JP2001049044A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JP2001049044A JP2001049044A JP11221452A JP22145299A JP2001049044A JP 2001049044 A JP2001049044 A JP 2001049044A JP 11221452 A JP11221452 A JP 11221452A JP 22145299 A JP22145299 A JP 22145299A JP 2001049044 A JP2001049044 A JP 2001049044A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- rubber
- nickel
- rubber composition
- organic acid
- 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.)
- Pending
Links
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はゴム組成物に関し、
更に詳しくはスチールコード被覆ゴム用の接着助剤とし
て有用な初期接着力及び耐水接着保持性に優れたゴム組
成物に関する。TECHNICAL FIELD The present invention relates to a rubber composition,
More specifically, the present invention relates to a rubber composition having excellent initial adhesive strength and water-resistant adhesive holding property, which is useful as an adhesive aid for steel cord-coated rubber.
【０００２】[0002]
【従来の技術】空気入りタイヤにはタイヤの補強のため
にスチールコードなどのコードを用いているが、かかる
スチールコードでタイヤを構成するためにはスチール材
料とゴム材料との接触面での接着性に問題があった。こ
のために、スチールの表面を処理したり、接着用配合剤
をゴムに添加することが行われている。2. Description of the Related Art A cord such as a steel cord is used for a pneumatic tire to reinforce the tire. However, in order to constitute a tire with such a steel cord, bonding at a contact surface between a steel material and a rubber material is required. There was a problem with sex. For this purpose, the surface of steel is treated or an adhesive compound is added to rubber.
【０００３】特公昭５１−４１９１５号公報にナフテン
酸コバルト、ナフテン酸ニッケルとアルキルフェノール
樹脂との組み合わせによる接着性被覆ゴムが記載されて
いる。しかしニッケル塩との組み合わせは接着力が充分
でないという問題がある。特公平４−２２１２０５号公
報にはメタクレゾール樹脂と有機酸コバルトの組み合わ
せが開示されているが、これも接着力がまだ充分でない
という問題がある。また森ら（第１１回エラストマー討
論会、１９９８年１２月）は有機酸ニッケルと亜鉛メッ
キとの組み合せを開示しているが黄銅メッキに対する記
載はない。[0003] JP-B-51-41915 discloses an adhesive coated rubber obtained by combining cobalt naphthenate, nickel naphthenate and an alkylphenol resin. However, the combination with the nickel salt has a problem that the adhesive strength is not sufficient. Japanese Patent Publication No. 221205/1992 discloses a combination of a meta-cresol resin and an organic acid cobalt, but also has a problem that the adhesive strength is still insufficient. Mori et al. (11th Elastomer Symposium, December 1998) disclose a combination of nickel organic acid and zinc plating, but do not describe brass plating.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明は前記
した従来技術の問題点を解決して、初期接着力及び耐水
接着保持性のいずれにも優れたスチールコード被覆ゴム
用の接着助剤として有用なゴム組成物を提供することを
目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention solves the above-mentioned problems of the prior art and provides an adhesive agent for a steel cord-coated rubber excellent in both initial adhesive strength and water-resistant adhesive retention. An object is to provide a useful rubber composition.
【０００５】[0005]
【課題を解決するための手段】本発明に従えば、原料ゴ
ム１００重量部に対して有機酸ニッケルをニッケル元素
として０．０５〜０．５重量部含み、そしてレゾルシン
・ホルマリン（ＲＦ）樹脂をレゾルシン（Ｒ）分とホル
マリン（Ｆ）分の合計量で１〜７重量部含むゴム組成物
が提供される。According to the present invention, an organic acid nickel is contained in an amount of 0.05 to 0.5 part by weight as a nickel element based on 100 parts by weight of a raw rubber, and a resorcinol-formalin (RF) resin is used. There is provided a rubber composition containing 1 to 7 parts by weight in total of resorcinol (R) and formalin (F).
