CN111961433A - 一种无溶剂聚氨酯胶粘剂 - Google Patents
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Abstract
本发明公开了一种无溶剂聚氨酯胶粘剂,解决了有的无溶剂聚氨酯胶粘剂在用于食品或药品包装袋的粘接时,其中未反应完全的异氰酸酯单体容易与水反应生成芳香族胺,芳香族胺是一种有毒的致癌物质,危害食品或药品的食饮者的安全,且目前的粘合剂均没有抑菌作用的问题,本发明包括组分A、组分B和锐钛矿纳米二氧化钛,所述组分A为异氰酸酯和多元醇反应所得,所述组分B采用聚酯多元醇、聚醚多元醇和锐钛矿纳米二氧化钛混合而成,所述组分A和组分B的官能团摩尔比为‑NCO:‑OH=(1.5‑2):1。本发明具有PPA溶出量小,安全等优点。
Description
技术领域
本发明涉及聚氨酯胶粘剂技术领域,具体涉及一种无溶剂聚氨酯胶粘剂。
背景技术
目前,在药品、食品包装中,复合膜包装已经成为主流,复合膜是将多种膜复合在一起,以便获得更好的综合性能的包材,在膜的复合过程中,会用到胶粘剂,在复合膜中使用最多的是有溶剂聚氨酯胶粘剂,但是随着环保要求越来越高,人们对环保产品的追求使得人们开始研究无溶剂胶粘剂,从而促进了无溶剂胶粘剂的发展。
在无溶剂聚氨酯胶粘中,主要是利用异氰酸酯与羟基反应形成具有粘合性能胶粘剂,但是在反应过程中,往往会存在异氰酸酯单体残留,当异氰酸酯单体与水反应就会生成芳香族胺,芳香族胺通过膜层进入到食品或药品中,另外,是当异氰酸酯单体通过膜层进入到食品和药品中后,与食品和药品中的水反应生成芳香族胺,从而危害食品和药品食引者的安全。
另外,目前的胶粘剂无抑菌功能,不利于药品和食品的长期保存。
因此,有必要基于现有技术,提出一种改进的无溶剂聚氨酯胶粘剂。
发明内容
本发明所要解决的技术问题是:现有的无溶剂聚氨酯胶粘剂在用于食品或药品包装袋的粘接时,其中未反应完全的异氰酸酯单体容易与水反应生成芳香族胺,芳香族胺是一种有毒的致癌物质,危害食品或药品的食饮者的安全,且目前的粘合剂均没有抑菌作用。
本发明通过下述技术方案实现:
一种无溶剂聚氨酯胶粘剂,包括组分A和组分B,所述组分A为异氰酸酯和多元醇反应所得,所述组分B采用聚酯多元醇、聚醚多元醇和锐钛矿纳米二氧化钛混合而成,所述组分A和组分B的官能团摩尔比为-NCO:-OH=(1.5-2):1。
本发明的设计原理为:在胶粘剂中加入锐钛矿纳米二氧化钛光催化剂,其中光催化剂对水有吸附作用,会将粘合剂中的少量水进行吸附,并产生高活性的羟基,且光生电子与氧分子反应生成超氧离子自由基,进一步生成羟基自由基,产生的羟基会与其中游离的异氰酸酯单体反应,进一步减少其中的异氰酸酯单体量,从而减少有毒芳香族胺的生成。
同时二氧化钛在光照条件下,会发生光催化作用,产生的高活性基团会杀灭周围的细菌,这样可以提高粘合剂的抗菌性,当羟基活性基团扩散至食品或药品中时,还可以对药品中的细菌进行处理,因此,加入二氧化钛同时起到了抑菌和减少芳香族胺的双重作用。
而之所以选择锐钛矿纳米二氧化钛,是因为锐钛矿型纳米二氧化钛的光催化性能最好。
本发明优选一种无溶剂聚氨酯胶粘剂,还包括憎水剂,所述憎水剂为聚硅氧烷,在胶粘剂的组分中加入憎水剂,这样在胶粘剂固化后对水产生排斥作用,从而使得进入到胶粘剂层中的水极少,减少异氰酸酯与水的反应,从而进一步减少了初级芳香族胺的形成,对于极少量水混入到胶粘剂中后,也会因为二氧化钛的吸附作用和光照产生光生空穴而被处理为羟基,进一步参与到与异氰酸酯反应中,使得异氰酸酯单体的含量进一步减少,从而降低了产生芳香族胺的风险。
进一步地,所述憎水剂分为两份,其中一份加入到组分A中,另一份加入到组分B中。
另外,聚硅氧烷还起到交联作用,使得胶粘剂与基材更好地进行粘接。
进一步地,所述聚硅氧烷的加入量:组分A中加入1-2%,组分B中加入1-2%。
本发明优选一种无溶剂聚氨酯胶粘剂,所述纳米二氧化钛占组分B的质量为2-4%。
