CN110643250B - 水溶性涂液及涂布有水溶性涂液的聚酯光学薄膜 - Google Patents

水溶性涂液及涂布有水溶性涂液的聚酯光学薄膜 Download PDF

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CN110643250B
CN110643250B CN201910371271.0A CN201910371271A CN110643250B CN 110643250 B CN110643250 B CN 110643250B CN 201910371271 A CN201910371271 A CN 201910371271A CN 110643250 B CN110643250 B CN 110643250B
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water
coating
polyester
soluble
inorganic particles
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CN110643250A (zh
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廖德超
曹俊哲
郑文瑞
陈政宏
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Nan Ya Plastics Corp
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Abstract

本发明提供一种水溶性涂液及涂布有水溶性涂液的聚酯光学薄膜。水溶性涂液具有涂布于一聚酯薄膜基材的表面上形成一涂层的用途。水溶性涂液依重量比，包含以下成分，且以下各成分的总和为100wt％：⑴2‑40wt％的丙烯酸酯接枝改质的聚氨酯树脂；⑵0.5‑30wt％的交联剂；⑶0.05‑30wt％的填充粒子混合液；⑷0.05‑10wt％的添加剂，选自助剂、触媒或共溶剂中的一种或以上；⑸50‑85wt％的水。其中，成分(3)的填充粒子混合液的组成，包含：a)20‑95wt％的无机粒子，无机粒子是选自氧化硅、氧化钛、氧化铝、碳酸钙、磷酸钙或硫酸钡中的一种或以上；b)0.5‑30wt％的表面改质剂，以对无机粒子表面改质。

Description

水溶性涂液及涂布有水溶性涂液的聚酯光学薄膜
技术领域
本发明涉及一种水溶性涂液，具有涂布于聚酯薄膜基材的表面上形成涂层的用途，特别是一种涂布这种涂层的聚酯光学薄膜，具高透明性及低雾度外，其涂层还具优异抗沾黏性、接着性及滑性等特性。
背景技术
液晶显示器的背光模块基材，例如，扩散膜或增亮膜等，是由聚酯光学薄膜例如双轴延伸的PET光学薄膜制成。聚酯光学薄膜的透明性、雾度与滑性，与聚酯光学薄膜的结晶程度，以及，与所添加的微米级滑剂的种类和含量有关外，另一个重要因素也与涂布在聚酯薄膜基材上面的涂层的物性息息相关。涂层的成分中，除了聚酯树脂外，还添加微细无机粒子来改善聚酯薄膜的滑性。除了涂层的折射率及表面平整性会影响聚酯光学薄膜的透明性外，涂层中的微细无机粒子的分散程度，也会影响聚酯光学薄膜的透明性。
