JP4020688B2 - Rubber composition - Google Patents

Rubber composition Download PDF

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Publication number
JP4020688B2
JP4020688B2 JP2002128230A JP2002128230A JP4020688B2 JP 4020688 B2 JP4020688 B2 JP 4020688B2 JP 2002128230 A JP2002128230 A JP 2002128230A JP 2002128230 A JP2002128230 A JP 2002128230A JP 4020688 B2 JP4020688 B2 JP 4020688B2
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Japan
Prior art keywords
silica
weight
rubber
parts
silanol
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JP2002128230A
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JP2003321576A (en
Inventor
直也 網野
克己 林田
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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Description

【0001】
【発明の属する技術分野】
本発明はゴム組成物に関し、更に詳しくは摩擦力の高い、特にタイヤトレッド用として好適なゴム組成物に関する。
【0002】
【従来の技術】
空気入りタイヤ用ゴム組成物にシリカを配合することによりタイヤのウェット性能を向上させ、かつ転がり抵抗を低減させる技術が知られている。しかしながら、シリカは、ゴム中で凝集しやすいために、分散不良塊となりやすく、そのために微少変形領域でゴムの弾性率E’が高くなる問題があった。摩擦に対する研究の結果として、微少変形領域のE’を低下させることによりゴムの摩擦力を向上させることが可能であることがわかっている。
【0003】
【発明が解決しようとする課題】
従って、本発明は、ゴム組成物中にシリカを配合してタイヤのウェット性能を向上させると共に転がり抵抗を低減させようとする従来の技術の問題点である、ゴム中でのシリカの凝集による分散不良塊の生成を抑えることを目的とする。
【0004】
【課題を解決するための手段】
本発明に従えば(i)ジエン系ゴム100重量部、 ii 単位表面積当りのシラノール基結合量が5個/nm2 以上のシリカ(A)5〜80重量部及び単位表面積当りのシラノール基結合量が4個/nm2 以下のシリカ(B)5〜80重量部並びに( iii )シリカ(A)及びシリカ(B)の合計配合量の2〜15重量%のシランカップリング剤を含んでなり、単位表面積当りのシラノール基結合量が4個/ nm 2 以下のシリカ(B)がシリカ表面のシラノール基の少なくとも一部を、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、トリメチルシリル基及びトリエチルシリル基から選ばれた炭化水素基によって置換した疎水化シリカであるゴム組成物が提供される。
【0005】
【発明の実施の形態】
ゴム組成物中にシリカを配合した場合のシリカの凝集力は、シリカ表面のシラノール基の量を増大させることで増加する。しかしながら、シリカとシランカップリング剤との反応性もシラノール基の量に依存しており、シラノール基の量を減少させるとゴムの補強性が低下するので所望の補強効果が得られなくなる。そこで、本発明者らはシラノール基の量が多く補強性の高いシリカと、シラノール基の量が少なく凝集力が低いシリカの2種類のシリカを適量ブレンドし、好ましくはさらにシランカップリング剤を配合することによってシリカ本来の補強性を維持しつつゴム中でのシリカの凝集を抑制することができることを見出した。
【0006】
本発明でいうシラノール基の結合量の測定は、澤登純一、小野茂之、伊藤眞義:高分子論文集、57巻、6号、356頁(2000)によるもので、具体的にはシリカ表面のシラノール基をジメチルクロロシランを用いてジメチルシリル基置換し、FT−IR法で測定し、別に求めた検量線より決定した。比表面積はBET吸着法を用いて測定した。
【0007】
本発明に係るゴム組成物に配合するジエン系ゴムは従来からゴム組成物、特に空気入りタイヤのトレッド用ゴム組成物に汎用されている任意のゴムとすることができ、例えば天然ゴム(NR)、各種ブタジエンゴム(BR)、各種スチレン−ブタジエン共重合体ゴム(SBR)、ポリイソプレンゴム(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)、エチレン−プロピレン−ジエン共重合体ゴム(EPDM)、スチレン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴム、イソプレン−ブタジエン共重合体ゴム等が挙げられる。これらのゴムは、単独又は任意の混合物として用いることができる。
【0008】
本発明に係るゴム組成物に配合されるシリカは、ジエン系ゴム100重量部に対し、単位表面積あたりのシラノール基結合量が5個/nm2 以上の補強性の高いシリカ(A)5〜80重量部、好ましくは10〜75重量部、と単位表面積当りのシラノール基結合量が4個/nm2 以下の凝集力の低いシリカ(B)5〜80重量部、好ましくは10〜75重量部とを併用する。
【0009】