本发明优选一种无溶剂聚氨酯胶粘剂,所述组分A中的异氰酸酯为2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、碳化二亚胺改性的4,4'-二苯基甲烷二异氰酸酯中的至少一种。
本发明优选一种无溶剂聚氨酯胶粘剂,所述组分A的制备过程如下:将多异氰酸酯和多元醇混合加热反应后再与聚硅氧烷混合。
本发明优选一种无溶剂聚氨酯胶粘剂,所述组分B的制备过程如下:将聚酯多元醇、聚醚多元醇和锐钛矿纳米二氧化钛混合均匀,即得到B组分。
本发明优选一种无溶剂聚氨酯胶粘剂,所述组分B的制备过程如下:将聚酯多元醇和聚醚多元醇混合均匀之后,加入聚硅氧烷混合均匀,再加入锐钛矿纳米二氧化钛混合均匀,即得到B组分。
在组分A和组分B中均加入憎水剂,使得两者中含有的水量均极少,减少水的引入。
在具体使用时,将组分A和组分B按照比例混合使用。
为了发挥锐钛矿纳米二氧化钛的效果,在组分A和组分B混合使用前,先要进行紫外光照射,使得二氧化钛产生光催化效果对胶粘剂中的细菌进行灭除,且促进二氧化钛与水结合产生活性羟基基团,与异氰酸酯单体反应,减少异氰酸酯单体的量。
本发明具有如下的优点和有益效果:
1、本发明通过在胶粘剂中加入锐钛矿纳米二氧化钛,减少胶粘剂中芳香族胺的溢出,同时起到了抑菌作用,降低药品或食品的毒害风险。
2、本发明在胶粘剂中加入憎水剂,可以进一步减少环境中的水分进入到胶粘剂中,减少异氰酸酯单体与水反应,降低芳香族胺的溶出量。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,下面结合实施例,对本发明作进一步的详细说明,本发明的示意性实施方式及其说明仅用于解释本发明,并不作为对本发明的限定。
实施例1
将100份的4,4'-二苯基甲烷二异氰酸酯与30份聚酯二元醇混合均匀,在50-60℃条件下保温1.5-2.0小时,缓慢升温至85±5℃,恒温反应4小时,降温至室温,然后加入1.5份聚硅氧烷混合均匀,得到组分A,组分A中异氰酸酯百分含量为17±0.2%。
直接将50份聚酯二元醇和50份聚醚二元醇混合后,再加入2份聚硅氧烷混合均匀,另外再加入2份锐钛矿纳米二氧化钛,然后真空脱水,作为组分B。
锐钛矿纳米二氧化钛的粒径为20-30nm。
实施例2
本实施例与实施例1的区别在于,所述组分A和组分B中不加入憎水剂。
具体实施过程如下:
将70份的4,4'-二苯基甲烷二异氰酸酯与30份聚酯二元醇混合均匀,在50-60℃条件下保温1.5-2.0小时,缓慢升温至85±5℃,恒温反应4小时,降温至室温,得到组分A,组分A中异氰酸酯百分含量为17±0.2%。
直接将50份聚酯二元醇和50份聚醚二元醇混合后,另外再加入2份锐钛矿纳米二氧化钛,然后真空脱水作为组分B。
实施例3
本实施例与实施例1的区别在于,所述组分B中不加入锐钛矿纳米二氧化钛。
具体实施过程如下:
将100份的4,4'-二苯基甲烷二异氰酸酯与30份聚酯二元醇混合均匀,在50-60℃条件下保温1.5-2.0小时,缓慢升温至85±5℃,恒温反应4小时,降温至室温,然后加入1.5份聚硅氧烷,得到组分A,组分A中异氰酸酯百分含量为17±0.2%。
直接将50份聚酯二元醇和50份聚醚二元醇混合后,再加入2份聚硅氧烷混合均匀,然后真空脱水作为组分B。
实施例4
空白对照:本实施例与实施例1的区别在于,所述组分A和组分B中均不加入憎水剂和锐钛矿纳米二氧化钛。
将上述实施例的组分A和组分B按照质量比10:9的比例进行混合使用,混合时同时先用紫外灯照射20min。
对上述实施例的胶粘剂的芳香胺溶出情况进行检测,具体方法如下:
在无溶剂复合机上将组分A和组分B混合好的聚氨酯胶粘剂涂布在PET膜上,涂布量为3.5g/m2,然后与CPP复合,静置固化5天,然后裁切10cm*10cm的PET-CPP复合膜,热封复合膜制成袋体并在其中加入乙醇溶液,并进行高温灭菌45min,灭菌温度为120℃,采用液相色谱对芳香胺进行了测定。
测定结果如下表1所示:
