CN101910269A - 可硬化的反应树脂体系 - Google Patents
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Abstract
本发明涉及一种作为双组分物料加工的可硬化的反应树脂体系,其含树脂成分(A)、硬化剂(B)和分散于树脂成分(A)中的聚合物颗粒(C),在该反应型树脂体系中的聚合物颗粒(C)的含量大于25-50重量%。
Description
背景技术
本发明涉及一种按独立权利要求前序部分的可硬化的反应树脂体系及其应用
基于通过化学反应硬化的树脂的体系在制备工业构件和部件中有很大意义。如果这类反应树脂体系用于绝缘目的,则其通常具有高填料含量。高填料含量导致该硬化的反应树脂体系的高耐热性和高机械稳定性。
由DE 10345139 A1已知基于环氧树脂的这类反应树脂体系。其填料含量最高达90重量%。更高的填料含量用其所述的体系是不可实现的,因为否则会对浇注料的粘度和可加工性有不利影响。但高的填料含量会不利于材料的流动性或伸缩性。
发明内容
本发明的目的是提供一种可硬化的反应树脂体系,其具有高的热稳定性并同时具有优良的断裂伸长,且仍可良好加工。
本发明的目的是通过提供一种反应树脂体系实现的,该体系可作为双组分体系使用,且包括高份量的分散于反应树脂的树脂组分中的聚合物颗粒。该反应树脂体系在加工时具有优良的可流动性,在硬化状态下有高的热稳定性和电绝缘性。
用从属权利要求中所述措施,本发明的反应树脂体系可得到有利扩展。
因此该反应树脂体系优选含表面改性的硅氧烷弹性体颗粒作为聚合物颗粒,以确保在反应树脂体系的树脂基质上的优良结合。使用该硅氧烷弹性体颗粒的特别优点在于,如果添加该硅氧烷弹性体颗粒,则该添加对该体系的玻璃化转变温度仅有小的影响,但同时提高了热稳定性和/或电击穿强度。此外,其优点是硅氧烷弹性体颗粒是不挥发的。
在一个特别有利的实施方案中,该反应树脂体系含环氧化物,任选地与双酚A、双酚B和/或双酚F相混合来作为树脂成分。所得的树脂体系有高的交联度和由此在硬化状态下有高的机械稳定性。
实施例
本发明的反应树脂体系含三种基础组分,即树脂组分A、硬化剂B和分散于树脂组分A中的聚合物颗粒C。此外,还可含填料D以及通常的添加剂如除泡剂、抗沉降剂和粘附促进剂。
作为树脂组分A原则上可使用各种单体型的可交联化合物或这类化合物的混合物。特别有利的是使用含至少一个环氧化物官能团的化合物,任选地是与其它含或不含环氧化物官能团的化合物相混合。如二环氧化物、三环氧化物或四环氧化物是适用的,下面示例性给出可市售购得的化合物。特别适用的是脂环族、优选环形环氧化的二环氧化物,如(I)和(VI)。
该树脂组分A可包含化合物(I)-(VII)中的一种或多种以及其它树脂组分。或者或附加地还可单独或彼此混合或与合适的环氧树脂组分相互混合地使用例如基于双酚A、双酚B和/或双酚F、PUR或氰酸酯的树脂组分。
此外,还可使用酚醛清漆-环氧树脂,特别是下列组成的甲酚-酚醛清漆-环氧树脂作为树脂成分:
在该反应树脂体系中,树脂组分A的含量达5-65重量%,优选达10-50重量%,特别是达15-40重量%。
为确保呈双组分体系的反应树脂体系的可加工性,还可采用硬化剂B。为此例如酸酐类如六氢化邻苯二甲酸酐(HHPSA)、六氢化甲基邻苯二甲酸酐(MHHPSA)、甲基降冰片烯二酸酐(MNSA)或相应的胺是适用的。
此外,作为第三组分,该反应树脂体系还含分散于树脂组分A中的聚合物颗粒C。其特别是含聚硅氧烷的聚合物,其中组分C优选是一种或多种硅氧烷在树脂组分A中的分散体。优选使用呈粒径为10nm-100μm的硅氧烷树脂颗粒或硅氧烷弹性体颗粒形式的硅氧烷颗粒。该硅氧烷颗粒可基本上具有呈如由PMMA形成的聚合物层形式的化学改性表面(所谓的芯-壳颗粒);但已表明,表面官能化的硅氧烷颗粒对本发明的目的是更合适的。或者,由丙烯腈-丁二烯-苯乙烯共聚物(ABS)组成的硅氧烷嵌段共聚物或弹性体颗粒也是适用的。
该反应树脂体系的聚合物颗粒C的含量为例如大于25至最多50重量%,优选大于25至最多40重量%,特别是大于25至最多30重量%。
该反应树脂体系优选只含少量的矿物质填料D,通过对其进行合适的选择可降低该反应树脂体系在硬化状态下的收缩,并提高该反应树脂体系在硬化状态下的热稳定性或断裂强度。填料D例如可呈纳米颗粒形式,其中纳米颗粒意指其平均粒度分布d50在纳米范围的微粒级分。适用的填料材料例如是氧化铝、白垩、碳化硅、氮化硼、炭黑或滑石。该填料D优选含由石英粉或石英料或其混合物制成的颗粒。
在反应树脂体系中的总填料量例如小于10重量%,优选小于7重量%,特别是小于5重量%。该反应树脂体系也可不含矿物质填料。
本发明的反应树脂体系不仅可用作浸渍树脂,还可用作浇注料。在例如为浸渍电动线圈而作为浸渍树脂加工时,该相应的线圈呈旋转态,并且或者浸入液态浸渍树脂中,或者将液态浸渍树脂滴加到旋转的线圈上。该浸渍线圈的硬化例如可用热或经UV辅助的交联实现。
如果该反应树脂体系作为浇注料使用,则在较高温度下浇注为成型件。该反应树脂体系在相应加热时有如此低的粘度和如此高的毛细作用,以致也可在浇注时浇注不利的几何形状,如直径<300μm的浇注缝。
