CN111497404A - 一种长效转光的转光膜及其制备方法 - Google Patents

一种长效转光的转光膜及其制备方法 Download PDF

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CN111497404A
CN111497404A CN202010363315.8A CN202010363315A CN111497404A CN 111497404 A CN111497404 A CN 111497404A CN 202010363315 A CN202010363315 A CN 202010363315A CN 111497404 A CN111497404 A CN 111497404A
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light conversion
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CN111497404B (zh
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陈焰
胡广齐
梁敏婷
郑明东
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Foshan Onmillion Nano Materials Co ltd
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Abstract

本发明提供一种长效转光的转光膜及其制备方法，所述转光膜包括第一转光层、设置在第一转光层上的抗老化层和设置在抗老化层上的第二转光层；所述第一转光层包括由阻隔层进行表面包覆的转光载体树脂层。该转光膜首先吸收太阳光中的紫外线并转化为蓝光，有利于进行抗菌并为植物生长提供蓝光；再用抗老化层来吸收第二转光层吸收剩余的紫外线，使得到达第一转光层的紫外线降低至最少，减少紫外线对第一转光层中对紫外线不稳定的转光剂的影响，从而实现对第一转光层的保护；最后利用由PVDC或EVOH制成的阻隔层对第一转光层进行表面包覆，使其制得的转光膜兼具防水汽和氧气以及防紫外线的功能，实现含稳定性差的转光剂的转光膜的长效转光。

Description

一种长效转光的转光膜及其制备方法
技术领域
本发明属于转光材料领域，尤其涉及一种长效转光的转光膜及其制备方法。
背景技术
转光膜是一种新兴的控制型功能农膜，能够将太阳光中的紫外光和黄绿光转换成对农作物生长更为有利的长波光线，从而提高光能利用率。转光膜中必须添加转光剂，才能实现光转换的功能。目前市场上的转光剂主要为稀土类的化合物，稀土类化合物的转光性能较好，但其在太阳光尤其是紫外线照射下，表现出稳定性差的缺陷，主要为转光效率衰减严重，尤其是组成为MS：Eu，Re的转光剂。至今为止，为克服稀土类的化合物转光剂稳定性差的缺陷，即使采用11层共挤技术，制得的转光膜使用寿命上限仅为6～8个月，远达不到农用使用要求，且成本昂贵，以至于该类转光剂制成的转光膜尚无法商品化。
发明内容
本发明的目的在于提供一种长效转光的转光膜及其制备方法。
本发明所采取的技术方案是：
本发明的第一个方面，提供：
一种长效转光的转光膜，包括第一转光层、设置在第一转光层上的抗老化层和设置在抗老化层上的第二转光层；上述第一转光层包括由阻隔层进行表面包覆的转光载体树脂层。
优选的，上述第一转光层包括至少一层由阻隔层进行表面包覆的转光载体树脂层；上述第二转光层包括至少一层转光载体树脂层，上述第一转光层和上述抗老化层之间任意层或者上述第二转光层和上述抗老化层之间任意层可以任选地***至少一层树脂层。
优选的，所述第一转光层的转光载体树脂层和第二转光层的转光载体树脂层分别保护基体树脂和转光剂。
优选的，上述第一转光层的转光载体树脂层的转光剂组成为MS：Eu，Re；其中，M选自Ca、Sr、Ba、Zn、Fe、Mg，Ti的至少一种；Re选自Ce、Dy、Mn、Sm、Yb、Tb的至少一种，添加量占第一转光层的转光载体树脂层质量的0.1％～90％。
