JP3894626B2 - Rubber composition for tire - Google Patents
Rubber composition for tire Download PDFInfo
- Publication number
- JP3894626B2 JP3894626B2 JP24404197A JP24404197A JP3894626B2 JP 3894626 B2 JP3894626 B2 JP 3894626B2 JP 24404197 A JP24404197 A JP 24404197A JP 24404197 A JP24404197 A JP 24404197A JP 3894626 B2 JP3894626 B2 JP 3894626B2
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- JP
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- Prior art keywords
- rubber composition
- weight
- parts
- rubber
- tire
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- 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.)
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Description
【0001】
【発明の属する技術分野】
本発明は、高温加硫によっても物性の低下をきたすことがなく、かつスチールコードとの接着性を損なうことのないタイヤ用ゴム組成物に関する。
【0002】
【従来の技術】
従来、タイヤ性能を高めるために、スチールコードをゴム組成物で被覆してなるシート状物でベルト層やカーカス層等のタイヤ部品を構成していた。そして、近年、このようなタイヤ部品を用いたタイヤの生産性を高めるために、高温下(180℃程度)に短時間でタイヤ加硫することが行われるようになった。
【0003】
しかしながら、高温下でタイヤ加硫を行うとタイヤ部品を構成するゴム組成物の物性が低下すると共に、そのゴム組成物とスチールコードとの接着性、特に初期接着性および加硫後の吸湿による接着性(耐水接着性)が低下するという問題があった。
そこで、高温加硫におけるスチールコードとゴム組成物との接着性を高めるために、ヘキサメチロールメラミンペンタメチルエーテル(PMMM)の部分縮合物とクレゾール樹脂をゴムに配合してなるゴム組成物を用いることが提案されている(特開平4-39340 号公報) 。しかし、このゴム組成物を用いても接着性の低下を十分に抑えるのは困難であった。
【0004】
【発明が解決しようとする課題】
本発明の目的は、高温加硫によっても物性の低下をきたすことがなく、かつスチールコードとの接着性、特に加硫時の初期接着性および加硫後の耐水接着性を損なうことのないタイヤ用ゴム組成物を提供することにある。
【0005】
【課題を解決するための手段】
本発明のタイヤ用ゴム組成物は、原料ゴム100重量部に対し、ヘキサメトキシメチロールメラミンの部分縮合物を1.0〜5.0重量部、クレゾール樹脂を0.5〜5.0重量部配合してなり、前記クレゾール樹脂中のメタクレゾール樹脂分が80〜95%であることを特徴とする。
このように、ヘキサメトキシメチロールメラミン(HMMM)の部分縮合物を用いるため、上記目的の達成が可能となる。
【0006】
【発明の実施の形態】
原料ゴムとしては、天然ゴム、合成イソプレンゴム、スチレン−ブタジエン共重合体ゴム等の一般にタイヤ用として用いられるゴムを使用すればよい。
ヘキサメトキシメチロールメラミン(HMMM)の部分縮合物は、下記式を有する化合物である。縮合度は1〜3程度である。
【0007】
【化1】
【0008】
このヘキサメトキシメチロールメラミン(HMMM)の部分縮合物は、クレゾール樹脂に対して反応性の低いメチレンドナーとして作用する。反応性が高いと高温加硫に際して反応が速く進行し、ゴム組成物中にて十分な溶融流れが生じなくなるので、ゴム組成物の物性が低下すると共に、十分なスチールコードとゴム組成物との接着性が得られない。特開平4-39340 号公報に記載のようにヘキサメチロールメラミンペンタメチルエーテル(PMMM)の部分縮合物を用いると、PMMMの部分縮合物は水酸基(−OH)を有するため反応性が高いので、ゴム組成物の物性の低下をきたすと共に接着性が悪くなってしまう。
【0009】
ヘキサメトキシメチロールメラミン(HMMM)の部分縮合物としては、市販品を用いればよい。市販品としては、例えば、CYTEC INDUSTRIES INC.製の Cyrez 964を挙げることができる。このHMMMの配合量は、上記原料ゴム100重量部に対し1.0〜5.0重量部である。1.0重量部未満では十分な加硫後の吸湿による接着性(耐水接着性)が得られなくなり、5.0重量部を超えると物性の低下が大きくなるからである。
【0010】
クレゾール樹脂もまた市販品を用いることができる。このクレゾール樹脂としては、クレゾール樹脂中のメタクレゾール樹脂分が80〜95%のものを用いる。メタクレゾール樹脂分が80%未満ではゴム組成物の硬化後の剛性が低下することになり、一方、95%超ではクレゾール樹脂の反応性が高くなるからである。
【0011】
クレゾール樹脂は、上記原料ゴム100重量部に対し0.5〜5.0重量部配合する。0.5重量部未満では十分な加硫後の吸湿による接着性(耐水接着性)が得られなくなり、一方、5.0重量部を超えると物性の低下が大きくなってしまう。
本発明のタイヤ用ゴム組成物は、上記原料ゴムに対し、これらのHMMM、クレゾール樹脂を配合してなるものであるが、必要に応じて、カーボンブラック、硫黄等の他の配合剤を適宜配合してもよい。
【0012】
【実施例】
表1に示す配合内容(重量部)でゴム組成物(比較例1〜4、実施例1〜5)を作製し、下記によりその加硫物性、初期接着性、および耐水接着性を評価した。この結果を表1に示す。
引張特性:
JIS K 6301 に準拠。
【0013】
JIS硬度:
JIS K 6253 に準拠。
初期接着性:
12.5mm間隔で互いに平行に並べた黄銅メッキスチールコード(1×5構造)の両側からゴム組成物をコーティングして埋め込み、幅25mmのシートにして試験サンプルとした。この試験サンプルを180℃、12分加硫し、ついでASTM D 2229に準拠してそのサンプルからコードを引き抜き、そのときの引き抜き力(指数)とゴム被覆率(ゴム付き)%で評価した。数値の大きい方が優れている。
【0014】
耐水接着性:
加硫後の上記試験サンプルを切断して4週間70℃の温水中に浸漬した後、上記と同様にASTM D 2229に準拠して評価した。
【0015】
【表1】
【0016】
注)*1 スミカノール610、住友化学社製。
*2 SP7000、日触スケネクタデー社製。
*3 160 ℃、15分加硫の際の数値を100 としたときの保持率。
表1から明らかなように、本発明のゴム組成物(実施例1〜5)は、比較例1〜4に比して、高温下(180℃)の加硫によっても物性の低下をきたすことがなく、かつスチールコードとの初期接着性および耐水接着性に優れていることが判る。
【0017】
【発明の効果】
以上説明したように本発明のタイヤ用ゴム組成物は、原料ゴム100重量部に対し、ヘキサメトキシメチロールメラミンの部分縮合物を1.0〜5.0重量部、クレゾール樹脂を0.5〜5.0重量部配合してなり、このクレゾール樹脂中のメタクレゾール樹脂分が80〜95%であるため、高温加硫によっても物性の低下をきたすことがなく、かつスチールコードとの接着性、特に加硫時の初期接着性および加硫後の耐水接着性を損なうことがない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber composition for tires that does not cause deterioration in physical properties even by high-temperature vulcanization and does not impair adhesion with a steel cord.
