JPS61110602A - Pneumatic tire having improved durability by short-fiber-reinforced rubber - Google Patents
Pneumatic tire having improved durability by short-fiber-reinforced rubberInfo
- Publication number
- JPS61110602A JPS61110602A JP59232568A JP23256884A JPS61110602A JP S61110602 A JPS61110602 A JP S61110602A JP 59232568 A JP59232568 A JP 59232568A JP 23256884 A JP23256884 A JP 23256884A JP S61110602 A JPS61110602 A JP S61110602A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- carcass ply
- short fiber
- pneumatic tire
- short
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C5/00—Inflatable pneumatic tyres or inner tubes
- B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
- B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Tires In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、カーカスプライとインナーライナーの間にカ
ーカスプライの糸の配列方向に対して比較的大きな角度
を持って配向している短繊維補強ゴムを設けることによ
って、「コード出」を防ぎ、結果としてインナーライナ
ー、チューブの耐久Ｍを著しく向上させた空気入りタイ
ヤを擢供することである。Detailed Description of the Invention (Field of Industrial Application) The present invention provides short fiber reinforcement between a carcass ply and an inner liner, which is oriented at a relatively large angle with respect to the direction in which the threads of the carcass ply are arranged. To provide a pneumatic tire that prevents "cord coming out" by providing rubber and, as a result, significantly improves the durability M of the inner liner and tube.
（従来の技術）
従来の構造のタイヤに於いては、カーカスプライの内側
に直接にインナーライナーが配置されている。しかしな
がら、加硫する段階において、インナーライナーゴムが
埋設ゴムでコーティングされたカーカスプライのコード
間に流れ込み、所望された設計通りのカーカスライン上
にカーカスプライコードを配列できないことがしばしば
あった。(Prior Art) In a tire with a conventional structure, an inner liner is placed directly inside the carcass ply. However, during the vulcanization stage, the inner liner rubber often flows between the cords of the carcass ply coated with embedded rubber, making it impossible to arrange the carcass ply cords on the carcass line as desired.
これは、加硫の際にブラダ−によるタイヤ内に加印され
る圧力の増加に伴ない、インナーライナーゴムは張力を
受けると同時にカーカスプライコー１及び埋設ゴムに強
く押えつけられ、カーカスプライコ−１”の間にインナ
ーライナーゴムが押し込まれ、この結果プライコーティ
ングゴムのコードからの離脱がおこり、プライセパレー
ションの原因となる。This is due to the fact that as the pressure applied inside the tire by the bladder increases during vulcanization, the inner liner rubber is subjected to tension and at the same time is strongly pressed against the carcass ply coat 1 and the embedded rubber. -1'', the inner liner rubber is forced into the cord, and as a result, the ply coating rubber separates from the cord, causing ply separation.
１Ｆた、使用末期に於いて、最も繰り返し歪がかかる部
分であるショルダー部のインナーライナーがコ−Ｆのに
でさらに薄くなる現象が起こり昂く、このようになると
−見、カーカスプライのコードが出て来たように見える
ので、これを「コーＩ゛出」と呼んでいる。At the end of the first stage of use, the inner liner in the shoulder area, which is the part that is subjected to the most repeated strain, becomes thinner due to the cord F. When this happens, the cord of the carcass ply becomes thinner. Because it looks like it's coming out, this is called "Ko I" coming out.
このようになるとチューブレスタイヤに於いては、当然
のことながらインナーライナーの薄くなった所では、空
気の透過量が多くなるので好ましくなく、チューブを使
用するタイヤに於いては、チューブがタイヤの内面に浮
き出たコードによって局部的に歪を受けるので比較的早
い時期に破れてしまう問題点があった。This is undesirable in tubeless tires because the amount of air permeation increases in areas where the inner liner is thin, and in tires that use tubes, the tube is located on the inner surface of the tire. There was a problem in that the cords were locally distorted by the protruding cords, causing them to break relatively quickly.
−１−記問題点を解決する為に多くの対策が考えられて
来た。例えば、インナーライナーを厚くする方法である
。しかし、この方法では、大きな欠点が２つある。１つ
は、厚くする分だ４Ｊコス１アツプになり、タイヤの価
格が上シ１するのでニーーリ゛−にえ１して余分な１ｊ
＋ Ｊｎを掛けることじなるからでル。Many countermeasures have been devised to solve the problem described in -1-. For example, one method is to thicken the inner liner. However, this method has two major drawbacks. One is that the thicker the tire, the 4J cost increases by 1, and the tire price increases by 1, so the extra 1J is added to the knee.
Multiplying + Jn is the same thing.
あ。もう１つは、厚くする分だりタイヤの小雨が増える
ので燃費がその分増えるという欠点である。a. Another drawback is that the thicker the tire, the more light rain on the tire, which increases fuel consumption.
チューブレスタイヤに於いては、インナーライナーに空
気透過性の極めて低いハロゲン化ブチルゴムを使用する
が、このゴムはエネルギーロスが非常に大きい為、低燃
費性に与える影響は極めて大きいといえる。In tubeless tires, halogenated butyl rubber, which has extremely low air permeability, is used for the inner liner, but this rubber has a very large energy loss, so it can be said that it has an extremely large effect on fuel efficiency.
他にインナーライナーとカーカスプライの間に緩衝的な
ゴム層を設けるという方法も考えられた。Another method considered was to provide a cushioning rubber layer between the inner liner and the carcass ply.
全面的にゴム層を入れる場合と部分的に入れる場合と両
方あるが、本来「コード出」は、タイヤショルダー部に
しか起こらないので部分的に対処する方が優れている。There are both cases where the rubber layer is applied completely and cases where it is applied only partially, but it is better to deal with it partially because cord protrusion only occurs in the shoulder area of the tire.
しかし、充分な効果が期待出来る程度にする為には、挿
入するゴム層を厚くする必要があり、そのようにすると
タイヤ内面の形状が変ってしまうので、空気の圧力容器
たるタイヤの内面形状として好ましくなってしまうとい
う欠点があった。インナーライナーとカーカスプライの
間に全面的にゴム層を設けるのでは、前に示した例と同
し欠点を持つことになり、好ましくない。However, in order to achieve a sufficient effect, it is necessary to thicken the inserted rubber layer, and this will change the shape of the inner surface of the tire, so the shape of the inner surface of the tire, which is a pressure vessel for air, must be made thicker. It had the disadvantage of becoming undesirable. Providing a rubber layer over the entire surface between the inner liner and the carcass ply is not preferred because it has the same drawbacks as the previous example.
