CN114231148A - 一种耐磨成像层涂料、全息烫印膜、塑料产品及制备方法 - Google Patents
一种耐磨成像层涂料、全息烫印膜、塑料产品及制备方法 Download PDFInfo
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Abstract
本申请实施例提供一种耐磨成像层涂料、全息烫印膜、塑料产品及制备方法,涉及塑料装饰领域。耐磨成像层涂料,其按重量份数计包括:多羟基聚丙烯酸树脂20‑50份;固化剂10‑20份;抗老化剂0.1‑1份;硝化棉5‑30份;溶剂25‑50份;其中,多羟基聚丙烯酸树脂的羟值为70‑100;固化剂为芳香族聚异氰酸酯。全息烫印膜包括由上至下依次层叠设置的基膜层、离型层、耐磨成像层、蒸镀层和胶层,耐磨成像层是采用上述的耐磨成像层涂料涂布,并模压全息图像、熟化得到。耐磨成像层的耐候性好、模压性能好,满足全息烫印膜应用于塑料基材的要求。
Description
技术领域
本申请涉及塑料装饰领域,具体而言,涉及一种耐磨成像层涂料、全息烫印膜、塑料产品及制备方法。
背景技术
全息烫金膜由于其亮丽的金属光泽,丰富多彩的全息图案,在烟酒医药等快消品包装行业中受到广泛运用。由于快消品的使用周期比较短,因此快消品包装对全息烫金膜的耐候性(如耐磨、耐温等)无特殊要求,而在一些耐用消费品领域,如电器外壳、化妆品包装瓶外壳、汽车进气格栅等,由于产品使用周期长、使用环境苛刻,原本用于快消品包装的普通全息烫金膜在烫印后的耐候性较差,难以满足要求。
目前,应用于塑料基材的烫金膜一般采用硬度较高的树脂制成,以保证其耐候性;但由于树脂硬度较高,导致模压效果差,无法转移全息图案。所以市面上应用于塑料基材的烫金膜大多为无全息的亮金或亮银烫金膜,极大的限制了全息技术在塑料基材烫印领域的运用。
发明内容
本申请实施例的目的在于提供一种耐磨成像层涂料、全息烫印膜及塑料产品,耐磨成像层的耐候性好、模压性能好,满足全息烫印膜应用于塑料基材的要求。
第一方面,本申请实施例提供了一种耐磨成像层涂料,其按重量份数计包括:
其中,多羟基聚丙烯酸树脂的羟值为70-100;固化剂为芳香族聚异氰酸酯。
在上述技术方案中,耐磨成像层涂料中的多羟基丙烯酸树脂和芳香族聚异氰酸酯固化得到耐磨成像层,多羟基丙烯酸树脂中的羟基与芳香族聚异氰酸酯反应交联提高了涂层强度,同时芳香族聚异氰酸酯在涂层分子链中引入苯环刚性官能团,进一步增加了成像层的强度。
在一种可能的实现方式中,多羟基聚丙烯酸树脂的酸价为5-10,软化范围120-180℃,分子量为50000-80000;
和/或,固化剂为封闭性脂肪族多异氰酸酯、甲苯二异氰酸酯和二苯甲烷二异氰酸酯中的至少一种。
在一种可能的实现方式中,溶剂按重量份数计包括20-40份丁酮、5-10份环己酮;
和/或,抗老化剂为受阻胺类、受阻酚类、苯并三唑类、三嗪类抗老化剂中的至少一种;
和/或,耐磨成像层涂料按重量份数计还包括0.1-0.5份有机硅类流平剂。
第二方面,本申请实施例提供了一种全息烫印膜,其包括由上至下依次层叠设置的基膜层、离型层、耐磨成像层、蒸镀层和胶层,耐磨成像层是采用第一方面提供的耐磨成像层涂料涂布,并模压全息图像、熟化得到。
