CN104870592B - 光学膜用粘着剂组合物及表面保护膜 - Google Patents
光学膜用粘着剂组合物及表面保护膜 Download PDFInfo
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- CN104870592B CN104870592B CN201380065202.8A CN201380065202A CN104870592B CN 104870592 B CN104870592 B CN 104870592B CN 201380065202 A CN201380065202 A CN 201380065202A CN 104870592 B CN104870592 B CN 104870592B
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 51
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- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 12
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- C08G18/24—Catalysts containing metal compounds of tin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C09J2471/00—Presence of polyether
Abstract
本发明的光学膜用粘着剂组合物含有65~85质量%的(A)重均分子量为10万~60万的(甲基)丙烯酸类树脂、10~30质量%的(B)数均分子量为500~1500的聚氧亚烷基多元醇、1.0~5.0质量%的(C)聚异氰酸酯、0.2~1.0质量%的(D)离子化合物和0.005~0.1质量%的(E)锡类催化剂。本发明的光学膜用粘着剂组合物具有抗静电性及透明性优异、对粘着体的污染性及腐蚀性低的优点。
Description
技术领域
本发明涉及一种光学膜用粘着剂组合物及表面保护膜。
背景技术
近年来,在光学部件以及电子部件领域,以表面保护为目的,广泛使用层积聚乙烯、聚酯、聚丙烯等透明保护膜(透明基片)与粘着剂的表面保护膜。该表面保护膜存在如下问题,在从粘着片剥离脱模膜时、以及从被粘接体剥离粘着片时,若带上静电,则会吸附周围的污物而污染光学部件以及电子部件。
因此,开发了赋予抗静电性的粘着剂,例如,在专利文献1及2中,公开了一种在丙烯酸类共聚物中作为抗静电剂添加聚醚多元醇的粘着剂。但是,作为抗静电剂添加聚醚多元醇的粘着剂在透明性上存在问题,从保证品质的角度考虑,无法用于对透明性有需求的表面保护膜。
另外,在专利文献3中公开了一种通过将聚醚多元醇接枝到丙稀酸类聚合物上,使抗静电性和透明性共存的粘着剂。但是,该粘着剂由于其酸值高,因而存在难以用于ITO膜等不能被腐蚀的光学部件的问题。
现有技术文献
专利文献
专利文献1:特开平6-128539号公报
专利文献2:特开第2005-325255号公报
专利文献3:特开第2010-6980号公报
发明内容
本发明要解决的技术问题
本发明的目的在于,鉴于上述现有技术所存在的问题,提供一种抗静电性及透明性优异、对被粘接体的污染性及腐蚀性低的光学膜用粘着剂组合物以及表面保护膜。
解决技术问题的技术手段
本发明的发明人以光学膜用粘着剂组合物所具有的上述问题点为背景进行了深入研究,结果发现一种光学膜用粘着剂组合物表现出良好的抗静电性及透明性、对被粘接体的污染性及腐蚀性低,进而完成了本发明,所述光学膜用粘着剂组合物以特定的重量比例含有特定重均分子量的(甲基)丙烯酸树脂、特定数均分子量的聚氧亚烷基多元醇、聚异氰酸酯、离子化合物及锡类催化剂。