他の対策として、インナーライナーとカーカスプライの
間にゴムコーチイドコードを互いにコードの角度が３０
度以」二になるようにして配置する考え方も（足幅され
たが、確かに「コード出」に対しては、効果があったが
、コードの配向方向に対して弾性率が高過ぎるので、本
来のラジアルタイヤの特徴を消す方向に働き、好ましく
なかった。従って現在のところ、タイヤの本来の性能を
損うことなく、「コード出」を有効に防止する方法が見
つかっていないのが現状である。Another measure is to use a rubber coachoid cord between the inner liner and the carcass ply so that the angle of the cords to each other is 30.
The idea of arranging the cord so that it is 2 degrees wide (the foot width was increased, but it was certainly effective for ``cord protrusion''), but the elastic modulus was too high in the direction of the cord orientation. This was undesirable as it worked in the direction of erasing the original characteristics of radial tires.Therefore, at present, no method has been found to effectively prevent "cord development" without impairing the original performance of the tire. It is.
（発明が解決しようとする問題点）
本発明の目的は、カーカスプライの糸の配列方向に対し
て比較的大きな角度を持って配向している短繊維補強ゴ
ムをタイヤのショルダー部のカーカスプライとインナー
ライナーの間に設けることによって、本来のタイヤＰ１
能を何らＩｌｌなうことなく、「コード出ｊと言う現象
が有効に防１に出来、結果としてインナーライナー、チ
ューブの１ｍ１久１’１を著しく向上させた空気入りタ
イヤを提供するごとにある。(Problems to be Solved by the Invention) An object of the present invention is to combine short fiber reinforced rubber, which is oriented at a relatively large angle with respect to the direction in which the threads of the carcass ply are arranged, into a carcass ply in the shoulder region of a tire. By providing between the inner liner, the original tire P1
Our goal is to provide a pneumatic tire that can effectively prevent the phenomenon called "cord ejection," and as a result, has significantly improved the length of the inner liner and tube. .
（問題点を解決するための手段）
（１）多数のコードが平行に配列されたゴム引き二ｌ−
ド層から成るカーカスプライと、このカーカスプライの
両端部をビード部で折り返し、係止した空気入りタイヤ
に於いて、少なくともタイヤのショルダー部区域のカー
カスプライとインナーライナーの間に平均径１μｍ以下
、平均長さくｌ、）と平均径（１１）の比（Ｌ／ｒｌ）
が８以上である短繊維を５重量部以上含有するゴム組成
物から成る、厚さ０．３〜２．０ｍｍの加硫可能なゴム
シート層を備えていることを特徴とする空気入りタイヤ
。(Means for solving the problem) (1) Rubber-lined two l-in which many cords are arranged in parallel
In a pneumatic tire in which a carcass ply consisting of a double layer and both ends of this carcass ply are folded back at a bead part and locked, an average diameter of 1 μm or less is formed between the carcass ply and the inner liner in at least the shoulder region of the tire. Ratio of average length l, ) to average diameter (11) (L/rl)
1. A pneumatic tire comprising a vulcanizable rubber sheet layer having a thickness of 0.3 to 2.0 mm and made of a rubber composition containing 5 parts by weight or more of short fibers having a diameter of 8 or more.
（２） カーカスプライの糸の配列方向と短繊維補強
ゴム中の短繊維の配向方向との角度が４０度〜９０度で
あることを特徴とする特許請求の範囲第一記載の空気入
りタイヤ。(2) The pneumatic tire according to claim 1, wherein the angle between the direction in which the threads of the carcass ply are arranged and the direction in which the short fibers in the short fiber reinforced rubber are oriented is from 40 degrees to 90 degrees.
（３）加硫後の短繊維補強ゴムに於いて短繊維の配列方
向に引張った１５０χ歪時の弾性率（Ｍ１）と、短繊維
の配列方向と角度の方向に引張った１５０χ歪時の弾性
率（Ｍ２）の比（Ｍ１／Ｍ２）が２．５以上であること
を特徴とする特許請求の範囲第一項記載の空気入りタイ
ヤ。(3) Elastic modulus (M1) of short fiber reinforced rubber after vulcanization at 150χ strain when pulled in the direction of short fiber arrangement, and elasticity at 150χ strain when pulled in the direction of the short fiber arrangement and angle. The pneumatic tire according to claim 1, wherein the ratio (M1/M2) of the ratio (M2) is 2.5 or more.
（４） カーカスプライに沿って計測した場合、もっ
ともタイヤショルダー部区域内面の曲率半径の小さい部
位を中心に、その両端１ｃＩＩＩずつ以−りの断面方向
長さを有する短繊維補強ゴムで覆っていることを特徴と
する特許請求の範囲第一項記載の空気入りタイヤ。(4) When measured along the carcass ply, the area with the smallest radius of curvature on the inner surface of the tire shoulder area is covered with short fiber reinforced rubber having a length in the cross-sectional direction of 1cIII or more at each end. A pneumatic tire according to claim 1, characterized in that:
リマーから成っており、ゴムの部分のフェノールホルム
アルデヒド系樹脂の縮合物を介してグラフトしているこ
とを特徴とする特許請求の範囲第一項記載の空気入りタ
イヤ。2. The pneumatic tire according to claim 1, wherein the pneumatic tire is made of a rubber part and is grafted via a condensate of phenol formaldehyde resin in the rubber part.
（作 用）
本発明で、短繊維の平均径を１μｍ以下に限定したのは
、次のような理由による。(Function) The reason why the average diameter of the short fibers is limited to 1 μm or less in the present invention is as follows.
