CN101679644A - 树脂分散体 - Google Patents

树脂分散体 Download PDF

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CN101679644A
CN101679644A CN200880016344A CN200880016344A CN101679644A CN 101679644 A CN101679644 A CN 101679644A CN 200880016344 A CN200880016344 A CN 200880016344A CN 200880016344 A CN200880016344 A CN 200880016344A CN 101679644 A CN101679644 A CN 101679644A
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G·库尔曼
A·布鲁兹
C·罗曼
M·施瓦布
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Abstract

本发明涉及一种树脂分散体,一种制备所述树脂分散体的方法和一种产品。为了制备树脂分散体,在其加工过程中避免释放污染物质,提出所述树脂分散体包含(I)30至100重量%的环氧树脂和0至70重量%的酚醛清漆树脂,基于两种树脂组分的质量计,以及(II)4至18重量%的基于蓖麻油乙氧基化物、氢化蓖麻油乙氧基化物、烷基酚乙氧基化物、脂肪醇乙氧基化物、油酸乙氧基化物、羰基合成醇乙氧基化物、脂肪醇乙氧基化物和/或聚乙烯醇的共分散剂,基于总质量计,和(III)任选地0至20重量%的其它常规添加物,基于总质量计。

Description

树脂分散体
本发明涉及树脂分散体,制备所述树脂分散体的方法和产品。
为了制备构件的浸渍体
Figure G2008800163444D00011
而使用树脂分散体,其至今通常由水性甲阶酚醛树脂和丙烯酸酯分散体构成。例如,基于甲阶酚醛树脂的分散体是可用水稀释的,然而,它在甲醛硬化时分解,由此生产只能在特别为此设计的装置上实施。丙烯酸酯分散体可以在不释放破坏环境的物质的情况下硬化,然而,硬化的产品具有低的玻璃化转变温度。
基于环氧树脂和酚醛清漆的分散体在现有技术中是已知的。例如JP 58-027716描述了一种制备酚醛树脂/酚醛清漆-分散体的方法和作为环氧树脂硬化剂的胺(特别是咪唑)。另外,由US RE37,023已知一种由甲阶酚醛树脂和醚化的BPA树脂构成的分散体,其中也用溶剂。
本发明的目的在于,提供一种树脂分散体,在其加工过程中避免了给环境造成负担的(umweltbelastenden)物质的释放。
上述目的根据本发明由此得以实现,提供一种基于环氧树脂和酚醛清漆树脂以及其它添加物的水性树脂分散体,其中所述树脂分散体包含:
(I)30至100重量%的环氧树脂和0至70重量%的酚醛清漆树脂,基于两种树脂组分的质量计,以及
(II)4至18重量%的基于蓖麻油乙氧基化物、氢化蓖麻油乙氧基化物、烷基酚乙氧基化物、脂肪醇乙氧基化物、油酸乙氧基化物、羰基合成醇乙氧基化物、脂肪醇乙氧基化物和/或聚乙烯醇的共分散剂,基于总质量计,和
(III)任选地0至20重量%的其它常规添加物,基于总质量计。
作为组分(I)的环氧树脂可以使用每个分子具有至少两个环氧基团的所有环氧树脂,其熔化范围优选低于90℃。使用具有较高熔化范围的环氧树脂时,由于所使用的环氧树脂的粘度升高可能造成工艺过程的困难。优选的还有室温下为液态的环氧化合物,如双酚的二缩水甘油醚或基于双酚A二缩水甘油醚的预扩链
Figure G2008800163444D00021
的树脂。特别优选的是低粘度的树脂,如基于环烯烃或四缩水甘油基二苯胺的环氧树脂,或者还有固态环氧树脂例如环氧化酚醛清漆与所谓反应性稀释剂的混合物。环氧树脂可以任选地用其它聚合物例如聚酯、丙烯酸酯、有机硅聚合物或聚乙烯基衍生物来改性。
作为组分(I)的酚醛清漆使用在酸性环境中制备的酚类化合物与醛的共聚物,在其制备过程中酚类化合物∶醛的比例优选为1∶0.4至1∶0.8。这种共聚物可以不用单体来制备。在比例大于1∶0.8时,所产生的酚醛清漆粘度过高,在比例小于1∶0.4时,树脂是过于水溶性的并因此更难以分散。
作为酚类化合物可以使用单环酚或多环酚或所述化合物种类的混合物,也就是既使用单环酚也使用多环酚。对此的实例是作为优选的变化方案的酚本身,及其烷基取代的类似物,例如邻甲酚、间甲酚或对甲酚,二甲苯或更高级烷基化的酚,此外还有卤素取代的酚,如氯代酚、溴代酚和多元酚如间苯二酚或邻苯二酚,以及多环酚如萘酚、双酚A或双酚F。
