CN112469568B - 保护膜和片材 - Google Patents

保护膜和片材 Download PDF

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Publication number
CN112469568B
CN112469568B CN201980049143.2A CN201980049143A CN112469568B CN 112469568 B CN112469568 B CN 112469568B CN 201980049143 A CN201980049143 A CN 201980049143A CN 112469568 B CN112469568 B CN 112469568B
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China
Prior art keywords
polyolefin resin
protective film
resin layer
transparent polyolefin
layer
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CN201980049143.2A
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English (en)
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CN112469568A (zh
Inventor
村田大辅
大久保透
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Toppan Inc
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Toppan Printing Co Ltd
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Abstract

提供包含耐候性优异的透明聚烯烃树脂层的保护膜、以及使用了该保护膜的片材。根据本实施方式的保护膜(10)至少包含透明聚烯烃树脂层(11)，相对于透明聚烯烃树脂层(11)中所含的100质量份的透明烯烃树脂，透明聚烯烃树脂层(11)在0.05质量份以上5质量份以下的范围内含有由下述通式(I)表示的受阻胺类光稳定剂。(通式(I)中，R是碳原子数为1至18的烷基或者碳原子数为5至8的环烷基。)

Description

保护膜和片材
技术领域
本发明涉及保护膜以及使用了该保护膜的片材。
背景技术
以往，普通的印刷品对紫外线和水等的耐受性不高。因此，在诸如室外用装饰片材和海报之类的需要对紫外线和水等具有耐受性(耐候性)的用途中，为了保护印刷品，在表层上设置了透明保护膜。
作为透明保护膜的材料，除了耐候性优异的氟树脂和丙烯酸类树脂以外，还适当地使用在成本上有利的聚烯烃树脂等，但是，由于聚烯烃树脂本身的耐候性大多是不足够的，因此一般会使用(例如)受阻胺类光稳定剂等添加剂。需要说明的是，作为在聚烯烃树脂中添加有受阻胺类光稳定剂的保护膜，例如有专利文献1中所记载的材料。
这种受阻胺类光稳定剂存在有高分子型和低分子型，高分子型通常在聚烯烃等树脂中难以移动，因此难以起霜(bloom)或渗出，使得保护膜的耐候性得以长时间维持。另一方面，已知低分子型的作为光稳定剂的性能高于高分子型，但是可能会起霜或渗出。
另外，市场上存在有三种主要类型的受阻胺类光稳定剂：NH型、N烷基型、NO烷基型。NH型的自由基捕获效率高，但是其是碱性的，因此在实际暴露中可能会由于酸性雨等而失去活性。另外，N烷基型的耐水性通常优于NH型，并且与聚烯烃树脂的相容性也优异，但是自由基捕获效率低。此外，NO烷基型是低碱性的且自由基捕获效率也高，因而显示出作为光稳定剂的高性能。