表1.不同实施例的芳香胺溶出量
测试组 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
PPA溶出量(ppb) | 3.5 | 7.8 | 6.7 | 15.4 |
从上述表1可以看出,憎水剂的加入和锐钛矿纳米二氧化钛的加入有利于减少无溶剂聚氨酯胶粘剂中芳香族胺的溶出量,利于保障食饮者的安全。
对其粘度进行测试,40℃,30分钟后均在5000mpa.s以下,满足使用要求。
本发明中,“PPA”表示芳香族胺。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种无溶剂聚氨酯胶粘剂,其特征在于,包括组分A和组分B,所述组分A为异氰酸酯和多元醇反应所得,所述组分B采用聚酯多元醇、聚醚多元醇和锐钛矿纳米二氧化钛混合而成,所述组分A和组分B的官能团摩尔比为-NCO:-OH=(1.5-2):1。
2.根据权利要求1所述的一种无溶剂聚氨酯胶粘剂,其特征在于,还包括憎水剂,所述憎水剂为聚硅氧烷。
3.根据权利要求1或2所述的一种无溶剂聚氨酯胶粘剂,其特征在于,所述纳米二氧化钛占组分B的质量为2-4%。
4.根据权利要求1或2所述的一种无溶剂聚氨酯胶粘剂,其特征在于,所述组分A中的异氰酸酯2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、碳化二亚胺改性的4,4'-二苯基甲烷二异氰酸酯中的至少一种。
5.根据权利要求1或2所述的一种无溶剂聚氨酯胶粘剂,其特征在于,所述组分A的制备过程如下:将多异氰酸酯和多元醇混合,加热反应后与聚硅氧烷混合。
6.根据权利要求1或2所述的一种无溶剂聚氨酯胶粘剂,其特征在于,所述组分B的制备过程如下:将聚酯多元醇、聚醚多元醇和锐钛矿纳米二氧化钛混合均匀,即得到B组分。
7.根据权利要求1或2所述的一种无溶剂聚氨酯胶粘剂,其特征在于,所述组分B的制备过程如下:将聚酯多元醇和聚醚多元醇混合均匀之后,加入聚硅氧烷混合均匀,再加入锐钛矿纳米二氧化钛混合均匀,即得到B组分。
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JPWO2009101741A1 (ja) * | 2008-02-13 | 2011-06-02 | 株式会社イーテック | Icカード又はicタグ用接着剤 |
CN102533200A (zh) * | 2012-02-29 | 2012-07-04 | 广州睿腾化工产品有限公司 | 双组份聚氨酯胶粘剂 |
JP2015052063A (ja) * | 2013-09-06 | 2015-03-19 | 積水フーラー株式会社 | 湿気硬化型ホットメルト接着剤 |
CN108084949A (zh) * | 2017-12-21 | 2018-05-29 | 新纳奇材料科技江苏有限公司 | 一种纳米改性双组分无溶剂软包装粘合剂及其制备方法 |
CN109370500A (zh) * | 2018-09-17 | 2019-02-22 | 中山大学 | 一种聚氨酯胶粘剂及其制备方法 |
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CN102533200A (zh) * | 2012-02-29 | 2012-07-04 | 广州睿腾化工产品有限公司 | 双组份聚氨酯胶粘剂 |
JP2015052063A (ja) * | 2013-09-06 | 2015-03-19 | 積水フーラー株式会社 | 湿気硬化型ホットメルト接着剤 |
CN108084949A (zh) * | 2017-12-21 | 2018-05-29 | 新纳奇材料科技江苏有限公司 | 一种纳米改性双组分无溶剂软包装粘合剂及其制备方法 |
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