使所述酚或酚类组分与醛,特别是甲醛或分解出甲醛的化合物反应生成所期望的酚醛清漆。所述酚醛清漆可以通过常规的改性剂,例如环氧树脂、橡胶、聚乙烯醇缩丁醛和无机添加物来改性。
环氧树脂的量为30至100重量%,酚醛清漆的量为70至0重量%,基于两种树脂组分的质量计。制备纯的环氧树脂分散体的优点是,可以按照与例如其它分散体混合的需要而提供该分散体。然而,优选的是具有30至80重量%的环氧树脂的树脂分散体,因为酚醛清漆起到环氧树脂的硬化剂的作用,因此不需要额外的硬化剂。还优选50至80重量%的环氧树脂,由此达到最佳的网络密度。
作为另外的组分(II),根据本发明的水性树脂分散体包含4至至18重量%,优选3至10重量%的基于蓖麻油乙氧基化物、氢化蓖麻油乙氧基化物、烷基酚乙氧基化物、脂肪醇乙氧基化物、油酸乙氧基化物、羰基合成醇乙氧基化物、脂肪醇乙氧基化物和/或聚乙烯醇的共分散剂,基于总质量计。小于4重量%的共分散剂无法起到足够的作用,在大于18重量%的情况下会使硬化的产品的最终性质,例如水溶性恶化。
特别优选的是,使用既起到乳化剂作用也起到保护胶体作用的聚乙烯醇。另外优选的是,聚乙烯醇具有80至95%的水解度和30000至70000g/mol的分子量,这对乳液的稳定性有积极作用。
此外,作为其它组分,本发明的树脂分散体可以包含至少一种稳定剂-优选以0.2至2重量%的浓度,基于总混合物的质量计-基于高分子醇,或者还有纤维素衍生物、淀粉、糊精、聚丙烯酸和/或它们的共聚物的盐、聚-N-乙烯基甲基丙烯酰胺、乙烯基吡咯烷酮共聚物和/或声音(Stimme)保护胶体。因此分散体的稳定性得到了提高。又特别优选的是,所述稳定剂是甲氧基纤维素,因为这种稳定剂在最低浓度下已经起作用。
根据本发明的树脂分散体还可以包含0至1.5重量%的其它组分如促进硬化反应的物质,例如路易斯酸或咪唑,基于整个混合物的质量计。有利的是咪唑,除了促进作用之外,它还保证了所促进的分散体在数小时至数天的稳定性。
另外,本发明的树脂分散体还可以包含浓度优选为0.05至3重量%的加工助剂,基于整个混合物的质量计,如用于改善成膜作用的均化剂或用于调节特殊性能的物质,例如用于提高柔性的丙烯酸酯分散体。示例性地提到乙二醇和/或聚二甲基硅氧烷。还可以考虑添加染料、润湿剂和催化剂作为其它添加物。
本发明的树脂分散体的固体浓度优选为30-50%。视应用领域而定,更低的固体浓度也是可能的(约10%)。
基于环氧树脂和酚醛清漆树脂以及其它添加物的本发明的树脂分散体的制备可以通过包括下列步骤的方法进行:
a.至少将共分散剂混入到基本上处于熔融状态的组分(I)中,和
b.将水和任选地其它添加物在<100℃的温度下混入到在步骤a)中所获得的混合物中。
组分(I)优选在90至150℃,优选至125℃的温度下熔融,从而可以确保排除组分提前反应。所述温度范围还由于粘度的原因是有利的,从而得到组分(I)的均匀混合物。添加共分散剂并将混合物冷却到<100℃。随后,添加优选25%-50%的水,基于总质量计。任选地在搅拌和冷却下添加额外的水。固体树脂含量优选为30至50%。
一般来说,按照什么顺序和在什么温度下将共分散剂和组分(I)或水与其它添加物相互混合是无关紧要的。
特别优选的是,在步骤b)添加稳定剂,由此可以使用温度敏感的稳定剂。
另外有利的是,在得到步骤b)的混合物之后再向树脂分散体中混入其它添加物例如催化剂、染料和润湿剂。
但是还可能的是,以下面的方式制备基于环氧树脂和酚醛清漆树脂以及其它添加物的本发明的水性树脂分散体,将树脂分散体的组分(I)、(II)和(III)和水通过引入剪切能互相混合。由此可以放弃对组分的加热并且因此避免了与此相关的操作问题。
所述方法例如在分散研磨机或涡轮密封式混合机(Turboinnenmischern)中实施,预置水并且添加共分散剂和任选地其它添加物。然后在搅拌下添加环氧树脂和酚醛清漆,并且引入足够的剪切能。
未交联的本发明的水性树脂分散体可以例如通过涂抹、喷射或刮涂简单且不复杂地施加到纤维、纤维非织造网、织物、羊毛或光滑表面形式的纺织品的、矿物的、金属的或还有塑料的表面上,由此将所述表面改性。随后可以进行干燥过程。在交联期间或之后没有甲醛或其它溶剂,其对环境或气味造成负担。从现在开始,本发明的树脂分散体可以覆盖水溶性甲阶酚醛树脂和丙烯酸酯的应用领域。
根据实施例应详细说明本发明:
在21的具有搅拌器、温度计、滴液漏斗和加热夹套的烧瓶中,将120g酚醛清漆和280g环氧树脂在60分钟内加热至约110℃。随后在30分钟内在搅拌下添加290g 23.5%的聚乙烯醇水溶液。在此,将温度保持在约75至85℃。随后在约75-85℃在搅拌下,在90分钟内计量加入310g水。将所形成的分散体缓慢冷却到约40℃。所述分散体具有在20℃下为5080mPas的粘度和约47.6%的固含量。