若NO烷基型低分子光稳定剂不存在渗出的问题，则其是有前途的材料，但是当将该光稳定剂应用于透明聚烯烃时，尚不清楚哪种材料具有优异的耐渗出性并且赋予高耐候性。
现有技术文献
专利文献
专利文献1：日本特开2017-197639号公报
发明内容
发明所要解决的问题
针对上述问题，本发明的目的在于提供一种包含耐候性优异的透明聚烯烃树脂层的保护膜、以及使用了该保护膜的片材。
用于解决问题的手段
作为深入研究的结果，本发明人发现，通过向透明聚烯烃树脂中添加具有特定结构的低分子受阻胺类光稳定剂而得的保护膜以及使用了该保护膜的片材实现了上述目标，从而完成本发明。需要说明的是，上述“低分子”是指(例如)重均分子量为1500以下的分子。
用于解决上述问题的本发明的一个方面是一种保护膜，其至少包含透明聚烯烃树脂层，特征在于，相对于上述透明聚烯烃树脂层中所含的100质量份的透明烯烃树脂，上述透明聚烯烃树脂层在0.05质量份以上5质量份以下的范围内含有由下述通式(I)表示的受阻胺类光稳定剂。
[化学式1]
(通式(I)中，R是碳原子数为1至18的烷基或者碳原子数为5至8的环烷基。)
发明的效果
根据本发明的一个方面，提供了包含耐候性优异的透明聚烯烃树脂层的保护膜、以及使用了该保护膜的片材。
附图简要说明
[图1]为表示根据本发明第一实施方式的保护膜的截面的示意图。
[图2]为表示根据本发明第二实施方式的装饰片的截面的示意图。
具体实施方式
[第一实施方式]
作为本发明的第一实施方式，使用图1对通过在透明聚烯烃树脂层11上设置表面保护层12而得的保护膜10的构成进行说明。其中，在以下所说明的各个附图中，对彼此对应的部分赋予相同的符号，并且关于重复部分，适当地省略后述的说明。另外，本实施方式例示了用于体现本发明的技术思想的构成，各部分的材质、形状、结构、配置、尺寸等不限于下述说明。本发明的技术思想可以在权利要求书记载的权利要求项所规定的技术范围内进行各种变更。
(透明聚烯烃树脂层)
根据本实施方式的保护膜10具备：透明聚烯烃树脂层11、以及在透明聚烯烃树脂层11的一个表面侧(即透明聚烯烃树脂层11的上层)形成的表面保护层12。
作为构成根据本实施方式的透明聚烯烃树脂层11的烯烃树脂，除了聚丙烯、聚乙烯、聚丁烯等以外，还可列举出(例如)使α烯烃(例如丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一碳烯、1-十二碳烯、十三碳烯、1-十四碳烯、1-十五碳烯、1-十六碳烯、1-十七碳烯、1-十八碳烯、1-十九碳烯、1-二十碳烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、9-甲基-1-癸烯、11-甲基-1-十二碳烯、12-乙基-1-十四碳烯等)均聚或2种以上共聚而得的材料；诸如乙烯/乙酸乙烯酯共聚物、乙烯/乙烯醇共聚物、乙烯/甲基丙烯酸甲酯共聚物、乙烯/甲基丙烯酸乙酯共聚物、乙烯/甲基丙烯酸丁酯共聚物、乙烯/丙烯酸甲酯共聚物、乙烯/丙烯酸乙酯共聚物、乙烯/丙烯酸丁酯共聚物之类的使乙烯或α烯烃与除此以外的其他单体共聚而得的材料。此外，在谋求提高保护膜10的表面强度的情况下，优选使用(例如)高结晶性的聚丙烯。
透明聚烯烃树脂层11包含由下述通式(I)表示的受阻胺类光稳定剂，并且由下式(II)表示的碳酸＝双(2,2,6,6-四甲基-1-十一烷基氧基哌啶-4-基)酯是特别期望的。
[化学式2]
需要说明的是，在通式(I)中，R是碳原子数为1至18的烷基或者碳原子数为5至8的环烷基。
[化学式3]
受阻胺类光稳定剂的配合量没有特别的限定，可以根据透明聚烯烃树脂层11的厚度、后述的粘接层20及基材30等各种条件而适当地设定，但是，相对于透明聚烯烃树脂层11中所含的100质量份的烯烃树脂，通常在0.05质量份以上5质量份以下的范围内，优选在0.1质量份以上3质量份以下的范围内。若受阻胺类光稳定剂的配合量小于0.05质量份，则可能无法对透明聚烯烃树脂层赋予充分的耐候性，若超过5质量份，则保护膜的耐受性(耐候性)不变，但是与表面保护层等的粘接性可能会降低，因而是不优选的。