下面示例性示出该反应树脂体系或其组成(重量%)的实施例和在硬化状态下产生的特性。
组成:
实施例 | 1 | 对比例 | 2 |
树脂组分A | 40双酚A/环氧化物 | 40双酚A/环氧化物 | 37脂环族环氧化物 |
硬化剂 | 33.5HHPSA/MHHPSA | 33.5MNSA | 38.3HHPSA/MHHPSA |
聚合物颗粒C硅氧烷弹性体 | 26.5 | 13.25 | 25.1 |
填料(纳米颗粒) | 13.25 |
上述组成产生下列特性:
实施例 | 1 | 2 | 3 |
玻璃化转变温度[℃] | 125 | 146 | |
热膨胀系数[10-6*1/℃] | <60 | <45 | |
E-模量弯曲实验/拉伸实验[N/mm2] | 1500 | ||
断裂应力[N/mm2] | 62/41 | 60/40 | |
断裂伸长[%] | 8/6 | 8/6 |
该反应树脂体系由于其在硬化状态下的热稳定性而特别适用于至少有时在160-220℃的温度下使用的构件。
因此,如作为浇注料的本发明的反应树脂体系例如可用于浇注高压致动器或类似的电器或电子构件。此外,可用该反应树脂体系浸渍电动线圈。
Claims (10)
1.可硬化的反应树脂体系,特别是浇注料、层压树脂或浸渍树脂,其作为双组分物料进行加工,并含有树脂组分(A)、硬化剂(B)和分散于树脂组分(A)中的聚合物颗粒(C),其中在该反应树脂体系中的聚合物颗粒(C)的含量为大于25至最高50重量%。
2.权利要求1的反应树脂体系,其特征在于,所述聚合物颗粒(C)是经表面改性的。
3.权利要求1或2的反应树脂体系,其特征在于,所述聚合物颗粒(C)呈芯-壳颗粒状。
4.上述权利要求之一的反应树脂体系,其特征在于,分散于树脂组分(A)中的聚合物颗粒(C)是硅氧烷弹性体颗粒。
5.权利要求4的反应型树脂体系,其特征在于,所述硅氧烷弹性体颗粒的粒径为10nm-100μm。
6.上述权利要求之一的反应树脂体系,其特征在于,所述树脂组分(A)包含环氧树脂。
7.权利要求6的反应树脂体系,其特征在于,所述环氧树脂是基于双官能或更高官能环氧树脂的树脂。
8.上述权利要求之一的反应树脂体系,其特征在于,所述树脂组分(A)包含基于双酚A、双酚B和/或双酚F的树脂。
9.权利要求1-8之一的反应树脂体系在浸渍电动线圈中的应用。
10.权利要求1-8之一的反应树脂体系在浇注高压致动器中的应用。
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DE102008005155A DE102008005155A1 (de) | 2008-01-18 | 2008-01-18 | Härtbares Reaktionsharzsystem |
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PCT/EP2008/066204 WO2009089957A1 (de) | 2008-01-18 | 2008-11-26 | Härtbares reaktionsharzsystem |
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JP (1) | JP5254359B2 (zh) |
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US4668736A (en) * | 1984-07-18 | 1987-05-26 | Minnesota Mining And Manufacturing Company | Fast curing epoxy resin compositions |
DE3674902D1 (de) * | 1985-06-26 | 1990-11-15 | Dow Chemical Co | Mit rubber modifizierte epoxyzusammensetzungen. |
DE3634084A1 (de) * | 1986-10-07 | 1988-04-21 | Hanse Chemie Gmbh | Modifiziertes reaktionsharz, verfahren zu seiner herstellung und seine verwendung |
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DE10051051A1 (de) * | 2000-10-14 | 2002-04-18 | Bosch Gmbh Robert | Silikonmodifizierte Einkomponentenvergußmasse |
DE10057111C1 (de) * | 2000-11-16 | 2002-04-11 | Bosch Gmbh Robert | Wärmeleitfähige Vergußmasse |
CN1205265C (zh) * | 2000-11-29 | 2005-06-08 | 范蒂科股份公司 | 具有高力学强度值的填充环氧树脂体系 |
