CN103792610A - 偏振板的制造方法 - Google Patents

偏振板的制造方法 Download PDF

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Publication number
CN103792610A
CN103792610A CN201310475913.4A CN201310475913A CN103792610A CN 103792610 A CN103792610 A CN 103792610A CN 201310475913 A CN201310475913 A CN 201310475913A CN 103792610 A CN103792610 A CN 103792610A
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China
Prior art keywords
transparent protective
protective film
polaroid
film
mentioned
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CN201310475913.4A
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CN103792610B (zh
Inventor
中田美惠
竹田哲郎
村山俊介
山下智弘
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Nitto Denko Corp
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Nitto Denko Corp
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    • G02B5/30—Polarising elements
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Abstract

本发明提供一种偏振板的制造方法，其是在一对辊间在偏振片的两面贴合透明保护膜的偏振板的制造方法，该方法可以抑制在偏振片与透明保护膜之间产生的气泡。在偏振片的两面隔着粘接层贴合第一透明保护膜及第二透明保护膜的偏振板的制造方法中，第一透明保护膜及第二透明保护膜的弹性(弹性模量×厚度(μm))不同，并且通过将上述3片膜同时穿过一对辊间而压接，将上述偏振片投入所述一对辊问而使之穿过的搬送方向向上述透明保护膜当中的高弹性膜一侧倾斜。

Description

偏振板的制造方法
技术领域
本发明涉及一种在偏振片的两面隔着粘接层地贴合第一透明保护膜及第二透明保护膜的偏振板的制造方法。
背景技术
以往，在具有规定的水分率的偏振片的两面贴合透明保护膜来制造偏振板，此时，通常使用水系胶粘剂或粘合剂。作为在偏振片的两面贴合透明保护膜的方法，例如采用：在一对辊间搬送偏振片并且在其两面搬送透明保护膜而同时贴合透明保护膜的同时层压法；在一对辊间搬送偏振片并且在其一面搬送透明保护膜而贴合后，继而在偏振片的另一面贴合透明保护膜的逐次层压法。
但是，当利用上述的层压法进行偏振片与透明保护膜的贴合时，会有在所得的偏振板中的偏振片与透明保护膜之间产生气泡的问题。
针对上述问题，专利文献1中，提出了如下的做法，即，在逐次层压法中，通过将偏振片和第一透明保护膜以使第一透明保护膜处于第一金属辊一侧的方式穿过第一金属辊与第一弹性辊这一对辊间，从而压接而形成层叠膜，然后，不将该层叠膜卷绕，而是通过将该层叠膜和第二透明保护膜以使第二透明保护膜处于第二金属辊一侧的方式穿过第二金属辊与第二弹性辊这一对辊间，从而压接而形成偏振板。
另外，专利文献2中提出了如下的层压膜的制造方法，其特征在于，对膜表面的伴生空气，利用在水中的溶解度为0.1cm3／cm3H2O(20℃、1atm)以上的置换气体进行吹扫，在将各膜表面用上述置换气体置换后的状态下，进行上述贴合。
此外，在专利文献3中，提出如下方法，即，在将偏振膜与保护膜利用胶粘剂贴合时，将上述胶粘剂的粘度控制为3～20mPa·s(25℃)。专利文献4中，记载了将厚度不同的透明保护膜贴合在偏振片的两面而制造偏振板的方法。就专利文献3、4而言，可以适用于同时层压法。但是，专利文献3的目的在于改善偏振板的外观，专利文献4的目的在于抑制偏振板的卷曲，而不能说是抑制了有关上述气泡的问题。
现有技术文献
专利文献
专利文献1：日本特开2008037092号公报