根据需要，透明聚烯烃树脂层11也可以配合有(例如)不与上述受阻胺类光稳定剂相对应的其他光稳定剂、紫外线吸收剂、热稳定剂、防粘连剂、催化剂捕获剂、着色剂、光散射剂及光泽度调节剂等各种添加剂。
作为其他光稳定剂的例子，可列举出(例如)2-(3,5-二叔丁基-4-羟基苄基)-2’-正丁基丙二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯等受阻胺类光稳定剂。
作为紫外线吸收剂的例子，可列举出(例如)2,4-双(2,4-二甲基苯基)-6-(2-羟基-4-正辛基氧基苯基)-s-三嗪、2,4,6-三(2-羟基-4-己氧基-3-甲基苯基)-s-三嗪、2-[2-羟基-4-(2-乙基己氧基)苯基]-4,6-二联苯基-s-三嗪、2-[[2-羟基-4-[1-(2-乙基己氧基羰基)乙氧基]苯基]]-4,6-二苯基-s-三嗪等羟基苯基三嗪化合物；2-(5-氯-2H-苯并三唑-2-基)-6-叔丁基-4-甲基苯酚、2-(5-氯-2-苯并三唑基)-6-叔丁基对甲酚等苯并三唑类的紫外线吸收剂。其中，优选使透明聚烯烃树脂层11中包含羟基苯基三嗪类紫外线吸收剂和苯并三唑类紫外线吸收剂中的至少一种。
紫外线吸收剂的配合量没有特别的限定，可以根据透明聚烯烃树脂层11的厚度、后述的粘接层20及基材30等各种条件而适当地设定，但是，相对于100质量份的烯烃树脂，通常在0.1质量份以上2质量份以下的范围内。若紫外线吸收剂的配合量小于0.1质量份，则可能无法对透明聚烯烃树脂层赋予充分的耐候性。此外，若紫外线吸收剂的配合量超过2质量份，则紫外线吸收剂会从保护膜10中渗出，在通过使保护膜10和基材30接合而成的片材的密合性和设计性上可能会产生问题。另外，在透明聚烯烃树脂层11中会观察到显著的白浊倾向，在设计性上可能会产生问题。
透明聚烯烃树脂层11的制作方法没有特别的限定，可以使用(例如)压延成膜、挤出成膜等常规的方法，可以形成包含上述烯烃树脂、羟基苯基三嗪类紫外线吸收剂及各种添加物的透明烯烃树脂层。
为了赋予设计性，透明聚烯烃树脂层11上可以设置表面凹凸。作为设置凹凸的方法，例如有：在将透明聚烯烃树脂膜挤出成形后进行热压花加工的方法、在挤出成形时使用设置有凹凸的冷却辊进行挤出成形同时进行压花加工的方法。
(表面保护层)
根据本实施方式的表面保护层12是用于对保护膜10赋予耐候性、耐擦伤性、耐污染性、设计性等功能而设置的；作为表面保护层12的材料，没有特别的限定，例如可以适当地从氨基甲酸酯类、丙烯酸类、丙烯酸有机硅类、氟类、环氧类等树脂材料中适当选择使用。
根据需要，表面保护层12可以配合有(例如)紫外线吸收剂、热稳定剂、光稳定剂、防粘连剂、催化剂捕获剂、着色剂、光散射剂和光泽度调节剂等各种添加剂。作为紫外线吸收剂和光稳定剂，可以使用(例如)适用于上述透明聚烯烃树脂层11的材料。
表面保护层12的形成方法没有特别的限定，可以通过以下方式形成表面保护层12：使上述材料成为涂液，采用(例如)凹版涂布、微凹版涂布、逗式涂布、刮刀涂布、模涂布等常规方法涂布所得涂液，然后经由热固化、紫外线固化等适合于材料的方法使其固化，从而形成表面保护层12。
另外，可以在将透明聚烯烃树脂层11接合于后述的基材30上以后再设置表面保护层12。
[第二实施方式]
作为本发明的第二实施方式，使用图2对通过将根据第一实施方式的保护膜10与基材30接合而形成的装饰片40的构成进行说明。
装饰片40通过经由粘接层20将具备表面保护层12和透明聚烯烃树脂层11的保护膜10(即根据第一实施方式的保护膜10)接合至基材30而构成。需要说明的是，在图2中示出了通过经由粘接层20将保护膜10所具备的透明聚烯烃树脂层11与后述的基材30所具备的图案层32接合而得的装饰片40。
