JPH08259738A - Rubber composition for tread - Google Patents
Rubber composition for treadInfo
- Publication number
- JPH08259738A JPH08259738A JP7064460A JP6446095A JPH08259738A JP H08259738 A JPH08259738 A JP H08259738A JP 7064460 A JP7064460 A JP 7064460A JP 6446095 A JP6446095 A JP 6446095A JP H08259738 A JPH08259738 A JP H08259738A
- Authority
- JP
- Japan
- Prior art keywords
- rubber composition
- rubber
- weight
- carbon black
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 56
- 239000005060 rubber Substances 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000006229 carbon black Substances 0.000 claims abstract description 27
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 150000002900 organolithium compounds Chemical class 0.000 claims abstract 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006237 Intermediate SAF Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 3
- 235000019241 carbon black Nutrition 0.000 description 23
- 239000002174 Styrene-butadiene Substances 0.000 description 15
- 238000005096 rolling process Methods 0.000 description 11
- 238000004073 vulcanization Methods 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- -1 glycidoxy, methacryl Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VJBCNMFKFZIXHC-UHFFFAOYSA-N azanium;2-(4-methyl-5-oxo-4-propan-2-yl-1h-imidazol-2-yl)quinoline-3-carboxylate Chemical compound N.N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O VJBCNMFKFZIXHC-UHFFFAOYSA-N 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical group 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 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
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、低燃費タイヤ用のトレ
ッド用ゴム組成物に関し、特に湿潤路面でのグリップ性
能を改良したトレッド用ゴム組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition for a tread for a fuel efficient tire, and more particularly to a rubber composition for a tread having improved grip performance on a wet road surface.
【０００２】[0002]
【従来の技術】タイヤの低燃費性能を向上させるため
に、ゴム成分として、乳化重合ＳＢＲを用いた従来のゴ
ム組成物では、カーボンブラックの配合量を低下、ある
いはプロセスオイル量を減少させる等の手法が取られて
いた。すなわち、カーボンブラック配合量の減少によ
り、転がり抵抗を小さくすることができる。一方、カー
ボンブラックやプロセスオイルの配合量の減少に伴い、
ウェット性能が低下することが知られている。2. Description of the Related Art In order to improve the fuel efficiency of tires, in a conventional rubber composition using emulsion-polymerized SBR as a rubber component, the amount of carbon black compounded is decreased or the amount of process oil is decreased. The method was taken. That is, the rolling resistance can be reduced by reducing the amount of carbon black compounded. On the other hand, as the blending amount of carbon black and process oil decreases,
Wet performance is known to decrease.
【０００３】転がり抵抗については、乳化重合ＳＢＲよ
りは有機リチウムを開始剤として合成される溶液重合Ｓ
ＢＲの方が良好であり、またウェット性能については、
ガラス転移温度の高い溶液重合ＳＢＲが良好であること
がわかっている。しかし、ガラス転移点の高い溶液重合
ＳＢＲは、ウェット性能が良好であるものの、ガラス転
移温度の低い溶液重合ＳＢＲに比して低燃費性能及び低
温脆性に関して劣っている。Regarding rolling resistance, solution polymerization S synthesized by using organolithium as an initiator is more preferable than emulsion polymerization SBR.
BR is better, and regarding wet performance,
It has been found that a solution-polymerized SBR having a high glass transition temperature is good. However, although the solution-polymerized SBR having a high glass transition point has good wet performance, it is inferior in fuel efficiency and low-temperature brittleness as compared with the solution-polymerized SBR having a low glass transition temperature.
