JP2004035690A - Rubber composition for tire - Google Patents
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- JP2004035690A JP2004035690A JP2002193729A JP2002193729A JP2004035690A JP 2004035690 A JP2004035690 A JP 2004035690A JP 2002193729 A JP2002193729 A JP 2002193729A JP 2002193729 A JP2002193729 A JP 2002193729A JP 2004035690 A JP2004035690 A JP 2004035690A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、再生ゴムの利用に関し、更に詳しくは、樹脂架橋ブチルゴムの再生ゴムをタイヤ用ゴム組成物に再利用することに関する。
【０００２】
【従来の技術】
従来より、加硫ゴムの再生は、廃棄加硫ゴムを粗粉砕した後に脱硫剤を加え、高温でロールなどを用いて脱硫再生している。しかし、この方法では、ゴム分子の主鎖が切断され易く、新材ゴムに比べて物性が低下するという問題があった。
一方、二軸押出し機を用いて、高剪断力と温度をかけて硫黄加硫ゴムを処理することにより、硫黄の結合を選択的に切断し、ゴムの劣化を最小にして硫黄加硫ゴムを再生する技術も、特開平９−２２７７２４号公報により公知である。
しかし、一般に、樹脂架橋のブチルゴムは、その再生が困難であるとするのが従来の技術常識であった。
【０００３】
【発明が解決しようとする課題】
したがって、本発明では、樹脂架橋ゴムの有効な再生技術を提供し、これにより得られる樹脂架橋ゴムの再生ゴムをタイヤ用ゴム組成物に利用することを目的とする。
【０００４】
【課題を解決するための手段】
本発明によれば、樹脂架橋された架橋ゴムの架橋結合が切断され、微細な粒径のカーボンブラックを含有している再生ゴムを１〜１００重量％含むタイヤ用ゴム組成物が提供される。
【０００５】
また、本発明によれば、樹脂架橋された架橋ゴムが温度２２０〜３５０℃、剪断圧力１０〜１５０ｋｇ／ｃｍ２ の条件にて処理された再生ゴムを含むタイヤ用ゴム組成物が提供される。
【０００６】
また、本発明によれば、樹脂架橋された架橋ゴムが温度２２０〜３５０℃、剪断圧力１０〜１５０ｋｇ／ｃｍ２ の条件にて処理された再生ゴムに更に酸化マグネシウムを添加したタイヤ用ゴム組成物が提供される。
【０００７】
また、本発明によれば、前記再生ゴム原料と新材未加硫ゴムとを混合し、加硫、成形したタイヤ製品が提供される。
【０００８】
【発明の実施の形態】
本発明では、樹脂架橋されたゴムを押出し機を用いて、温度２２０〜３５０℃、剪断圧力１０〜１５０ｋｇ／ｃｍ２ の条件で処理した再生ゴムは、その架橋結合のみが選択的に破断でき、物性の低下なしにこれを再生物として有効に使用できることを見い出したものである。
【０００９】
本発明の再生処理に供される樹脂架橋された架橋ゴムとしては、廃棄物の対象となるアルキルフェノールホルムアルデヒド樹脂架橋剤で架橋されてなる樹脂架橋ブチルゴムである。この樹脂架橋ブチルゴムは、従来再生が困難とされていたが、本発明の再生処理により、簡単な操作で、効率的に粘着性の良好な再生ブチルゴムに変換することができ、かつこの再生処理によってもその物性の低下が少ないのでこれを単独で、あるいはまた、新材のブチルゴムと所定の比で配合してタイヤ用ゴム組成物として有効に再利用が可能となった。
【００１０】
本発明の熱と剪断力を利用する再生処理における加熱温度は、樹脂架橋ブチルゴムを構成する架橋剤成分であるアルキルフェノールホルムアルデヒド樹脂の解重合可能温度以上であることが好ましく、その具体的最適温度は、樹脂の種類その他の条件によって異なるが、通常２２０℃以上、特に２２０〜３５０℃が好ましい。２２０℃以下では、解重合が事実上起らず、また、３５０℃以上では解重合の度合が多くなり過ぎてブチルゴムが低分子量化され過ぎ、再生収率が低下すると共に、更には再生ブチルゴム表面に炭化が起る等して好ましくない。
【００１１】
なお、解重合可能温度範囲において、比較的低温度で加熱すると高強度を有する再生ブチルゴムが得られ、また、比較的高温度で加熱すると低強度、高伸度を有する再生ブチルゴムが得られる。
【００１２】