现有技术中的聚氨酯树脂，有机械强度低、不耐UV光、耐热性、与耐水性差等缺点。尤其是，聚酯光学薄膜的涂层成分中，包含聚氨酯树脂及微细无机粒子时，聚氨酯树脂与无机粒子间的兼容性差。如果无机粒子分散不均匀，会产生团聚的现象。例如，中国大陆专利公开号CN103171223A1，提到一种高透明性及抗沾黏性佳的聚酯光学薄膜，其涂液配方包括水性聚氨酯树脂及使用0.04-6μm微细无机粒子等，但无机粒子在聚氨酯树脂间会分散不均匀易造成团聚。当聚酯光学薄膜经过延伸后，涂层的这种团聚现象，会在团聚的无机粒子周围产生空隙，从而导致涂层表面平整性不佳。这些不佳的因素都会影响到聚酯光学薄膜的透光率、雾度和滑性。
当用途作为液晶显示器的背光模块基材使用时，聚酯光学薄膜的涂层，对供其涂布的聚酯薄膜基材、以及，对液晶显示材料(以下简称LCD材料)中经UV硬化的高折射率丙烯酸酯树脂涂层，都必须同时具有优良的接着性。
但，聚酯光学薄膜的涂层，若纯为丙烯酸酯树脂，虽耐候性佳，不但对LCD材料中经UV硬化的高折射率丙烯酸酯树脂的接着性不佳，对聚酯薄膜基材的接着性也不佳；同样情形，聚酯光学薄膜的涂层，若纯为聚酯树脂，虽对聚酯薄膜基材的接着性甚佳，但对LCD材料中经UV硬化的丙烯酸酯树脂的接着性仍不佳。
此外，聚酯光学薄膜的涂层，是涂布在聚酯薄膜基材的一面或两面，如果涂层不具备优异抗沾黏性，聚酯光学薄膜于收卷时易沾黏在一起，这种沾黏现象会影响聚酯光学薄膜的后续加工、剪裁或包装。尤其是，聚酯光学薄膜的表面，受到沾黏后，会形成白雾、条纹及细微晶点，会影响聚酯光学薄膜的外观与应用。
更具体而言，聚酯光学薄膜作为液晶显示器的背光模块基材使用时，聚酯光学薄膜的涂层，是需要具备优异抗沾黏性、优良接着性及滑性等特性。
发明内容
本发明所要解决的技术问题在于，提供一种水溶性涂液。水溶性涂液具有涂布于一聚酯薄膜基材的表面上形成一涂层的用途。水溶性涂液依重量比，包含以下成分，且以下各成分的总和为100wt％：⑴2-40wt％的丙烯酸酯接枝改质的聚氨酯树脂；⑵0.5-30wt％的交联剂；⑶0.05-30wt％的填充粒子混合液；⑷0.05-10wt％的添加剂，选自助剂、触媒或共溶剂中的一种或以上；⑸50-85wt％的水。其中，成分(3)的填充粒子混合液的组成，包含：a)20-95wt％的无机粒子，无机粒子是选自氧化硅、氧化钛、氧化铝、碳酸钙、磷酸钙或硫酸钡中的一种或以上；b)0.5-30wt％的表面改质剂，以对无机粒子表面改质。
优选地，成分⑶的无机粒子的粒径，介于0.005-3μm。
优选地，表面经过改质的无机粒子的浓度，占水溶性涂液的固含量的0.01％-6％。
优选地，丙烯酸酯接枝改质的聚氨酯树脂，是使用由下列成分组成的丙烯酸酯单体进行接枝改质，且以下各成分的总和为100wt％：
(a)含烷基的(甲基)丙烯酸酯90-95wt％；
(b)含羟基的(甲基)丙烯酸酯4-9wt％；
(c)含羧基的乙烯基单体1-5wt％。
优选地，含羧基的乙烯基单体选自丙烯酸、甲基丙烯酸、衣康酸、丁烯酸、马来酸、富马酸或马来酸酐中的一种或以上。
优选地，成分⑵的交联剂，选自三聚氰胺交联剂、羟甲基改质的三聚氰胺衍生物交联剂、异氰酸酯系交联剂、氮丙啶系交联剂、恶唑啉系交联剂或碳二亚胺系交联剂中的一种或以上。
优选地，成分⑶的表面改质剂，选自乙烯基硅烷偶联剂、环氧基硅烷偶联剂、苯乙烯基硅烷偶联剂、甲基丙烯酰氧基硅烷偶联剂、丙烯酰氧基硅烷偶联剂、氨基硅烷偶联剂、异氰脲酸酯基硅烷偶联剂、脲基硅烷偶联剂或异氰酸盐硅烷偶联剂中的一种或以上。
优选地，成分(4)的助剂，选自含硅的添加剂、含氟的添加剂、或含硅/氟混合成分的添加剂。
优选地，成分(4)的共溶剂，选自甲醇、乙醇、正丙醇、异丙醇、丁醇、异丁醇、二甲基亚砜、丙酮或四氢呋喃溶剂中的一种或以上。
本发明所要解决的技术问题在于，提供一种聚酯光学薄膜。聚酯光学薄膜具有一双轴延伸的聚酯薄膜基材，且聚酯光学薄膜的其中一表面，使用如前述的水溶性涂液涂布而构成的一涂层。
