JPS59126441A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JPS59126441A JPS59126441A JP259783A JP259783A JPS59126441A JP S59126441 A JPS59126441 A JP S59126441A JP 259783 A JP259783 A JP 259783A JP 259783 A JP259783 A JP 259783A JP S59126441 A JPS59126441 A JP S59126441A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- sulfur
- sepiolite
- weight
- composition
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 組成物に関する。[Detailed description of the invention] Regarding the composition.
一般にタイヤのトレンドゴム,カーカス又はベルトのト
ソビングゴム,ビードエーペツクスあるいはコンベアー
ベルトの補強芯体のコードゴム等はゴム製品のうちでも
特に高い強度が要求され、そのため比較的多量の硫黄が
配合される。この場合未加硫配合ゴムの貯蔵中に溶解し
た硫黄が未加硫ゴム表面に析出するいわゆるブルーミン
グ現象が発生する。このブルーミング現象は混練等でゴ
ム中に溶解した可溶性硫黄がコムの内部から外表面に移
行することによるもので、これを防止するため従来から
不溶性硫黄を使用することが試みられている。しかしな
がらゴム配合剤として一般に用いられる老化防止剤に含
まれる第1級アミンが不溶性硫黄を可溶性硫黄に転移を
起こさせるととが知られており、更に不溶性硫黄は通常
の混練、加工条件(温度100〜140℃)で可溶性硫
黄に転移するため、混練法の未加硫ゴムを貯蔵しておく
となおブルーミング現象が発生し、この方法でも充分な
解決手段であるといえない状態である。In general, trend rubber for tires, tossing rubber for carcass or belts, bead apex, and cord rubber for reinforcing cores of conveyor belts require particularly high strength among rubber products, and therefore a relatively large amount of sulfur is blended. . In this case, a so-called blooming phenomenon occurs in which sulfur dissolved during storage of the unvulcanized rubber compound precipitates on the surface of the unvulcanized rubber. This blooming phenomenon is caused by soluble sulfur dissolved in the rubber during kneading, etc., migrating from the inside of the comb to the outer surface of the comb, and attempts have been made to use insoluble sulfur to prevent this. However, it is known that primary amines contained in anti-aging agents commonly used as rubber compounding agents cause the transformation of insoluble sulfur into soluble sulfur. 140 DEG C.), so even if unvulcanized rubber obtained by the kneading method is stored, a blooming phenomenon still occurs, and even this method cannot be said to be a sufficient solution.
本発明はかかる問題点を解決し未加硫ゴムにおける硫黄
のブルーミング現象を効果的に防止し接着性,強度等の
改善されたゴム組成物を提案するものである。The present invention solves these problems and proposes a rubber composition that effectively prevents the sulfur blooming phenomenon in unvulcanized rubber and has improved adhesiveness, strength, etc.
本発明はジエン系ゴム100重量部に硫黄を吸着さゼた
セビオライトの粉末を1〜40重量部配置部たことを特
徴とするゴム組成物である。The present invention is a rubber composition characterized in that 1 to 40 parts by weight of Seviolite powder adsorbed with sulfur is added to 100 parts by weight of diene rubber.
本発明で用いられるセビオライトは珪酸及び酸化マグネ
シウムを主成分とする天然の粘土鉱物である。そして組
成は次の一般式で示される二種類のものが多く産出され
ている。Seviolite used in the present invention is a natural clay mineral whose main components are silicic acid and magnesium oxide. There are two types of minerals produced in large quantities, with the composition shown by the following general formula.