本来、短繊維に歪（応力）がかかった場合、短繊維の両
末端に大きな剪断応力がかかり、その剪断応力によって
、短繊維の両末端から亀裂が発生、成長して短繊維補強
ゴム組成物特有の大きなりリーブを生じる傾向が強かっ
た。その剪断応力は短繊維の形状に大きく依存している
ことが分かっており、当然のことながら短繊維が小さけ
れば小さい程、短繊維の両末端にかかる歪も小さくなる
ので剪断応力も小さくなる。短繊維１個当りの補強効果
も小さくなるが、個数が多くなるので全体として見れば
、短繊維が入ることによって耐疲労性、特に繰り返し歪
を受けた後のクリープが大きくなるのを防ぎ、短繊維補
強の目的である高弾性率、優れた耐カット性および本発
明に利用している構造粘性を発現させることが出来るの
である。Originally, when strain (stress) is applied to short fibers, large shearing stress is applied to both ends of the short fibers, and due to the shear stress, cracks occur and grow from both ends of the short fibers, resulting in a short fiber reinforced rubber composition. There was a strong tendency to produce a characteristic large leeway. It is known that the shear stress greatly depends on the shape of the short fibers, and naturally, the smaller the short fibers, the smaller the strain applied to both ends of the short fibers, and therefore the smaller the shear stress. Although the reinforcing effect per short fiber becomes smaller, the number of short fibers increases, so looking at it as a whole, the presence of short fibers improves fatigue resistance, especially prevents creep after repeated strain, and improves short fiber strength. It is possible to exhibit the high elastic modulus, excellent cut resistance, and structural viscosity utilized in the present invention, which are the objectives of fiber reinforcement.
上記短繊維補強メリットを出させる為には、アスペクト
費（Ｌ／Ｄ）が８以上であることが必要であり、このア
スペクト比を８以上に保って短繊維両末端にかかる剪断
応力を問題にならないレベルまで下げるには、短繊維の
平均径を１μｍ以下にいｔ口ｌればならない。In order to bring out the short fiber reinforcement benefits mentioned above, the aspect ratio (L/D) must be 8 or more, and by keeping this aspect ratio at 8 or more, the shear stress applied to both ends of the short fibers can be reduced. In order to reduce the average diameter of the short fibers to a level of 1 μm or less, it is necessary to reduce the average diameter of the short fibers to 1 μm or less.
本発明中、短繊維の量を５重量部以上に限定したのは、
５ｍｍ部よりも少ないと本発明の目的である構造粘性が
小さく、効果が期待出来ないからである。本発明で問題
となる構造粘性とは、低い歪速度領域では、極めて高い
粘度を示すが、高い歪速度領域では逆に低い粘度を示す
性質のことであり、本発明では、後述するように短繊維
を極力配向させ、その配向方向とコードの方向との角度
差をコンＩ・ロールすることによって、構造粘性の効果
を最大に使い、加硫時の短繊維補強ゴム層のゴム流れを
防ぐことが出来るので設計通りのタイヤを得ることが可
能となる。In the present invention, the amount of short fibers is limited to 5 parts by weight or more because
This is because if the thickness is less than 5 mm, the structural viscosity, which is the object of the present invention, will be low and no effect can be expected. The structural viscosity that is a problem in the present invention is a property that exhibits extremely high viscosity in a low strain rate region, but conversely exhibits a low viscosity in a high strain rate region. By orienting the fibers as much as possible and controlling the angle difference between the orientation direction and the cord direction, we can maximize the effect of structural viscosity and prevent rubber flow in the short fiber reinforced rubber layer during vulcanization. This makes it possible to obtain tires as designed.
本発明中、短繊維を含有するゴム組成物ゴムシートの厚
さを０．２〜２．０ｍ１１に限定したのは、０．２ｍｍ
よりも薄いゴムシートを工業的に生産するのは困難であ
るし、また、本発明の目的がカーカスプライコードの間
にインナーライナーが食い込んで行くのを防ぐ為に、こ
のような現象がもっとも起り易いショルダー部（特にカ
ーカスプライの二）−ドに沿って計測した場合、もっと
も曲率半径の小さい部分を含み、その両端］ｃａ＋以−
にの領域）にカーカスプライとインナーライナーを離す
ことと長期間使用しても、ゴム流れ（クリープ）が少な
く、「コード出ｊを有効に防止する「短繊維を含有する
ゴム組成物」を配置する技術に関するものであるので０
．２ｍｍよりも薄いと効果が期待出来ず、逆に２．抛−
を越えると、カーカス形状が空気の圧力容器たるタイヤ
に相応しくないものとなるし、それを防止する為、カー
カスプライとインナーライナーの全面に「短繊維を含有
するゴム組成物」を配置するのでは、タイヤの重量が必
要以上に増加するのみならず、燃費を増加させたり、高
速耐久性を著しく低下させるので好ましくない。In the present invention, the thickness of the rubber sheet of the rubber composition containing short fibers is limited to 0.2 to 2.0 m11.
It is difficult to industrially produce a rubber sheet thinner than this, and since the purpose of the present invention is to prevent the inner liner from digging in between the carcass ply cords, this phenomenon is most likely to occur. When measured along the easy shoulder part (especially the second carcass ply), it includes the part with the smallest radius of curvature, and both ends]ca+
The carcass ply and inner liner are separated from each other in the inner liner area), and a rubber composition containing short fibers is placed in the inner liner, which reduces rubber flow (creep) even after long-term use and effectively prevents cords from coming out. 0 because it is related to the technology to
．． If it is thinner than 2mm, no effect can be expected;抛－
If it exceeds this, the shape of the carcass becomes unsuitable for a tire that is a pressure vessel for air, and to prevent this, a ``rubber composition containing short fibers'' may be placed on the entire surface of the carcass ply and inner liner. This is not preferable because it not only increases the weight of the tire more than necessary, but also increases fuel consumption and significantly reduces high-speed durability.
本発明中、カーカスプライのコードの配列方向と短繊維
補強ゴム中の短繊維の配向方向との角度は３０度〜９０
度が好ましが、これはこの角度の範囲で短繊維補強の構
造粘性が最も発揮出来るからである。また加硫後のゴム
に於いても、この角度の範囲で最も有効に「コード出」
を防ぐことが出来る。In the present invention, the angle between the arrangement direction of the cords of the carcass ply and the orientation direction of the short fibers in the short fiber reinforced rubber is 30 degrees to 90 degrees.
This is because the structural viscosity of the short fiber reinforcement can be maximized within this angle range. Also, in the rubber after vulcanization, the most effective "cord release" is within this angle range.
can be prevented.