为使能更进一步了解本发明的特征及技术内容，请参阅以下有关本发明的详细说明。
具体实施方式
本发明公开一种水溶性涂液，使用用途为供涂布于聚酯薄膜基材的表面上，从而形成聚酯光学薄膜的涂层，该水溶性涂液(或涂层)的配方，依重量比，包含以下成分，且以下各成分的总和为100wt％：
⑴2-40wt％的丙烯酸酯接枝改质的聚氨酯树脂；
⑵0.5-30wt％的交联剂；优选用量为5-20wt％；
⑶0.05-30wt％的填充粒子混合液；
⑷0.05-10wt％的添加剂；及
⑸50-85wt％的水，作为溶媒使用。
其中，成分⑶的填充粒子混合液，包含：
a)20-95wt％的无机粒子；优选用量为20-90wt％，特优选用量为50-80wt％；且选自氧化硅、氧化钛、氧化铝、碳酸钙、磷酸钙或硫酸钡中的一种以上；
b)0.5-30wt％的表面改质剂；优选用量为5-20wt％。
本发明的水溶性涂液，其中，表面经过改质的无机粒子浓度，占水溶性涂液的固含量的0.01％-6％。
所述成分(1)的丙烯酸酯接枝改质的聚氨酯树脂，其合成方法，包含以下步骤，基于包含去离子水的总反应原料量：
(1)预聚物的制备：
将15-25wt％的聚酯(醚)多元醇，真空脱水，加入装有搅拌器、温度计和冷凝管的反应器中，待油浴温度达到70-80℃时，加入5-12wt％的脂肪族二异氰酸酯，进行合成反应。
(2)预聚物的稀释及扩链：
预聚物反应2-3小时后，再加入10-30wt％的丙烯酸酯单体稀释降低黏度，持温85-90℃，直到NCO理论当量比值(NCO/OH)为1.1-2.3，再加入1.5-3.0wt％的乙二胺基乙磺酸钠(AAS)，续反应25-40分钟。
(3)水分散：
将步骤(2)反应制得的聚合物降温至室温，在转速500rpm高速剪切力下，加入35-55wt％的去离子水，再加入0.1-0.5wt％的乙二胺，进行扩链反应约30分钟，制得不含溶剂的磺酸盐型水性聚氨酯分散液。
(4)丙烯酸酯合成：
对步骤(3)的磺酸盐型水性聚氨酯分散液，加入0.3-1.0wt％的十二烷基硫酸钠(SLS)乳化剂混合形成乳化液，升温至50-70℃后，滴加0.01-0.10wt％的过硫酸铵水溶液(APS)起始剂，进行聚合丙烯酸酯，续升温至75-85℃，在此温度下恒温1-3小时，降温至50-70℃后，加入0.01-0.08wt％的还原剂，制得所述丙烯酸酯接枝改质的聚氨酯树脂。
用于接枝改质的丙烯酸酯(单体)的组成，依重量比，包含以下成分，且以下各成分的总和为100wt％：
(a)含烷基的(甲基)丙烯酸酯90-95wt％；
(b)含羟基的(甲基)丙烯酸酯4-9wt％；及
(c)含羧基的乙烯基单体1-5wt％。
所述含烷基的(甲基)丙烯酸酯选自(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸甲氧基乙酯或(甲基)丙烯酸乙氧基甲酯中的一种单独使用或一种以上混合并用。
所述含羟基的(甲基)丙烯酸选自(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸4-羟基丁酯、丙烯酸氯-2-羟基丙酯、二乙二醇单(甲基)丙烯酸酯或烯丙醇中的一种单独使用或一种以上混合并用。
所述含羧基的乙烯基单体选自由丙烯酸、甲基丙烯酸、衣康酸、丁烯酸、马来酸、富马酸或马来酸酐中的一种单独使用或一种以上混合并用。
所述成分(2)的交联剂，选自三聚氰胺交联剂、三聚氰胺与甲醛缩合的羟甲基改质的三聚氰胺衍生物交联剂、异氰酸酯系交联剂、氮丙啶系交联剂、恶唑啉系交联剂或碳二亚胺系交联剂中的一种单独使用或一种以上混合并用。