シリカ(A)とシリカ(B)の合計量はジエン系ゴム100重量部当り10〜120重量部、好ましくは20〜100重量部でシリカ(A)/シリカ(B)(重量比)は0.1〜0.9、好ましくは0.2〜0.8である。シリカ(A)の配合量が多過ぎるとシリカの凝集力が大きくなって分散不良塊が生じて微少変形領域のE’が高くなって、タイヤのウェット性能向上効果が不十分であるという問題が生じやすくなり、逆にシリカ(B)の配合量が多過ぎると所望の補強効果が得られなくなり、ゴムのモジュラスが低下するためにタイヤの操縦安定性が低下するという問題が生じやすくなる。
【0010】
本発明において使用するシリカ(A)は従来の補強性シリカであり、例えばNipsil AQ(日本シリカ工業)、トクシール UR(徳山ソーダ)、ULTRASIL VN3(デグッサ)などとして市販されているシリカを用いることができる。
【0011】
本発明において使用するシリカ(B)はシリカ表面のシラノール基の一部又は全部を前記炭化水素基(即ちメチル基、エチル基、プロピル基、メトキシ基、エトキシ基、トリメチルシリル基、トリエチルシリル基)で置換した疎水化シリカやポリシロキサン化合物でシリカ表面を被覆した表面処理シリカを含み、例えばSS−20,SS−30P(日本シリカ工業)などとして市販されている。
【0012】
本発明に従えば、従来から汎用されているシランカップリング剤をシリカ(A)及び(B)の合計配合量に対し2〜15重量%、更に好ましくは3〜12重量%配合する。好ましいシランカップリング剤はシラノール基を有する含硫黄シランカップリング剤であり、具体的にはビス−(3−(トリエトキシシリル)−プロピル)テトラスルフィド、ビス−(3−(トリエトキシシリル)−プロピル)ジスルフィド、メルカプトプロピル−トリメトキシシラン、メルカプトプロピル−トリエトキシシランなどの化合物をあげることができる。
【0013】
本発明のゴム組成物には、上記必須成分以外に、常法に従って、カーボンブラックなどの他の補強剤、加硫剤、加硫促進剤、老化防止剤、活性剤、プロセスオイル、可塑剤、滑剤、充填剤などの一般的な配合剤をそれぞれ必要量配合することができる。
【0014】
【実施例】
以下、実施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いうまでもない。
【0015】
実施例1〜3及び比較例1〜2
サンプルの調製
16リットルの密閉式バンバリーミキサーを用いて、表Iに示す配合(重量部)で、加硫促進剤及び硫黄を除く成分を3〜5分間混合し、ゴム温度が160℃に達した時点で放出した。次にオープンロールを用いてこのゴム組成物に加硫促進剤及び硫黄を加えて、15×15×0.2cmの金型中で160℃で30分間加硫した。この加硫シートを以下の方法で試験した。結果は表Iに示す。
【0016】
評価試験方法
引張特性
JIS K 6251に準拠して、300%モジュラス(M300)(MPa)、破断強度TB(MPa)及び破断伸度EB(%)を測定した。
E’,tanδ
(株)東洋精機製作所製、粘弾性スペクトロメーターを用いて、初期歪10%、振幅±2%及び周波数20Hzの条件で、0℃及び60℃の粘弾性特性を測定した。
【0017】
【表1】

Figure 0004020688
【0018】
表I脚注
Nipol 9528R:日本ゼオン(株)製SBR(スチレン含量35%、37.5phr 油展品)
N339:昭和キャボット(株)製カーボンブラック
NIPSIL AQ:日本シリカ工業(株)製湿式シリカ(シラノール基量6個/nm2
疎水シリカ:日本シリカ(株)製SS−30P(シラノール基量1個/nm2
【0019】
Si−69:DEGUSSA製シランカップリング剤
SANTOFLEX 6PPD:FLEXSYS製老化防止剤
サンノック:大内新興化学(株)製 ワックス
酸化亜鉛3種:正同化学工業(株)製
ステアリン酸:日本油脂(株)製
アロマオイル:富士興産(株)製
SANTOCURE CZ:FLEXSYS製 加硫促進剤
硫黄:(株)軽井沢精練所製
【0020】
表Iの結果から明らかなようにシリカに疎水シリカをブレンドした場合、モジュラスは同等であるが、E’が低下し、tanδが向上した。これは、シリカ表面のシラノール基の数が少ないために、シリカが凝集しにくく、また、ZnO等を吸着しにくいためと考えられる。そのため、ゴム中でのシリカの分散が向上し、また補強性が低いものの架橋密度は向上するので、モジュラスは同等になると考えられる。
【0021】
【発明の効果】
以上の通り、本発明に従えば、シラノール基の量が多く補強性の高いシリカとシラノール基の量が少なく凝集力が低いシリカを適量ブレンドすることによって、シリカの凝集が抑制されているために、微少歪域でE’が低く、路面凹凸へのゴムの追従性が高まるために摩擦力が高く、タイヤトレッド用として好適なゴム組成物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber composition, and more particularly to a rubber composition having a high frictional force and particularly suitable for use in a tire tread.
[0002]
[Prior art]
A technique for improving the wet performance of a tire and reducing rolling resistance is known by blending silica with a rubber composition for a pneumatic tire. However, since silica easily aggregates in rubber, it tends to be a poorly dispersed lump, and there is a problem that the elastic modulus E ′ of the rubber becomes high in a minute deformation region. As a result of studies on friction, it has been found that the frictional force of rubber can be improved by reducing E ′ in the micro-deformation region.
