JP4499408B2 - Rubber composition for tire - Google Patents
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Description
本発明は、氷雪路面での氷上摩擦性能を向上させたタイヤ用ゴム組成物に関する。 The present invention relates to a rubber composition for tires that has improved on-ice friction performance on icy and snowy road surfaces.
氷雪路面の走行を目的として、スパイクタイヤの使用やタイヤへのチェーンの装着がなされてきたが、粉塵問題などの環境問題が発生するため、これらにかわる氷雪路面走行用タイヤとしてスタッドレスタイヤが開発された。 Spike tires have been used and chains attached to tires for the purpose of running on snowy and snowy roads, but environmental problems such as dust problems have occurred, so studless tires have been developed as tires for snowy and snowy roads that can replace them. It was.
スタッドレスタイヤは一般路面に比べ、氷雪路面では著しく摩擦係数が低下し、滑りやすくなるので、材料面および設計面での工夫がなされている。たとえば、低温特性に優れたジエン系ゴムを配合すること、タイヤ表面の凹凸を変化させ表面エッジ成分を増加させること、および引っ掻き効果のある無機フィラーや繊維を配合することが行なわれてきた（たとえば、特許文献１参照）。 Studless tires have a significantly reduced friction coefficient on icy and snowy road surfaces and are more slippery than ordinary road surfaces, and therefore have been devised in terms of materials and design. For example, blending a diene rubber excellent in low temperature characteristics, changing the unevenness of the tire surface to increase the surface edge component, and blending inorganic fillers and fibers having a scratch effect (for example, , See Patent Document 1).
しかし、依然として、スパイクタイヤに比べ、スタッドレスタイヤの氷雪路面での氷上摩擦性能は充分とはいえず、さらなる改善が求められている。 However, the friction performance on ice on snowy and snowy road surfaces of studless tires is still insufficient as compared with spiked tires, and further improvements are required.
本発明は、氷上摩擦性能を向上させたタイヤ用ゴム組成物を提供することを目的とする。 An object of the present invention is to provide a rubber composition for tires having improved friction performance on ice.
本発明は、天然ゴム、イソプレンゴム、スチレン−ブタジエンゴムおよびブタジエンゴムからなる群から選ばれる１種以上のゴム成分１００重量部に対して、元素半導体および／または化合物半導体を０．５〜１５０重量部含有するタイヤ用ゴム組成物に関する。 The present invention provides an element semiconductor and / or a compound semiconductor in an amount of 0.5 to 150 weights per 100 weight parts of at least one rubber component selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber and butadiene rubber. The present invention relates to a rubber composition for a tire containing part.
また、本発明は、天然ゴム、イソプレンゴム、スチレン−ブタジエンゴムおよびブタジエンゴムからなる群から選ばれる１種以上のゴム成分１００重量部に対し、元素半導体、化合物半導体および遷移金属酸化物からなる群から選ばれる１種以上に、ＩＡ族、IVＡ族、ＶＡ族、IIIＢ族、IVＢ族、ＶＢ族、VIＢ族およびVIIＢ族からなる群から選ばれる１種以上のイオンをドーピングした化合物を０．５〜１５０重量部含有するタイヤ用ゴム組成物に関する。 Further, the present invention relates to a group consisting of an elemental semiconductor, a compound semiconductor and a transition metal oxide with respect to 100 parts by weight of at least one rubber component selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber and butadiene rubber. A compound doped with one or more ions selected from the group consisting of Group IA, Group IVA, Group VA, Group IIIB, Group IVB, Group VB, Group VIB, and Group VIIB to one or more selected from 0.5 It is related with the rubber composition for tires containing -150 weight part.
本発明によれば、元素半導体および／または化合物半導体を、あるいは元素半導体、化合物半導体および遷移金属酸化物からなる群から選ばれる１種以上に、ＩＡ族、IVＡ族、ＶＡ族、IIIＢ族、IVＢ族、ＶＢ族、VIＢ族およびVIIＢ族からなる群から選ばれる１種以上のイオンをドーピングした化合物を、特定量配合することにより、氷上摩擦性能を向上させたタイヤ用ゴム組成物を提供することができる。 According to the present invention, the element semiconductor and / or compound semiconductor, or at least one selected from the group consisting of elemental semiconductors, compound semiconductors, and transition metal oxides, is included in Group IA, Group IVA, Group VA, Group IIIB, IVB To provide a rubber composition for tires having improved friction performance on ice by blending a specific amount of a compound doped with one or more ions selected from the group consisting of Group IV, VB, VIB and VIIB Can do.
