CN107429128B - 粘接膜及其制造方法 - Google Patents
粘接膜及其制造方法 Download PDFInfo
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- CN107429128B CN107429128B CN201680001518.4A CN201680001518A CN107429128B CN 107429128 B CN107429128 B CN 107429128B CN 201680001518 A CN201680001518 A CN 201680001518A CN 107429128 B CN107429128 B CN 107429128B
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Classifications
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Abstract
本发明提供一种在各种表面保护膜用途等中使用的粘接膜,其鱼眼少,机械强度和耐热性优异,尘埃的附着少,具有良好的粘接特性。该粘接膜在聚酯膜的至少一个面具有膜厚为10μm以下的粘接层,该粘接层含有玻璃化转变温度在0℃以下的树脂和抗静电剂。
Description
技术领域
本发明涉及粘接膜及其制造方法,涉及作为例如树脂板、金属板等的输送时、保管时、加工时的防止受伤和防止附着污染物用等的表面保护膜等,鱼眼少、机械强度和耐热性优异、尘埃的附着少、具有良好的粘接特性的粘接膜及其制造方法。
背景技术
目前,在树脂板、金属板和玻璃板等在输送时、保管时、加工时的防止受伤和防止附着污染物,液晶面板、偏光板等电子相关领域中使用的部件在加工时的防止受伤、防止附着粉尘或污染物,汽车在输送时、保管时的防止附着污染物以及保护汽车涂装以隔离酸雨,柔性印刷基板在镀敷和蚀刻处理时的保护等的用途中,表面保护膜被广泛地使用。
对这些表面保护膜要求:在树脂板、金属板和玻璃板等各种被粘附体的运输时、保管时或加工时等,对该被粘附体具有适度的粘接力,通过附着在被粘附体的表面,对该被粘附体的表面进行保护,在目的结束后容易剥离。为了解决这些课题,提出了将聚烯烃系的膜用于表面保护的方案(专利文献1、2)。
然而,由于作为表面保护膜基材使用聚烯烃系的膜,所以一般被称作“鱼眼”的、由于膜基材原料导致的胶状物或劣化物造成的缺陷不能被去除,例如,在贴合表面保护膜的状态下对被粘附体进行检查时,存在成为探测表面保护膜的缺陷等的障碍的问题。
另外,作为表面保护膜的基材,要求在与被粘附体进行贴合时等该基材不因各种加工时的张力而拉伸那样的具有一定程度的机械强度的膜,但由于聚烯烃系的膜一般来说机械强度差,所以存在不适用于由于重视生产效率而提高加工速度等所导致的高张力的加工的缺点。
而且,在为了提高加工速度或各种特性等的加工温度的高温化上,聚烯烃系的膜也由于热收缩稳定性不好而尺寸稳定性差。因此,要求即使进行高温加工时热变形也小、尺寸稳定性优异的膜。
另外,一般来说塑料膜存在剥离时或由于摩擦会产生静电(剥离带电或摩擦带电)使尘埃附着的缺点,特别对于避免异物的用途,例如在偏光板等的光学部件的制造工序中作为保护膜使用的情况下会成为问题。
现有技术文献
专利文献
专利文献1:日本特开平5-98219号公报
专利文献2:日本特开2007-270005号公报
发明内容
发明所要解决的课题
本发明是鉴于上述实际情况而完成的发明,其解决课题在于提供一种在各种表面保护膜用途等中使用的、鱼眼少、机械强度和耐热性优异、尘埃的附着少,具有良好的粘接特性的粘接膜。
用于解决课题的方法
本发明人鉴于上述实际情况,进行了潜心研究,结果发现:使用具有特定构成的粘接膜,能够容易地解决上述的课题,从而完成了本发明。
即,本发明的第一主旨在于一种粘接膜,其特征在于,在聚酯膜的至少一个面,具有膜厚为10μm以下的粘接层,该粘接层含有玻璃化转变温度在0℃以下的树脂和抗静电剂。
而且,本发明的第二主旨在于粘接膜的制造方法,其特征在于,在聚酯膜的至少一个面设置含有玻璃化转变温度在0℃以下的树脂和抗静电剂的涂布层后,至少在一个方向上进行拉伸。
发明的效果
根据本发明的粘接膜,能够提供作为各种表面保护膜,鱼眼少、机械强度和耐热性优异、尘埃的附着少、具有良好的粘接特性的膜,其工业价值高。
具体实施方式
为了解决课题的鱼眼的降低、机械强度的提高以及耐热性的提高,想到需要大幅改变基材膜的基础材料,进行了各种研究,结果发现,通过使用与现有使用的聚烯烃系材料大不相同的聚酯系的材料,能够达到上述要求。然而,由于大幅改变了基材膜的材料系,粘接特性会大幅度降低,使用一般的聚酯膜如论如何都无法达到。因此,通过在基材膜上设置粘接层以图进行改善,从而完成了本发明。
构成粘接膜的聚酯膜可以是单层结构也可以是多层结构,除了2层、3层结构以外,只要是不超出本发明的主旨的范围内,还可以是4层或其以上的多层,没有特别限定。优选为2层以上的多层结构,使各个层具有特征谋求多功能化。
所使用的聚酯可以是均聚聚酯也可以是共聚聚酯。由均聚聚酯构成的情况下,优选使芳香族二羧酸与脂肪族二醇缩聚得到的均聚聚酯。作为芳香族二羧酸可以列举对苯二甲酸、2,6-萘二羧酸等,作为脂肪族二醇可以列举乙二醇、一缩二乙二醇、1,4-环己烷二甲醇等。作为代表性的聚酯可以例示聚对苯二甲酸乙二醇酯等。另一方面,作为共聚聚酯的二羧酸成分可以列举间苯二甲酸、邻苯二甲酸、对苯二甲酸、2,6-萘二羧酸、己二酸、癸二酸、羟基羧酸(例如,对羟基苯甲酸等)等的一种或两种以上,作为二醇成分可以列举乙二醇、一缩二乙二醇、丙二醇、丁二醇、4-环己烷二甲醇、新戊二醇等的一种或两种以上。
从制成能够耐受各种加工条件的膜的观点出发,优选机械强度和耐热性(加热时的尺寸稳定性)高,因此有时优选共聚聚酯成分少。具体的说,形成共聚聚酯的单体在聚酯膜中所占的比例通常为10摩尔%以下、优选为5摩尔%以下的范围,进一步优选为在均聚聚酯聚合时作为副产物生成的程度,即含有3摩尔%以下的二醚成分的程度。作为聚酯更优选的形态而言,考虑到机械强度和耐热性,在上述化合物之中,更优选由对苯二甲酸和乙二醇聚合而成的聚对苯二甲酸乙二醇酯或者聚萘二甲酸乙二醇酯形成的膜,从制造的容易程度、作为表面保护膜等的用途的操作性考虑,更优选由聚对苯二甲酸乙二醇酯形成的膜。
作为聚酯的聚合催化剂,没有特别限制,能够使用现有公知的化合物,可以列举例如锑化合物、钛化合物、锗化合物、锰化合物、铝化合物、镁化合物、钙化合物等。其中,从廉价的观点出发,优选锑化合物,另外,钛化合物、锗化合物由于催化剂活性高,以少量就能够进行聚合,在膜中残留的金属量少,所以使膜的透明性变高,因此优选。而且,由于锗化合物昂贵,所以更优选使用钛化合物。
在为使用钛化合物得到的聚酯的情况下,钛元素含量通常为50ppm以下,优选1~20ppm,进一步优选为2~10ppm的范围。若钛化合物的含量过多,则在将聚酯熔融挤出的工序中聚酯的劣化被促进,有时成为黄色感强的膜,另外,若含量过少,则聚合效率差,有导致成本上升或无法得到具有充分强度的膜的情况。另外,在使用利用钛化合物得到的聚酯的情况下,出于抑制熔融挤出工序中的劣化的目的,为了降低钛化合物的活性优选使用磷化合物。作为磷化合物,考虑聚酯的生产效率和热稳定性,优选正磷酸。磷元素含量为,相对于熔融挤出的聚酯量,通常为1~300ppm,优选为3~200ppm,进一步优选为5~100ppm的范围。若磷化合物的含量过多,有可能成为胶化和异物的原因,另外,若含量过少,则不能充分降低钛化合物的活性,有时成为具有黄色感的膜。
以赋予易滑性、防止在各工序中产生损伤、提高抗粘连特性为目的,也可以在聚酯层中配合颗粒。配合颗粒的情况下,配合的颗粒的种类只要是能够赋予易滑性的颗粒就没有特别限定,作为具体例可以列举例如:二氧化硅、碳酸钙、碳酸镁、碳酸钡、硫酸钙、磷酸钙、磷酸镁、高岭土、氧化铝、氧化锆、氧化钛等的无机颗粒;丙烯酸树脂、苯乙烯树脂、尿素树脂、酚醛树脂、环氧树脂、苯并胍胺树脂等有机颗粒等。而且,还能够使用在聚酯制造工序中使催化剂等金属化合物的一部分沉淀、微分散而得到的析出颗粒。这些之中,特别是从容易以少量表现效果的观点出发,优选二氧化硅颗粒、碳酸钙颗粒。
颗粒的平均粒径通常为10μm以下,优选为0.01~5μm,进一步优选为0.01~3μm的范围。若平均粒径超过10μm,则有时会担忧膜的透明性降低导致的不良情况。
进而,聚酯层中的颗粒含量虽然与颗粒的平均粒径需要兼顾所以不能一概而论,但通常为5重量%以下,优选为0.0003~3重量%的范围,进一步优选为0.0005~1重量%的范围。若颗粒含量超过5重量%的情况下,有时会担忧颗粒的脱落或膜的透明性降低等不良情况。若没有颗粒的情况下,或者颗粒少的情况下,由于有滑动性不充分的情况,所以有时需要想办法通过在粘接层中加入颗粒来提高滑动性等。
对于所使用的颗粒的形状也没有特别限定,可以使用球状、块状、棒状、扁平状等任意形状。另外,对于其硬度、比重、颜色等也没有特别限制。这些一系列的颗粒可以依照需要并用2种以上。
作为向聚酯层中添加颗粒的方法,没有特别限定,可以采用现有公知的方法。例如,可以在制造构成各层的聚酯的任意的阶段进行添加,但优选在酯化或酯交换反应结束后添加为好。
聚酯膜中,除了上述的颗粒以外,还能够按照需要添加现有公知的紫外线吸收剂、抗氧化剂、抗静电剂、热稳定剂、润滑剂、染料、颜料等。
聚酯膜的厚度只要是能够作为膜进行制膜的范围就没有特别限定,通常为2~350μm,优选为5~200μm,进一步优选为8~75μm的范围。
对于膜的制造例进行具体的说明,但不受以下的制造例的任何限定,能够采用通常已知的制膜法。
一般来说,通过将树脂熔融、片材化后,以提高强度等为目的进行拉伸,制作成膜。
例如,制造双轴拉伸聚酯膜的情况下,可以列举以下的方法。
该方法为:首先,使用挤出机将聚酯原料从模具熔融挤出,使用冷却辊将熔融片材冷却固化得到未拉伸片材。这种情况下,为了提高片材的平面性,优选提高片材与旋转冷却筒的密合性,优选采用静电施加密合法或液体涂布密合法;
接下来,将得到的未拉伸片材沿一个方向使用辊或拉幅机方式的拉伸机进行拉伸。拉伸温度通常为70~120℃,优选为80~110℃,拉伸倍率通常为2.5~7倍,优选为3.0~6倍;
接下来,沿与第一阶段的拉伸方向垂直的方向进行拉伸。拉伸温度通常为70~170℃,拉伸倍率通常为2.5~7倍,优选为3.0~6倍;
继而,在180~270℃的温度在拉紧状态下或在30%以内的松弛状态下进行热处理,得到双轴取向膜。
在上述的拉伸中,也能够采用以两阶段以上进行一个方向的拉伸的方法。这种情况下,优选以最终使两个方向的拉伸倍率分别为上述范围的方式进行。
另外,对于构成粘接膜的聚酯膜的制造,也能够采用同时双轴拉伸法。同时双轴拉伸法是,将上述的未拉伸片材控制在通常为70~120℃、优选为80~110℃的温度的状态下沿机械方向和宽度方向同时进行拉伸使其取向的方法,作为拉伸倍率,以面积倍率计通常为4~50倍,优选为7~35倍,进一步优选为10~25倍。之后,继而,通常在180~270℃的温度在紧拉下或在30%以内的松弛下进行热处理,得到拉伸取向膜。采用上述的拉伸方式的同时双轴拉伸装置能够采用螺旋方式、缩放(pantograph)方式、线性驱动方式等现有公知的拉伸方式。
