CN106702757A - 聚氨酯超细纤维合成革制备过程中的水性浸渍树脂及应用 - Google Patents

聚氨酯超细纤维合成革制备过程中的水性浸渍树脂及应用 Download PDF

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CN106702757A
CN106702757A CN201611149940.2A CN201611149940A CN106702757A CN 106702757 A CN106702757 A CN 106702757A CN 201611149940 A CN201611149940 A CN 201611149940A CN 106702757 A CN106702757 A CN 106702757A
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synthetic leather
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杨银龙
韩芹
杜明兵
刘国
张�浩
张其斌
段伟东
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SHANGHAI HUAFON MICREOFIBRE TECHNOLOGY Co Ltd
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Abstract

本发明公开了一种聚氨酯超细纤维合成革制备过程中的水性浸渍树脂及应用,所述水性浸渍树脂,含有能溶于甲苯的聚合物微粒,所述的聚合物微粒为聚烯烃微粒或聚苯乙烯微粒中的一种以上。所述的水性浸渍树脂,可用于制备水性聚氨酯超细纤维合成革。本发明使用水性聚氨酯乳液代替溶剂型聚氨酯树脂,极大地降低了环境污染,利用甲苯减量的工艺特点,在不增加工序的条件下,通过改变聚合物微粒的大小与多少来调整泡孔结构的大小与多少,从而实现产品的多样化,减量出来的聚合物微粒与海相一起回收再利用,该方法制备的水性聚氨酯超细纤维合成革拥有较为细密的泡孔结构。