本発明のタイヤ用ゴム組成物は、ゴム成分、ならびに元素半導体および／または化合物半導体からなる。 The rubber composition for tires of the present invention comprises a rubber component, and an element semiconductor and / or a compound semiconductor.
ゴム成分は、天然ゴム、イソプレンゴム、スチレン−ブタジエンゴムおよびブタジエンゴムからなる群から選ばれる少なくとも１種からなる。 The rubber component is composed of at least one selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber and butadiene rubber.
天然ゴムとブタジエンゴムを混合して用いた場合、下限としては、ブタジエンゴムの含有量がゴム成分中に５重量％であることが好ましく、１５重量％であることがより好ましい。また、上限としては８０重量％であることが好ましく、７０重量％であることがより好ましい。含有量が５重量％未満では、低温特性を発揮しない傾向があり、８０重量％をこえると、破壊特性が悪化する傾向がある。 When natural rubber and butadiene rubber are mixed and used, the lower limit is that the content of butadiene rubber is preferably 5% by weight and more preferably 15% by weight in the rubber component. Moreover, as an upper limit, it is preferable that it is 80 weight%, and it is more preferable that it is 70 weight%. If the content is less than 5% by weight, the low-temperature characteristics tend not to be exhibited, and if it exceeds 80% by weight, the fracture characteristics tend to deteriorate.
元素半導体としては、ダイヤモンド、シリコン、ゲルマニウム、α−スズ、砒素、アンチモン、ビスマス、セレンおよびテルル（好ましくはシリコン、ゲルマニウム）などがあげられる。 Examples of the elemental semiconductor include diamond, silicon, germanium, α-tin, arsenic, antimony, bismuth, selenium, and tellurium (preferably silicon, germanium).
化合物半導体としては、IIIＢ−ＶＢ族元素からなるＡｌＳｂ、ＧａＰ、ＧａＡｓ、ＧａＳｂ、ＩｎＰ、ＩｎＡｓ、ＩｎＳｂ、IIＢ−VIＢ族元素からなるＺｎＯ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＨｇＳｅ、ＨｇＴｅ、ＩＡ−ＶＢ族元素からなるＣｓ3Ｓｂ、ＩＢ−VIＢ族元素からなるＣｕ2Ｏ、Ａｇ2Ｓ、Ａｇ2Ｓｅ、IIＡ−IVＢ族元素からなるＭｇ2Ｓｉ、Ｍｇ2Ｇｅ、IIＢ−ＶＢ族元素からなるＺｎ3Ａｓ2、ＺｎＳｂ、ＣｄＳｂ、IIIＢ−IVＢ族元素からなるＧａＳ、IVＢ−IVＢ族元素からなるＳｉＣ、IVＢ−VIＢ族元素からなるＳｎＯ2、ＰｂＯ、ＰｂＳ、ＰｂＳｅ、ＰｂＴｅ、ＶＢ−VIＢ族元素からなるＢｉ2Ｓｅ3、Ｂｉ2Ｔｅ3、ＩＢ−IIIＢ−VIＢ族元素からなるＣｕＩｎＳ2、IIＢ−IVＢ−Ｖ族元素からなるＣＤＧＥＰ2などがあげられる。 Examples of compound semiconductors include AlSb, GaP, GaAs, GaSb, InP, InAs, InSb, and IIB-VIB group elements made of IIIB-VB group elements. , Cs 3 Sb composed of Group IA-VB elements, Cu 2 O composed of Group IB-VIB elements, Ag 2 S, Ag 2 Se, Mg 2 Si composed of Group IIA-IVB elements, Mg 2 Ge, Group IIB-VB Zn 3 As 2 consisting of elements, ZnSb, CdSb, GaS consisting of IIIB-IVB group elements, SiC consisting of IVB-IVB group elements, SnO 2 consisting of IVB-VIB group elements, PbO, PbS, PbSe, PbTe, VB- consists Bi 2 Se 3, Bi 2 Te 3, consisting of IB-IIIB-VIB group elements CuInS 2, IIB-IVB-V group elements consisting of group VIB element Such as DGEP 2, and the like.