(原材)
基材30具备：原材31、以及在原材31的一个表面侧设置的图案层32。
作为原材31，可以从(例如)薄页纸、钛纸、树脂浸渍纸等纸；聚乙烯、聚丙烯、聚丁烯、聚苯乙烯、聚碳酸酯、聚酯、聚酰胺、乙烯-乙酸乙烯酯共聚物、聚乙烯醇、丙烯酸等合成树脂或这些合成树脂的发泡体；乙烯-丙烯共聚物橡胶、乙烯-丙烯-二烯共聚物橡胶、苯乙烯-丁二烯共聚物橡胶、苯乙烯-异戊二烯-苯乙烯嵌段共聚物橡胶、苯乙烯-丁二烯-苯乙烯嵌段共聚物橡胶、聚氨酯等橡胶；有机或无机类的无纺布；合成纸；铝、铁、金、银等的金属箔等当中任意地选择。
为了补充原材31对与原材31邻接的层的密合性，可以在原材31的单面或双面上设置底漆层(未示出)，也可以对原材31的单面或双面进行电晕处理、等离子体处理、臭氧处理、电子束处理、紫外线处理、重铬酸处理等表面处理。
(图案层)
图案层32是(例如)使用油墨对原材31施加的图案印刷。用于形成图案层32的油墨可以包含粘合剂，作为该粘合剂，可以从(例如)硝化棉、纤维素、氯乙烯-乙酸乙烯酯共聚物、聚乙烯醇缩丁醛、聚氨酯、丙烯酸类、聚酯类等或它们的改性产物当中适当地选择使用。另外，它们可以是水性类型、溶剂类型、乳液类型中的任一种，并且可以是单液类型，也可以是使用固化剂的2液类型。
作为使用于形成图案层32的油墨固化的方法，可列举出通过紫外线、电子束等的照射来使油墨固化的方法。其中，最常用的方法是使用氨基甲酸酯类的油墨并通过异氰酸酯来使其固化的方法。
除了这些粘合剂以外，在用于形成图案层32的油墨中还添加了在常规油墨中所含的颜料、染料等着色剂，体质颜料，溶剂，光稳定剂等各种添加剂等。作为通用性高的颜料，可列举出(例如)缩合偶氮、不溶性偶氮、喹吖啶酮、异吲哚啉、蒽醌、咪唑酮、钴、酞菁、碳、氧化钛、氧化铁、云母等珠光颜料等。
设置图案层32的方法没有特别的限定，例如可以使用凹版印刷、胶版印刷、丝网印刷、柔版印刷、喷墨印刷等常规的印刷方法。
(粘接层)
粘接层20没有特别的限定，例如可以通过采用适当地选自氨基甲酸酯类、丙烯酸类、丙烯酸有机硅类、氟类、环氧类等树脂材料的油墨化材料、并使用(例如)凹版涂布、微凹版涂布、逗式涂布、刮刀涂布、模涂布等常规涂布方法来形成。
将保护膜10接合至基材30的方法没有特别的限定，根据需要，可以使用(例如)经由粘接层20的热层压、挤出层压、干式层压、夹心层压等各种层压方法。
对于构成根据本实施方式的装饰片40的各层的厚度，考虑到印刷操作性和成本等，原材31期望设为20μm至150μm，粘接层20期望设为1μm至20μm，透明聚烯烃树脂层11期望设为20μm至200μm，表面保护层12期望设为3μm至20μm。另外，装饰片40的总厚度适当地设在45μm至250μm的范围内。
以下，示出实施例和比较例以对本发明进行详细说明。
<实施例1>
以厚度为80μm的方式，对通过将0.3质量份的紫外线吸收剂(Tinuvin 1600；BASF日本(股)制)以及作为光稳定剂的0.5质量份的由下式(4)表示的光稳定剂(光稳定剂A)(ADEKA STAB LA-81；(股)ADEKA制)添加到100质量份的透明均聚聚丙烯树脂(Prime PP；(股)Prime Polymer制)而得的树脂组合物进行熔融挤出，从而获得了实施例1的保护膜。
接下来，通过使用2液型氨基甲酸酯油墨(V180；东洋油墨(股)制)在具有遮蔽性的聚乙烯原材(厚度70μm)上凹版印刷木纹图案以设置图案层(厚度3μm)，从而获得基材，经由干式层压用粘接剂(Takelac A540；三井化学(股)制)(厚度2μm)将上述保护膜干式层压在所得的基材上。进一步地，在上述保护膜上涂布形成由丙烯酸多元醇(甲基丙烯酸甲酯与2-羟基甲基丙烯酸酯的共聚物)和固化剂(六亚甲基二异氰酸酯的氰尿酸酯体(nuratebody))构成的2液固化型聚氨酯树脂层(层厚度8μm)以作为表面保护层，从而获得了实施例1的装饰片。