【０００４】このため、低燃費性とウェット性能とを改
良させるゴム組成物として、特開平５−３３１３１９号
公報には、溶液重合ＳＢＲ、表面活性が大きいカーボン
ブラック（カーボンブラック表面にカルボニル基、カル
ボキシル基、ヒドロシル基等の酸素官能基が多数存在す
るカーボンブラック）及びシランカップリング剤を配合
したゴム組成物が提案されている。表面活性の高いカー
ボンブラックは転がり抵抗が良好であること、及びシラ
ンカップリング剤の配合によりウェットグリップが向上
することを利用している。しかし、これらのゴム組成物
も、ウェット性能の満足しえる程の向上は認められず、
さらには、組成物の引っ張り強度が低下し、耐摩耗性が
悪く、工程面で加硫前の押出ゴムの安定性が悪い、加硫
速度が遅い等の問題点がある。Therefore, as a rubber composition for improving fuel economy and wet performance, JP-A-5-331319 discloses a solution-polymerized SBR, carbon black having a large surface activity (carbon black surface having carbonyl group, carboxyl group). A rubber composition has been proposed which contains a silane coupling agent and a carbon black having a large number of oxygen functional groups such as groups and hydrosil groups. Carbon black, which has high surface activity, has good rolling resistance, and the fact that wet grip is improved by blending a silane coupling agent is utilized. However, these rubber compositions also do not show a satisfactory improvement in wet performance,
Further, there are problems that the tensile strength of the composition is lowered, the abrasion resistance is poor, the stability of the extruded rubber before vulcanization is poor in the process side, and the vulcanization rate is slow.
【０００５】本発明は、低燃費タイヤ用ゴムにおいて、
加工性に影響を及ぼさない上に、ＷＥＴ性能が改良され
たゴム組成物を提供する。The present invention relates to a rubber for a fuel-efficient tire,
Provided is a rubber composition which does not affect the processability and has improved WET performance.
【０００６】[0006]
【課題を解決するための手段】本発明のトレッド用ゴム
組成物は、ゴム成分の２０重量％以上が、有機リチウム
化合物を開始剤とする、分岐部分が錫で結合されている
スチレンブタジエン共重合体であって、ゴム成分１００
重量部あたり、カーボンブラックを３０〜８０重量部、
及びシリル化剤を２〜１５重量部配合してなる。In the rubber composition for a tread of the present invention, 20% by weight or more of the rubber component is a styrene-butadiene copolymer which has an organic lithium compound as an initiator and a branched portion is bound with tin. Rubber component 100
30 to 80 parts by weight of carbon black per part by weight,
And 2 to 15 parts by weight of a silylating agent.
【０００７】すなわち、本発明のゴム組成物に用いられ
るゴム成分の２０重量％以上は、アルキルリチウム開始
剤を用いて重合して溶液重合により製造されるランダム
共重合体である。本発明に用いられる溶液重合ＳＢＲ
は、結合スチレンをランダムな形で５〜４０％含み、ブ
タジエンはビニル量が１５〜８０％含み、分子量分布
（重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ））が
１．０〜３．０の範囲にある分岐状スチレンブタジエン
共重合体であることが好ましい。そして、さらに分岐部
分の結合が錫で結合していることが好ましい。尚、溶液
重合ＳＢＲは、油展の形で用いてもよいし、非油展の形
で用いてもよい。That is, 20% by weight or more of the rubber component used in the rubber composition of the present invention is a random copolymer produced by solution polymerization by polymerizing with an alkyllithium initiator. Solution polymerization SBR used in the present invention
Contains 5 to 40% of bound styrene in a random form, butadiene contains 15 to 80% of vinyl, and has a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.0 to 3. It is preferably a branched styrene-butadiene copolymer in the range of 0. Further, it is preferable that the branch portion is further bound by tin. The solution-polymerized SBR may be used in an oil-extended form or a non-oil-extended form.