接下来对于构成粘接膜的粘接层的形成进行说明。作为粘接层的形成方法可以列举例如涂敷、转印、层压等方法。从粘接层的形成的容易程度考虑,优选通过涂敷形成。
作为通过涂敷进行的方法,可以是通过在膜制造的工序内进行的在线涂敷方式设置,也可以通过将事先制造的膜在体系外进行涂敷的离线涂敷进行设置。更优选通过在线涂敷形成。
在线涂敷具体地说,是在将形成膜的树脂从熔融挤出直至拉伸后热固定并卷起为止的任意阶段进行涂敷的方法。通常是对于熔融、骤冷得到的未拉伸片材,经过拉伸的单轴拉伸膜,热固定前的双轴拉伸膜,热固定后卷起前的膜的任意种进行涂敷。虽不限定为以下的方法,但在例如依次双轴拉伸中,特别是优选在沿长度方向(纵向)拉伸的单轴拉伸膜进行涂敷后沿横向进行拉伸的方法。根据所述方法,由于能够将制膜和粘接层形成同时进行,所以在制造成本上有优势,另外,由于在涂敷后进行拉伸,所以也能够使粘接层的厚度通过拉伸倍率进行变化,与离线涂敷相比,更容易进行薄膜涂敷。
另外,通过在拉伸前在膜上设置粘接层,能够将粘接层与基材膜一起拉伸,由此能够使粘接层牢固地密合于基材膜。而且,在双轴拉伸聚酯膜的制造中,通过使用夹子等一边将膜端部夹住一边拉伸,能够在纵向和横向上限制膜,在热固定工序中,能够不产生褶皱等在维持平面性的状态下来施加高温。
因此,由于能够使在涂敷后实施的热处理达到其他方法无法达到的高温,所以使粘接层的成膜性提高,能够使粘接层与基材膜更牢固地密合,进而,能够形成牢固的粘接层。特别对于使交联剂反应是非常有效。
根据上述的通过在线涂敷的工序,由于粘接层的形成有无不会使膜尺寸有大的变化,受伤或附着异物的风险也不会随粘接层的形成有无而有大的变化,因此,相比另外进行一个涂敷工序的离线涂敷具有大的优点。而且,进行各种研究的结果,发现在线涂敷还具有能够减少将本发明的膜贴合在被粘附体时的粘接层的成分的转移、也就是减少胶残留的优点。这被认为是由于能够以离线涂敷中不能得到的高温进行热处理,粘接层与基材膜更加牢固地密合的结果。
在本发明中,必要条件是具有包含玻璃化转变温度在0℃以下的树脂和抗静电剂的膜厚为10μm以下的粘接层。
发明人发现,通过使用玻璃化转变温度在0℃以下的树脂,能够赋予聚酯膜适度的粘接特性。作为玻璃化转变温度在0℃以下的树脂能够使用现有公知的树脂。作为树脂的具体例可以列举聚酯树脂、丙烯酸树脂、聚氨酯树脂、聚乙烯树脂(聚乙烯醇、氯乙烯-乙酸乙烯酯共聚物等)等,其中特别是在考虑粘接特性或涂布性时,优选聚酯树脂、丙烯酸树脂、聚氨酯树脂。进一步,考虑到较强力的粘接特性或膜的再利用性,优选聚酯树脂、丙烯酸树脂,另外,考虑到与作为基材的聚酯膜的密合性或与聚酯系材料的贴合的情况下,优选聚酯树脂,考虑到更强力的粘接特性或与丙烯酸系材料的贴合、降低向被粘附体的粘接成分的转移(残胶)、与背面侧的粘连特性的情况下,最优选丙烯酸树脂。
聚酯树脂是指,可以列举作为主要构成成分例如后述的多元羧酸和多元羟基化合物构成的物质。即,作为多元羧酸能够使用对苯二甲酸、间苯二甲酸、邻苯二甲酸、酞酸、4,4'-联苯二羧酸、2,5-萘二羧酸、1,5-萘二羧酸和2,6-萘二羧酸、2,7-萘二羧酸、1,4-环己烷二羧酸、2-钾代磺基对苯二甲酸、5-钠代磺基间苯二甲酸、己二酸、壬二酸、癸二酸、十二烷二羧酸、戊二酸、琥珀酸、偏苯三酸、均苯三酸、苯均四酸、偏苯三酸酐、苯二甲酸酐、对羟基苯甲酸、偏苯三酸单钾盐和这些的酯形成性衍生物等,作为多元羟基化合物能够使用乙二醇、1,2-丙二醇、1,3-丙二醇(propyleneglycol)、1,3-丙烷二醇(propanediol)、1,4-丁二醇、1,6-己二醇、2-甲基-1,5-戊二醇、新戊二醇、1,4-环己烷二甲醇、对苯二甲醇、双酚A-乙二醇加成物、一缩二乙二醇、二缩三乙二醇、聚乙二醇、聚丙二醇、聚丁二醇、聚氧亚丁基二醇、二羟甲基丙酸、甘油、三羟甲基丙烷、二羟甲基乙磺酸钠、二羟甲基丙酸钾等。这些化合物之中,各自适当选取1种以上,通过常规方法进行缩聚反应合成聚酯树脂即可。
上述之中,为了使玻璃化转变温度降低至0℃以下,优选构成成分中含有脂肪族多元羧酸、脂肪族多元羟基化合物。一般来说,聚酯树脂是由芳香族多元羧酸和还含有脂肪族的多元羟基化合物构成,因此为了使玻璃化转变温度低于通常的聚酯树脂的玻璃化转变温度,含有脂肪族多元羧酸是有效的。从降低玻璃化转变温度的观点出发,脂肪族多元羧酸之中,碳原子数多的比较好,碳原子数通常为6以上(己二酸),优选为8以上,进一步优选为10以上的范围,上限通常为20。
另外,从提高粘接特性的观点出发,作为上述脂肪族多元羧酸在聚酯树脂中的酸成分中的含量,通常为2摩尔%以上,优选为4摩尔%以上,进一步优选为6摩尔%以上,特别优选为10摩尔%以上,上限通常为50摩尔%。
在脂肪族多元羟基化合物中,为了降低玻璃化转变温度,优选碳原子数为4以上(丁二醇),作为其在聚酯树脂中的羟基成分的含量,通常为10摩尔%以上,优选为30摩尔%以上的范围。
考虑到对于在线涂敷的适应性,优选制成水系,为此优选聚酯树脂中含有磺酸、磺酸金属盐、羧酸、羧酸金属盐。特别是从在水中的分散性良好的点出发,优选磺酸、磺酸金属盐,特别优选磺酸金属盐。
使用上述的磺酸、磺酸金属盐、羧酸、羧酸金属盐的情况下,作为在构成聚酯树脂中的酸成分中的含量,通常为0.1~10摩尔%,优选为0.2~8摩尔%的范围。通过在上述范围内使用能够使在水中的分散性良好。
另外考虑到在线涂敷涂布层的涂布外观、对于聚酯膜的密合性或粘连、进而考虑到作为表面保护膜使用的情况下减少对于被粘附体的残胶,作为聚酯树脂中的酸成分,优选在一定程度上含有芳香族多元羧酸。作为在聚酯树脂中的酸成分中的比例,芳香族多元羧酸通常为30摩尔%以上,优选为50摩尔%以上,进一步优选为60摩尔%以上的范围,上限通常为98摩尔%。另外,在芳香族多元羧酸之中从粘接特性的观点出发,对苯二甲酸、间苯二甲酸等苯环结构优于萘环结构。为了进一步提高粘接特性优选同时使用2种以上的芳香族多元羧酸。
用于提高粘接特性的聚酯树脂的玻璃化转变温度必须为0℃以下,优选为-10℃以下,进一步优选为-20℃以下的范围,下限通常为-60℃。通过以上述范围使用,容易制成具有最适合的粘接特性的膜。
丙烯酸树脂是指由含有丙烯酸系、甲基丙烯酸系的单体的聚合性单体构成的聚合物(以下,有将丙烯酸和甲基丙烯酸合起来缩写为(甲基)丙烯酸的情况)。这些可以是均聚物或者共聚物,进而可以是与丙烯酸系、甲基丙烯酸系的单体以外的聚合性单体的共聚物中的任意种。
另外,还包含这些聚合物与其它的聚合物(例如聚酯、聚氨酯等)的共聚物。例如为嵌段共聚物、接枝共聚物。或者,还包含在聚酯溶液或者聚酯分散液中将聚合性单体聚合得到的聚合物(根据情况会是聚合物的混合物)。同样地,还包含在聚氨酯溶液、聚氨酯分散液中将聚合性单体聚合得到的聚合物(根据情况会是聚合物的混合物)。同样地还包含在其他的聚合物溶液或分散液中将聚合性单体聚合得到的聚合物(根据情况会是聚合物混合物)。然而,考虑到粘接特性、在被粘附体的残胶,优选不含有聚酯或聚氨酯等其他的聚合物(仅由含有碳-碳双键的聚合性单体(可以是均聚物也可以是共聚物)构成的(甲基)丙烯酸树脂)。
作为上述聚合性单体没有特别限定,特别是作为代表性的化合物可以列举例如:丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、富马酸、马来酸、柠康酸这样的各种含有羧基的单体类以及这些的盐;(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、羟基富马酸单丁酯、羟基衣康酸单丁酯这样的各种的含有羟基的单体类;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸月桂酯这样的各种(甲基)丙烯酸酯类;(甲基)丙烯酰胺、二丙酮丙烯酰胺、N-羟甲基丙烯酰胺或(甲基)丙烯腈等各种含氮的化合物;苯乙烯、α-甲基苯乙烯、二乙烯基苯、乙烯基甲苯这样的各种苯乙烯衍生物;丙酸乙烯酯、乙酸乙烯酯这样的各种的乙烯基酯类;γ-甲基丙烯酰氧丙基三甲氧基硅烷、乙烯基三甲氧基硅烷等各种含硅的聚合性单体类;含磷的乙烯系单体类;氯乙烯、偏氯乙烯这样的各种的卤化乙烯类;丁二烯这样的各种共轭二烯类。
为了使玻璃化转变温度降低至0℃以下,需要使用均聚物的玻璃化转变温度在0℃以下的(甲基)丙烯酸系,可以列举例如:丙烯酸乙酯(玻璃化转变温度:-22℃)、丙烯酸正丙酯(玻璃化转变温度:-37℃)、丙烯酸异丙酯(玻璃化转变温度:-5℃)、丙烯酸正丁酯(玻璃化转变温度:-55℃)、丙烯酸正己酯(玻璃化转变温度:-57℃)、丙烯酸-2-乙基己酯(玻璃化转变温度:-70℃)、丙烯酸正辛酯(玻璃化转变温度:-65℃)、丙烯酸异辛酯(玻璃化转变温度:-83℃)、丙烯酸正壬酯(玻璃化转变温度:-63℃)、甲基丙烯酸正壬酯(玻璃化转变温度:-35℃)、丙烯酸异壬酯(玻璃化转变温度:-82℃)、丙烯酸正癸酯(玻璃化转变温度:-70℃)、甲基丙烯酸正癸酯(玻璃化转变温度:-45℃)、丙烯酸异癸酯(玻璃化转变温度:-55℃)、甲基丙烯酸异癸酯(玻璃化转变温度:-41℃)、丙烯酸十二烷基酯(玻璃化转变温度:-30℃)、甲基丙烯酸十二烷基酯(玻璃化转变温度:-65℃)、丙烯酸十三烷基酯(玻璃化转变温度:-75℃)、甲基丙烯酸十三烷基酯(玻璃化转变温度:-46℃)、丙烯酸十四烷基酯(玻璃化转变温度:-56℃)、丙烯酸(2-羟基乙基)酯(玻璃化转变温度:-15℃)等。
上述之中,为了提高粘接特性,为烷基的碳原子数通常为4以上、优选为4~30、进一步优选为4~20、特别优选为4~14的范围的(甲基)丙烯酸烷基酯。从工业上被大量生产、操作性和供应稳定性的观点出发,含有丙烯酸正丁酯、丙烯酸-2-乙基己酯的(甲基)丙烯酸树脂是最合适的。
在酯末端具有碳原子数为4以上的烷基的(甲基)丙烯酸酯单元在(甲基)丙烯酸树脂中的含量通常为20重量%以上,优选为35~99重量%,进一步优选为50~98重量%,特别优选为65~95重量%,最优选为75~90重量%的范围。在酯末端具有碳原子数为4以上的烷基的(甲基)丙烯酸酯单元的含量越多,粘接特性越强。相反,在含量过少的情况下,也有粘接力不够充分的情况。
上述(甲基)丙烯酸树脂中,均聚物的玻璃化转变温度在0℃以下,在酯末端具有碳原子数不足4的烷基的(甲基)丙烯酸酯单元的含量通常为50重量%以下,优选为40重量%以下,进一步优选为30重量%以下的范围。通过以上述范围使用,可以具有良好的粘接特性。
另外,从能够降低粘接成分向被粘附体的转移的观点出发,上述之中优选在酯末端含有碳原子数为2以下的化合物或具有环状结构的化合物,进一步优选碳原子数为1的化合物或芳香族化合物。作为具体例可以列举甲基丙烯酸甲酯,丙烯腈,苯乙烯,丙烯酸环己酯作为优选化合物。
(甲基)丙烯酸树脂中的上述在酯末端含有碳原子数为2以下的化合物单元的含量通常为50重量%以下,优选为1~40重量%,进一步优选为3~30重量%,特别优选为5~20重量%的范围。该单元的含量少时,能够在不使粘接特性大幅降低的前提下,赋予适度范围的粘接特性,另外,相反地,含量多时,则能够减少粘接成分向被粘附体的转移。因此,只要是在上述范围,就容易达到粘接特性和降低转移这两个目的。