专利文献2：日本特开2010125702号公报
专利文献3：日本特开2002365432号公报
专利文献4：日本特开2008-122790号公报
发明内容
发明所要解决的课题
本发明的目的在于，提供一种偏振板的制造方法，其是在一对辊间在偏振片的两面贴合透明保护膜的偏振板的制造方法，该方法可以抑制在偏振片与透明保护膜之间产生的气泡。
用于解决课题的方法
本发明人等为了解决上述课题而进行了深入研究，结果发现，利用以下所示的偏振板的制造方法可以达成上述目的，从而完成了本发明。
即，涉及一种偏振板的制造方法，其特征在于，是在偏振片的两面隔着粘接层而贴合第一透明保护膜及第二透明保护膜的偏振板的制造方法，
其中，上述第一透明保护膜及第二透明保护膜的以弹性模量(MPa)×厚度(μm)的值所定义的弹性不同，将具有高弹性的一方定义为高弹性膜，将具有低弹性的一方定义为低弹性膜，
并且，将将上述一对辊的各中心点与在上述一对辊间将上述3片膜(上述偏振片、第一透明保护膜及第二透明保护膜)贴合的接点连结的线定义为第一假想线，将与该第一假想线正交的方向的线定义为第二假想线，
在上述情况下，
通过将上述3片膜同时穿过一对辊间而压接，
并且，将上述偏振片投入到上述一对辊间而使之穿过的搬送方向比上述第二假想线更倾斜于高弹性膜一侧。
在上述偏振板的制造方法中，上述第二假想线与偏振片的搬送方向所成的角度优选为超过0°且为1°以下的范围。
发明的效果
以往，在利用同时层压法来制造第一透明保护膜／偏振片／第二透明保护膜的偏振板的制造方法中，在一对辊间，沿垂直方向投入在中央被层叠的偏振片。该方法中，在第一透明保护膜及第二透明保护膜具有不同的弹性(弹性模量×厚度)的情况下，由于上述弹性的差，在同时层压时会产生应变，因而容易在偏振片中引入褶皱，会有在褶皱的部分产生气泡的情况。另外，偏振片容易变得褶皱，而当变得褶皱时，会有在所得的偏振板的褶皱的部分引入气泡、或者变得不均匀的情况。
本发明的偏振板的制造方法中，在一对辊间，在偏振片的两面贴合具有不同的弹性的第一透明保护膜及第二透明保护膜，然而在将偏振片投入到一对辊间时，在上述第一透明保护膜及第二透明保护膜中，将偏振片向弹性高的高弹性膜一侧倾斜。这样，即使在使用弹性不同的第一透明保护膜及第二透明保护膜的情况下，也可以利用偏振片的投入角度的控制来改善褶皱，从而制造出可以抑制气泡的偏振板。
利用上述制造方法得到的偏振板可以获得在各膜间没有气泡的产生、也没有褶皱的产生或条纹状的凹凸不均的外观良好的偏振板。该偏振板可以实现面内均匀性优异、高析像度、并且高对比度的液晶显示装置(LCD)，电致发光显示装置(ELD)等图像显示装置。
附图说明
图1是表示本发明的偏振板的制造方法的概略图的一例。
图2是本发明的偏振板的制造方法的说明图的一例。
符号说明
A、偏振片
B1、第一透明保护膜(低弹性膜)
B2、第二透明保护膜(高弹性膜)
R1、第一辊
R2、第二辊
M、角度变更机构
具体实施方式
以下，在参照附图的同时对本发明的偏振板的制造方法进行说明。图1是表示本发明的偏振板的制造方法的一例的图，通过使第一透明保护膜B1和第二透明保护膜B2穿过第一辊R1与第二辊R2这一对辊间而压接，从而在偏振片A的两面形成偏振板L。图1中，第一透明保护膜B1和第二透明保护膜B2的以各自的弹性模量(MPa)×厚度(μm)的值所定义的弹性不同。第二透明保护膜B2的弹性高于第一透明保护膜B1的弹性，第二透明保护膜B2是高弹性膜，第一透明保护膜B1是低弹性膜。
另外，图1中，将连结辊R1、R2的各中心点c1、c2与在上述一对辊R1、R2之间同时将上述3片膜(偏振片A、第一透明保护膜B1及第二透明保护膜B2)贴合的接点p1的线设为第一假想线s1来表示。另外，作为与上述第一假想线s1正交的方向的线而示出第二假想线s2。本发明中，通过使上述3片膜同时穿过一对辊R1、R2之间而使其压接，而如图1所示，将上述偏振片A投入到上述一对辊R1、R2之间而使之穿过的搬送方向(图1中与偏振片A相同)比上述第二假想线s2更倾斜于高弹性膜(第二透明保护膜B2)一侧。
另外，图1中，将上述第二假想线s2作为中心线，将其设为0°线。示出第二假想线s2与偏振片A的搬送线所成的角度(倾斜角θ)。在相对于第二假想线s2(中心线)而言偏振片A的搬送方向倾斜于高弹性膜(第二透明保护膜B2)的情况下，将上述倾斜角θ以“+”来表示。需要说明的是，图1中，将偏振片A的搬送线倾斜于低弹性膜(第一透明保护膜B1)时的上述倾斜角θ以“一”来表示。
优选将上述倾斜角θ控制为超过0°且在2°以下的范围。从抑制气泡的产生的观点考虑，上述倾斜角θ更优选为0.1°以上，进一步优选为0.5°以上。另一方面，从搬送性的观点考虑，上述倾斜角θ优选为1.5°以下，更优选为1°以下。