【０００６】[0006]
【発明の実施の形態】スチール被覆ゴムとして接着助剤
として有機酸のニッケル塩とＲＦ樹脂とを併用すること
により、初期接着力及び耐水接着保持性のいずれにも優
れた接着性能有する接着助剤を開発することに成功し
た。ニッケル塩は一般的にコバルト塩より初期接着力は
低いが、ＲＦ樹脂を加えることにより初期接着力を安定
的に向上させることができる。一方耐水接着保持性はニ
ッケル塩よりコバルト塩の方が優れている。そのため、
有機酸のニッケル塩とＲＦ樹脂とを併用することにより
両方の接着性を著るしく高くすることができる。BEST MODE FOR CARRYING OUT THE INVENTION An adhesive aid having excellent adhesive performance in both initial adhesive strength and water-resistant adhesive retention by using a nickel salt of an organic acid and an RF resin together as an adhesive aid as a steel-coated rubber. Successfully developed. Nickel salts generally have lower initial adhesion than cobalt salts, but the addition of RF resin can stably improve the initial adhesion. On the other hand, the cobalt salt is superior to the nickel salt in water resistance and adhesion retention. for that reason,
The combined use of a nickel salt of an organic acid and an RF resin can significantly increase the adhesiveness of both.
【０００７】本発明に係るゴム組成物に使用することが
できる原料ゴムとしては、従来からスチールコード被覆
ゴム用として使用されているゴムを用いることができ
る。具体的には天然ゴム、ポリイソプレンゴムが原料ゴ
ム１００重量部中５０重量部以上含まれるゴムなどをあ
げることができる。[0007] As the raw rubber that can be used in the rubber composition according to the present invention, rubber conventionally used for rubber coated with steel cord can be used. Specific examples include natural rubber and rubber containing polyisoprene rubber in an amount of 50 parts by weight or more based on 100 parts by weight of the raw rubber.
【０００８】本発明に係るゴム組成物には前記原料ゴム
１００重量部に対し、有機酸のニッケル塩（例えばナフ
テン酸、ステアリン酸、ロジン酸、ネオデカン酸などの
有機酸のニッケル塩があげられ、好ましくはナフテン酸
ニッケルなどである）をニッケル元素として０．０５〜
０．５重量部、好ましくは０．０１〜０．０３重量部配
合する。この配合量が少な過ぎると接着が不充分である
ので好ましくなく、逆に多過ぎると接着が低下するので
好ましくない。The rubber composition according to the present invention includes a nickel salt of an organic acid (for example, a nickel salt of an organic acid such as naphthenic acid, stearic acid, rosin acid and neodecanoic acid) with respect to 100 parts by weight of the raw rubber. Preferably nickel naphthenate or the like) as a nickel element in an amount of from 0.05 to
0.5 parts by weight, preferably 0.01 to 0.03 parts by weight. If the amount is too small, the adhesion is insufficient, which is not preferable. On the contrary, if the amount is too large, the adhesion is unfavorably reduced.
【０００９】本発明に係るゴム組成物に配合されるレゾ
ルシン・ホルマリン（ＲＦ）樹脂としては、従来のＲＦ
樹脂を用いることができるが、Ｒ分がメタ含量９０重量
％以上、好ましくは９５重量％以上のメタクレゾール樹
脂であり、またＦ分がペンタメトキシメチルメラミンも
しくはヘキサメトキシメチルメラミンであるのが好まし
い。The resorcinol-formalin (RF) resin blended in the rubber composition according to the present invention includes a conventional RF
Although a resin can be used, it is preferable that the R component is a metacresol resin having a meta content of 90% by weight or more, preferably 95% by weight or more, and the F component is pentamethoxymethylmelamine or hexamethoxymethylmelamine.
【００１０】本発明に係るゴム組成物に配合されるＲＦ
樹脂の配合量は原料ゴム１００重量部に対し、レゾルシ
ン（Ｒ）分とホルマリン（Ｆ）分との合計量で１〜７重
量部、好ましくは２〜５重量部配合する。この配合量が
少な過ぎると接着が充分でないので好ましくなく、逆に
多過ぎると発熱性が大きくなるので好ましくない。[0010] RF compounded in the rubber composition according to the present invention
The resin is compounded in an amount of 1 to 7 parts by weight, preferably 2 to 5 parts by weight, as the total of resorcinol (R) and formalin (F), based on 100 parts by weight of the raw rubber. If the amount is too small, the adhesion is not sufficient, which is not preferable. On the contrary, if the amount is too large, the heat generation becomes large, which is not preferable.
