CN109594351B - 一种球用无溶剂生态皮及其制备方法 - Google Patents

一种球用无溶剂生态皮及其制备方法 Download PDF

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CN109594351B
CN109594351B CN201811459510.XA CN201811459510A CN109594351B CN 109594351 B CN109594351 B CN 109594351B CN 201811459510 A CN201811459510 A CN 201811459510A CN 109594351 B CN109594351 B CN 109594351B
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苏星
许畅
黄万里
刘兵
陈茂祥
笪丽红
黄春寿
胡兆阳
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Anhui Anli Material Technology Co Ltd
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Abstract

本发明公开了一种球用无溶剂生态皮的制备方法，包括以下步骤：制备聚氨酯复合层，所述聚氨酯复合层包括面层和中间层；将热固型双组份无溶剂发泡聚氨酯树脂浆料涂覆于所述中间层的表面，加热烘干，形成无溶剂层后；随后再收卷夹布，剥离离型纸制得球用无溶剂生态皮。使用无溶剂发泡聚氨酯作为粘接层，在改善皮膜手感及回弹性的前提下，耐水解耐用性能也得到了大幅度提高，在面层聚氨酯中添加了耐磨助剂，在改善表面耐磨耐刮性能的同时，耐黄变性能也得以改善，在最后增加了收卷夹布的过程，解决了皮膜背面粘连、不好打卷的问题。

