JP2763251B2 - Pneumatic tire - Google Patents
Pneumatic tireInfo
- Publication number
- JP2763251B2 JP2763251B2 JP5118671A JP11867193A JP2763251B2 JP 2763251 B2 JP2763251 B2 JP 2763251B2 JP 5118671 A JP5118671 A JP 5118671A JP 11867193 A JP11867193 A JP 11867193A JP 2763251 B2 JP2763251 B2 JP 2763251B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- parts
- average
- pneumatic tire
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、空気入りタイヤに関
し、更に詳しくは氷上及び雪上走行性能、特に耐摩耗性
の低下を抑えながら又は実質上低下させることなく、氷
上及び雪上走行における初期及び経時性能を改良した空
気入りタイヤに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pneumatic tire, and more particularly to a pneumatic tire, and more particularly, to the initial and temporal running on ice and snow while suppressing or substantially reducing the running performance on ice and snow. The present invention relates to a pneumatic tire with improved performance.
【０００２】[0002]
【従来の技術】従来、積雪寒冷地において、冬期時に自
動車が走行する場合には、タイヤにスパイクを打ち込ん
だスパイクタイヤを用いるか又はタイヤの外周にタイヤ
チェーンを装着して雪上・氷上路での安全を確保してい
る。しかしながら、スパイクタイヤ又はタイヤチェーン
を装着したタイヤでは、道路の摩耗や損傷が発生し易
く、それが粉塵となって公害を引き起こし、大きな環境
問題となる。このような安全問題と環境問題とを解決す
るために、スパイクやチェーンを使用せずに雪上路及び
氷上路における制動性、駆動性を有したスタッドレスタ
イヤが現在急速に普及しつつある。2. Description of the Related Art Conventionally, when a car travels in winter in a snowy and cold area, a spike tire having a spike applied to the tire is used, or a tire chain is mounted on the outer periphery of the tire, and the tire is mounted on a snowy or icy road. Safety is ensured. However, spike tires or tires equipped with a tire chain are liable to cause road abrasion and damage, which becomes dust and causes pollution, which is a major environmental problem. In order to solve such a safety problem and an environmental problem, studless tires having braking and driving properties on snowy roads and icy roads without using spikes or chains are now rapidly spreading.
【０００３】このスタッドレスタイヤとして、氷上摩擦
力を向上させるために凝着効果（トレッド表面が氷路面
に着いてその氷路面の表面形状に追随すること）の高い
低硬度加硫ゴム組成物をマトリックスゴムに配合してト
レッド部を構成したタイヤが提案されている（特開昭63
-92659号公報、特開昭 63-172750号公報、特開平 4-382
09号公報及び特開平 3-10907号公報など参照）。In order to improve the frictional force on ice, a low-hardness vulcanized rubber composition having a high adhesion effect (that the tread surface reaches an ice road surface and follows the surface shape of the ice road surface) is used as a matrix for the studless tire. There has been proposed a tire in which a tread portion is formed by mixing with rubber (Japanese Patent Application Laid-Open No. Sho 63/63).
-92659, JP-A-63-172750, JP-A-4-382
No. 09 and Japanese Patent Application Laid-Open No. 3-10907).
【０００４】しかしながら、特開昭６３−９２６５９号
公報にはガラス転移点が−50℃以下で粒径1000μｍ以下
の軟らかい粉末加硫ゴムを配合した空気入りタイヤが開
示されているが、マトリックスゴムの凝着効果が十分で
なく、氷上性能が必ずしも満足いくものではなかった。However, Japanese Patent Application Laid-Open No. 63-92659 discloses a pneumatic tire containing a soft powder vulcanized rubber having a glass transition point of -50 ° C. or less and a particle size of 1000 μm or less. The adhesion effect was not sufficient, and the performance on ice was not always satisfactory.
【０００５】一方、特開昭６０−１３９５０３号公報に
は高硬度ゴム粒子を配合したトレッドゴムを用いるスタ
ッドレスタイヤが開示されているが、ゴム粒子自体の凝
着効果が低いため、氷上性能が必ずしも満足のいくもの
ではなかった。On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 60-139503 discloses a studless tire using a tread rubber containing high-hardness rubber particles. However, since the adhesion effect of the rubber particles themselves is low, the performance on ice is not necessarily improved. It was not satisfactory.
【０００６】更に、特開平４−３８２０９号公報には低
硬度ゴム粒子及び短繊維を配合することが記載されてい
るが、ゴム粒子の粒径が比較的大きいため、耐摩耗性及
び混合加工性の点で不充分なものであった。また特開平
３−１０９０７号公報には予め加硫した平均粒径 0.5〜
３mmの低硬度加硫ゴム組成物をマトリックスゴムに配合
して氷上性能を改良することが提案されているが、この
空気入りタイヤもマトリックスゴムの凝着効果が十分で
なく、氷上性能が必ずしも満足いくものではない。Further, Japanese Patent Application Laid-Open No. 4-38209 discloses that low-hardness rubber particles and short fibers are compounded. However, since the rubber particles have a relatively large particle size, wear resistance and mixing processability are reduced. Was inadequate. JP-A-3-10907 discloses a pre-vulcanized average particle size of 0.5 to 0.5.
It has been proposed to improve the performance on ice by blending a 3 mm low hardness vulcanized rubber composition with the matrix rubber, but this pneumatic tire does not have sufficient adhesion effect of the matrix rubber, and the performance on ice is not always satisfactory. It doesn't work.
【０００７】[0007]
【発明が解決しようとする課題】以上の通り、従来技術
においては氷上摩擦力が十分でなく、また混合加工性が
困難であるという問題があった。従って、本発明は、こ
のような従来技術の問題を解消し、特に氷上及び雪上走
行の初期及び経時性能を著しく改良すると共に、耐摩耗
性及び混合加工性に優れた空気入りタイヤを提供するこ
とを目的とする。As described above, in the prior art, there was a problem that the frictional force on ice was not sufficient and the mixing processability was difficult. Accordingly, the present invention is to solve such a problem of the prior art, and to provide a pneumatic tire excellent in abrasion resistance and mixing workability, in particular, while remarkably improving the initial and aging performance of traveling on ice and snow. With the goal.