上述(甲基)丙烯酸树脂中,具有环状结构的化合物单元的含量通常为50重量%以下,优选为1~45重量%,进一步优选为5~40重量%的范围。该单元含量少时,则能够在不使粘接特性大幅降低的前提下,赋予适度范围的粘接特性,另外,相反地,含量多时,则能够减少粘接成分向被粘附体的转移。因此,只要是在上述范围,就容易达到粘接特性和降低转移这两个目的
从粘接特性的观点出发,作为构成(甲基)丙烯酸树脂的单体,均聚物的玻璃化转变温度在0℃以下的单体的含量,作为相对于(甲基)丙烯酸树脂整体的比例,通常为30重量%以上,优选为45重量%以上,进一步优选为60重量%以上,特别优选为70重量%以上的范围。另外,上限通常为99重量%。通过在该范围内使用,容易得到良好的粘接特性。
另外,使粘接特性提高的均聚物的玻璃化转变温度在0℃以下的单体的玻璃化转变温度通常为-20℃以下,优选为-30℃以下,进一步优选为-40℃以下,特别优选为-50℃以下,下限通常为-100℃。通过在该范围内使用,能够使制造具有适度的粘接特性的膜变得容易。
作为用于提高粘接特性的更适当的(甲基)丙烯酸树脂的形态,丙烯酸正丁酯和丙烯酸-2-乙基己酯在(甲基)丙烯酸树脂中的合计含量通常为30重量%以上,优选为40重量%以上,进一步优选为50重量%以上,特别优选为60重量%以上,最优选为70重量%以上的范围,上限通常为99重量%。特别是想要通过使用少量交联剂使粘接成分不向被粘附体转移的情况下,虽然依所使用的(甲基)丙烯酸树脂的组成或粘接层的组成而不同,但丙烯酸-2-乙基己酯的含量通常为90重量%以下,优选为80重量%以下的范围。
另外,考虑到在线涂敷中的适用等,为了制成能够用于水系的(甲基)丙烯酸树脂,也可以导入各种亲水性官能团。作为亲水性官能团优选列举羧酸基、羧酸盐基、磺酸基、磺酸盐基、羟基,其中从耐水性的观点优选羧酸基、羧酸盐基、羟基。
作为羧酸的导入,可以列举使丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、富马酸、马来酸、柠康酸这样各种含有羧基的单体共聚。上述之中,由于能够有效地在水中分散,优选丙烯酸、甲基丙烯酸。
羟基的导入可以列举使(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、羟基富马酸单丁酯、羟基衣康酸单丁酯这样的各种含羟基的单体共聚。上述之中,考虑到工业上的操作容易性,优选(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸4-羟基丁酯。
另外,作为交联反应基,也可以含有如(甲基)丙烯酸二甲基氨基乙酯这样的含有氨基的单体的共聚物或如(甲基)丙烯酸缩水甘油酯这样的含有环氧基的单体的共聚物。然而,若含量过多则对粘接特性有影响,所以需要设为适度的量。
(甲基)丙烯酸树脂中的含有亲水性官能团的单体的比例通常为30重量%以下,优选为1~20重量%,进一步优选为2~15重量%,特别优选为3~10重量%的范围。通过在上述范围内使用,容易在水系中展开。
用于提高粘接特性的(甲基)丙烯酸树脂的玻璃化转变温度必须是0℃以下,优选为-10℃以下,进一步优选为-20℃以下的范围,特别优选为-30℃以下的范围,下限通常为-80℃。通过在上述范围内使用,容易制成具有最合适的粘接特性的膜。另外,在需要考虑降低粘接成分向被粘附体的转移的情况下,通常为-70℃以上,优选为-60℃以上,进一步优选为-50℃以上的范围。
聚氨酯树脂是指在分子内具有氨酯键的高分子化合物,通常通过多元醇与异氰酸酯的反应制造。作为多元醇,可以列举聚碳酸酯多元醇类、聚醚多元醇类、聚酯多元醇类、聚烯烃多元醇类、丙烯酸多元醇类,这些化合物可以单独使用,也可以使用多种。
聚碳酸酯多元醇类由多元醇类与碳酸酯化合物通过脱醇反应得到。作为多元醇类,可以列举乙二醇,1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇1,4-环己二醇、1,4-环己烷二甲醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、新戊二醇、3-甲基-1,5-戊二醇、3,3-二羟甲基庚烷等。作为碳酸酯化合物可以列举碳酸二甲酯、碳酸二乙酯、碳酸二苯酯,碳酸亚乙酯等,作为由这些的反应得到的聚碳酸酯系多元醇类,可以列举例如聚(1,6-亚己基)碳酸酯、聚(3-甲基-1,5-亚戊基)碳酸酯等。
从提高粘接特性的观点出发,优选链状的烷基链的碳原子数通常为4~30、优选为4~20、进一步优选为6~12的范围的二元醇成分构成的聚碳酸酯多元醇。其中,从工业上的大量生产、操作性和供应稳定性好的观点上,含有1,6-己二醇或者选自1,4-丁二醇、1,5-戊二醇、1,6-己二醇中的至少2种二元醇的共聚聚碳酸酯多元醇是最适合的。
作为聚醚多元醇类,可以列举聚乙二醇、聚丙二醇、聚乙烯丙烯二醇、聚四亚甲基醚二醇、聚六亚甲基醚二醇等。
从提高粘接特性的观点出发,形成聚醚的单体是含有碳原子数通常为2~30、优选为3~20、进一步优选为4~12的范围的脂肪族二醇、特别直链脂肪族二醇的聚醚多元醇。
作为聚酯多元醇类,可以列举:由多元羧酸(丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、癸二酸、富马酸、马来酸、对苯二甲酸、间苯二甲酸等)或这些的酸酐与多元醇(乙二醇、一缩二乙二醇、二缩三乙二醇、丙二醇、一缩二丙二醇、二缩三丙二醇、丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、2-甲基-1,3-丙二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、2-甲基-2,4-戊二醇、2-甲基-2-丙基-1,3-丙二醇、1,8-辛二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇、2,5-二甲基-2,5-己二醇、1,9-壬二醇、2-甲基-1,8-辛二醇、2-丁基-2-乙基-1,3-丙二醇、2-丁基-2-己基-1,3-丙二醇、环己二醇、双羟基甲基环己烷、苯二甲醇、双羟基乙氧基苯、烷基二烷醇胺、内酯二醇等)的反应得到的聚酯多元醇、具有聚己内酯等内酯化合物的衍生物单元的聚酯多元醇等。
考虑到粘接特性,上述多元醇类之中,聚碳酸酯多元醇类和聚醚多元醇类更适于使用,聚碳酸酯多元醇类特别适合。
作为为了得到聚氨酯树脂所使用的聚异氰酸酯化合物,可以例示:甲苯二异氰酸酯、苯二甲基二异氰酸酯、亚甲基二苯基二异氰酸酯、亚苯基二异氰酸酯、萘二异氰酸酯、联甲苯胺二异氰酸酯等芳香族二异氰酸酯;α,α,α',α'-四甲基苯二甲基二异氰酸酯等具有芳香环的脂肪族二异氰酸酯;亚甲基二异氰酸酯、亚丙基二异氰酸酯、赖氨酸二异氰酸酯、三甲基六亚甲基二异氰酸酯、六亚甲基二异氰酸酯等脂肪族二异氰酸酯;环己烷二异氰酸酯、甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、异亚丙基二环己基二异氰酸酯等脂环族二异氰酸酯等。这些能够单独使用,也可以同时使用多种。
合成聚氨酯树脂时可以使用扩链剂,作为扩链剂只要是具有2个以上与异氰酸酯基反应的活性基团的物质就没有特别限制,一般来说能够主要使用具有2个羟基或氨基的扩链剂。
作为具有2个羟基的扩链剂,能够列举例如:乙二醇、丙二醇、丁二醇等脂肪族二醇;苯二甲醇、双羟基乙氧基苯等芳香族二醇;羟基特戊酸新戊二醇酯等的酯二醇这样的二醇类。另外,作为具有2个氨基的扩链剂,可以列举例如:甲苯二胺、苯二甲胺、二苯基甲二胺等芳香族二胺;乙二胺、丙二胺、己二胺、2,2-二甲基-1,3-丙二胺、2-甲基-1,5-戊二胺、三甲基己二胺、2-丁基-2-乙基-1,5-戊二胺、1,8-辛二胺、1,9-壬二胺、1,10-癸二胺等脂肪族二胺;1-氨基-3-氨基甲基-3,5,5-三甲基环己烷、二环己基甲二胺、异亚丙基环己基-4,4'-二胺、1,4-二氨基环己烷、1,3-双氨基甲基环己烷等脂环族二胺等。
聚氨酯树脂可以以溶剂为介质,但优选以水为介质。为了使聚氨酯树脂在水中分散或溶解,有使用乳化剂的强制乳化型、在聚氨酯树脂中导入亲水性基团的自乳化型或水溶型等。特别是在聚氨酯树脂的结构中导入离子基团而离聚物化的自乳化型,液体的储存稳定性和得到的涂布层的耐水性、透明性优异,故而优选。
另外,作为导入的离子基团,可以列举羧基、磺酸、磷酸、膦酸、季铵盐等各种基团,优选羧基。作为在聚氨酯树脂中导入羧基的方法,能够在聚合反应的各阶段中采取各种方法。例如有:在合成预聚物时,使用具有羧基的树脂作为共聚成分的方法;使用具有羧基的成分作为多元醇、聚异氰酸酯、扩链剂等的一个成分的方法。特别优选使用含有羧基的二醇,根据该成分的投料量来导入所希望量的羧基的方法。
例如,能够对于用于聚氨酯树脂聚合的二元醇,使二羟甲基丙酸、二羟甲基丁酸、双-(2-羟基乙基)丙酸、双-(2-羟基乙基)丁酸等共聚。另外,该羧基优选制成以氨、胺、碱金属类、无机碱类等中和后的盐的形态。特别优选为氨、三甲胺、三乙胺。
这样的聚氨酯树脂可以使用在涂布后的干燥工序中中和剂脱离了的羧基作为其它交联剂的交联反应位点。由此,在涂布前液体状态的稳定性优异的基础上,能够进一步改善所得到的涂布层的耐久性、耐溶剂性、耐水性、抗粘连性等。
作为用于提高粘接特性的聚氨酯树脂的玻璃化转变温度,必须是0℃以下,优选为-10℃以下,进一步优选为-20℃以下,特别优选为-30℃以下的范围,下限通常为-80℃。通过在上述范围内使用,容易制成具有最合适的粘接特性的膜。
抗静电剂是为了防止在各种工序中尘埃的附着等,为了降低膜表面的表面电阻而使用的。作为抗静电剂,没有特别限制,能够使用现有公知的抗静电剂,由于耐热性、耐湿热性良好,所以优选高分子型的抗静电剂。作为高分子型的抗静电剂,可以列举例如导电聚合物、具有铵基的化合物、具有磺酸基的化合物,聚醚化合物、甜菜碱化合物等。这些之中,从特别能够降低表面电阻、提高抗静电性能的观点出发,优选导电聚合物。另外,从难以着色的观点出发,优选具有铵基的化合物、具有磺酸基的化合物。
进一步进行探讨的结果发现,在作为抗静电剂使用导电聚合物的情况下,作为同时使用的玻璃化转变温度在0℃以下的树脂使用聚酯树脂时,与使用丙烯酸树脂、聚氨酯树脂等其他的树脂相比抗静电性能优异,在同时满足粘接力的方面优越。另外还发现使用导电聚合物以外的抗静电剂的情况下,丙烯酸树脂能够同时满足粘接力和抗静电性能的方面最优异。
作为导电聚合物可以列举例如聚噻吩系、聚苯胺系、聚吡咯系、聚乙炔系等,其中例如适合使用将聚(3,4-亚乙基二氧噻吩)与聚苯乙烯磺酸并用这样的聚噻吩系。导电聚合物在使电阻值变低的点上,比上述其他的抗静电剂合适。然而,在另一方面,对于重视着色或成本的用途上,需要想办法减少使用量等。
具有铵基的化合物是指在分子内具有铵基的化合物,可以列举脂肪族胺、脂环族胺和芳香族胺的铵化物等。具有铵基的化合物优选为高分子型的具有铵基的化合物,该铵基优选不是作为平衡离子,而是被组合入高分子的主链和/或侧链中的结构。例如,可以列举由加聚性的含有铵基或胺等铵基前体的单体聚合得到的聚合物制成具有铵基的高分子化合物,适合使用。作为聚合物,既可以是将加聚性的含有铵基或胺等铵基前体的单体均聚,也可以是含有这些的单体与其他的单体的共聚物。
具有铵基的化合物之中,从抗静电性、耐热稳定性优异的点出发,优选具有吡咯烷鎓环的化合物。