Description

一种球用无溶剂生态皮及其制备方法
技术领域
本发明属于高分子材料领域，具体涉及一种球用无溶剂生态皮及其制备方法。
背景技术
传统的机缝足球革表面材质多为TPU皮膜材料或者湿式的合成革材料，如专利CN201610759084.6公开了一种TPU发泡合成革，包括：基布、贴附在所述基布层上的TPU发泡层、贴附在所述TPU发泡层上的TPU膜层，TPU皮膜材料不发泡，手感偏硬，耐寒性能差，且为了得到表面不同纸纹和颜色，TPU皮膜需要进行二次贴面，容易有溶剂残留。
湿式合成革大多采用溶剂型聚氨酯树脂，使得生产制造过程中会产生大量的废液废气，不仅损害了一线工作人员的身心健康，也严重的污染了环境。专利CN205295765U公开了一种运动用球合成革，自上而下依次是面层、发泡层和基布，该专利的球革即是传统的湿式聚氨酯的结构。申请号为CN201520730467.1专利公开了一种机缝球用聚氨酯合成革，结构包括背涂涂层、基布层、湿法贝斯涂层和干法涂层，它同样属于传统球革的范畴。
发明内容
基于此，本发明提供了一种球用无溶剂生态皮的制备方法，使用无溶剂发泡聚氨酯作为粘接层，在改善皮膜手感及回弹性的前提下，耐水解耐用性能也得到了大幅度提高，在面层聚氨酯中添加了耐磨助剂，在改善表面耐磨耐刮性能的同时，耐黄变性能也得以改善，在最后增加了收卷夹布的过程，解决了皮膜背面粘连、不好打卷的问题。
为了实现上述目的，本发明采用以下技术方案：
一种球用无溶剂生态皮的制备方法，包括以下步骤：
a、制备聚氨酯复合层，所述聚氨酯复合层包括面层和中间层；
b、将热固型双组份无溶剂发泡聚氨酯树脂浆料涂覆于所述中间层的表面，形成无溶剂粘接层；
c、随后再收卷夹布，剥离离型纸制得球用无溶剂生态皮。
进一步的，在步骤a中，所述制备聚氨酯复合层的具体步骤为：首先将面层聚氨酯浆料涂覆于离型纸表面，于100～130℃加热烘干，制得面层；再将中间层聚氨酯浆料涂覆于所述面层，于100～130℃加热烘干，制得中间层；其中，面层聚氨酯浆料和中间层聚氨酯浆料的涂覆所用的刀头间隙均为20～25丝。
优选的，所述面层聚氨酯浆料由以下组分按质量份数构成：
Figure BDA0001888381130000021
所述中间层聚氨酯浆料由以下组分按质量份数构成：
Figure BDA0001888381130000022
优选的，所述面层聚氨酯浆料中的聚氨酯树脂和所述中间层聚氨酯浆料中的聚氨酯树脂分别独立的选自聚醚型聚氨酯、聚酯型聚氨酯、脂肪族聚氨酯中的至少一种。
优选的，所述耐磨助剂为聚四氟乙烯。
进一步的，所述步骤b的具体步骤为将热固型双组份无溶剂发泡聚氨酯树脂浆料涂覆于所述中间层表面，于100～110℃烘1～1.5min，形成无溶剂粘接层后，再于120～130℃烘4～5min，其中涂覆所用的刀头间隙为25～30丝。
进一步的，所述热固型双组份无溶剂发泡聚氨酯树脂浆料由聚酯型组合A料和聚醚聚碳混合型B料预聚体按照混合比100:(51～62)混合而成，其中，所述聚酯型组合A料由100～120份聚酯型A料(聚酯型A料为聚酯多元醇和其他组分的混合料)、40～60份填料、0.03～0.05份催化剂、0.3～0.5份水按照质量份数构成，所述聚醚聚碳混合型B料预聚体为聚醚型异氰酸酯预聚体和聚碳型异氰酸酯预聚体的混合物。
优选的，所述填料为氢氧化铝、碳酸钙中的一种或两种；
所述催化剂为甲基锡类催化剂、胺类催化剂中的一种或两种。
进一步的，所述收卷夹布所用的基布为水刺无纺布。
本发明的另一个目的在于提供一种球用无溶剂生态皮。
与现有技术相比，本发明具有以下有益效果：
1、使用无溶剂发泡聚氨酯作为粘接层，无溶剂的泡孔层属于闭孔型结构，泡孔中充满气体而不外泄，支持性能好，一定形变后能够恢复，故制得的生态皮手感丰满回弹性好；且由于泡孔材料上亲水基团较少，闭孔结构不易吸附导致水解的氧气和水蒸气等分子，使得制得的生态皮的耐水解耐用性能也得到了大幅度提高。
2、本发明面层添加了耐磨助剂，材料表层的聚氨酯的高分子材料呈现网状结构，聚四氟乙烯的表面张力为18～20dynes/cm，是已知高分子中较低的，它填充在材料的网状结构的网眼中，一方面改善表面耐磨耐刮性能，另一方面对聚氨酯的网丝起到保护作用，宏观上表现材料的耐紫外黄变性能也得以改善。
3、本发明聚醚聚碳混合型B料预聚体为聚醚型异氰酸酯预聚体和聚碳型异氰酸酯预聚体的混合物，与聚酯型异氰酸酯预聚体相比，聚醚型异氰酸酯预聚体与A料形成的结构耐水解老化性能更优异，但是机械性能稍差，聚碳型异氰酸酯预聚体与A料形成的结构机械性能优异，聚醚聚碳混合型B料与A料形成的结构结合了各自的优点，且产品的耐水解老化性能和机械性能不低于普通产品。
4、本发明的制备方法通过最后进行收卷夹布，避免了皮膜在卷取过程中无溶剂的发泡层与聚氨酯的面层直接接触粘合，后续材料加工放卷取走夹布即可，从而解决了皮膜背面粘连、不好打卷的问题。
5、采用无溶剂发泡工艺制得球革用生态皮膜，不仅手感柔软、回弹性佳，且具有环境友好、耗能较少等特点。此外，无溶剂一次成型工艺即可赋予皮膜表面不同的花纹及颜色，加工简单，外观效果丰富。
具体实施方式
下面结合具体的实施例对本发明的技术方案做进一步清楚完整的说明。
以下实施例中各原料的来源为：水刺无纺布布基为杭州路先革基布有限公司的UD055；聚氨酯树脂LT-140、LY-90NPC、SA-50、色浆PU白578、聚酯型A料AL-1025A、聚醚聚碳混合型B料AL-5040B预聚体均来源于合肥安利聚氨酯新材料有限公司(本公司的产品与常规聚氨酯树脂、色浆的主要活性成分相同，本发明中为实验方便采用的本公司产品，仅用于举例，具体保护范围请以权利要求书为准)，耐磨助剂采用的是聚四氟乙烯粉末为上海博军实业有限公司产品，紫外线吸收剂为上海亚基化工有限公司的UV-2268，抗氧剂为台湾双键化工有限公司的CS-1300，催化剂为南通艾德旺有限公司的NX-128，催化剂为德音公司的DY-2958。
实施例1
本实施例中的球用无溶剂生态皮包括面层、中间层与无溶剂层，其中面层聚氨酯浆料各组分质量份数为120份LT-140、30份N,N-二甲基甲酰胺、2份紫外线吸收UV2268、0.1份抗氧剂CS-1300、2份耐磨助剂XK-920、15份色浆PU白578混合而成；中间层聚氨酯浆料由120份SA-50、30份N,N-二甲基甲酰胺、2份紫外线吸收剂UV2268、20份色浆PU白578混合而成；无溶剂层聚氨酯浆料由聚酯型组合A料和聚醚聚碳混合型B料预聚体按照混合比100:58混合而成，其中，聚酯型组合A料由100份AL-1025A料、40份氢氧化铝、0.007份催化剂NX-128、0.03份催化剂DY-2958、0.5份水混合而成，聚醚聚碳混合型B料预聚体为AL-5040B预聚体。
具体制备步骤如下：
a、将面层聚氨酯树脂浆料用刀头间隙为20丝涂覆于离型纸表面，于130℃加热烘干，制得面层；
b、将中间层聚氨酯树脂浆料用刀头间隙为20丝涂覆于面层，于130℃加热烘干，制得中间层；
c、将无溶剂聚氨酯浆料用刀头间隙为25丝涂覆于中间层表面，于110℃烘1min，形成无溶剂层后，在120℃烘5min
d、再收卷夹布，剥离离型纸制得球用无溶剂生态皮。
实施例2
本实施例中的球用无溶剂生态皮包括面层、中间层与无溶剂层，其中面层聚氨酯浆料各组分质量份数为100份LY-90NPC、10份N,N-二甲基甲酰胺、1份紫外线吸收UV2268、0.2份抗氧剂CS-1300、2份耐磨助剂XK-920、20份色浆PU白578混合而成；中间层聚氨酯浆料由100份SA-50、10份N,N-二甲基甲酰胺、1份紫外线吸收剂UV2268、15份色浆PU白578混合而成；无溶剂层聚氨酯浆料由聚酯型组合A料和聚醚聚碳混合型B料预聚体按照混合比100:51混合而成，其中，聚酯型组合A料由110份AL-1025A料、50份氢氧化铝、0.02份催化剂NX-128、0.03份催化剂DY-2958、0.3份水混合而成，聚醚聚碳混合型B料预聚体为AL-5040B预聚体。
具体制备步骤如下：
a、将面层聚氨酯树脂浆料用刀头间隙为25丝涂覆于离型纸表面，于110℃加热烘干，制得面层；
b、将中间层聚氨酯树脂浆料用刀头间隙为25丝涂覆于面层，于110℃加热烘干，制得中间层；
c、将无溶剂聚氨酯浆料用刀头间隙为30丝涂覆于中间层表面，于105℃烘1.5min，形成无溶剂层后，在125℃烘5min
d、再收卷夹布，剥离离型纸制得球用无溶剂生态皮。
实施例3
本实施例中的球用无溶剂生态皮包括面层、中间层与无溶剂层，其中面层聚氨酯浆料各组分质量份数为150份LY-90NPC、50份N,N-二甲基甲酰胺、2份紫外线吸收UV2268、0.15份抗氧剂CS-1300、1份耐磨助剂XK-920、16份色浆PU白578混合而成；中间层聚氨酯浆料由150份SA-50、50份N,N-二甲基甲酰胺、1.5份紫外线吸收剂UV2268、18份色浆PU白578混合而成；无溶剂层聚氨酯浆料由聚酯型组合A料和聚醚聚碳混合型B料预聚体按照混合比100:62混合而成，其中，聚酯型组合A料由120份AL-1025A料、60份碳酸钙、0.01份催化剂NX-128、0.02份催化剂DY-2958、0.4份水混合而成，聚醚聚碳混合型B料预聚体为AL-5040B预聚体。
具体制备步骤如下：
a、将面层聚氨酯树脂浆料用刀头间隙为22丝涂覆于离型纸表面，于100℃加热烘干，制得面层；
b、将中间层聚氨酯树脂浆料用刀头间隙为22丝涂覆于面层，于100℃加热烘干，制得中间层；
c、将无溶剂聚氨酯浆料用刀头间隙为30丝涂覆于中间层表面，于100℃烘1min，形成无溶剂层后，在130℃烘4min
d、再收卷夹布，剥离离型纸制得球用无溶剂生态皮。
将实施例1～3中制得的球用无溶剂生态皮进行相关性能测试，测试结果和测试标准见下表：
Figure BDA0001888381130000051
由上表测试结果可知，采用本申请的制备方法制得的球用无溶剂生态皮其耐磨性能和耐黄变性能在于TPU球革相同水平的条件下，本发明的球用无溶剂生态皮在手感和回弹性方面明显优于TPU球革产品。
以上所述，仅为本发明较佳的具体实施方式，但本发明保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此本发明保护范围以权利要求书的保护范围为准。

Claims (7)

1.一种球用无溶剂生态皮的制备方法，其特征在于：包括以下步骤：
a、制备聚氨酯复合层，所述聚氨酯复合层包括面层和中间层，所述面层是由聚氨酯树脂100~150份、N,N-二甲基甲酰胺 10~50份、紫外线吸收剂1~2份、抗氧剂0.1~0.2份、耐磨助剂1~2份和色浆15~20份按照质量份构成的面层聚氨酯浆料形成，所述中间层是由聚氨酯树脂100~150份、N,N-二甲基甲酰胺10~50份、紫外线吸收剂1~2份和色浆15~20份按照质量份构成的中间层聚氨酯浆料形成；
b、将热固型双组份无溶剂发泡聚氨酯树脂浆料涂覆于所述中间层的表面，形成无溶剂粘接层，所述热固型双组份无溶剂发泡聚氨酯树脂浆料由聚酯型组合A料和聚醚聚碳混合型B料预聚体按照质量比100:(51~62)混合而成，其中，所述聚酯型组合A料由100~120份聚酯型A料、40~60份填料、0.03~0.05份催化剂、0.3~0.5份水按照质量份数构成，所述聚酯型A料为聚酯多元醇和其他组分的混合料，所述填料为氢氧化铝、碳酸钙中的一种或两种，所述催化剂为甲基锡类催化剂、胺类催化剂中的一种或两种；所述聚醚聚碳混合型B料预聚体为聚醚型异氰酸酯预聚体和聚碳型异氰酸酯预聚体的混合物；
c、随后再收卷夹布，剥离离型纸制得球用无溶剂生态皮；所述球用无溶剂生态皮在后续使用时放卷取走夹布。
2.如权利要求1所述的制备方法，其特征在于：在步骤a中，所述制备聚氨酯复合层的具体步骤为：首先将面层聚氨酯浆料涂覆于离型纸表面，于100~130℃加热烘干，制得面层；再将中间层聚氨酯浆料涂覆于所述面层，于100~130℃加热烘干，制得中间层；其中，面层聚氨酯浆料和中间层聚氨酯浆料的涂覆所用的刀头间隙均为20~25丝。
3.如权利要求1所述的制备方法，其特征在于：所述面层聚氨酯浆料中的聚氨酯树脂和所述中间层聚氨酯浆料中的聚氨酯树脂分别独立的选自聚醚型聚氨酯、聚酯型聚氨酯、脂肪族聚氨酯中的至少一种。
4.如权利要求1所述的制备方法，其特征在于：所述耐磨助剂为聚四氟乙烯。
5.如权利要求1所述的制备方法，其特征在于：所述步骤b的具体步骤为将热固型双组份无溶剂发泡聚氨酯树脂浆料涂覆于所述中间层的表面，于100~110℃烘1~1.5min，形成无溶剂粘接层后，再于120~130℃烘4~5min，其中涂覆所用的刀头间隙为25~30丝。
6.如权利要求1所述的制备方法，其特征在于：所述收卷夹布所用的基布为水刺无纺布。
7.一种用权利要求1~6任一项所述的制备方法制得的球用无溶剂生态皮。
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