この角度よりも小さい範囲で短繊維を配向させるならば
、短繊維は無配向にした方が好ましい。If the short fibers are to be oriented within a range smaller than this angle, it is preferable that the short fibers be non-oriented.
カーカスプライのコード配列方向と短繊維補強ゴＪ、中
の短繊維の配向方向との角度は「鋭角Ｊの方を測定して
いる。The angle between the cord arrangement direction of the carcass ply and the orientation direction of the short fibers in the short fiber reinforcement layer J is measured at the acute angle J.
本発明に於いては、加法後の短繊維補強ゴムに於いて短
繊維の配列方向に引張った１５０χ歪時の弾性率（Ｍ１
）と、短繊維の配列方向と直角の方向に引張った】５０
χ歪時の弾性率（Ｍ２）の比（Ｍ１／Ｍ２）が２．５以
」二であることが好ましいが、この指標は、短繊維の配
向の程度を示しており、この程度に配向させた短繊維を
含有するゴム組成物を−Ｌ述のようにカーカスプライの
コードの配列方向と短繊維補強ゴム中の短繊維の配向方
向との角度を３０度〜９０度にした時に最も大きな効果
を生み出す。In the present invention, the modulus of elasticity at 150χ strain (M1
) and pulled in the direction perpendicular to the direction in which the short fibers are arranged]50
It is preferable that the ratio (M1/M2) of the elastic modulus (M2) at the time of χ strain is 2.5 or more, but this index indicates the degree of orientation of the short fibers, and The greatest effect is obtained when the rubber composition containing short fibers is made to have an angle of 30 degrees to 90 degrees between the arrangement direction of the cords of the carcass ply and the orientation direction of the short fibers in the short fiber reinforced rubber as described in -L. produce.
なお、本発明の短繊維補強ゴムはタイヤシッルダ一部区
域にのみ配置するか、もしく ｔｉｔ、カーカスに沿っ
て一方のビード部から他方のビード部Ｐにわたって配置
してもよい。The short fiber reinforced rubber of the present invention may be disposed only in a partial area of the tire sill, or may be disposed along the carcass from one bead part to the other bead part P.
本発明に於いては、短繊維の材料としてリマーであるこ
とが好ましいが、これは、アミド基を有するポリマーが
結晶し易く、かつ結晶の配向が比較的容易で球晶等を作
り難いので短繊維の耐疲労性が優れている為である。ま
た、アミド基を有するポリマーの結晶融点は、通常２０
０℃以」二であり、耐熱性の点からも問題がないからで
ある。In the present invention, it is preferable to use remer as the material for the short fibers, but this is difficult to use because polymers with amide groups tend to crystallize and orientation of crystals is relatively easy, making it difficult to form spherulites. This is because the fibers have excellent fatigue resistance. In addition, the crystal melting point of a polymer having an amide group is usually 20
This is because the temperature is 0° C. or lower, and there is no problem in terms of heat resistance.
本発明に於いて、短繊維とゴムの部分は、フェノールホ
ルムアルデヒド系樹脂の縮合物を介してグラフトしてい
ることが好ましいが、これは、短繊維とゴム部分の接着
力を増加させることによって耐疲労性を向上させること
が出来るからである。In the present invention, it is preferable that the short fibers and the rubber part are grafted via a condensate of phenol formaldehyde resin, which increases the adhesive strength between the short fibers and the rubber part, thereby increasing the durability. This is because fatigue resistance can be improved.
但し、短繊維の材質としては、上記に限定されるもので
はなく、シンジオタタティック−１，２−ポリブタジェ
ン、アイソタテイックポリプロピレン等の熱可塑性ポリ
マーも可能である。However, the material of the short fibers is not limited to those mentioned above, and thermoplastic polymers such as syndiotatic-1,2-polybutadiene and isotatic polypropylene are also possible.
（実施例１〜７）
実施例１〜７では本発明のタイヤが従来のタイヤに比べ
て、耐久性に於いて著しく改良されていることを示す。(Examples 1 to 7) Examples 1 to 7 show that the tires of the present invention are significantly improved in durability compared to conventional tires.
＋１１短繊維の製法
１５０℃、１１００ｒｐにセットしたＯＯＣバンバリー
ミキサ−（神戸製鋼製）に１００℃のムーニー粘度が２
５の天然ゴム１４００ ｇ、及びＮ−（３−メタクリロ
イルオキシ−２−ヒドロキシプロピル）−Ｎ’−フェニ
ル−Ｐ−フェニレンジアミン［ツクラックＧ−１、大向
新興製］１４ｇを投入し、１分間素線後、６−ナイロン
（商品名：１０３０Ｂ、宇部興産■製、融点２２１’Ｃ
１分子量３００００） ７００ｇを投入し、７分間混練
りした。この間にミキサー内の温度は２３２℃まで上昇
し、６−ナイロンは溶融した。+11 Short fiber manufacturing method Mooney viscosity at 100°C is 2 in an OOC Banbury mixer (manufactured by Kobe Steel) set at 150°C and 1100 rpm.
1400 g of the natural rubber from No. 5 and 14 g of N-(3-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-P-phenylenediamine [Tsukrac G-1, manufactured by Ohmukai Shinko Co., Ltd.] were added, and the mixture was allowed to stand for 1 minute. After the wire, 6-nylon (product name: 1030B, manufactured by Ube Industries ■, melting point 221'C
1 molecular weight: 30,000) was added and kneaded for 7 minutes. During this time, the temperature inside the mixer rose to 232°C, and the 6-nylon melted.