优选的，上述第二转光层的转光载体树脂层的转光剂选自BaMgAl10O17:Eu2+、CaF2:Eu2+的至少一种，添加量占第二转光层质量的0.01％～10％。
优选的，上述阻隔层包括基体树脂和PVDC或基体树脂和EVOH，所述PVDC或者EVOH的添加量为阻隔层质量的0.1％～90％。
优选的，上述抗老化层包括基体树脂和光稳定剂。
优选的，上述光稳定剂选自有机硅烷光稳定剂、水杨酸类光稳定剂、二苯甲酮类光稳定剂、苯并***类光稳定剂、三嗪类光稳定剂、丙烯酸酯类光稳定剂、没食子酸、邻羟基苯甲酸苯脂、二氧化钛、氧化锌、二氧化锡、二氧化铈、氧化铝、氧化铁、氧化镁、二氧化硅、氧化锆、氧化镁、碳量子点、石墨烯量子点、半导体量子点的至少一种。
优选的，上述长效转光的转光膜还包括设置于第一转光层下的树脂层和防流滴层。
优选的，上述防流滴层包括基体树脂和流滴剂。
优选的，上述流滴剂选自单硬脂酸甘油酯、山梨糖醇酐脂肪酸酯、椰子油酸二乙醇酰胺、辛基酚聚氧乙烯醚的至少一种。
优选的，上述树脂层包括聚乙烯层、聚对苯二甲酸乙二醇酯层、聚乙烯醇层、聚丙烯层中的至少一种。
优选的，上述基体树脂包括聚乙烯、聚对苯二甲酸乙二醇酯、聚乙烯醇、聚丙烯中的至少一种。
优选的，上述转光膜的厚度为5～200μm，上述第一转光层的厚度为1～180μm，上述第二转光层的厚度为1～180μm。
优选的，上述第一转光层的转光载体树脂膜的厚度为1～150μm，上述第二转光层的转光载体树脂膜的厚度为1～150μm，上述阻隔层的厚度为1～100μm。
优选的，上述树脂层的厚度为1～100μm，上述防流滴层的厚度为1～100μm。
本发明的第二个方面，提供：
上述长效转光的转光膜的制备方法，包括如下步骤：
(1)分别制备阻隔层和第一转光层的转光载体树脂层后，用阻隔层包覆第一转光层的转光载体树脂层得到第一转光层预混料；
(2)分别制备第二转光层预混料、抗老化层预混料、树脂层预混料、防流滴层预混料；
(3)将第二转光层预混料、抗老化层预混料、第一转光层预混料和任选地树脂层预混料、防流滴层预混料加入共挤出机，进行多层共挤出，得到具有多层结构的转光膜。
本发明的有益效果是：
1.在第一转光层上设置抗老化层并在抗老化层上设置第二转光层，需要第二转光层首先吸收太阳光中的紫外线并转化为蓝光，有利于进行抗菌并为植物生长提供蓝光；其次设置抗老化层来吸收第二转光层吸收剩余的紫外线，使得到达第一转光层的紫外线降低至最少，减少紫外线对第一转光层中对紫外线不稳定的转光剂的影响，从而实现对第一转光层的保护；最后，由于组成为MS：Eu，Re的转光剂接触紫外线、水汽和氧气后稳定性差，转光效率衰减严重，则利用由PVDC(Poly(vinylidene chloride)，聚偏二氯乙烯)或EVOH(Ethylene vinyl alcohol copolymer，乙烯/乙烯醇共聚物)制成的阻隔层对其进行表面包覆，其一能阻隔空气中的水汽和氧气，其二能吸收太阳光中的黄绿光，转化为促进植物生长的红光，实现发射光主峰波长620nm～680nm之间可调，由此固定排列结构制成的转光膜，兼具防水汽和氧气以及防紫外线的功能，实现含稳定性差的转光剂的转光膜的长效转光。
2.本发明的转光膜中利用PVDC或EVOH制成的阻隔层对稳定性差的转光剂进行表面包覆，在不降低其转光效率的同时，能阻隔水汽和氧气等对转光剂的影响，提高转光剂的稳定性，实现转光剂组成为MS：Eu，Re的转光膜的商品化，更延长了转光膜的使用寿命，节约了农作物的种植成本。
附图说明
图1为实施例1转光膜的结构示意图。
图2为实施例2转光膜的结构示意图。
图3为实施例3转光膜的结构示意图。
图4为对比例1转光膜的结构示意图。
图5为对比例2转光膜的结构示意图。
图6为实施例1转光膜的吸收光谱和发射光谱随氙灯老化时间变化图。
图7为对比例1转光膜的吸收光谱和发射光谱随氙灯老化时间变化图。
图8为对比例2转光膜的吸收光谱和发射光谱随氙灯老化时间变化图。
附图标记说明：10第一转光层；20抗老化层；30第二转光层；40树脂层；50防流滴层；101阻隔层；102转光载体树脂层。