Claims (13)

1、基于环氧树脂和酚醛清漆树脂以及其它添加物的水性树脂分散体,其特征在于,所述树脂分散体包含
(I)30至100重量%的环氧树脂和0-70重量%的酚醛清漆树脂,基于两种树脂组分的质量计,以及
(II)4至18重量%的基于蓖麻油乙氧基化物、氢化蓖麻油乙氧基化物、烷基酚乙氧基化物、脂肪醇乙氧基化物、油酸乙氧基化物、羰基合成醇乙氧基化物、脂肪醇乙氧基化物和/或聚乙烯醇的共分散剂,基于总质量计,和
(III)任选地0至20重量%的其它常规添加物,基于总质量计。
2、根据权利要求1的基于环氧树脂和酚醛清漆树脂以及其它添加物的水性树脂分散体,其特征在于,所述树脂分散体包含
(I)30至80重量%的环氧树脂和70-20重量%的酚醛清漆树脂,基于两种树脂组分的质量计,以及
(II)4至18重量%的基于蓖麻油乙氧基化物、氢化蓖麻油乙氧基化物、烷基酚乙氧基化物、脂肪醇乙氧基化物、油酸乙氧基化物、羰基合成醇乙氧基化物、脂肪醇乙氧基化物和/或聚乙烯醇的共分散剂,基于总质量计,和
(III)任选地0至20重量%的其它常规添加物,基于总质量计。
3、根据前述权利要求中至少一项的树脂分散体,其特征在于,所述环氧树脂的熔化范围<90℃。
4、根据前述权利要求中至少一项的树脂分散体,其特征在于,所述酚醛清漆树脂是苯酚-甲醛树脂,在其制备过程中苯酚∶甲醛的比例为1∶0.4至1∶0.8。
5、根据前述权利要求中至少一项的树脂分散体,其特征在于,所述共分散剂的量为3至10重量%,基于总质量计。
6、根据前述权利要求中至少一项的树脂分散体,其特征在于,作为其它添加物包含稳定剂。
7、根据前述权利要求中至少一项的树脂分散体,其特征在于,作为其它添加物包含催化剂、染料或润湿剂。
8、制备基于环氧树脂和酚醛清漆树脂以及其它添加物的水性树脂分散体的方法,包括下列步骤:
a.至少将共分散剂混入到基本上处于熔融状态的组分(I)中,和
b.将水和任选地其它添加物在<100℃的温度下混入到在步骤a)中所获得的混合物中。
9、根据权利要求8的方法,其特征在于,在步骤b)中添加稳定剂。
10、根据权利要求8和/或9的方法,其特征在于,在得到步骤b)中的混合物之后,还向所述树脂分散体中混入其它添加物,如催化剂、染料和润湿剂。
11、制备基于环氧树脂和酚醛清漆树脂以及其它添加物的水性树脂分散体的方法,其特征在于,通过引入剪切能使所述树脂分散体的组分(I)、(II)和(III)与水互相混合。
12、具有未交联或交联的表面层的产品,其通过施加根据前述权利要求中至少一项的树脂分散体而制得。
13、根据权利要求1-7中至少一项的水性树脂分散体的用途,用于纤维、纤维非织造网、织物、羊毛或光滑表面形式的纺织品的、矿物的、金属的或塑料的表面的改性。
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