CN114953687A - 一种在线涂覆抗紫外线的聚酯薄膜及制备方法 - Google Patents
一种在线涂覆抗紫外线的聚酯薄膜及制备方法 Download PDFInfo
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- polyester film
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Abstract
本发明涉及高分子薄膜技术领域,为了解决现有产品生产效率低、不环保和成本高的技术问题,提供了一种在线涂覆抗紫外线的聚酯薄膜及制备方法,包括基材和涂覆在基材面的耐UV的涂覆液,所述基材具有中间层和共挤复合于所述中间层上下面的表层,所述中间层由膜级有光聚脂切片构成,所述表层由膜级有光聚酯切片和二氧化硅功能性母料构成。在双向拉伸聚酯薄膜生产线上涂覆,对纵向拉伸后的聚酯薄膜表面进行化学处理,涂覆一层具有耐UV功能的涂覆层,再经过横向拉伸和挥发干燥,得到抗紫外线及高透光率的聚酯薄膜基膜,不用线外涂布或在拉伸时添加抗UV材料,相比之下提高了生产效率,降低了成本,无抗UV材料的挥发更加环保。
Description
技术领域
本发明涉及高分子薄膜技术领域,尤其涉及一种在线涂覆抗紫外线的聚酯薄膜及制备方法。
背景技术
双向拉伸聚酯薄膜具有优异的物理性能、化学性能以及尺寸稳定性、透明性、可回收性,被广泛应用于家电装饰、室外装饰、电子材料以及太阳能背板等用途,需要能够应对太阳光照射以及强灯光照射等,产品的抗紫外线性能和耐候性越好,则使用寿命越长。
为了提高聚酯薄膜的耐UV(紫外线)性能,目前有两种方法,第一种是在双向拉伸生产线上生产出聚酯薄膜后,线外再在聚酯薄膜表面进行涂布,涂上耐UV胶达到耐UV的效果,这种二次加工的方法生产效率低,且该油性UV胶有机活性稀释剂的刺激性和毒性问题使得其在环保方面没有优势,存在VOC(挥发性有机化合物)排放;第二种方法是在生产双向拉伸聚酯薄膜时添加抗UV材料,如紫外线吸收剂、光稳定剂等,造成生产成本过高。
发明内容
本发明的目的在于提供一种在线涂覆抗紫外线的聚酯薄膜及制备方法,以解决现有产品生产效率低、不环保和成本高的技术问题。
为实现上述目的,本发明的一种在线涂覆抗紫外线聚酯薄膜及制备方法的具体技术方案如下:
作为本发明的一个方面,提供了一种在线涂覆抗紫外线的聚酯薄膜,包括基材和涂覆在基材面的耐UV的涂覆液,所述基材具有中间层和共挤复合于所述中间层上下面的表层,所述中间层由膜级有光聚脂切片构成,所述表层由膜级有光聚酯切片和二氧化硅功能性母料构成。
进一步的,所述表层的原料组分按质量百分比计如下:
膜级有光聚酯切片70%~90%;
二氧化硅功能性母料10%~30%。
优选的,所述涂覆液组分按质量百分比计如下:
水性耐UV乳液25%~40%;
固化剂2%~5%;
表面活性剂1%~3%;
功能助剂1%~2%;
去离子水50%~70%。
进一步的,所述水性耐UV乳液,包括耐UV环氧丙烯酸酯和/或不饱和聚酯和/或聚氨酯类丙烯酸酯和/或聚酯类丙烯酸酯。
进一步的,所述耐UV环氧丙烯酸酯先以双酚A环氧树脂、环氧大豆油、丙烯酸和马来酸酐合成具有羧基的环氧丙烯酸酯低聚物,再经胺中和后制得;所述聚酯丙烯酸酯由端羟基聚酯与丙烯酸酯化反应而得,或由端羧基聚酯与甲基丙烯酸缩水甘油酯反应而得。
进一步的,所述基材的厚度为12~250μm。
作为本发明的另一个方面,提供了一种在线涂覆抗紫外线的聚酯薄膜制备方法,使用上述的基材和涂覆液,包括如下步骤:
步骤S1,将聚酯薄膜经结晶、干燥和脱水后熔融挤出,再经衣架式模头、冷鼓冷却后制成聚酯薄膜铸片;
步骤S2,将聚酯薄膜铸片在第一温度下预热,沿纵向在第二温度下拉伸第一预定倍数;
步骤S3,在聚酯薄膜铸片的一面涂抹涂覆液,并进行预加热和干燥;
步骤S4,将聚酯薄膜铸片在第三高温下预热,沿横向在第四温度下拉伸第二预定倍数,进行热定型;
步骤S5,进行牵引和收卷,制备完成。
进一步的,在步骤S1中,所述结晶的温度范围为155~165℃,所述干燥的温度范围为165~175℃,所述干燥的时间范围为4~6小时,熔融挤出及模头的温度范围为275~285℃,冷鼓冷却的温度范围为20~30℃。
进一步的,在步骤S2中,所述第一温度的范围为60~75℃,第二温度的范围为75~85℃,所述第一预定倍数的范围为3.0~3.4倍。