【０００８】[0008]
【課題を解決するための手段】本発明に従えば、トレッ
ド部がマトリックスゴムと低硬度粉末ゴムと中空微粒子
と液状ポリマーと短繊維とから構成され、前記低硬度粉
末ゴムは平均粒径１０００μｍ未満で、低硬度粉末ゴム
中のゴム分１００重量部当りカーボン２０重量部以下を
含むか又は含まないで、その配合量がマトリックスゴム
１００重量部当り１〜１０重量部であり、中空微粒子が
平均粒径１０〜１２０μｍでかつ平均肉厚０．１〜１５
μｍであり、液状ポリマーが平均分子量６，０００〜６
０，０００の低分子量ジエン系ポリマーでその配合量が
マトリックスゴム１００重量部当り５〜５０重量部であ
り、さらに前記短繊維がアスペクト比（長さ／径の比）
１０〜１０００である空気入りタイヤが提供される。According to the present invention, the tread portion is composed of a matrix rubber, a low hardness powder rubber, hollow fine particles, a liquid polymer and short fibers, and the low hardness powder rubber has an average particle diameter of less than 1000 μm. With low hardness powder rubber
With or without carbon 20 parts by weight or less per 100 parts by weight of the rubber component, the compounding amount is 1 to 10 parts by weight per 100 parts by weight of the matrix rubber, and the hollow fine particles have an average particle diameter of 10 to 120 μm and Average thickness 0.1-15
μm, and the liquid polymer has an average molecular weight of 6,000 to 6
A low molecular weight diene-based polymer having a molecular weight of 5,000 to 50 to 50 parts by weight per 100 parts by weight of a matrix rubber, and a short fiber having an aspect ratio (length / diameter ratio).
A number of pneumatic tires are provided.
【０００９】本発明に係る空気入りタイヤの構造には特
に限定はなく、従来から知られている任意の構造の空気
入りタイヤ、更には現在開発中の各種構造の空気入りタ
イヤ構造とすることができ、要はトレッド部を前記構成
のものとすればよい。The structure of the pneumatic tire according to the present invention is not particularly limited, and any pneumatic tire having any conventionally known structure, or any other pneumatic tire structures currently under development may be used. What is essential is that the tread portion has the above configuration.
【００１０】以下、その一例を添付図１を参照して説明
する。図１は本発明の空気入りタイヤの好ましい一例の
子午線方向半断面説明図である。図１において、本発明
の空気入りタイヤＡは、左右一対のビード部11，11とこ
れらビード部11，11に連結する左右一対のサイドウォー
ル部12，12とこれらサイドウォール部12，12間に配され
るトレッド部13からなる。左右一対のビード部11，11間
にはカーカス層14が装架されており、トレッド部13にお
いては、この外周を取り囲むようにベルト層15が配置さ
れている。10はトレッド表面である。An example will be described below with reference to FIG. FIG. 1 is a half sectional view in the meridian direction of a preferred example of the pneumatic tire of the present invention. In FIG. 1, a pneumatic tire A of the present invention includes a pair of left and right bead portions 11, a pair of left and right side wall portions 12, 12 connected to the bead portions 11, 11, and between the side wall portions 12, 12. The tread portion 13 is provided. A carcass layer 14 is mounted between the pair of left and right bead portions 11, 11, and a belt layer 15 is arranged in the tread portion 13 so as to surround the outer periphery. 10 is a tread surface.
【００１１】本発明では、トレッド部13は、前述の如
く、平均粒径が1000μｍ未満の低硬度加硫ゴム組成物、
平均粒径が10〜 120μｍで平均肉厚が 0.1〜15μｍの中
空微粒子、平均分子量が 6,000〜60,000の低分子量ジエ
ン系ポリマー及びアスペクト比が10〜1000の短繊維をマ
トリックスゴムに配合した配合物から構成される。In the present invention, as described above, the tread portion 13 has a low hardness vulcanized rubber composition having an average particle size of less than 1000 μm,
A mixture of hollow fine particles having an average particle size of 10 to 120 μm and an average thickness of 0.1 to 15 μm, a low molecular weight diene polymer having an average molecular weight of 6,000 to 60,000, and a short fiber having an aspect ratio of 10 to 1000 is mixed with a matrix rubber. Be composed.
【００１２】本発明においてトレッド部を構成するゴム
配合物に配合されるマトリックスゴムの種類は特に限定
されるものではないが、好ましくは、天然ゴム、ポリイ
ソプレンゴム、ポリブタジエンゴム、スチレン−ブタジ
エン共重合体ゴム、又はこれらをブレンドしたものが用
いられる。このマトリックスゴムには、常法により、カ
ーボンブラック、軟化剤等の配合剤が適宜配合される。In the present invention, the type of the matrix rubber compounded in the rubber compound constituting the tread portion is not particularly limited, but is preferably a natural rubber, a polyisoprene rubber, a polybutadiene rubber, a styrene-butadiene copolymer. A united rubber or a blend thereof is used. A compounding agent such as carbon black and a softening agent is appropriately compounded in the matrix rubber by an ordinary method.
【００１３】カーボンブラックとしては、トレッド用と
して通常使用されているものであれば、特にその種類は
限定されない。カーボンブラックの配合量は原料ゴム 1
00重量部に対して40〜 100重量部が好ましく、40重量部
未満では補強性で劣り、耐摩耗性が低下する傾向にある
ので好ましくない。 100重量部を超えると発熱が高くな
る傾向にあるので好ましくない。The type of carbon black is not particularly limited as long as it is commonly used for treads. Raw material rubber 1
It is preferably from 40 to 100 parts by weight with respect to 00 parts by weight, and if the amount is less than 40 parts by weight, the reinforcing property is inferior and the abrasion resistance tends to decrease. Exceeding 100 parts by weight is not preferred because heat generation tends to increase.
【００１４】本発明においてトレッド部を構成するゴム
配合物には平均粒径が1000μｍ未満、好ましくは10〜 4
00μｍの低硬度粉末ゴムを配合する。この平均粒径が10
00μｍを超えると、空気入りタイヤの耐摩耗性が低下
し、また空気入りタイヤ製造時の混合加工性が劣るので
好ましくない。In the present invention, the rubber compound constituting the tread portion has an average particle size of less than 1000 μm, preferably 10 to 4 μm.
A low hardness powder rubber of 00 μm is compounded. This average particle size is 10
If it exceeds 00 μm, the abrasion resistance of the pneumatic tire is reduced, and the mixing processability during the production of the pneumatic tire is poor.