所述填充粒子混合液中的无机粒子，粒径介于0.005-3μm。视聚酯光学薄膜的物性需求，例如透明度、雾度、滑性或抗沾黏性等特性的需求，所述填充粒子混合液中的无机粒子，可搭配组合不同大小粒径的无机粒子。当无机粒子的粒径愈大，聚酯光学薄膜的涂层，在高温下的抗沾效果愈好。当无机粒子的分散性愈佳，无机粒子愈不易团聚，聚酯光学薄膜及其涂层愈透明，雾度愈低。
所述填充粒子混合液中的表面改质剂，选自乙烯基硅烷偶联剂、环氧基硅烷偶联剂、苯乙烯基硅烷偶联剂、甲基丙烯酰氧基硅烷偶联剂、丙烯酰氧基硅烷偶联剂、氨基硅烷偶联剂、异氰脲酸酯基硅烷偶联剂、脲基硅烷偶联剂或异氰酸盐硅烷偶联剂中的一种单独使用或一种以上混合并用。
无机粒子经过表面改质剂的改质后，可改善粒子团聚、分散性不佳、兼容性低、接着性低等缺点，尤其是，无机粒子可以在涂层中形成微球，且稍微凸起于涂层表面，有效改善了聚酯光学薄膜的涂层的抗沾黏性问题。收卷时，借助无机粒子稍微凸起于涂层表面，聚酯光学薄膜其处于收卷状态的薄膜与薄膜之间会形成空气层，而空气层的存在能降低薄膜与薄膜之间的摩擦系数，也降低了彼此相互间的沾黏性，从而避免薄膜间发生沾黏现象，解决了往昔聚酯光学薄膜收卷易出现沾黏的问题。
所述成分(4)的添加剂，包括助剂、触媒或共溶剂中的一种单独使用或一种以上混合并用。其中，添加助剂可以调整涂液的表面张力，提升聚酯光学薄膜的涂层(或涂布膜)的平坦度以及与聚酯基材间的润湿性。添加触媒可以控制涂液的架桥反应速率。添加共溶剂可以控制涂液中的液态成份的挥发速率。
所述触媒为无机物质、盐类、有机物质、碱性物质或酸性物质。所述共溶剂为甲醇、乙醇、正丙醇、异丙醇、丁醇、异丁醇、二甲基亚砜、丙酮或四氢呋喃溶剂中的一种或以上。
所述助剂包括含硅的添加剂、含氟的添加剂、或含硅/氟混合成分的添加剂。所述含硅的添加剂，选自BYK公司的BYK307、BYK325、BYK331、BYK380N或BYK381中的一种单独使用或一种以上混合并用。
所述含氟的添加剂，选自3M公司的FC-4430、FC-4432、美国杜邦公司的Zonyl FSN-100或日本大金公司的DSX中的一种单独使用或一种以上混合并用。
所述含硅/氟混合成分的添加剂，选自BYK公司的BYK346、BYK347或BYK348中的一种单独使用或一种以上混合并用。
本发明的水溶性涂液(或涂层)，可以采用线外(off-line)或在线(in-line)涂布方式，涂布在聚酯薄膜基材的表面上形成聚酯光学薄膜的涂层。而且，所制得的聚酯光学薄膜，具有高透明性、低雾度、优良的抗黏层性、接着性及滑性等特性，适合应用于如LCD或CRT用的扩散膜、增亮膜、保护膜等。
以下各实施例与各比较例的聚酯光学薄膜(简称光学膜)，是依照以下评估方法进行评估。
(1)光透过率及雾度测试：
采用Tokyo Denshoku Co.,Ltd.Haze Meter，型号为TC-HIII，测试光学膜样品的光透过率及雾度值，其方法符合JIS K7705规范。光透过率越高、雾度值越低代表光学膜的光学性质越佳。
(2)对光学胶密着性测试：
采用量宏公司曝光机，型号为Model F300S+AJ-6-UVL，测试光学膜样品涂布面对扩散膜或增亮膜用的丙烯酸酯UV胶的接着性，其方法符合ASTM D3359规范。以12号涂布棒，将国内生产扩散膜或增亮膜用的光学胶涂布于光学膜样品的涂布面后，经UV曝光机曝光干燥，以百格刀划百格后，再将3M 600型胶带贴于百格试样上，密着后撕离胶带进行接着性评估。
(3)UV光照射后对光学胶密着性测试：
光学膜样品的涂布面，先以UV光曝光，经曝光能量500mJ/cm2后，续以前述测试方法(2)进行对光学胶密着性测试，评估光学胶密着性。