本发明如以下(1)~(10)所示。
(1)一种光学膜用粘着剂组合物,其特征在于,该光学膜用粘着剂组合物含有65~85质量%的(A)(甲基)丙烯酸类树脂、10~30质量%的(B)聚氧亚烷基多元醇(polyoxyalkylenepolyol)、1.0~5.0质量%的(C)聚异氰酸酯、0.2~1.0质量%的(D)离子化合物和0.005~0.1质量%的(E)锡类催化剂,(A)(甲基)丙烯酸类树脂的重均分子量为10万~60万,且(B)聚氧亚烷基多元醇的数均分子量为500~1500。
(2)在(1)中所述的光学膜用粘着剂组合物,其特征在于,上述(A)(甲基)丙烯酸类树脂作为共聚成分含有0.5~10mol%的具有羟基的(甲基)丙稀酸类单体。
(3)在(2)中所述的光学膜用粘着剂组合物,其特征在于,上述具有羟基的(甲基)丙稀酸类单体为2-羟乙基(甲基)丙烯酸酯。
(4)在(1)~(3)的任一项中所述的光学膜用粘着剂组合物,其特征在于,上述(A)(甲基)丙烯酸类树脂作为共聚成分含有15~50mol%的(甲基)丙烯酸甲酯。
(5)在(1)~(4)的任一项中所述的光学膜用粘着剂组合物,其特征在于,其酸值为0~5mgKOH/g。
(6)在(1)~(5)的任一项中所述的光学膜用粘着剂组合物,其特征在于,上述(D)离子化合物为碱金属盐。
(7)在(1)~(6)的任一项中所述的光学膜用粘着剂组合物,其特征在于,上述(E)锡类催化剂为二月桂酸二辛基锡。
(8)一种表面保护膜,其特征在于,在透明基材上的一个面上形成使在(1)~(7)的任一项中记载的光学膜用粘着剂组合物固化而得到的粘着剂层。
(9)在(8)中所述的表面保护膜,其特征在于,表面电阻率值为1.0×1010Ω/□以下,且雾度为1.2以下。
(10)在(8)或(9)中所述的表面保护膜,其特征在于,上述透明基材是厚度为5~200μm的聚对苯二甲酸乙二醇酯、聚乙烯、聚丙烯、聚苯乙烯、聚酰亚胺、聚乙烯醇、聚氯乙烯或纤维素。
发明效果
根据本发明,可以提供一种抗静电性及透明性优异、对被粘接体的污染性及腐蚀性低的光学膜用粘着剂组合物、以及表面保护膜。
具体实施方式
下面对本发明进行详细说明。
本发明的光学膜用粘着剂组合物含有(A)(甲基)丙烯酸类树脂、(B)聚氧亚烷基多元醇、(C)聚异氰酸酯、(D)离子化合物和(E)锡类催化剂。
本发明的(甲基)丙烯酸类树脂是指丙烯酸类树脂或甲基丙烯酸类树脂,另外(甲基)丙烯酸酯是指丙烯酸酯或甲基丙烯酸酯。此外,(甲基)丙烯酸酯类树脂是指全部构成单体的80mol%以上为(甲基)丙稀酸酯类单体的聚合物。
(A)(甲基)丙烯酸类树脂
作为在本发明的(A)(甲基)丙烯酸类树脂的聚合中使用的(甲基)丙烯酸类单体,没有特别的限制,优选其不具有羧基(化学式:-COOH)。作为(甲基)丙烯酸类单体的例子,可以列举:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸正己酯、2-乙基己基(甲基)丙烯酸酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸硬脂酸酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸异硬脂酸酯等(甲基)丙烯酸烷基酯,(甲基)丙烯酸环己酯、(甲基)丙烯酸降冰片酯(norbornyl(meth)acrylate)、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸降冰片烷基酯(norbornanyl(meth)acrylate)、二环戊烯基(甲基)丙烯酸酯、二环戊烯基氧基乙基(甲基)丙烯酸酯、二环戊基(甲基)丙烯酸酯、二环戊基氧基乙基(甲基)丙烯酸酯、三环癸烷二羟甲基二(甲