进一步的,在步骤S3中,涂抹涂覆液的厚度为0.2~0.8μm;在步骤S4中,所述第三温度的范围为95~115℃,第四温度的范围为115~135℃,所述第二预定倍数的范围为3.0~3.5倍。
本发明提供的一种在线涂覆抗紫外线的聚酯薄膜及制备方法具有以下优点:
在双向拉伸聚酯薄膜生产线上涂覆,对纵向拉伸后的聚酯薄膜表面进行化学处理,涂覆一层具有耐UV功能的涂覆层,再经过横向拉伸和挥发干燥,得到抗紫外线及高透光率的聚酯薄膜基膜,不用线外涂布或在拉伸时添加抗UV材料,相比之下提高了生产效率,降低了成本,无抗UV材料的挥发更加环保。
采用在线涂复处理的方法来实现聚酯薄膜基材的耐UV功能,无需为了抗紫外线功能再进行线外涂布油性UV涂层,也无需在原材料切片中加入抗UV添加剂,从而简化抗UV薄膜的生产流程和大大降低生产成本。同时使聚酯薄膜保持高透光率的优良特性。另外,涂层厚度为0.2~0.8μm,能有效吸收295~400nm波长的紫外辐射,从而达到防止材料产生黄变的效果,延长产品的使用寿命。
附图说明
图1为本发明提供的一种在线涂覆抗紫外线的聚酯薄膜的制备方法流程图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明提供了一种在线涂覆抗紫外线的聚酯薄膜,包括基材和涂覆在基材面的耐UV的涂覆液,基材具有中间层和共挤复合于中间层上下面的表层,中间层由膜级有光聚脂切片构成,表层由膜级有光聚酯切片和二氧化硅功能性母料构成。
其中,中间层的原料组分按质量百分比计,膜级有光聚脂切片占100%;表层的原料组分按质量百分比计,膜级有光聚酯切片占70%~90%,二氧化硅功能性母料占10%~30%。
进一步的,基材的厚度为12~250μm,优选厚度75~188μm。
涂覆液组分按质量百分比计,配比范围如下:
水性耐UV乳液25%~40%;
固化剂2%~5%;
表面活性剂1%~3%;
功能助剂1%~2%;
去离子水50%~70%。
水性耐UV涂覆液配方由上述的一种或多种配制而成。
其中,水性耐UV乳液由环氧丙烯酸酯、不饱和聚酯、聚氨酯类丙烯酸酯、聚酯类丙烯酸酯中的一种或多种组成。固化剂优选亲水性脂肪族异氰酸酯。表面活性剂包括改性聚二甲基硅氧烷。功能助剂包括消泡剂和成膜助剂,消泡剂包括聚醚改性聚硅氧烷等;成膜助剂包括丁基乙二醇、丁基二甘醇、乙二醇醚(如DPnB)或酯醇(如伊士曼Texanol)等。
在一实施方式中,水性耐UV乳液包括耐UV环氧丙烯酸酯和/或不饱和聚酯和/或聚氨酯类丙烯酸酯和/或聚酯类丙烯酸酯。
在一实施方式中,耐UV环氧丙烯酸酯先以双酚A环氧树脂、环氧大豆油、丙烯酸和马来酸酐合成具有羧基的环氧丙烯酸酯低聚物,再经胺中和后制得自乳化水性UV树脂。
在一实施方式中,不饱和聚酯是通过传统的多元醇和多元酸缩聚反应得到的。为提高亲水性,必须利用带有亲水基团或链段的单体参与反应,如聚乙二醇和苯四酸等。
在一实施方式中,聚氨酯丙烯酸酯乳液采用DMPA(二羟甲基丙酸)作为二醇组分之一与二异氰酸酯反应生成半封闭体,再用HEMA(甲基丙烯酸羟乙酯)等活性单体封端,最后用胺或氨水中和制得。
在一实施方式中,聚酯类丙烯酸酯由端羟基聚酯与丙烯酸酯化反应而得,或由端羧基聚酯与甲基丙烯酸缩水甘油酯反应而得。
本发明还提供了一种在线涂覆抗紫外线的聚酯薄膜制备方法,使用上述的基材和涂覆液,包括如下步骤:
步骤S1,将聚酯薄膜经结晶、干燥和脱水后熔融挤出,再经衣架式模头、冷鼓冷却后制成聚酯薄膜铸片;
步骤S2,将聚酯薄膜铸片在第一温度下预热,沿纵向在第二温度下拉伸第一预定倍数;
步骤S3,在聚酯薄膜铸片的一面涂抹上水性高阻隔的涂覆液,并进行预加热和干燥;
步骤S4,将聚酯薄膜铸片在第三高温下预热,沿横向在第四温度下拉伸第二预定倍数,进行热定型,热定型温度220~240℃,冷却区温度180℃或以下,使薄膜在横拉机中得以松弛和进行热定形;
步骤S5,进行牵引和收卷聚酯薄膜,制备完成。
作为其中一个实施方式,在步骤S1中,结晶的温度范围为155~165℃,干燥的温度范围为165~175℃,干燥的时间范围为4~6小时,熔融挤出及模头的温度范围为275~285℃,冷鼓冷却的温度范围为20~30℃。
作为其中一个实施方式,在步骤S2中,第一温度的范围为60~75℃,第二温度的范围为75~85℃,所述第一预定倍数的范围为3.0~3.4倍。