具体实施方式
为了使本发明的发明目的、技术方案及其技术效果更加清晰，以下结合具体实施方式，对本发明进行进一步详细说明。应当理解的是，本说明书中描述的具体实施方式仅仅是为了解释本发明，并非为了限定本发明。
下面结合具体实施例对本发明作进一步的解释和说明。
实施例1：
如图1所示，一种长效转光的转光膜包括第一转光层10、设置在第一转光层10上的抗老化层20、设置在抗老化层20上的第二转光层30；第一转光层10包括由阻隔层101进行表面包覆的转光载体树脂层102，阻隔层101由PVDC和聚乙烯组成，厚度为12μm，转光载体树脂层102由聚乙烯和稀土无机硫化物转光剂组成，厚度为25μm；抗老化层20由聚对苯二甲酸乙二醇酯和邻羟基苯甲酸苯脂组成，厚度为10μm；第二转光层30由聚乙烯和转光剂BaMgAl10O17:Eu2+组成，厚度为20μm；转光膜的总厚度为67μm。
实施例2：
如图2所示，一种长效转光的转光膜包括第一转光层10、设置在第一转光层10上的抗老化层20、设置在抗老化层20上的第二转光层30、第一转光层和抗老化层之间***一层树脂层40、设置在第一转光层10下的树脂层40和防流滴层50；第一转光层10包括由阻隔层101进行表面包覆的转光载体树脂层102，阻隔层101由PVDC和聚丙烯组成，厚度为32μm，转光载体树脂层102由聚乙烯和稀土无机硫化物转光剂组成，厚度为18μm；抗老化层20由聚乙烯和二氧化钛组成，厚度为18μm；第二转光层30由聚丙烯和转光剂BaMgAl10O17:Eu2+组成，厚度为10μm；树脂层40由聚丙烯组成，厚度为25μm；防流滴层50由聚丙烯和山梨糖醇酐脂肪酸酯组成，厚度为13μm；转光膜的总厚度为141μm。
本实施例制备的长效转光的转光膜的吸收光谱和发射光谱如图6所示，从图6可看出，依据本发明技术方案涉及的转光膜，由于第一转光层、抗老化层和第二转光层的位置关系顺序，使得第一转光层发射强度光衰减很少，且在氙灯老化500h后仍保持较好的发射强度。
实施例3：
如图3所示，一种长效转光的转光膜包括第一转光层10、设置在第一转光层10上的抗老化层20、设置在抗老化层20上的第二转光层30，抗老化层与第二转光层之间***一层树脂层40、设置在第一转光层10下的树脂层40和防流滴层50；第一转光层10包括三层分别由阻隔层101进行表面包覆的转光载体树脂层102，每层阻隔层101由PVDC和聚丙烯组成，厚度为17μm，每层转光载体树脂层102由聚乙烯和稀土无机硫化物转光剂组成，厚度为20μm；第一转光层中的还***一层由聚对苯二甲酸乙二醇酯制成的树脂层40，厚度为13μm；抗老化层20由聚乙烯和二氧化钛组成，厚度为5μm；第二转光层30由聚丙烯和转光剂BaMgAl10O17:Eu2+组成，厚度为8μm；树脂层40由聚对苯二甲酸乙二醇酯组成，厚度为13μm；防流滴层由聚丙烯和山梨糖醇酐脂肪酸酯组成，厚度为9μm；转光膜的总厚度为172μm。
对比例1：
如图4所示，一种转光膜包括第一转光层10、设置在第一转光层10上的第二转光层30、设置在第一转光层10下的树脂层40和防流滴层50；第一转光层10包括由阻隔层101进行表面包覆的转光载体树脂层102，阻隔层101由PVDC和聚丙烯组成，厚度为32μm，转光载体树脂层102由聚乙烯和稀土无机硫化物转光剂组成，厚度为18μm；第二转光层30由聚丙烯和转光剂BaMgAl10O17:Eu2+组成，厚度为10μm；树脂层40由聚丙烯组成，厚度为25μm；防流滴层50由聚丙烯和山梨糖醇酐脂肪酸酯组成，厚度为13μm；转光膜的总厚度为94μm。
本对比例制备的长效转光的转光膜的吸收光谱和发射光谱如图7所示，从图7可看出，由于不加抗老化层，第一转光层的发射光强度呈现较为显著的下降趋势，且随着氙灯老化时间延长，在无抗老化层的保护下，第一转光层的发射光强度衰减明显。
对比例2：
