CN104903387A - 施用于复合帘线的浸渍方法 - Google Patents
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Abstract
本发明涉及一种施用于由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成的复合帘线的浸渍方法,其基本上包括以下步骤:制备初次浸渍溶液(11),将初次浸渍溶液施用于帘线上(12),施加初次热处理(13),制备二次浸渍溶液(14),将二次浸渍溶液施用于帘线上(15),施加初次热处理(16),并作为补强材料用于橡胶内。
Description
发明领域
本发明涉及一种施用于复合帘线(hybrid cord)的浸渍方法,所述复合帘线由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成,其作为补强材料用于橡胶中。
发明背景
如今,由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成的复合帘线的粘合,通过除用于粘合尼龙6.6帘线的浸渍溶液之外,在主要(二次)浸渍之前使用初次表面活化浸渍溶液来完成。在表面活化浸渍内的初次浸渍过程中,将增强表面润湿能力的化学品和增强表面活性的化学品溶解在水中。在二次浸渍中,使用由间苯二酚、甲醛和胶乳混合物组成的浸渍溶液(RFL)。此外,存在其中将炭黑分散体加入到二次浸渍中的应用。
在现有技术中,在初次浸渍后,在240-249℃下施加60-75秒的热处理。在二次浸渍后,再次在240-249℃下使用热处理将帘线处理60-75秒。
所有这些加工均用于使用作橡胶补强材料的纤维粘合到橡胶上。由于这个原因,为了提供所需的粘合性,用特殊的浸渍化学品涂布纤维,并通过浸渍来热制(cooked)。使用所述方法浸渍的芳族聚酰胺和芳族聚酰胺-尼龙6.6复合帘线显示出比尼龙6.6纤维构成的帘线低60%-70%的粘合性。这样的比率是不够的,尤其是在充气轮胎中用作冠带层带条的芳族聚酰胺和芳族聚酰胺-尼龙6.6复合帘线中。由于粘合性不足,因此在轮胎冠带层会出现高速轮胎破裂下的层分离。
使用通过现有已知方法浸渍的芳族聚酰胺和芳族聚酰胺-尼龙6.6复合帘线来制造载重斜交轮胎是不可行的。所述帘线的低粘合性值限制了用作橡胶补强材料的领域。
已知技术部分地提供了芳族聚酰胺和芳族聚酰胺-尼龙6.6复合帘线在橡胶上的粘合性。通过这种方法,所述帘线结构作为补强材料用于各种应用。这些帘线的表面在初次浸渍中通过表面活化材料(环氧树脂)活化,所述纤维在二次浸渍中得以与RFL溶液形成化学键。炭黑分散体也在机械上增加了粘合性。
现有技术条件下,在首次浸渍中用于增强表面润湿能力的材料(气溶胶)降低了在首次浸渍溶液中存在的表面活化材料(环氧树脂)的活性,并导致RFL破裂和在热处理过程后与帘线表面分离。除了表面润湿剂,用于调节首次浸渍溶液pH的苛性(NaOH)溶液也会减少环氧树脂的活性,并降低表面粘合能力。此外,初次浸渍后经长时间在高温下的热处理,帘线表面可以看到结壳(crustation)和开裂,并且结壳层破裂并与帘线表面分离。
此外,在现有技术条件下,二次浸渍中炭黑分散体的粒度在3-4毫米范围内。由于该粒度不能提供均匀分布,炭黑颗粒的活性预期会随着粘合性机械降低而增大。这导致经浸渍处理的帘线上的粘合性值沿着帘线而变化。二次浸渍后施加的高温和长期热处理导致含有炭黑的RFL层开裂和结壳并与帘线表面分离。在不含有炭黑的RFL溶液中,所述不利影响超过40-50%。
发明概述
本发明的目的是提供一种施用于复合帘线的浸渍方法,其中表面活化剂的活性得到提高。
本发明的另一目的是提供一种施用于复合帘线的浸渍方法,其中借助于具有高均匀性的炭黑分散体,粘合性值沿着帘线和织物宽度均匀分布。
本发明的又一目的是提供一种施用于复合帘线的浸渍方法,其中热处理时间相对于现有技术被缩短,并由此防止施用浸渍溶液的结壳和开裂。
本发明的详细说明
一种施用于复合帘线以实现本发明目的的浸渍方法图解在附图中,其中
图1为该方法的流程图。
一种施用于复合帘线以实现本发明目的的浸渍方法(10)包括以下步骤:
- 制备初次浸渍溶液(11),
- 将初次浸渍溶液施用于帘线上(12),
- 施加初次热处理(13),
- 制备二次浸渍溶液(14),
制备第一相(141)
制备第二相(142)
制备第三相(143)