(4)涂层的填充粒子分散性测试：
光学膜样品的涂布面，使用Hitachi S5000型扫描式电子显微镜测试其填充粒子的分散性，首先将样品固定于碳胶上，再利用镀金机，镀上金或白金薄膜，并以10000倍的测试倍率进行观察。
(5)涂层抗沾黏性的温度：
以崴镱公司热封试验机，型号HST-H3，测试光学膜样品的涂层抗沾黏性的温度。测试条件：取两片光学膜样品，将样品的涂布膜表面相对，热封压力2MPa、热封时间2分钟，进行不同温度的抗沾黏性测试。热封后，两片样品可轻易分开，且表面无痕迹，记录此温度即为光学膜样品的涂层抗沾黏性的极限温度。
[预制丙烯酸酯接枝改质的聚氨酯树脂]
(1)预聚物的制备：
将100g的PTMG2000(聚醚二元醇，分子量2000)、6.5g的1,4-BG(1,4-丁二醇，分子量90)依次加入反应器中，匀速搅拌下升温至80℃，之后加入43g异佛尔酮二异氰酸酯，升温至85-90℃，并在此温度下反应2-3小时。
(2)预聚物的稀释及扩链：
接着，批次加入140g的甲基丙烯酸甲酯(MMA)、8g的丙烯酸2羟乙酯(2-HEA)、4.8g的丙烯酸乙酯(EA)稀释降黏，对预聚物再加入10g的乙二胺基乙磺酸钠(AAS)，续反应25-40分钟。
(3)水分散：
完成反应后，将步骤(2)所得的预聚物降温至室温，在500rpm转速下加入300g的去离子水，再加入1g的乙二胺进行扩链反应约30分钟，制得磺酸盐型水性聚氨酯乳液。
(4)丙烯酸酯合成：
在快速搅拌下，将4.8g的乳化剂十二烷基硫酸钠(SLS)加入步骤(3)的磺酸盐型水性聚氨酯乳液，升温至50-70℃，之后滴加0.40g的过硫酸铵水溶液(APS)，续升温至75-85℃，于此温度恒温1-3小时，降温至50-70℃后，加入0.12g的叔丁基过氧化氢水溶液(TBHP)及0.12g的甲醛合次硫酸氢钠(SFS)，反应30分钟，得到丙烯酸酯接枝改质的聚氨酯树脂。
【实施例1】
将PET粒充分干燥后，送料至挤出机熔融挤出，并经过表面温度为25℃的冷却筒冷却及固化，得到未延伸的PET片(Sheet)，经加热后，在拉伸比为4倍下进行纵向单轴延伸，制得单轴延伸PET膜。
取由下列成分均匀搅拌而成的水溶性涂液：
⑴8.5克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵1.0克的三聚氰胺系交联剂；
⑶2.1克的填充粒子混合液；取0.05克的阴离子界面活性剂A、0.45克的非离子界面活性剂B、0.05克的含硅化合物及1.05克的高分子聚合物(聚酯树脂)为处理剂；对0.10克的100nm氧化硅粒子A及0.40克的30nm氧化硅粒子B进行改质；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸81.89克的水溶媒。
对预制的单轴延伸PET膜进行单面涂布处理，将预制的水溶性涂液均匀涂布在单轴延伸PET膜上，然后，涂布完成的单轴延伸PET膜，以固定夹引导到105℃的加热区，经干燥及去除涂层的水分后，再送入125℃的加热区；经过3.5倍的横向延伸后，制得具有单面涂层的双轴延伸的PET膜，接着，再经过235℃处理8秒钟，制得膜厚50μm且具有单面涂层的聚酯光学薄膜。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
【实施例2】
同实施例1的制法，制得膜厚50μm且具有单面涂层的聚酯光学薄膜。但水溶性涂液改为使用由下列成分均匀搅拌而成：
⑴8.75克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵0.8克的三聚氰胺系交联剂及0.5克的恶唑啉系交联剂；