基)丙烯酸酯等环状(甲基)丙烯酸烷基酯,甲氧基乙基(甲基)丙烯酸酯、乙氧基乙基(甲基)丙烯酸、丁氧基乙基(甲基)丙烯酸酯、2-甲氧基乙氧基乙基(甲基)丙烯酸酯、2-乙氧基乙氧基乙基(甲基)丙烯酸酯等烷氧基烷基(甲基)丙烯酸酯,甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯等烷氧基(聚)亚烷基二醇(甲基)丙烯酸酯,八氟戊基(甲基)丙烯酸酯等氟化烷基(甲基)丙烯酸酯,N,N-二甲基氨基乙基(甲基)丙烯酸酯、N,N-二乙基氨基乙基(甲基)丙烯酸酯等二烷基氨基烷基(甲基)丙烯酸酯,(甲基)丙烯酰胺、双丙酮(甲基)丙烯酰胺等具有酰胺基的(甲基)丙烯酸酯,(甲基)丙烯酸缩水甘油酯等具有环氧基的(甲基)丙烯酸酯,硅氧烷改性(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等多官能团(甲基)丙烯酸酯。它们可以单独使用,或者2种以上组合使用。
若考虑到(A)(甲基)丙烯酸类树脂与(B)聚氧亚烷基多元醇的互溶性,即考虑到使光学膜用粘着剂组合物固化而得到的粘着剂层的透明性,作为(A)(甲基)丙烯酸类树脂的共聚成分优选含有15~50mol%丙烯酸甲酯或甲基丙烯酸甲酯,更加优选含有25~45mol%。
另外,从本发明的(A)(甲基)丙烯酸类树脂能够通过聚异氰酸酯与聚氧亚烷基多元醇反应而一体化(透明性提高)的角度考虑,作为共聚组分优选含有具有羟基的(甲基)丙烯酸类单体。作为具有羟基的(甲基)丙烯酸类单体的例子,可以列举2-羟乙基(甲基)丙烯酸酯、2-羟丙基(甲基)丙烯酸酯、4-羟丁基(甲基)丙烯酸酯、1,3-丁二醇(甲基)丙烯酸酯、1,4-丁二醇(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯、3-甲基戊二醇(甲基)丙烯酸酯等具有羟基的(甲基)丙烯酸酯等。其中,在共聚性和反应性方面来看,优选2-羟乙基(甲基)丙烯酸酯。作为(A)(甲基)丙烯酸类树脂的共聚成分优选含有0.5~10mol%具有羟基的(甲基)丙烯酸类单体,更加优选含有0.6~8.0mol%。
另外,在本发明的(A)(甲基)丙烯酸类树脂中,在不损害聚合性的范围内,作为共聚成分可以使用其他聚合性单体。作为这种聚合性单体的例子,可以列举丙烯腈、甲基丙烯腈、苯乙烯、α-甲基苯乙烯、乙酸乙烯酯、丙酸乙烯酯、硬脂酸乙烯酯、氯乙烯、偏氯乙烯、烷基乙烯基醚、乙烯基甲苯、乙烯基吡啶、乙烯基吡咯烷酮、衣康酸二烷基酯、富马酸二烷基酯、烯丙基醇、丙烯酰氯、甲基乙烯基酮、N-丙烯酰胺基甲基三甲基氯化铵、烯丙基三甲基氯化铵、二甲基烯丙基乙烯基酮等。
本发明的(A)(甲基)丙烯酸类树脂的重均分子量需为10万~60万,优选为15万~50万,更加优选为20万至~40万。重均分子量小于10万时,由于凝聚力变小而发生糊状物的残留。另一方面,重均分子量大于60万时,(A)(甲基)丙烯酸类树脂与(B)聚氧亚烷基多元醇的互溶性变差,从而所得到的粘着剂层的透明性变差。
这里的重均分子量通过以下方式计算:使用凝胶渗透色谱(昭和电工株式会社制造,Shodex(注册商标)GPC-101),以下列条件在常温下进行测定,通过聚苯乙烯换算而算得。
柱:昭和电工株式会社制造,Shodex(注册商标)LF-804
柱温:40℃
试样:共聚物的0.2质量%四氢呋喃溶液
流速:1mL/分钟
洗脱液:四氢呋喃
另外,本发明的(A)(甲基)丙烯酸类树脂的玻璃化转变温度(Tg)优选为-80~0℃,更加优选为-70~-10℃。Tg比0℃高时,对于被粘接体的润湿变差,不优选。另一方面,Tg比-80℃低时,可能会由于凝聚力变小而发生糊状物的残留,不优选。此外,(A)(甲基)丙烯酸类树脂的Tg可以通过适当改变所使用的单体成分和组成比来进行调节。