また、再生処理における剪断応力は１０〜１５０ｋｇ／ｃｍ２ が好適である。この条件下で剪断力をかけると、廃棄ブチルゴムの樹脂架橋結合が切断されるが、ゴム分子の主鎖の切断は回避することができる。この剪断操作によって、廃ブチルゴム中に含まれるカーボンブラックの粒径も１００μｍ以下に微細化される。かかる剪断操作を採用することによって、再生ブチルゴム特性の劣化を防止することができる。上記剪断応力が１０ｋｇ／ｃｍ２ 未満である場合には、カーボンブラックの微細化および再生ブチルゴム中へのカーボンブラックの分散が不充分となり、再生ゴムタイヤ製品の所望のゴム特性が得られなくなる。他方、上記剪断応力が１５０ｋｇ／ｃｍ２ より大きい場合には、ブチルゴム分子における主鎖が切断され、この条件で得られる再生ゴムを用いたタイヤ製品のゴム特性が大きく低下する。
【００１３】
前記廃ブチルゴムの所定の温度および剪断応力下における剪断操作には、例えば、通常の一軸、二軸、多軸のいずれの方式の押出し機の使用も可能である。この処理時間には、特に制約はなく、通常、例えば、１〜２０分程度である。
【００１４】
本発明方法に供する廃棄樹脂架橋ブチルゴムは、アルキルフェノールホルムアルデヒド樹脂で加硫されたブチルゴムであればいずれでもよい。加硫剤であるアルキルフェノールホルムアルデヒド樹脂としては、例えば、商品名「タッキロール２０１」（住友化学）、「ヒタノール２５０１」（日立化成）、臭素化された樹脂「タッキロール２５０」（住友化学）等、いずれの使用も可能であり、また、ブチルゴムも、不飽和度の異なるもの、塩素化や臭素化されたもの等いずれの使用も可能である。
【００１５】
本発明による再生ブチルゴムに対して、所定量の酸化マグネシウムを加えたゴム組成物を用いてタイヤ製品とする場合には、再生ブチルゴムのみを用いた場合に比してよりタイヤ特性の優れたタイヤ製品が得られる。この酸化マグネシウムの添加剤は、通常、ゴム組成物１００重量部に対して、０．５〜１０重量部加えることが好ましい。
【００１６】
本発明により得られる再生ブチルゴムは、新材ブチルゴムとそのゴム物性がほとんど同じであるので、これを単独で、あるいは新材ブチルゴムと配合して、通常１〜１００重量％の配合量のタイヤ用ゴム組成物として、タイヤ製品の各種部材、例えば、ブラダー、チューブおよびインナーライナー等として有効に使用できる。
【００１７】
【実施例】
以下、実施例および比較例によ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はない。
再生ブチルゴムの製造
再生ブチルゴムの製造は、例えば、ゴム工業便覧（第四版）、日本ゴム協会編、第３７６頁に記載されている方法によって行った。本再生の原料としてタイヤ用チューブを使用しており、その評価は、ＪＩＳ Ｋ ６３１３に記載されている。
ブラダー再生ブチルゴムの製造
タイヤの加硫時に使用するブラダーの使用済品を粉砕し、５ｍｍ程度にした。これを一軸押出機により２２０〜３５０℃、剪断圧力１０〜１５０ｋｇ／ｃｍ２ の条件により再生した。
【００１８】
試験サンプルの作製
表１に示す加硫促進剤と硫黄を除く成分を１．８リットルの密閉型ミキサーで３〜５分間混練し、１６５±５℃に達したときに放出したマスターバッチに加硫促進剤と硫黄を８インチのオープンロール混練し、ゴム組成物を得た。得られたゴム組成物の未加硫物性（ムーニービス、ムーニー粘度）を測定した。
次に、このゴム組成物を１５×１５×０．２ｃｍの金型中で１６０℃で２０分間プレス加硫して試験片（ゴムシート）を作製し、加硫物性（加硫度、ブランク引張り、引張強さ、硬度、伸び、粘弾性）を測定した。
【００１９】
各例において得られた組成物の未加硫物性および加硫物性の試験方法は、以下のとおりである。
未加硫物性
１）ムーニースコーチ：ＪＩＳ Ｋ ６３００に基づき１３５℃にて粘度が５ポイント上昇する時間（分）を測定した。
２）ムーニー粘度：ＪＩＳ Ｋ ６３００に基づき１００℃にて測定した。
加硫物性
３）加硫度：レオメーターを用いて、ＪＩＳ Ｋ ６３００に基づき１６０℃にて測定した。
４）ブランク引張り：引張応力（Ｍ）、引張強さ（ＴＢ ）、伸び（ＥＢ ）をＪＩＳ Ｋ ６３０１に準拠して測定した。
５）硬度：ＪＩＳ Ｋ ６３０１に準拠して測定した。
６）粘弾性：ｔａｎδ（２０℃，６０℃）を東洋精機製作所製レオログラフソリッドを用い、初期歪み１０％、動的歪み２％、周波数２０Ｈｚで粘弾性を測定する（試料幅：５ｍｍ）と共に、ＪＩＳ Ｋ ６３９４に準拠してＥ′，Ｅ″を測定した。
【００２０】
実施例１〜４および比較例１〜３