与具有吡咯烷鎓环的化合物的氮原子结合的2个取代基分别独立地为烷基、苯基等,这些烷基、苯基可以取代有以下所示的基团。能够取代的基团有例如羟基、酰胺基、酯基、烷氧基、苯氧基、萘氧基、硫代烷氧基、硫代苯氧基、环烷基、三烷基铵烷基、氰基、卤素。另外,与氮原子结合的2个取代基可以进行化学结合,例如,-(CH2)m-(m=2~5的整数),-CH(CH3)CH(CH3)-,-CH=CH-CH=CH-,-CH=CH-CH=N-,-CH=CH-N=C-,-CH2OCH2-,-(CH2)2O(CH2)2-等。
具有吡咯烷鎓环的聚合物可以通过对二烯丙基胺衍生物使用自由基聚合催化剂进行环化聚合而得到。聚合可以在作为溶剂的水或者甲醇、乙醇、异丙醇、甲酰胺、二甲基甲酰胺、二噁烷、乙腈等极性溶剂中,使用过氧化氢、过氧化苯甲酰、过氧化叔丁基等聚合引发剂通过公知的方法实施,但不限定于这些。也可以将二烯丙基胺衍生物与具有聚合性的存在碳-碳不饱和键的化合物作为共聚成分。
另外,在抗静电性和耐湿热稳定性优异的点上,也优选具有下述式(1)的结构的高分子。可以是均聚物或共聚物,进而也可以将其它多个成分共聚。
例如,上述式中取代基R1是氢原子或碳原子数为1~20的烷基、苯基等烃基,R2是—O—,-NH—或—S—,R3是碳原子数1~20的亚烷基或能够满足式1的结构的其他的结构,R4、R5、R6分别独立地是氢原子、碳原子数1~20的烷基、苯基等烃基,或羟基烷基等附带了官能团的烃基,X-是各种平衡离子。
上述中,特别从抗静电性、耐湿热稳定性优异的观点考虑,式(1)中,取代基R1优选为氢原子或碳原子数1~6的烷基,R3优选为碳原子数1~6的烷基,优选R4、R5、R6分别独立地为氢原子或碳原子数1~6的烷基,进一步优选R4、R5、R6的任意1个为氢原子,其他的取代基为碳原子数1~4的烷基。
作为上述的具有铵基的化合物的铵基的反离子(平衡离子)的阴离子,可以列举例如卤素离子、磺酸根、磷酸根、硝酸根、烷基磺酸根、羧酸根等的离子。
另外,具有铵基的化合物的数均分子量通常为1000~500000,优选为2000~350000,进一步优选为5000~200000。若分子量不足1000,则有涂膜的强度变弱或耐热稳定性差的情况。另外,分子量超过500000的情况下,涂布液的粘度会变高,有操作性或涂布性变差的情况。
具有磺酸基的化合物是指在分子内含有磺酸或者磺酸盐的化合物,例如适合使用聚苯乙烯磺酸或其衍生物等大量存在磺酸或者磺酸盐的化合物。
作为聚苯乙烯磺酸或其衍生物,在对位具有磺酸或磺酸盐的结构体从抗静电性的观点为优选。另外,既可以是均聚物,也可以是含有其他成分的共聚物,从抗静电性的观点出发,聚苯乙烯磺酸或其衍生物的比例接近均聚物更好,通常为80重量%以上,优选为90重量%以上的范围。
作为磺酸基的部分,可以是磺酸的状态,也可以是与1价的金属离子或者铵离子等的磺酸盐的状态。在抗静电性更优异的观点上,更优选磺酸的状态或者1价的金属盐的状态(其中优选锂盐或钠盐这样的小的金属离子)。而且优选磺酸的状态的量多于磺酸盐的状态的量,作为磺酸的量相对于磺酸和磺酸盐的总和,通常为60%以上,进一步优选为70%以上,特别优选为80%以上的范围。另外,从着色的观点,优选稍微增加磺酸盐的量(稍微减少磺酸的量),这种情况下,作为上述磺酸的量,通常为99%以下,优选为97%以下,进一步优选为95%以下的范围。
聚苯乙烯磺酸或其衍生物的分子量,作为数均分子量通常为5000~100000,优选10000~50000的范围。通过在上述范围内使用,容易得到良好的抗静电性能和适合涂布性。
作为聚醚化合物,可以列举例如在侧链具有聚氧化乙烯、聚醚酯酰胺、聚乙二醇的丙烯酸树脂等。
另外,为了提高粘接层的外观或进一步降低表面电阻值,还能同时使用例如聚氧化烯、甘油,聚甘油、对甘油或者于聚甘油的氧化烯烃的加成物等的多元醇化合物或者聚醚化合物。
作为聚氧化烯或其衍生物优选的物质为具有氧化乙烯或氧化丙烯结构的结构。若氧化烯烃结构中的烷基过长,则疏水性变强,在涂布液中的均匀分散性变差,有使抗静电性变差的倾向。特别优选氧化乙烯。
聚甘油是指聚合2个以上甘油的化合物,聚合度通常为2~20的范围。使用甘油的情况下,有透明性稍差的情况。
另外,对甘油或聚甘油的氧化烯加成物是指具有在甘油或聚甘油的羟基上加成氧化烯或其衍生物的结构的物质。
这里,加成在每个甘油或聚甘油结构的羟基上的氧化烯或其衍生物的结构可以不同。另外,至少分子中的1个羟基被加成即可,没有必要使全部的羟基加成有氧化烯或其衍生物。
另外,作为加成在甘油或聚甘油的氧化烯或其衍生物优选的是,具有氧化乙烯或氧化丙烯结构的结构。若氧化烯结构中的烷基链过长,则疏水性变强,有在涂布液中的均匀分散性变差、抗静电性变差的倾向。特别优选为氧化乙烯。另外,其加成数特别优选作为最终的化合物的重均分子量在300~2000的范围。
另外,从粘接层的强度的观点优选同时使用交联剂。在严酷的条件下,因所使用的树脂不同,也会有粘接成分向被粘附体转移的情况,但通过同时使用交联剂,能够改善粘接层向被粘附体的转移。
作为交联剂,能够使用现有公知的材料,可以列举例如三聚氰胺化合物、异氰酸酯系化合物、环氧化合物、噁唑啉化合物、碳二亚胺系化合物、硅烷偶联化合物、酰肼化合物、氮丙啶化合物等。这些之中,优选三聚氰胺化合物、异氰酸酯系化合物、环氧化合物、噁唑啉化合物、碳二亚胺系化合物、硅烷偶联化合物,进一步,从能够适度维持、容易调整粘接力的观点,更优选三聚氰胺化合物、异氰酸酯系化合物、环氧化合物,特别优选通过同时使用异氰酸酯系化合物和环氧化合物抑制粘接力的降低。另外,在能够特别地减少向被粘附体的转移的观点上,优选三聚氰胺化合物、异氰酸酯系化合物,其中特别优选三聚氰胺化合物。而且从粘接层的强度的观点,特别优选三聚氰胺化合物。另外这些的交联剂可以是1种,也可以同时使用2种以上。
需要说明的是,因粘接层的结构或交联剂的种类,有在粘接层中的交联剂的含量过多时使粘接特性过分降低的情况。所以需要注意在粘接层中的含量。
三聚氰胺化合物是指在化合物中具有三聚氰胺骨架的化合物,能够使用例如烷醇化三聚氰胺衍生物、使烷醇化三聚氰胺衍生物与醇反应而部分或者全部醚化得到的化合物以及这些的混合物。作为用于醚化的醇,优选使用甲醇、乙醇、异丙醇、正丁醇、异丁醇等。另外,作为三聚氰胺化合物可以使用单体、二聚物以上的多聚物的任意种,或者这些的混合物。考虑到与各种化合物的反应性,优选在三聚氰胺化合物中含有羟基。而且,也能够使用将三聚氰胺的一部分与尿素等共缩聚而形成的物质,为了提高三聚氰胺化合物的反应性,也能够使用催化剂。
异氰酸酯系化合物是指异氰酸酯或者封端异氰酸酯所代表的具有异氰酸酯衍生物结构的化合物。作为异氰酸酯,可以例示例如:甲苯二异氰酸酯、苯二甲基二异氰酸酯、亚甲基二苯基二异氰酸酯、亚苯基二异氰酸酯、萘二异氰酸酯等芳香族异氰酸酯;α,α,α',α'-四甲基苯二甲基二异氰酸酯等具有芳香环的脂肪族异氰酸酯;亚甲基二异氰酸酯、亚丙基二异氰酸酯、赖氨酸二异氰酸酯、三甲基六亚甲基二异氰酸酯、六亚甲基二异氰酸酯等脂肪族异氰酸酯;环己烷二异氰酸酯、甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(4-环己基异氰酸酯)、异亚丙基二环己基二异氰酸酯等脂环族异氰酸酯等。另外,也可以列举这些异氰酸酯的缩二脲化物、异氰脲酸酯化物、脲二酮化物,碳二亚胺改性体等的聚合物或衍生物。这些物质可以单独使用,也可以多种同时使用。上述异氰酸酯之中,为了避免紫外线导致的黄变,相较于芳香族异氰酸酯,更优选脂肪族异氰酸酯或脂环族异氰酸酯。
以封端异氰酸酯的状态使用的情况下,作为其封端剂,可以列举例如:亚硫酸氢盐类;苯酚、甲酚、乙基苯酚等酚系化合物;丙二醇单甲醚、乙二醇、苯甲醇、甲醇、乙醇等醇系化合物;丙二酸二甲酯、丙二酸二乙酯、异丁酰乙酸甲酯、乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰丙酮等活性亚甲基系化合物;丁硫醇、十二烷基硫醇等硫醇系化合物;ε-己内酰胺、δ-戊内酰胺等内酰胺系化合物;二苯基苯胺、苯胺、环乙亚胺等胺系化合物;乙酰苯胺、乙酸酰胺这样的酰胺化合物;甲醛、乙醛肟、丙酮肟,甲基乙基酮肟,环己酮肟等肟系化合物,这些可以单独或者2种以上同时使用。上述中从能够特别有效地降低粘接层向被粘附体的转移性的观点,优选使用由活性亚甲基系化合物封端的异氰酸酯化合物。
另外,异氰酸酯系化合物可以以单体使用,也可以是作为与各种聚合物的混合物或结合物使用。在提高异氰酸酯系化合物的分散性或交联性的意义上,优选使用与聚酯树脂和/或聚氨酯树脂的混合物和/或结合物。
环氧化合物是指在分子内具有环氧基的化合物,可以列举例如:环氧氯丙烷与乙二醇、聚乙二醇、甘油、聚甘油、双酚A等的羟基、氨基的缩合物,有多环氧化合物、二环氧化合物、单环氧化合物、缩水甘油胺化合物等。作为多环氧化合物,可以列举例如:山梨醇聚缩水甘油醚、聚甘油聚缩水甘油醚、季戊四醇聚缩水甘油醚、二甘油聚缩水甘油醚、三缩水甘油三(2-羟基乙基)异氰酸酯、甘油聚缩水甘油醚、三羟甲基丙烷聚缩水甘油醚,作为二环氧化合物,可以列举例如:新戊二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、间苯二酚二缩水甘油醚、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、聚四亚甲基二醇二缩水甘油醚,作为单环氧化合物,可以列举例如:烯丙基缩水甘油醚、2-乙基己基缩水甘油醚、苯基缩水甘油醚,作为缩水甘油胺化合物可以列举N,N,N',N'-四缩水甘油基-间苯二甲胺、1,3-双(N,N-二缩水甘油氨基)环己烷等。
从粘接特性良好的观点出发,上述之中优选聚醚系的环氧化合物。另外,作为环氧基的量,相较于2官能,优选3官能以上的多官能的多环氧化合物。
噁唑啉化合物是指在分子内具有噁唑啉基的化合物,特别优选含有噁唑啉基的聚合物,能够通过将加聚性含有噁唑啉基的单体单独或与其他的单体聚合来制作。加聚性含有噁唑啉基的单体可以列举2-乙烯基-2-噁唑啉、2-乙烯基-4-甲基-2-噁唑啉、2-乙烯基-5-甲基-2-噁唑啉、2-异丙烯基-2-噁唑啉、2-异丙烯基-4-甲基-2-噁唑啉、2-异丙烯基-5-乙基-2-噁唑啉等,可以使用这些之中的1种或2种以上的混合物。这些之中,2-异丙烯基-2-噁唑啉由于工业上也容易获得,视为优选。其他的单体只要是能够与加聚性含有噁唑啉基的单体共聚的单体就没有限制,可以列举例如(甲基)丙烯酸烷基酯(作为烷基有甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、2-乙基己基、环己基)等(甲基)丙烯酸酯类;丙烯酸、甲基丙烯酸、衣康酸、马来酸、富马酸、巴豆酸、苯乙烯磺酸以及它们的盐(钠盐、钾盐、铵盐、叔胺盐等)等不饱和羧酸类;丙烯腈、甲基丙烯腈等不饱和腈类;(甲基)丙烯酰胺、N-烷基(甲基)丙烯酰胺、N,N-二烷基(甲基)丙烯酰胺、(作为烷基有甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、2-乙基己基、环己基等)等不饱和酰胺类;乙酸乙烯酯、丙酸乙烯酯等乙烯酯类;甲基乙烯醚、乙基乙烯醚等乙烯醚类;乙烯、丙烯等α-烯烃类;氯乙烯、偏氯乙烯、氟化乙烯等含卤素的α,β-不饱和单体类;苯乙烯、α-甲基苯乙烯等α,β-不饱和芳香族单体等,能够使用这些之中的1种或2种以上的单体。