ついで、ノボラック型フェノールホルムアルデヒド初朋
縮合物（明相化成■製、商品名５５０ＰＬ）３０ｇを投
入し、７分間混練り後、ヘキサメチレンテトラミン３ｇ
を投入し、２．５分間混練りして（この間にミキサー自
身の温度は２３０℃）グラフト反応させた後、ダンピン
グした。得られた混練の物をノズルの内径２１１Ｉｌ、
長さと内径との比（Ｌ／１１）が２の円形ダイを有する
３０ＩＩＩＩＩφ押出機（池貝社製）を用いてグイ設定
温度２３５℃で紐状に押出し、押出物を０℃の冷却水で
冷却固化し、ついでガイドロールを経てボビンにドラフ
ト比９で３５ｍ／分の速度で巻き取った。この巻き取り
物を一昼夜室温で真空乾燥し、付着水を除いた後、この
巻き取り物約５００本を束ねてシート状（厚さ２１１１
１％幅１５０ｍｍ）とし、このシート状物をロール間隙
０．２ｍｍ、温度６０℃の一対の圧延ロールで約１０倍
にロール圧延して、強化ゴム組成物（マスターバンチ）
（試料１）を得た。Next, 30 g of novolac type phenol formaldehyde Hatsutomo condensate (manufactured by Meisho Kasei ■, trade name 550PL) was added, and after kneading for 7 minutes, 3 g of hexamethylenetetramine was added.
was added and kneaded for 2.5 minutes (during which time the temperature of the mixer itself was 230°C) to cause a graft reaction, and then dumped. The obtained kneaded material was heated to a nozzle with an inner diameter of 211Il,
Using a 30IIIφ extruder (manufactured by Ikegai Co., Ltd.) having a circular die with a length-to-inner diameter ratio (L/11) of 2, the extrudate was extruded into a string at a set temperature of 235°C, and the extrudate was cooled with cooling water at 0°C. After solidification, it was then wound onto a bobbin via guide rolls at a draft ratio of 9 and a speed of 35 m/min. After vacuum-drying this roll for a day and night at room temperature to remove adhering water, approximately 500 rolls were bundled into a sheet (thickness: 211 mm).
1% width 150 mm), and this sheet-like material was roll-rolled to about 10 times its size with a pair of rolling rolls with a roll gap of 0.2 mm and a temperature of 60°C to obtain a reinforced rubber composition (master bunch).
(Sample 1) was obtained.
（２）分別、グラフト率測定
実施例１で得られた強化ゴム組成物２ｇをベンゼン２０
０ｍＮに室温で添加し、強化ゴム組成物のゴム分を溶解
させ、えられたスラリーを室温を遠心分離して溶液部分
と沈澱部分とに分けた。沈澱部分について前記の操作を
７回繰り返し行なった後、沈澱部分を乾燥してナイロン
繊維を得た。このナイロン繊維をフェノールと第ルソジ
クロルベンゼン１：３（重量比）の混合溶媒に溶解させ
、１１の核磁気共鳴スペクトル（ＮＨＲ）で分析（内部
標準：テトラメチルシラン）し、ＮＭＩＩチャートから
天然ゴムに起因するメチル基及びメチレン基、６−ナイ
ロンに起因するＣＯ基に隣接したメチレン基、Ｎｌ＋基
に隣接したメチレン基及び他の３個のメチレン基の各々
ピークについて、切り堆り面積法により６−ナイロンと
天然ゴムとのモル比を求めて、グラフト率を算出した。(2) Fractionation and graft ratio measurement 2 g of the reinforced rubber composition obtained in Example 1 was mixed with 20% of benzene.
0 mN at room temperature to dissolve the rubber component of the reinforced rubber composition, and the resulting slurry was centrifuged at room temperature to separate into a solution portion and a precipitate portion. After repeating the above operation seven times for the precipitated portion, the precipitated portion was dried to obtain nylon fibers. This nylon fiber was dissolved in a mixed solvent of phenol and rusodichlorobenzene 1:3 (weight ratio), analyzed by nuclear magnetic resonance spectroscopy (NHR) of 11 (internal standard: tetramethylsilane), and determined from the NMII chart that natural The peaks of the methyl group and methylene group originating from rubber, the methylene group adjacent to the CO group originating from 6-nylon, the methylene group adjacent to the Nl+ group, and the other three methylene groups were determined by the cut area method. The graft ratio was calculated by determining the molar ratio of 6-nylon and natural rubber.
また前記のナイロン繊維の形状を繊維約２００本につい
て１万倍の倍率で走査型電子顕微鏡を用いて測定した。Further, the shape of about 200 fibers was measured using a scanning electron microscope at a magnification of 10,000 times.
繊維は断面が円形の極めて細い短繊維であった。結果を
第３表に示す。The fibers were extremely thin short fibers with a circular cross section. The results are shown in Table 3.
実施例１〜７のビードフィラー用ゴム組成物は第１表の
配合成分を７０℃、７０ｒｐｍにセットしたＯＯＣバン
バリーミキサ−神戸製鋼製）で混練りして作成した。The rubber compositions for bead fillers of Examples 1 to 7 were prepared by kneading the ingredients shown in Table 1 in an OOC Banbury mixer (manufactured by Kobe Steel, Ltd.) set at 70° C. and 70 rpm.
（１）コード出の有無：内圧８．Ｑ ｋｇ／ ｃｓ”で
５万ｌｖ実車走行させ、コード出の有無を確認した。(1) Presence or absence of cord output: Internal pressure 8. The actual vehicle was run at 50,000 lv at ``Q kg/cs'' to confirm whether or not a code appeared.
（２）θ：カー力ススプライコード配列方向と短繊維補
強ゴムの短繊維の廃校方向との角度。(2) θ: Angle between the Kerr force spry cord arrangement direction and the short fiber discard direction of the short fiber reinforced rubber.
（３）カーカスプライコードとインナーライナーの内側
までの距離（理論値；ｆｉ）
→カーカスプライコード表面から、タイヤの最も内側（
インナーライナーの表面）までの距離。(3) Distance between the carcass ply cord and the inside of the inner liner (theoretical value; fi) → From the surface of the carcass ply cord to the innermost side of the tire (
distance to the inner liner surface).
具体的には、コーティングゴムの厚さとインナーライナ
ーのゴムの厚さを加えたもの。Specifically, the thickness of the coating rubber plus the thickness of the inner liner rubber.
（４）カーカスプライコードとインナーライナーの内側
までの距離（実測値：ｍｍ）
→カーカスプライコードとタイヤの最も内側までの距離
。(4) Distance between the carcass ply cord and the inside of the inner liner (actual value: mm) → Distance between the carcass ply cord and the innermost side of the tire.
（５）カーカスプライコードとインナーライナーの内側
までの距離の測定値
一カーカスブライのコードにそって計測した場合、最も
曲率の小さい部分を含み、その両端１ａｌＩで最も薄い
部分を計測した。(5) Measurement value of the distance between the carcass ply cord and the inside of the inner liner - When measured along the carcass ply cord, the thinnest portion including the part with the smallest curvature was measured at both ends 1alI.