【００１１】本発明に係るゴム組成物に前記必須成分に
加えて、ゴム組成物に一般に配合されている任意の配合
剤、例えば硫黄、補強剤、軟化剤、老化防止剤、加硫促
進剤、充填剤、可塑剤、等を必要に応じて、通常の配合
量の範囲で適宜配合することができる。In the rubber composition according to the present invention, in addition to the essential components, any compounding agent generally compounded in the rubber composition, for example, sulfur, a reinforcing agent, a softener, an antioxidant, a vulcanization accelerator, Fillers, plasticizers, and the like can be appropriately blended as needed within the usual range of blending amounts.
【００１２】[0012]
【実施例】以下、実施例によって本発明を更に説明する
が、本発明の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。EXAMPLES The present invention will be further described with reference to the following examples, but it goes without saying that the scope of the present invention is not limited to these examples.
【００１３】実施例１〜３及び比較例１〜２ 下記配合のゴムマスターバッチに表Ｉに示す量（重量
部）のナフテン酸コバルト、ナフテン酸ニッケル又はス
テアリン酸を配合し、硫黄（６重量部）及び加硫促進剤
ＤＺ（Ｎ，Ｎジシクロヘキシルベンゾチアジルスルフェ
ンアミド）（０．５重量部）を加えて加硫（１６０℃×
２０分又は１７０℃×１０分）し、各種試験を行なっ
た。結果を表Ｉに示す。 Examples 1 to 3 and Comparative Examples 1 and 2 Cobalt naphthenate, nickel naphthenate or stearic acid in the amounts (parts by weight) shown in Table I were blended into a rubber master batch having the following composition, and sulfur (6 parts by weight) ) And a vulcanization accelerator DZ (N, N dicyclohexylbenzothiazylsulfenamide) (0.5 parts by weight) and vulcanization (160 ° C. ×
(20 minutes or 170 ° C. × 10 minutes) to perform various tests. The results are shown in Table I.
【００１４】 ゴムマスターバッチ 成 分 重量部 天然ゴム １００ カーボンブラック（ＨＡＦ−１Ｓ） ６０ 亜鉛華 １０ ステアリン酸 ０．３ 老化防止剤６Ｃ*1 ２ 加硫促進剤ＤＺ*2 ０．５ 硫黄（８０％） ７．５ *1：Ｎ−フェニレン−Ｎ′（１，３−ジメチルブチル）−ｐ−フェニレンジア ミン *2：Ｎ，Ｎ−ジシクロヘキシルベンゾチアジルスルフェンアミド[0014] Rubber Masterbatch Component Parts by weight Natural rubber 100 Carbon black (HAF-1S) 60 zinc oxide 10 0.3 antioxidant stearate 6C * 1 2 Vulcanization accelerator DZ * 2 0.5 Sulfur (80% 7.5) * 1 : N-phenylene-N '(1,3-dimethylbutyl) -p-phenylenediamine * 2 : N, N-dicyclohexylbenzothiazylsulfenamide
【００１５】物性試験方法は以下の通りである。 引張試験：ＪＩＳ Ｋ ６３０１に準拠し、１００％及
び３００％伸長応力と破断強度、破断伸びを測定した。The physical property test method is as follows. Tensile test: 100% and 300% elongation stress, breaking strength and breaking elongation were measured according to JIS K6301.
【００１６】老化試験：８０℃のオーブン中に９０時間
放置した試料とＪＩＳ Ｋ ６３０１に準拠し、１００
％及び３００％伸長応力と破断強度、破断伸びを測定し
た。 高温試験：１００℃の恒温槽内で、１００％及び３００
％伸長応力と破断強度、破断伸びを測定した。Aging test: A sample left for 90 hours in an oven at 80 ° C. and 100
% And 300% elongation stress, breaking strength and breaking elongation were measured. High temperature test: 100% and 300% in a thermostat at 100 ° C
% Elongation stress, breaking strength, and breaking elongation were measured.