如图5所示，一种转光膜，包括第一转光层10、设置在第一转光层10上的第二转光层30、设置在第一转光层10下的树脂层40和防流滴层50。第一转光层10包括转光载体树脂层102(无阻隔层101包裹)，转光载体树脂层102由聚乙烯和稀土无机硫化物转光剂组成，厚度为18μm；第二转光层30由聚丙烯和转光剂BaMgAl10O17:Eu2+组成，厚度为10μm；树脂层40由聚丙烯组成，厚度为25μm；防流滴层50由聚丙烯和山梨糖醇酐脂肪酸酯组成，厚度为13μm；转光膜的总厚度为66μm。
本对比例制备的长效转光的转光膜的吸收光谱和发射光谱如图8所示，从图8可看出，由于无抗老化层且第一转光层表面无阻隔材料包覆，第一转光层的发射光强度呈现非常显著的下降趋势，衰减速度快，随着氙灯老化时间的延长，在无抗老化层和阻隔层的保护下，第一转光层的发射光强度衰减明显，在氙灯照射老化500h后，几乎已无发射光强度。
测试例：
对实施例1～3和对比例1～3中的转光膜进行透氧量测试，测试结果如表1所示：
表1
Figure BDA0002475742680000051
Figure BDA0002475742680000061
从表1可看出，对比例2中由于第一转光层无阻隔层包裹，其透氧量明显增大，而有阻隔层保护的第一转光层制成的转光膜，其透氧量低至1.0cm3/m2·24h·0.1MPa左右，可以有效防止水汽对第一转光层中转光材料的负面影响，从而延长转光膜的使用寿命。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

1.一种长效转光的转光膜，其特征在于：包括第一转光层、设置在第一转光层上的抗老化层和设置在抗老化层上的第二转光层；所述第一转光层包括由阻隔层进行表面包覆的转光载体树脂层。
2.根据权利要求1所述长效转光的转光膜，其特征在于：所述第一转光层包括至少一层由阻隔层进行表面包覆的转光载体树脂层；所述第二转光层包括至少一层转光载体树脂层，所述第一转光层和所述抗老化层之间任意层或者所述第二转光层和所述抗老化层之间任意层可以任选地***至少一层树脂层。
3.根据权利要求2所述长效转光的转光膜，其特征在于：所述第一转光层的转光载体树脂层和第二转光层的转光载体树脂层分别包括基体树脂和转光剂。
4.根据权利要求3所述长效转光的转光膜，其特征在于：所述第一转光层的转光载体树脂层的转光剂组成为MS：Eu，Re；其中，M选自Ca、Sr、Ba、Zn、Fe、Mg，Ti的至少一种；Re选自Ce、Dy、Mn、Sm、Yb、Tb的至少一种，添加量占第一转光层的转光载体树脂层质量的0.01％～10％。
5.根据权利要求3所述长效转光的转光膜，其特征在于：所述第二转光层的转光载体树脂层的转光剂选自BaMgAl10O17:Eu2+、CaF2:Eu2+的至少一种，添加量占第二转光层质量的0.01％～10％。
6.根据权利要求1所述长效转光的转光膜，其特征在于：所述阻隔层由基体树脂和PVDC或者基体树脂和EVOH组成，所述PVDC或者EVOH的添加量为阻隔层质量的0.1％～90％。
7.根据权利要求1所述长效转光的转光膜，其特征在于：所述抗老化层由基体树脂和光稳定剂组成。
8.根据权利要求7所述长效转光的转光膜，其特征在于：所述光稳定剂选自有机硅烷光稳定剂、水杨酸类光稳定剂、二苯甲酮类光稳定剂、苯并***类光稳定剂、三嗪类光稳定剂、丙烯酸酯类光稳定剂、没食子酸、邻羟基苯甲酸苯脂、二氧化钛、氧化锌、二氧化锡、二氧化铈、氧化铝、氧化铁、氧化镁、二氧化硅、氧化锆、氧化镁、碳量子点、石墨烯量子点、半导体量子点的至少一种。
9.根据权利要求1所述长效转光的转光膜，其特征在于：所述长效转光的转光膜还包括设置于第一转光层下的树脂层和防流滴层。
10.一种权利要求1～9任一项所述组成的长效转光的转光膜的制备方法，其特征在于：包括如下步骤：
(1)分别制备阻隔层和第一转光层的转光载体树脂层后，用阻隔层包覆第一转光层的转光载体树脂层得到第一转光层预混料；
(2)分别制备第二转光层预混料、抗老化层预混料、树脂层预混料、防流滴层预混料；
(3)将第二转光层预混料、抗老化层预混料、第一转光层预混料和任选地树脂层预混料、防流滴层预混料加入共挤出机，进行多层共挤出，得到具有多层结构的转光膜。
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