CN100473687C - 粘接橡胶组合物 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- 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
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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Abstract
本申请公开了粘接橡胶组合物,其含有100重量份的橡胶成分和0.1到3重量份的平均颗粒度不大于50μm的乙酰丙酮酸金属盐。这种粘接橡胶组合物的断裂特性得到了改进。
Description
所属技术领域
本发明涉及粘接橡胶组合物,更具体而言,涉及混入预定量的指定颗粒度的乙酰丙酮酸金属盐、从而使其断裂性质得到了改良的粘接橡胶组合物。
背景技术
为了橡胶和金属的粘接、例如轮胎的钢丝帘线橡胶的粘接,通常加入有机钴酸盐。存在多种有机钴酸盐。其中,乙酰丙酮酸钴用于防止氧化和降解并改善粘接(例如,参见日本未审专利公开(Kokai)No.54-47778,日本未审专利公开(Kokai)No.5-65370等)。另一方面,被设计用于与金属粘接的橡胶例如经常用作复合材料例如轮胎的钢丝帘线,因此,物理强度或断裂性质变得重要。但是,乙酰丙酮酸钴是一种不溶于橡胶、而且分散性也不好的物质,因此,经常会引起如物理强度变化、特别断裂强度降低的问题。
发明内容
由此,本发明的目的是改善含有乙酰丙酮酸钴或其它乙酰丙酮酸金属盐的粘接橡胶组合物的断裂性质。
本发明提供了一种粘接橡胶组合物,其含有100重量份的橡胶成份和0.1到3重量份的其平均颗粒度为50μm或更小的乙酰丙酮酸金属盐。
本发明还提供了通过将100重量份橡胶成分和其平均颗粒度为50μm或更小的乙酰丙酮酸金属盐在混合期间最高140℃或更低的温度下的混合制得的一种粘接橡胶组合物。
实现本发明的最佳模式
在本文的说明书及权利要求中,单数形式涵盖了复数形式,除非从上下文可以清楚知道该形式是单数。
在本发明中,我们发现,当将混入粘接橡胶组合物中的乙酰丙酮酸金属盐的颗粒度被制成特定大小或者更小,并且优选进一步确定混合的温度为特定温度或更低,则粘接橡胶组合物合物的断裂性能会得到明显改善。
作为本发明的粘接橡胶组合物中可用的乙酰丙酮酸金属盐,例如可使用乙酰丙酮酸钴(II),乙酰丙酮酸钴(III),乙酰丙酮酸镍(II),乙酰丙酮酸锆(IV),乙酰丙酮酸锌(II),乙酰丙酮酸铜(II),乙酰丙酮酸铁(II),乙酰丙酮酸铁(III),乙酰丙酮酸铬(III),乙酰丙酮酸锰(II),乙酰丙酮酸钼(II)等。在这些化合物中,特别优选使用乙酰丙酮酸钴(II)和/或乙酰丙酮酸钴(III)。
在本发明的粘接橡胶组合物中,平均颗粒度为50μm或更小、优选10到20μm的乙酰丙酮的金属盐,以100重量份的橡胶成分为基础计算,以0.1到3重量份、优选0.5到2重量份的量加入,在保持很好的粘合特性的同时,其断裂性质得到改善。如果乙酰丙酮酸的金属盐的颗粒度大于50μm,则这样制得橡胶组合物的粘合能力和断裂强度会不恰当地降低。如果混入量少于0.1重量份,就不能达到所期望的效果,相反,如果混入量多于3重量份,则断裂强度会不适当地降低。
另外,在本发明的粘接橡胶组合物中,当将预定量的具有预定颗粒度的乙酰丙酮酸金属盐混入橡胶组合物时,更优选将混入过程中所达到的最高温度控制在140℃或更低的温度范围内,优选90到120℃。当混合在这一温度范围内实施时,在橡胶中的乙酰丙酮酸金属盐的分散会更好,断裂强度的降低会得到进一步抑制。
作为本发明的粘接橡胶组合物中可用的橡胶组分,可以单独使用任何可用作轮胎橡胶的橡胶(如基于二烯的橡胶),也可以使用其混合物。
具体而言,各种类型的天然橡胶(NR)或基于二烯的合成橡胶如各种类型的聚丁二烯橡胶(BR)、苯乙烯-丁二烯共聚物橡胶(SBR)、聚异戊二烯橡胶(IR)、丁基橡胶(IIR)、丙烯腈-丁二烯共聚物橡胶、氯丁二烯橡胶、乙烯-丙烯-二烯共聚物橡胶、苯乙烯-异戊二烯共聚物橡胶苯乙烯-丁二烯共聚物橡胶等都可以作为例子。从粘接和橡胶的强度的角度而言,其中大量使用了天然橡胶的混合物是所希望的。
通常用于本发明的粘接橡胶组合物中的硫,在100重量份的橡胶成分中,优选混入3到10重量份,更优选5到8重量份。如果硫的混入量小,粘接易于变坏,反过来,如果混入量太大,得到的橡胶组合物的性质会降低,在老化之后粘接也容易变坏。
本发明的粘接橡胶组合物还可以含有另一种硫化剂或交联剂、硫化或交联促进剂、碳黑、硅胶、或其它增强填料、各种油、抗氧化剂、填料、软化剂、增塑剂、各种其它类型的配合剂和轮胎用的常用助剂等。这些配合剂和助剂的加入量,在不违背本发明的目的的情况下,可采用常规量。其中,优选的碳黑是N234级或N330级,用量为45到65phr[即,以100重量份的橡胶为基础的重量份数]。特别优选混入3到11phr的锌白、1phr或更少的硬脂酸、1phr或更少的硫化促进剂。
实施例
为了进一步阐明本发明现给出了下述实施例,对照例和标准例。但是本发明的范围不言而喻并非局限于这些例子。
标准例1、实施例1-2和对照例1
根据ASTM D1871,表1所列每一配方的组分都在120℃的混合温度下混合。所得到的每一种未硫化橡胶组合物都具有3+9+15(0.17)结构(注:指直径0.17mm的3、9和15束的三层绞合结构(twisted structure),其中埋有埋藏长度为25mm的镀黄铜的钢丝帘线。而后,在148℃下硫化45分钟以制得样品。每一样品都在130℃、湿度95%的条件下静置72小时以便进行湿热降解。然后,将钢丝帘线抽出,测定橡胶覆盖率(%)。
结果见表I。数值越大橡胶覆盖率越高,抗湿热破坏的能力越好。
实施例1-3、对照例2和标准例1-2
