CN116587760B - 一种环保型bopp镭射转移膜 - Google Patents
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Abstract
本发明涉及镭射转移膜技术领域,具体为一种环保型BOPP镭射转移膜,包括BOPP基膜、镭射模压层和镀铝层;以重量份数计,所述镭射模压层由以下原料制成:聚醚二元醇200‑220份、二异氰酸酯90‑100份、2,2‑双(羟甲基)丙酸15‑30份、有机锡催化剂0.1‑0.5份、丙烯酸类单体10‑20份、双酰胺类单体5‑10份、无机光引发剂5‑10份、过硫酸盐引发剂0.01‑0.02份、三乙胺2‑4份、水80‑100份,本发明所制备的BOPP镭射转移膜具有良好的耐高温性能,且耐水性好,可挥发性有机物释放量少,更加绿色环保,可以满足食品包装材料的要求。
Description
技术领域
本发明涉及镭射转移膜技术领域,具体为一种环保型BOPP镭射转移膜。
背景技术
镭射转移是指镭射模压花面图案通过特殊的方式转移到其他载体上面,镭射转移的图形可以是文字也可以是图形、线条,镭射包装材料自从投入市场后,在食品、药品、日化用品、烟酒等领域的应用得到迅速地推广,已经成为世界印刷包装行业最前沿的技术产品。
目前的镭射转移膜主要以BOPP(双向拉伸聚丙烯薄膜)、PET(聚对苯二甲酸类塑料)为基膜,以透明合成树脂作为镭射转移涂料,目前的镭射转移涂料含有大量的醇类、酯类、酮类溶剂,既不环保、也不安全,对生产环境与大气环境带来了污染,也对相关操作人员的职业健康带来了风险,同时, 成品的VOCs指标难以控制,无法满足食品包装材料要求。
发明内容
发明目的:针对上述技术问题,本发明提出了一种环保型BOPP镭射转移膜。
所采用的技术方案如下:
一种环保型BOPP镭射转移膜,包括BOPP基膜、镭射模压层和镀铝层;
以重量份数计,所述镭射模压层由以下原料制成:
聚醚二元醇200-220份、二异氰酸酯90-100份、2,2-双(羟甲基)丙酸15-30份、有机锡催化剂0.1-0.5份、丙烯酸类单体10-20份、双酰胺类单体5-10份、无机光引发剂5-10份、过硫酸盐引发剂0.01-0.02份、三乙胺2-4份、水80-100份。
进一步地,所述二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4, 4’-二环己基甲烷二异氰酸酯、三甲基六亚甲基二异氰酸酯中的任意一种或多种组合。
进一步地,所述丙烯酸类单体包括丙烯酸、甲基丙烯酸甲酯和丙烯酸丁酯;
所述丙烯酸、甲基丙烯酸甲酯和丙烯酸丁酯的重量比为1-3:8-15:3-6。
所述双酰胺类化合物为窗体顶端进一步地,所述双酰胺类单体的结构式如下:
R为羟基或C1-C6的烷羟基。
进一步地,所述双酰胺类单体为N-烯丙基-N'-(4-羟苯基)草酰胺,其结构式如下:
。
进一步地,所述无机光引发剂为纳米氧化锌。
进一步地,所述纳米氧化锌的表面包覆有二乙烯基苯-马来酸酐共聚物。
进一步地,所述所述无机光引发剂的制备方法如下:
将纳米氧化锌加入到乙酸乙酯中,超声分散后,加入自由基引发剂继续超声10-30min后,于氮气保护下,将二乙烯基苯和马来酸酐加入,升温至60-80℃反应10-20h,恢复室温后抽滤,所得产物用乙酸乙酯洗涤后干燥即可。
本发明还提供了一种环保型BOPP镭射转移膜的制备方法:
将聚醚二元醇升温至70-90℃,再将二异氰酸酯和有机锡催化剂加入,反应1-2h后加入丙烯酸类单体减少反应体系黏度,再加入2,2-双(羟甲基)丙酸和双酰胺类单体,继续反应2-4h后,加入三乙胺中和,得到预聚物, 将所述预聚物缓慢加入水中,搅拌30-60min后再加入无机光引发剂和过硫酸盐引发剂,升温至40-50℃进行自由基聚合反应3-5h,得到镭射涂料,在所述BOPP基膜上涂布所述镭射涂料,经紫外光辐照固化后得到涂层,将模压版加热到130-150℃,在高温状态下将模压版上的镭射信息烫印到所述涂层上得到镭射模压层,最后再真空镀铝得到镀铝层。
进一步地,紫外光辐照固化时间为10-20min。
本发明的有益效果:
本发明提供了一种环保型BOPP镭射转移膜,镭射模压层采用光固化聚氨酯丙烯酸酯涂料,引入双酰胺类化合物作为多重氢键超分子结构,当高温模压时,氢键断裂,有利于镭射图案的形成,冷却后,氢键重新恢复将图案固定,具有很好的模压显示效果,而且双酰胺类化合物中的不饱和双键又可以与丙烯酸类单体进行交联,提高镭射模压层的整体内聚强度和耐水性能,通过控制各组分比例,避免了整个树脂体系固化程度太高而失去可塑性,出现模压不出镭射图案的情况;
由于纳米氧化锌的光电特性,当体系中存在水以及氧气时,纳米氧化锌会在足够的紫外光照射下与它们发生反应,然后产生活性羟基自由基,从而引发光聚合反应,在本发明中纳米氧化锌既是无机光引发剂,又是无机填料,对于提高涂膜的力学强度起到了积极作用,利用二乙烯基苯-马来酸酐共聚物对纳米氧化锌进行包覆,提高了纳米氧化锌的分散性能,而且二乙烯基苯-马来酸酐共聚物还有改善涂膜光泽和耐水性的作用,有助于成膜;
本发明所制备的BOPP镭射转移膜具有良好的耐高温性能,且耐水性好,可挥发性有机物释放量少,更加绿色环保,可以满足食品包装材料的要求。
附图说明
图1为本发明实施例1中BOPP镭射转移膜的结构示意图,图中标号分别代表:
1-BOPP基膜、2-镭射模压层、3-镀铝层;
具体实施方式
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。本发明未提及的技术均参照现有技术,除非特别指出,以下实施例和对比例为平行试验,采用同样的处理步骤和参数。
实施例1:
一种环保型BOPP镭射转移膜,包括BOPP基膜1、镭射模压层2和镀铝层3;
以重量份数计,镭射模压层由以下原料制成:
聚醚二元醇N210 210份、异佛尔酮二异氰酸酯95份、2,2-双(羟甲基)丙酸20份、二丁基锡二月桂酸酯0.2份、丙烯酸2份、甲基丙烯酸甲酯8份、丙烯酸丁酯3份、N-烯丙基-N'-(4-羟苯基)草酰胺8份、无机光引发剂10份、过硫酸钾0.01份、三乙胺4份、水90份。
所述双酰胺类化合物为窗体顶端其中,无机光引发剂的制备方法如下:
将20g纳米氧化锌加入到250ml乙酸乙酯中,超声分散30min后,加入5g BPO继续超声30min,于氮气保护下,将100g二乙烯基苯和50g马来酸酐加入,搅拌均匀并升温至70℃反应15h,恢复室温后抽滤,所得产物用乙酸乙酯洗涤后50℃干燥10h即可。
上述环保型BOPP镭射转移膜的制备方法:
将聚醚二元醇N210升温至80℃,再将异佛尔酮二异氰酸酯和二丁基锡二月桂酸酯加入,反应2h后,加入丙烯酸、甲基丙烯酸甲酯和丙烯酸丁酯的混合物作为稀释剂以减少反应体系黏度,搅拌均匀后,再加入2,2-双(羟甲基)丙酸和N-烯丙基-N'-(4-羟苯基)草酰胺,继续反应2h后,加入三乙胺中和,得到预聚物,将预聚物缓慢加入水中,搅拌40min后再加入无机光引发剂和过硫酸钾,升温至40-50℃进行自由基聚合反应3h,得到镭射涂料,在BOPP基膜上涂布所述镭射涂料,经紫外光辐照固化15min后得到厚度约为2μm的涂层,将模压版加热到140℃,在高温状态下将模压版上的镭射信息烫印到涂层上得到镭射模压层,真空镀铝机在0.04 Pa的真空条件下,将铝丝加热到1400℃汽化,然后附着在镭射模压层上形成厚度约100nm的镀铝层。
实施例2:
一种环保型BOPP镭射转移膜,包括BOPP基膜1、镭射模压层2和镀铝层3;
以重量份数计,镭射模压层由以下原料制成:
聚醚二元醇N210 220份、异佛尔酮二异氰酸酯100份、2,2-双(羟甲基)丙酸30份、二丁基锡二月桂酸酯0.5份、丙烯酸2份、甲基丙烯酸甲酯8份、丙烯酸丁酯3份、N-烯丙基-N'-(4-羟苯基)草酰胺10份、无机光引发剂10份、过硫酸钾0.02份、三乙胺4份、水100份。
所述双酰胺类化合物为窗体顶端其中,无机光引发剂的制备方法同实施例1。
上述环保型BOPP镭射转移膜的制备方法:
将聚醚二元醇N210升温至90℃,再将异佛尔酮二异氰酸酯和二丁基锡二月桂酸酯加入,反应2h后,加入丙烯酸、甲基丙烯酸甲酯和丙烯酸丁酯的混合物作为稀释剂以减少反应体系黏度,搅拌均匀后,再加入2,2-双(羟甲基)丙酸和N-烯丙基-N'-(4-羟苯基)草酰胺,继续反应4h后,加入三乙胺中和,得到预聚物,将预聚物缓慢加入水中,搅拌60min后再加入无机光引发剂和过硫酸钾,升温至40-50℃进行自由基聚合反应5h,得到镭射涂料,在BOPP基膜上涂布所述镭射涂料,经紫外光辐照固化20min后得到厚度约为2μm的涂层,将模压版加热到150℃,在高温状态下将模压版上的镭射信息烫印到涂层上得到镭射模压层,真空镀铝机在0.04 Pa的真空条件下,将铝丝加热到1400℃汽化,然后附着在镭射模压层上形成厚度约100nm的镀铝层。
实施例3:
一种环保型BOPP镭射转移膜,包括BOPP基膜1、镭射模压层2和镀铝层3;
以重量份数计,镭射模压层由以下原料制成:
聚醚二元醇N210 200份、异佛尔酮二异氰酸酯90份、2,2-双(羟甲基)丙酸15份、二丁基锡二月桂酸酯0.1份、丙烯酸2份、甲基丙烯酸甲酯8份、丙烯酸丁酯3份、N-烯丙基-N'-(4-羟苯基)草酰胺5份、无机光引发剂5份、过硫酸钾0.01份、三乙胺2份、水80份。
所述双酰胺类化合物为窗体顶端其中,无机光引发剂的制备方法同实施例1。
上述环保型BOPP镭射转移膜的制备方法:
将聚醚二元醇N210升温至70℃,再将异佛尔酮二异氰酸酯和二丁基锡二月桂酸酯加入,反应1h后,加入丙烯酸、甲基丙烯酸甲酯和丙烯酸丁酯的混合物作为稀释剂以减少反应体系黏度,搅拌均匀后,再加入2,2-双(羟甲基)丙酸和N-烯丙基-N'-(4-羟苯基)草酰胺,继续反应2h后,加入三乙胺中和,得到预聚物,将预聚物缓慢加入水中,搅拌30min后再加入无机光引发剂和过硫酸钾,升温至40-50℃进行自由基聚合反应3h,得到镭射涂料,在BOPP基膜上涂布所述镭射涂料,经紫外光辐照固化10min后得到厚度约为2μm的涂层,将模压版加热到130℃,在高温状态下将模压版上的镭射信息烫印到涂层上得到镭射模压层,真空镀铝机在0.04 Pa的真空条件下,将铝丝加热到1400℃汽化,然后附着在镭射模压层上形成厚度约100nm的镀铝层。
对比例1:
与实施例1基本相同,区别在于,不加入N-烯丙基-N'-(4-羟苯基)草酰胺。
对比例2:
与实施例1基本相同,区别在于,纳米氧化锌不经过二乙烯基苯-马来酸酐共聚物包覆。
性能测试:
①将本发明实施例1-3及对比例1-2中所制备的镭射涂料作为试样进行性能测试:
固含量对镭射涂料性能都有着重要影响,按《涂料固体含量测定法》(GB1725-79)进行测定,单位:%;
吸水率的大小可以直观地反映涂料的耐水性能,准备一块洁净的玻璃片称量其质量,记为m1,将镭射涂料在洁净的玻璃表面上流延成膜,60℃干燥至恒重,记为m2,再将涂有镭射涂料的玻璃片浸入蒸馏水中浸泡24h,取出,室温下风干,称量得质量m3。
吸水率=[(m3-m2)/(m2-m1)]×100%,单位:%;