【００１５】低硬度粉末ゴムはタイヤ加硫後もその形状
が保たれるよう、予めゴム配合物を加硫したものが好ま
しく、原料ゴムとしては、例えば、天然ゴム、ポリイソ
プレンゴム、ポリブタジエンゴム、スチレン−ブタジエ
ン共重合体ゴム、ハロゲン化ブチルゴム、又はこれらの
２種以上をブレンドしたものを使用することができる。
カーボンブラックは配合しても配合しなくてもよいが、
配合する場合にはゴム100重量部当り20重量部以下とす
るのがよい。これはカーボンブラックの配合量が増加す
ると、マトリックスゴムとのモジュラス差が小さくな
り、また凝着効果が低下するため氷上性能などが改良さ
れないからである。なお、カーボンブラックは配合しな
い方が好ましい。Preferably, the low hardness powder rubber is obtained by vulcanizing a rubber compound in advance so that the shape is maintained even after vulcanizing the tire. Examples of the raw rubber include natural rubber, polyisoprene rubber, polybutadiene rubber, and the like. Styrene-butadiene copolymer rubber, halogenated butyl rubber, or a blend of two or more of these can be used.
Carbon black may or may not be blended,
When blended, the amount is preferably not more than 20 parts by weight per 100 parts by weight of rubber. This is because when the amount of carbon black is increased, the difference in modulus from the matrix rubber is reduced, and the adhesion effect is reduced, so that the performance on ice and the like are not improved. In addition, it is preferable not to mix carbon black.
【００１６】本発明においてトレッド部を構成するゴム
配合物中における低硬度粉末ゴムの配合量はマトリック
スゴム 100重量部当り１〜10重量部であり、２〜４重量
部が特に好ましい。この配合量が１重量部未満では氷上
性能の改良が不充分であり、逆に10重量部を超えると耐
摩耗性が低下するので好ましくない。In the present invention, the compounding amount of the low hardness powder rubber in the rubber compound constituting the tread portion is 1 to 10 parts by weight, particularly preferably 2 to 4 parts by weight, per 100 parts by weight of the matrix rubber. If the amount is less than 1 part by weight, the performance on ice is insufficiently improved, and if it exceeds 10 parts by weight, the abrasion resistance is lowered, which is not preferable.
【００１７】本発明においてトレッド部を構成するゴム
配合物中に使用する中空微粒子は、平均粒径10〜 120μ
ｍ、平均肉厚 0.1〜15μｍ、平均比重 0.2〜1.0 のもの
である。中空微粒子の平均粒径が10μｍ未満では氷雪路
走行性能の向上が不十分となり、 120μｍを超えるとト
レッド表面の耐摩耗性、耐久性等が悪化する傾向にあ
る。平均肉厚が 0.1μｍ未満では混合作業中に中空微粒
子が壊れ易くなり、結果的に氷雪路走行性能の向上が不
十分となり、逆に平均肉厚が10μｍを超えると中空微粒
子の中空部分の体積が少なくなり、氷雪路走行性能の向
上が不十分となる。平均比重は、それ程厳格ではない
が、平均比重が 0.2未満では混合作業中に中空微粒子が
壊れ易くなり、1.0 を超えると中空微粒子の中空部分の
体積が少なくなることになり、目的の氷雪路走行性能の
向上が不十分となる。In the present invention, the hollow fine particles used in the rubber compound constituting the tread portion have an average particle diameter of 10 to 120 μm.
m, average thickness 0.1-15 μm, average specific gravity 0.2-1.0. If the average particle diameter of the hollow fine particles is less than 10 μm, the improvement in running performance on ice and snow roads becomes insufficient, and if it exceeds 120 μm, the abrasion resistance and durability of the tread surface tend to deteriorate. When the average thickness is less than 0.1 μm, the hollow fine particles are easily broken during the mixing operation, and as a result, the performance on ice and snow roads is insufficiently improved. Conversely, when the average thickness exceeds 10 μm, the volume of the hollow portion of the hollow fine particles is reduced. And the improvement of running performance on ice and snowy roads becomes insufficient. Although the average specific gravity is not so strict, if the average specific gravity is less than 0.2, the hollow fine particles are easily broken during the mixing operation, and if the average specific gravity is more than 1.0, the volume of the hollow portion of the hollow fine particles becomes small, and the intended traveling on ice and snow roads is reduced. Insufficient performance improvement.
【００１８】この中空微粒子としては、例えば、ガラス
バルーン、シラスバルーン、フライアッシュ、炭素質バ
ルーンなどの無機質微小中空体、フェノール樹脂、エポ
キシ樹脂、尿素樹脂等の樹脂系の微小中空体などの公知
のものを用いることができる。中空微粒子のゴムに対す
る配合量にはそれ程限定はないが、マトリックスゴム10
0重量部に対し５重量部以下が好ましく、２重量部以下
が更に好ましい。この配合量は少なくても低硬度粉末ゴ
ムとの相乗効果により目的とする氷雪路走行性能は十分
改善される。逆に多過ぎると、目的とする改良効果はあ
まり変化せず、トレッドの耐摩耗性、耐久性等が悪化し
てしまうおそれがある。Examples of the hollow fine particles include known fine hollow bodies such as inorganic fine hollow bodies such as glass balloons, shirasu balloons, fly ash, and carbonaceous balloons, and fine resin hollow bodies such as phenol resins, epoxy resins, and urea resins. Can be used. There is no particular limitation on the compounding amount of the hollow fine particles with respect to the rubber.
It is preferably at most 5 parts by weight, more preferably at most 2 parts by weight, based on 0 parts by weight. Even if the compounding amount is small, the target running performance on ice and snowy roads is sufficiently improved by the synergistic effect with the low hardness powder rubber. Conversely, if the amount is too large, the desired improvement effect does not change much, and the abrasion resistance and durability of the tread may be deteriorated.