作为其中一个实施方式,在步骤S3中,涂抹涂覆液的厚度为0.2~0.8μm。
作为其中一个实施方式,在步骤S4中,所述第三温度的范围为95~115℃,第四温度的范围为115~135℃,第二预定倍数的范围为3.0~3.5倍。
使用氙灯老化试验结果:
实验时涂覆面面向为灯光照射面,以便吸收紫外线。
本发明提供的一种在线涂覆抗紫外线的聚酯薄膜及制备方法,该水性涂覆液环保,无VOC排放。通地在线涂覆工艺,操作简单,生产效率高,生产成本相对于线外涂布和抗紫外线切片技术方案低。
在双向拉伸聚酯薄膜的生产流程中增加在线涂覆,即聚酯薄膜铸片在纵向拉伸之后经过在线涂覆设备将水性涂覆液涂在聚酯薄膜铸片表面上,再经过横向拉伸和挥发干燥得到。涂层厚度为0.2~0.8μm,薄膜表面很薄的抗UV涂层即可实现目标功能,不增加最终产品的厚度。聚酯薄膜的涂覆面能有效吸收295~400nm波长的紫外辐射,从而达到防止材料产生黄变的效果,延长产品的使用寿命。
以上所述仅为本发明的较佳实施例而已,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、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种在线涂覆抗紫外线的聚酯薄膜,包括基材和涂覆在基材面的耐UV的涂覆液,其特征在于,所述基材具有中间层和共挤复合于所述中间层上下面的表层,所述中间层由膜级有光聚脂切片构成,所述表层由膜级有光聚酯切片和二氧化硅功能性母料构成。
2.根据权利要求1所述的一种在线涂覆抗紫外线的聚酯薄膜,其特征在于,所述表层的原料组分按质量百分比计如下:
膜级有光聚酯切片 70%~90%;
二氧化硅功能性母料 10%~30%。
3.根据权利要求2所述的一种在线涂覆抗紫外线的聚酯薄膜,其特征在于,所述涂覆液组分按质量百分比计如下:
水性耐UV乳液 25%~40%;
固化剂 2%~5%;
表面活性剂 1%~3%;
功能助剂 1%~2%;
去离子水 50%~70%。
4.根据权利要求3所述的一种在线涂覆抗紫外线的聚酯薄膜,其特征在于,所述水性耐UV乳液,包括耐UV环氧丙烯酸酯和/或不饱和聚酯和/或聚氨酯类丙烯酸酯和/或聚酯类丙烯酸酯。
5.根据权利要求4所述的一种在线涂覆抗紫外线的聚酯薄膜,其特征在于,所述耐UV环氧丙烯酸酯先以双酚A环氧树脂、环氧大豆油、丙烯酸和马来酸酐合成具有羧基的环氧丙烯酸酯低聚物,再经胺中和后制得;所述聚酯丙烯酸酯由端羟基聚酯与丙烯酸酯化反应而得,或由端羧基聚酯与甲基丙烯酸缩水甘油酯反应而得。
6.根据权利要求2所述的一种在线涂覆抗紫外线的聚酯薄膜,其特征在于,所述基材的厚度为12~250μm。
7.一种在线涂覆抗紫外线的聚酯薄膜制备方法,其特征在于,使用如权利要求1至6任一项所述的基材和涂覆液,包括如下步骤:
步骤S1,将聚酯薄膜经结晶、干燥和脱水后熔融挤出,再经衣架式模头、冷鼓冷却后制成聚酯薄膜铸片;
步骤S2,将聚酯薄膜铸片在第一温度下预热,沿纵向在第二温度下拉伸第一预定倍数;
步骤S3,在聚酯薄膜铸片的一面涂抹涂覆液,并进行预加热和干燥;
步骤S4,将聚酯薄膜铸片在第三高温下预热,沿横向在第四温度下拉伸第二预定倍数,进行热定型;
步骤S5,进行牵引和收卷,制备完成。
8.根据权利要求7所述的一种在线涂覆抗紫外线的聚酯薄膜制备方法,其特征在于,在步骤S1中,所述结晶的温度范围为155~165℃,所述干燥的温度范围为165~175℃,所述干燥的时间范围为4~6小时,熔融挤出及模头的温度范围为275~285℃,冷鼓冷却的温度范围为20~30℃。
9.根据权利要求8所述的一种在线涂覆抗紫外线的聚酯薄膜制备方法,其特征在于,在步骤S2中,所述第一温度的范围为60~75℃,第二温度的范围为75~85℃,所述第一预定倍数的范围为3.0~3.4倍。
10.根据权利要求9所述的一种在线涂覆抗紫外线的聚酯薄膜制备方法,其特征在于,在步骤S3中,涂抹涂覆液的厚度为0.2~0.8μm;在步骤S4中,所述第三温度的范围为95~115℃,第四温度的范围为115~135℃,所述第二预定倍数的范围为3.0~3.5倍。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101012351A (zh) * | 2007-01-30 | 2007-08-08 | 华南理工大学 | 耐候防锈水性涂料及其制备方法 |