＋６１タイヤサイズ
→１１Ｒ２２，５：タイヤ総幅→１１インチ、へん平率
→９０、リム径→２２．５インチのラジアルタイヤ以上
の結果から次のことが言える。+61 tire size → 11R22,5: Radial tire with total tire width → 11 inches, flattening ratio → 90, and rim diameter → 22.5 inches From the above results, the following can be said.
本発明の短繊維補強ゴムを使用すれば、加硫工程でのゴ
ム流れが少なく、カーカスプライコードの上のゴムコー
ティング、インナーライナーの厚さをほぼ設計通りに、
設定出来ることが分る。If the short fiber reinforced rubber of the present invention is used, there will be less rubber flow during the vulcanization process, and the rubber coating on the carcass ply cord and the thickness of the inner liner can be adjusted almost as designed.
I see that it can be configured.
また、短繊維補強ゴム層を設けると、例えば、実施例５
では短繊維補強ゴム層は０．４ｆｌであり、カーカスプ
ライコードの上にあるべきゴムの厚さは、３．２關であ
り、しかるに加硫後も理論値のゴムの厚さを殆ど保って
いた。もし、この０６４Ｎの短繊維補強ゴム層を取除け
ば、比較例１になり加硫後のゴムの厚さは１．４鶴とな
ってしまう、これを考えれば、−見、短繊維補強ゴム層
を設けた為に周囲のゴムまで流動し難くなったように見
える。Further, when a short fiber reinforced rubber layer is provided, for example, Example 5
In this case, the short fiber reinforced rubber layer is 0.4 fl, and the thickness of the rubber that should be on the carcass ply cord is 3.2 fl, but the theoretical value of the rubber thickness is almost maintained even after vulcanization. Ta. If this 064N short fiber reinforced rubber layer is removed, Comparative Example 1 will be obtained and the thickness of the rubber after vulcanization will be 1.4 mm. It appears that the layer made it difficult for the surrounding rubber to flow.
しかし、そんなことが起こるはずはなく、短繊維補強ゴ
ム層が殆ど流動しない為に流動バリア一層となって他の
ゴムの流動を妨げたものであり、短繊維補強ゴム層と隣
接ゴム層間においてゴム流動を抑止する相互作用があっ
たものと考えられる。However, such a thing should not happen, and since the short fiber reinforced rubber layer hardly flows, it acts as a flow barrier and prevents the flow of other rubbers, and between the short fiber reinforced rubber layer and the adjacent rubber layer, the rubber layer It is thought that there was an interaction that inhibited the flow.
さらに、カーカスプライコードの配列方向と短織維補強
ゴムの短繊維の配向方向との角度は３０〜９０度が好ま
しいことが分る。Furthermore, it is found that the angle between the arrangement direction of the carcass ply cords and the orientation direction of the short fibers of the short woven fiber reinforced rubber is preferably 30 to 90 degrees.
ここで、コード出のメジャーとして加硫後のカーカスプ
ライコードの上のゴムの厚さと５万ｋｍ走行後のコード
出の有無で評価した。Here, as a measure of cord protrusion, the thickness of the rubber on the carcass ply cord after vulcanization and the presence or absence of cord protrusion after running for 50,000 km were evaluated.
大施■−二１
実施例６〜８では本発明に使用する短繊維の平均径が１
μｍ以下及びアスペクト比（Ｌ／Ｄ）が８以上に限定さ
れることを示す。Oshi ■-21 In Examples 6 to 8, the average diameter of the short fibers used in the present invention was 1
Indicates that the aspect ratio (L/D) is limited to 8 or more.
試料ｌの製法に準じて使用するナイロン樹脂の粉末の平
均粒径を変化させて、短繊維の平均径を変えて第３表に
示す試料を作成した。The samples shown in Table 3 were prepared by varying the average particle size of the nylon resin powder used and the average diameter of the short fibers according to the manufacturing method of Sample 1.
第１表
諜継コ１１ ６６重量部 −
一天然ゴＪ、 ５６６重部
１（Ｘ１１重部液状ＩＲ５５
カーボンブランク（１１＾Ｆ） ４０
６０ステアリン酸 ２２
老イ［ｊ＋ｌＪＩ ］
ｌ亜鉛華 ３５
力１１１’Ａ促ｉＵリ （Ｎｏｂｓ）
０．７ ０．６イオウ
３５
リターダ−０，５０，５
短繊維の量（重置面 ２２ ０Ｈ］
／Ｍ ２ −〜−−一−−−−−−・ ３．６
１．０・液状ＩＲ−−−−− クラレイソプレンケ
ミカ／Ｌ４１１！ｌＪ１．ＩＲ−５０・老化防１１済１
〜− − 大向新興化学工業（財）製ツクランク８１０
−Ｎ＾・Ｎｏｈｓ−−−−大向新興化学工業■製ツクセ
ラー−ＭＳＡ−Ｇ・短繊維の量（重量部）二言鵡旧の中
の短繊維の量をゴム組成物中のゴム、１００重量部当り
に含まれている短繊維の量で示したものです。1st intelligence officer 11 66 parts by weight -
Ichitengo J, 566 heavy parts
1 (X11 heavy liquid IR55 carbon blank (11^F) 40
60 stearic acid 22 old I [j+lJI]
l Zinc White 35 Force 111'A Urge iUli (Nobs)
0.7 0.6 sulfur
35 Retarder-0, 50, 5 Amount of short fibers (overlapping surface 22 0H)
/M 2 −〜−−−−−−−・3.6
1.0・Liquid IR---- Clary Isoprene Chemica/L411! lJ1. IR-50・Aging prevention 11 completed 1
～ − − Tsurank 810 manufactured by Ohmukai Shinko Chemical Industry (Incorporated)
-N^・Nohs---Tsukseller manufactured by Ohmukai Shinko Kagaku Kogyo ■MSA-G・Amount of short fibers (parts by weight) The amount of short fibers in the rubber composition, 100 It is expressed as the amount of short fibers contained per part by weight.
以下、実施例に基づきさらに説明する。Hereinafter, further explanation will be given based on examples.