Description

聚氨酯超细纤维合成革制备过程中的水性浸渍树脂及应用
技术领域
本发明涉及聚氨酯超细纤维合成革的制备方法,具体涉及水性浸渍树脂。
背景技术
超细纤维合成革是由超细纤维和聚氨酯构成的复合材料,具有结构仿真性、透气性、柔软性等特点,是真皮的理想替代材料之一,广泛应用于沙发、汽车、箱包、制鞋等领域。目前,国内超细纤维合成革大多数都是甲苯减量工艺制备而成,其典型步骤如下:1)通过海岛型无纺布浸渍聚氨酯的DMF溶液,并在DMF-H2O溶液中凝固形成聚氨酯微孔;2)通过热甲苯抽出纤维中的海相;3)通过干燥、上油、染色等处理工艺制成超细纤维合成革基布;4)通过贴面或磨皮等工艺制成成品革。该工艺的优点在于超细纤维合成革中的聚氨酯组分拥有大量的微孔结构,制成的合成革手感丰满、柔软、真皮感强;缺点在于过程中大量使用了溶剂DMF,对环境造成一定的污染,且在回收DMF时需要消耗大量的能源。
水性聚氨酯超细纤维合成革在制备过程中,通过将溶剂型聚氨酯浸渍液更换成水性聚氨酯浸渍液,减少了生产过程中的溶剂使用。但海岛型无纺布浸渍水性聚氨酯树脂时如何产生微孔结构一直困扰着水性超细纤维合成革的发展。国内同行提出过一些方法,如机械发泡、盐浴凝聚、酸浴凝聚、化学发泡等。但机械发泡会被海岛型无纺布过滤掉部分气泡而难以控制,盐浴和酸浴凝聚会增加革的脆性而引起柔韧性不够,化学发泡目前还没有适用于水性聚氨酯体系的发泡剂。
发明内容
本发明的目的在于提供一种聚氨酯超细纤维合成革制备过程中的水性浸渍树脂及应用,以克服现有技术存在的缺陷。
本发明所述的水性浸渍树脂,含有能溶于甲苯的聚合物微粒,所述的聚合物微粒为聚烯烃微粒或聚苯乙烯微粒中的一种以上;
优选的,所述的水性浸渍树脂,由以下重量份的组分组成:
所述的聚烯烃选自聚乙烯、聚丙烯中的一种或两种,所述的聚烯烃微粒和聚苯乙烯微粒的D50为8~16微米;
所述的聚烯烃微粒可采用市售产品,如:聚乙烯微粒可采用南京天诗新材料科技有限公司牌号为PEW-0204、PEW-0221的产品等,聚丙烯微粒可采用南京天诗新材料科技有限公司牌号为PPW-0901的产品等;
或者,将聚乙烯、聚丙烯或聚苯乙烯球磨粉碎至D50为8~16微米即可;
所述的水性聚氨酯乳液的固体重量份为35~55%,较好的为40~50%;
所述的水性聚氨酯乳液的100%模量为1.0~5.0Mpa,较好的为3.0~5.0MPa;
所述的润湿剂为聚醚改性硅油,可采用市售产品如XIAMETER OFX-5211FLUID等。
所述的增稠剂为聚丙烯酸水溶液,可采用市售产品Gel ALA等。
所述的水性浸渍树脂的制备方法为常规的物理混合方法,将上述组分混合均匀,即可获得粘度3000~5500mPa.S@25℃的所述的水性浸渍树脂;
所述的水性浸渍树脂,可用于制备水性聚氨酯超细纤维合成革,应用方法,包括如下步骤:
(1)将海岛型无纺布浸渍于所述的含有聚合物微粒的水性浸渍树脂中,控制含液率在80~100%,然后刮除海岛型无纺布表面的树脂,90~130℃烘干,得浸渍基布;
(2)将上述浸渍基布投入甲苯中进行减量,甲苯温度为75~80℃,时间为2~3小时,将减量后的基布在110~130℃下干燥,得原生基布;
(3)然后通过常规的方法,对获得的原生基布进行后处理,即可获得所述的水性聚氨酯超细纤维合成革;
所述的后处理的方法为常规的,本领域的技术人员可以按照文献(如文献:曲建波.合成革工艺学[M].化学工业出版社,2010.)报道的方法进行原生基布的染色、上油、磨皮、磨绒等工艺处理得到水性超细纤维聚氨酯合成革基布,该基布可用于沙发革、手套革、汽车内饰革、鞋革等的生产,根据目标产品的不同,可选择不同100%模量和固体重量份的水性聚氨酯乳液、不同重量份及大小的聚合物微粒等来实现。
本发明的技术原理是:
利用所述聚合物微粒溶于热甲苯的特点,在配制水性浸渍树脂时向其中加入聚合物微粒,并在甲苯减去海岛纤维海相形成超细纤维的同时减去浸渍树脂中的聚合物微粒,从而形成聚氨酯微孔,模拟了常规超细纤维合成革中聚氨酯组分的泡孔结构,实现了水性超细纤维合成革的丰满、柔软、真皮感强的特点。
与现有技术相比,本发明的有益效果是:
使用水性聚氨酯乳液代替溶剂型聚氨酯树脂,极大地降低了环境污染,利用甲苯减量的工艺特点,在不增加工序的条件下,通过改变聚合物微粒的大小与多少来调整泡孔结构的大小与多少,从而实现产品的多样化,减量出来的聚合物微粒与海相一起回收再利用,该方法制备的水性聚氨酯超细纤维合成革拥有较为细密的泡孔结构。
附图说明
图1为实施例1的产物的电镜照片。
图2为实施例2的产物的电镜照片。
图3为实施例3的产物的电镜照片。
图4为对比实施例1的产物的电镜照片。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应该理解,这些实施例仅用于说明本发明,而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的改进和调整,仍属于本发明的保护范围。以下实施例所用原料均为市售或者自制。
实施例1
本实施例的水性超细纤维合成革的制备步骤如下:
水性浸渍树脂的配制:
表1
将表1中原料混合均匀,制得粘度为约3000mPa·S@25℃的水性浸渍树脂。
原生基布的制备:
将海岛型无纺布浸渍于该水性浸渍树脂,控制含液率100%,用刮刀将表面树脂刮掉,然后在90℃烘箱中烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用75℃甲苯减量3小时,并将减量完成的基布在130℃扩幅干燥设备上烘干,制得原生基布。
将原生基布按照文献报道的方法经过染色、上油、磨皮、贴面,即可获得所述的水性聚氨酯超细纤维合成革,可用于制男鞋。
采用复纳科学仪器(上海)有限公司的PHENOM台式扫描电镜及其孔洞统计分析系统分析聚氨酯树脂组分的微孔孔径D50。采用标准ISO17235-2002来检测皮革的柔软度。测试结果及手感如下:
聚氨酯组分微孔孔径D50:15.9微米,柔软度:3.4,手感:柔软丰满、真皮感强。电镜照片见图1。
实施例2
水性浸渍树脂的配制:
表2
将表2中原料混合均匀,制得粘度为约5500mPa·S@25℃的水性浸渍树脂。
原生基布的制备:
将海岛型无纺布浸渍于该水性浸渍树脂,控制含液率80%,用刮刀将表面树脂刮掉,然后在130℃烘箱中烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用80℃甲苯减量2小时,并将减量完成的基布在120℃扩幅干燥设备上烘干,制得原生基布;
将原生基布按照文献报道的方法经过染色、磨绒、上油制得绒面水性超细纤维合成革,可用于女靴靴筒等。
采用复纳科学仪器(上海)有限公司的PHENOM台式扫描电镜及其孔洞统计分析系统分析聚氨酯树脂组分的微孔孔径D50。采用标准ISO17235-2002来检测皮革的柔软度。测试结果及手感如下:
聚氨酯组分微孔孔径D50:8.2微米,柔软度:5.2,手感:柔软丰满、悬垂感佳。电镜照片见图2。
实施例3
本实施例的水性超细纤维合成革的制备步骤如下:
水性浸渍树脂的配制:
表3
将表3中原料混合均匀,制得粘度为约4500mPa·S@25℃的水性浸渍树脂。
基布的制备:
将海岛型无纺布浸渍于水性浸渍树脂,控制含液率90%,用刮刀将表面树脂刮掉,然后在120℃烘箱中烘干,制得浸渍基布;将浸渍基布投入到减量工序中,用80℃甲苯减量2小时,并将减量完成的基布在130℃扩幅干燥设备上烘干,制得原生基布。
将原生基布按照文献报道的方法经过染色、上油、磨皮、贴面制得水性超细纤维合成革,可用于女鞋等。
采用复纳科学仪器(上海)有限公司的PHENOM台式扫描电镜及其孔洞统计分析系统分析聚氨酯树脂组分的微孔孔径D50。采用标准ISO17235-2002来检测皮革的柔软度。测试结果及手感如下:
聚氨酯组分微孔孔径D50:11.8微米,柔软度:4.8,手感:柔软丰满、柔韧性佳。电镜照片见图3。
对比实施例1
将实施例1中的水性浸渍树脂不加入聚乙烯微粒,并保证浸渍树脂中聚氨酯的固含量不变,故水性浸渍树脂配比为:100%模量为5.5MPa、固含量为55%的水性聚氨酯乳液100份,去离子水30份,XIAMETER OFX-5211FLUID 0.1份,Gel ALA 0.1份。其余工艺不变,制得水性超细纤维合成革。
采用复纳科学仪器(上海)有限公司的PHENOM台式扫描电镜及其孔洞统计分析系统分析聚氨酯树脂组分的微孔孔径D50。采用标准ISO17235-2002来检测皮革的柔软度。测试结果及手感如下:
聚氨酯组分微孔孔径D50:无微孔,柔软度:2.2,手感:塑感强、手感硬、弹性差。电镜照片见图4。
从以上各实施例及对比实施例可知,本发明的水性浸渍树脂及水性聚氨酯超纤纤维合成革的制备方法获得了细密的微孔结构,实现了水性超细纤维合成革的丰满、柔软、真皮感强的特点。

