CN101068965B - 热固性塑料复合纤维成型件及生产方法 - Google Patents

热固性塑料复合纤维成型件及生产方法 Download PDF

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CN101068965B
CN101068965B CN2005800236352A CN200580023635A CN101068965B CN 101068965 B CN101068965 B CN 101068965B CN 2005800236352 A CN2005800236352 A CN 2005800236352A CN 200580023635 A CN200580023635 A CN 200580023635A CN 101068965 B CN101068965 B CN 101068965B
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F·J·穆勒
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Abstract

本发明涉及由以天然纤维和/或合成纤维为基的纤维材料生产的热固性塑料复合纤维成型件，这种纤维材料借助一种热固性塑料粘结剂粘合。为生产热固性塑料复合纤维成型件，一方面保持酚醛树脂复合纤维成型件良好的力学、吸声和燃烧特性，另一方面尽可能排除每一种由酚醛树脂形成的气味，由此提出，将至少一种吸附剂在热固性塑料粘结剂的预硬化和/或完全硬化过程中埋到纤维成型件的表面上和/或内部。

Description

热固性塑料复合纤维成型件及生产方法
本发明涉及由以天然纤维和/或合成纤维为基的纤维材料制成的热固性塑料复合纤维成型件，纤维通过一种热固性塑料粘结剂粘结。
由纤维制成的成型件在汽车制造中作为诸如空气调节吸声部件及具有高表面强度和碎裂强度的成型件得到应用。通常这种成型件通过挤压造型以及同时进行的硬化处理由酚醛树脂复合纤维层(无纺织物)制成。
这种产品的缺点是，有时主要在温度和湿度增加的影响下会散发出难闻的气味，这大部分是由硬化剂(环六次甲基四胺)或者说其氨化分解产物导致的。
这一问题根据EP-A 0 254 807通过以下方法来解决，即用一种粉末状混合物来作为粘接剂使用，该混合物由一种不会热反应的酚醛树脂和一种或多种由酚醛树脂，氨基树脂或环氧树脂组成的组合物的凝结产物构成。尽管这样可以避免由环六次甲基四胺产生的气味，但酚醛树脂的残余气味仍旧存在。
本发明的任务是制造一种热固性塑料复合纤维成型件，其中一方面保留了酚醛树脂复合纤维成型件的良好的力学、吸声和燃烧技术特性，另一方面尽可能排除每一种由酚醛树脂产生的气味。
本任务的解决方案通过热固性塑料复合纤维成型件实现，其中在纤维成型件的表面和/或内部，在热固性塑料粘结剂的预硬化和/或完全硬化过程中添加至少一种吸附剂。
尤其令人意外的是，根据热固性塑料复合纤维成型件的生产过程(在压力和温度下)，在该生产过程中一般释放足以耗尽吸附剂的吸附能力的产物，而吸附剂的吸附能力仍足以在纤维成型件的使用过程中事后吸附形成气味的产物。
特别优选相对于热固性塑料粘结剂含有浓度为1到30重量份额、优选15到20重量份额的吸附剂。
为保证粘结剂和吸附剂在生产过程中良好混合，有利的是：吸附剂的颗粒大小与粘结剂的颗粒大小相匹配，也就是说，与粘结剂的颗粒大小的偏差不应超过±20％。
现有技术中已知数种不同的材料可以作为吸附剂使用，例如硅胶，沸石或铝硅酸盐。然而特别优选的吸附剂是活性炭。活性炭的特有性质在流动性、活动性或即使在熔融性上都在热固性塑料复合纤维成型件的生产过程中几乎不会引起变化。
所有可以自然硬化，或者配有硬化剂或硬化催化剂、并在高于某个特定温度时会硬化成高聚物的树脂都可以作为热固性塑料粘结剂使用。可使用的树脂有邻苯二甲酸二丙烯树脂、环氧树脂、尿素树脂、三聚氰胺树脂、三聚氰胺-尿素树脂、三聚氰胺-酚醛树脂、酚醛树脂、和不饱和聚酯树脂及其相应的组合物。作为其它成分，在粘结剂中还包含按一般方式使用的硬酯酸盐、二氧化硅，润滑剂、内部分离介质和/或抗燃剂。
优选的粘结剂是那些以酚醛树脂和/或环氧树脂和/或环氧-聚酯树脂混合物为基的粘结剂，其中可以存在不同的成分。也可以使用油漆工业的残渣、所谓的粉末油漆残渣。
作为以酚醛树脂为基的粘结剂可以使用所有由苯酚化合物和醛构成的凝结产物，特别是由苯酚、甲酚或二甲苯酚和甲醛构成的凝结产物，更确切地说不仅可以使用可溶性酚醛树脂，而且可以使用通常的酚醛清漆-硬化剂混合物，特别指酚醛清漆-环六次甲基四胺混合物。所使用的酚醛树脂一般呈粉末状。以环氧树脂为基的粘结剂一般是由每个分子含至少两个环氧基的环氧化物与一种硬化剂组成的粉末状混合物。作为硬化剂优选隐性(latent)硬化剂或者至少那种能保证在混合后和硬化时刻之间留有足够的加工时间的硬化剂。对此例如酸酐、咪唑衍生物，但优选例如由EP-B 0 518 908公开的酚醛清漆或金属复合物。
吸附剂优选与热固性塑料粘结剂组合、也就是与其混合地加入纤维材料内或纤维材料上。这样就不需要附加工序将吸附剂添加到纤维成型件中。但通常也可以在纤维成型件上，将一种由吸附剂制成的混合物或者含吸附剂的混合物制成的铺垫铺放在未硬化的纤维成型件(半成品和/或制成品)上，由此完成在硬化过程中吸附剂的埋入。
作为纤维可以使用无机纤维，例如玻璃纤维，也可以使用有机纤维材料或任何纤维混合物。
优选使用有机纤维如羊毛、棉花、人造羊毛、黄麻、亚麻、大麻、聚酯纤维或丙烯纤维和它们的混合物。
所使用的纤维材料中大部分可以用纺织废料撕裂获得。
这些纤维可以按照已知的方法(例如空气动力学方法，梳理过程)用相应的粘结剂混合，并铺设成各个纤维层(毛毡，例如梳毛机毛网)。粘结剂与纤维材料的比例可以根据应用场合变更，其范围在10-40到90-60之间。各个纤维层或如此生产的纤维束(Gelege)(半成品)可以按照公知的方式按尺寸制作，并或者进行预硬化，或者在稍后的时刻在模塑成型时完全硬化，或纤维束立即作为平面材料在高于热固性塑料粘结剂的硬化温度的温度下硬化。
按照本发明的热固性塑料复合纤维成型件的生产优选采用空气动力学方法。在这种方法中，将已经预先开松的纤维材料进一步散开，被气流抓住、运送、并在孔筛滚筒上运行制成毛毡。粘结剂和吸附剂可以同时和/或彼此分别呈粉末状通过滚筒、振动槽或者类似的配料设备撒入毛毡。在一个后置的系统中，通过涡流使粘接剂紧凑而均匀的分布在毛毡材料中。接着将现在含粘结剂的纤维产品在纤维幅面的横截面上的抽吸作用下汇合到在吸入滚筒之间形成的缝隙中，并重新制成毛毡。
毛毡幅面被短暂加热，以使热固性塑料粘结剂熔化并固着于纤维上，但并不完全硬化。然后将毛毡幅面冷却并成形。最终将如此生产的半成品在必要时在模塑成型下按已知方式进行挤压并硬化，此处也可以将多个这种半成品相互叠置并相互挤压到一起并硬化。
粘结剂的硬化及由此最终纤维毛毡到非织造物的固化同样可以采用不同的技术(热冷压工艺或优选的热压工艺)。在热压工艺中，毛毡在较低的温度下在硬化管道中预干燥/预硬化，并在随后的热压过程中相应变形。
根据实施例对本发明进行更详细地说明：
具体实施方式
将粘结剂Bakelite
Figure 058236352_0
PF 7077 TP(德国Bakelite股份公司产品)与给定剂量的活性炭(与粘结剂有关)混合，将混合物撒在纤维材料上，分布到纤维毛毡中，接着在190℃下挤压5分钟，以使粘结剂完全硬化。然后在80℃或100℃下将该构件退火5小时，用气体色层分析法分析。下面给出的值是三次测量曲线的面积平均值。
Figure 2005800236352A00800011
由表可看出，通过添加5％的活性炭明显降低了至少苯酚的排放。由结果可以推论，按照传统方法生产的热固性塑料复合纤维成型件在使用过程中即使在极端的条件(热，潮湿空气)下也不会释放出形成气味的物质。而其他的特性如力学，吸声和燃烧特性并不会损失。