⑶1.95克的填充粒子混合液；取0.25克的阴离子界面活性剂A、0.25克的非离子界面活性剂B、0.05克的含硅化合物及1.05克的高分子聚合物(聚酯树脂)为处理剂；对0.10克的100nm氧化硅粒子A及0.25克的30nm氧化硅粒子B进行改质；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸81.49克的水溶媒。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
【实施例3】
同实施例1的制法，制得膜厚50μm且具有单面涂层的聚酯光学薄膜。但水溶性涂液改为使用由下列成分均匀搅拌而成：
⑴8.0克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵1.0克的三聚氰胺系交联剂及0.5克的恶唑啉系交联剂；
⑶2.0克的填充粒子混合液；取0.45克的阴离子界面活性剂A、0.05克的非离子界面活性剂B、0.05克的含硅化合物及1.05克的高分子聚合物(聚酯树脂)为处理剂；对0.30克的100nm氧化硅粒子A及0.10克的30nm氧化硅粒子B进行改质；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸81.99克的水溶媒。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
【实施例4】
同实施例1的制法，制得膜厚50μm且具有单面涂层的聚酯光学薄膜。但水溶性涂液改为使用由下列成分均匀搅拌而成：
⑴8.5克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵1.0克的恶唑啉系交联剂；
⑶2.1克的填充粒子混合液；取0.45克的阴离子界面活性剂A、0.05克的非离子界面活性剂B、0.1克的含硅化合物及1.0克的高分子聚合物(聚酯树脂)为处理剂；对0.40克的100nm氧化硅粒子A及0.10克的30nm氧化硅粒子B进行改质；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸81.89克的水溶媒。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
【实施例5】
同实施例1的制法，制得膜厚50μm且具有单面涂层的聚酯光学薄膜。但水溶性涂液改为使用由下列成分均匀搅拌而成：
⑴8.75克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵0.5克的三聚氰胺系交联剂及0.8克的恶唑啉系交联剂；
⑶2.1克的填充粒子混合液；取0.05克的阴离子界面活性剂A、0.45克的非离子界面活性剂B、0.1克的含硅化合物及1.0克的高分子聚合物(聚酯树脂)为处理剂；对0.10克的100nm氧化硅粒子A及0.40克的30nm氧化硅粒子B进行改质；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸81.34克的水溶媒。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
【实施例6】
同实施例1的制法，制得膜厚50μm且具有双面涂层的聚酯光学薄膜。但水溶性涂液改为使用由下列成分均匀搅拌而成：
⑴8.0克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵0.5克的三聚氰胺系交联剂及1.0克的恶唑啉系交联剂；