m (H2O)4 (OH)4 MgB 5i12
05゜(H2O)6゜(111Mg8H2(Si40
.、)、 3 H2Oそしてゼオライトは繊維状の結晶
を形成し、その内部に十数オングストロームの大きさの
空隙が繊維長手方向に形成されており、換言すれば結晶
内部にトンネルを内蔵した多孔性結晶である。ゼオライ
トのような結晶構造の特異性に基づき、硫黄分子を結晶
内に吸着する機能を有する。特に王環状の結晶構造を有
する所謂可溶性硫黄を有機溶剤に溶解し、これに前記セ
とオライドの粉末とともに加熱処理をすると前記可溶性
硫黄は鎖状の不溶性硫黄に転移した形でセビオライト粉
末に吸着される。これはセビオライトの結晶内部の空隙
が十数オングストロームの大きさであり、王環状の結晶
構造である可溶性硫黄を収納できないため、これを非結
晶の鎖状分子、つまり不溶性硫黄として結晶内部に吸着
するものである。そして硫黄を吸着したセビオライトを
通常の加硫条件下で加熱(120℃〜160“C)する
ことにより、不溶性硫黄がセビオライトの結晶から放出
されるとともに、王環状の可溶性硫黄に転移して架橋反
応に関与する。本発、明はセビオライトのかかる特性を
利用するもので混練、加工済の未加硫ゴムの状態では硫
黄をゼオライト結晶内にとじこめておき硫黄がゴム表面
に移動するのを防止するとともに加硫時には硫黄を可溶
性硫黄として結晶内部から放出せしめることにより効果
的な加硫を達成するものである。m (H2O)4 (OH)4 MgB 5i12
05゜(H2O)6゜(111Mg8H2(Si40
.. , ), 3 H2O and zeolite form fibrous crystals, inside which voids of tens of angstroms in size are formed in the longitudinal direction of the fibers.In other words, it is a porous crystal with tunnels built inside the crystal. It is. Based on the unique crystal structure of zeolite, it has the ability to adsorb sulfur molecules within the crystal. In particular, when so-called soluble sulfur, which has a ring-shaped crystal structure, is dissolved in an organic solvent and heat-treated together with the ceolide powder, the soluble sulfur is transferred to chain-like insoluble sulfur and adsorbed on the ceviolite powder. Ru. This is because the void inside the Seviolite crystal is about 10-odd angstroms in size, and cannot accommodate soluble sulfur, which has a ring-shaped crystal structure, so it is adsorbed inside the crystal as amorphous chain molecules, that is, insoluble sulfur. It is something. Then, by heating the sulfur-adsorbed Seviolite under normal vulcanization conditions (120°C to 160"C), insoluble sulfur is released from the Seviolite crystals and transferred to soluble sulfur in the form of a ring, resulting in a crosslinking reaction. The present invention utilizes such characteristics of Seviolite, and in the state of kneaded and processed unvulcanized rubber, sulfur is trapped in zeolite crystals to prevent sulfur from migrating to the rubber surface. At the same time, effective vulcanization is achieved by releasing sulfur as soluble sulfur from inside the crystal during vulcanization.
前記セビオライトは粉末状で使用され、粒子径は通拗5
0〜200メソシュのものである。The Seviolite is used in powder form, and the particle size is typically 5.
It is from 0 to 200 mesosh.
粉末の粒子径が細かい程硫黄吸着性能は優れるとともに
加硫ゴム物性も向上する。The finer the particle size of the powder, the better the sulfur adsorption performance and the better the physical properties of the vulcanized rubber.
次に一般式(H2O)4 (OH)4MgB 5i4
20ろ0(1(20)/1〜8で示されるセビオライト
粉末の基本的物理特性を第1表に示す。Next, the general formula (H2O)4 (OH)4MgB 5i4
Table 1 shows the basic physical properties of Seviolite powder expressed as 2000(1(20)/1 to 8).
第 1 表
本発明ではセビオライトの配合量は1〜40重量部の範
囲、好ましくは2〜30重量部である。Table 1 In the present invention, the amount of Seviolite blended is in the range of 1 to 40 parts by weight, preferably 2 to 30 parts by weight.