Claims (9)

1.由以天然纤维和/或合成纤维为基的纤维材料生产的热固性塑料复合纤维成型件，这种纤维材料借助热固性塑料粘结剂粘合，其特征在于，将至少一种吸附剂在热固性塑料粘结剂的预硬化和/或完全硬化过程中埋到纤维成型件的表面上和/或内部；其中，热固性塑料粘结剂取自邻苯二甲酸二丙烯树脂、环氧树脂、尿素树脂、三聚氰胺树脂、三聚氰胺-尿素树脂、三聚氰胺-酚醛树脂、酚醛树脂、和不饱和聚酯树脂。
2.按权利要求1所述的热固性塑料复合纤维成型件，其特征在于，相对于热固性塑料粘结剂含有浓度为1到30重量份额的吸附剂。
3.按权利要求2所述的热固性塑料复合纤维成型件，其特征在于，相对于热固性塑料粘结剂含有浓度为15到20重量份额的吸附剂。
4.按前述权利要求中任一项所述的热固性塑料复合纤维成型件，其特征在于，颗粒大小与粘结剂的颗粒大小相匹配。
5.按权利要求1所述的热固性塑料复合纤维成型件，其特征在于，所述吸附剂是活性炭。
6.按前述权利要求1至3中任一项所述的热固性塑料复合纤维成型件，其特征在于，所述粘结剂是一种以酚醛树脂、环氧树脂和/或环氧-聚酯树脂混合物为基的粘结剂。
7.用于生产按权利要求1至6中任一项所述的热固性塑料复合纤维成型件的方法，其特征在于，将所述吸附剂在热固性塑料复合纤维成型件的生产过程中埋入具有热固性塑料粘结剂的混合物中。
8.用于生产按权利要求1至6中任一项所述的热固性塑料复合纤维成型件的方法，其特征在于，所述纤维成型件用空气动力学方法生产。
9.用于生产按权利要求1至6中任一项所述的热固性塑料复合纤维成型件的方法，其特征在于，模塑成型用热压工艺实现。
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