在上述技术方案中,耐磨成像层是采用上述的耐磨成像层涂料涂布,并模压全息图像、熟化得到,耐磨成像层涂料中的羟基丙烯酸树脂中的羟基与芳香族聚异氰酸酯反应交联提高了涂层强度,同时芳香族聚异氰酸酯在涂层分子链中引入苯环刚性官能团,进一步增加了成像层的强度。该耐磨成像层固化速度适中,涂膜平坦透明:在成像层涂布干燥时初步固化,此时成像层硬度较低,便于模压,同时具有一定强度又不至于模压时粘版;在镀铝后放入烘箱进一步熟化,交联度增加,涂层强度提高,因此耐磨性能,耐候性优异。因此,本申请解决了模压性能好的树脂不耐磨,耐磨性能好的树脂模压性能差的困境,拓展了全息技术在塑料底材用烫金膜的应用,丰富了塑料底材的烫金装饰的表观效果。
在一种可能的实现方式中,离型层对应的涂料按重量份数计包括:
在上述技术方案中,特定的离型层对于耐磨成像层的离型效果好,尤其是经过依次经过初步固化和熟化后。离型层对应的涂料中含有有机硅改性丙烯酸树脂,一方面有机硅改性丙烯酸树脂可提高涂布时的流平性能,另一方面该树脂表面能低,在摩擦时充当润滑剂的作用,该全息烫印膜烫印后离型层会留在物品上,有机硅改性丙烯酸树脂的引入可提高耐磨性能。
在一种可能的实现方式中,胶层对应的胶水按重量份数计包括:
在上述技术方案中,通过特定的胶层,使烫印膜整体能够较好的附着于塑料底材上。
在一种可能的实现方式中,蒸镀层为厚度300-700埃的铝层。
第三方面,本申请实施例提供了一种第二方面提供的全息烫印膜的制备方法,其包括以下步骤:
采用离型层对应的涂料在基膜上涂布形成离型中间层;
采用第一方面提供的耐磨成像层涂料在离型中间层上涂布、并模压全息图像形成耐磨成像中间层;
在耐磨成像中间层上镀金属得到蒸镀层,随后进行熟化,离型中间层对应成为离型层,耐磨成像中间层对应成为耐磨成像层;
采用胶层对应的胶水在熟化后的蒸镀层上涂布形成胶层。
在上述技术方案中,该生产工艺流程简单,可快速大规模工业化生产。
在一种可能的实现方式中,熟化方法是:先于75-85℃下在熟化20-36小时,再在95-100℃下熟化20-36小时。
在上述技术方案中,该耐磨成像层为交联反应得到,由于耐磨成像层涂料涂布时温度较低,模压后仍然存在大量未反应的活性位点,可视为低聚物,此时耐磨成像中间层分子量较低。先在较低温度下熟化可使绝大部分低聚物交联,随着反应的进行,聚合物涂层分子量增高,聚合物交联网络难以继续交联,需要在更高的温度下进行提供反应所需活化能。如果全程设置高温,会造成诸多副反应的发生,影响聚合物涂层的表观和耐候性能。
第四方面,本申请实施例提供了一种塑料产品,其包括塑料底材,以及粘附于塑料底材上的装饰膜,装饰膜是由第二方面提供的全息烫印膜烫印得到。
在上述技术方案中,耐磨成像层的耐候性好,满足全息烫印膜应用于塑料基材的要求,具体可用于电器外壳,化妆品塑料包装等耐用消费品装饰领域。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚,下面将对本申请实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
下面对本申请实施例的耐磨成像层涂料、全息烫印膜、塑料产品及制备方法进行具体说明。
本申请实施例提供一种耐磨成像层涂料,其按重量份数计包括:多羟基聚丙烯酸树脂20-50份;固化剂10-20份;抗老化剂0.1-1份;硝化棉5-30份;丁酮20-40份、环己酮5-10份;助剂0.1-0.5份。
其中,多羟基聚丙烯酸树脂的羟值为70-100,酸价为5-10,软化范围120-180℃,分子量为50000-80000。“羟值”是指1g样品中的羟基所相当的氢氧化钾的毫克数;“酸价”是指中和1克化学物质所需的氢氧化钾(KOH)的毫克数,对应游离羧酸基团数量。
其中,固化剂为芳香族聚异氰酸酯,固化剂为封闭性脂肪族多异氰酸酯、甲苯二异氰酸酯和二苯甲烷二异氰酸酯中的至少一种。