此处,Tg是指由以下方法求得的Tg。从(A)(甲基)丙烯酸类树脂中采取10mg试样,使用差示扫描量热计(DSC),以10℃/分钟的升温速度将温度从-80℃变化为200℃来进行差示扫描量热测定,将基于玻璃化转变的吸热起始温度设为Tg。此外,在观察到两个Tg的情况下,取两个Tg的平均值。
本发明的(A)(甲基)丙烯酸类树脂的聚合方法没有特别的限制,可以通过溶液聚合、乳液聚合、本体聚合、悬浮聚合、交替共聚等公知方法进行聚合。其中,特别适宜的是溶液聚合。
另外,所得到的共聚物为无规共聚物、嵌段共聚物等均可。
在(A)(甲基)丙烯酸类树脂的聚合中使用的聚合引发剂没有特别的限制,可以从公知的聚合引发剂中适当地选择使用。优选列举下列油溶性聚合引发剂,例如:2,2'-偶氮二(异丁腈)、2,2'-偶氮二(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮二(2,4-二甲基戊腈)、2,2'-偶氮二(2-甲基丁腈)、1,1'-偶氮二(环己烷-1-腈)、2,2'-偶氮二(2,4,4-三甲基戊烷)、二甲基-2,2'-偶氮二(2-甲基丙酸酯)等偶氮聚合引发剂,过氧化苯甲酰、叔丁基过氧化氢、二叔丁基过氧化物、叔丁基过氧苯甲酸酯、二枯基过氧化物、1,1-二(叔丁基过氧)-3,3,5-三甲基环己烷、1,1-二(叔丁基过氧)环十二烷等过氧化物类聚合引发剂等。这些聚合引发剂可以单独使用,也可以2种以上组合使用。聚合引发剂的用量为通常的用量即可,例如,相对于单体100质量份,可以从0.01~5质量份左右的范围中进行选择,优选为0.02~4质量份的范围,更加优选为0.03~3质量份的范围。
此外,在溶液聚合中,可以使用各种普通溶剂。作为这样的溶剂,可以列举下列有机溶剂:乙酸乙酯、乙酸正丙酯、乙酸正丁酯等酯类,甲苯、苯等芳烃类,正己烷、正庚烷等脂肪烃类,环己烷、甲基环己烷等脂环烃类,甲基乙基酮、甲基异丁基酮等酮类等。这些溶剂可以单独使用,也可以2种以上组合使用。
另外,作为本发明的(A)(甲基)丙烯酸类树脂的添加量,需为65~85质量%,更加优选为70~85质量%。添加量比65质量%少时,会污染被粘接体,另一方面,添加量超过85质量%时,得不到充分的带电特性。
(B)聚氧亚烷基多元醇
作为本发明的(B)聚氧亚烷基多元醇,只要是具有醚基的聚合物多元醇则没有特别的限制,可以适当使用公知的聚合物多元醇。作为(B)聚氧亚烷基多元醇的例子,可以列举聚乙二醇、聚丙二醇、聚四亚甲基醚二醇及它们的衍生物或共聚物等。其中,出于容易调整与(甲基)丙烯酸类树脂的互溶性的理由,优选聚丙二醇。它们可以单独使用,也可以2种以上混合使用。
本发明的(B)聚氧亚烷基多元醇的数均分子量需为500~1500,优选为800~1200。数均分子量超过1500时,粘着剂层的透明性变差。另一方面,数均分子量小于500时,会有发生糊状物的残留的可能性,不优选。数均分子量是通过GPC(凝胶渗透色谱)进行测定而得到的。
另外,作为本发明的(B)聚氧亚烷基多元醇的添加量,需为10~30质量%,更加优选为15~25质量%。添加量比10质量%少时,得不到充分的带电特性,另一方面,添加量超过30质量%时,会污染被粘接体。
(C)聚异氰酸酯
作为本发明的(C)聚异氰酸酯,可以列举芳香族类、脂肪族类、脂环类等的聚异氰酸酯。作为(C)聚异氰酸酯的例子,可例举1,4-四亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯(HDI)、2-甲基-1,5-戊烷二异氰酸酯、3-甲基-1,5-戊烷二异氰酸酯、三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、环己基二异氰酸酯、甲苯二异氰酸酯(TDI)、氢化甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、氢化二苯基甲烷二异氰酸酯、聚苯甲烷聚异氰酸酯、二甲苯二异氰酸酯、氢化二甲苯二异氰酸酯、四甲基苯二甲基二异氰酸酯、降冰片烯二异氰酸酯、萘二异氰酸酯、三羟甲基丙烷/甲苯二异氰酸酯三聚体加成物、三羟甲基丙烷/六亚甲基二异氰酸酯三聚体加成物、六亚甲基二异氰酸酯的异氰脲酸酯体等异氰酸酯加成物、聚醚聚异氰酸酯、聚酯聚异氰酸酯等。这些物质可以单独使用,也可以2种以上组合使用。