KR100780582B1 (ko) * | 2003-06-09 | 2007-11-29 | 카네카 코포레이션 | 변성 에폭시 수지의 제조방법 |
EP1518889B1 (de) * | 2003-09-29 | 2008-06-11 | Robert Bosch Gmbh | Härtbares Reaktionsharzsystem |
DE10345139A1 (de) | 2003-09-29 | 2005-04-21 | Bosch Gmbh Robert | Härtbares Reaktionsharzsystem |
DE102004034416A1 (de) * | 2004-07-15 | 2006-02-02 | "Stiftung Caesar" (Center Of Advanced European Studies And Research) | Flüssige, strahlunghärtende Zusammensetzungen |
US20060182949A1 (en) * | 2005-02-17 | 2006-08-17 | 3M Innovative Properties Company | Surfacing and/or joining method |
DE102005015605B4 (de) * | 2005-04-05 | 2008-04-17 | Schill + Seilacher "Struktol" Aktiengesellschaft | Phosphororganische Verbindungen enthaltende Prepolymere und Verwendungen dafür |
JP4379387B2 (ja) * | 2005-06-27 | 2009-12-09 | パナソニック電工株式会社 | エポキシ樹脂無機複合シート及び成形品 |
US20070116961A1 (en) * | 2005-11-23 | 2007-05-24 | 3M Innovative Properties Company | Anisotropic conductive adhesive compositions |
DE102006031079B4 (de) * | 2006-07-05 | 2010-04-08 | Siemens Ag | Werkzeugmaschine mit einem Piezoaktor |
US20080051524A1 (en) * | 2006-08-28 | 2008-02-28 | Henkel Corporation | Epoxy-Based Compositions Having Improved Impact Resistance |
EP2098571A1 (de) * | 2008-03-07 | 2009-09-09 | Robert Bosch GmbH | Modifiziertes Reaktionsharz |
-
2001
- 2001-11-26 US US12/735,299 patent/US20110003946A1/en not_active Abandoned
-
2008
- 2008-01-18 DE DE102008005155A patent/DE102008005155A1/de not_active Withdrawn
- 2008-11-26 WO PCT/EP2008/066204 patent/WO2009089957A1/de active Application Filing
- 2008-11-26 KR KR1020107015820A patent/KR20100113516A/ko not_active Application Discontinuation
- 2008-11-26 CN CN2008801249974A patent/CN101910269A/zh active Pending
- 2008-11-26 JP JP2010542549A patent/JP5254359B2/ja not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109844983A (zh) * | 2016-10-14 | 2019-06-04 | 罗伯特·博世有限公司 | 用于接触部件的半成品 |
Also Published As
Publication number | Publication date |
---|---|
KR20100113516A (ko) | 2010-10-21 |
JP5254359B2 (ja) | 2013-08-07 |
US20110003946A1 (en) | 2011-01-06 |
DE102008005155A1 (de) | 2009-07-23 |
JP2011511854A (ja) | 2011-04-14 |
WO2009089957A1 (de) | 2009-07-23 |
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