セビオライトの硫黄吸着量は粘土鉱物100重量部に対
して硫黄を約100重量部まで吸着しうる。セビオライ
トはおもに不溶性硫黄の支持担体として機能するもので
あり、したがって所なお本発明の組成物では硫黄がゴム
100重量部tこ対して1〜10重量部含置部るようt
こセビオライト粉末の配合量及びセビオライトへの硫黄
の吸着量が調整される。不発明番よ硫黄を多部?こ用い
る配合系tこ特に好適であり、従来硫黄を約3重量部以
上用いる所謂ノ1イサルファー配合でブル−ミング現象
が常をこ問題となってbまたが本発明ではかかる問題は
ほとんど起こらなu XOなお硫黄が10重量部を越え
ると、それtこ伴なうセビオライトの配合量も増大し、
加硫コ゛ムの基本特性な低−Fする傾向にあるため好ま
しくなし)。Seviolite can adsorb up to about 100 parts by weight of sulfur per 100 parts by weight of clay mineral. Seviolite primarily functions as a support carrier for insoluble sulfur, and therefore, in the composition of the present invention, sulfur is contained in an amount of 1 to 10 parts by weight per 100 parts by weight of rubber.
The blending amount of Seviolite powder and the amount of sulfur adsorbed on Seviolite are adjusted. You have a lot of sulfur? This compounding system is particularly suitable, and in the past, blooming phenomenon has always been a problem with so-called isulfur compounding containing about 3 parts by weight or more of sulfur, but in the present invention, such a problem almost never occurs. Note that when sulfur exceeds 10 parts by weight, the amount of Seviolite that accompanies it also increases,
This is not preferred because it tends to have low -F, which is a basic characteristic of vulcanized combs).
次に本発明に用いられるジエン系ゴムは天然ゴム、合成
イソプレンゴム、スチVンーフ゛タジエンゴム、ブチル
ゴム、ブタジエンコ゛ム等−般に用いられているゴムを
単独あるつは混合して用いられるが、このほかKPDM
、EPT等のゴムも適宜、混合しうる。また本発明では
カーボンブラック等の充填剤、オイル等の可塑剤、−フ
ェノール系樹脂等の強化剤のは力・加硫促進音1j、老
化防止剤、有機酸コバルト等の接着助剤をも必要に応じ
が配合されることは勿論である。特に本発明では所謂ハ
イサルファー配合系、換言すれば高い硬度及び強度を必
要とするタイヤのビードエーペックスゴムあるいはベル
ト、カーカスのトッピングゴム配合として最適である。Next, the diene rubber used in the present invention may be any of commonly used rubbers such as natural rubber, synthetic isoprene rubber, steel V-butadiene rubber, butyl rubber, butadiene rubber, etc., and may be used singly or in combination. Other KPDM
Rubbers such as , EPT, etc. may also be appropriately mixed. In addition, the present invention also requires fillers such as carbon black, plasticizers such as oil, reinforcing agents such as phenolic resins, vulcanization accelerators, anti-aging agents, and adhesion aids such as organic acid cobalt. Of course, the ingredients may be mixed accordingly. In particular, the present invention is suitable for so-called high sulfur compounding systems, in other words, as bead apex rubbers for tires that require high hardness and strength, or topping rubber compounds for belts and carcass.
実施例
第2表に示す基本配合において硫黄及びセピオライトの
量を種々変四して未加硫ゴムの物性及びブルーミング現
象及び加硫ゴム物性を計画した。EXAMPLE The physical properties of unvulcanized rubber, the blooming phenomenon, and the physical properties of vulcanized rubber were planned by varying the amounts of sulfur and sepiolite in the basic formulation shown in Table 2.