噁唑啉化合物的噁唑啉基量通常为0.5~10mmol/g,优选为1~9mmol/g,进一步优选为3~8mmol/g,特别优选为4~6mmol/g的范围。通过在上述范围内使用,耐久性提高,容易调整粘接特性。
碳二亚胺系化合物是指在分子内具有1个以上碳二亚胺或者碳二亚胺衍生物结构的化合物。为了获得更良好的粘接层的强度等,优选在分子内具有2个以上碳二亚胺或碳二亚胺衍生物结构的多碳二亚胺系化合物。
碳二亚胺系化合物能够通过现有公知的技术合成,一般来说,利用二异氰酸酯化合物的缩合反应。作为二异氰酸酯化合物没有特别限定,芳香族系、脂肪族系均可以使用,具体可以列举甲苯二异氰酸酯、二甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、亚苯基二异氰酸酯、萘二异氰酸酯、六亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯、环己烷二异氰酸酯、甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基二异氰酸酯、二环己基甲烷二异氰酸酯等。
另外在不使本发明的效果消失的范围内,为了提高多碳二亚胺系化合物的水溶性或水分散性,也可以添加表面活性剂、和/或添加聚氧化烯烃、二烷基氨基醇的季铵盐、羟基烷基磺酸盐等亲水性单体后使用。
硅烷偶联化合物是指在1个分子中具有有机官能团和烷氧基等水解基团的有机硅化合物。可以列举例如:3-缩水甘油基丙基甲基二甲氧基硅烷、3-缩水甘油基丙基三甲氧基硅烷、3-缩水甘油基丙基甲基二乙氧基硅烷、3-缩水甘油基丙基三乙氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷等含有环氧基的化合物;乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷等含有乙烯基的化合物;对苯乙烯基三甲氧基硅烷、对苯乙烯基三乙氧基硅烷等含有苯乙烯基的化合物;3-(甲基)丙烯酰氧丙基三甲氧基硅烷、3-(甲基)丙烯酰氧丙基三乙氧基硅烷、3-(甲基)丙烯酰氧丙基甲基二甲氧基硅烷、3-(甲基)丙烯酰氧丙基甲基二乙氧基硅烷等含有(甲基)丙烯酸基的化合物;3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三乙氧基硅烷、N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基甲基二乙氧基硅烷、3-三乙氧基甲硅烷基-N-(1,3-二甲基亚丁基)丙基胺、N-苯基-3-氨基丙基三甲氧基硅烷、N-苯基-3-氨基丙基三乙氧基硅烷等含有氨基的化合物;三(三甲氧基甲硅烷基丙基)异氰脲酸酯、三(三乙氧基甲硅烷基丙基)异氰脲酸酯等含有异氰脲酸酯基的化合物;3-巯基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、3-巯基丙基甲基二甲氧基硅烷、3-巯基丙基甲基二乙氧基硅烷等含有巯基的化合物等。
上述化合物中,从保持粘接层的强度和粘接力的观点出发,更优选含有环氧基的硅烷偶联化合物、含有乙烯基或(甲基)丙烯酸基等含有双键的硅烷偶联化合物、含有氨基的硅烷偶联化合物。
需要说明的是,这些交联剂是在干燥过程、制膜过程中,以使其反应来提高粘接层的性能的设计被使用。能够推测得到的粘接层中存在这些交联剂的未反应物、反应后的化合物或者这些的混合物。
另外,从粘接层的外观、粘接力的调整、粘接层的强化、与基材膜的密合性、抗粘连性、防止粘接成分向被粘附体的转移等的观点出发,也能够同时使用玻璃化转变温度超过0℃的树脂。作为玻璃化转变温度超过0℃的树脂,能够使用现有公知的材料。其中,优选聚酯树脂、丙烯酸树脂、聚氨酯树脂以及聚乙烯(聚乙烯醇、氯乙烯乙酸乙烯酯共聚物等),考虑到粘接层的外观、对于粘接力的影响,优选选自聚酯树脂、丙烯酸树脂和聚氨酯树脂的树脂。然而,因使用方法不同,也有使粘接力大幅降低的担忧,所以需要注意。
另外,粘接层的形成中,为了改良粘连或滑动性、调整粘接特性,也能够同时使用颗粒。但是,由于根据使用的颗粒的种类不同也有使粘接力降低的情况,所以需要注意。在不使粘接力过度降低的情况下,所使用的颗粒的平均粒径相对于粘接层的膜厚,通常为3倍以下,优选为1.5倍以下,进一步优选为1.0倍以下,特别优选为0.8倍以下的范围。特别在希望直接发挥粘接层的树脂的粘接性能的情况下,有时也优选粘接层中不含颗粒。
在膜的与粘接层相反一侧的面上,为了赋予各种功能可以设置功能层。
例如,为了减轻因粘接层导致的膜的粘连也优选设置脱模层,为了防止因膜的剥离起电或摩擦起电引起的周围的灰尘等附着等所导致的缺陷而设置抗静电层也是优选方式。该功能层能够通过涂敷设置,既可以通过在线涂敷设置,也可以采用离线涂敷。从制造成本和通过在线的热处理使脱模性能或抗静电性能等的稳定化的观点出发,优选使用在线涂敷。
例如,在膜的与粘接层相反一侧的面上设置脱模功能层的情况下,作为功能层中含有的脱模剂没有特别限制,能够使用现有公知的脱模剂,可以列举例如含有长链烷基的化合物、氟化合物、有机硅化合物、蜡等。这些之中,在污染性小、减轻粘连性能好的点上,优选使用长链烷基化合物、氟化合物,在特别要重视减少粘连的情况下优选有机硅化合物。另外,为了提高表面的去污性,蜡是有效的。这些脱模剂可以单独使用,也可以使用多种。
含有长链烷基的化合物是指碳原子数通常为6以上、优选为8以上、进一步优选为12以上的具有直链或者支链的烷基的化合物。作为烷基可以列举例如己基、辛基、癸基、十二烷基、十八烷基,二十二烷基等。具有烷基的化合物可以列举例如各种含有长链烷基的高分子化合物、含有长链烷基的胺化合物、含有长链烷基的醚化合物、含有长链烷基的季铵盐等。考虑到耐热性、污染性,优选高分子化合物。另外,从有效地得到脱模性的观点出发,更优选在侧链具有长链烷基的高分子化合物。
在侧链具有长链烷基的高分子化合物是能够通过使具有反应性基团的高分子和具有能够与该反应性基团反应的烷基的化合物反应而得到。作为上述反应性基团,可以列举例如羟基、氨基、羰基、酸酐等。作为具有这些反应性基团的化合物可以列举例如聚乙烯醇、聚乙烯亚胺、聚乙烯胺、含有反应性基团的聚酯树脂、含有反应性基团的聚(甲基)丙烯酸树脂等。这些之中考虑到脱模性和操作容易性,优选聚乙烯醇。
上述的具有能够与反应性基团反应的烷基的化合物可以列举例如:异氰酸己酯、异氰酸辛酯、异氰酸癸酯、异氰酸月桂酯、异氰酸十八烷基酯、异氰酸二十二烷基酯等含有长链烷基的异氰酸酯、己酰氯、辛酰氯、癸酰氯、十二酰氯、十八酰氯、二十二酰氯等含有长链烷基的酰氯、含有长链烷基的胺、含有长链烷基的醇等。这些之中,考虑到脱模性和操作容易性,优选含有长链烷基的异氰酸酯,特别优选异氰酸十八烷基酯。
另外,在侧链具有长链烷基的高分子化合物也能够通过(甲基)丙烯酸长链烷基酯的聚合物或(甲基)丙烯酸长链烷基酯与其他的含有乙烯基的单体的共聚而得到。(甲基)丙烯酸长链烷基酯可以列举例如(甲基)丙烯酸己酯、甲基)丙烯酸辛酯,(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷基酯,(甲基)丙烯酸十八烷基酯,(甲基)丙烯酸二十二烷基酯等。
作为氟化合物,是在化合物中含有氟原子的化合物。从通过在线涂敷时的涂布外观的点出发,优选使用有机系氟化合物,可以列举例如含有全氟烷基的化合物、含有氟原子的烯烃化合物的聚合物、氟代苯等芳香族氟化合物等。从脱模性的观点优选具有全氟烷基的化合物。进一步,氟化合物也能够使用后述的含有长链烷基化合物的化合物。
具有全氟烷基的化合物可以列举例如(甲基)丙烯酸全氟烷基酯、(甲基)丙烯酸全氟烷基甲基酯、(甲基)丙烯酸2-全氟烷基乙基酯、(甲基)丙烯酸3-全氟烷基丙基酯、(甲基)丙烯酸3-全氟烷基-1-甲基丙基酯、(甲基)丙烯酸3-全氟烷基-2-丙烯基酯等含有全氟烷基的(甲基)丙烯酸酯及其聚合物;全氟烷基甲基乙烯醚、2-全氟烷基乙基乙烯醚、3-全氟丙基乙烯醚、3-全氟烷基-1-甲基丙基乙烯醚、3-全氟烷基-2-丙烯基乙烯醚等含有全氟烷基的乙烯醚及其聚合物等。考虑到耐热性、污染性,优选为聚合物。聚合物可以只是单一化合物也可以是多个化合物的聚合物。另外,从脱模性的观点出发,全氟烷基优选碳原子数为3~11。进一步也可以是与后述的含有长链烷基化合物的化合物的聚合物。另外,从与基材的密合性的观点出发,也优选为与氯乙烯的聚合物。
有机硅化合物是指在分子内具有有机硅结构的化合物,可以列举例如二甲基硅酮、二乙基硅酮等烷基有机硅、另外还有具有苯基的苯基硅酮、甲基苯基硅酮等。有机硅也能够使用具有各种官能团的有机硅,可以列举例如醚基、羟基、氨基、环氧基、羧酸基、氟等的卤素基、全氟烷基、各种烷基或各种芳香族基团等烃基等。作为其他的官能团,通常也可以是具有乙烯基的有机硅、或氢原子直接与硅原子结合的氢化有机硅,可以并用两者,也可以作为加成型(乙烯基与氢化硅烷的加成反应而形成的类型)的有机硅使用。
另外,作为有机硅化合物,也可以使用丙烯酸接枝有机硅、有机硅接枝丙烯酸、氨基改性有机硅、全氟烷基改性有机硅等改性有机硅。考虑到耐热性、污染性,优选使用固化型有机硅树脂,作为固化型的种类,能够使用缩聚型、加成型、活化能量线固化型等任意的固化反应型。这些之中,特别在制成卷状时的背面转印少的观点上,优选缩聚型有机硅化合物。
作为使用有机硅化合物时的优选方式,从背面转印少、在水系溶剂中的分散性良好、对于在线涂敷的适应性高的观点出发,优选含有聚醚基的有机硅化合物。聚醚基既可以存在于有机硅的侧链和/或末端,也可以存在于主链。从在水系溶剂中的分散性的观点出发,优选存在于侧链和/或末端。
聚醚基能够使用现有公知的结构。从在水系溶剂中的分散性的观点出发,相较于芳香族聚醚基,优选脂肪族聚醚基,在脂肪族聚醚基中,优选烷基聚醚基。另外,从位阻导致的合成上的观点出发,相较于支链烷基聚醚基,优选直链烷基聚醚基,其中,优选含有碳原子数为8以下的直链烷基的聚醚基。而且,在展开的溶剂为水的情况下,考虑到在水中的分散性,优选聚乙二醇基或聚丙二醇基,特别最合适的是聚乙二醇基。
关于聚醚基的醚键的个数,从提高对水系溶剂的分散性和功能层的耐久性的观点出发,通常为1~30个,优选为2~20个,进一步优选为3~15个的范围。醚键少则分散性变差,相反,过多则耐久性或脱模性能变差。
在有机硅的侧链或者末端具有聚醚基的情况下,聚醚基的末端没有特别限定,能够使用羟基、氨基、巯基、烷基和苯基等烃基、羧酸基、磺酸基、醛基、缩醛基等各种官能团。其中,考虑到在水中的分散性或用于提高功能层的强度的交联性,优选羟基、氨基、羧酸基、磺酸基,特别是最优选羟基。
含有聚醚基的有机硅的聚醚基的含量,将有机硅的硅氧键设为1时,以摩尔比的比例计,通常为0.001~0.30%,优选为0.01~0.20%,进一步优选为0.03~0.15%,特别优选为0.05~0.12%的范围。通过在该范围内使用,能够保持在水中的分散性和功能层的耐久性以及良好的脱模性。
关于含有聚醚基的有机硅的分子量,考虑到在水系溶剂中的分散性,优选分子量不过大,另外,考虑到功能层的耐久性和脱模性能,优选大的分子量。要求使这两者的特性平衡,作为数均分子量,通常为1000~100000,优选为3000~30000,进一步优选为5000~10000的范围。