再生ブチルゴム、ブラダー再生ブチルゴムについて各種未加硫、加硫物性について測定した。また、ブラダー再生ブチルゴムに酸化マグネシウムを加えたときの各種物性についても測定した。結果を以下の表１に示す。
【００２１】
【表１】
タイヤ評価
実施例２のコンパウンドをタイヤのインナーライナーとして使用した。
適用サイズ：１８５／７０Ｒ１４
空気漏れ試験を実施したところ、３ケ月で７％空気圧が低下したが、これは従来のブチルライナーと同等であった。他の室内耐久テストでも従来のブチルライナーと同等であった。また、フィールドの耐久試験を実施したところ、８万ｋｍ走行しても異常が発生しなかった。
【００２３】
【発明の効果】
表１により示されるように、本発明の再生ブチルゴムは、その新材ゴムに比して各物性において低下することはなく、また、タイヤ評価に示されるように、新材ブチルゴムと同様に有効にタイヤ用ゴム材として使用することができる。また、本発明のブチルゴムの再生方法によれば、極めて容易に廃ゴムを再生することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the use of recycled rubber, and more particularly, to recycling recycled rubber of resin-crosslinked butyl rubber into a rubber composition for tires.
[0002]
[Prior art]
BACKGROUND ART Conventionally, vulcanized rubber is regenerated by adding a desulfurizing agent after coarsely pulverizing waste vulcanized rubber and using a roll or the like at a high temperature for desulfurization regeneration. However, this method has a problem that the main chain of the rubber molecule is easily cut, and the physical properties are lower than that of the new rubber.
On the other hand, by using a twin-screw extruder and applying high shearing force and temperature to the sulfur vulcanized rubber, sulfur bonds are selectively cut, minimizing rubber deterioration and reducing the sulfur vulcanized rubber. The technique of reproducing is also known from JP-A-9-227724.
However, it has generally been common knowledge in the prior art that resin-crosslinked butyl rubber is generally difficult to regenerate.
[0003]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide an effective technique for regenerating a resin crosslinked rubber, and to use the regenerated rubber of the resin crosslinked rubber obtained thereby in a rubber composition for a tire.
[0004]
[Means for Solving the Problems]
According to the present invention, there is provided a rubber composition for a tire containing 1 to 100% by weight of a recycled rubber containing carbon black having a fine particle diameter, in which a crosslinked bond of a resin-crosslinked rubber is cut.