元素半導体と化合物半導体は、以下の経験則により選ばれる。
（Ｎｅ／Ｎａ）＋ｂ＝８
Ｎｅ：分子式に含まれる価電子数
Ｎａ：分子式に含まれるIVＢ〜VIIＢ族元素の原子数
ｂ：Ｎａとして数えた原子がこれと同種の原子と作る結合の数
Elemental semiconductors and compound semiconductors are selected according to the following rule of thumb.
(Ne / Na) + b = 8
Ne: number of valence electrons included in molecular formula Na: number of atoms of group IVB to VIIB elements included in molecular formula b: number of bonds formed by atoms counted as Na and the same kind of atoms
例えば、シリコンのＮｅは４、Ｎａは１、ｂは４であり、それぞれの値を上記経験則に当てはめると８となる。また、ＩｎＳｂのＮｅは８、Ｎａは１、ｂは０であり、それぞれの値を上記経験則に当てはめると８となる。 For example, Ne of silicon is 4, Na is 1, and b is 4, and when each value is applied to the above empirical rule, it becomes 8. Further, Ne of InSb is 8, Na is 1, and b is 0. When each value is applied to the above empirical rule, it becomes 8.
元素半導体および／または化合物半導体の配合量は、ゴム成分１００重量部に対して、０．５〜１５０重量部である。下限としては、１．０重量部であることが好ましい。配合量が０．５重量部未満では、氷上性能の向上がみられない。また、１５０重量部をこえると、耐摩耗性が悪化する。 The compounding amount of the elemental semiconductor and / or compound semiconductor is 0.5 to 150 parts by weight with respect to 100 parts by weight of the rubber component. The lower limit is preferably 1.0 part by weight. If the blending amount is less than 0.5 parts by weight, no improvement in performance on ice is observed. Moreover, when it exceeds 150 weight part, abrasion resistance will deteriorate.
また、本発明のタイヤ用ゴム組成物は、ゴム成分、ならびに元素半導体、化合物半導体および遷移金属酸化物からなる群から選ばれる１種以上に、ＩＡ族、IVＡ族、ＶＡ族、IIIＢ族、IVＢ族、ＶＢ族、VIＢ族およびVIIＢ族からなる群から選ばれる１種以上のイオンをドーピングした化合物からなる。 The tire rubber composition of the present invention includes a rubber component and at least one selected from the group consisting of an elemental semiconductor, a compound semiconductor, and a transition metal oxide, and includes IA group, IVA group, VA group, IIIB group, IVB. And a compound doped with one or more ions selected from the group consisting of Group VB, Group VIB, VIB and VIIB.
ゴム成分、元素半導体および化合物半導体は、前記したものを用いる。 The rubber components, elemental semiconductors, and compound semiconductors are as described above.
前記遷移金属酸化物としては、Ｖ2Ｏ3、ＴｉＯ、ＴｉＯ2、Ｆｅ2Ｏ3、ＮｉＯなどがあげられる。 Examples of the transition metal oxide include V 2 O 3 , TiO, TiO 2 , Fe 2 O 3 , and NiO.