第5表から本発明の実施例は粘土鉱物を含まないものと
、はぼ同程度の物理特性を示す一方、硫黄のブルーミン
グ現象が大幅に改善されていることが認められる。更に
硫黄及び粘土鉱物をそれぞれ単独にゴムに配合したもの
と比較しても加硫ゴム物性及びブルーミング現象の改善
が認められる。From Table 5, it can be seen that the examples of the present invention exhibit almost the same physical properties as those not containing clay minerals, while the sulfur blooming phenomenon is significantly improved. Furthermore, improvements in the physical properties of the vulcanized rubber and the blooming phenomenon are also observed when compared to rubber in which sulfur and clay minerals are individually blended.
第 2 表
注1)セピオライトは6gメツシュの粉末圧2)硫黄と
粘土鉱物の重量比が1:1で100メツシユの粉末
注3】圧1)注2)のセピオライトはいずれも(H2O
)4 (OHI、l MgB Si 1205o(H2
O)6.Bの組成を有する。Table 2 Note 1) Sepiolite has a powder pressure of 6 g mesh 2) The weight ratio of sulfur and clay minerals is 1:1 and the powder weight is 100 mesh Note 3] Pressure 1) Note 2) Sepiolite is (H2O
)4 (OHI, l MgB Si 1205o(H2
O)6. It has a composition of B.
第6表 特許出願人 住友ゴム工業株式会社 代理人 弁理士 仲 村 義 平Table 6 Patent applicant: Sumitomo Rubber Industries, Ltd. Agent: Patent Attorney Yoshihira Nakamura
Claims (3)
ゴム100重量部に対して1〜40重量部配置部たこと
を特徴とするゴム組成物。(1) A rubber composition comprising 1 to 40 parts by weight of sepiolite powder adsorbed with sulfur per 100 parts by weight of diene rubber.
、に対して2〜30重量部配置部てなる特許請求の範囲
第1項記載のゴム組成物。(2) The rubber composition according to claim 1, comprising 2 to 30 parts by weight of sepiolite powder per 100 parts by weight of diene rubber.
ゴム組成物。(3) The rubber composition according to claim 1, wherein sepiolite is a clay mineral represented by the general formula %.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP259783A JPS59126441A (en) | 1983-01-10 | 1983-01-10 | Rubber composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP259783A JPS59126441A (en) | 1983-01-10 | 1983-01-10 | Rubber composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59126441A true JPS59126441A (en) | 1984-07-21 |
JPH0461019B2 JPH0461019B2 (en) | 1992-09-29 |
Family
ID=11533790
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP259783A Granted JPS59126441A (en) | 1983-01-10 | 1983-01-10 | Rubber composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59126441A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997012933A1 (en) * | 1995-09-29 | 1997-04-10 | Sunstar Giken Kabushiki Kaisha | Heat-vulcanizable rubber composition |
WO2013065769A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber composition and use therefor |
WO2013065768A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber anti-aging agent |
JP2015534592A (en) * | 2012-09-14 | 2015-12-03 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co.KGaA | Improved adhesive composition comprising sulfur impregnated particulate solid |
-
1983
- 1983-01-10 JP JP259783A patent/JPS59126441A/en active Granted
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997012933A1 (en) * | 1995-09-29 | 1997-04-10 | Sunstar Giken Kabushiki Kaisha | Heat-vulcanizable rubber composition |
US6066690A (en) * | 1995-09-29 | 2000-05-23 | Sunstar Giken Kabushiki Kaisha | Heat-vulcanizable rubber composition |
WO2013065769A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber composition and use therefor |
WO2013065768A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber anti-aging agent |
JP2013095857A (en) * | 2011-11-01 | 2013-05-20 | Sumitomo Chemical Co Ltd | Rubber composition and use therefor |
JP2013095856A (en) * | 2011-11-01 | 2013-05-20 | Sumitomo Chemical Co Ltd | Rubber anti-aging agent |
JP2015534592A (en) * | 2012-09-14 | 2015-12-03 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co.KGaA | Improved adhesive composition comprising sulfur impregnated particulate solid |
Also Published As
Publication number | Publication date |
---|---|
JPH0461019B2 (en) | 1992-09-29 |
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