另外,作为本发明的(C)聚异氰酸酯的添加量,需为1.0~5.0质量%,更加优选为2.0~4.0质量%。添加量比1.0质量%少时,得不到充分的凝聚力,另一方面,添加量超过5.0质量%时,粘着层变得过硬,对被粘接体的润湿性变差。
(D)离子化合物
作为本发明中使用的(D)离子化合物,可以列举由阴离子和阳离子构成的、在25℃下为液体状态或固体状态的离子化合物。具体而言,可以列举碱金属盐、离子液体(在25℃下为液体状态)、表面活性剂等。其中,出于难以污染被粘接体的理由,优选碱金属盐。
作为碱金属盐,可以列举由锂、钠、钾等碱金属阳离子与阴离子形成的化合物,具体而言,可以列举氯化钠、氯化钾、氯化锂、高氯酸锂、氯酸钾、硝酸钾、硝酸钠、碳酸钠、硫氰酸钠、LiBr、LiI、LiBF4、LiPF6、LiSCN、醋酸钠、藻酸钠、木质素磺酸钠、甲苯磺酸钠、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3C等。这些碱金属盐可以单独使用,也可以2种以上组合使用。
另外,作为本发明的(D)离子化合物的添加量,需为0.2~1.0质量%,更加优选为0.3~0.8质量%。添加量比0.2质量%少时,得不到充分的带电特性,另一方面,添加量超过1.0质量%时,会污染被粘接体。
(E)锡类催化剂
作为本发明的(E)锡类催化剂,可以列举二月桂酸二丁基锡、二乙基己酸二丁基锡(dibutyl tin di ethylhexoate)、二月桂酸二辛基锡等。其中,出于(C)聚异氰酸酯的固化性良好、且安全性高的理由,优选二月桂酸二辛基锡。
另外,作为本发明的(D)锡类催化剂的添加量,需为0.005~0.1质量%,更加优选为0.01~0.05质量%。添加量比0.005质量%少时,得不到充分的凝聚力,另一方面,添加量超过0.1质量%时,(甲基)丙烯酸类树脂的稳定性变差而使其适用期变短。
本发明的光学膜用粘着剂组合物的酸值优选为0~5mgKOH/g,优选为0~1mgKOH/g,更加优选为0~0.3mgKOH/g,最优选为0~0.1mgKOH/g。若酸值比5mgKOH/g高,则ITO膜等不能被腐蚀的材料变得难以使用。此外,组合物的酸值是以JIS K0070为标准而测定的值。例如,以如下方式进行测定。
用精密天平在100ml锥形瓶中精确称量2g左右的试样,向其中添加乙醇/二乙醚=1/1(质量比)的混合溶剂10ml进行溶解。进一步向该容器中添加1~3滴酚酞乙醇溶液作为指示剂,充分搅拌直至试样均匀。以0.1N的氢氧化钾-乙醇溶液对其进行滴定,以指示剂的稀薄红色持续至30秒时为中和终点。将通过利用下列通式(1)而由此结果得到的值记为组合物酸值。
[数学式1]
酸值(mgKOH/g)=[B×f×5.611]/S (1)
上式中,B为0.1N的氢氧化钾-乙醇溶液的用量(ml),f为0.1N的氢氧化钾-乙醇溶液的当量浓度(factor),S为试样的采用量(g)。
另外,在本发明的光学膜用粘着剂组合物中,在不损害透明性的范围内,也可以根据需要添加公知的各种添加剂。作为添加剂,可以列举增塑剂、表面润滑剂、流平剂、软化剂、抗氧化剂、抗老化剂、光稳定剂、紫外线吸收剂、阻聚剂、苯并三唑类等光稳定剂、磷酸酯类及其他的阻燃剂、表面活性剂等的抗静电剂等。