<实施例2>
在实施例1中添加0.75质量份的光稳定剂A作为光稳定剂，除此以外，通过与实施例1同样的方法获得了实施例2的装饰片。
<实施例3>
在实施例1中添加1.0质量份的光稳定剂A作为光稳定剂，除此以外，通过与实施例1同样的方法获得了实施例3的装饰片。
<比较例1>
在实施例1中添加0.5质量份的由下式(B)所示的光稳定剂(光稳定剂B)(Tinuvin123；BASF日本(股)制)作为光稳定剂，除此以外，通过与实施例1同样的方法获得了比较例1的装饰片。
<比较例2>
在实施例1中添加0.75质量份的光稳定剂B作为光稳定剂，除此以外，通过与实施例1同样的方法获得了比较例2的装饰片。
<比较例3>
在实施例1中添加1.0质量份的光稳定剂B作为光稳定剂，除此以外，通过与实施例1同样的方法获得了比较例3的装饰片。
<比较例4>
在实施例1中添加0.5质量份的由下式(C)所示的光稳定剂(光稳定剂C)(TinuvinNOR 371；BASF日本(股)制)作为光稳定剂，除此以外，通过与实施例1同样的方法获得了比较例4的装饰片。
<比较例5>
在实施例1中添加0.75质量份的光稳定剂C作为光稳定剂，除此以外，通过与实施例1同样的方法获得了比较例5的装饰片。
<比较例6>
在实施例1中添加1.0质量份的光稳定剂C作为光稳定剂，除此以外，通过与实施例1同样的方法获得了比较例6的装饰片。
[化学式4]
[化学式5]
[化学式6]
<评价>
对于在上述实施例和比较例中所得的装饰片，采用以下方法评价了耐候性。下表1中示出了评价结果。
根据以下标准对装饰片在耐候加速试验后的外观进行目视评价。在耐候加速试验中，使用EYE Super UV测试仪(SUV-W161；岩崎电气(股))，在63℃的黑板温度和65mW/cm2的照度下，将(UV照射20小时+冷凝4小时)作为1个循环，对分别实施了20个循环(480小时)、25个循环(600小时)和30个循环(720小时)之后的装饰片的外观进行目视评价。
(目视评价标准)
○：在装饰片中没有外观变化
△：在装饰片中观察到白化
×：在装饰片中观察到破裂
需要说明的是，若耐候性的评价为“○”和“△”，则在使用上没有问题，因而评价为合格。
[表1]
如表1所示，对于在实施例1至实施例3中例示的根据本实施方式的保护膜和装饰片，通过向透明烯烃树脂层中添加具有上述特定结构的受阻胺类光稳定剂，从而显示出比现有的NO烷基型受阻胺类光稳定剂(即Tinuvin 123和Tinuvin NOR 371)以上的耐候性。
工业实用性
本发明除了可以在室外用于装饰片、海报、标牌等的片材，还可以用作门窗的表面材料、地板材料等室内用片材。
符号的说明
10 保护膜
11 透明聚烯烃树脂层
12 表面保护层
20 粘接层
30 基材
31 原材
32 图案层
40 装饰片

Claims (4)

1.一种保护膜，其至少包含透明聚烯烃树脂层和在所述透明聚烯烃树脂层的上层形成的表面保护层，特征在于，
相对于所述透明聚烯烃树脂层中所含的100质量份的透明烯烃树脂，所述透明聚烯烃树脂层在0.05质量份以上5质量份以下的范围内含有由下述通式(I)表示的受阻胺类光稳定剂，
所述表面保护层由2液固化型聚氨酯树脂形成，
所述聚氨酯树脂为甲基丙烯酸甲酯与甲基丙烯酸酯2-羟基乙酯的共聚物，
[化学式1]
通式(I)中，R是碳原子数为1至18的烷基或者碳原子数为5至8的环烷基。
2.根据权利要求1所述的保护膜，特征在于，所述透明聚烯烃树脂层进一步包含羟基苯基三嗪类紫外线吸收剂和苯并三唑类紫外线吸收剂中的至少一者。
3.根据权利要求1或权利要求2所述的保护膜，特征在于，所述受阻胺类光稳定剂是由下式(II)表示的结构，
[化学式2]
4.一种片材，特征在于，其至少包含权利要求1至权利要求3中任一项所述的保护膜，以及基材。
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