通过混合这些相使它们静置(144),
将粘合性改进化学品加入到混合物中(145),
将炭黑分散体加入到混合物中(146),
将蜡乳化液(wax emulsion)加入到混合物中(147),
混合所有材料(148),
- 将二次浸渍溶液施用于帘线上(15),
- 施加二次热处理(16)。
在本发明的施用于复合帘线的浸渍方法(10)中,首先将环氧树脂与水混合,并制备要施用于由芳族聚酰胺和芳族聚酰胺-尼龙6.6构成的复合帘线的初次浸渍溶液(11)。为此,将比率占97-98 wt%的水和比率占2-3%的环氧树脂混合在一起。不同于现有技术,初次浸渍溶液中不使用气溶胶和碳酸钠溶液。
将所制备的初次浸渍溶液采用浸泡法施用于复合帘线(12)。在本发明的优选实施方案中,使由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成的复合帘线保持浸泡在初次浸渍溶液内0.2-5秒。
在复合帘线上施用初次浸渍溶液后(12),对所述帘线施以最长60秒和最高温度240℃的热处理(13)。在本发明的优选实施方案中,初次热处理(13)在215-230℃的范围内施加15-45秒。
首先,制备三种不同的相以制备二次浸渍溶液(14)。在制备第一相(141)时,将水、28%氢氧化铵水溶液和75%间苯二酚-甲醛水溶液混合。在本发明的优选实施方案中,在第一相中存在75-85 wt%的水、3-5 wt%的28%氢氧化铵水溶液、10-15 wt%的75%间苯二酚-甲醛水溶液。
将水和41%乙烯基吡啶胶乳乳化液(latex emulsion)混合在一起以制备第二相(142)。在本发明的优选实施方案中,在第二相中存在5-10 wt%的水,和90-95 wt%的41%乙烯基吡啶胶乳乳化液。
将水和37%甲醛溶液混合以制备第三相(143)。在本发明的优选实施方案中,在第三相中存在70-85 wt%的水,和15-30 wt%的37%甲醛。
按照重量比2、7:4、4:1将所述制备的三种不同的相混合在一起,并使其静置10-14以熟化(144)。随后,向所述组合物中加入占组合物1-5%的一种或多种粘合性改进剂(145)。
在加入粘合性改进剂后,以占组合物的10-20 wt%加入炭黑分散体的25%水溶液(146)。所述炭黑分散体的粒度为0.1-0.4微米,最优选的粒度为0.2-0.35微米。
将全部的组合物搅拌均匀后,以占组合物的3-5 wt%加入的95%蜡乳化液(147),并将最终组合物连续搅拌1小时(148)。
将在混合所有材料(148)后获得的二次浸渍溶液,通过浸泡法施用于已施用了初次浸渍溶液的复合帘线上(15)。在本发明的优选实施方案中,使这些帘线在二次浸渍溶液中保持浸泡0.2-5秒。
在复合帘线上施用二次浸渍溶液(15)后,对所述帘线施以最长60秒和最高温度240℃的二次热处理(13)。在本发明的优选实施方案中,二次热处理(13)在225-240℃的范围内施加15-45秒。
本发明公开范围内的浸渍溶液和热处理施用方法可用于所有其中存在由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成的用作补强材料的复合帘线的实施方案中。使用本发明的浸渍方法(10)制备的复合帘线优选作为补强材料存在于车辆轮胎、软管及传送带中。
由经本发明的施用于复合帘线的浸渍方法(10)浸渍的帘线构成的补强织物具有100-200厘米,优选120-160厘米的宽度。每分米所述橡胶补强织物的帘线数为50-80,优选60-150。
本发明浸渍方法(10)的初次浸渍溶液组合物中除去了现有技术中初次浸渍溶液中的气溶胶(表面润湿剂)和苛性钠(pH调节剂)。因此,作为表面活化剂的环氧树脂的活性能够得以提高。此外,施用初次浸渍溶液(12)后的初次热处理(13)的温度相比现有技术中的值降低了5-10%,并且热处理的时间减少了50-60%。因此,防止了由高温及长时间的热处理导致的帘线上的结壳和破裂的问题。
在本发明的方法(10)中,用于二次浸渍溶液的炭黑分散体的粒度也减少至现有技术中使用的粒度的二十分之一(1/20)。通过这种方法,炭黑分散体的均匀性提高,并且粘合性值能够沿帘线及织物的宽度均匀分布。此外,二次浸渍后施加的热处理的温度降低了7-10%,且热处理的时间降低了50-60%。通过这种方法,防止了二次浸渍溶液中存在的RFL溶液的结壳和开裂以及与帘线表面分离的现象,并且RFL层的处理温度保持在熟化温度以下,从而使得在橡胶内部实现完全熟化。