[0005]
Further, according to the present invention, there is provided a rubber composition for a tire including a recycled rubber in which a crosslinked rubber crosslinked with a resin is treated at a temperature of 220 to 350 ° C and a shear pressure of 10 to 150 kg / cm 2 .
[0006]
Further, according to the present invention, a rubber composition for a tire, in which magnesium oxide is further added to a reclaimed rubber obtained by treating a crosslinked rubber crosslinked with a resin at a temperature of 220 to 350 ° C and a shear pressure of 10 to 150 kg / cm 2 . Is provided.
[0007]
Further, according to the present invention, there is provided a tire product obtained by mixing the above-mentioned recycled rubber raw material and a new unvulcanized rubber, vulcanizing and molding.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, a recycled rubber obtained by treating a resin cross-linked rubber with an extruder at a temperature of 220 to 350 ° C. and a shear pressure of 10 to 150 kg / cm 2 can selectively break only its cross-linking, It has been found that this can be effectively used as a regenerated product without deterioration in physical properties.
[0009]
The resin-crosslinked rubber to be subjected to the regeneration treatment of the present invention is a resin-crosslinked butyl rubber which is crosslinked with an alkylphenol formaldehyde resin crosslinking agent to be a waste. Conventionally, this resin-crosslinked butyl rubber has been considered difficult to regenerate. However, the regeneration treatment of the present invention makes it possible to efficiently convert it into a good-adhesion regenerated butyl rubber with a simple operation. Since the physical properties of these rubbers are little reduced, they can be effectively reused as a rubber composition for tires by using the rubber alone or in combination with a new material, butyl rubber, at a predetermined ratio.
[0010]
The heating temperature in the regeneration treatment using heat and shear force of the present invention is preferably not lower than the depolymerizable temperature of the alkylphenol formaldehyde resin which is a crosslinking agent component constituting the resin crosslinked butyl rubber, and the specific optimum temperature is Although it depends on the type of resin and other conditions, it is usually 220 ° C. or higher, and particularly preferably 220 to 350 ° C. At a temperature of 220 ° C. or less, depolymerization practically does not occur, and at a temperature of 350 ° C. or more, the degree of depolymerization becomes too large, the butyl rubber becomes too low in molecular weight, the regeneration yield decreases, and the surface of the regenerated butyl rubber Is not preferred because carbonization occurs.
[0011]
When heated at a relatively low temperature within the depolymerizable temperature range, a regenerated butyl rubber having high strength is obtained, and when heated at a relatively high temperature, a regenerated butyl rubber having low strength and high elongation is obtained.
[0012]
Further, the shear stress in the regeneration treatment is preferably from 10 to 150 kg / cm 2 . When a shearing force is applied under this condition, the resin cross-linking of the waste butyl rubber is broken, but the breaking of the main chain of the rubber molecule can be avoided. By this shearing operation, the particle size of the carbon black contained in the waste butyl rubber is also reduced to 100 μm or less. By employing such a shearing operation, it is possible to prevent deterioration of the properties of the recycled butyl rubber. If the shear stress is less than 10 kg / cm 2 , the fineness of the carbon black and the dispersion of the carbon black in the recycled butyl rubber become insufficient, and the desired rubber properties of the recycled rubber tire product cannot be obtained. On the other hand, when the shear stress is larger than 150 kg / cm 2 , the main chain of the butyl rubber molecule is cut, and the rubber properties of the tire product using the recycled rubber obtained under this condition are greatly reduced.
[0013]
For the shearing operation of the waste butyl rubber under a predetermined temperature and shear stress, for example, an ordinary extruder of any one of a single-screw, a twin-screw, and a multi-screw type can be used. The processing time is not particularly limited, and is usually, for example, about 1 to 20 minutes.
[0014]
The waste resin crosslinked butyl rubber used in the method of the present invention may be any butyl rubber vulcanized with an alkylphenol formaldehyde resin. Examples of the alkylphenol formaldehyde resin as a vulcanizing agent include, for example, any of trade names “Tackilol 201” (Sumitomo Chemical), “Hitanol 2501” (Hitachi Chemical), and brominated resin “Tackilol 250” (Sumitomo Chemical). It is also possible to use any of butyl rubbers, such as those having different degrees of unsaturation, chlorinated or brominated, and the like.