另外,出于涂布时的粘度调整的目的,也可以使用有机溶剂对本发明的光学膜用粘着剂组合物进行稀释。作为能够使用的有机溶剂,可以列举例如甲基乙基酮、丙酮、醋酸乙酯、四氢呋喃、二噁烷、环己酮、正己烷、甲苯、二甲苯、正丙醇、异丙醇、醋酸正丙酯等。这些有机溶剂可以单独使用,也可以2种以上混合使用。
本发明的表面保护膜在透明基材上的一个面上形成有使上述光学膜用粘着剂组合物固化而得到的粘着剂层。粘着剂层的厚度通常为3~100μm,优选为5~50μm。
作为透明基材,可以列举例如聚对苯二甲酸乙二醇酯、聚乙烯、聚丙烯、聚苯乙烯、聚酰亚胺、聚乙烯醇、聚氯乙烯、纤维素等。透明基材的厚度通常为5~200μm,优选为10~100μm左右。
此外,在透明基材的一个面上,根据需要,可以实施以下处理:由硅氧烷类、氟类、长链烷类等脱模剂进行的脱模处理;以及防污处理、酸处理、碱处理、底漆处理、电晕处理、等离子体处理、紫外线处理等易粘着处理。
另外,作为透明基材,优选使用经过抗静电处理的透明基材。作为在透明基材上实施的抗静电处理,没有特别的限制,可以使用下列通常使用的方法:至少在常用的透明基材的一个面上设置抗静电层的方法,或者将抗静电剂混炼到透明基材中的方法。
此外,对于本发明的表面保护膜的粘着剂层的形成,可以使用公知的涂布法(coating method,涂工法),可以使用例如凹印辊涂布机、逆辊涂布机、辊舐涂布机、浸渍辊式涂布机、棒式涂布机、刮刀涂布机、喷涂机、逗号式涂布机、直接式涂布机等惯用的涂布机进行涂布。
在本发明的表面保护膜中,根据需要,以保护粘着面为目的,可以在粘着剂层表面上贴合隔离膜(separator)。作为构成隔离膜的基材,虽然有纸和塑料膜,但从表面平滑性优异的角度出发,适合使用塑料膜。作为该膜,只要是可以保护上述粘着剂层的膜即可,没有特别的限制,可以列举例如聚乙烯膜、聚丙烯膜、聚对苯二甲酸乙二醇酯膜、聚丁烯薄膜等。
由于如上所述构成的本发明的表面保护膜的粘着面的表面电阻率值为1.0×1010Ω/□以下,且雾度为1.2以下,因此可以用于容易产生静电的塑料制品等。其中尤其适宜用作用于保护液晶显示等中所用的偏光板、波板、相位差板、光学补偿膜、反射片、增亮膜等光学部件表面的表面保护膜。
实施例
下面通过实施例及比较例对本发明进行更具体的说明,但本发明并不限定于这些实施例。
<(甲基)丙烯酸类树脂(A-1)~(A-3)的合成>
在配备有冷却管、氮气导入管、温度计及搅拌装置的反应容器中,加入500质量份乙酸正丙酯、265质量份2-乙基己基丙烯酸酯(0.53mol)、41质量份丙烯酸异冰片酯(0.07mol)、105质量份甲基丙烯酸甲酯(0.39mol)、2质量份2-羟乙基丙烯酸酯(0.007mol)及0.4质量份2,2'-偶氮二(异丁腈),在氮气流中以95℃进行8小时聚合,得到玻璃化转变温度为-30℃、重均分子量为25万的(甲基)丙烯酸类树脂(A-1)。此外,(甲基)丙烯酸类树脂的玻璃化转变温度及重均分子量的测定按上文所述的方法进行。
另外,除了如表1所示更换所使用的单体之外,以与(甲基)丙烯酸类树脂(A-1)相同的方式合成(甲基)丙烯酸类树脂(A-2)和(甲基)丙烯酸类树脂(A-3)。对于(甲基)丙烯酸类树脂(A-2)~(A-3),进行玻璃化转变温度及重均分子量的测定。结果示于表1中。
<实施例1~2及比较例1~7>
以表2所示组成添加(甲基)丙烯酸类树脂、聚氧亚烷基多元醇、聚异氰酸酯、离子化合物及锡类催化剂,进一步用醋酸乙酯将固相组分的浓度调整为50质量%,通过在室温下用分散机(disper)进行混合,得到光学膜用粘着剂组合物溶液。在对厚度为38μm的聚对苯二甲酸乙二醇酯(PET)的一个面上实施剥离处理而形成的隔离膜的剥离处理面上,流延涂布该溶液使干燥后的厚度为50μm,在50℃下进行5分钟、并在110℃下进行3分钟加热干燥,进一步贴合厚度为50μm的PET膜,制成粘着片。
<酸值>
用上述方法测定各组合物的酸值。结果示于表2中。