[0003]
[Problems to be solved by the invention]
Therefore, the present invention is a dispersion of silica due to agglomeration in rubber, which is a problem of the prior art that attempts to improve tire wet performance and reduce rolling resistance by blending silica in a rubber composition. The purpose is to suppress the formation of defective lumps.
[0004]
[Means for Solving the Problems]
According to the present invention (i) a diene rubber 100 parts by weight, (ii) a silanol group bound per unit surface area of 5 / nm 2 or more silica (A) 5 to 80 parts by weight and silanol groups per unit surface area 5 to 80 parts by weight of silica (B) having a bond amount of 4 / nm 2 or less , and ( iii ) 2 to 15% by weight of the silane coupling agent based on the total amount of silica (A) and silica (B). The number of silanol group bonds per unit surface area is 4 / nm 2 Hydrophobic in which the following silica (B) has substituted at least part of silanol groups on the silica surface with a hydrocarbon group selected from methyl, ethyl, propyl, methoxy, ethoxy, trimethylsilyl and triethylsilyl groups A rubber composition that is a silanized silica is provided.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The cohesive strength of silica when silica is compounded in the rubber composition increases by increasing the amount of silanol groups on the silica surface. However, the reactivity between silica and the silane coupling agent also depends on the amount of silanol groups. If the amount of silanol groups is decreased, the reinforcing property of the rubber is lowered, so that a desired reinforcing effect cannot be obtained. Therefore, the present inventors blended an appropriate amount of two types of silica, a silica having a high amount of silanol groups and a high reinforcing property, and a silica having a low amount of silanol groups and a low cohesive force, preferably further containing a silane coupling agent. By doing so, it has been found that silica agglomeration in rubber can be suppressed while maintaining the original reinforcing property of silica.
[0006]
The measurement of the amount of silanol groups bound in the present invention is based on Sawato Junichi, Ono Shigeyuki, Ito Satoshi: Polymer Journal, Vol. 57, No. 6, p. 356 (2000), specifically, silanol on the silica surface. The group was substituted with dimethylsilyl group using dimethylchlorosilane, measured by FT-IR method, and determined from a separately obtained calibration curve. The specific surface area was measured using the BET adsorption method.