其中,抗老化剂为受阻胺类、受阻酚类、苯并三唑类、三嗪类抗老化剂中的至少一种。
其中,助剂包括有机硅类流平剂。
本申请实施例还提供一种全息烫印膜,其包括由上至下依次层叠设置的基膜层、离型层、耐磨成像层、蒸镀层和胶层。
本申请实施例中,基膜层厚度一般为12-25μm。
本申请实施例中,耐磨成像层厚度一般为0.5-1.2μm,耐磨成像层是采用上述的耐磨成像层涂料涂布,并模压全息图像、熟化得到。
本申请实施例中,离型层厚度一般为0.3μm-0.8μm,离型层是采用对应的涂料涂布,并熟化得到,离型层对应的涂料按重量份数计包括:热塑性丙烯酸树脂15-30份;有机硅改性丙烯酸树脂5-20份;氧化聚乙烯蜡6-10份;甲苯30-60份;丁酮20-40份。示例性地,热塑性丙烯酸树脂为科鼎MR7335改性热塑丙烯酸树脂;有机硅改性丙烯酸树脂湛新为MODAFLOWLAMBDA有机硅改性丙烯酸树脂。
本申请实施例中,胶层厚度一般为0.5-2μm,胶层是采用对应的涂料涂布得到,胶层对应的胶水按重量份数计包括:丙烯酸改性氯化聚丙烯树脂20-50份;聚丙烯酸甲酯10-25份;气相二氧化硅1-5份;甲苯15-50份;丁酮5-25份。示例性地,丙烯酸改性氯化聚丙烯树脂为瑞易德L250-27丙烯酸改性氯化聚丙烯树脂。
本申请实施例中,蒸镀层为厚度300-700埃的铝层。
本申请实施例还提供一种上述的全息烫印膜的制备方法,其包括以下步骤:
(1)采用上述离型层对应的涂料在基膜上涂布形成离型中间层。
(2)采用上述的耐磨成像层涂料在离型中间层上涂布、并模压全息图像形成耐磨成像中间层。
(3)在耐磨成像中间层上镀金属得到蒸镀层,随后整体进行熟化,熟化方法是:先于75-85℃下在熟化20-36小时,再在95-100℃下熟化20-36小时,经过熟化,离型中间层对应成为离型层,耐磨成像中间层对应成为耐磨成像层。
(4)采用上述胶层对应的胶水在熟化后的蒸镀层上涂布形成胶层。
本申请实施例还提供一种塑料产品,其包括塑料底材,以及粘附于塑料底材上的装饰膜,装饰膜是由上述的全息烫印膜烫印得到,具体地,装饰膜包括相对于塑料底材由近及远依次叠加设置的胶层、蒸镀层和耐磨成像层,且胶层、蒸镀层和耐磨成像层为全息烫印膜中的层结构。
塑料底材可以为HIPS、ABS、PP、PE等高分子材料这些经常用作电器外壳,化妆品塑料上,该全息烫印膜能够较好的附着于塑料底材上,可用于电器外壳,化妆品塑料包装等耐用消费品装饰领域。
以下结合实施例对本申请的特征和性能作进一步的详细描述。
实施例1
本实施例提供一种塑料底材用全息烫印膜,由上至下包括依次层叠的基膜层、离型层、成像层,铝层和胶层,其按照以下制备方法制得:本实施例提供一种塑料底材用全息烫印膜制备方法如下:
(1)配制离型层对应的涂料:按重量份数计,称取热塑性丙烯酸树脂(科鼎MR7335)30份,有机硅改性丙烯酸树脂(湛新MODAFLOW LAMBDA)5份,氧化聚乙烯蜡6份,甲苯35份,丁酮24份混合均匀;
采用离型层对应的涂料使用涂布机在20μm厚的基膜上涂布形成离型中间层。
(2)配制成像层涂料:按重量份数计,多羟基丙烯酸树脂(杰邦特8610丙烯酸树脂,酸价为5-10,软化范围120-180℃,分子量为50000-80000)32份,异氰酸酯16份,抗老化剂(巴斯夫1010受阻酚类老化剂)0.8份,硝化棉19份,助剂(道康宁DC-57流平剂)0.2份,丁酮25份,环己酮7份;
采用成像层涂料使用涂布机在离型中间层上涂布形成成像涂层,并用模压机在成像涂层上压制全息图案,得到成像中间层。