另外,考虑到功能层的随时间的变化和脱模性能、另外还有各种工序的污染性,优选有机硅的低分子成分(数均分子量为500以下)尽量少,它的量作为对于有机硅化合物整体的比例,通常为15重量%以下,优选为10重量%以下,进一步优选为5重量%以下的范围。另外,使用缩聚型有机硅的情况下,与硅键合的乙烯基(乙烯硅烷)、氢基(氢硅烷)以未反应的状态残留于功能层会成为各种性能随时间的变化的原因,因此作为在有机硅中的官能团量的含量优选为0.1摩尔%以下,更优选不含有。
由于单独涂布含有聚醚基的有机硅困难,优选在水中分散后使用。为了分散能够使用现有公知的各种分散剂,可以列举例如阴离子性分散剂、非离子性分散剂、阳离子性分散剂、两性分散剂。这些之中,考虑到含有聚醚基的有机硅的分散性以及与可用于形成功能层的含有聚醚基的有机硅以外的聚合物的相溶性,优选阴离子性分散剂和/或非离子性分散剂。另外,这些分散剂中,也能够使用氟化合物。
作为阴离子性分散剂可以列举十二烷基苯磺酸钠、烷基磺酸钠、烷基萘磺酸钠、二烷基磺基丁二酸钠、聚氧乙烯烷基醚硫酸钠、聚氧乙烯烷基烯丙基醚硫酸钠、聚氧亚烷基烯基醚硫酸铵盐等磺酸盐、硫酸酯盐系;月桂酸钠、油酸钾等羧酸盐系;烷基磷酸盐、聚氧乙烯烷基醚磷酸盐、聚氧乙烯烷基苯基醚磷酸盐等磷酸盐系。这些之中,从分散性良好的观点出发,优选磺酸盐系。
作为非离子性分散剂,可以列举例如:使氧化乙烯或氧化丙烯等氧化烯与高级醇或烷基酚等具有羟基的化合物加成而得到的醚型、甘油或糖类等多元醇与脂肪酸通过酯键键合而得到的酯型、向脂肪酸或多元醇脂肪酸酯加成了氧化烯而得到的酯-醚型、疏水基团与亲水基团通过酰胺键键合而得到的酰胺型等。这些之中,考虑到对水的溶解性、稳定性,优选醚型,再考虑到操作性,更优选加成氧化乙烯得到的类型。
关于分散剂的量,既依赖于所使用的含有聚醚基的有机硅的分子量和结构,也依赖于所使用的分散剂的种类,因此不能一概而论,但作为基准,分散剂的量以含有聚醚基的有机硅为1时,以重量比计,通常为0.01~0.5,优选为0.05~0.4,进一步优选为0.1~0.3的范围。
蜡是指选自天然蜡、合成蜡、配合有这些的蜡中的蜡。天然蜡是指植物系蜡、动物系蜡、矿物系蜡、石油蜡。作为植物系蜡可以列举小烛树蜡、巴西棕榈蜡、米糠蜡、木蜡、霍霍巴油等。作为动物系蜡可以列举蜜蜡、羊毛脂、鲸蜡等。作为矿物系蜡可以列举褐煤蜡、天然地蜡(ozocerite)、白地蜡(ceresine)等。作为石油蜡可以列举石蜡、微晶蜡、凡士林等。作为合成蜡可以列举合成烃、改性蜡、氢化蜡、脂肪酸、酰胺、胺、酰亚胺、酯、酮等。作为合成烃,可以列举例如费-托蜡(别名沙索蜡(Sasolwax))、聚乙烯蜡,除此以外,也包括作为低分子量的高分子(具体而言,数均分子量从500至20000的高分子)的以下的聚合物,即,可以列举聚丙烯、乙烯-丙烯酸共聚物、聚乙二醇、聚丙二醇、聚乙二醇和聚丙二醇的嵌段或接枝结合物等。作为改性蜡可以列举褐煤蜡衍生物、石蜡衍生物、微晶蜡衍生物等。这里的衍生物是指通过精制、氧化、酯化、皂化的任一种处理或这些处理的组合而得到的化合物。作为氢化蜡,可以列举氢化蓖麻油和氢化蓖麻油衍生物。
在上述之中,从性能稳定的观点出发,优选合成蜡,其中更优选聚乙烯蜡,进一步优选为氧化聚乙烯蜡。合成蜡的数均分子量从粘连等的特性的稳定性、操作性的观点出发,通常为500~30000,优选为1000~15000,进一步优选为2000~8000的范围。
在膜的与粘接层相反一侧的面设置抗静电功能层的情况下,作为功能层含有的抗静电剂没有特别限制,能够使用现有公知的抗静电剂,但从耐热性、耐湿热性良好的方面考虑,优选高分子型的抗静电剂。具体地说,可以列举与粘接层同样的抗静电剂。
在膜的与粘接层相反一侧的面能够设置的功能层含有上述的脱模剂和抗静电剂的双方、制成具有抗静电·脱模功能的功能层也是优选方式。
在功能层的形成中,为了提高涂布外观和透明性、控制滑动性,也可以同时使用聚酯树脂、丙烯酸树脂、聚氨酯树脂等各种聚合物、能够用于形成粘接层的交联剂。特别是在为了使功能层牢固、减少粘连的观点上,优选同时使用三聚氰胺化合物、噁唑啉化合物、异氰酸酯系化合物、环氧化合物、碳二亚胺系化合物,其中特别优选三聚氰胺化合物。
在不损害本发明的主旨的范围内,形成功能层时也能够为了改良粘连或滑动性同时使用颗粒。但由于功能层具有脱模性能的情况下大多具有充分的抗粘连性或滑动性,从功能层的外观的观点出发,也有优选不同时使用颗粒的情况。
而且在不损害本发明的主旨的范围内,在粘接层和功能层的形成时也可以按照需要同时使用消泡剂、涂布性改良剂、增粘剂、有机系润滑剂、抗静电剂、紫外线吸收剂、抗氧化剂、发泡剂、染料、颜料等。
玻璃化转变温度在0℃以下的树脂在构成粘接膜的粘接层中的比例,在同时使用的抗静电剂是导电聚合物的情况下,通常为10~99.9重量%,优选为30~99.8重量%,进一步优选为50~98重量%,特别优选为65~97重量%,最优选为75~94重量%的范围。另外,在同时使用的抗静电剂是导电聚合物以外的情况下,通常为10~90重量%,优选为30~85重量%,进一步优选为50~80重量%的范围。若含量过少,则粘接特性不够充分,另外相反在过多的情况下,由于抗静电剂的量少,抗静电性能变得不充分,有尘埃附着造成问题的情况。
作为在构成粘接膜的粘接层中的比例,抗静电剂在导电聚合物的情况下,通常为0.1~80重量%,优选为0.2~50重量%,进一步优选为0.5~30重量%,特别优选为1.0~20重量%,最优选为1.5~8重量%的范围。另外,抗静电剂在导电聚合物以外的情况下,通常为5~90重量%,优选为10~70%,进一步优选为15~50重量%的范围。抗静电剂的含量过少则抗静电性能变得不充分,尘埃的附着造成问题,相反,过多的情况下,由于玻璃化转变温度在0℃以下的树脂的量少,有粘接特性不充分的情况。
在粘接膜中,在与粘接层相反面的一侧设置具有脱模性能的功能层的情况下,作为在功能层中的比例,脱模剂的比例因脱模剂的种类而适当的量不同所以不能一概而论,但通常为3重量%以上,优选为15重量%以上,进一步优选为25~99重量%的范围。在少于3重量%的情况下有粘连降低不够充分的情况。
作为脱模剂使用长链烷基化合物、氟化合物的情况下,在功能层中的比例通常为5重量%以上,优选为15~99重量%,进一步优选为20~95重量%,特别优选为25~90重量%的范围。通过在上述范围内使用,可以有效地减轻粘连。另外,交联剂的比例通常为95重量%以下,优选为1~80重量%,进一步优选为5~70重量%,特别优选为10~50重量%的范围,作为交联剂,优选三聚氰胺化合物、异氰酸酯系化合物(其中特别优选使用活性亚甲基系化合物封端的封端异氰酸酯),从减轻粘连的观点出发,特别优选三聚氰胺化合物。
作为脱模剂使用缩聚型的有机硅化合物的情况下,在功能层中的比例通常为3重量%以上,优选为5~97重量%,进一步优选为8~95重量%,特别优选为10~90重量%的范围。通过在上述范围内使用,可以有效地减轻粘连。另外,交联剂的比例通常为97重量%以下,优选为3~95重量%,进一步优选为5~92重量%,特别优选为10~90重量%的范围。另外,作为交联剂,从减轻粘连的观点出发优选三聚氰胺化合物。
作为脱模剂使用加成型的有机硅化合物的情况下,在功能层中的比例通常为5重量%以上,优选为25重量%以上,进一步优选为50重量%以上,特别优选为70重量%以上的范围。上限通常为99重量%,优选为90重量%。通过在上述范围内使用,能够有效地减轻粘连,另外功能层的外观也变得良好。
作为脱模剂使用蜡的情况下,在功能层中的比例通常为10重量%以上,优选为20~90重量%,进一步优选为25~70重量%的范围。通过在上述范围内使用,容易减少粘连。但在以表面的去污性为目的使用蜡的情况下,能够减少上述的比例,通常为1重量%以上,优选为2~50重量%,进一步优选为3~30重量%的范围。另外,交联剂的比例通常为90重量%以下,优选为10~70重量%,进一步优选为20~50重量%的范围。另外,作为交联剂,从减少粘连的观点出发优选三聚氰胺化合物。
另一方面,在与粘接层相反面一侧设置具有抗静电性能的功能层的情况下,作为在功能层中的比例,抗静电剂的比例因抗静电剂的种类不同而适当的量不同,所以不能一概而论,但通常为0.5重量%以上,优选为3~90重量%,进一步优选为5~70重量%,特别优选为8~60重量%的范围。若少于0.5重量%,则抗静电效果不够充分,有防止周围的灰尘等附着的效果不充分的情况。
作为抗静电剂使用导电聚合物以外的抗静电剂的情况下,在抗静电层中的比例通常为5重量%以上,优选为10~90重量%,进一步优选为20~70重量%,特别优选为25~60重量%的范围。少于5重量%的情况下,抗静电效果不充分,有防止周围的灰尘等附着的效果不充分的情况。
作为抗静电剂使用导电聚合物的情况下,在抗静电层中的比例通常为0.5重量%以上,优选3~70重量%,进一步优选为5~50重量%,特别优选为8~30重量%的范围。若少于0.5重量%的情况下,抗静电效果不充分,有防止周围的灰尘等附着的效果不充分的情况。
粘接层或功能层中的成分的分析能够通过例如TOF-SIMS、ESCA、荧光X射线、IR等的分析进行。
关于粘接层或功能层的形成,优选以如下要领制造粘接膜:在膜上涂敷将上述一系列化合物制成溶液或溶剂的分散体、以固体成分浓度通常为0.1~80重量%左右为大致标准调整得到的液体。特别是通过在线涂敷设置的情况下,更优选水溶液或水分散体。以改良在水中的分散性、改良成膜性为目的,在涂布液中也可以含有少量的有机溶剂。另外,有机溶剂可以仅为1种,也可以适当地使用2种以上。
粘接层的膜厚必须为10μm以下,以1nm~4μm、10nm~1μm,20~700nm、30~600nm、50~480nm的顺序依次更加优选。通过使粘接层的膜厚在上述范围内,容易保持适度的粘接特性、抗静电特性、粘连特性。
由于一般的粘接层是超过10μm的厚的膜厚,这种情况下,例如,在用于偏光板制造用途的情况下,在将粘接膜与偏光板、相位差板或视野角扩大板等的被粘附体相贴合后剪裁时等,有明显发生粘接层中的粘接剂溢出的情况。
然而通过调整至上述的范围的膜厚,该溢出能够被限制在最小限度。该效果是在粘接层的膜厚越薄越良好。另外,粘接层的膜厚越薄,有时在膜上存在的粘接层的绝对量也越少,对于降低残胶、即粘接层的成分向被粘附体的转移也有效。而且还知道通过制成上述范围的膜厚,能够达到不过于强的适度的粘接力,例如,在用于偏光板制造工序等需要同时满足粘接性能和在贴合后剥离的剥离性能的用途中使用的情况下,能够容易地进行贴合-剥离的操作,能够制成最合适的膜。
膜厚越薄对于粘连特性越有效,通过在线涂敷形成粘接层的情况下,容易制造而为优选,但相反膜厚过薄的情况下,因粘接层的结构也会有粘接特性消失的情况,所以优选根据用途在上述合适的范围内使用。
功能层的膜厚因所设置的功能不同,所以不能一概而论,但例如,作为为了赋予脱模性能或抗静电性能的功能层,通常为1nm~3μm,优选为10nm~1μm,进一步优选为20~500nm,特别优选为20~200nm的范围。通过使用在上述范围内的功能层的膜厚,容易提高粘连特性、提高抗静电性能、形成良好的外观。