[0007]
The diene rubber compounded in the rubber composition according to the present invention can be any rubber conventionally used for rubber compositions, particularly rubber compositions for treads of pneumatic tires, such as natural rubber (NR). , Various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubber (IR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene copolymer rubber ( EPDM), styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, and the like. These rubbers can be used alone or as an arbitrary mixture.
[0008]
Silica blended in the rubber composition according to the present invention is highly reinforcing silica (A) 5 to 80 having a silanol group bond amount per unit surface area of 5 / nm 2 or more per 100 parts by weight of the diene rubber. Parts by weight, preferably 10 to 75 parts by weight, and 5 to 80 parts by weight, preferably 10 to 75 parts by weight, of low-cohesive silica (B) having a silanol group bonding amount per unit surface area of 4 / nm 2 or less. Use together.
[0009]
The total amount of silica (A) and silica (B) is 10 to 120 parts by weight, preferably 20 to 100 parts by weight per 100 parts by weight of diene rubber, and silica (A) / silica (B) (weight ratio) is 0.00. 1 to 0.9, preferably 0.2 to 0.8. If the amount of silica (A) is too large, the cohesive force of silica increases, resulting in poorly dispersed lump, resulting in a high E ′ in the micro-deformation region, and the effect of improving the wet performance of the tire is insufficient. Conversely, if the amount of silica (B) is too large, the desired reinforcing effect cannot be obtained, and the modulus of the rubber is lowered, so that the problem of lowering the steering stability of the tire tends to occur.
[0010]
The silica (A) used in the present invention is a conventional reinforcing silica. For example, silica commercially available as Nipsil AQ (Nippon Silica Industry), Toxeal UR (Tokuyama Soda), ULTRASIL VN3 (Degussa) or the like may be used. it can.
[0011]
On silica (B) used in the present invention is the hydrocarbon groups in which some or all of the silanol groups of the silica surface (i.e. a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a trimethylsilyl group, triethylsilyl group) It includes surface-treated silica whose surface is coated with a substituted hydrophobic silica or polysiloxane compound, and is commercially available, for example, as SS-20, SS-30P (Nippon Silica Industry).
[0012]
According to the present invention, a conventionally used silane coupling agent is added in an amount of 2 to 15% by weight, more preferably 3 to 12% by weight, based on the total amount of silica (A) and (B). A preferred silane coupling agent is a sulfur-containing silane coupling agent having a silanol group, specifically, bis- (3- (triethoxysilyl) -propyl) tetrasulfide, bis- (3- (triethoxysilyl)- And propyl) disulfide, mercaptopropyl-trimethoxysilane, mercaptopropyl-triethoxysilane, and the like.
[0013]
In the rubber composition of the present invention, in addition to the above essential components, other reinforcing agents such as carbon black, vulcanizing agents, vulcanization accelerators, anti-aging agents, activators, process oils, plasticizers, Necessary amounts of general compounding agents such as lubricants and fillers can be added.
[0014]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
[0015]
Examples 1-3 and Comparative Examples 1-2
Sample preparation Using a 16 liter closed Banbury mixer, the ingredients (parts by weight) shown in Table I were mixed for 3 to 5 minutes with ingredients other than the vulcanization accelerator and sulfur, and the rubber temperature reached 160 ° C. Released at the time. Next, a vulcanization accelerator and sulfur were added to the rubber composition using an open roll, and vulcanized at 160 ° C. for 30 minutes in a 15 × 15 × 0.2 cm mold. This vulcanized sheet was tested by the following method. The results are shown in Table I.
[0016]
Evaluation test method
Tensile properties 300% modulus (M300) (MPa), breaking strength TB (MPa) and breaking elongation EB (%) were measured according to JIS K 6251.
E ', tan δ
Using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd., viscoelastic properties at 0 ° C. and 60 ° C. were measured under conditions of an initial strain of 10%, an amplitude of ± 2%, and a frequency of 20 Hz.