US20130078460A1 (en) * | 2010-06-01 | 2013-03-28 | Basf Se | Paint, adhesive composition, bonding method and laminate |
CN103171223A (zh) * | 2013-03-11 | 2013-06-26 | 常州百佳薄膜科技有限公司 | 一种双向拉伸在线涂覆光学基膜及其制备方法 |
CN103612405A (zh) * | 2013-11-18 | 2014-03-05 | 江苏裕兴薄膜科技股份有限公司 | 在线涂布制备聚酯薄膜的方法 |
CN106279638A (zh) * | 2016-08-16 | 2017-01-04 | 浙江创赢新材料有限公司 | 聚多元酸改性uv固化环氧丙烯酸酯预聚体的制备方法 |
CN108912816A (zh) * | 2018-09-20 | 2018-11-30 | 永修县利君科技有限公司 | 一种led固化的水转印油墨 |
CN109749619A (zh) * | 2018-12-28 | 2019-05-14 | 东来涂料技术(上海)股份有限公司 | 一种超疏水性及耐沾污性水性uv涂料及其制备方法 |
CN111690334A (zh) * | 2020-06-17 | 2020-09-22 | 浙江南洋科技有限公司 | 一种背板用透明抗uv聚酯薄膜及其制备方法 |
CN113263758A (zh) * | 2021-05-17 | 2021-08-17 | 佛山赛和薄膜科技有限公司 | 一种高阻隔在线涂复聚酯薄膜的加工方法 |
CN113858744A (zh) * | 2021-10-09 | 2021-12-31 | 江苏邦宇薄膜技术有限公司 | 一种量子点膜用高阻隔聚酯薄膜及制备方法 |
-
2022
- 2022-05-11 CN CN202210513956.6A patent/CN114953687A/zh active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101012351A (zh) * | 2007-01-30 | 2007-08-08 | 华南理工大学 | 耐候防锈水性涂料及其制备方法 |
US20130078460A1 (en) * | 2010-06-01 | 2013-03-28 | Basf Se | Paint, adhesive composition, bonding method and laminate |
CN103171223A (zh) * | 2013-03-11 | 2013-06-26 | 常州百佳薄膜科技有限公司 | 一种双向拉伸在线涂覆光学基膜及其制备方法 |
CN103612405A (zh) * | 2013-11-18 | 2014-03-05 | 江苏裕兴薄膜科技股份有限公司 | 在线涂布制备聚酯薄膜的方法 |
CN106279638A (zh) * | 2016-08-16 | 2017-01-04 | 浙江创赢新材料有限公司 | 聚多元酸改性uv固化环氧丙烯酸酯预聚体的制备方法 |
CN108912816A (zh) * | 2018-09-20 | 2018-11-30 | 永修县利君科技有限公司 | 一种led固化的水转印油墨 |
CN109749619A (zh) * | 2018-12-28 | 2019-05-14 | 东来涂料技术(上海)股份有限公司 | 一种超疏水性及耐沾污性水性uv涂料及其制备方法 |
CN111690334A (zh) * | 2020-06-17 | 2020-09-22 | 浙江南洋科技有限公司 | 一种背板用透明抗uv聚酯薄膜及其制备方法 |
CN113263758A (zh) * | 2021-05-17 | 2021-08-17 | 佛山赛和薄膜科技有限公司 | 一种高阻隔在线涂复聚酯薄膜的加工方法 |
CN113858744A (zh) * | 2021-10-09 | 2021-12-31 | 江苏邦宇薄膜技术有限公司 | 一种量子点膜用高阻隔聚酯薄膜及制备方法 |
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