(3)使用真空镀铝机在成像中间层镀铝得到铝层,铝层厚度为300埃,随后将其放入烘箱先80℃下在熟化24小时,再在100℃下熟化24小时,离型中间层对应成为0.5μm厚的离型层,耐磨成像中间层对应成为1μm厚的耐磨成像层。
(4)配制胶层对应的胶水:按重量份数计,丙烯酸改性氯化聚丙烯树脂(瑞易德L250-27)46份,聚丙烯酸甲酯24份,气相二氧化硅2份,甲苯18份,丁酮10份,采用胶层对应的胶水使用涂布机在铝层上涂布形成1μm厚的胶层,得到塑料底材用全息烫印膜。
实施例2
本实施例提供一种塑料底材用全息烫印膜,其与实施例1大致相同,由上至下包括依次层叠的基膜层,离型层,成像层,铝层和胶层,不同之处在于:
离型层对应的涂料按重量份数计包括:热塑性丙烯酸树脂22份,有机硅改性丙烯酸树脂9份,氧化聚乙烯蜡10份,甲苯35份,丁酮24份。
耐磨成像层涂料按重量份数计包括:多羟基丙烯酸树脂28份,异氰酸酯14份,抗老化剂0.8份,硝化棉28份,助剂0.2份,丁酮22份,环己酮7份。
胶层对应的胶水按重量份数计包括:丙烯酸改性氯化聚丙烯树脂36份,聚丙烯酸甲酯19份,气相二氧化硅1份,甲苯28份,丁酮16份。
实施例3
本实施例提供一种塑料底材用全息烫印膜,其与实施例1大致相同,由上至下包括依次层叠的基膜层,离型层,成像层,铝层和胶层,不同之处在于:
离型层对应的涂料按重量份数计包括:热塑性丙烯酸树脂15份,有机硅改性丙烯酸树脂20份,氧化聚乙烯蜡6份,甲苯35份,丁酮24份。
成像层涂料按重量份数计包括:多羟基丙烯酸树脂42份,异氰酸酯11份,抗老化剂0.8份,硝化棉15份,助剂0.2份,丁酮32份,环己酮9份。
胶层对应的胶水按重量份数计包括:丙烯酸改性氯化聚丙烯树脂23份,聚丙烯酸甲酯12份,气相二氧化硅1.5份,甲苯42.5份,丁酮21份。
对比例1
本对比例提供一种全息烫印膜,其与实施例1大致相同,不同在于在于:成像层为普通成像层涂料形成,该成型层涂料按重量份数计包括:热塑性丙烯酸树脂45份,抗老化剂0.8份,硝化棉10份,助剂0.2份,丁酮25份,丁酯20份。
对比例2
本对比例提供一种全息烫印膜,其与实施例1大致相同,不同在于在于:离型层为普通离型层对应的涂料形成,该离型层对应的涂料按重量份数计包括:热塑性丙烯酸树脂20份,氧化聚乙烯蜡5份,甲苯45份,丁酮30份。
对比例3
本对比例提供一种全息烫印膜,其与实施例1大致相同,不同在于在于:胶层为普通胶水形成,该胶水涂料按重量份数计包括:聚丙烯酸甲酯25份,甲基丙烯酸羟乙酯30,气相二氧化硅1.5份,甲苯23.5份,丁酮20份。
对比例4
本对比例提供一种全息烫印膜,其与实施例1大致相同,不同在于未进行熟化处理。
将实施例1-3和对比例1-4的全息烫印膜分别烫印在PS板材和ABS板材上,烫印后对转移到基材上的涂层进行各项性能检测:
测试方法及结果如下:
1、耐擦伤性测试方法为:采用橡皮头耐磨测试仪负重500克,对烫金件的烫印涂层摩擦,500次摩擦后不露底为合格。
2、耐候性测试方法为:将烫金后的样条放置在老化试验箱中老化,将老化后的样板和老化前的样板进行比色,无黄变视为合格。
3、耐高低温冲击测试方法为:使用高低温循环试验机进行测试,试验后测试烫金样条的附着力,要求烫金表面无异常,附着力达到1级(参考GB/T 9286中表1评级)为合格。
4、高温潮态测试方法为:将烫金样条在60℃,湿度为95%的环境中放置72h,取出后放置12h后测试附着力。要求烫金表面无异常,附着力达到1级(参考GB/T 9286中表1评级)为合格。