ＩＡ族イオンとしては、Ｌｉ+、Ｎａ+、Ｋ+、Ｒｂ+、Ｃｓ+、IVＡ族イオンとしては、Ｔｉ4+、Ｚｒ4+、ＶＡ族イオンとしては、Ｔａ5+、Ｖ5+、Ｎｂ5+、IIIＢ族イオンとしては、Ａｌ3+、Ｂ3+、Ｇａ3+、Ｉｎ3+、Ｔｌ3+、IVＢ族イオンとしては、Ｃ4+、Ｓｉ4+、Ｇｅ4+、Ｓｎ4+、Ｐｂ4+、ＶＢ族イオンとしては、Ｎ3-、Ｐ3+、Ａｓ3+、Ｓｂ3+、Ｂｉ3+、VIＢ族イオンとしては、Ｏ2-、Ｓ2-、Ｓｅ2-、Ｔｅ2-があげられる。 The Group IA ions, Li +, Na +, K +, Rb +, Cs +, as the Group IVA ion, Ti 4+, Zr 4+, as the Group VA ions, Ta 5+, V 5+, Nb 5+ and IIIB group ions include Al 3+ , B 3+ , Ga 3+ , In 3+ , Tl 3+ , and IVB group ions include C 4+ , Si 4+ , Ge 4+ and Sn 4+. , Pb 4+ , VB group ions include N 3− , P 3+ , As 3+ , Sb 3+ , Bi 3+ , and VIB group ions include O 2− , S 2− , Se 2− , Te 2-
元素半導体、化合物半導体および遷移金属酸化物からなる群から選ばれる１種以上に、ＩＡ族、IVＡ族、ＶＡ族、IIIＢ族、IVＢ族、ＶＢ族、VIＢ族およびVIIＢ族からなる群から選ばれる１種以上のイオンをドーピングすることで、ドナーあるいはアクセプターとして働き、半導体の性質（ｎ型、ｐ型）を変えるという効果が得られる。 At least one selected from the group consisting of elemental semiconductors, compound semiconductors, and transition metal oxides is selected from the group consisting of Group IA, Group IVA, Group VA, Group IIIB, Group IVB, Group VB, Group VIB, and Group VIIB By doping one or more ions, an effect of acting as a donor or acceptor and changing the properties (n-type, p-type) of the semiconductor can be obtained.
元素半導体、化合物半導体および遷移金属酸化物からなる群から選ばれる１種以上に、前記イオンをドーピングした化合物は、製造が容易であり、コストがかからないという理由から、ＺｎＯにＡｌ3+イオンをドーピングした導電性酸化亜鉛を用いることが好ましい。 A compound in which one or more selected from the group consisting of elemental semiconductors, compound semiconductors, and transition metal oxides is doped with the above ions is easy to manufacture and inexpensive, so that ZnO is doped with Al 3+ ions. It is preferable to use conductive zinc oxide.
元素半導体、化合物半導体および遷移金属酸化物からなる群から選ばれる１種以上に、ＩＡ族、IVＡ族、ＶＡ族、IIIＢ族およびIVＢ族からなる群から選ばれる１種以上のイオンをドーピングした化合物の配合量は、ゴム成分１００重量部に対して、０．５〜１５０重量部である。配合量の下限としては、１．０重量部であることが好ましく、上限としては５０重量部であることが好ましい。配合量が０．５重量部未満では、氷上摩擦性能が充分に得られない。また、１５０重量部をこえると、耐摩耗性が低下する。 A compound obtained by doping one or more selected from the group consisting of elemental semiconductors, compound semiconductors, and transition metal oxides with one or more ions selected from the group consisting of Group IA, Group IVA, Group VA, Group IIIB, and Group IVB Is blended in an amount of 0.5 to 150 parts by weight per 100 parts by weight of the rubber component. The lower limit of the amount is preferably 1.0 part by weight, and the upper limit is preferably 50 parts by weight. If the blending amount is less than 0.5 parts by weight, the friction performance on ice cannot be sufficiently obtained. Moreover, when it exceeds 150 weight part, abrasion resistance will fall.
本発明のゴム組成物には、補強剤（充填剤）、加硫剤（架橋剤）、加硫促進剤、各種オイル、老化防止剤、軟化剤、可塑剤、カップリング剤などのタイヤ用または一般のゴム組成物用に配合される各種配合剤および添加剤を配合することができる。また、これらの配合剤、添加剤の配合量も一般的な量とすることができる。 The rubber composition of the present invention includes a reinforcing agent (filler), a vulcanizing agent (crosslinking agent), a vulcanization accelerator, various oils, an anti-aging agent, a softening agent, a plasticizer, a coupling agent, etc. Various compounding agents and additives blended for general rubber compositions can be blended. Moreover, the compounding quantity of these compounding agents and additives can also be made into a general quantity.