[0017]
[Table 1]
Figure 0004020688
[0018]
Table I Footnote Nipol 9528R: SBR manufactured by Nippon Zeon Co., Ltd. (35% styrene content, 37.5 phr oil exhibition product)
N339: Carbon black manufactured by Showa Cabot Co., Ltd. NIPSIL AQ: Nippon Silica Kogyo Co., Ltd. wet silica (silanol group amount 6 / nm 2 )
Hydrophobic silica: SS-30P (silanol group amount 1 / nm 2 ) manufactured by Nippon Silica Co., Ltd.
[0019]
Si-69: DEGUSSA silane coupling agent SANTOFLEX 6PPD: FLEXSYS anti-aging agent Sannock: Ouchi Shinsei Chemical Co., Ltd. Wax Zinc Oxide 3 types: Shodo Chemical Industry Co., Ltd. Stearic Acid: Nippon Oil & Fat Co. Aroma oil manufactured: SANKOCURE manufactured by Fujikosan Co., Ltd. CZ: manufactured by FLEXSYS Vulcanization accelerator sulfur: manufactured by Karuizawa Seiren Co., Ltd.
As is apparent from the results in Table I, when hydrophobic silica was blended with silica, the modulus was the same, but E ′ decreased and tan δ improved. This is presumably because the number of silanol groups on the silica surface is small, so that the silica is less likely to aggregate and it is difficult to adsorb ZnO or the like. Therefore, the dispersion of silica in the rubber is improved, and the crosslink density is improved although the reinforcing property is low, so the modulus is considered to be equal.
[0021]
【The invention's effect】
As described above, according to the present invention, silica agglomeration is suppressed by blending an appropriate amount of silica having a high amount of silanol groups and a high reinforcing property and silica having a low amount of silanol groups and a low cohesive force. In addition, since E ′ is low in a minute strain region and the followability of the rubber to the road surface unevenness is increased, the frictional force is high, and a rubber composition suitable for a tire tread can be obtained.

Claims (1)

(i)ジエン系ゴム100重量部、 ii 単位表面積当りのシラノール基結合量が5個/nm2 以上のシリカ(A)5〜80重量部及び単位表面積当りのシラノール基結合量が4個/nm2 以下のシリカ(B)5〜80重量部並びに( iii )シリカ(A)及びシリカ(B)の合計配合量の2〜15重量%のシランカップリング剤を含んでなり、単位表面積当りのシラノール基結合量が4個/ nm 2 以下のシリカ(B)がシリカ表面のシラノール基の少なくとも一部を、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、トリメチルシリル基及びトリエチルシリル基から選ばれた炭化水素基によって置換した疎水化シリカであるゴム組成物。 (I) 100 parts by weight of a diene rubber, ( ii ) 5 to 80 parts by weight of silica (A) having a silanol group bonding amount per unit surface area of 5 / nm 2 or more and 4 silanol group bonding amounts per unit surface area Per unit surface area, comprising 5 to 80 parts by weight of silica (B) of less than / nm 2 and ( iii ) 2 to 15% by weight of the silane coupling agent based on the total amount of silica (A) and silica (B) Has 4 silanol groups / nm 2 Hydrophobic in which the following silica (B) has substituted at least part of silanol groups on the silica surface with a hydrocarbon group selected from methyl, ethyl, propyl, methoxy, ethoxy, trimethylsilyl and triethylsilyl groups A rubber composition which is a silanized silica .
JP2002128230A 2002-04-30 2002-04-30 Rubber composition Expired - Fee Related JP4020688B2 (en)

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JP4622512B2 (en) * 2004-12-28 2011-02-02 横浜ゴム株式会社 Rubber composition
JP4566888B2 (en) * 2005-01-28 2010-10-20 住友ゴム工業株式会社 Rubber composition and tire having tread using the same
JP5016215B2 (en) * 2005-11-01 2012-09-05 東洋ゴム工業株式会社 Pneumatic tire
JP5478809B2 (en) * 2007-03-20 2014-04-23 東洋ゴム工業株式会社 Rubber composition and pneumatic tire
JP4875757B2 (en) * 2010-01-13 2012-02-15 住友ゴム工業株式会社 Rubber composition for tire and pneumatic tire

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