[0015]
When a tire product is obtained by using a rubber composition obtained by adding a predetermined amount of magnesium oxide to the reclaimed butyl rubber according to the present invention, a tire product having more excellent tire characteristics as compared to a case using only the reclaimed butyl rubber Is obtained. Usually, it is preferable to add 0.5 to 10 parts by weight of the magnesium oxide additive to 100 parts by weight of the rubber composition.
[0016]
The reclaimed butyl rubber obtained by the present invention has almost the same physical properties as the new butyl rubber. Therefore, the recycled butyl rubber is used alone or in combination with the new butyl rubber. The composition can be effectively used as various components of tire products, for example, bladders, tubes, inner liners, and the like.
[0017]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the technical scope of the present invention is not limited to these Examples.
Production of Recycled Butyl Rubber The production of recycled butyl rubber was carried out, for example, by the method described in Rubber Industry Handbook (4th edition), edited by The Japan Rubber Association, page 376. A tire tube is used as a raw material for the main regeneration, and the evaluation is described in JIS K 6313.
Manufacture of bladder recycled butyl rubber The used bladder used for vulcanizing the tire was pulverized to about 5 mm. This was regenerated by a single screw extruder under the conditions of 220 to 350 ° C. and a shear pressure of 10 to 150 kg / cm 2 .
[0018]
Preparation of test sample A vulcanization accelerator shown in Table 1 and components other than sulfur were kneaded in a 1.8 liter closed mixer for 3 to 5 minutes, and the master was released when the temperature reached 165 ± 5 ° C. The batch was kneaded with an 8-inch open roll with a vulcanization accelerator and sulfur to obtain a rubber composition. The unvulcanized physical properties (Mooney bis, Mooney viscosity) of the obtained rubber composition were measured.
Next, this rubber composition was press-vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 20 minutes to prepare a test piece (rubber sheet), and the vulcanization properties (vulcanization degree, blank tension). , Tensile strength, hardness, elongation and viscoelasticity) were measured.
[0019]
The test methods for the unvulcanized physical properties and the vulcanized physical properties of the compositions obtained in each example are as follows.
Unvulcanized physical properties 1) Mooney scorch: The time (minutes) at which the viscosity increased by 5 points at 135 ° C. was measured based on JIS K 6300.
2) Mooney viscosity: measured at 100 ° C. based on JIS K 6300.
Vulcanization properties 3) Degree of vulcanization : Measured at 160 ° C. using a rheometer based on JIS K 6300.
4) Blank tensile: Tensile stress (M), tensile strength (T B ), and elongation (E B ) were measured according to JIS K6301.
5) Hardness: measured according to JIS K6301.
6) Viscoelasticity: Measure viscoelasticity of tan δ (20 ° C., 60 ° C.) using a rheograph solid manufactured by Toyo Seiki Seisakusho at an initial strain of 10%, a dynamic strain of 2%, and a frequency of 20 Hz (sample width: 5 mm). At the same time, E ′ and E ″ were measured according to JIS K6394.
[0020]
Examples 1-4 and Comparative Examples 1-3
Various unvulcanized and vulcanized physical properties of the recycled butyl rubber and the bladder recycled butyl rubber were measured. In addition, various physical properties when magnesium oxide was added to the bladder recycled butyl rubber were also measured. The results are shown in Table 1 below.
[0021]
[Table 1]
Tire evaluation The compound of Example 2 was used as an inner liner of a tire.
Applicable size: 185 / 70R14
When an air leak test was performed, the air pressure was reduced by 7% in three months, which was equivalent to the conventional butyl liner. In other indoor durability tests, it was equivalent to the conventional butyl liner. In addition, when a field durability test was performed, no abnormality occurred even after traveling 80,000 km.
