CN105386328B - 一种三组分聚氨酯耐热人造革 - Google Patents

一种三组分聚氨酯耐热人造革 Download PDF

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CN105386328B
CN105386328B CN201510966118.4A CN201510966118A CN105386328B CN 105386328 B CN105386328 B CN 105386328B CN 201510966118 A CN201510966118 A CN 201510966118A CN 105386328 B CN105386328 B CN 105386328B
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王涨
胡方华
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Fujian Huaxia Synthetic Leather Co Ltd
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Abstract

本发明公开了一种三组分聚氨酯耐热人造革及其制造方法，在面层上涂覆一层三组分聚氨酯的涂饰层，该涂饰层由聚氨酯、硝化纤维素和丙烯酸甲酯在交联剂的作用下交联形成。本发明的三组分聚氨酯耐热人造革兼具聚氨酯、硝化纤维素和丙烯酸甲酯的性能，具有良好的机械性能以及耐热、耐候性，在制备过程中其混合涂料干燥迅速，而且制造工艺简单，生产成本低，符合实际生产要求。

Description

一种三组分聚氨酯耐热人造革
技术领域
本发明属于皮革技术领域，具体涉及一种三组分聚氨酯耐热人造革。
背景技术
天然皮革以其优异的性能和外观受到广大消费者的喜爱，但由于人口的膨胀和社会需求的不断增加，有限的天然皮革资源显得日益不足。人造革是一种外观、手感似天然皮革并可代替其使用的塑料制品，通常以织物为底基，涂覆合成树脂及各种塑料添加制成。随着各种人造皮革的发展，聚氨酯（PU）人造革以其质地轻软、耐磨、保暖、手感不受冷暖变化的影响，适于制作服装、较高级的包、袋和装饰用品，受到广大消费者的欢迎。
聚氨酯材料虽然具有高强度、高弹性、高伸长率和高耐磨性等诸多优点，但由于通用PU材料中含有耐热性较差的缩二脲结构与脲基甲酸酯结构，导致其热稳定性能较差，极大限制了PU材料的应用范围，使其各种优良性能得不到充分发挥。为了提高PU材料的耐热性能，常用的改进方法有：PU分子链中引入内能较大、降解温度较高的有机杂环基团；聚合物多元醇中引入含有热降解温度高的基团；PU分子链中引入不同的金属离子；PU与其它树脂共混；PU与其他树脂形成互穿聚合物网络（IPN）结构。方法和操作繁琐复杂，方法所需成本大，而且重金属离子有毒，方法易分层，起不到耐热性能的提高。通过PU与其它树脂形成互穿聚合物网络（IPN）能有效提高皮革耐热性，而且操作简单，成本低廉。
发明内容
本发明的目的在于针对现有技术不足，提供一种三组分聚氨酯耐热人造革及其制造方法。所制造的三组分聚氨酯耐热人造革具有优异的耐磨性、弹性和耐热性能，制造方法简单，成本低廉。
为实现上述目的，本发明采用如下技术方案：
三组分聚氨酯耐热人造革，包括面层，所述面层为聚氯乙烯或水性聚氨酯，其上设有涂饰层；所述涂饰层由A、B和C组分组成；A组分以重量份计其组成为：4, 4-二环己基甲烷二异氰酸酯30~50份、聚乙二醇15~30份、二月桂酸二丁基锡0.5~1.5份、1, 4-丁二醇0.5~1.5份和三羟甲基丙烷0.5~2份；B组分以重量份计其组成为：硝化纤维素10~15份；C组分以重量份计其组成为：丙烯酸甲酯10~15份和丙酮15~20份；A、B和C三组分的质量比为：70~100：15~20：15~20。