【００１９】本発明においてトレッド部を構成するゴム
配合物中に軟化剤として使用する液状ポリマー、即ち低
分子量ジエン系ポリマーは、ＧＰＣ（gel permeation c
hromatography ：ゲルパーミエーションクロマトグラフ
ィー）で測定し、ポリスチレンに換算した分子量が６，
０００〜６０，０００の低分子量ジエン系ポリマーであ
る。ＧＰＣの測定条件は以下の通りである。 溶媒 ： ＴＨＦ（テトラヒドロフラン） 濃度 ： ０．０５重量％ 流速 ： １ml／min カラム温度 ： ４０℃ カラム ： ウルトラスタイラジェル（商品名） この低分子量ジエン系ポリマーの分子量が６，０００未
満では、タイヤのアンダートレッド部への移行性があ
り、配合の目的が達せられないので好ましくなく、逆に
分子量が６０，０００を超えると、軟化効果が小さくな
り、目的とする物性が得られないので好ましくない。In the present invention, the liquid polymer used as a softening agent in the rubber compound constituting the tread portion, that is, the low molecular weight diene polymer is GPC (gel permeation c).
hromat og raphy: measured by gel permeation chromatography and the molecular weight converted to polystyrene is 6,
It is a low molecular weight diene polymer having a molecular weight of 000 to 60,000. GPC measurement conditions are as follows. Solvent: THF (tetrahydrofuran) Concentration: 0.05% by weight Flow rate: 1 ml / min Column temperature: 40 ° C. Column: Ultra Styragel (trade name) If the molecular weight of this low molecular weight diene polymer is less than 6,000, tire under It is not preferable because the compound has a migration property to the tread portion and the purpose of the blending cannot be achieved. Conversely, if the molecular weight exceeds 60,000, the softening effect decreases and the desired physical properties cannot be obtained, which is not preferable.
【００２０】本発明において用いる低分子量ジエン系ポ
リマーは原料ゴムの表面からにじみ出す現象（ブリー
ド）がなければ任意のジエン系ポリマー（例えばブタジ
エン重合体、イソプレン重合体、アクリルニトリルブタ
ジエン共重合体、芳香族ビニルブタジエン共重合体な
ど）とすることができ、好ましいジエン系ポリマーはシ
ス1.4 結合が70％以上、好ましくは75％以上のブタジエ
ン重合体である。これはシス結合が70％未満では低温硬
度が高く（硬く）なって氷上性能が落ちる傾向にあるか
らである。また、本発明に用いる低分子量ジエン系ポリ
マーは末端に一般式＞Ｃ＝Ｎ+ ＜官能基（例えばＮ−メ
チル−２−ピロリドン、Ｎ−メチル−β−プロピオラク
タム等）をつけたものが一般的に知られているが、本発
明で得られる効果は低分子量ポリマーの末端の構造には
依存せず、その基本構造によって得られるものである。
従って末端官能基があってもよいし、またその種類も問
わない。The low molecular weight diene polymer used in the present invention may be any diene polymer (for example, butadiene polymer, isoprene polymer, acrylonitrile butadiene copolymer, fragrance) if there is no bleeding from the surface of the raw rubber. Group-butadiene copolymer), and a preferred diene-based polymer is a butadiene polymer having a cis 1.4 bond of 70% or more, preferably 75% or more. This is because if the cis-bond is less than 70%, the low-temperature hardness tends to be high (hard) and the performance on ice tends to decrease. The low-molecular-weight diene polymer used in the present invention has a terminal having a general formula> C = N + <functional group (for example, N-methyl-2-pyrrolidone, N-methyl-β-propiolactam) at the terminal. Although generally known, the effects obtained in the present invention do not depend on the structure of the terminal of the low molecular weight polymer, but can be obtained by the basic structure thereof.
Therefore, there may be a terminal functional group, and the type thereof does not matter.
【００２１】本発明に従えば、分子量 6,000〜60,000、
好ましくは 6,000〜50,000の低分子量ジエン系ポリマー
をマトリックスゴム 100重量部当り５〜50重量部、好ま
しくは５〜30重量部配合する。この低分子量ジエン系ポ
リマーの配合量が５重量部未満では配合量が少な過ぎて
効果がなく、また50重量部を超えると未加硫ゴムのムー
ニー粘度が低下するため加工性が悪くなり実用的でな
い。According to the present invention, a molecular weight of 6,000 to 60,000,
Preferably, 6,000 to 50,000 low molecular weight diene polymers are blended in an amount of 5 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the matrix rubber. If the amount of the low-molecular-weight diene polymer is less than 5 parts by weight, the amount is too small to have no effect, and if it exceeds 50 parts by weight, the Mooney viscosity of the unvulcanized rubber decreases, resulting in poor processability and practical use. Not.
【００２２】本発明においてトレッド部を構成するゴム
配合物には更にアスペクト比が10〜1000、好ましくは10
〜300 の短繊維が配合される。かかる短繊維としては、
例えば、綿、絹などの天然繊維、セルロース系繊維、ポ
リアミド系繊維、ポリエステル系繊維、ビニロン等のポ
リビニルアルコール系繊維などの化学繊維、カーボン繊
維等の無機繊維を用いることができる。好ましくはナイ
ロン繊維に代表されるポリアミド系繊維、もしくはレー
ヨン等のセルロース系の短繊維がよい。特に、例えばγ
−アミノプロピルトリメトキシシランで表面処理した平
均長30μｍ、平均径 0.3μｍのナイロン６繊維を天然ゴ
ム 100重量部に対し50重量部配合したマスターバッチ
（宇部興産（株）よりUBEPOL-HE として市販）を好適に
用いることができる。スチール短繊維、銅系金属短繊維
等の金属短繊維を用いてもよい。なお、これらの短繊維
は２種以上併用してもよい。In the present invention, the rubber compound constituting the tread portion further has an aspect ratio of 10 to 1000, preferably 10 to 1000.
Up to 300 short fibers are incorporated. As such short fibers,
For example, natural fibers such as cotton and silk, cellulosic fibers, polyamide fibers, polyester fibers, chemical fibers such as polyvinyl alcohol fibers such as vinylon, and inorganic fibers such as carbon fibers can be used. Preferably, polyamide fibers typified by nylon fibers or cellulosic short fibers such as rayon are used. In particular, for example, γ
A masterbatch prepared by blending 50 parts by weight of nylon 6 fiber having an average length of 30 μm and an average diameter of 0.3 μm, surface-treated with aminopropyltrimethoxysilane, to 100 parts by weight of natural rubber (commercially available as UBEPOL-HE from Ube Industries, Ltd.) Can be suitably used. Short metal fibers such as steel short fibers and copper-based metal short fibers may be used. In addition, you may use these short fibers 2 or more types together.