【０００８】他のゴム成分としては、天然ゴム、合成イ
ソプレンゴム、ブタジエンゴム、乳化重合スチレンブタ
ジエンゴム、結合部分に錫を用いていない溶液重合スチ
レンブタジエンゴム、ニトリルゴム等のジエン系共重合
体のうちから１種あるいは複数種が使用される。本発明
に用いられるカーボンブラックは、粒径２５ｎｍ以上又
はＣＴＡＢ比表面積が９９未満のいわゆるＨＡＦクラス
カーボンを７０％以上含んでおり、残りのカーボンがＦ
ＥＦ、ＩＳＡＦ、ＳＡＦのいずれかから１種又は複数種
使用されたカーボンブラックである。ここで、ＣＴＡＢ
比表面積とは、ＡＳＴＭ Ｄ３７６５−９２Ａに準拠し
てトリメチルアンモニウムブロマイドの吸油量より求め
たカーボンブラック１ｇ当たりの比表面積（ｍ2 ）をい
う。ＨＡＦクラスのカーボンブラックは、ゴムに配合分
散させた場合、比較的低燃費になることが知られてお
り、一般的には低燃費タイヤ用として使用されている。
しかしながら、ウェット性能は、他のハード系カーボン
ブラック（例えば、ＳＡＦやＩＳＡＦ）に比べて劣って
いる。Other rubber components include natural rubber, synthetic isoprene rubber, butadiene rubber, emulsion-polymerized styrene-butadiene rubber, diene-based copolymers such as solution-polymerized styrene-butadiene rubber that does not use tin in the bonding portion, and nitrile rubber. One or more of these are used. The carbon black used in the present invention contains 70% or more of so-called HAF class carbon having a particle size of 25 nm or more or a CTAB specific surface area of less than 99, and the remaining carbon is F
It is a carbon black containing one or more of EF, ISAF, and SAF. Where CTAB
The specific surface area refers to a specific surface area (m 2 ) per 1 g of carbon black obtained from the oil absorption of trimethylammonium bromide according to ASTM D3765-92A. HAF class carbon black is known to have relatively low fuel consumption when compounded and dispersed in rubber, and is generally used for low fuel consumption tires.
However, the wet performance is inferior to other hard carbon blacks (for example, SAF and ISAF).
【０００９】本発明に用いられるシリル化剤は、下式で
示される化学構造を有している。式中、Ｒはアルキル基
であり、Ａはアルキルフェニル基であり、Ｂはアルキル
フェニル基又はアルコキシル基であり、Ｃはアルキルフ
ェニル基又はアルコキシル基である。The silylating agent used in the present invention has a chemical structure represented by the following formula. In the formula, R is an alkyl group, A is an alkylphenyl group, B is an alkylphenyl group or an alkoxyl group, and C is an alkylphenyl group or an alkoxyl group.
【００１０】[0010]
【化２】 Embedded image
【００１１】シリル化剤は、ゴム組成物に含まれる化合
物（カーボンブラックを含む）中のＯＨ，ＮＨＲ，ＣＯ
ＯＨ，ＣＯＮＨ，ＳＨ基などの活性水素と容易に反応し
て、これらの活性水素をＲ3 Ｓｉ基（本発明に係るシリ
ル化剤では、上記化学式中のＡ，Ｂ，及びＣがＲ3 に相
当する）で置換保護することにより、ゴムを疎水性に改
質できる。ここで、シランカップリング剤は、一般にＲ
ＳｉＸ3 （Ｒはビニル、グリシドキシ、メタクリル、ア
ミノ、メルカプト基などをもつ有機官能性基であり、Ｘ
は無機材料と反応する加水分解性基で、主に塩素とアル
コキシ基である）の化学構造を有し、有機ケイ素化合物
であるという点においてシリル化剤と共通している。し
かし、シランカップリング剤は、有機質（ゴム成分）と
無機質（シリカが存在しないゴム組成物においては、主
にカーボンブラック表面に存在するカルボキシル基やヒ
ドロキシル基等の酸性官能基）とをカップリング結合す
る性質を持っている。これらのシランカップリング剤
は、シリル化剤と同様にゴムの疎水化を起こすことがで
きるが、ゴム成分とカーボンブラックをカップリングす
る目的のカップリング剤では、今のところアルキルフェ
ニル基を含むシリル化剤程有効に疎水化できるカップリ
ング剤はなく、ウェット性能への寄与が小さい。The silylating agent is OH, NHR, CO in the compound (including carbon black) contained in the rubber composition.