所述的三组分聚氨酯耐热人造革的制造方法包括以下步骤：
（1）在离型纸上涂刮聚氯乙烯或者水性聚氨酯面层，经烘箱烘干形成具有一定花纹的面层皮膜；
（2）在步骤（1）制得的面层上涂刮聚氯乙烯或水性聚氨酯发泡层并且贴基布，经烘箱加温使其发泡凝胶，再与所述离型纸分离，得到人造革；
（3）将聚乙二醇和硝化纤维素混合，在真空环境下脱水30~60 min，在氮气保护下，加入4, 4-二环己基甲烷二异氰酸酯，随后加入二月桂酸二丁基锡，在80℃恒温下以30~50r/min的速度搅拌反应100~150 min后，加入小分子扩链剂1, 4-丁二醇反应20~40 min，得硝化纤维素-聚氨酯预聚体；
（4）将丙烯酸甲酯与硝化纤维素-聚氨酯预聚体以40~80 r/min的速度搅拌混合均匀，升温至60~80℃，加入交联剂三羟甲基丙烷，搅拌反应180~250 min，最后降温至40℃并保温，加入丙酮以80~120 r/min搅拌乳化得到三组分聚氨酯；
（5）将步骤（2）制得的人造革的面层用三版印刷机辊涂一层或者多层步骤（4）制得的三组分聚氨酯涂饰层，进入烘干即得三组分聚氨酯耐热人造革。
步骤（1）中面层皮膜厚度为0.1~1.5 mm，烘箱温度为100~120℃。
步骤（2）发泡层的涂刮厚度为0.15~2 mm，烘箱温度为120~200℃。
步骤（5）中烘干温度为55℃~80℃。
本发明中聚氨酯、硝化纤维素和丙烯酸甲酯在交联剂的作用下交联形成一种互穿网络的三组分聚氨酯，在聚氨酯、硝化纤维素和丙烯酸甲酯分子紧密结合后，丙烯酸甲酯单体向内部聚合形成核结构，聚氨酯和硝化纤维素在外形成壳结构，产物呈“核-壳”结构。该“核-壳”结构的三组分聚氨酯兼具聚氨酯、硝化纤维素和丙烯酸甲酯三者的优异性能。
本发明的有益效果在于：
（1）本发明的三组分聚氨酯耐热人造革兼具聚氨酯、硝化纤维素和丙烯酸甲酯的性能，具有良好的机械性能以及耐热、耐候性，在制备过程中其混合涂料干燥迅速；
（2）本发明的涂饰层为三组分聚氨酯，三组分的聚氨酯使其具有很好的耐热性，200℃下冲压10秒，人造革的表面不会出现亮面和发粘现象；
（3）本发明的人造革制造工艺简单，生产成本低，符合实际生产要求。
具体实施方式
以下结合具体实施例对本发明做进一步说明，但本发明不仅仅限于这些实施例。
实施例1
三组分聚氨酯耐热人造革，包括面层，所述面层为聚氯乙烯或水性聚氨酯，其上设有涂饰层；所述涂饰层由A、B和C组分组成；A组分以重量份计其组成为：4, 4-二环己基甲烷二异氰酸酯30份、聚乙二醇15份、二月桂酸二丁基锡0.5份、1, 4-丁二醇0.5份和三羟甲基丙烷0.5份；B组分以重量份计其组成为：硝化纤维素10份；C组分以重量份计其组成为：丙烯酸甲酯10份和丙酮15份；A、B和C三组分的质量比为：70：15：15。
所述的三组分聚氨酯耐热人造革的制造方法包括以下步骤：
（1）在离型纸上涂刮聚氯乙烯或者水性聚氨酯面层，经烘箱烘干形成具有一定花纹的面层皮膜；
（2）在步骤（1）制得的面层上涂刮聚氯乙烯或水性聚氨酯发泡层并且贴基布，经烘箱加温使其发泡凝胶，再与所述离型纸分离，得到人造革；
（3）将聚乙二醇和硝化纤维素混合，在真空环境下脱水30 min，在氮气保护下，加入4, 4-二环己基甲烷二异氰酸酯，随后加入二月桂酸二丁基锡，在80℃恒温下以30 r/min的速度搅拌反应100 min后，加入小分子扩链剂1, 4-丁二醇反应20min，得硝化纤维素-聚氨酯预聚体；