前実施例と同様に、第４表に示す各ゴム組成物を用いて
第５表のようなラジアルタイヤ（チューブレス）を試作
し、テスト結果を示す。Similarly to the previous example, radial tires (tubeless) as shown in Table 5 were prototyped using each of the rubber compositions shown in Table 4, and the test results are shown.
第５表
〔実ＩＪＩ４列９〜１０〕
実施例９〜ｌ叫、カーカスプライとインナーライナー間
に設置する短繊維補強ニーＮ、層の厚さ力（イ）、２−
膳〜２．Ｏ１■に限定されることを示す。結果を第６表
に示す。Table 5 [Actual IJI 4 rows 9-10] Examples 9-1, short fiber reinforcement knee N installed between carcass ply and inner liner, layer thickness force (a), 2-
Meal~2. Indicates that it is limited to O1■. The results are shown in Table 6.
第６表
カー力スブライ−トのインナーライナーの厚さく実１１
１１１直：龍）−・最低１１謹必要
＊ニゲーシカ’Ａ！ｉＢぎてシートに出来なかった。−
タイヤが作成出来なかった。Table 6 Thickness of inner liner of Kerriki SBRITE 11
111 Direct: Ryu) - Minimum 11 points required * Nigeshika'A! I couldn't make it into a sheet because it was too iB. −
Tires could not be created.
２８＆
割石例！−計Ｉゆ
実施例１３〜１５では、加硫後の短繊維補強ゴムにおい
て短繊維の配向方向に引張った５０χ歪時の弾性率（Ｍ
１）と、短繊維の配列方向と直角の方向に引張った５０
χ歪時の弾性率（Ｍ２）の比（Ｍ１／Ｍ２）が２．５以
−にであることが好ましいことを示す。28& Breaking stone example! - In Examples 13 to 15, the modulus of elasticity (M
1) and 50 when pulled in the direction perpendicular to the direction in which the short fibers are arranged.
This shows that the ratio (M1/M2) of the elastic modulus (M2) at the time of χ strain is preferably 2.5 or more.
ゴム組成物１中の短繊維の配向の程度をロールとプレス
を糾合−ロて変化さ・口だ。The degree of orientation of the short fibers in the rubber composition 1 can be changed by combining the roll and press.
例えば、プレスのみを使用し′（ゴムシートを作成すれ
ば、旧／Ｍ２・１．０となる。■−ルの間隔を狭くすれ
ば、旧／Ｍ２は大きくなる。結ｔ１！ｉ−第１１友に示
す。For example, if only a press is used to create a rubber sheet, the old /M2 will be 1.0. ■ - If the spacing between the bars is narrowed, the old /M2 will become larger. Conclusion t1!i - 11th Show it to a friend.
〔実施例１１〜１２〕
実施例１１〜１２では、短繊維補強ゴム中の短繊維の量
が５重量部数−トに限定されることを示す。第７表の各
ゴムの組成物を用いて、第８表に示すようなタイヤを１
１潴己同様に試作し、テスト結果を示す。[Examples 11-12] Examples 11-12 show that the amount of short fibers in the short fiber reinforced rubber is limited to 5 parts by weight. Using each rubber composition in Table 7, one tire as shown in Table 8 was made.
A prototype was made in the same way as 1st grade, and the test results are shown.
第８表
第９表
なお本発明の短繊維とはしては、特開昭５７−１０６３
２号公報で開示される１ｓｏ−ポリプロピレン短繊維を
使用し、本発明の本質的要件の「高い異方性」を出すよ
うにアレンジすれば十分に可能である。Table 8 Table 9 The short fibers of the present invention are as follows:
It is fully possible to use the 1so-polypropylene short fibers disclosed in Publication No. 2 and arrange it so as to exhibit "high anisotropy" which is an essential requirement of the present invention.
また、特公昭５１−４５２１号公報、特公昭５７−４５
３０号公ｔＵ３特公昭５７−３０６６２号公報で開示さ
れた５ｙｎ−１゜２−ポリブタジェン短繊維についても
同様に使用可能である。但し、最も好ましいのは、ナイ
ロン短繊維である。Also, Japanese Patent Publication No. 51-4521, Japanese Patent Publication No. 57-45
The 5yn-1°2-polybutadiene short fibers disclosed in Japanese Patent Publication No. 30, No. 30, 1983 can also be used. However, the most preferred is short nylon fibers.
また、本発明は上記実施例によって縛られるものではな
く、有機繊維をベルトに使用したラジアルタイヤ、ヘル
ドを有したバイアスタイヤ（ベルテソ「バイヤスタイヤ
）、バイアスタイヤ等に使用可能であるし、乗用車用タ
イヤのみならず、大型タイヤにも当然適用可能である。Furthermore, the present invention is not limited to the above-mentioned embodiments, and can be used for radial tires using organic fibers in the belt, bias tires with healds (Verteso "bias tires"), bias tires, etc., and can be used for passenger cars. It is naturally applicable not only to tires but also to large tires.
（発明の効果）
以ト各実施例により、本発明のミクロな短繊維で補強さ
れたゴム組成物をタイヤのショルダー部区域のカーカス
プライとインナーライナーの間に配置することにより、
ゴム流れが主として起因するボード出を抑制することが
でき耐久性に優れる空気入りタイヤを提供できる。(Effects of the Invention) According to each of the examples below, by disposing the rubber composition reinforced with micro short fibers of the present invention between the carcass ply and the inner liner in the shoulder region of the tire,
It is possible to provide a pneumatic tire that can suppress board ejection mainly caused by rubber flow and has excellent durability.