【００２３】この短繊維のゴムに対する配合量は、特に
は限定されないが、マトリックスゴム 100重量部に対し
１〜15重量部がよく、特に１〜５重量部が好ましい。本
発明では、この短繊維がトレッド部13のブロック表面及
び側面に沿って配向している。短繊維の配向の様子を図
２及び図３に示す。図２は本発明の空気入りタイヤの一
例のトレッド部の平面視説明図、図３はそのＫ−Ｋ’線
断面図である。図２及び図３に示すように短繊維17は、
トレッド部13のブロック16の表面ａ及び側面ｂに沿って
タイヤ周方向ＥＥ’に配向している。このように、短繊
維のほとんどはトレッド部のブロック表面及び側面に沿
って（周方向に沿って）配向するのが好ましい。The amount of the short fibers to be mixed with the rubber is not particularly limited, but is preferably 1 to 15 parts by weight, particularly preferably 1 to 5 parts by weight, per 100 parts by weight of the matrix rubber. In the present invention, the short fibers are oriented along the block surface and side surface of the tread portion 13. FIGS. 2 and 3 show how the short fibers are oriented. FIG. 2 is an explanatory plan view of a tread portion of an example of the pneumatic tire of the present invention, and FIG. 3 is a sectional view taken along line KK 'of FIG. As shown in FIGS. 2 and 3, the short fibers 17
It is oriented in the tire circumferential direction EE 'along the surface a and the side surface b of the block 16 of the tread portion 13. As described above, it is preferable that most of the short fibers are oriented along the block surface and the side surface of the tread portion (along the circumferential direction).
【００２４】このような短繊維の配向を得るためには、
トレッド部１３の押出成形に際して、ある程度のアスペ
クト比を持った繊維はマトリックスであるゴムの流れ方
向に並ぶ傾向があることを利用する。このような傾向
は、タイヤが加硫されるとき、モールドの突起部によっ
て未加硫トレッドゴムがモールドに沿って流れ、結果と
してモールド突起部に沿って短繊維１７が配向する。こ
れにより、トレッド部１３のブロック１６の表面ａ及び
側面ｂに沿って短繊維１７が配向することになる。ただ
し、短繊維１７は、一定のアスペクト比を有さないと、
トレッドゴム中でランダムに配列し、配向が行われない
ことになる。このため、短繊維は、アスペクト比１０〜
１０００、好ましくは１０〜３００であることが必要で
あり、好ましくは平均直径０．０５μｍ以上、平均長さ
１〜５０００μｍであるのが良く、更に好ましくは短繊
維は耐摩耗性の低下を防止し、かつ配向性に優れるの
で、０．０５〜０．８μｍの平均直径と１〜１００μｍ
の範囲内の平均長を有したポリアミド系短繊維である。
なお、アスペクト比が１０００を超えるとマトリックス
ゴム中における短繊維の分散が悪くなって充分な配向が
得られないので好ましくない。In order to obtain such short fiber orientation,
Upon extrusion of the tread portion 13, a certain degree of Asupe
The fact is that fibers having a low cut-off ratio tend to line up in the flow direction of the rubber as the matrix. This tendency is such that when the tire is vulcanized, the unvulcanized tread rubber flows along the mold by the protrusions of the mold, and as a result, the short fibers 17 are oriented along the mold protrusions. Thereby, the short fibers 17 are oriented along the surface a and the side surface b of the block 16 of the tread portion 13. However, if the short fibers 17 do not have a certain aspect ratio,
They are randomly arranged in the tread rubber and no orientation is performed. For this reason, short fibers have an aspect ratio of 10
It is necessary to be 1,000, preferably 10 to 300, preferably 0.05 μm or more in average diameter, and 1 to 5000 μm in average length. More preferably, short fibers prevent a decrease in abrasion resistance. , And excellent orientation, so that the average diameter of 0.05 to 0.8 μm and 1 to 100 μm
Is a polyamide-based short fiber having an average length within the range.
The aspect ratio is not preferable because no sufficient orientation can not be obtained by the variance of the short fibers becomes poor in the matrix rubber exceeds 1000.
【００２５】このように表面ａ及び側面ｂに短繊維17を
配向させたブロック16は、ブロック全体の剛性は著しく
高いが配向方向と直角方向、すなわち表面から内部方向
への弾性率はそれ程高くないという弾性率の異方性が発
現する。この異方性の発現により凝着効果の高い軟質ベ
ースゴムのブロック剛性が補強でき、ブロックエッジ効
果とゴムの凝着効果が最大限に両立できるため、氷雪路
での性能はむろん一般路での性能をも向上させることが
できる。In the block 16 in which the short fibers 17 are oriented on the surface a and the side surface b, the rigidity of the entire block is extremely high, but the elastic modulus in the direction perpendicular to the orientation direction, that is, from the surface to the inside is not so high. Anisotropy of the elastic modulus is expressed. The expression of this anisotropy reinforces the block rigidity of the soft base rubber, which has a high adhesion effect, and maximizes both the block edge effect and the rubber adhesion effect. Performance can also be improved.
【００２６】本発明において使用するゴム配合物には前
記した必須成分に加えて、タイヤ用に一般に配合される
各種添加剤を任意的に配合することができ、その配合量
も一般的な量とすることができる。このような任意的な
添加剤としては、例えば加硫促進剤、老化防止剤、充填
剤、可塑剤などをあげることができる。本発明に従った
空気入りタイヤは前記したゴム配合物を加硫してトレッ
ド部とする以外は一般的な方法及び装置を用いて製造す
ることができる。In the rubber compound used in the present invention, in addition to the above essential components, various additives generally used for tires can be optionally compounded. can do. Such optional additives include, for example, vulcanization accelerators, antioxidants, fillers, plasticizers, and the like. The pneumatic tire according to the present invention can be manufactured using a general method and apparatus except that the above-mentioned rubber compound is vulcanized into a tread portion.
【００２７】[0027]
【作用】本発明に従えば、空気入りタイヤのトレッド部
を構成するゴム配合物のマトリックスゴムに前記した特
定の低硬度粉末ゴム、中空微粒子、液状ポリマー及び短
繊維を配合するが、低硬度粉末ゴムを配合することによ
り、ゴム中にミクロの低モジュラス部ができて、氷上路
面などへの追従性が良くなり、また路面に接する粉末ゴ
ムは高い凝着効果をもたらし、これに特定の短繊維を併
用することで、低硬度粉末ゴムのブロックが補強され、
比較的粉末ゴム配合量が少ない領域でも充分な氷上摩擦
力が得られ、更に耐摩耗性、混合加工性等も改良され
る。According to the present invention, the above-mentioned specific low-hardness powder rubber, hollow fine particles, liquid polymer and short fibers are mixed with the matrix rubber of the rubber compound constituting the tread portion of the pneumatic tire. By compounding rubber, micro-low modulus parts are created in the rubber, which makes it easier to follow road surfaces on ice, and powder rubber in contact with the road surface has a high adhesion effect, By using together, the block of low hardness powder rubber is reinforced,
A sufficient frictional force on ice can be obtained even in a region where the amount of powdered rubber is relatively small, and the abrasion resistance, the mixing processability, etc. are also improved.
【００２８】本発明に従えば、更に、中空微粒子を配合
することにより、ゴム中にミクロな硬い部分ができて、
氷上路面への追従性が良くなり、またトレッド表面にで
きるミクロの凹凸にひっかき効果をもたらし、更に加え
て軟化剤として特定の液状ポリマーを使用することによ
り低硬度粉末ゴムの配合で低下する摩耗をカバーするこ
とができ、軟化剤のマイグレーションによるゴムの経時
変化を抑えることもできる。According to the present invention, by further mixing the hollow fine particles, a micro hard portion is formed in the rubber,
The ability to follow the road surface on ice is improved, and it has a scratching effect on the micro unevenness formed on the tread surface.In addition, by using a specific liquid polymer as a softening agent, the abrasion that is reduced by the compounding of low hardness powder rubber is reduced. It is possible to cover and to suppress the change with time of the rubber due to the migration of the softener.
【００２９】[0029]
【実施例】以下、実施例及び比較例に従って本発明を更
に詳しく説明するが、本発明の技術的範囲をこれらの実
施例に限定するものでないことは言うまでもない。実施例１〜４、参考例１〜３及び比較例１〜９ 表１及び２に示される配合内容（重量部）のトレッドゴ
ム配合物を用いて、図１に示される構造の空気入りラジ
アルタイヤを常法により作製した。このタイヤのサイズ
は185/70 R13 85Qカーカス層４のコード角度はタイヤ周
方向に対しほぼ90°とした。テスト車は1600ccのＦＦ車
を使用して次の評価を行った。結果は表３及び４に示
す。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples. Examples 1 to 4, Reference Examples 1 to 3 and Comparative Examples 1 to 9 Pneumatic radial tires having the structure shown in FIG. 1 using tread rubber compounds having the compounding contents (parts by weight) shown in Tables 1 and 2. Was prepared by a conventional method. As for the size of this tire, the cord angle of the 185/70 R13 85Q carcass layer 4 was approximately 90 ° with respect to the tire circumferential direction. The following evaluation was performed using a 1600cc FF vehicle as the test vehicle. The results are shown in Tables 3 and 4.
【００３０】動的ヤング率（周方向及び径方向）〔MPa
〕：新品及び乾燥路面を7000km走行した後の各テスト
タイヤのトレッドブロックの側面よりタイヤ回転軸に対
して周方向（タイヤ周方向に同じ）及び径方向にサンプ
ルを切り出し、東洋精機（株）製の粘弾性スペクトロメ
ーターを用いて、チャック間長さ10mm、幅５mm、厚さ２
mmの試料を周波数20Hz、初期歪10％、動的歪±２％、温
度０℃の条件で測定した。数値は大なる程、剛性が大き
いことを示す。[0030]Dynamic Young's modulus (circumferential and radial) [MPa
]: Each test after traveling 7000km on new and dry road surfaces
From the side of the tire tread block to the tire rotation axis
In the circumferential direction (same as the tire circumferential direction) and in the radial direction.
Viscoelastic spectrometer manufactured by Toyo Seiki Co., Ltd.
Using a heater, chuck length 10mm, width 5mm, thickness 2
mm sample, frequency 20Hz, initial strain 10%, dynamic strain ± 2%, temperature
The temperature was measured at 0 ° C. The higher the value, the higher the rigidity
To indicate that
【００３１】氷上路面での制動性能：氷盤上を初速30km
／ｈで走行し、制動した時の制動距離を測定し、従来タ
イヤ（対照例）の予備走行(300km）品を100 として指数
表示した。数値は大なる程、制動が良好であることを示
す。なお、タイヤはすべて乾燥路を300km 予備走行させ
た上で試験に供した。 Braking performance on ice: Initial speed 30 km on ice
/ H, and the braking distance when braking was measured. The index was displayed with 100 as the value of the conventional tire (control example) for preliminary running (300 km). The larger the value, the better the braking. All tires were subjected to a test after preliminary running on a dry road for 300 km.
【００３２】雪上路面での駆動性能：圧雪路面を乗用車
で制動を繰り返して、路面をツルツルにしたツルツル圧
雪路面において、５％(2.9°) 勾配の登坂試験を行い、
ゼロ発進方法により30ｍ区間の登坂加速タイムを計測
し、従来タイヤに対する指数で示した。数値は大なる
程、駆動性が良好であることを示す。なお、タイヤはす
べて乾燥路を300km 予備走行させた上で試験に供した。 Driving performance on a snowy road surface: A 5% (2.9 °) gradient uphill test was performed on a slippery snowy road surface in which a passenger car was repeatedly braked on a snowy road surface to make the road surface slippery.
The climbing acceleration time of the 30m section was measured by the zero start method, and was shown as an index for the conventional tire. The larger the numerical value, the better the driveability. All tires were subjected to a test after preliminary running on a dry road for 300 km.
【００３３】湿潤路面での制動性能：撤水したアスファ
ルト路面を初速40km／ｈで走行し、制動したときの制動
距離を測定し、従来タイヤ（対照例）を100 として指数
表示した。数値は大なる程、制動が良好であることを示
す。なお、タイヤはすべて乾燥路を300km 予備走行させ
た上で試験に供した。 Braking performance on wet road surface : The vehicle traveled on a drained asphalt road surface at an initial speed of 40 km / h, and the braking distance when braking was measured. The larger the value, the better the braking. All tires were subjected to a test after preliminary running on a dry road for 300 km.
【００３４】耐摩耗性（乾燥路面）：JATMA に規定され
ている設計常用荷重、空気圧の条件で乾燥路面を20,000
km走行した後、各タイヤの摩耗量を従来タイヤ（対照
例）の摩耗量に対する指数で示した。数値は大なる程、
耐摩耗性が良好であることを示す。 Abrasion resistance (dry road surface) : The dry road surface is 20,000 under the conditions of the design normal load and air pressure specified in JATMA.
After traveling km, the amount of wear of each tire was shown as an index to the amount of wear of the conventional tire (control). The larger the numerical value,
It shows that the abrasion resistance is good.