图2是将本发明的偏振板的制造方法的图1局部地放大后的说明图。图1中，在偏振片A的搬送方向与上述倾斜角θ为“0°”的方向一致的情况下，且在第一透明保护膜B1及第二透明保护膜B2的弹性相同的情况下，在接点p1，从偏振片A的两面均匀地进行第一透明保护膜B1及第二透明保护膜B2的贴合，因此可以抑制褶皱的产生、气泡的产生。另一方面，在同时层压法中，在第一透明保护膜B1及第二透明保护膜B2的弹性不同的情况下，如果仅在接点p1进行贴合，则会因上述弹性的差而产生应变，容易产生褶皱，其结果，也容易产生气泡。
如图2所示，根据本发明的偏振板的制造方法，首先，在接点p2，高弹性膜(第二透明保护膜B2)与偏振片A的一面接触。其后，在接点p1，低弹性膜(第一透明保护膜B1)与偏振片A的另一面接触，从而在接点p1将上述3片膜同时贴合。这样，可以认为：本发明中，通过先在接点p2使偏振片A与高弹性膜(第二透明保护膜B2)接触，从而可以减小与其后贴合的低弹性膜(第一透明保护膜B1)的应变。
另外，图1中，在将偏振片A向第一辊R1与第二辊R2这一对辊间搬送之前，设有偏振片A的角度变更机构M。利用角度变更机构M，可以控制上述倾斜角θ。通过使角度变更机构M在图1中沿左右移动，可以控制上述倾斜角θ。
需要说明的是，在第一辊R1与第二辊R2这一对辊间，将第一透明保护膜B1和第二透明保护膜B2隔着粘接层(未图示)而贴合在偏振片A的两面。上述粘接层既可以设置于第一透明保护膜B1、第二透明保护膜B2，也可以设置于偏振片A，还可以设置于两者。另外，可以通过在即将将偏振片A和第一透明保护膜B1、第二透明保护膜B2贴合之前，与调整好浓度或粘度的胶粘剂(溶液)或粘合剂(溶液)一起穿过第一辊R1与第二辊R2这一对辊间，从而进行压接。
需要说明的是，可以对辊的材质、辊直径、贴合时的搬送速度等适当地调整，另外，对粘接层的厚度也可以适当地调整。
作为上述第一辊R1、第二辊R2，例如可以使用弹性辊、金属辊中的任一种。第一辊R1、第二辊R2既可以相同，也可以不同。
作为弹性辊，可以优选使用金属制的芯部由橡胶层或树脂层涂布后的弹性辊。作为该橡胶层或树脂层的硬度，优选使用70以上的硬度，更优选使用80以上的硬度，进一步优选使用85以上的硬度。另外，为了防止膜表面的损伤，优选为100以下的硬度，更优选为95以下的硬度。作为此时的硬度，例如可以利用JIS K6253(1997)中公开的方法，使用市售的硬度计(A型)进行测定。需要说明的是，对于橡胶层或树脂层的厚度，从面压分布的均匀性的方面考虑，优选为1～15mm左右，更优选为3～10mm左右。
作为金属辊的材料，例如可以举出铁、不锈钢、钛、铝等。作为金属辊，从性价比及耐腐蚀性的方面考虑，适合为铁辊或不锈钢辊。
此外，作为上述辊的直径，由于直径越小则偏振片A与第一透明保护膜B1、第二透明保护膜B2所接触的面积就越小，因此施加于膜面的压力相对地变高。因此，作为辊的直径，优选使用250mm以下的直径，更优选使用200mm以下的直径。但是，如果该直径过小，则辊的耐久性变弱，因此无法施加足够的力，因而优选使用50mm以上的辊，更优选使用100mm以上的辊。
另外，贴合时的搬送速度没有特别限制，通常优选在2m／分钟～50m／分钟左右来调整。
另外，贴合时的辊间的层压压力没有特别限制，可以适当地设定。从调整的容易度或偏振板的生产率的方面考虑，层压压力优选为2MPa以上且5MPa以下左右，更优选为3MPa以上且4MPa以下。如果层压压力小于2MPa，则无法进行充分的挤压，因此会在膜间产生气泡。另外，如果层压压力大于5MPa，则会对辊或装置施加过度的负载，因此成为造成破损的原因。层压压力的测定是使用富士胶片公司制的压敏纸“Presscale”，将该压敏纸的颜色变化利用计算机图像处理进行二值化，利用对其发色面积和浓度所制作出的压力标准线的近似式来求出。
偏振片没有特别限制，可以使用各种的偏振片。作为偏振片，例如可以举出：使聚乙烯醇系膜、部分缩甲醛化聚乙烯醇系膜、乙烯·乙酸乙烯酯共聚物系部分皂化膜等亲水性高分子膜吸附碘或二色性染料等二色性材料而经单轴拉伸后的材料，聚乙烯醇的脱水处理物或聚氯乙烯的脱盐酸处理物等聚烯系取向膜等。它们当中优选为包含聚乙烯醇系膜和碘等二色性物质的偏振片。这些偏振片的厚度没有特别限制，然而一般来说为5～80μm左右。偏振片的厚度优选为15～35μm。如果偏振片的厚度过薄，则在与透明保护膜贴合时，容易受到损伤。另一方面，如果偏振片的厚度过厚，则干燥效率有变差的趋势，在生产率的方面不够理想。