随着所有这些改变,由芳族聚酰胺和芳族聚酰胺-尼龙6.6构成的复合帘线在橡胶上的粘合性值相比所有已知的现有技术增加了33%。因此,在所有其中仅由尼龙6和尼龙6.6纤维构成的帘线用作补强材料的实施方案中,由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成的复合帘线能够用作补强材料。
在这些基本概念的框架内,可以开发出本发明的施用于复合帘线的浸渍方法(10)的各种实施方案。本发明不能局限于本文中所描述的实例,且其实质上如权利要求书中所限定的那样。
Claims (12)
1.一种施用于复合帘线的浸渍溶液(10),将其施用于用作橡胶内补强材料的由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成的复合帘线,包括以下步骤:
- 制备初次浸渍溶液(11),
- 将初次浸渍溶液施用于帘线上(12),
- 施加初次热处理(13),
- 制备二次浸渍溶液(14),
制备第一相(141)
制备第二相(142)
制备第三相(143)
通过混合这些相使它们静置(144),
将粘合性改进化学品加入到混合物中(145),
将炭黑分散体加入到混合物中(146),
将蜡乳化液加入到混合物中(147),
混合所有材料(148),
将二次浸渍溶液施用于帘线上(15),
施加二次热处理(16);并且其特征在于以下步骤:
- 制备由环氧树脂和水组成的初次浸渍溶液(11),
- 在215-230℃的范围内施加15-45秒初次热处理(13),
- 将粒度为0.1-0.4微米的炭黑分散体加入到组合物中(146),
- 在225-240℃的范围内施加15-45秒二次热处理。
2.根据权利要求1的施用于复合帘线的浸渍方法(10),其特征在于制备初次浸渍溶液的步骤(11),其中将比率为97-98 wt%的水与比率为2-3%的环氧树脂混合。
3.根据在前任意一项权利要求的施用于复合帘线的浸渍方法(10),其特征在于将初次浸渍溶液施用于帘线上的步骤(12),其中将由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成的复合帘线浸渍在所述初次浸渍溶液中,并在其中保持0.2-5秒。
4.根据在前任意一项权利要求的施用于复合帘线的浸渍方法(10),其特征在于制备第一相的步骤(141),其中将75-85 wt%的水、3-5 wt%的28%氢氧化铵水溶液、10-15 wt%的75%间苯二酚-甲醛水溶液混合。
5.根据权利要求4的施用于复合帘线的浸渍方法(10),其特征在于制备第二相的步骤(142),其中将比率为5-10 wt%的水与比率为90-95 wt%的41%乙烯基吡啶胶乳乳化液混合。
6.根据权利要求5的施用于复合帘线的浸渍方法(10),其特征在于制备第三相的步骤(143),其中将比率为70-85 wt%的水与比率为15-30 wt%的37%甲醛溶液混合。
7.根据权利要求6的施用于复合帘线的浸渍方法(10),其特征在于通过混合使这些相静置的步骤(144),其中将第一相、第二相和第三相分别以2、7:4、4:1的比率混合,并使其静置10-14小时以熟化。
8.根据在前任意一项权利要求的施用于复合帘线的浸渍方法(10),其特征在于将比率为组合物的1-5 wt%的一种或多种粘合性改进剂加入到通过混合使这些相静置(144)后形成的组合物中的步骤(145)。
9.根据在前任意一项权利要求的施用于复合帘线的浸渍方法(10),其特征在于将炭黑分散体作为25%水溶液以组合物的10-20 wt%的比率加入到所述组合物中的步骤(146)。
10.根据在前任意一项权利要求的施用于复合帘线的浸渍方法(10),其特征在于将95%蜡乳化液以组合物的3-5 wt%的比率加入到所述组合物中的步骤(147)。
11.根据在前任意一项权利要求的施用于复合帘线的浸渍方法(10),其特征在于混合所有材料的步骤(148),其中将最终组合物连续搅拌至少1小时。
12.根据在前任意一项权利要求的施用于复合帘线的浸渍方法(10),其特征在于将二次浸渍溶液施用于帘线上的步骤(15),其中将已施用过初次浸渍溶液的由芳族聚酰胺和芳族聚酰胺-尼龙6.6纤维构成的复合帘线浸渍在所述二次浸渍溶液中,并在其中保持0.2-5秒。
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