【００３５】混合加工性：混合ゴムのまとまり、シーテ
ィング性、ロールでのバギング、押出物の状態などを５
点満点で採点した。評点が高いほど良好である。 Mixing processability : The cohesiveness of the mixed rubber, sheeting properties, bagging with a roll, the state of extrudate, etc.
Scored out of perfect scores. The higher the score, the better.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】[0038]
【表３】 [Table 3]
【００３９】[0039]
【表４】 [Table 4]
【００４０】 （１）ＢＲ…シス成分 ９８％、Ｔｇ−１０３℃ （２）Ｎ−（１，３−ジメチル）−Ｎ’−フェニル−ｐ
−フェニレンジアミン （３）Ｎ−第三−ブチル−２−ベンゾチアゾール・スル
フェンアミド （４）低硬度粉末ゴムＡ…ＮＲ純ゴムの加硫ゴム粉砕物
（平均粒径２００μｍ、カーボン０phr ） （５）低硬度粉末ゴムＢ…ＮＲ純ゴムの加硫ゴム粉砕物
（平均粒径１５００μｍ、カーボン０phr ） （６）低硬度粉末ゴムＣ…ＮＲの加硫ゴム粉砕物（平均
粒径２００μｍ、カーボン４０phr ） （７）短繊維Ａ…ナイロン６短繊維、平均長３０μｍ、
平均径０．３μｍ （８）短繊維Ｂ…セルロース系短繊維、平均長１５００
μｍ、平均径１２μｍ （９）短繊維Ｃ…カーバン短繊維、平均長５μｍ、平均
径１μｍ （１０）短繊維Ｄ…ポリエステル短繊維、平均長８００
０μｍ、平均径５μｍ （１１）中空微粒子Ａ…ガラスバルーン、平均粒径４０
μｍ、平均肉厚２μｍ、平均比重０．７ （１２）中空微粒子Ｂ…クレカスフェアー（炭素質バル
ーン）、平均粒径２００μｍ、平均肉厚６μｍ、平均比
重０．６ （１３）液状ポリマーＡ…液状ＢＲ Ｍｗ＝１５０００
１．４シス−８０％ （１４）液状ポリマーＢ…液状ＳＢＲ Ｍｗ＝５００
０，Ｓｔ＝３０重量％ （１５）液状ポリマーＣ…液状ＳＢＲ Ｍｗ＝６５００
０，Ｓｔ＝３０重量％[0040] (1) BR ... shea scan components 98%, Tg-103 ℃ ( 2) N- (1,3- dimethyl)-N'-phenyl -p
-Phenylenediamine (3) N-tert-butyl-2-benzothiazole sulfenamide (4) Low hardness powder rubber A: NR pure rubber vulcanized rubber pulverized product (average particle size 200 μm, carbon 0 phr) (5) ) Low hardness powder rubber B: pulverized rubber vulcanized product of NR pure rubber (average particle size 1500 μm, carbon 0 phr) (6) Low hardness powder rubber C: vulcanized rubber pulverized product of NR (average particle size 200 μm, carbon 40 phr) (7) Short fiber A: nylon 6 short fiber, average length 30 μm,
Average diameter 0.3 μm (8) Short fiber B: cellulosic short fiber, average length 1500
μm, average diameter 12 μm (9) short fiber C: carban short fiber, average length 5 μm, average diameter 1 μm (10) short fiber D: polyester short fiber, average length 800
0 μm, average diameter 5 μm (11) hollow fine particles A: glass balloon, average particle diameter 40
μm, average thickness 2 μm, average specific gravity 0.7 (12) Hollow fine particles B: Crecus sphere (carbonaceous balloon), average particle size 200 μm, average thickness 6 μm, average specific gravity 0.6 (13) Liquid polymer A ... Liquid BR Mw = 15000
1.4 cis-80% (14) Liquid polymer B: liquid SBR Mw = 500
0, St = 30% by weight (15) Liquid polymer C: liquid SBR Mw = 6500
0, St = 30% by weight
【００４１】表３及び４に示したように、対照例は従来
の典型的なタイヤ配合で、低硬度粉末ゴム及び短繊維を
配合していない。表３及び４では、この従来のタイヤを
100とし、他の例の評価値を指数表示した。本発明に係
る実施例１〜４のタイヤは、従来のタイヤに比較して湿
潤路における制動性能には変化がなく、耐摩耗性も殆ど
低下は認められず、氷上及び雪上での初期及び経時性能
が著しく改良されている。なお、参考例１〜３は本出願
人の他の出願に係るデータを示す。As shown in Tables 3 and 4, the control example is a conventional typical tire formulation, and does not include a low hardness powder rubber and short fibers. Tables 3 and 4 show this conventional tire.
The evaluation value of the other examples was indicated as an index by setting it to 100. The tires of Examples 1 to 4 according to the present invention showed no change in braking performance on wet roads, hardly any decrease in abrasion resistance, and initial and aging on ice and snow as compared with conventional tires. Performance has been significantly improved. Reference Examples 1 to 3 show data according to another application of the present applicant.
【００４２】これに対し、比較例１の配合は中空微粒子
及び液状ポリマーを配合していないため、氷上走行性能
の経時変化が大きく、比較例２の配合は粉末ゴムの粒径
が1000μｍを超えるため、耐摩耗性の低下が著しく低下
して実用的でない。比較例３の配合は粉末ゴム中のカー
ボン量が多いために氷雪路における性能向上が認められ
ず、比較例４は粉末ゴムの配合量が多過ぎるため耐摩耗
性が著しく低下する。比較例５及び６は短繊維のアスペ
クト比が本発明の範囲外であるため氷雪路における性能
改善が認められず、また比較例７では中空微粒子の粒径
が 120μｍより大きいため耐摩耗性の低下も大きく、混
合加工性も劣る。比較例８では液状ポリマーの分子量が
6,000未満のため、氷上性能が経時的に低下し、比較例
９では液状ポリマーの分子量が60,000を超えるため、軟
化効果が不十分で氷上性能の改良が認められず、経時変
化も大きい。On the other hand, the compound of Comparative Example 1 did not contain the hollow fine particles and the liquid polymer, so that the running performance on ice greatly changed with time. The compound of Comparative Example 2 had a particle diameter of the powdered rubber exceeding 1000 μm. In addition, the wear resistance is significantly reduced, which is not practical. In the compound of Comparative Example 3, no improvement in performance on icy and snowy roads was observed because the amount of carbon in the powder rubber was large, and in Comparative Example 4, the wear resistance was significantly reduced because the compounding amount of the powder rubber was too large. Comparative Examples 5 and 6 showed no improvement in performance on ice and snow roads because the aspect ratio of the short fibers was out of the range of the present invention. In Comparative Example 7, the abrasion resistance decreased because the diameter of the hollow fine particles was larger than 120 μm. And the mixing processability is poor. In Comparative Example 8, the molecular weight of the liquid polymer was
Since the molecular weight of the liquid polymer in Comparative Example 9 exceeds 60,000, the softening effect is insufficient, and no improvement in on-ice performance is observed.