Claims (10)

1.聚氨酯超细纤维合成革制备过程中的水性浸渍树脂,其特征在于,含有能溶于甲苯的聚合物微粒,所述的聚合物微粒为聚烯烃微粒或聚苯乙烯微粒中的一种以上。
2.根据权利要求1所述的聚氨酯超细纤维合成革制备过程中的水性浸渍树脂,其特征在于,由以下重量份的组分组成:
3.根据权利要求2所述的聚氨酯超细纤维合成革制备过程中的水性浸渍树脂,其特征在于,所述的聚烯烃选自聚乙烯、聚丙烯中的一种或两种,所述的聚烯烃微粒和聚苯乙烯微粒的D50为8~16微米。
4.根据权利要求2所述的聚氨酯超细纤维合成革制备过程中的水性浸渍树脂,其特征在于,所述的水性聚氨酯乳液的固体重量份为35~55%,所述的水性聚氨酯乳液的100%模量为1.0~5.0Mpa。
5.根据权利要求2所述的聚氨酯超细纤维合成革制备过程中的水性浸渍树脂,其特征在于,所述的润湿剂为聚醚改性硅油;
所述的增稠剂为聚丙烯酸水溶液。
6.根据权利要求1~5任一项所述的聚氨酯超细纤维合成革制备过程中的水性浸渍树脂,其特征在于,粘度为3000~5500mPa.S@25℃。
7.根据权利要求1~6任一项所述的聚氨酯超细纤维合成革制备过程中的水性浸渍树脂的应用,其特征在于,用于制备水性聚氨酯超细纤维合成革。
8.根据权利要求7所述的应用,其特征在于,应用方法,包括如下步骤:
(1)将海岛型无纺布浸渍于所述的含有聚合物微粒的水性浸渍树脂中,然后刮除海岛型无纺布表面的树脂,得浸渍基布;
(2)将上述浸渍基布投入甲苯中进行减量,得原生基布;
(3)然后对获得的原生基布进行后处理,即可获得所述的水性聚氨酯超细纤维合成革。
9.根据权利要求8所述的应用,其特征在于,步骤(1)中,将海岛型无纺布浸渍于所述的含有聚合物微粒的水性浸渍树脂中,控制含液率在80~100%,然后刮除海岛型无纺布表面的树脂,90~130℃烘干,得浸渍基布。
10.根据权利要求8所述的应用,其特征在于,步骤(2)中,将上述浸渍基布投入甲苯中进行减量,甲苯温度为75~80℃,时间为2~3小时,将减量后的基布在110~130℃下干燥,得原生基布。
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