[0002]
[Prior art]
Conventionally, in order to improve tire performance, tire parts such as a belt layer and a carcass layer have been configured with a sheet-like material formed by coating a steel cord with a rubber composition. In recent years, in order to increase the productivity of tires using such tire components, tire vulcanization has been performed at high temperatures (about 180 ° C.) in a short time.
[0003]
However, when the tire is vulcanized at high temperatures, the physical properties of the rubber composition constituting the tire component are reduced, and the adhesion between the rubber composition and the steel cord, particularly the initial adhesion and adhesion due to moisture absorption after vulcanization. There was a problem that the property (water-resistant adhesiveness) deteriorated.
Therefore, in order to improve the adhesion between the steel cord and the rubber composition in high-temperature vulcanization, a rubber composition obtained by blending rubber with a partial condensate of hexamethylol melamine pentamethyl ether (PMMM) and a cresol resin is used. Has been proposed (JP-A-4-39340). However, even when this rubber composition is used, it is difficult to sufficiently suppress the decrease in adhesiveness.
[0004]
[Problems to be solved by the invention]
An object of the present invention is a tire that does not deteriorate in physical properties even by high-temperature vulcanization, and does not impair the adhesion to a steel cord, particularly the initial adhesion during vulcanization and the water-resistant adhesion after vulcanization. It is to provide a rubber composition for use.
[0005]
[Means for Solving the Problems]
The rubber composition for tires of the present invention contains 1.0 to 5.0 parts by weight of a partial condensate of hexamethoxymethylolmelamine and 0.5 to 5.0 parts by weight of cresol resin with respect to 100 parts by weight of raw rubber. Ri greens and, metacresol resin content in the cresol resin is characterized 80% to 95% der Rukoto.
Thus, since the partial condensate of hexamethoxymethylolmelamine (HMMM) is used, the above object can be achieved.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
As the raw rubber, rubber generally used for tires such as natural rubber, synthetic isoprene rubber, styrene-butadiene copolymer rubber may be used.
A partial condensate of hexamethoxymethylolmelamine (HMMM) is a compound having the following formula. The degree of condensation is about 1 to 3.
[0007]
[Chemical 1]
[0008]
This partial condensate of hexamethoxymethylolmelamine (HMMM) acts as a methylene donor that is less reactive with cresol resins. If the reactivity is high, the reaction proceeds fast during high-temperature vulcanization, and a sufficient melt flow does not occur in the rubber composition, so that the physical properties of the rubber composition are reduced and sufficient steel cord and rubber composition Adhesiveness cannot be obtained. When a partial condensate of hexamethylol melamine pentamethyl ether (PMMM) is used as described in JP-A-4-39340, since the partial condensate of PMMM has a hydroxyl group (—OH), the reactivity is high. The physical properties of the composition are lowered and the adhesiveness is deteriorated.