【００４３】[0043]
【発明の効果】以上説明したように、本発明によれば、
トレッド部に特定の、低硬度粉末ゴム、中空微粒子、液
状ゴム及び短繊維を配合することにより一般湿潤路にお
ける走行性能を損なうことなく、耐摩耗性の低下を実質
的になくし、初期及び走行後の氷雪路走行性能を大幅に
向上させることが可能となる。As described above, according to the present invention,
By blending specific low-hardness powder rubber, hollow fine particles, liquid rubber and short fibers in the tread portion, the running performance on general wet roads is not impaired, and the wear resistance is not substantially reduced. On snowy and snowy roads.
【図１】本発明の空気入りタイヤの一例の子午線方向半
断面説明図である。FIG. 1 is a half sectional view in the meridian direction of an example of a pneumatic tire of the present invention.
【図２】本発明の空気入りタイヤの一例のトレッド部の
平面視説明図である。FIG. 2 is an explanatory plan view of a tread portion of an example of the pneumatic tire of the present invention.
【図３】図２におけるＫ−Ｋ’線断面図である。FIG. 3 is a sectional view taken along line K-K ′ in FIG. 2;
10…トレッド表面 11…ビード部 12…サイドウォール 13…トレッド部 14…カーカス層 15…ベルト層 16…ブロック 17…短繊維 10 ... tread surface 11 ... bead part 12 ... side wall 13 ... tread part 14 ... carcass layer 15 ... belt layer 16 ... block 17 ... short fiber
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−67341（ＪＰ，Ａ) 特開 平４−38209（ＪＰ，Ａ) 特開 昭63−92659（ＪＰ，Ａ) 特公 昭60−33136（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 1/00 - 101/14 C08K 3/00 - 13/08 B60C 1/00 B60C 11/00 B60C 11/14──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-67341 (JP, A) JP-A-4-38209 (JP, A) JP-A-63-92659 (JP, A) 33136 (JP, B2) (58) Fields investigated (Int. Cl. 6 , DB name) C08L 1/00-101/14 C08K 3/00-13/08 B60C 1/00 B60C 11/00 B60C 11/14
Claims (2)
末ゴムと中空微粒子と液状ポリマーと短繊維とから構成
され、前記低硬度粉末ゴムは平均粒径１０００μｍ未満
で、低硬度粉末ゴム中のゴム分１００重量部当りカーボ
ン２０重量部以下を含むか又は含まないで、その配合量
がマトリックスゴム１００重量部当り１〜１０重量部で
あり、中空微粒子が平均粒径１０〜１２０μｍでかつ平
均肉厚０．１〜１５μｍであり、液状ポリマーが平均分
子量６，０００〜６０，０００の低分子量ジエン系ポリ
マーでその配合量がマトリックスゴム１００重量部当り
５〜５０重量部であり、さらに前記短繊維がアスペクト
比（長さ／径の比）１０〜１０００である空気入りタイ
ヤ。1. A tread portion comprising a matrix rubber, a low-hardness powder rubber, hollow fine particles, a liquid polymer and short fibers, wherein the low-hardness powder rubber has an average particle size of less than 1000 μm and a rubber content in the low-hardness powder rubber. With or without carbon 20 parts by weight or less per 100 parts by weight, the compounding amount is 1 to 10 parts by weight per 100 parts by weight of the matrix rubber, and the hollow fine particles have an average particle diameter of 10 to 120 μm and an average thickness of 0. The liquid polymer is a low molecular weight diene polymer having an average molecular weight of 6,000 to 60,000, and the compounding amount thereof is 5 to 50 parts by weight per 100 parts by weight of the matrix rubber. A pneumatic tire having a ratio (length / diameter ratio) of 10 to 1,000.
〜 100μｍの範囲内の平均長を有するポリアミド系短繊
維である請求項１に記載の空気入りタイヤ。2. The staple fiber has an average diameter of 0.05 to 0.8 μm and
The pneumatic tire according to claim 1, wherein the pneumatic tire is a polyamide short fiber having an average length in a range of from 100 µm to 100 µm.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5118671A JP2763251B2 (en) | 1993-05-20 | 1993-05-20 | Pneumatic tire |
| CA002123828A CA2123828C (en) | 1993-05-20 | 1994-05-18 | Pneumatic vehicle tire |
| US08/246,276 US5591279A (en) | 1993-05-20 | 1994-05-19 | Pneumatic vehicle tire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5118671A JP2763251B2 (en) | 1993-05-20 | 1993-05-20 | Pneumatic tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06328908A JPH06328908A (en) | 1994-11-29 |
| JP2763251B2 true JP2763251B2 (en) | 1998-06-11 |
Family
ID=14742336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5118671A Expired - Fee Related JP2763251B2 (en) | 1993-05-20 | 1993-05-20 | Pneumatic tire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2763251B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188012A (en) * | 1995-01-09 | 1996-07-23 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JPH1128914A (en) * | 1997-07-10 | 1999-02-02 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JP2001219717A (en) * | 1999-12-02 | 2001-08-14 | Bridgestone Corp | Pneumatic tire |
| US9105382B2 (en) | 2003-11-14 | 2015-08-11 | Tundra Composites, LLC | Magnetic composite |
| US8841358B2 (en) | 2009-04-29 | 2014-09-23 | Tundra Composites, LLC | Ceramic composite |
| JP4970840B2 (en) * | 2006-05-09 | 2012-07-11 | 住友ゴム工業株式会社 | studless tire |
| JP5393141B2 (en) * | 2008-12-29 | 2014-01-22 | 住友ゴム工業株式会社 | Rubber composition and tire using the same |
-
1993
- 1993-05-20 JP JP5118671A patent/JP2763251B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06328908A (en) | 1994-11-29 |
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