It easily reacts with active hydrogens such as OH, CONH, and SH groups to convert these active hydrogens into R 3 Si groups (in the silylating agent according to the present invention, A, B, and C in the above chemical formula are converted into R 3 s) . The rubber can be modified to be hydrophobic by substitution protection with (corresponding equivalent). Here, the silane coupling agent is generally R
SiX 3 (R is an organic functional group having a vinyl, glycidoxy, methacryl, amino, mercapto group, etc., and X
Is a hydrolyzable group that reacts with an inorganic material, and has a chemical structure of mainly chlorine and an alkoxy group), and is common to silylating agents in that it is an organosilicon compound. However, the silane coupling agent is a coupling bond between an organic substance (rubber component) and an inorganic substance (in a rubber composition where silica is not present, an acidic functional group such as a carboxyl group or a hydroxyl group mainly present on the surface of carbon black). Have the property to These silane coupling agents can cause the hydrophobicity of the rubber like the silylating agent, but the coupling agent for the purpose of coupling the rubber component and the carbon black does not currently contain the silyl group containing an alkylphenyl group. There is no coupling agent that can be made hydrophobic as effectively as the agent, and its contribution to the wet performance is small.
【００１２】本発明のトレッド用ゴム組成物には、上記
成分以外に、公知の加硫剤、加硫促進剤、軟化剤、老化
防止剤等が配合され、更に必要に応じて加硫遅延剤、粘
着付与剤等が配合され得る。In addition to the above components, the rubber composition for a tread of the present invention contains known vulcanizing agents, vulcanization accelerators, softening agents, antioxidants, etc., and, if necessary, vulcanization retarders. , Tackifiers and the like may be added.
【００１３】[0013]
【実施例】以下、本発明を具体的実施例に基づいて説明
する。尚、ゴム組成物の配合にあたり、ＳＢＲとして
は、表１に示す３種類（〜）のＳＢＲを用いた。こ
のうち、ＳＢＲ及びＳＢＲが、本発明にかかる溶液
重合ＳＢＲ（ｓ−ＳＢＲ）である。また、シリル化剤又
はシランカップリング剤としては、表２に示す４種類
（〜）を用いた。カーボンブラックとしては、昭和
キャボット製のＨＡＦ Ｎ３５１（カーボンブラック
ａ）と三菱化学製のＩＳＡＦ Ｎ２２０（カーボンブラ
ックｂ）を用いた。EXAMPLES The present invention will be described below based on specific examples. In addition, in compounding the rubber composition, as the SBR, three types (to) of SBR shown in Table 1 were used. Among these, SBR and SBR are solution polymerization SBR (s-SBR) concerning this invention. As the silylating agent or silane coupling agent, four types (to) shown in Table 2 were used. As the carbon black, HAF N351 (carbon black a) manufactured by Showa Cabot and ISAF N220 (carbon black b) manufactured by Mitsubishi Chemical were used.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【表２】 [Table 2]
【００１６】表３及び表４に示す配合組成を有するゴム
組成物Ｎｏ．１〜１１を調製した。表３のゴム組成物Ｎ
ｏ．１〜７はカーボンブラックの含有量が５０ｐｈｒの
ものであり、表４のゴム組成物Ｎｏ．８〜１１はカーボ
ンブラックの含有量が７０ｐｈｒのものである。ゴム組
成物Ｎｏ．１〜３及びＮｏ．８〜１０が本発明に係る実
施例であり、その他のゴム組成物は比較例である。尚、
表３及び表４に示すプロセスオイル量は、油展ゴムに含
まれるオイル量を含まない量である。Rubber composition No. 1 having the compounding composition shown in Tables 3 and 4. 1-11 were prepared. Rubber composition N in Table 3
o. 1 to 7 have a carbon black content of 50 phr, and the rubber composition Nos. 8 to 11 have a carbon black content of 70 phr. Rubber composition No. 1-3 and No. 8 to 10 are examples according to the present invention, and other rubber compositions are comparative examples. still,
The amount of process oil shown in Tables 3 and 4 is an amount that does not include the amount of oil contained in the oil-extended rubber.