作为形成粘接层或功能层的方法,能够使用例如凹版涂布、逆向辊涂布、模涂、气刀涂(air doctor coat)、刮板涂(blade coat)、棒涂(rod coat)、条涂(bar coat)、淋涂(curtain coat)、刮刀涂(knife coat)、传送辊涂(transfer roll coat)、挤压涂(squeezecoat)、浸涂(dip coat)、辊舐涂布(kiss coat)、喷涂、压延涂布(calendar coat)、挤出涂布(extrusion coat)等现有公知的涂敷方式。
关于在膜上形成粘接层时的干燥和固化条件没有特别限定,但使用涂敷的方法的情况下,对于涂敷液中使用的水等溶剂的干燥,通常为70~150℃,优选为80~130℃,进一步优选为90~120℃的范围。干燥的时间通常为3~200秒,优选为5~120秒的范围。另外,为了提高粘接层的强度,在膜制造工序中优选设置热处理工序。热处理温度通常为180~270℃,优选为200~250℃,进一步优选为210~240℃的范围。热处理时间通常为3~200秒,优选为5~120秒的范围。
另外,依照需要可以并用热处理和紫外线照射等活性能量线照射。可以在构成本发明的粘接膜的膜上预先实施电晕处理、等离子体处理等表面处理。
粘接层的粘接力,设为通过后述测定方法测定的对于聚甲基丙烯酸甲酯板的粘接力,通常为1~5000mN/cm,优选为3~3000mN/cm,进一步优选为5~500mN/cm,特别优选为7~300mN/cm,最优选为10~100mN/cm的范围。在上述范围,能够同时满足粘接性能和贴合后进行剥离的剥离性能,能够使其成为用于进行粘接-剥离的操作的各种工序的最合适的叠层体。另外,膜的粘连特性也容易变得良好。
作为粘接膜的粘连性,将粘接膜的粘接层侧的面与相反侧的面(有功能层的情况下是功能层一侧的面)相重合,在40℃、80%RH、10kg/cm2,20小时的条件下加压后的剥离载荷通常为100g/cm以下,优选为30g/cm以下,进一步优选为20g/cm以下,特别优选为10g/cm以下,最优选为8g/cm以下的范围。通过设在上述范围内,容易避免粘连的风险,能够制成实用性高的膜。
作为粘接层的抗静电性能,表面电阻值通常为1×1012Ω以下,优选为1×1011Ω以下,进一步优选为5×1010Ω以下的范围。在上述范围内的情况下,能够成为尘埃等的附着少的膜。
另外,在功能层一侧也需要抗静电性的用途上,功能层的表面电阻值通常为1×1012Ω以下,优选为1×1011Ω以下,进一步优选为5×1010Ω以下的范围。在上述范围内的情况下,会成为尘埃等的附着更少的膜。
另外,将与粘接层相反一侧的面的膜表面(具有功能层的情况下为功能层一侧的面)变粗糙有时也可以是用于改善与粘接层一侧的粘连特性的手段之一。虽然因粘接层的种类或粘接力而不能一概而论,但不论功能层,有通过表面粗糙度改善粘连特性的目的的情况下,与粘接层相反一侧的面的膜表面的算术平均粗糙度(Sa)通常为5nm以上,优选为8nm以上,进一步优选为30nm以上的范围,上限没有特别限制,但从透明性的观点出发为300nm。需要说明的是,通过在与粘接层相反一侧的面设置脱模的功能层等的方法而脱模性良好的情况下,该脱模性处于支配地位,Sa的影响小,所以不需要特别注意,但在脱模性弱的情况下,有Sa的影响变大的情况,会成为有效的改善粘连特性等的手段。然而,将Sa增大会使雾度变高、透明性降低,因此需要依照用途分别应对,对于特别重视透明性的情况下优选考虑通过脱模层改善粘连。
实施例
以下,对于本发明通过实施例进行更详细的说明,但本发明只要不超过其主旨就不限定于以下的实施例。另外,本发明所使用的测定法以及评价方法如下所述。
(1)聚酯的特性粘度的测定方法:
精确称量去除与聚酯不相溶的其他的聚合物成分和颜料的聚酯1g,加入苯酚/四氯乙烷=50/50(重量比)的混合溶剂100ml使其溶解,在30℃进行测定。
(2)平均粒径(d50:μm)的测定方法:
将使用株式会社岛津制作所制造的离心沉降式粒度分布测定装置SA-CP3型测定的等价球形分布中的累计(重量基准)50%的值作为平均粒径。
(3)算术平均粗糙度(Sa)的测定方法:
对于膜表面,利用株式会社菱化系统(Ryoka Systems Inc.)制造的非接触表面-层截面形状测量系统VertScan(注册商标)R550GML,在以下条件下测定,CCD相机:SONY HR-50 1/3',物镜:20倍,镜筒:1X Body,可变焦距镜头:No Relay,滤波片:530white,测定模式:Wave,使用以4次多项式修正后的输出。
(4)粘接层和功能层的膜厚测定方法:
将粘接层或功能层的表面使用RuO4染色,包埋在环氧树脂中。之后,将通过超薄切片法制作的切片使用RuO4染色,对粘接层剖面使用TEM(株式会社日立高科技制造H-7650,加速电压100kV)进行测定。
(5)玻璃化转变温度:
利用株式会社PERKINELMER JAPAN制造的差示扫描量热装置(DSC)8500,从-100~200℃至,以每分钟10℃的升温条件进行测定。
(6)数均分子量测定方法:
使用GPC(TOSOH株式会社制HLC-8120GPC)进行测定。数均分子量换算为聚苯乙烯计算。
(7-1)粘接力评价方法(粘接力1):
在聚甲基丙烯酸甲酯板(株式会社KURARAY制造COMOGLAS(注册商标),厚度1mm)的表面,将5cm宽的本发明的粘接膜的粘接层面使用5cm宽的2kg橡胶辊滚压1个往复,在室温放置1小时后测定剥离力。剥离力使用株式会社岛津制作所制造“Ezgraph”,在拉伸速度300mm/分钟的条件下,进行180°剥离。
(7-2)粘接力评价方法(粘接力2):
将(7-1)的聚甲基丙烯酸甲酯板变更为使用后述比较例1中得到的没有粘接层的聚酯膜表面(厚度25μm)来评价粘接力,除此以外,都与(7-1)同样地进行了评价。
(8)粘接特性的评价方法:
将1张A4尺寸的粘接膜的粘接层一侧彼此重叠,用手指按压进行了粘接特性的评价。将仅用手指轻轻按压,膜就互相贴合能够保持弯曲状态的情况设为5分,将使用手指使劲按压,膜才能相互贴合能够保持弯曲状态的情况设为4分,将使用手指使劲按压,膜虽然相互贴合能够保持弯曲状态,但在3秒内剥离的情况下设为3分,将使用手指使劲按压虽然可见膜有微小的粘接特性,但完全不能保持弯曲的状态的情况设为2分,将即使用手指使劲按压也完全没有粘接特性的情况设为1分。实际使用上,优选3分以上。
(9)表面电阻的测定方法:
基于后述(9-1)的方法,对粘接层的表面电阻进行了测定。利用(9-1)的方法,由于不能充分测定低于1×108Ω的表面电阻率,对于在(9-1)中未能测定的膜使用(9-2)的方法。
需要说明的是,表面电阻超过1×1014Ω的情况下记录为“-”。
(9-1)使用日本惠普株式会社制造高电阻测定器:HP4339B和测定电极:HP16008B,在23℃、50%RH的测定气氛下将聚酯膜充分调湿后,对于在施加电压100V时1分钟后的涂布层的表面电阻进行了测定。
(9-2)使用三菱化学株式会社制造低电阻计:Loresta-GP MCP-T600,在23℃、50%RH的测定气氛中将样品进行30分钟的调湿后,对涂布层的表面电阻进行了测定。
(10)功能层(抗静电层)侧的尘埃附着性评价方法:
在23℃、50%RH的测定气氛下将聚酯膜充分调湿后,使用棉布将抗静电层擦拭10个来回。将它轻轻地靠近粉碎的烟草的灰上,将灰的附着状况依照以下基准进行了评价。
A:即使将膜与灰接触也没有附着。
B:将膜与灰接触会有极少量附着。
C:将膜与灰接触会有少量附着。
D:将膜靠近灰就会有大量的附着。
(11)粘连特性的测定方法:
准备2张测定的聚酯膜,将粘接层一侧和与粘接层相反一侧(设有功能层的情况下为功能层一侧)重叠,将12cm×10cm的面积在40℃、80%RH、10kg/cm2、20小时的条件下进行压制。之后,将两膜之间依照ASTM D1893所规定的方法进行剥离,对该剥离载荷进行测定。
需要说明的是,超过300g/cm也不能充分测定的情况或膜发生断裂的情况下记录为“-”。
(12)粘接层的残胶(抗转移附着性)评价方法:
将1张A4尺寸的粘接膜的粘接层一侧和后述比较例1的没有粘接层的A4尺寸的聚酯膜重叠并用手指使劲按压贴合后,将具有粘接层的膜剥离,对比较例1的没有粘接层的膜表面进行观察,若没有残胶(粘接层的转移附着痕迹)则规定为“A”,用手指使劲按压处的20%以下的范围有残胶(有少量粘接层的转移附着痕迹)的情况下规定为B,超过用手指使劲按压处的20%的范围有残胶的情况下规定为C。
在实施例和比较例中使用的聚酯如以下方式准备。
<聚酯(A)的制造方法>
将对苯二甲酸二甲酯100重量份、乙二醇60重量份、相对于生成的聚酯为30ppm的酸式磷酸乙酯、作为催化剂的相对于生成聚酯为100ppm的四水合乙酸镁,在氮气氛下,以260℃进行酯化反应。接着,添加相对于生成聚酯为50ppm的钛酸四丁酯,用2小时30分钟升温至280℃,并且减压至绝对压力为0.3kPa,进一步用80分钟进行熔融缩聚,得到特性粘度为0.63且一缩二乙二醇量为2摩尔%的聚酯(A)。
<聚酯(B)的制造方法>
将对苯二甲酸二甲酯100重量份、乙二醇60重量份、作为催化剂将相对于生成聚酯为900ppm的四水合乙酸镁,在氮气氛下,以225℃进行酯化反应。接着,添加相对于生成聚酯为3500ppm的正磷酸,添加相对于生成聚酯为70ppm的二氧化锗,用2小时30分钟升温至280℃,并且减压至绝对压力为0.4kPa,再用85分钟进行熔融缩聚,得到特性粘度为0.64且一缩二乙二醇量为2摩尔%的聚酯(B)。
<聚酯(C)的制造方法>
在聚酯(A)的制造方法中,除了在熔融聚合前添加了平均粒径为2μm的二氧化硅颗粒0.3重量份以外,都以与聚酯(A)的制造方法同样的方法得到聚酯(C)。
<聚酯(D)的制造方法>
在聚酯(A)的制造方法中,除了在熔融聚合前添加了平均粒径为3.2μm的二氧化硅颗粒0.6重量份以外,都以与聚酯(A)的制造方法同样的方法得到聚酯(D)。
构成粘接层和功能层的化合物例如下所述。
(化合物例)
·聚酯树脂:(IA)
由下述组成构成的聚酯树脂(玻璃化转变温度:-20℃)的水分散体
单体组成:(酸成分)十二烷二羧酸/对苯二甲酸/间苯二甲酸/间苯二甲酸-5-磺酸钠//(二醇成分)乙二醇/1,4-丁二醇=20/38/38/4//40/60(mol%)
·(甲基)丙烯酸树脂:(IB)
由下述组成构成的丙烯酸树脂(玻璃化转变温度:-50℃)的水分散体
丙烯酸-2-乙基己酯/甲基丙烯酸甲酯/甲基丙烯酸=85/12/3(重量%)
·(甲基)丙烯酸树脂:(IC)
由下述组成构成的丙烯酸树脂(玻璃化转变温度:-40℃)的水分散体
丙烯酸-2-乙基己酯/丙烯酸正丁脂/甲基丙烯酸甲酯/甲基丙烯酸(2-羟基乙基)酯/丙烯酸=58/20/15/5/2(重量%)
·抗静电剂(导电聚合物):(IIA)
并用聚苯乙烯磺酸的聚(3,4-亚乙二氧基噻吩)
·抗静电剂(季铵盐化合物):(IIB)
在主链中具有吡咯烷鎓环的以下述组成聚合得到的聚合物
二烯丙基二甲基氯化铵/二甲基丙烯酰胺/N-羟甲基丙烯酰胺=90/5/5(mol%)。数均分子量为30000。
·抗静电剂(具有铵基的化合物):(IIC)
由下述式(2)的结构单元构成的平衡离子为甲烷磺酸离子的数均分子量为50000的高分子化合物。
·抗静电剂(具有磺酸基化合物):(IID)
在对位具有磺酸和磺酸盐基的苯乙烯磺酸及其盐的均聚物,在聚合物中的磺酸和磺酸盐的比例是磺酸为90%,磺酸钠盐为10%,数均分子量20000的高分子化合物。