補強剤としては、主にカーボンブラックを用いることが好ましい。 As the reinforcing agent, it is preferable to mainly use carbon black.
カーボンブラックのヨウ素吸着量は、３０〜３００ｍｇ／ｇであることが好ましい。ヨウ素吸着量の下限としては、６０ｍｇ／ｇであることがより好ましく、上限としては、２００ｍｇ／ｇであることがより好ましい。ヨウ素吸着量が３０ｍｇ／ｇ未満では、補強性が少ない傾向があり、３００ｍｇ／ｇをこえると、加工性が悪化する傾向がある。 The iodine adsorption amount of carbon black is preferably 30 to 300 mg / g. The lower limit of the iodine adsorption amount is more preferably 60 mg / g, and the upper limit is more preferably 200 mg / g. If the iodine adsorption amount is less than 30 mg / g, the reinforcing property tends to be less, and if it exceeds 300 mg / g, the workability tends to deteriorate.
カーボンブラックの配合量は、ゴム成分１００重量部に対して５〜２００重量部であることが好ましい。配合量が５重量部未満では、補強効果が得られない傾向があり、２００重量部をこえると加工性が低下する傾向がある。 The compounding amount of carbon black is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the rubber component. If the blending amount is less than 5 parts by weight, the reinforcing effect tends not to be obtained, and if it exceeds 200 parts by weight, the workability tends to be lowered.
本発明のタイヤは、本発明のタイヤ用ゴム組成物を用いて通常の方法で製造される。すなわち、必要に応じて前記添加剤を配合した本発明のタイヤ用ゴム組成物を、未加硫の段階でタイヤの各部材の形状にあわせて押出し加工し、タイヤ成型機上にて通常の方法で成形することにより、未加硫タイヤを形成する。この未加硫タイヤを加硫機中で加熱加圧することによりタイヤを得る。 The tire of the present invention is produced by a usual method using the tire rubber composition of the present invention. That is, if necessary, the rubber composition for a tire according to the present invention blended with the additive is extruded in accordance with the shape of each member of the tire at an unvulcanized stage, and is then subjected to a normal method on a tire molding machine. An unvulcanized tire is formed by molding with. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.
以下、実施例にもとづいて本発明を詳細に説明するが、本発明はこれらのみに制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not restrict | limited only to these.
実施例および比較例で使用した原料を以下にまとめて示す。
天然ゴム：テックビーハング社製のＲＳＳ＃３
ブタジエンゴム：宇部興産（株）製のＵＢＥＰＯＬ−ＢＲ１５０Ｂ
カーボンブラック：昭和キャボット（株）製のショウワブラックＮ２２０（ヨウ素吸着量：１１８ｍｇ／ｇ）
オイル：出光興産（株）製のダイナプロセスオイルＰＳ３２３
ワックス：大内新興化学工業（株）製のサンノックワックス
老化防止剤：大内新興化学工業（株）製のノクラック６Ｃ（Ｎ−１，３−ジメチルブチル−Ｎ’−フェニル−ｐ−フェニレンジアミン）
ステアリン酸：日本油脂（株）製のステアリン酸
亜鉛華：三井金属鉱業（株）製の亜鉛華１号
導電性酸化亜鉛：ハクスイテック（株）製の導電性酸化亜鉛２３−Ｋ
硫黄：鶴見化学工業（株）製の粉末硫黄
加硫促進剤１：大内新興化学工業（株）製のノクセラーＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアジル−スルフェンアミド）
加硫促進剤２：大内新興化学工業（株）製のノクセラーＤ（ジフェニルグアニジン）
The raw materials used in the examples and comparative examples are summarized below.
Natural rubber: RSS # 3 manufactured by Tech Bee Hang
Butadiene rubber: UBEPOL-BR150B manufactured by Ube Industries, Ltd.