表II各配方的组分在其各自的预定混合温度下混合而制成橡胶组合物,然后将得到的组合物在148℃下加压45分使其硫化从而形成2mm厚的橡胶片。从每一片上,冲压出JIS NO.3的哑铃形试验片并测定其断裂强度(根据JIS K251)。
结果见表II,以在不同混合温度下的对照例2的值作为100计。值越大,断裂强度的降低被抑制的越多,因此就越好。
从表I和表II的结果可以清楚看出,应用了平均颗粒度为50μm或更小的乙酰丙酮酸金属盐的粘接橡胶组合物与现有技术的应用了颗粒度为100μm或200μm的同种盐的那些相比较,在保持其粘合能力的同时,其断裂强度更好。另外可以清楚看出,在混合温度为140℃或更低时,与更高的混合温度相比,断裂强度的降低可以受到更多抑制。
工业可用性
本发明的粘接橡胶组合物保持了其与钢丝帘线和其它金属构件的粘合能力,同时,作为一种橡胶其断裂性质更为优良,因此,可以有效的用作覆盖轮胎的钢丝帘线及卡车和公共汽车等的钢丝帘线橡胶的橡胶组合物。
Claims (3)
1.粘接橡胶组合物,其含有100重量份的橡胶成分和0.1到3重量份的平均颗粒度为50μm或更小的乙酰丙酮酸金属盐,其中橡胶成分和乙酰丙酮酸金属盐在混合时所达到最高温度是140℃或更低的温度下混合。
2.权利要求1的粘接橡胶组合物,其中所述乙酰丙酮酸金属盐是乙酰丙酮酸钴(II)或乙酰丙酮酸钴(III)或其混合物。
3.使用权利要求1或2的粘接橡胶组合物的轮胎。
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JP2004146629A JP3844478B2 (ja) | 2004-05-17 | 2004-05-17 | 接着用ゴム組成物 |
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EP (1) | EP1712590A4 (zh) |
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FR2945814B1 (fr) | 2009-05-19 | 2011-07-01 | Michelin Soc Tech | Composition de caoutchouc pour pneumatique comportant un compose acetylacetonate |
FR2947274B1 (fr) * | 2009-06-24 | 2013-02-08 | Michelin Soc Tech | Composition de caoutchouc pour pneumatique comportant un compose acetylacetonate |
KR101433164B1 (ko) | 2012-09-03 | 2014-08-22 | 한국타이어 주식회사 | 타이어 벨트 토핑용 고무 조성물 및 이를 이용하여 제조된 타이어 |
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JPS5350246A (en) * | 1976-10-20 | 1978-05-08 | Bridgestone Corp | Rubber composition having good adhesion to metal |
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CA2305626C (en) * | 1997-10-10 | 2008-02-19 | Rhodia Limited | Rubber adhesion promoters |
JP2000302914A (ja) * | 1999-04-21 | 2000-10-31 | Ohtsu Tire & Rubber Co Ltd :The | タイヤ用ゴム組成物 |
JP2003277547A (ja) * | 2002-03-26 | 2003-10-02 | Yokohama Rubber Co Ltd:The | タイヤトレッド用ゴム組成物 |
EP1690704B1 (en) * | 2003-10-27 | 2009-03-11 | The Yokohama Rubber Co., Ltd. | Tire wheel assembly |
-
2004
- 2004-05-17 JP JP2004146629A patent/JP3844478B2/ja not_active Expired - Fee Related
-
2005
- 2005-05-12 CN CNB2005800018589A patent/CN100473687C/zh not_active Expired - Fee Related
- 2005-05-12 US US10/584,995 patent/US20090111920A1/en not_active Abandoned
- 2005-05-12 EP EP05741313A patent/EP1712590A4/en not_active Withdrawn
- 2005-05-12 WO PCT/JP2005/009104 patent/WO2005111141A1/ja not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP1712590A1 (en) | 2006-10-18 |
JP2005325302A (ja) | 2005-11-24 |
CN1906244A (zh) | 2007-01-31 |
JP3844478B2 (ja) | 2006-11-15 |
WO2005111141A1 (ja) | 2005-11-24 |
EP1712590A4 (en) | 2009-08-19 |
US20090111920A1 (en) | 2009-04-30 |
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