就将聚乙烯醇系膜用碘染色而经单轴拉伸后的偏振片而言，例如可以通过将聚乙烯醇浸渍在碘的水溶液中而染色，拉伸到原长的3～7倍而制成。根据需要，也可以浸渍在硼酸或碘化钾等的水溶液中。此外，根据需要也可以在染色前将聚乙烯醇系膜浸渍在水中而进行水洗。通过将聚乙烯醇系膜水洗，从而除了可以清洗掉聚乙烯醇系膜表面的污物或防粘连剂以外，因使聚乙烯醇系膜膨润而还具有防止染色的不均等不均一的效果。拉伸既可以在用碘染色后进行，也可以一边染色一边拉伸，还可以在拉伸后用碘染色。也可以在硼酸或碘化钾等的水溶液中或水浴中进行拉伸。
另外，偏振片的水分率没有特别限制，通常来说优选水分率为8～30重量％，更优选为10～20重量％。偏振片的水分率越低，则干燥工序中的干燥效率就进一步提高，从而可以提高生产速度，从这种生产率的方面考虑而优选。另外，偏振片的水分率越低，就可以得到光学特性越好的偏振板，从这一点考虑而优选。另一方面，如果偏振片的水分率过低，则偏振片的作为膜而言的刚性提高，容易受到损伤，容易产生外观缺陷。此种偏振片的水分率一般可以利用偏振片的制造工序中的干燥处理的条件来调整，然而根据需要也可以另外设置调湿处理工序，可以实施向水浴中的浸渍或水滴的喷雾、或者再次的加热干燥或减压干燥。
另外，偏振片的制造方法并不限定于上述制造方法，只要满足水分率为8～30重量％(优选为水分率10～20重量％)，就可以使用其他的制造方法来制造偏振片。例如，可以是干式拉伸法，或者可以是向聚对苯二甲酸乙二醇酯(PET)等聚合物膜中炼入二色性物质并进行制膜、拉伸这样的方法，可举出将沿一个轴向取向的液晶作为主体(host)且在其中将二色性染料作为客体(guest)这样的O型的偏振片(美国专利5，523，863号、日本特表平3-503322号公报)、使用了二色性的溶致液晶等的E型的偏振片(美国专利6，049，428号)。
上述第一透明保护膜及第二透明保护膜的弹性模量没有特别限制，然而适合使用1000～10000MPa的范围的保护膜。上述弹性模量优选为1200～5000MPa，更优选为1300～4000MPa。需要说明的是，上述第一透明保护膜及第二透明保护膜只要在上述弹性方面具有差别，则上述第一透明保护膜及第二透明保护膜的弹性模量既可以相同，也可以不同。
上述透明保护膜的弹性模量是依照JIS K7127的拉伸试验法测得的值(N／mm2＝MPa)。具体来说，依照下述的基准来测定弹性模量。
求出弹性模量(曲线图的斜率)时的横轴：应变(strain)(％)
求出弹性模量(曲线图的斜率)时的纵轴：拉伸应力σ(MPa＝N／mm2)＝F／试验片的初期截面积A(mm2)
求出弹性模量(曲线图的斜率)时的范围：应变0.05～0.25％间的线性回归
试验片形状：带状(测定间距离100mm、宽50mm)
卡盘间距离：100mm
第一透明保护膜及第二透明保护膜的厚度可以适当地确定，然而一般来说从强度或处置性等操作性、薄层性等方面考虑，优选为20～200μm左右，更优选为30～100μm。第一透明保护膜及第二透明保护膜的厚度在上述范围中，则干燥效率好，可以使卷筒(原反)的卷长条化，因此从生产率的方面考虑而优选。另一方面，如果第一透明保护膜及第二透明保护膜的厚度变大，则干燥效率差，在生产率的方面不够理想。
对于第一透明保护膜及第二透明保护膜而言，以使利用上述弹性模量(MPa)×厚度(μm)的积所定义的弹性不同的方式，选择各自的弹性模量、厚度。对于上述第一透明保护膜及第二透明保护膜，将具有高弹性的一方定义为高弹性膜，将具有低弹性的一方定义为低弹性膜。
另外，对于上述高弹性膜的弹性与上述低弹性膜的弹性的差，从褶皱的观点考虑，优选为超过0且为170000以下的情况。特别是，在上述差为1000以上、进一步为3000以上的情况下，容易因弹性的差而产生应变，可以很好地应用本发明。
作为上述第一透明保护膜及第二透明保护膜，可以使用各种膜。上述第一透明保护膜及第二透明保护膜以使一方为高弹性膜而另一方为低弹性膜的方式来选择各自的材料、厚度。高弹性膜、低弹性膜的弹性的控制可以通过选择材料(弹性模量)不同的第一透明保护膜及第二透明保护膜来进行，在材料(弹性模量)相同的情况下，可以利用厚度来控制。