Carbon black: Showa Black N220 manufactured by Showa Cabot Co., Ltd. (Iodine adsorption amount: 118 mg / g)
Oil: Idemitsu Kosan Co., Ltd. Dyna Process Oil PS323
Wax: Sunnock wax anti-aging agent manufactured by Ouchi Shinsei Chemical Industry Co., Ltd .: NOCRACK 6C (N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine) manufactured by Ouchi Shinko Chemical Industry Co., Ltd. )
Stearic acid: Zinc stearate manufactured by Nippon Oil & Fats Co., Ltd .: Zinc Hana No. 1 conductive zinc oxide manufactured by Mitsui Mining & Smelting Co., Ltd .: Conductive zinc oxide 23-K manufactured by Hakusitec Co., Ltd.
Sulfur: powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. 1: Noxeller CZ (N-cyclohexyl-2-benzothiazyl-sulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator 2: Noxeller D (diphenylguanidine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
実施例１〜３および比較例 Examples 1-3 and comparative examples
表１に示す、硫黄、加硫促進剤を除く配合成分を、１．７リットルの密閉型バンバリーミキサーを用いて３〜５分間混練りし、温度が１５０℃以上に達した時点で配合ゴムを排出し、ベース練りゴムとした。ベース練りゴム、硫黄および加硫促進剤をオープンロールで混練りし、加硫することによりゴム組成物を得た。 The compounding ingredients excluding sulfur and vulcanization accelerator shown in Table 1 are kneaded for 3 to 5 minutes using a 1.7 liter closed Banbury mixer, and when the temperature reaches 150 ° C. or higher, the compounded rubber is added. Drained and used as base kneaded rubber. A rubber composition was obtained by kneading the base kneaded rubber, sulfur and vulcanization accelerator with an open roll and vulcanizing.
（氷上摩擦試験）
温度制御された恒温室内に設置された氷面上にゴム試験片を一定加重で押しつけ、一定速度で滑らせるときの抵抗（摩擦力）を検出することにより行なった。試験条件は、氷温および恒温室温度を−２℃および−５℃に設定し、速度２０ｋｍ／ｈ、接地圧力２ｋｇ／ｃｍ2となるように加重をかけた。なお、結果は、比較例を１００とし、指数表示した。数値が大きいほど、摩擦力が高いことを示す。
(Friction test on ice)
The test was performed by pressing a rubber test piece with a constant load on an ice surface installed in a temperature-controlled temperature-controlled room and detecting the resistance (friction force) when sliding at a constant speed. As test conditions, ice temperature and temperature-controlled room temperature were set to −2 ° C. and −5 ° C., and weight was applied so that the speed was 20 km / h and the ground pressure was 2 kg / cm 2 . The results are shown as an index with a comparative example of 100. The larger the value, the higher the friction force.
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| JP2003429574A JP4499408B2 (en) | 2003-12-25 | 2003-12-25 | Rubber composition for tire |
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| JP4499408B2 true JP4499408B2 (en) | 2010-07-07 |
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| JP4630013B2 (en) * | 2004-07-02 | 2011-02-09 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09315106A (en) * | 1996-05-30 | 1997-12-09 | Toto Ltd | Tire and brake pad |
| WO2002053634A1 (en) * | 2001-01-02 | 2002-07-11 | Societe De Technologie Michelin | Rubber composition made with diene elastomer and a reinforcing silicon carbide |
| JP2002234947A (en) * | 2001-02-09 | 2002-08-23 | Hakusui Tech Co Ltd | Conductive material compounded rubber composition and its preparation process |
| JP2005132865A (en) * | 2003-10-28 | 2005-05-26 | Kyushu Hakusui Corp | Rubber composition comprising inorganic reinforcing agent compounded therein |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2467920A1 (en) * | 2001-12-10 | 2003-06-19 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09315106A (en) * | 1996-05-30 | 1997-12-09 | Toto Ltd | Tire and brake pad |
| WO2002053634A1 (en) * | 2001-01-02 | 2002-07-11 | Societe De Technologie Michelin | Rubber composition made with diene elastomer and a reinforcing silicon carbide |
| JP2002234947A (en) * | 2001-02-09 | 2002-08-23 | Hakusui Tech Co Ltd | Conductive material compounded rubber composition and its preparation process |
| JP2005132865A (en) * | 2003-10-28 | 2005-05-26 | Kyushu Hakusui Corp | Rubber composition comprising inorganic reinforcing agent compounded therein |
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