Claims (1)
から成るカーカスプライと、このカーカスプライの両端
部をビード部で折り返し、係止した空気入りタイヤに於
いて、少なくともタイヤのショルダー部区域のカーカス
プライとインナーランサーの間に平均径１μｍ以下、平
均長さ（Ｌ）と平均径（Ｄ）の比（Ｌ／Ｄ）が８以上で
ある短繊維を５重量部以上含有するゴム組成物から成る
厚さ０．２〜２．０ｍｍの加硫可能なゴムシート層を備
えていることを特徴とする短繊維補強ゴムにより耐久性
の改善された空気入りタイヤ。 ２、カーカスプライの糸の配列方向と短繊維補強ゴム中
の配向方向との角度が３０度〜９０度であることを特徴
とする特許請求の範囲第一項記載の空気入りタイヤ。 ３、加硫後の短繊維補強ゴムに於いて短繊維の配列方向
に引張った１５０％歪時の弾性率（Ｍ１）と、短繊維の
配列方向と角度の方向に引張った１５０％歪時の弾性率
（Ｍ２）の比（Ｍ１／Ｍ２）が２．５以上であることを
特徴とする特許請求の範囲第一項記載の空気入りタイヤ
。 ４、カーカスプライに沿って計測した場合、もっともタ
イヤショルダー部区域内面の曲率半径の小さい部位を中
心に、その両端１ｃｍずつ以上の断面方向長さを有する
短繊維補強ゴムで覆っていることを特徴とする特許請求
の範囲第一項記載の空気入りタイヤ。 ５、短繊維が、▲数式、化学式、表等があります▼基を
有する熱可塑性ポリマーから成っており、ゴムの部分の
フェノールホルムアルデヒド系樹脂の縮合物を介してグ
ラフトしていることを特徴とする特許請求の範囲第一項
記載の空気入りタイヤ。[Scope of Claims] 1. A carcass ply consisting of a rubberized cord layer in which a large number of cords are arranged in parallel, and a pneumatic tire in which both ends of this carcass ply are folded back and locked at a bead portion, at least At least 5 parts by weight of short fibers with an average diameter of 1 μm or less and a ratio of average length (L) to average diameter (D) (L/D) of 8 or more are placed between the carcass ply and the inner lancer in the shoulder area of the tire. 1. A pneumatic tire with improved durability due to short fiber reinforced rubber, comprising a vulcanizable rubber sheet layer with a thickness of 0.2 to 2.0 mm made of a rubber composition containing the rubber composition. 2. The pneumatic tire according to claim 1, wherein the angle between the direction in which the threads of the carcass ply are arranged and the orientation direction in the short fiber reinforced rubber is 30 degrees to 90 degrees. 3. Elastic modulus (M1) at 150% strain when stretched in the direction of short fiber arrangement in the short fiber reinforced rubber after vulcanization, and 150% strain when stretched in the direction of the short fiber arrangement and angle. The pneumatic tire according to claim 1, wherein the ratio (M1/M2) of elastic modulus (M2) is 2.5 or more. 4. When measured along the carcass ply, the area with the smallest radius of curvature on the inner surface of the tire shoulder area is covered with short fiber reinforced rubber having a cross-sectional length of 1 cm or more at each end. A pneumatic tire according to claim 1. 5. The short fiber is made of a thermoplastic polymer having a ▲ mathematical formula, chemical formula, table, etc. group, and is characterized by being grafted via a condensate of phenol formaldehyde resin in the rubber part A pneumatic tire according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59232568A JP2545059B2 (en) | 1984-11-05 | 1984-11-05 | Pneumatic radial tire with improved durability due to short fiber reinforced rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59232568A JP2545059B2 (en) | 1984-11-05 | 1984-11-05 | Pneumatic radial tire with improved durability due to short fiber reinforced rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61110602A true JPS61110602A (en) | 1986-05-28 |
| JP2545059B2 JP2545059B2 (en) | 1996-10-16 |
Family
ID=16941378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59232568A Expired - Fee Related JP2545059B2 (en) | 1984-11-05 | 1984-11-05 | Pneumatic radial tire with improved durability due to short fiber reinforced rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2545059B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6342620A (en) * | 1986-08-07 | 1988-02-23 | 株式会社クボタ | Clogging detector of threshing apparatus |
| JPS6382801A (en) * | 1986-09-26 | 1988-04-13 | Ohtsu Tire & Rubber Co Ltd | Pneumatic tire |
| JPS6389805U (en) * | 1986-12-03 | 1988-06-10 | ||
| JPH07186609A (en) * | 1993-12-28 | 1995-07-25 | Sumitomo Rubber Ind Ltd | Pneumatic tire |
| US6634397B1 (en) * | 1997-04-28 | 2003-10-21 | The Goodyear Tire & Rubber Company | Tire having floating reinforcement in the shoulder/sidewall |
| WO2005007423A1 (en) * | 2003-07-17 | 2005-01-27 | The Yokohama Rubber Co., Ltd. | Pneumatic tire with improved durability |
| JP2007119614A (en) * | 2005-10-28 | 2007-05-17 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and pneumatic tire using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55152606A (en) * | 1979-05-15 | 1980-11-28 | Bridgestone Corp | Interiorly reinforced carcass for pneumatic tire |
| JPS5920704A (en) * | 1982-07-24 | 1984-02-02 | Bridgestone Corp | Tire |
-
1984
- 1984-11-05 JP JP59232568A patent/JP2545059B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55152606A (en) * | 1979-05-15 | 1980-11-28 | Bridgestone Corp | Interiorly reinforced carcass for pneumatic tire |
| JPS5920704A (en) * | 1982-07-24 | 1984-02-02 | Bridgestone Corp | Tire |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6342620A (en) * | 1986-08-07 | 1988-02-23 | 株式会社クボタ | Clogging detector of threshing apparatus |
| JPS6382801A (en) * | 1986-09-26 | 1988-04-13 | Ohtsu Tire & Rubber Co Ltd | Pneumatic tire |
| JPS6389805U (en) * | 1986-12-03 | 1988-06-10 | ||
| JPH07186609A (en) * | 1993-12-28 | 1995-07-25 | Sumitomo Rubber Ind Ltd | Pneumatic tire |
| US6634397B1 (en) * | 1997-04-28 | 2003-10-21 | The Goodyear Tire & Rubber Company | Tire having floating reinforcement in the shoulder/sidewall |
| WO2005007423A1 (en) * | 2003-07-17 | 2005-01-27 | The Yokohama Rubber Co., Ltd. | Pneumatic tire with improved durability |
| US7404424B2 (en) | 2003-07-17 | 2008-07-29 | The Yokohama Rubber Co., Ltd. | Pneumatic tire with buffer rubber layer |
| JP2007119614A (en) * | 2005-10-28 | 2007-05-17 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and pneumatic tire using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2545059B2 (en) | 1996-10-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |