CN112250823B - 一种抗汗液的材料及其制备方法与应用 - Google Patents

一种抗汗液的材料及其制备方法与应用 Download PDF

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CN112250823B
CN112250823B CN202011161491.XA CN202011161491A CN112250823B CN 112250823 B CN112250823 B CN 112250823B CN 202011161491 A CN202011161491 A CN 202011161491A CN 112250823 B CN112250823 B CN 112250823B
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thermoplastic polyurethane
organic silicon
sweat
aliphatic organic
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CN112250823A (zh
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战振生
宋红玮
李庆钊
刘德富
刘建文
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Miracll Chemicals Co Ltd
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Abstract

本发明提供一种抗汗液的材料及其制备方法与应用。所述抗汗液的材料为贴合在一起的脂肪族有机硅热塑性聚氨酯薄膜和芳香族热塑性聚氨酯，其中，所述脂肪族有机硅热塑性聚氨酯薄膜的未贴合的一面与人手部接触。本发明在芳香族热塑性聚氨酯弹性体手机套表面引入脂肪族有机硅聚氨酯弹性体薄膜，从而尽可能避免了人的手部与芳香族热塑性聚氨酯弹性体的接触。由于引进了有机硅提升了材料的抗脏污性能和耐渗透性，另一方面由于引入了脂肪族异氰酸酯避免了汗液等对结构的影响。综合来看，采用本发明生产的手机保护套的实际抗黄变效果较好，使用寿命长，给消费者带来的最终体验较好。

Description

一种抗汗液的材料及其制备方法与应用
技术领域
本发明涉及手机保护套制备领域，具体涉及一种抗汗液的材料及其制备方法与应用。
背景技术
热塑性聚氨酯弹性体的硬度范围比较广泛，具有非常好的强度，耐磨性能，透明度好，可广泛应用于手机保护套，腕带，薄膜，热熔胶膜等领域。目前，手机保护套领域所使用的热塑性聚氨酯弹性体主要为芳香族热塑性聚氨酯，硬度主要为85A-55D，具有透明度好，注塑加工效率高，产品表面无水纹等优点，另外通过在配方中添加紫外线吸收剂和光稳定剂可以提高其抗黄性能。
但芳香族热塑性聚氨酯手机保护套在实际使用过程中仍然会发黄较快，甚至发红，即便通过添加足量的光稳定剂和紫外线吸收剂提高其抗紫外线性能，仍改善不明显，手机保护套的使用寿命仍然很短，给消费者的体验很差。这主要是因为在实际使用过程中太阳光中的紫外线由于与手机套的接触时间较少，对手机套的影响也小，而且像三星，华为等品牌护套厂所使用的TPU原材料的抗紫外线性能较高。手机套在短时间内容易变黄最主要的原因是因为受到汗液的影响，汗液中的氯化钠，乳酸，油酸甘油酯等容易渗透到芳香族热塑性聚氨酯弹性体保护套中从而造成其结构改变产生一些醌的发色基团从而变色。
脂肪族热塑性聚氨酯弹性体中的脂肪族异氰酸酯不容易因紫外线和汗液等影响产生结构改变，但脂肪族热塑性聚氨酯弹性体在采用注塑加工工艺进行加工的时候由于成型偏慢加工性能较差，比较容易出现变形和表面水纹的问题，而且在实际使用过程中容易出现蠕变而造成消费者佩戴过程中变大的问题，而影响其应用。
发明内容
本发明针对上述现有技术存在的不足，提供一种抗汗液的材料及其制备方法。
本发明所提供的抗汗液的材料，为贴合在一起的脂肪族有机硅热塑性聚氨酯薄膜和芳香族热塑性聚氨酯材料，其中，所述脂肪族有机硅热塑性聚氨酯薄膜的未贴合的一面与人手部接触。
所述脂肪族有机硅热塑性聚氨酯薄膜由脂肪族有机硅热塑性聚氨酯A制备；
所述脂肪族有机硅热塑性聚氨酯A由下述原料制备得到：端羟基有机硅嵌段聚醚、多元醇、脂肪族异氰酸酯和扩链剂；
其中，所述端羟基有机硅嵌段聚醚为数均分子量为600-3000g/mol的端羟基有机硅嵌段聚醚，端基为羟基，主链为硅氧键，由端氢硅油与烯丙基聚醚反应制备得到，具体方法可以参考印染助剂第35卷第10期《端羟基有机硅嵌段聚醚的合成》。
所述多元醇可包括聚酯多元醇，聚醚多元醇，聚己内酯多元醇和聚碳酸酯多元醇中的一种或多种；
所述脂肪族异氰酸酯包括二环己基甲烷二异氰酸酯，六亚甲基二异氰酸酯中的一种或两种；
所述扩链剂可包括乙二醇，丁二醇，丙二醇和己二醇中的一种或多种；
多元醇与端羟基有机硅嵌段聚醚的质量比可为50：50-95：5，具体可为70：30或80：20；
所述脂肪族有机硅热塑性聚氨酯A的硬度为60A-65D，优选90A。
所述芳香族热塑性聚氨酯材料由芳香族热塑性聚氨酯B制备；
所述芳香族热塑性聚氨酯B由下述原料制备得到：多元醇、芳香族异氰酸酯和扩链剂；
所述多元醇包括聚酯多元醇，聚醚多元醇，聚己内酯多元醇和聚碳酸酯多元醇中的一种或多种；
所述芳香族异氰酸酯可为二苯基甲烷二异氰酸酯和甲苯二异氰酸酯中的一种或多种；
所述扩链剂包括乙二醇，丁二醇，丙二醇或己二醇中的一种或多种；
所述芳香族热塑性聚氨酯B的硬度为85A-65D，优选95A。
上述抗汗液的材料通过包括如下步骤的方法制备得到：
(1)制备脂肪族有机硅热塑性聚氨酯薄膜；
(2)将脂肪族有机硅热塑性聚氨酯薄膜贴合在芳香族热塑性聚氨酯材料表面。
上述方法步骤(2)中，通过吸塑工艺将脂肪族有机硅热塑性聚氨酯薄膜贴合在芳香族热塑性聚氨酯材料表面；
或，
所述脂肪族有机硅热塑性聚氨酯薄膜通过热熔胶采用热贴合工艺贴合在芳香族热塑性聚氨酯材料表面。
上述抗汗液的材料在制备抗汗液的电子产品保护套中的应用也属于本发明的保护范围。
所述应用中，所述电子产品可为手机、ipad等。
本发明还提供一种抗汗液的手机保护套。
本发明所提供的抗汗液的手机保护套由上述抗汗液的材料制备得到，其中，所述抗汗液的材料中，脂肪族有机硅热塑性聚氨酯薄膜的未与芳香族热塑性聚氨酯材料贴合的一侧与人手部接触。
上述抗汗液的手机保护套通过包括如下步骤的方法制备得到：
(1)通过注塑工艺制备芳香族热塑性聚氨酯手机保护套；
(2)制备脂肪族有机硅热塑性聚氨酯薄膜；
(3)将脂肪族有机硅热塑性聚氨酯薄膜贴合在芳香族热塑性聚氨酯手机保护套表面。
上述方法步骤(3)中，通过吸塑工艺将脂肪族有机硅热塑性聚氨酯薄膜贴合在芳香族热塑性聚氨酯手机保护套表面；
或，
所述脂肪族有机硅热塑性聚氨酯薄膜通过热熔胶采用热贴合工艺贴合在芳香族热塑性聚氨酯手机保护套表面。
本发明在芳香族热塑性聚氨酯弹性体手机套表面引入脂肪族有机硅聚氨酯弹性体薄膜，从而尽可能避免了人的手部与芳香族热塑性聚氨酯弹性体的接触。由于引进了有机硅提升了材料的抗脏污性能和耐渗透性，另一方面由于引入了脂肪族异氰酸酯避免了汗液等对结构的影响。综合来看，采用本发明生产的手机保护套的实际抗黄变效果较好，使用寿命长，给消费者带来的最终体验较好。
具体实施方式
下面通过具体实施例对本发明进行说明，但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
实施例1
采用双螺杆挤出工艺生产的芳香族热塑性聚氨酯B1通过注塑工艺制备厚度为1mm的手机保护套，通过流延工艺采用双螺杆挤出工艺生产的脂肪族有机硅热塑性聚氨酯AS1制备薄膜，最终采用吸塑工艺制备表面带有脂肪族有机硅热塑性聚氨酯薄膜的手机保护套产品。然后在该产品外表面涂上人工酸性汗液，进行耐手汗测试，并测试色差。
实施例2
采用双螺杆挤出工艺生产的芳香族热塑性聚氨酯B2通过注塑工艺制备厚度为1mm的手机保护套，通过流延工艺采用双螺杆挤出工艺生产的脂肪族有机硅热塑性聚氨酯AS1制备薄膜，最终采用吸塑工艺制备表面带有脂肪族有机硅热塑性聚氨酯薄膜的手机保护套产品。然后在该产品外表面涂上人工酸性汗液，进行耐手汗测试，并测试色差。
实施例3
采用双螺杆挤出工艺生产的芳香族热塑性聚氨酯B2通过注塑工艺制备厚度为1mm的手机保护套，通过流延工艺采用双螺杆挤出工艺生产的脂肪族有机硅热塑性聚氨酯AS2制备薄膜，最终采用吸塑工艺制备表面带有脂肪族有机硅热塑性聚氨酯薄膜的手机保护套产品。然后在该产品外表面涂上人工酸性汗液，进行耐手汗测试，并测试色差。
对比例1
采用双螺杆挤出工艺生产的芳香族热塑性聚氨酯B1通过注塑工艺制备厚度为1mm的手机保护套，然后在该产品外表面涂上人工酸性汗液，进行耐手汗测试，并测试色差。
对比例2
采用双螺杆挤出工艺生产的芳香族热塑性聚氨酯B2通过注塑工艺制备厚度为1mm的手机保护套，然后在该产品外表面涂上人工酸性汗液，进行耐手汗测试，并测试色差。
对比例3
采用双螺杆挤出工艺生产的芳香族热塑性聚氨酯B1通过注塑工艺制备厚度为1mm的手机保护套，通过流延工艺采用双螺杆挤出工艺生产的脂肪族热塑性聚氨酯A1制备薄膜，最终采用吸塑工艺制备表面带有脂肪族有机硅热塑性聚氨酯薄膜的手机保护套产品。然后在该产品外表面涂上人工酸性汗液，进行耐手汗测试，并测试色差。
其中：
芳香族TPU的抗UV性能测试条件如下：4小时UV照射(340nm，0.63W/m2,60度)加上4小时50度湿气曝光为一个循环，共测试9个循环。抗黄等级的判定采用九级色卡进行判定。
酸性汗液的配制方法如下：用烧杯量取去离子水1000ml，用分析天平称取氯化钠20g，磷酸氢二钠10g溶解于烧杯中。待充分溶解后用微量移液器吸取乳酸将pH值调整到4±0.5范围内。
耐手汗测试:将无纺布在配置好的酸性汗液中充分浸泡，并贴在手机套产品的外表面。然后置于55度95湿度的环境中48小时。然后将手机套产品外表面的酸性汗液擦拭干净。常温下静置2小时用色差仪测试LAB值并与测试前的LAB值进行计算得到色差ΔE。
实验结果如下:
Figure BDA0002744377990000051
Figure BDA0002744377990000061
注：本领域的技术人员可以根据上述表格中护套材料的原料组成及硬度、薄膜层原料的组成及硬度计算出各个组分的比例进行试验。
从以上结果可以看出，本专利制备的手机保护套抗手汗效果比较好。
在本说明书的描述中，术语“一个实施例”、“一些实施例”、“具体实施例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或实例。而且，描述的具体特征、结构、材料或特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种抗汗液的材料,为贴合在一起的脂肪族有机硅热塑性聚氨酯薄膜和芳香族热塑性聚氨酯材料，其中，所述脂肪族有机硅热塑性聚氨酯薄膜的未贴合的一面与人手部接触；
所述脂肪族有机硅热塑性聚氨酯薄膜由脂肪族有机硅热塑性聚氨酯A制备；
所述脂肪族有机硅热塑性聚氨酯A由下述原料制备得到：端羟基有机硅嵌段聚醚、多元醇、脂肪族异氰酸酯和扩链剂；
所述端羟基有机硅嵌段聚醚的数均分子量为600-3000g/mol；
所述多元醇包括聚酯多元醇，聚醚多元醇和聚碳酸酯多元醇中的一种或多种；
所述脂肪族异氰酸酯包括二环己基甲烷二异氰酸酯，六亚甲基二异氰酸酯中的一种或两种；
所述扩链剂包括乙二醇，丁二醇，丙二醇和己二醇中的一种或多种；
多元醇与端羟基有机硅嵌段聚醚的质量比为：7:3。
2.根据权利要求1 所述的抗汗液的材料，其特征在于：所述脂肪族有机硅热塑性聚氨酯A的硬度为：60A-65D。
3.根据权利要求1所述的抗汗液的材料，其特征在于：所述芳香族热塑性聚氨酯材料由芳香族热塑性聚氨酯B制备；
所述芳香族热塑性聚氨酯B由下述原料制备得到：多元醇、芳香族异氰酸酯和扩链剂；
所述多元醇包括聚酯多元醇，聚醚多元醇和聚碳酸酯多元醇中的一种或多种；
所述芳香族异氰酸酯为二苯基甲烷二异氰酸酯和甲苯二异氰酸酯中的一种或多种；
所述扩链剂包括乙二醇，丁二醇，丙二醇或己二醇中的一种或多种；
所述芳香族热塑性聚氨酯B的硬度为：85A-65D。
4.制备权利要求1-3中任一项所述的抗汗液的材料的方法，包括如下步骤：
（1）制备脂肪族有机硅热塑性聚氨酯薄膜；
（2）将脂肪族有机硅热塑性聚氨酯薄膜贴合在芳香族热塑性聚氨酯材料表面。
5.根据权利要求4所述的方法，其特征在于：步骤（2）中，通过吸塑工艺将脂肪族有机硅热塑性聚氨酯薄膜贴合在芳香族热塑性聚氨酯材料表面，
或，步骤（2）中，所述脂肪族有机硅热塑性聚氨酯薄膜通过热熔胶采用热贴合工艺贴合在芳香族热塑性聚氨酯材料表面。
6.权利要求1-3中任一项所述的抗汗液的材料在制备抗汗液的电子产品保护套中的应用。
7.根据权利要求6所述的应用，其特征在于：所述电子产品为手机、ipad。
8.一种抗汗液的手机保护套，由权利要求1-3中任一项所述的抗汗液的材料制备得到，所述抗汗液的材料中，脂肪族有机硅热塑性聚氨酯薄膜的未与芳香族热塑性聚氨酯材料贴合的一侧与人手部接触。
9.制备权利要求8所述的抗汗液的手机保护套的方法，包括如下步骤：
（1）通过注塑工艺制备芳香族热塑性聚氨酯手机保护套；
（2）制备脂肪族有机硅热塑性聚氨酯薄膜；
（3）将脂肪族有机硅热塑性聚氨酯薄膜贴合在芳香族热塑性聚氨酯手机保护套表面。
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