作为形成上述透明保护膜的材料，优选为透明性、机械强度、热稳定性、水分阻断性、各向同性等优异的材料。例如可以举出聚对苯二甲酸乙二醇酯或聚萘二甲酸乙二醇酯等聚酯系聚合物、二乙酰基纤维素或三乙酰基纤维素等纤维素系聚合物、聚甲基丙烯酸甲酯等丙烯酸系聚合物、聚苯乙烯或丙烯腈·苯乙烯共聚物(AS树脂)等苯乙烯系聚合物、聚碳酸酯系聚合物等。另外，作为形成上述透明保护膜的聚合物的例子，还可以举出聚乙烯、聚丙烯、环系或具有降冰片烯结构的聚烯烃、乙烯·丙烯共聚物这样的聚烯烃系聚合物、氯乙烯系聚合物、尼龙或芳香族聚酰胺等酰胺系聚合物、酰亚胺系聚合物、砜系聚合物、聚醚砜系聚合物、聚醚醚酮系聚合物、聚苯硫醚系聚合物、乙烯醇系聚合物、偏氯乙烯系聚合物、乙烯醇缩丁醛系聚合物、芳基化物系聚合物、聚甲醛系聚合物、环氧系聚合物、或上述聚合物的混合物等。需要说明的是，在偏振片上通常借助胶粘剂层来贴合透明保护膜，而作为透明保护膜，可以使用(甲基)丙烯酸系、氨基甲酸酯系、丙烯酰基氨基甲酸酯系、环氧系、硅酮系等的热固化性树脂或紫外线固化型树脂。在透明保护膜中也可以含有1种以上的任意的合适的添加剂。作为添加剂，例如可以举出紫外线吸收剂、抗氧化剂、润滑剂、增塑剂、脱模剂、防着色剂、阻燃剂、成核剂、防静电干扰剂、颜料、着色剂等。透明保护膜中的上述热塑性树脂的含量优选为50～100重量％，更优选为50～99重量％，进一步优选为60～98重量％，特别优选为70～97重量％。在透明保护膜中的上述热塑性树脂的含量为50重量％以下的情况下，有可能无法充分地体现出热塑性树脂本来具有的高透明性等。
作为本发明的透明保护膜，优选使用选自纤维素树脂(聚合物)、聚碳酸酯树脂(聚合物)、环状聚烯烃树脂(环系或具有降冰片烯结构的聚烯烃)及(甲基)丙烯酸类树脂中的任意至少一种。
另外，从偏振特性或耐久性及粘接特性提高等方面考虑，也可以对透明保护膜表面利用电晕处理、等离子体处理、火焰处理、臭氧处理、底涂处理、辉光处理、皂化处理来进行表面改性处理。这些表面改性处理当中，在作为透明保护膜而使用纤维素树脂(聚合物)的情况下，优选利用碱等进行皂化处理。
对上述透明保护膜的没有粘接偏振片的一面，也可以实施硬涂层或防反射处理、以抗粘连、扩散或防眩为目的的处理。
需要说明的是，上述防反射层、抗粘连层、扩散层、防眩层等，除了可以设置成透明保护膜本身以外，也可以以作为另外的光学层并与透明保护膜有区别的层的形式来设置。
上述粘接层没有特别限制，可以使用水系、溶剂系、热熔系、自由基固化型的各种形态的材料。上述偏振片与透明保护膜的贴合中所用的粘接层只要在光学上是透明的，就没有特别限制。在上述偏振片与透明保护膜的贴合中所用的粘接层的形成中，优选为水系胶粘剂或自由基固化型胶粘剂。
作为形成胶粘剂层的水系胶粘剂，没有特别限定，例如可以例示出乙烯基聚合物系、明胶系、乙烯基系胶乳系、聚氨酯系、异氰酸酯系、聚酯系、环氧系等。此种由水系胶粘剂构成的胶粘剂层可以以水溶液的涂布干燥层等形式而形成，而在该水溶液的制备时，根据需要，还可以配合交联剂或其他的添加剂、酸等催化剂。作为上述水系胶粘剂，优选使用含有乙烯基聚合物的胶粘剂等，作为乙烯基聚合物，优选聚乙烯醇系树脂。另外，在聚乙烯醇系树脂中，可以含有硼酸或硼砂、戊二醛或三聚氰胺、草酸等水溶性交联剂。特别是在作为偏振片而使用聚乙烯醇系的聚合物膜的情况下，从粘接性的方面考虑，优选使用含有聚乙烯醇系树脂的胶粘剂。此外，从提高耐久性的方面考虑，更优选含有具有乙酰乙酰基的聚乙烯醇系树脂的胶粘剂。
上述聚乙烯醇系树脂没有特别限定，然而从粘接性的方面考虑优选平均聚合度为100～3000左右，平均皂化度为85～100摩尔％左右。另外，作为胶粘剂水溶液的浓度，只要根据目标的胶粘剂层的厚度适当地决定即可，没有特别限定，然而优选为0.1～15重量％，更优选为0.5～10重量％。如果该溶液浓度过高，则粘度过度上升，因此容易产生条纹状的凹凸不均，如果溶液浓度过低，则涂布性变差，容易变得不均。
就聚乙烯醇系树脂而言，可以举出将聚乙酸乙烯酯皂化而得的聚乙烯醇；其衍生物；以及乙酸乙烯酯与具有共聚性的单体的共聚物的皂化物；将聚乙烯醇加以缩醛化、氨基甲酸酯化、醚化、接枝化、磷酸酯化等而成的改性聚乙烯醇。作为上述单体，可以举出马来酸(酐)、富马酸、巴豆酸、衣康酸、(甲基)丙烯酸等不饱和羧酸及其酯类，乙烯、丙烯等α
烯烃，(甲基)烯丙基磺酸(钠)、磺酸钠(单烷基马来酸酯)、二磺酸钠烷基马来酸酯、N羟甲基丙烯酰胺、丙烯酰胺烷基磺酸碱盐、N一乙烯基吡咯烷酮、N一乙烯基吡咯烷酮衍生物等。这些聚乙烯醇系树脂可以单独使用一种或并用两种以上。
含有乙酰乙酰基的聚乙烯醇系树脂可以使聚乙烯醇系树脂与双烯酮利用公知的方法进行反应而得到。例如可以举出将聚乙烯醇系树脂分散于乙酸等溶剂中再向其中添加双烯酮的方法，将聚乙烯醇系树脂预先溶解于二甲基甲酰胺或二噁烷等溶剂中再向其中添加双烯酮的方法等。另外，还可以举出使双烯酮气体或液状双烯酮直接与聚乙烯醇接触的方法。
含有乙酰乙酰基的聚乙烯醇系树脂的乙酰乙酰基改性度只要为0.1摩尔％以上，就没有特别限定。如果小于0.1摩尔％，则胶粘剂层的耐水性不够充分，因而不合适。乙酰乙酰基改性度优选为0.1～40摩尔％左右，更优选为1～20摩尔％，特别优选为2～7摩尔％。如果乙酰乙酰基改性度超过40摩尔％，则与交联剂的反应点变少，耐水性的提高效果小。此种乙酰乙酰基改性度可以使用核磁共振装置(NMR：Nuclear MagneticResonance)来测定。