5、耐盐水性测试方法为:长度的2/3放置于40℃中含5%NaCL的水溶液浸泡72h,取出用滤纸吸干掉表面的水,立即检查外观,放置24h后测试附着力。要求漆膜均无起泡、脱落、龟裂、起雾、变色,附着力不低于1级为合格。
6、耐酒精测试方法为:用沾湿工业酒精(95%)的绸布,包在500g砝码上,垂直放置于烫金表面。垂直方向不加压,水平方向来回滑动50次(往复为一次),速度为20次~30次/min,行程为10cm。要求测试次数≥50次,烫金表面无变色、露底为合格。
7、耐酸碱性测试方法为:将配置的酸(碱)液滴2滴~5滴于漆膜表面同一处,常温下放置30min后进行观察。注1:酸性:NaCL 10g,Na2HPO42.5g,乳酸1g,纯净水1L,pH=4.5;碱性:NaCL 10g,Na2HPO42.5g,碳铵(NH4HCO3)1g,纯净水1L,pH=8.7。烫金表面无异常为合格。
表1检测结果
由上述测试结果可以看出,本申请制备出的塑料底材用全息烫印膜适用于PS板材和ABS板材等3C家电常用塑料基材上;烫印后的涂层图案具有优异的耐候性,耐磨性能和良好的模压性能。而采用其他方法制得的全息烫印膜无法兼具耐候性、耐磨性能和模压性能,以对比例1为例,其成像层模压效果好,但耐候性差。
综上所述,本申请实施例的耐磨成像层涂料、全息烫印膜及塑料产品,耐磨成像层的耐候性好、模压性能好,满足全息烫印膜应用于塑料基材的要求。
以上所述仅为本申请的实施例而已,并不用于限制本申请的保护范围,对于本领域的技术人员来说,本申请可以有各种更改和变化。凡在本申请的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本申请的保护范围之内。
Claims (10)
2.根据权利要求1所述的耐磨成像层涂料,其特征在于,所述多羟基聚丙烯酸树脂的酸价为5-10,软化范围120-180℃,分子量为50000-80000;
和/或,所述固化剂为封闭性脂肪族多异氰酸酯、甲苯二异氰酸酯和二苯甲烷二异氰酸酯中的至少一种。
3.根据权利要求1所述的耐磨成像层涂料,其特征在于,所述溶剂按重量份数计包括20-40份丁酮、5-10份环己酮;
和/或,所述抗老化剂为受阻胺类、受阻酚类、苯并三唑类、三嗪类抗老化剂中的至少一种;
和/或,所述耐磨成像层涂料按重量份数计还包括0.1-0.5份有机硅类流平剂。
4.一种全息烫印膜,其特征在于,其包括由上至下依次层叠设置的基膜层、离型层、耐磨成像层、蒸镀层和胶层,所述耐磨成像层是采用如权利要求1至3中任一项所述的耐磨成像层涂料涂布,并模压全息图像、熟化得到。
7.根据权利要求4所述的全息烫印膜,其特征在于,所述蒸镀层为厚度300-700埃的铝层。
8.一种全息烫印膜的制备方法,其特征在于,其包括以下步骤:
采用离型层对应的涂料在基膜上涂布形成离型中间层;
采用如权利要求1至3中任一项所述的耐磨成像层涂料在离型中间层上涂布、并模压全息图像形成耐磨成像中间层;
在所述耐磨成像中间层上镀金属得到蒸镀层,随后进行熟化,所述离型中间层对应成为离型层,所述耐磨成像中间层对应成为耐磨成像层;
采用胶层对应的胶水在熟化后的所述蒸镀层上涂布形成胶层。
9.根据权利要求8所述的全息烫印膜的制备方法,其特征在于,所述熟化方法是:先于75-85℃下在熟化20-36小时,再在95-100℃下熟化20-36小时。
10.一种塑料产品,其特征在于,其包括塑料底材,以及粘附于所述塑料底材上的装饰膜,所述装饰膜是由如权利要求4至7中任一项所述的全息烫印膜烫印得到。
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