【００１７】各ゴム組成物について、下記評価方法に従
って、スコーチタイム、加硫時間、未加硫ゴム肌、耐摩
耗性、転がり抵抗、ウェットグリップ性を評価した。ゴ
ム組成物の配合組成及び評価結果を併せて、表３及び表
４に示す。尚、評価結果は、表３のゴム組成物Ｎｏ．１
〜７についてはＮｏ．４を１００とした指数で表し、表
４のゴム組成物Ｎｏ．８〜１１についてはＮｏ．１１を
１００とした指数で表している。 〔評価方法〕 （ａ）スコーチタイム（単位：分） 島津製作所製のムーニー測定機ＳＭＶ２０１にて１３０
℃の条件で測定した。スコーチタイム（分）が短い程、
初期加硫が進みやすく、加工性が悪いことを示す。 （ｂ）加硫時間（単位：分） 日本合成ゴム製のキュラストメータタイプＶにて１６０
℃の条件で測定した。加硫時間が長い程、加工性が劣る
ことを示す。 （ｃ）未加硫ゴム肌 ８インチロールを用いて、厚さ２．０ｍｍ程度の薄さで
押し出した未加硫ゴムの押し出し肌を目視で観察し、そ
の結果を良〜不良でランクづけした。押し出し肌が悪い
と、タイヤのコンポーネントを組立てる際に作業性が悪
くなり、さらには、タイヤの均一性が悪くなる。 （ｄ）耐摩耗性 岩本製作所製のランボーン摩耗試験機を用いて、荷重２
ｋｇ一定で、スリップ率４０％及び６０％の条件で測定
した。指数が大きい程、耐摩耗性が良好であることを示
す。 （ｅ）転がり抵抗 各ゴム組成物を用いて、２０５／６５Ｒ１５ ＳＰ４０
００ＴＬサイズのタイヤを試作し、タイヤ単品での転が
り抵抗を測定した。ゴム組成物Ｎｏ．４の測定値を１０
０として、他のゴム組成物の測定値を指数で表した。指
数が小さい程、転がり抵抗が小さくて燃費性が良好であ
ることを示す。 （ｆ）ＷＥＴ評価 各ゴム組成物を用いて、２０５／６５Ｒ１５ ＳＰ４０
００ＴＬサイズのタイヤを試作し、試作したタイヤをト
ヨタセプターに装着し、湿潤アスファルト路面を所定の
回転半径で旋回した際の周回タイムでもって計測した。
指数が大きい程、旋回タイムが小さくてウェットグリッ
プが良好であることを示す。Each rubber composition was evaluated for scorch time, vulcanization time, unvulcanized rubber skin, abrasion resistance, rolling resistance and wet grip property according to the following evaluation methods. The compounding composition of the rubber composition and the evaluation results are also shown in Tables 3 and 4. The evaluation results are shown in Table 3 below. 1
No. 7 to No. 7 4 is expressed as an index with 100 as the rubber composition No. 4 in Table 4. For Nos. 8 to 11, No. It is represented by an index with 11 being 100. [Evaluation method] (a) Scorch time (unit: minutes) 130 with a Mooney measuring machine SMV201 manufactured by Shimadzu Corporation
It was measured under the condition of ° C. The shorter the scorch time (minutes),
It shows that initial vulcanization proceeds easily and processability is poor. (B) Vulcanization time (unit: minutes) 160 with a Japanese synthetic rubber curlastometer type V
It was measured under the condition of ° C. The longer the vulcanization time, the poorer the workability. (C) Unvulcanized rubber skin The extruded skin of unvulcanized rubber extruded with a thickness of about 2.0 mm was visually observed using an 8-inch roll, and the results were ranked as good or bad. . Poor extruded skin results in poor workability when assembling tire components and, in addition, poor tire uniformity. (D) Wear resistance Using a Lambourn abrasion tester manufactured by Iwamoto Seisakusho, load 2
The measurement was performed under conditions of a constant kg and a slip ratio of 40% and 60%. The larger the index, the better the wear resistance. (E) Rolling resistance Using each rubber composition, 205 / 65R15 SP40
A tire of size 00TL was manufactured as a prototype, and the rolling resistance of the tire alone was measured. Rubber composition No. 4 measured value is 10
The measured value of other rubber compositions was expressed as an index of 0. The smaller the index, the smaller the rolling resistance and the better the fuel economy. (F) WET Evaluation Using each rubber composition, 205 / 65R15 SP40
A 00TL size tire was prototyped, the prototyped tire was mounted on a Toyota Scepter, and the time was measured by the lap time when turning on a wet asphalt road surface with a predetermined turning radius.