作为交联剂，可以没有特别限定地使用一般在胶粘剂中使用的交联剂，例如在使用了如前所述的聚乙烯醇系树脂的胶粘剂的情况下，可以优选使用具有至少2个与聚乙烯醇系树脂具有反应性的官能团的化合物。例如，可以举出乙二胺、三亚乙基二胺、六亚甲基二胺等具有亚烷基和2个氨基的烷基二胺类；甲苯二异氰酸酯、氢化甲苯二异氰酸酯、三羟甲基丙烷甲苯二异氰酸酯加成物、三苯基甲烷三异氰酸酯、亚甲基双(4一苯基甲烷三异氰酸酯)、异佛尔酮二异氰酸酯及它们的酮肟封端物或苯酚封端物等异氰酸酯类；乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙三醇二缩水甘油醚或丙三醇三缩水甘油醚、1，6一己二醇二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、二缩水甘油基苯胺、二缩水甘油基胺等环氧类；甲醛、乙醛、丙醛、丁醛等单醛类；乙二醛、丙二醛、丁二醛、戊二醛、马来二醛、邻苯二甲醛等二醛类；羟甲基尿素、羟甲基三聚氰胺、烷基化羟甲基尿素、烷基化羟甲基三聚氰胺、甲基胍胺、苯胍胺与甲醛的缩合物等氨基甲醛树脂；以及钠、钾、镁、钙、铝、铁、镍等二价金属、或三价金属的盐及其氧化物。它们当中，优选为氨基甲醛树脂，特别优选为具有羟甲基的羟甲基化合物。
交联剂的配合量一般来说相对于树脂100重量份为0.1～35重量份左右，优选使用10～25重量份的交联剂，然而在重视胶粘剂的耐久性的情况下，为了改变从胶粘剂的制备到形成胶粘剂层的时间(可用时间)变短这一情况，配合30重量份以上且46重量份以下、更优选配合32重量份以上且40重量份以下的交联剂也是有效的。
作为自由基固化型胶粘剂，可以例示出电子束固化型、紫外线固化型等活性能量射线固化型、热固化型等的各种材料，然而优选能够在短时间内固化的活性能量射线固化型。特别优选紫外线固化型。
作为固化性成分，可以举出具有(甲基)丙烯酰基的化合物、具有乙烯基的化合物。这些固化性成分可以使用单官能的固化性成分或二官能以上的固化性成分中的任一种。另外，这些固化性成分可以单独使用1种、或组合使用2种以上。作为这些固化性成分，例如优选为具有(甲基)丙烯酰基的化合物，例如可以举出各种的环氧(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、或各种的(甲基)丙烯酸酯系单体等。
固化型胶粘剂含有固化性成分，而除了上述成分以外，还与固化的类型对应地添加自由基引发剂。在以电子束固化型使用上述胶粘剂的情况下，并非特别需要在上述胶粘剂中含有自由基引发剂，然而在以紫外线固化型、热固化型使用的情况下，使用自由基引发剂。对于自由基引发剂的使用量，在每100重量份固化性成分中，通常为0.1～10重量份左右，优选为0.5～3重量份。
另外，在上述胶粘剂中，可以含有金属化合物填料。通过金属化合物填料可以控制胶粘剂层的流动性，使膜厚稳定化，从而可以得到具有良好的外观、面内均匀且粘接性没有不均的偏振板。
另外，在胶粘剂层的形成中，可以优选使用能够在无溶剂或低溶剂状态下贴合的干式层压法。作为该干式层压法，只要使用以往公知的干式层压用胶粘剂及贴合方法即可，可以在本发明中使用该方法。由此，会有进一步减少条纹状的凹凸不均等的效果。
作为上述干式层压用胶粘剂，可以举出二液固化型胶粘剂、二液溶剂型胶粘剂、单液无溶剂型胶粘剂等。作为二液固化型胶粘剂，可以使用丙烯酸系的树脂等，作为二液溶剂型胶粘剂，可以使用聚酯系、芳香族聚酯系、脂肪族聚酯系、聚酯／聚氨酯系、聚醚／聚氨酯系的树脂等，作为单液无溶剂型胶粘剂(湿气固化型类型)，可以使用聚醚／聚氨酯系树脂等。
上述胶粘剂层如果需要也可以适当地含有添加剂。作为添加剂的例子，可以举出以羰基化合物等为代表的借助电子束来提高固化速度或灵敏度的敏化剂，硅烷偶联剂、钛偶联剂等偶联剂，以环氧乙烷为代表的粘接促进剂，提高与透明保护膜的润湿性的添加剂，以丙烯酰氧基化合物或烃系(天然、合成树脂)等为代表的提高机械强度或加工性等的添加剂，紫外线吸收剂、防老化剂、染料、加工助剂、离子捕获剂、抗氧化剂、增粘剂、填料(金属化合物填料以外)、增塑剂、流平剂、发泡抑制剂、防静电干扰剂、耐热稳定剂、耐水解稳定剂等稳定剂等。
通过在上述偏振片的两面隔着胶粘剂层来贴合透明保护膜，从而可以获得偏振板，然而也可以在胶粘剂层与透明保护膜、或胶粘剂层与偏振片之间设置底涂层或易粘接处理层等。