【００１７】接着性：ＡＳＴＭ Ｄ ２２２９に準拠
し、引き抜き力とゴム付きの評価を実施した（埋込み長
さ１／２インチ）。温水接着は７０℃温水中に２週間浸
漬後引抜き試験を行なった。蒸気接着は１３０℃の蒸気
中に４８時間放置したのち引抜き試験を行なった。Adhesion: Pull-out force and evaluation of rubber adhesion were performed according to ASTM D 2229 (embedding length: 1/2 inch). For the hot water bonding, a pull-out test was performed after dipping in 70 ° C. hot water for 2 weeks. For the steam bonding, a pull-out test was carried out after leaving in a steam at 130 ° C. for 48 hours.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表Ｉには、ナフテン酸ニッケルとＲＦ樹脂
の効果を示した。比較例１はナフテン酸コバルト系とＲ
Ｆ樹脂を併用したものであるが、温水接着の１７０℃×
１０分加硫が接着不良である。実施例１（ナフテン酸ニ
ッケル２部とＲＦ樹脂の系）と比較例１を比較すると、
実施例１の方が、モジュラスが高く破断強度も高い。ま
た温水接着も高い。この傾向は実施例２のナフテン酸ニ
ッケル１部の場合ではモジュラス破断強度は低下するが
接着は良好である。Table I shows the effect of nickel naphthenate and RF resin. Comparative Example 1 shows that cobalt naphthenate and R
F resin is used in combination.
Ten minutes of vulcanization resulted in poor adhesion. Comparison between Example 1 (2 parts of nickel naphthenate and RF resin) and Comparative Example 1 shows that
Example 1 has higher modulus and higher breaking strength. Also, hot water adhesion is high. In the case of 1 part of nickel naphthenate of Example 2, the tendency is that the modulus at break strength is reduced but the adhesion is good.
【００２０】実施例３はナフテン酸ニッケル１部とステ
アリン酸１部を併用したものであるが、１６０℃×２０
分の接着がやや低いものの経時の接着は良好である。物
性のレベルも高い。比較例２はナフテン酸ニッケル系で
樹脂を除去したものであるが、経時の接着が、温水接着
蒸気接着とも不良である。以上のようにナフテン酸ニッ
ケルとＲＦ樹脂の併用では物性接着とも高いレベルを実
験させることができる。In Example 3, 1 part of nickel naphthenate and 1 part of stearic acid were used in combination.
Although the adhesion is slightly lower, the adhesion over time is good. Physical properties are also high. In Comparative Example 2, the resin was removed with a nickel naphthenate-based resin, but the adhesion with the lapse of time was poor with both hot water adhesion and vapor adhesion. As described above, the combined use of nickel naphthenate and the RF resin makes it possible to experiment with a high level of physical adhesion.
【００２１】表IIには比較例１と実施例１を１×３
（０．２８mm）のスチールコードをベルト部に用いたタ
イヤのスチールコード被覆ゴムに用いたタイヤ（１９５
／７０Ｒ１４）を作り、７０℃×９０％温度中で放置し
たのちベルト部を剥離してゴム被覆系を１〜５の段階で
評価した（センターとエッジ）。この結果から実施例１
が接着がよいことがわかる。Table II shows Comparative Example 1 and Example 1 as 1 × 3
Tires (195) used for steel cord coated rubber of tires using (0.28 mm) steel cords for the belt portion
/ 70R14), left at 70 ° C. × 90% temperature, peeled off the belt part, and evaluated the rubber coating system on a scale of 1 to 5 (center and edge). From these results, Example 1
Shows that the adhesion is good.