黏度对镭射涂料的稳定性和性能有着一定的影响,在15℃的条件下使用黏度仪对试样进行测试,单位:cst。
取1g试样,采用Agilent7890GC/5975MSD气相色谱质谱联用仪、Agilent7694E顶空进样器对TVOC(可挥发性有机物)进行测定,单位:μg。
测试结果如下表1所示:
由上表1可知,本发明所制备的镭射涂料吸水率低和可挥发性有机物释放量少,具有极佳的流平性能。
②将本发明实施例1-3及对比例1-2中所制备的BOPP镭射转移膜作为试样,将试样置于烘箱中,烘烤温度设定为60℃,分别在10、20、30d时检测其转移性能,与BOPP基膜的分离性能是否出现变化;
测试结果如下表2所示:
由上表2可知,本发明所制备的BOPP镭射转移膜具有良好的耐高温性能。
以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种环保型BOPP镭射转移膜,其特征在于,包括BOPP基膜、镭射模压层和镀铝层;
以重量份数计,所述镭射模压层由以下原料制成:
聚醚二元醇200-220份、二异氰酸酯90-100份、2,2-双(羟甲基)丙酸15-30份、有机锡催化剂0.1-0.5份、丙烯酸类单体10-20份、双酰胺类单体5-10份、无机光引发剂5-10份、过硫酸盐引发剂0.01-0.02份、三乙胺2-4份、水80-100份。
2.如权利要求1所述的环保型BOPP镭射转移膜,其特征在于,所述二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4, 4’-二环己基甲烷二异氰酸酯、三甲基六亚甲基二异氰酸酯中的任意一种或多种组合。
3.如权利要求1所述的环保型BOPP镭射转移膜,其特征在于,所述丙烯酸类单体包括丙烯酸、甲基丙烯酸甲酯和丙烯酸丁酯;
所述丙烯酸、甲基丙烯酸甲酯和丙烯酸丁酯的重量比为1-3:8-15:3-6。
4.如权利要求1所述的BOPP镭射转移膜,其特征在于,所述双酰胺类单体的结构式如下:
,
R为羟基或C1-C6的烷羟基。
5.如权利要求4所述的环保型BOPP镭射转移膜,其特征在于,所述双酰胺类单体的结构式如下:
。
6.如权利要求1所述的环保型BOPP镭射转移膜,其特征在于,所述无机光引发剂为纳米氧化锌。
7.如权利要求6所述的环保型BOPP镭射转移膜,其特征在于,所述纳米氧化锌的表面包覆有二乙烯基苯-马来酸酐共聚物。
8.如权利要求7所述的环保型BOPP镭射转移膜,其特征在于,所述无机光引发剂的制备方法如下:
将纳米氧化锌加入到乙酸乙酯中,超声分散后,加入自由基引发剂继续超声10-30min后,于氮气保护下,将二乙烯基苯和马来酸酐加入,升温至60-80℃反应10-20h,恢复室温后抽滤,所得产物用乙酸乙酯洗涤后干燥即可。
9.一种如权利要求7所述的环保型BOPP镭射转移膜的制备方法,其特征在于,将聚醚二元醇升温至70-90℃,再将二异氰酸酯和有机锡催化剂加入,反应1-2h后加入丙烯酸类单体减少反应体系黏度,再加入2,2-双(羟甲基)丙酸和双酰胺类单体,继续反应2-4h后,加入三乙胺中和,得到预聚物,将所述预聚物缓慢加入水中,搅拌30-60min后再加入无机光引发剂和过硫酸盐引发剂,升温至40-50℃进行自由基聚合反应3-5h,得到镭射涂料,在所述BOPP基膜上涂布所述镭射涂料,经紫外光辐照固化后得到涂层,将模压版加热到130-150℃,在高温状态下将模压版上的镭射信息烫印到所述涂层上得到镭射模压层,最后再真空镀铝得到镀铝层。
10.如权利要求9所述的环保型BOPP镭射转移膜的制备方法,其特征在于,紫外光辐照固化时间为10-20min。
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