在利用上述制造方法形成的胶粘剂层由水系胶粘剂等形成的情况下，上述胶粘剂层的厚度优选为30～300nm。上述胶粘剂层的厚度更优选为60～250nm。另一方面，在胶粘剂层由固化型胶粘剂形成的情况下，上述胶粘剂层的厚度优选为0.1～200μm。更优选为0.5～50μm，进一步优选为0.5～10μm。
在上述偏振板的制造方法中，在将偏振片与透明保护膜贴合后，根据胶粘剂的种类，可实施固化工序。在使用水系胶粘剂的情况下，可实施干燥工序。干燥工序的干燥条件通常为干燥温度40～100℃左右、干燥时间1～10分钟左右。在自由基固化型胶粘剂的情况下，例如可照射电子束、紫外线等。
利用本发明的制造方法得到的偏振板在实际使用时可以以与其他的光学层层叠后的光学膜的形式来使用。对于该光学层，没有特别限定，然而例如可以使用1层或2层以上的反射板或半透射板、相位差板(包括1／2或1／4等的波长板)、视角补偿膜等有时在液晶显示装置等的形成中使用的光学层。特别是，优选为在本发明的偏振板上再层叠反射板或半透射反射板而成的反射型偏振板或半透射型偏振板、在偏振板上再层叠相位差板而成的楕圆偏振板或圆偏振板、在偏振板上再层叠视角补偿膜而成的广视角偏振板、或者在偏振板上再层叠亮度提高膜而成的偏振板。
本发明的偏振板或光学膜可以优选用于液晶显示装置等各种装置的形成等中。液晶显示装置的形成可以遵循惯例来进行。即，液晶显示装置一般来说通过将液晶单元和偏振板或光学膜、以及根据需要使用的照明系统等构成部件适当地组装后再装入驱动电路等来形成，而在本发明中除了使用本发明的偏振板或光学膜这点以外，没有特别限定，可以遵循惯例。对于液晶单元而言，例如也可以使用TN型或STN型、π型等任意类型的液晶单元。
可以形成在液晶单元的一侧或两侧配置有偏振板或光学膜的液晶显示装置、或在照明系统中使用了背光灯或反射板的装置等适当的液晶显示装置。该情况下，本发明的偏振板或光学膜可以设置于液晶单元的一侧或两侧。在两侧设置偏振板或光学膜的情况下，它们既可以相同，也可以不同。此外，在液晶显示装置的形成时，例如可以将扩散板、防眩层、防反射膜、保护板、棱镜阵列、透镜阵列片、光扩散板、背光灯等适当的部件在适当的位置配置1层或2层以上。
另外，本发明的制造方法可以适用于如下的带有粘合剂层的偏振板的制造方法，即，所述带有粘合剂层的偏振板使用偏振板作为第一膜，使用设有粘合剂层的间隔件作为第二膜，在偏振板上设有粘合剂层。另外，本发明的制造方法可以适用于如下的带有表面保护膜的偏振板或带有粘合剂层的偏振板的制造方法，即，所述带有表面保护膜的偏振板或带有粘合剂层的偏振板使用带有粘合剂层的偏振板或偏振板作为第一膜，使用表面保护膜作为第二膜。
在上述偏振板上层叠光学功能层的情况下，优选使用隔着胶粘剂层或粘合剂层来层叠的方法。作为此时的胶粘剂层或粘合剂层，特别优选使用由粘合剂构成的粘合剂层。
作为由粘合剂构成的粘合剂层，例如可以利用丙烯酸系、硅酮系、聚酯系、聚氨酯系、聚醚系、橡胶系等遵循惯例的适当的粘合剂来形成。作为该粘合剂，从防止由吸湿造成的发泡现象或剥离现象、防止由热膨胀差等造成的光学特性的降低或液晶单元的翘曲、以及高品质且耐久性优异的图像显示装置的形成性等方面考虑，优选为吸湿率低而耐热性优异的粘合剂层，此外，从防止偏振板等的光学特性的变化的方面考虑，优选固化或干燥时不需要高温的加工过程、且不需要长时间的固化处理或干燥时间的粘合剂层。从此种观点考虑，在偏振板或光学膜中优选使用丙烯酸系粘合剂。另外，也可以在上述粘合剂中添加微粒而制成显示出光扩散性的粘合剂层等。
此种胶粘剂层或粘合剂层只要根据需要设于必需的面即可，例如如果针对本发明这样的由偏振片和透明保护膜所得到的偏振板而言，则只要根据需要在偏振板的单面或两面，即，在透明保护膜中与偏振片贴附的相反一侧的面，设置粘合剂层即可。作为这样在为了层叠光学功能层而使用的情况下的由粘合剂构成的粘合剂层的干燥后的厚度而言，没有特别限定，然而一般来说为1～500μm左右，优选为5～200μm，更优选为10～100μm。通过将胶粘剂层或粘合剂层的厚度设为该范围，就可以缓解与偏振板或光学功能层的尺寸行为相伴的应力。
在上述由粘合剂构成的粘合剂层露出于表面的情况下，出于防止将该粘合剂层用于实用前这一期间的污染等目的，优选利用间隔件进行临时覆盖。间隔件优选使用：在依照上述的保护膜等的适当的膜上根据需要设有借助硅酮系或长链烷基系、氟系或硫化钼等适当的剥离剂的剥离涂层的间隔件。
另外，作为表面保护膜，可以使用按照在基材膜上设置粘合剂层，从而可以与该粘合剂层一起将基材膜剥离的方式所形成的膜。
通过在上述偏振片的两面隔着粘接层来贴合透明保护膜，从而可以得到偏振板，然而也可以在粘接层与透明保护膜或偏振片之间设置底涂层或易粘接处理层等。
[实施例]