[0023]
【The invention's effect】
As shown in Table 1, the recycled butyl rubber of the present invention does not decrease in various physical properties as compared with the new rubber, and as shown in the tire evaluation, is as effective as the new butyl rubber. It can be used as a rubber material for tires. Further, according to the method for regenerating butyl rubber of the present invention, waste rubber can be regenerated very easily.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002193729A JP4338365B2 (en) | 2002-07-02 | 2002-07-02 | Rubber composition for tire |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002193729A JP4338365B2 (en) | 2002-07-02 | 2002-07-02 | Rubber composition for tire |
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| Publication Number | Publication Date |
|---|---|
| JP2004035690A true JP2004035690A (en) | 2004-02-05 |
| JP4338365B2 JP4338365B2 (en) | 2009-10-07 |
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|---|---|---|---|
| JP2002193729A Expired - Lifetime JP4338365B2 (en) | 2002-07-02 | 2002-07-02 | Rubber composition for tire |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007320992A (en) * | 2006-05-30 | 2007-12-13 | Yokohama Rubber Co Ltd:The | Rubber composition for tire inner liner |
| JP2008126634A (en) * | 2006-11-24 | 2008-06-05 | Sumitomo Rubber Ind Ltd | Manufacturing method of rubber composition for recycled inner liners |
| JP2015052031A (en) * | 2013-09-05 | 2015-03-19 | 横浜ゴム株式会社 | Rubber composition for tire inner liner and pneumatic tire using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5766006A (en) | 1995-06-26 | 1998-06-16 | Murljacic; Maryann Lehmann | Tooth shade analyzer system and methods |
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|---|---|---|---|---|
| JPS52117384A (en) * | 1976-03-26 | 1977-10-01 | Kogyo Gijutsuin | Regenerating method of resin vulcanized butyl rubber |
| JPS61176648A (en) * | 1985-02-01 | 1986-08-08 | Yokohama Rubber Co Ltd:The | Rubber composition for inner liner of tire |
| JPH02231202A (en) * | 1989-03-02 | 1990-09-13 | Sumitomo Rubber Ind Ltd | Pneumatic tire |
| JPH09132005A (en) * | 1985-01-14 | 1997-05-20 | Hercules Inc | Pneumatic tire with liner layer |
| JPH09227724A (en) * | 1995-12-19 | 1997-09-02 | Toyota Central Res & Dev Lab Inc | Reclaimed desulfurized rubber, its production and production of reclaimed rubber article |
| WO2000074913A1 (en) * | 1999-06-08 | 2000-12-14 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of reclaiming crosslinked rubber and molded article of reclaimed rubber |
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2002
- 2002-07-02 JP JP2002193729A patent/JP4338365B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52117384A (en) * | 1976-03-26 | 1977-10-01 | Kogyo Gijutsuin | Regenerating method of resin vulcanized butyl rubber |
| JPH09132005A (en) * | 1985-01-14 | 1997-05-20 | Hercules Inc | Pneumatic tire with liner layer |
| JPS61176648A (en) * | 1985-02-01 | 1986-08-08 | Yokohama Rubber Co Ltd:The | Rubber composition for inner liner of tire |
| JPH02231202A (en) * | 1989-03-02 | 1990-09-13 | Sumitomo Rubber Ind Ltd | Pneumatic tire |
| JPH09227724A (en) * | 1995-12-19 | 1997-09-02 | Toyota Central Res & Dev Lab Inc | Reclaimed desulfurized rubber, its production and production of reclaimed rubber article |
| WO2000074913A1 (en) * | 1999-06-08 | 2000-12-14 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of reclaiming crosslinked rubber and molded article of reclaimed rubber |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007320992A (en) * | 2006-05-30 | 2007-12-13 | Yokohama Rubber Co Ltd:The | Rubber composition for tire inner liner |
| JP2008126634A (en) * | 2006-11-24 | 2008-06-05 | Sumitomo Rubber Ind Ltd | Manufacturing method of rubber composition for recycled inner liners |
| JP2015052031A (en) * | 2013-09-05 | 2015-03-19 | 横浜ゴム株式会社 | Rubber composition for tire inner liner and pneumatic tire using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4338365B2 (en) | 2009-10-07 |
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