[0009]
A commercially available product may be used as a partial condensate of hexamethoxymethylolmelamine (HMMM). Examples of commercially available products include CYTEC INDUSTRIES INC. Mention may be made of Cyrez 964. The amount of HMMM is 1.0 to 5.0 parts by weight per 100 parts by weight of the raw rubber. This is because if the amount is less than 1.0 part by weight, sufficient adhesiveness due to moisture absorption after vulcanization (water-resistant adhesiveness) cannot be obtained, and if it exceeds 5.0 parts by weight, the physical properties decrease greatly.
[0010]
A commercial product can also be used as the cresol resin. As this cresol resin, those having a metacresol resin content of 80 to 95% in the cresol resin are used . This is because if the metacresol resin content is less than 80%, the rigidity of the rubber composition after curing decreases, while if it exceeds 95%, the reactivity of the cresol resin increases.
[0011]
The cresol resin is blended in an amount of 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the raw rubber. If the amount is less than 0.5 part by weight, sufficient adhesion (moisture resistance) due to moisture absorption after vulcanization cannot be obtained.
The tire rubber composition of the present invention is formed by blending these HMMM and cresol resin with the above raw rubber, and optionally blending other compounding agents such as carbon black and sulfur as necessary. May be.
[0012]
【Example】
Rubber compositions (Comparative Examples 1 to 4, Examples 1 to 5) were prepared with the blending contents (parts by weight) shown in Table 1, and the vulcanized physical properties, initial adhesiveness, and water resistant adhesiveness were evaluated as follows. The results are shown in Table 1.
Tensile properties :
Conforms to JIS K 6301.
[0013]
JIS hardness :
Conforms to JIS K 6253.
Initial adhesion :
The rubber composition was coated and embedded from both sides of brass-plated steel cords (1 × 5 structure) arranged in parallel with each other at 12.5 mm intervals, and a 25 mm wide sheet was obtained as a test sample. This test sample was vulcanized at 180 ° C. for 12 minutes, and then the cord was pulled out from the sample in accordance with ASTM D 2229. The pulling force (index) and rubber coverage (with rubber)% at that time were evaluated. Larger numbers are better.
[0014]
Water-resistant adhesion :
The test sample after vulcanization was cut and immersed in warm water at 70 ° C. for 4 weeks, and then evaluated according to ASTM D 2229 in the same manner as described above.
[0015]
[Table 1]
[0016]
Note) * 1 Sumikanol 610, manufactured by Sumitomo Chemical Co., Ltd.
* 2 SP7000, manufactured by Nichichu Schenectaday.
* 3 Retention rate when the value for vulcanization at 160 ° C for 15 minutes is 100.
As is clear from Table 1, the rubber compositions (Examples 1 to 5) of the present invention also have lower physical properties than those of Comparative Examples 1 to 4 even by vulcanization at high temperatures (180 ° C.). It can be seen that there is no initial adhesion to the steel cord and excellent water-resistant adhesion.
[0017]
【The invention's effect】
As described above, the tire rubber composition of the present invention has a partial condensate of hexamethoxymethylolmelamine in an amount of 1.0 to 5.0 parts by weight and a cresol resin in an amount of 0.5 to 5 with respect to 100 parts by weight of the raw rubber. .0 parts by Ri and Na by blending, metacresol resin content is 80% to 95% der because of the cresol resin, without causing deterioration of physical properties due to the high temperature vulcanization, and adhesion to the steel cord In particular, the initial adhesion during vulcanization and the water-resistant adhesion after vulcanization are not impaired.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24404197A JP3894626B2 (en) | 1997-09-09 | 1997-09-09 | Rubber composition for tire |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24404197A JP3894626B2 (en) | 1997-09-09 | 1997-09-09 | Rubber composition for tire |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH1180432A JPH1180432A (en) | 1999-03-26 |
JP3894626B2 true JP3894626B2 (en) | 2007-03-22 |
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ID=17112844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24404197A Expired - Fee Related JP3894626B2 (en) | 1997-09-09 | 1997-09-09 | Rubber composition for tire |
Country Status (1)
Country | Link |
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JP (1) | JP3894626B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9056527B2 (en) | 2011-05-17 | 2015-06-16 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire and pneumatic tire |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4647947B2 (en) * | 2004-07-16 | 2011-03-09 | 住友ゴム工業株式会社 | Rubber composition for covering carcass fiber cord and carcass fiber cord coated thereby |
JP5009510B2 (en) | 2005-05-25 | 2012-08-22 | 住友ゴム工業株式会社 | Rubber composition for coating carcass cord and carcass cord coated thereby |
JP5185528B2 (en) * | 2006-12-21 | 2013-04-17 | 住友ゴム工業株式会社 | Rubber composition for coating steel cord, and tire having belt or breaker obtained by coating steel cord with the same |
-
1997
- 1997-09-09 JP JP24404197A patent/JP3894626B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9056527B2 (en) | 2011-05-17 | 2015-06-16 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire and pneumatic tire |
Also Published As
Publication number | Publication date |
---|---|
JPH1180432A (en) | 1999-03-26 |
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