（4）将丙烯酸甲酯与硝化纤维素-聚氨酯预聚体以40 r/min的速度搅拌混合均匀，升温至60℃，加入交联剂三羟甲基丙烷，搅拌反应180 min，最后降温至40℃并保温，加入丙酮以80120 r/min搅拌乳化得到三组分聚氨酯；
（5）将步骤（2）制得的人造革的面层用三版印刷机辊涂一层或者多层步骤（4）制得的三组分聚氨酯涂饰层，进入烘干即得三组分聚氨酯耐热人造革。
步骤（1）中面层皮膜厚度为0.1 mm，烘箱温度为100℃。
步骤（2）发泡层的涂刮厚度为0.15 mm，烘箱温度为120℃。
步骤（5）中烘干温度为55℃。
三组分聚氨酯耐热人造革的耐热性能指标如下：
耐热性：200℃冲压10秒，无亮面无发粘。
实施例2
三组分聚氨酯耐热人造革，包括面层，所述面层为聚氯乙烯或水性聚氨酯，其上设有涂饰层；所述涂饰层由A、B和C组分组成；A组分以重量份计其组成为：4, 4-二环己基甲烷二异氰酸酯50份、聚乙二醇30份、二月桂酸二丁基锡1.5份、1, 4-丁二醇1.5份和三羟甲基丙烷2份；B组分以重量份计其组成为：硝化纤维素15份；C组分以重量份计其组成为：丙烯酸甲酯15份和丙酮20份；A、B和C三组分的质量比为：100： 20：20。
所述的三组分聚氨酯耐热人造革的制造方法包括以下步骤：
（1）在离型纸上涂刮聚氯乙烯或者水性聚氨酯面层，经烘箱烘干形成具有一定花纹的面层皮膜；
（2）在步骤（1）制得的面层上涂刮聚氯乙烯或水性聚氨酯发泡层并且贴基布，经烘箱加温使其发泡凝胶，再与所述离型纸分离，得到人造革；
（3）将聚乙二醇和硝化纤维素混合，在真空环境下脱水60 min，在氮气保护下，加入4, 4-二环己基甲烷二异氰酸酯，随后加入二月桂酸二丁基锡，在80℃恒温下以50 r/min的速度搅拌反应150 min后，加入小分子扩链剂1, 4-丁二醇反应40 min，得硝化纤维素-聚氨酯预聚体；
（4）将丙烯酸甲酯与硝化纤维素-聚氨酯预聚体以80 r/min的速度搅拌混合均匀，升温至60~80℃，加入交联剂三羟甲基丙烷，搅拌反应250 min，最后降温至40℃并保温，加入丙酮以120 r/min搅拌乳化得到三组分聚氨酯；
（5）将步骤（2）制得的人造革的面层用三版印刷机辊涂一层或者多层步骤（4）制得的三组分聚氨酯涂饰层，进入烘干即得三组分聚氨酯耐热人造革。
步骤（1）中面层皮膜厚度为1.5 mm，烘箱温度为120℃。
步骤（2）发泡层的涂刮厚度为2 mm，烘箱温度为200℃。
步骤（5）中烘干温度为80℃。
三组分聚氨酯耐热人造革的耐热性能指标如下：
耐热性：200℃冲压10秒，无亮面无发粘。
实施例3
三组分聚氨酯耐热人造革，包括面层，所述面层为聚氯乙烯或水性聚氨酯，其上设有涂饰层；所述涂饰层由A、B和C组分组成；A组分以重量份计其组成为：4, 4-二环己基甲烷二异氰酸酯40份、聚乙二醇20份、二月桂酸二丁基锡1份、1, 4-丁二醇1份和三羟甲基丙烷1份；B组分以重量份计其组成为：硝化纤维素12份；C组分以重量份计其组成为：丙烯酸甲酯12份和丙酮18份；A、B和C三组分的质量比为：80：18：18。
所述的三组分聚氨酯耐热人造革的制造方法包括以下步骤：
（1）在离型纸上涂刮聚氯乙烯或者水性聚氨酯面层，经烘箱烘干形成具有一定花纹的面层皮膜；
（2）在步骤（1）制得的面层上涂刮聚氯乙烯或水性聚氨酯发泡层并且贴基布，经烘箱加温使其发泡凝胶，再与所述离型纸分离，得到人造革；
（3）将聚乙二醇和硝化纤维素混合，在真空环境下脱水50 min，在氮气保护下，加入4, 4-二环己基甲烷二异氰酸酯，随后加入二月桂酸二丁基锡，在80℃恒温下以40 r/min的速度搅拌反应120 min后，加入小分子扩链剂1, 4-丁二醇反应30 min，得硝化纤维素-聚氨酯预聚体；