The larger the index, the shorter the turning time and the better the wet grip.
【００１８】[0018]
【表３】 [Table 3]
【００１９】[0019]
【表４】 [Table 4]
【００２０】表３のＮｏ．１〜３とＮｏ．４との比較か
ら、シリル化剤の配合により転がり抵抗及び耐摩耗性を
保持しつつ、ウェットグリップの向上を図ることができ
ることがわかる。尚、耐摩耗性、ウェットグリップ性の
向上の程度、及び転がり抵抗に対する影響はシリル化剤
の種類により相違する（Ｎｏ．１及びＮｏ．３参照）。No. 3 in Table 3 1-3 and No. From the comparison with No. 4, it is understood that the addition of the silylating agent can improve the wet grip while maintaining the rolling resistance and the abrasion resistance. The degree of improvement in wear resistance and wet grip properties, and the effect on rolling resistance differ depending on the type of silylating agent (see No. 1 and No. 3).
【００２１】また、シリル化剤に代えてシランカップリ
ング剤を配合した場合には、ウェットグリップの顕著な
向上が認められない上に、シランカップリング剤の種類
により未加硫ゴム肌が悪く、加硫時間も長くて加工性に
劣ったり（Ｎｏ．６参照）、スコーチタイムが短く加工
性が低下したりする（Ｎｏ．７参照）。さらに、Ｎｏ．
５とＮｏ．１との比較から、カーボンブラックを所定量
配合するとともにシリル化剤を配合した場合であって
も、ゴム成分として所定割合以上は溶液重合ＳＢＲを含
有しない場合には、ウェット性能が劣り、転がり抵抗も
劣る。When a silane coupling agent is blended in place of the silylating agent, no noticeable improvement in wet grip is observed, and the unvulcanized rubber surface is poor depending on the type of silane coupling agent. The vulcanization time is long and the workability is poor (see No. 6), and the scorch time is short and the workability is low (see No. 7). Furthermore, No.
5 and No. From the comparison with No. 1, even when a predetermined amount of carbon black and a silylating agent are mixed, when the solution-polymerized SBR is not contained in a predetermined proportion or more as a rubber component, the wet performance is poor and the rolling resistance is low. Is also inferior.
【００２２】表４から、シリル化剤の配合量が多すぎる
と、ウェットグリップ性の効果は、本発明の範囲内の配
合量の場合とそれほど変わらないのに対し、耐摩耗性が
劣ることがわかる。また、カーボンブラック配合量を増
やすあるいはゴム成分における溶液重合ＳＢＲの割合を
増加することにより、耐摩耗性を向上させることができ
るが（Ｎｏ．８〜１０）、このような組成においてもシ
リル化剤の配合量が多すぎると耐摩耗性の低下を招く
（Ｎｏ．１１参照）。From Table 4, when the amount of the silylating agent is too large, the effect of wet grip property is not so different from the case of the amount within the range of the present invention, but the wear resistance is inferior. Recognize. Further, the wear resistance can be improved by increasing the amount of carbon black compounded or increasing the ratio of the solution-polymerized SBR in the rubber component (No. 8 to 10). If the compounding amount of is too large, the wear resistance is lowered (see No. 11).
【００２３】[0023]
【発明の効果】本発明のトレッド用ゴム組成物は、耐摩
耗性を低下させることなく、転がり抵抗が小さく、ウェ
ットグリップ性も優れている。従って、本発明のゴムを
組成物を用いて、トレッド部を構成したタイヤを製造す
れば、低燃費で耐久性に優れ、しかもウェットグリップ
性能に優れたタイヤを得ることができる。EFFECTS OF THE INVENTION The rubber composition for a tread of the present invention has low rolling resistance and excellent wet grip properties without lowering wear resistance. Therefore, when a tire having a tread portion is manufactured by using the rubber composition of the present invention, a tire having low fuel consumption, excellent durability and excellent wet grip performance can be obtained.