⑶2.05克的填充粒子混合液；取0.25克的阴离子界面活性剂A、0.25克的非离子界面活性剂B、0.1克的含硅化合物及1.0克的高分子聚合物(聚酯树脂)为处理剂；对0.15克的100nm氧化硅粒子A及0.30克的30nm氧化硅粒子B进行改质；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸81.94克的水溶媒。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
【比较例1】
同实施例1的制法，制得膜厚50μm且具有单面涂层的聚酯光学薄膜。但水溶性涂液改为使用由下列成分均匀搅拌而成，且填充粒子未经过改质：
⑴8.5克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵1.0克的三聚氰胺系交联剂；
⑶0.4克的30nm氧化硅粒子B；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸83.59克的水溶媒。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
【比较例2】
同实施例1的制法，制得膜厚50μm且具有单面涂层的聚酯光学薄膜。但水溶性涂液改为使用由下列成分均匀搅拌而成，且填充粒子未经过改质：
⑴8.5克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵1.0克的三聚氰胺系交联剂；
⑶0.10克的100nm氧化硅粒子A及0.3克的30nm氧化硅粒子B；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸83.59克的水溶媒。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
【比较例3】
同实施例1的制法，制得膜厚50μm且具有单面涂层的聚酯光学薄膜。但水溶性涂液改为使用由下列成分均匀搅拌而成：
⑴8.50克的丙烯酸酯接枝改质的聚氨酯树脂；
⑵0.1克的三聚氰胺系交联剂；
⑶2.1克的填充粒子混合液；取0.05克的阴离子界面活性剂A、0.45克的非离子界面活性剂B、0.05克的含硅化合物及1.05克的高分子聚合物(聚酯树脂)为处理剂；对0.10克的100nm氧化硅粒子A及0.40克的30nm氧化硅粒子B进行改质；
⑷0.1克的触媒、5克的异丙醇、1.4克的丁基纤维素及0.01克的含硅或氟助剂化合物；及
⑸82.79克的水溶媒。
测试聚酯光学薄膜的物理性能，测试结果如表1所示。
表1
Figure BDA0002050042720000131
结果讨论：
1.实施例1-6制得的聚酯光学薄膜的涂层成分中，有添加丙烯酸酯接枝改质的聚氨酯树脂，作为液晶显示器的背光模块基材使用时，聚酯光学薄膜的涂层，对光学胶的密着性及经UV光照射后对光学胶的密着性均佳。
另外，涂层成分中的无机粒子，经表面改质剂后，在涂层中的分散性良好，所以，聚酯光学薄膜制品的光透过率佳、雾度佳；而且，涂层成分中的无机粒子，是使用混掺不同粒径的无机粒子，可以改善PET基材的滑性，同时使聚酯光学薄膜的涂层提高了抗沾黏性的温度。
比较例1-2制得的聚酯光学薄膜的涂层成分中，无机粒子没有经过表面改质，聚酯光学薄膜制品的光透过率较差，雾度也较差。