（4）将丙烯酸甲酯与硝化纤维素-聚氨酯预聚体以60 r/min的速度搅拌混合均匀，升温至70℃，加入交联剂三羟甲基丙烷，搅拌反应200 min，最后降温至40℃并保温，加入丙酮以100 r/min搅拌乳化得到三组分聚氨酯；
（5）将步骤（2）制得的人造革的面层用三版印刷机辊涂一层或者多层步骤（4）制得的三组分聚氨酯涂饰层，进入烘干即得三组分聚氨酯耐热人造革。
步骤（1）中面层皮膜厚度为1 mm，烘箱温度为110℃。
步骤（2）发泡层的涂刮厚度为1 mm，烘箱温度为150℃。
步骤（5）中烘干温度为65℃。
三组分聚氨酯耐热人造革的耐热性能指标如下：
耐热性：200℃冲压10秒，无亮面无发粘。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (4)

1.一种三组分聚氨酯耐热人造革的制备方法，其特征在于：所述人造革包括面层，所述面层为聚氯乙烯或水性聚氨酯，其上设有涂饰层；所述涂饰层由A、B和C组分组成；A组分以重量份计其组成为：4, 4-二环己基甲烷二异氰酸酯30~50份、聚乙二醇15~30份、二月桂酸二丁基锡0.5~1.5份、1, 4-丁二醇0.5~1.5份和三羟甲基丙烷0.5~2份；B组分以重量份计其组成为：硝化纤维素10~15份；C组分以重量份计其组成为：丙烯酸甲酯10~15份和丙酮15~20份；A、B和C三组分的质量比为：70~100：15~20：15~20；制备方法包括以下步骤：
（1）在离型纸上涂刮聚氯乙烯或者水性聚氨酯面层，经烘箱烘干形成具有一定花纹的面层皮膜；
（2）在步骤（1）制得的面层上涂刮聚氯乙烯或水性聚氨酯发泡层并且贴基布，经烘箱加温使其发泡凝胶，再与所述离型纸分离，得到人造革；
（3）将聚乙二醇和硝化纤维素混合，在真空环境下脱水30~60 min，在氮气保护下，加入4, 4-二环己基甲烷二异氰酸酯，随后加入二月桂酸二丁基锡，在80℃恒温下以30~50 r/min的速度搅拌反应100~150 min后，加入小分子扩链剂1, 4-丁二醇反应20~40 min，得硝化纤维素-聚氨酯预聚体；
（4）将丙烯酸甲酯与硝化纤维素-聚氨酯预聚体以40~80 r/min的速度搅拌混合均匀，升温至60~80℃，加入交联剂三羟甲基丙烷，搅拌反应180~250 min，最后降温至40℃并保温，加入丙酮以80~120 r/min搅拌乳化得到三组分聚氨酯；
（5）将步骤（2）制得的人造革的面层用三版印刷机辊涂一层或者多层步骤（4）制得的三组分聚氨酯涂饰层，进入烘干即得三组分聚氨酯耐热人造革。
2. 根据权利要求1所述的三组分聚氨酯耐热人造革的制备方法，其特征在于：步骤（1）中面层皮膜厚度为0.1~1.5 mm，烘箱温度为100~120℃。
3. 根据权利要求1所述的方法，其特征在于：步骤（2）发泡层的涂刮厚度为0.15~2 mm，烘箱温度为120~200℃。
4.根据权利要求1所述的方法，其特征在于：步骤（5）中烘干温度为55℃~80℃。
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CN101486798A (zh) * 2009-02-13 2009-07-22 西安交通大学 一种自乳化型水性硝化纤维乳液及其制备方法
CN102504167A (zh) * 2011-10-10 2012-06-20 嘉兴禾欣化学工业有限公司 硝化纤维素改性水性聚氨酯树脂的制备方法
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CN101486798A (zh) * 2009-02-13 2009-07-22 西安交通大学 一种自乳化型水性硝化纤维乳液及其制备方法
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