成分を第二混合段階で後入れした例Ｅ〜Ｈであると、反発弾性率と−１０℃硬さに改善効果が認められ、転がり抵抗性能とスノー制動性能のバランスがより高度に改善されていた。また、耐摩耗性についても顕著な改善効果が得られた。これに対し、第二混合段階で後入れしたゴム成分が少なすぎる例Ｂでは、改善効果は得られなかった。逆に、多量の変性Ｓ−ＳＢＲを後入れした例Ｃでは、例Ａに対して、転がり抵抗性能及び耐摩耗性が悪化していた。 The results are as shown in Table 2 and are examples E to H in which a predetermined amount of rubber component was added later in the second mixing stage with respect to examples A and D in which normal mixing was performed in the same manner as in the first example. And the improvement effect was recognized by the resilience elastic modulus and -10 degreeC hardness, and the balance of rolling resistance performance and snow braking performance was improved more highly. In addition, a remarkable improvement effect was obtained with respect to wear resistance. On the other hand, the improvement effect was not obtained in Example B in which the amount of the rubber component added later in the second mixing stage is too small. On the contrary, in Example C in which a large amount of modified S-SBR was added later, the rolling resistance performance and the wear resistance were deteriorated as compared with Example A.
Claims (5)
前記マスターバッチに残部のゴム成分１０〜４０質量部を混合する第二混合段階と、を含むタイヤトレッド用ゴム組成物の製造方法。
（ＣnＨ2n+1Ｏ）3Ｓｉ−ＣmＨ2m−Ｓ−ＣＯ−ＣkＨ2k+1 …（１）
（式中、ｎは１〜３の整数、ｍは１〜５の整数、ｋは２〜９の整数である。） 100 parts by mass of a rubber component containing 60 to 90 parts by mass of a modified solution-polymerized styrene butadiene rubber introduced with a functional group containing a hetero atom, and 10 to 40 parts by mass of a butadiene rubber synthesized using a rare earth element-based catalyst. Among them, 40 to 110 parts by mass of a rubber component containing 60 to 90 parts by mass of the modified solution-polymerized styrene butadiene rubber, 40 to 110 parts by mass of all fillers containing 30 to 110 parts by mass of silica, A first mixing stage in which a master batch is prepared by kneading -30% by mass of the silane coupling agent represented by the following general formula (1) ;
A second mixing step of mixing 10 to 40 parts by mass of the remaining rubber component with the masterbatch, and a method for producing a tire tread rubber composition.
(C n H 2n + 1 O ) 3 Si-C m H 2m -S-CO-C k H 2k + 1 ... (1)
(In the formula, n is an integer of 1 to 3, m is an integer of 1 to 5, and k is an integer of 2 to 9.)
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| JP2016079329A (en) * | 2014-10-20 | 2016-05-16 | 日本ゼオン株式会社 | Rubber composition for tire, rubber crosslinked article and tire |
| JP6520096B2 (en) * | 2014-12-11 | 2019-05-29 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP6848232B2 (en) * | 2016-07-05 | 2021-03-24 | 横浜ゴム株式会社 | Rubber composition for tires |
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| WO2018230221A1 (en) * | 2017-06-12 | 2018-12-20 | 株式会社ブリヂストン | Rubber composition for tread, tread member, and tire |
| JP7119639B2 (en) * | 2018-06-26 | 2022-08-17 | 住友ゴム工業株式会社 | Method for producing rubber composition |
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