·三聚氰胺化合物:(IIIA)
六甲氧基羟甲基三聚氰胺
·环氧化合物:(IIIB)
作为多官能多环氧化合物的聚甘油聚缩水甘油醚
·聚醚化合物:(IV)
在二甘油结构上的聚氧化乙烯加成物。重均分子量为350。
·脱模剂(含有长链烷基的化合物):(VA)
向4口烧瓶中加入二甲苯200份,异氰酸十八烷基酯600份,在搅拌下加热。从二甲苯开始回流的时间开始,将平均聚合度500、皂化度88摩尔%的聚乙烯醇100份逐次少量每隔10分钟加入,总耗时大约2小时。加完聚乙烯醇后,进一步进行2小时回流,结束反应。待反应混合物冷却至大约80℃,加入到甲醇中,因反应生成物作为白色沉淀物析出,所以将此沉淀物过滤分离,加入二甲苯140份,加热至完全溶解后,再加入甲醇使其沉淀,将该操作重复数次后,使用甲醇洗涤沉淀物,将其干燥破碎后得到脱模剂。
·脱模剂(氟化合物):(VB)
由下述组成构成的氟化合物的水分散体
丙烯酸十八烷基酯/甲基丙烯酸全氟己基乙酯/氯乙烯=66/17/17(重量%)
·含有聚醚基的缩聚型有机硅:(VC)
在二甲基硅酮的侧链,以摩尔比计,相对于二甲基硅氧烷100含有乙二醇链为8的聚乙二醇(末端为羟基)为1的、数均分子量为7000的含有聚醚基的有机硅(将有机硅的硅氧烷键规定为1的情况下,以摩尔比的比例计,聚醚基的醚键为0.07)。数均分子量为500以下的低分子成分为3%,不存在与硅键合的乙烯基(乙烯基硅烷)、氢基(氢化硅烷)。需要说明的是,本化合物是以重量比计,将含有聚醚基的有机硅作为1时,将十二烷基苯磺酸钠以0.25的比例配合,进行水分散得到的。
·蜡:(VD)
向具备搅拌机、温度计、温度控制器的内容量为1.5L的乳化设备中,加入熔点105℃、酸值16mgKOH/g、密度0.93g/mL、数均分子量为5000的氧化聚乙烯蜡300g、离子交换水650g和十甘油单油酸酯表面活性剂50g、48%的氢氧化钾水溶液10g,进行氮置换后,密封,在150℃进行1小时的高速搅拌后冷却至130℃,在400气压下通过高压均化器,冷却至40℃,得到蜡乳液。
·聚酯树脂:(VIA)
由下述组成构成的聚酯树脂(玻璃化转变温度:50℃)的水分散体
单体组成:(酸成分)对苯二甲酸/间苯二甲酸/间苯二甲酸-5-磺酸钠//(二醇成分)乙二醇/1,4-丁二醇/一缩二乙二醇=50/46/4//70/20/10(mol%)
·(甲基)丙烯酸树脂:(VIB)
由下述组成构成的丙烯酸树脂(玻璃化转变温度10℃)的水分散体
丙烯酸正丁酯/丙烯酸乙酯/甲基丙烯酸甲酯/甲基丙烯酸(2-羟基乙基)酯/丙烯酸=10/52/30/5/3(重量%)
·(甲基)丙烯酸树脂:(VIC)
由下述组成构成的丙烯酸树脂(玻璃化转变温度:40℃)的水分散体
丙烯酸乙酯/甲基丙烯酸甲酯/N-羟甲基丙烯酰胺/丙烯酸=48/45/4/3(重量%)
实施例1:
将聚酯(A)、(B)、(C)分别以91重量%、3重量%、6重量%的比例混合的混合原料作为最外层(表层)的原料,将聚酯(A)、(B)分别以97重量%、3重量%的比例混合的混合原料作为中间层的原料,分别供给至两台挤出机,各自在285℃熔融后,以2种3层(表层/中间层/表层=3:19:3的排出量)的层结构共挤出至设定为40℃的冷却辊上,使其冷却固化得到未拉伸片材。
接下来,利用辊的圆周速度差在膜温度85℃沿纵向拉伸3.3倍后,在该纵向拉伸膜的一个面涂布下述表1所示的涂布液A1,使粘接层的膜厚(干燥后)成为150nm,在相反一侧的面涂布下述表2所示的涂布液B1,使功能层的膜厚(干燥后)成为30nm,导入拉幅机中,在90℃干燥10秒钟后,在横向上在110℃拉伸4.3倍,在230℃进行10秒钟热处理后,沿横向进行2%松弛,得到厚度为25μm、粘接层的背面一侧(功能层一侧)的表面的Sa为9nm的聚酯膜。
对得到的聚酯膜进行评价发现,与聚甲基丙烯酸甲酯板的粘接力为6mN/cm,观察到粘接特性,表面电阻为2×109Ω,具有良好的抗静电性能。另外,没有残胶(抗转移附着性)是良好的。该膜的特性示于下述表3。
实施例2~77:
在实施例1中,除了将涂布剂组成变更为表1和2所示的涂布剂组成以外,都与实施例1同样地制造,得到聚酯膜。得到的聚酯膜如下述表3~7所示,粘接力、表面电阻以及抗转移附着性良好。
实施例78:
将聚酯(A)、(B)、(C)分别以91重量%、3重量%、6重量%的比例混合的混合原料作为最外层(表层1)的原料,将聚酯(A)、(B)、(D)分别以72重量%、3重量%、25重量%的比例混合的混合原料作为最外层(表层2)的原料,将聚酯(A)、(B)分别以97重量%、3重量%的比例混合的混合原料作为中间层的原料,分别供应至两台挤出机,各自在285℃熔融后,以3种3层(表层1/中间层/表层2=6:13:6的排出量)的层结构共挤出至设定为40℃的冷却辊上,使其冷却固化得到未拉伸片材。接下来,利用辊圆周速度差,在膜温度为85℃沿纵向拉伸3.3倍后,在该纵向拉伸膜的表层1一侧涂布下述表1所示的涂布液A1,使粘接层的膜厚(干燥后)成为250nm,导入拉幅机中,在90℃干燥10秒钟后,沿横向在110℃拉伸4.3倍,在230℃进行10秒钟热处理后,沿横向进行2%松弛,得到厚度25μm、粘接层的背面一侧(表层2一侧、功能层一侧)的表面的Sa为30nm的聚酯膜。
对得到的聚酯膜进行评价发现,与聚甲基丙烯酸甲酯板的粘接力为10mN/cm,粘接特性良好,表面电阻为1×109Ω,具有良好的抗静电性能。另外,没有残胶(抗转移附着性)是良好的。该膜的特性示于下述表7。
实施例79~84:
在实施例78中,除了将涂布剂组成变更为表1所示的涂布剂组成以外,都与实施例78同样地制造,得到聚酯膜。得到的聚酯膜如下述表7所示,粘接力、表面电阻以及抗转移附着性良好。
实施例85:
将聚酯(A)、(B)、(C)分别以91重量%、3重量%、6重量%的比例混合的混合原料作为最外层(表层1)的原料,将聚酯(A)、(B)、(D)分别以47重量%、3重量%、50重量%的比例混合的混合原料作为最外层(表层2)的原料,将聚酯(A)、(B)分别以97重量%、3重量%的比例混合的混合原料作为中间层的原料,分别供应至两台挤出机,各自在285℃熔融后,以3种3层(表层1/中间层/表层2=4:17:4的排出量)的层结构共挤出至设定为40℃的冷却辊上,使其冷却固化得到未拉伸片材。接下来,利用辊圆周速度差,在膜温度85℃沿纵向拉伸3.3倍后,在该纵向拉伸膜的表层1一侧,涂布下述表1所示的涂布液A1,使粘接层的膜厚(干燥后)成为250nm,导入拉幅机中,在90℃干燥10秒钟后,沿横向在110℃拉伸4.3倍,在230℃进行10秒钟热处理后,沿横向进行2%松弛,得到厚度25μm、粘接层的背面一侧的表面的Sa为55nm的聚酯膜。
对得到的聚酯膜进行评价发现,与聚甲基丙烯酸甲酯板的粘接力为10mN/cm,粘接特性良好,表面电阻为1×109Ω,具有良好的抗静电性能。另外,没有残胶(抗转移附着性)是良好的。该膜的特性示于下述表7。
实施例86~91:
在实施例85中,除了将涂布剂组成变更为表1所示的涂布剂组成以外,都与实施例85同样地制造,得到聚酯膜。得到的聚酯膜如下述表7所示,粘接力、表面电阻以及抗转移附着性良好。
实施例92:
在实施例1中,除了未设置粘接层以外都与实施例1同样地制造,得到聚酯膜。在该没有粘接层的聚酯膜上,涂布下述表1所示的涂布液A4,使粘接层的膜厚(干燥后)成为350nm,在100℃干燥1分钟,得到通过离线涂敷的未拉伸的叠层了粘接层的聚酯膜。得到的聚酯膜如表7所示,粘接力以及表面电阻良好。然而,残胶(抗转移附着性)较多。
比较例1:
在实施例1中,除了未设置粘接层以及功能层以外都与实施例1同样地制造,得到聚酯膜。对得到的聚酯膜进行评价发现,如下述表8所示,是没有粘接力和表面电阻的膜。
比较例2~9:
在实施例1中,除了将涂布剂组成变更为表1所示的涂布剂组成以外,都与实施例1同样地制造,得到聚酯膜。得到的聚酯膜如表8所示,结果是可以观察到没有粘接力的情况、表面电阻差的情况。
比较例10:
在比较例1中得到的没有粘接层和功能层的聚酯膜上,涂布下述表1所示的涂布液C1使粘接层的膜厚(干燥后)成为20μm,以100℃进行3分钟的干燥,得到通过离线涂敷的未拉伸的形成有粘接层的聚酯膜。向比较例1的没有粘接层和功能层的聚酯膜,贴合上述得到的膜的粘接层一侧后进行裁断,发现了在实施例中未见到的粘接层的成分的溢出,其结果令人担忧由于粘接成分会导致污染。另外,粘接力未能很好地测定。其他的特性如表8所示。
[表1]
[表2]
[表3]
[表4]
[表5]
[表6]
[表7]
[表8]
产业上的可利用性
本发明的粘接膜能够在例如防止树脂板、金属板等的运输时、保管时或加工时受伤或附着污染物等时使用的表面保护膜等的用途中,适合用于要求鱼眼少、机械强度和耐热性优异、尘埃的附着少、具有良好的粘接特性的用途。
Claims (14)
1.一种粘接膜,其特征在于:
在聚酯膜的至少一个面具有膜厚为1~700nm的粘接层,该粘接层含有玻璃化转变温度在0℃以下的树脂和抗静电剂,该粘接层对聚甲基丙烯酸甲酯板的粘接力为1~300mN/cm,玻璃化转变温度在0℃以下的树脂是含有在酯末端具有碳原子数为4以上的烷基的(甲基)丙烯酸酯单元的(甲基)丙烯酸树脂。
2.如权利要求1所述的粘接膜,其特征在于:
粘接层含有交联剂。
3.如权利要求2所述的粘接膜,其特征在于:
交联剂是选自三聚氰胺化合物、异氰酸酯系化合物、环氧化合物、噁唑啉化合物、碳二亚胺系化合物、硅烷偶联化合物、酰肼化合物、氮丙啶化合物中的至少一种。
4.如权利要求1~3中任一项所述的粘接膜,其特征在于:
在膜的与粘接层相反一侧的面具有功能层。
5.如权利要求1~3中任一项所述的粘接膜,其特征在于:
抗静电剂是高分子型的抗静电剂。
6.如权利要求5所述的粘接膜,其特征在于:
高分子型的抗静电剂是导电聚合物。
7.如权利要求1~3中任一项所述的粘接膜,其特征在于:
所述粘接力为1~100mN/cm。
8.一种粘接膜的制造方法,其特征在于:
通过在聚酯膜的至少一个面设置含有玻璃化转变温度在0℃以下的树脂和抗静电剂的涂布层后,至少在一个方向上进行拉伸,制造具有膜厚为1~700nm且对聚甲基丙烯酸甲酯板的粘接力为1~300mN/cm的粘接层的粘接膜,玻璃化转变温度在0℃以下的树脂是含有在酯末端具有碳原子数为4以上的烷基的(甲基)丙烯酸酯单元的(甲基)丙烯酸树脂。
9.如权利要求8所述的粘接膜的制造方法,其特征在于:
粘接层含有交联剂。
10.如权利要求9所述的粘接膜的制造方法,其特征在于:
交联剂是选自三聚氰胺化合物、异氰酸酯系化合物、环氧化合物、噁唑啉化合物、碳二亚胺系化合物、硅烷偶联化合物、酰肼化合物、氮丙啶化合物中的至少一种。
11.如权利要求8~10中任一项所述的粘接膜的制造方法,其特征在于:
在膜的与粘接层相反一侧的面具有功能层。
12.如权利要求8~10中任一项所述的粘接膜的制造方法,其特征在于:
抗静电剂是高分子型的抗静电剂。
13.如权利要求12所述的粘接膜的制造方法,其特征在于:
高分子型的抗静电剂是导电聚合物。
14.如权利要求8~10中任一项所述的粘接膜的制造方法,其特征在于:
所述粘接力为1~100mN/cm。
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