Claims (4)
ウム化合物を開始剤とする、分岐部分が錫で結合されて
いるスチレンブタジエン共重合体であって、 ゴム成分１００重量部あたり、カーボンブラックを３０
〜８０重量部、及びシリル化剤を２〜１５重量部配合し
てなるトレッド用ゴム組成物。1. 20% by weight or more of a rubber component is a styrene-butadiene copolymer having an organolithium compound as an initiator and having a branched portion bonded with tin, and carbon black per 100 parts by weight of the rubber component. 30
A rubber composition for a tread, which comprises -80 parts by weight and 2-15 parts by weight of a silylating agent.
合スチレンをランダムな形で５〜４０％含み、ブタジエ
ンはビニル量が１５〜８０％含み、 且つ分子量分布（重量平均分子量（Ｍｗ）／数平均分子
量（Ｍｎ））が１．０〜３．０の範囲にあることを特徴
とする請求項１に記載のトレッド用ゴム組成物。2. The styrene-butadiene copolymer contains 5 to 40% of bound styrene in a random form, butadiene contains 15 to 80% of vinyl, and has a molecular weight distribution (weight average molecular weight (Mw) / number average). The rubber composition for tread according to claim 1, wherein the rubber composition has a molecular weight (Mn) of 1.0 to 3.0.
粒径２５ｎｍ以上又はＣＴＡＢ比表面積が９９未満であ
って、 残部のカーボンブラックは、ＦＥＦ、ＩＳＡＦ及びＳＡ
Ｆの群から選ばれる少なくとも１種であることを特徴と
する請求項１又は２に記載のトレッド用ゴム組成物。3. 70% by weight or more of carbon black is
The particle size is 25 nm or more or the CTAB specific surface area is less than 99, and the balance carbon black is FEF, ISAF and SA.
It is at least 1 sort (s) selected from the group of F, The rubber composition for treads of Claim 1 or 2 characterized by the above-mentioned.
物であることを特徴とする請求項１〜３のいずれかに記
載のトレッド用ゴム組成物。 【化１】 式中、Ｒはアルキル基であり、Ａはアルキルフェニル基
であり、Ｂはアルキルフェニル基又はアルコキシル基で
あり、Ｃはアルキルフェニル基又はアルコキシル基であ
る。4. The rubber composition for tread according to claim 1, wherein the silylating agent is a compound represented by the following formula. Embedded image In the formula, R is an alkyl group, A is an alkylphenyl group, B is an alkylphenyl group or an alkoxyl group, and C is an alkylphenyl group or an alkoxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06446095A JP3515826B2 (en) | 1995-03-23 | 1995-03-23 | Rubber composition for tread |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06446095A JP3515826B2 (en) | 1995-03-23 | 1995-03-23 | Rubber composition for tread |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08259738A true JPH08259738A (en) | 1996-10-08 |
| JP3515826B2 JP3515826B2 (en) | 2004-04-05 |
Family
ID=13258878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06446095A Expired - Fee Related JP3515826B2 (en) | 1995-03-23 | 1995-03-23 | Rubber composition for tread |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3515826B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246711A (en) * | 2006-03-16 | 2007-09-27 | Sumitomo Rubber Ind Ltd | Rubber composition for inner liner |
| JP2007246712A (en) * | 2006-03-16 | 2007-09-27 | Sumitomo Rubber Ind Ltd | Rubber composition for tread |
| JP2007284509A (en) * | 2006-04-14 | 2007-11-01 | Yokohama Rubber Co Ltd:The | Rubber composition for rubber roll and rubber roll |
-
1995
- 1995-03-23 JP JP06446095A patent/JP3515826B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246711A (en) * | 2006-03-16 | 2007-09-27 | Sumitomo Rubber Ind Ltd | Rubber composition for inner liner |
| JP2007246712A (en) * | 2006-03-16 | 2007-09-27 | Sumitomo Rubber Ind Ltd | Rubber composition for tread |
| JP2007284509A (en) * | 2006-04-14 | 2007-11-01 | Yokohama Rubber Co Ltd:The | Rubber composition for rubber roll and rubber roll |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3515826B2 (en) | 2004-04-05 |
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