<表面电阻率值>
将所得到的粘着片切断为40mm×40mm的大小后,将它们在温度为23℃及相对湿度为65%的环境下放置3小时进行湿度调节,然后剥离隔离膜,以JIS K6911所记载的方法测定粘着面的表面电阻率。结果示于表2中。此外,表面电阻率值越小,表示抗静电性能越高。
<透明性>
将所得到的粘着片切取为30mm×30mm的大小,剥离粘着片的隔离膜,以贴合在玻璃板上后的形成品为测定用试样。对于测定用试样,使用株式会社村上色彩技术研究所制造的“HR-100型”,利用雾度计NM-150(株式会社村上色彩技术研究所)进行雾度的测定。雾度(%)是由漫透射率除以总的透光率、再乘以100而算得。此外,n的数值设为3次,采用其平均值。测得总的透光率(%)。结果示于表2中。此外,雾度值的值越小,表示透明性越高。
<粘着片的粘着力测定>
将所得到的粘着片切取为25mm×100mm的大小,剥离粘着片的隔离膜,将粘着面(测定面)贴合到试验板上,用2kg的橡胶辊(rubber roller,宽度:约50mm)往返一次,制成测定用试样。作为试验板,使用了玻璃板。将所得到的测定用试样在温度为23℃及相对湿度为50%的环境下放置24小时后,以JIS Z0237为标准,以300mm/分钟的剥离速度进行180°方向的拉伸试验,测得粘着片对玻璃板的粘着力(N/25mm)。以得到的测定值为粘着力。结果示于表2中。
<对被粘接体的污染性>
将以上得到的粘着片切取为50mm×50mm的大小,粘着到剥离了隔离膜的玻璃板上。将此试样在70℃下放置5天后,剥离粘着片用肉眼确认对玻璃表面的污染性,用以下标准进行评价。结果示于表2中。
○:与贴合前的玻璃表面相比无变化。
×:确认到玻璃表面有糊状物残留。
[表1]
*1:甲基丙烯酸甲酯
*2:丙烯酸异冰片酯
*3:2-乙基己基丙烯酸酯
*4:2-羟乙基丙烯酸酯
Claims (10)
1.一种光学膜用粘着剂组合物,其特征在于,该组合物含有:
65~85质量%的(A)(甲基)丙烯酸类树脂、
10~30质量%的(B)聚氧亚烷基多元醇、
1.0~5.0质量%的(C)聚异氰酸酯、
0.2~1.0质量%的(D)离子化合物、
0.005~0.1质量%的(E)锡类催化剂,
(A)(甲基)丙烯酸类树脂的重均分子量为10万~60万,且(B)聚氧亚烷基多元醇的数均分子量为500~1500。
2.如权利要求1所述的光学膜用粘着剂组合物,其特征在于,所述(A)(甲基)丙烯酸类树脂作为共聚成分含有0.5~10mol%的具有羟基的(甲基)丙稀酸类单体。
3.如权利要求2所述的光学膜用粘着剂组合物,其特征在于,所述具有羟基的(甲基)丙稀酸类单体为2-羟乙基(甲基)丙烯酸酯。
4.如权利要求1至3中任一项所述的光学膜用粘着剂组合物,其特征在于,所述(A)(甲基)丙烯酸类树脂作为共聚成分含有15~50mol%的(甲基)丙烯酸甲酯。
5.如权利要求1至3中任一项所述的光学膜用粘着剂组合物,其特征在于,其酸值为0~5mgKOH/g。
6.如权利要求1至3中任一项所述的光学膜用粘着剂组合物,其特征在于,所述(D)离子化合物为碱金属盐。
7.如权利要求1至3中任一项所述的光学膜用粘着剂组合物,其特征在于,所述(E)锡类催化剂为二月桂酸二辛基锡。
8.一种表面保护膜,其特征在于,在透明基材上的一个面上形成使权利要求1至7中任一项所述的光学膜用粘着剂组合物固化而得到的粘着剂层。
9.如权利要求8所述的表面保护膜,其特征在于,表面电阻率值为1.0×1010Ω/□以下,且雾度为1.2以下。
10.如权利要求8或9所述的表面保护膜,其特征在于,所述透明基材是厚度为5~200μm的聚对苯二甲酸乙二醇酯、聚乙烯、聚丙烯、聚苯乙烯、聚酰亚胺、聚乙烯醇、聚氯乙烯或纤维素。
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