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【発明の効果】以上の通り、従来のスチールコード被覆
ゴムは有機酸コバルトを含むが、有機酸コバルトを用い
るとコバルトによる耐水接着保持性の低下とポリマーへ
の劣化効果による物性低下との問題があった。しかし、
本発明ではニッケル塩とＲＦ樹脂とを組み合わせること
によって、かかる問題を解決して初期接着力及び耐水保
持性の両性能に優れたスチールコード被覆ゴム用接着助
剤を得ることができる。As described above, the conventional steel cord-coated rubber contains an organic acid cobalt. However, when the organic acid cobalt is used, there is a problem that the water-resistant adhesive holding property of the cobalt is deteriorated and the physical properties are deteriorated due to the effect of deterioration to the polymer. there were. But,
In the present invention, by combining a nickel salt and an RF resin, such a problem can be solved and an adhesion aid for steel cord-coated rubber excellent in both initial adhesion and water resistance can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 61:12） (Ｃ０８Ｌ 21/00 61:08） Ｆターム(参考） 4J002 AC001 AC011 AC061 CC052 CC062 EG006 FD202 FD206 GN01 4J040 CA011 CA091 EB042 EB062 EB132 HB25 HB27 LA06 MA03 MA12 MB02 NA16 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (reference) C08L 61:12) (C08L 21/00 61:08) F term (reference) 4J002 AC001 AC011 AC061 CC052 CC062 EG006 FD202 FD206 GN01 4J040 CA011 CA091 EB042 EB062 EB132 HB25 HB27 LA06 MA03 MA12 MB02 NA16
Claims (2)
ッケルをニッケル元素として０．０５〜０．５重量部含
み、そしてレゾルシン・ホルマリン（ＲＦ）樹脂をレゾ
ルシン（Ｒ）分とホルマリン（Ｆ）分の合計量で１〜７
重量部含むゴム組成物。1. A rubber composition containing 0.05 to 0.5 parts by weight of an organic acid nickel as a nickel element with respect to 100 parts by weight of a raw rubber, and a resorcinol-formalin (RF) resin containing resorcinol (R) and formalin (F). 1-7 in total
A rubber composition containing parts by weight.
重量％以上のメタクレゾール樹脂であり、Ｒ分がペンタ
メトキシメチルメラミンもしくはヘキサメトキシメチル
メラミンである請求項１に記載のゴム組成物。2. The R content of the RF resin has a meta content of 90.
The rubber composition according to claim 1, which is a meta-cresol resin in an amount of not less than% by weight, and an R content is pentamethoxymethylmelamine or hexamethoxymethylmelamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11221452A JP2001049044A (en) | 1999-08-04 | 1999-08-04 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11221452A JP2001049044A (en) | 1999-08-04 | 1999-08-04 | Rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001049044A true JP2001049044A (en) | 2001-02-20 |
Family
ID=16766958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11221452A Pending JP2001049044A (en) | 1999-08-04 | 1999-08-04 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001049044A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003268162A (en) * | 2002-03-20 | 2003-09-25 | Yokohama Rubber Co Ltd:The | Rubber composition for covering steel code |
| KR20030080722A (en) * | 2002-04-10 | 2003-10-17 | 주식회사 효성 | Steel cord for tire having improved adhesiveness and corrosion resistance |
| CN105047424A (en) * | 2015-06-17 | 2015-11-11 | 黑龙江大学 | Method for preparing carbon-material electrode by employing phenolic-basis carbon spheres containing nickel |
| WO2021261481A1 (en) * | 2020-06-23 | 2021-12-30 | 横浜ゴム株式会社 | Pneumatic tire |
-
1999
- 1999-08-04 JP JP11221452A patent/JP2001049044A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003268162A (en) * | 2002-03-20 | 2003-09-25 | Yokohama Rubber Co Ltd:The | Rubber composition for covering steel code |
| KR20030080722A (en) * | 2002-04-10 | 2003-10-17 | 주식회사 효성 | Steel cord for tire having improved adhesiveness and corrosion resistance |
| CN105047424A (en) * | 2015-06-17 | 2015-11-11 | 黑龙江大学 | Method for preparing carbon-material electrode by employing phenolic-basis carbon spheres containing nickel |
| WO2021261481A1 (en) * | 2020-06-23 | 2021-12-30 | 横浜ゴム株式会社 | Pneumatic tire |
| JP2022002919A (en) * | 2020-06-23 | 2022-01-11 | 横浜ゴム株式会社 | Pneumatic tire |
| JP6996592B2 (en) | 2020-06-23 | 2022-01-17 | 横浜ゴム株式会社 | Pneumatic tires |
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