2.填充粒子混合液中的无机粒子的粒径愈大，聚酯光学薄膜制品的涂层的抗沾黏性的温度愈高，实施例3及4的聚酯光学薄膜制品，涂层使用大粒径的无机粒子，涂层的抗沾黏性的温度，高达100℃以上。相对地，比较例1的聚酯光学薄膜制品，涂层不使用大粒径的无机粒子，也不添加表面改质剂进行改质，涂层的抗沾黏性的温度较差，只达70℃，是本发明主要改善的项目之一。
3.比较例3的制得的聚酯光学薄膜，涂层的成分中，虽使用混掺不同粒径的无机粒子，也添加表面改质剂进行改质，收到涂层分散性良好的效果，但交联剂的添加量不足，导致涂层反应不完全，涂层的抗沾黏性的温度仍较差。
综上所述，本发明的聚酯光学薄膜制品的涂层成分中，由丙烯酸酯接枝改质的聚氨酯树脂、交联剂、经过表面改质的无机粒子溶液及其它添加剂等组成，涂布于聚酯光学基材上形成聚酯光学薄膜的涂层，可显著改善聚酯光学薄膜的透明性、雾度、接着性、滑性及抗沾黏性等特性。
以上所公开的内容仅为本发明的优选可行实施例，并非因此局限本发明的权利要求书的保护范围，所以凡是运用本发明说明书内容所做的等效技术变化，均包含于本发明的权利要求书的保护范围内。

Claims (9)

1.一种水溶性涂液，具有涂布于一聚酯薄膜基材的表面上形成一涂层的用途，其特征在于，所述水溶性涂液依重量比，包含以下成分，且以下各成分的总和为100wt％：
⑴2-40wt％的丙烯酸酯接枝改质的聚氨酯树脂；
⑵0.5-30wt％的交联剂；
⑶0.05-30wt％的填充粒子混合液；
⑷0.05-10wt％的添加剂，选自助剂、触媒或共溶剂中的一种或以上；以及
⑸50-85wt％的水；
其中，成分(3)的填充粒子混合液的组成，包含：
a)20-95wt％的无机粒子，所述无机粒子是选自氧化硅、氧化钛、氧化铝、碳酸钙、磷酸钙或硫酸钡中的一种或以上；及
b)0.5-30wt％的表面改质剂，以对所述无机粒子表面改质；
其中，所述丙烯酸酯接枝改质的聚氨酯树脂，是使用由下列成分组成的丙烯酸酯单体进行接枝改质，且以下各成分的总和为100wt％：
(a)含烷基的(甲基)丙烯酸酯90-95wt％；
(b)含羟基的(甲基)丙烯酸酯4-9wt％；
(c)含羧基的乙烯基单体1-5wt％。
2.根据权利要求1所述的水溶性涂液，其特征在于，成分⑶的所述无机粒子的粒径，介于0.005-3微米。
3.根据权利要求1所述的水溶性涂液，其特征在于，表面经过改质的无机粒子的浓度，占水溶性涂液的固含量的0.01％-6％。
4.根据权利要求1所述的水溶性涂液，其特征在于，所述含羧基的乙烯基单体选自丙烯酸、甲基丙烯酸、衣康酸、丁烯酸、马来酸、富马酸或马来酸酐中的一种或以上。
5.根据权利要求1所述的水溶性涂液，其特征在于，成分⑵的交联剂，选自三聚氰胺交联剂、羟甲基改质的三聚氰胺衍生物交联剂、异氰酸酯系交联剂、氮丙啶系交联剂、恶唑啉系交联剂或碳二亚胺系交联剂中的一种或以上。
6.根据权利要求1所述的水溶性涂液，其特征在于，成分⑶的表面改质剂，选自乙烯基硅烷偶联剂、环氧基硅烷偶联剂、苯乙烯基硅烷偶联剂、甲基丙烯酰氧基硅烷偶联剂、丙烯酰氧基硅烷偶联剂、氨基硅烷偶联剂、异氰脲酸酯基硅烷偶联剂、脲基硅烷偶联剂或异氰酸盐硅烷偶联剂中的一种或以上。
7.根据权利要求1所述的水溶性涂液，其特征在于，成分(4)中的助剂，选自含硅的添加剂、含氟的添加剂、或含硅/氟混合成分的添加剂。
8.根据权利要求1所述的水溶性涂液，其特征在于，成分(4)中的共溶剂，选自甲醇、乙醇、正丙醇、异丙醇、丁醇、异丁醇、二甲基亚砜、丙酮或四氢呋喃溶剂中的一种或以上。
9.一种聚酯光学薄膜，其特征在于，具有一双轴延伸的聚酯薄膜基材，且其中的一表面，使用如权利要求1所述的水溶性涂液涂布而构成的一涂层。
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