以下使用实施例及比较例对本发明进行更具体的说明，然而本发明并不受这些实施例及比较例限定。
(偏振片的水分率测定方法)
从所得的偏振片中，切出180mm×500mm的样品，测定出其初期重量(W(g))。将该样品在120℃的干燥机内放置2小时后，测定出干燥后重量(D(g))。根据这些测定值，利用下式求出水分率。
水分率(％)＝{(W-D)／W}×100
(偏振片的制作)
使用厚75μm的聚乙烯醇膜((株)Kuraray制：VF-PS7500，宽1000mm)，在30℃的纯水中浸渍60秒的同时以2.5倍的拉伸倍率拉伸，在30℃的碘水溶液(重量比：纯水／碘(I)／碘化钾(KI)＝100／0.01／1)中染色45秒，在4重量％硼酸水溶液中以使拉伸倍率为5.8倍的方式拉伸，在纯水中浸渍10秒后，在保持膜的张力的状态下在60℃下干燥5分钟而得到偏振片。该偏振片的厚度为25μμm，水分率为15重量％。
(带有粘接层的透明保护膜的制作)
将PVA树脂(日本合成化学工业(株)制：Gohsenol)100重量份和交联剂(大日本油墨化学工业(株)制：WATERSOL)35重量份溶解于纯水3760重量份中而制备出胶粘剂。将该胶粘剂利用狭缝式模头涂布在厚60μm的三乙酰纤维素(TAC)膜(富士胶片公司制：TD60UL，弹性模量4000MPa)的单面侧后，在85℃下干燥1分钟，得到具有厚0.1μm的粘接层的带有粘接层的TAC膜。
实施例1
(偏振板的制作)
利用图1所示的方法，制作出偏振板。在偏振片A中使用上述偏振片，在第一透明保护膜B1中使用上述带有粘接层的TAC膜。在第二透明保护膜B2中，使用了带有粘接层的丙烯酸类膜。带有粘接层的丙烯酸类膜除了使用厚40μm的丙烯酸类膜(弹性模量2000MPa)来代替TAC膜而以外，与上述带有粘接层的TAC膜相同地制作。如图1所示，带有粘接层的TAC膜(第一透明保护膜B1)从第一辊R1侧搬送，带有粘接层的丙烯酸类膜(第二透明保护膜B2)从第二辊R2侧搬送。作为第一辊R1、第二辊R2，使用了直径200mm的铁辊。
(偏振片的投入角度的调整方法)
对于偏振片的搬送方向与中央线(第二假想线s2)所成的倾斜角θ，以中央线(第二假想线s2)作为0°，将向高弹性膜侧倾斜的情况设为正侧，将向低弹性膜侧倾斜的情况设为负侧。倾斜角θ是通过在层压部(接点p1)的上部60cm位置安装可动式的辊，使该辊向左右移动而进行调整的。
在上述中，各膜的搬送速度为20m／分钟。需要说明的是，利用上述操作得到的偏振板在贴合后在80℃下干燥2分钟。
实施例2～7、比较例1～9
在实施例1中，除了将第一透明保护膜、第二透明保护膜的种类、偏振片的倾斜角θ如表1所示地改变以外，与实施例1相同地操作而得到偏振板。
对实施例及比较例中制作的偏振板，进行了下述评价。将结果示于表1中。
(气泡的确认)
从所得的偏振板中切出1000mm×1000mm的样品，确认了偏振片与TAC膜之间的气泡的数目。
(搬送性)
基于下述基准评价了制造偏振板时的搬送性。
○：在搬送中在辊上没有引入褶皱等的情况。
×：在搬送中在辊上引入了褶皱的情况。
表1中，TAC：表示厚60μm的三乙酰纤维素膜(富士胶片公司制：TD60UL，弹性模量4000MPa)；
ACRYL：表示厚40μm的丙烯酸类膜(弹性模量2000MPa)；
COP：表示厚50μm的环状聚烯烃膜(日本ZEON公司制ZEONOR，弹性模量1800MPa)。但是，实施例5中使用了厚40μm的TAC。
从上述表1的结果可以清楚地看到，根据本发明的实施例，可以抑制在偏振片与透明保护膜之间产生的气泡，从而制造偏振板。实施例当中，倾斜角θ为1°以下的例子的搬送性也良好。

Claims (2)

1.一种偏振板的制造方法，其特征在于，是在偏振片的两面隔着粘接层贴合第一透明保护膜及第二透明保护膜的偏振板的制造方法，
其中，所述第一透明保护膜及第二透明保护膜的以弹性模量MPa×厚度μm的值所定义的弹性不同，将具有高弹性的一方定义为高弹性膜，将具有低弹性的一方定义为低弹性膜，
并且，将连结所述一对辊的各辊的中心点与在所述一对辊间将所述3片膜即所述偏振片、第一透明保护膜及第二透明保护膜贴合的接点的线定义为第一假想线，将与该第一假想线正交的方向的线定义为第二假想线，
在上述情况下，
通过将所述3片膜同时穿过一对辊间而压接，
并且，将所述偏振片投入到所述一对辊间而使之穿过的搬送方向比所述第二假想线更倾斜于高弹性膜一侧。
2.根据权利要求1所述的偏振板的制造方法，其特征在于，
所述第二假想线与偏振片的搬送方向所成的角度在超过0°且为1°以下的范围。
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