技术领域technical field
本发明涉及起偏镜用粘合剂组合物及起偏镜用粘合片。具体而言，涉及直接附着于起偏镜、贴合起偏镜与光学构件的起偏镜用粘合剂组合物及起偏镜用粘合片。This invention relates to the adhesive composition for polarizers, and the adhesive sheet for polarizers. Specifically, it is related with the adhesive composition for polarizers and the adhesive sheet for polarizers which directly adhere to a polarizer, and bond a polarizer and an optical member.
现有技术current technology
在液晶显示装置(LCD)的液晶单元中，根据图像形成方法有时必须于显示器基板的两面配置偏振片，在此偏振片的单侧形成用于粘贴于液晶单元等其它光学部件的粘合剂层。In the liquid crystal cell of a liquid crystal display device (LCD), depending on the image forming method, it is sometimes necessary to arrange a polarizing plate on both sides of the display substrate, and form an adhesive layer on one side of the polarizing plate to be attached to other optical components such as a liquid crystal cell .
一般而言，偏振片在由聚乙烯醇类膜与碘等二色性色素所构成的起偏镜的两面设置有透明保护膜。起偏镜存在物理性强度弱，在加工方向上容易破裂等问题，因此至少在单面、通常为两面上经由粘接剂层而贴合上述透明保护膜。以往的液晶单元所使用的偏振片是在2片三乙酰纤维素(TAC)类保护膜之间挟持有起偏镜的3层结构，或于TAC类保护膜与环烯烃聚合物(COP)类保护膜之间挟持有起偏镜的3层结构。In general, a polarizing plate is provided with a transparent protective film on both surfaces of a polarizer made of a polyvinyl alcohol film and a dichroic dye such as iodine. Polarizers have problems such as weak physical strength and easy cracking in the machine direction, so at least one surface, usually both surfaces, are bonded with the above-mentioned transparent protective film via an adhesive layer. The polarizer used in conventional liquid crystal cells has a three-layer structure in which a polarizer is sandwiched between two triacetyl cellulose (TAC)-based protective films, or a TAC-based protective film and a cycloolefin polymer (COP)-based polarizer. A 3-layer structure with a polarizer sandwiched between protective films.
在将偏振片粘贴于液晶单元等时，通常使用粘合剂。由于可将偏振片瞬间固定、在使偏振片粘固时不需要干燥工序等的便利性，因此事先在偏振片单面设置粘合剂作为粘合剂层。When affixing a polarizing plate to a liquid crystal cell or the like, an adhesive is usually used. An adhesive is provided on one side of the polarizer in advance as an adhesive layer because the polarizer can be instantly fixed and a drying step is not required to fix the polarizer.
在将偏振片贴合于液晶单元时有产生静电。这样的静电成为引起液晶单元的故障或因带电而异物吸附所造成的异物卡入的原因，因此粘合剂层必须具有防静电性能。例如，专利文献1～3中，为了使粘合剂层具有防静电性能，一般含有离子性化合物。Static electricity may be generated when the polarizing plate is bonded to the liquid crystal cell. Such static electricity causes failure of the liquid crystal cell and foreign matter jamming due to charging and adsorption of foreign matter, so the pressure-sensitive adhesive layer must have antistatic performance. For example, in Patent Documents 1 to 3, in order to impart antistatic performance to the pressure-sensitive adhesive layer, an ionic compound is generally contained.
另外，近年来由于智能手机等触摸面板的薄型化而使液晶单元的光学部件也向薄型化发展。偏振片也不例外，已提出了在起偏镜的至少一侧形成了保护膜的偏振片来取代透明保护膜(专利文献4)。另外，提出了形成了使严苛环境下的耐久性提高的保护膜的偏振片(专利文献5)。另外，为了偏振片的薄膜化，研究了取消偏振片的粘合剂层所设置侧的透明保护膜，而在起偏镜上直接设置粘合剂层的结构的偏振片。In addition, in recent years, due to the thinning of touch panels such as smartphones, the thickness of optical components of liquid crystal cells has also been reduced. The polarizing plate is no exception, and a polarizing plate in which a protective film is formed on at least one side of a polarizer has been proposed instead of a transparent protective film (Patent Document 4). Moreover, the polarizing plate which formed the protective film which improved the durability in severe environments is proposed (patent document 5). In addition, in order to reduce the thickness of the polarizing plate, a polarizing plate having a structure in which the adhesive layer is directly provided on the polarizer without the transparent protective film on the side where the adhesive layer of the polarizing plate is provided has been studied.
现有技术文献prior art literature
专利文献patent documents
专利文献1：日本特开2013-100386号公报Patent Document 1: Japanese Patent Laid-Open No. 2013-100386
专利文献2：日本特开2013-108031号公报Patent Document 2: Japanese Unexamined Patent Publication No. 2013-108031
专利文献3：日本特开2014-62264号公报Patent Document 3: Japanese Patent Laid-Open No. 2014-62264
专利文献4：日本特开2003-185842号公报Patent Document 4: Japanese Patent Laid-Open No. 2003-185842
专利文献5：日本特开2010-9027号公报Patent Document 5: Japanese Patent Laid-Open No. 2010-9027
发明内容Contents of the invention
发明所要解决的问题The problem to be solved by the invention
然而，根据本发明人等的研究表明，在取消起偏镜的透明保护膜、在起偏镜上直接设置粘合剂层的情况下，如果使用现有的具有防静电性能的粘合剂层，则存在作为起偏镜的构成要件的聚乙烯醇(PVA)所吸附取向的碘等二色性色素发生脱色(起偏镜劣化)的情况。However, according to the research of the present inventors, etc., if the transparent protective film of the polarizer is canceled and the adhesive layer is directly arranged on the polarizer, if the existing adhesive layer with antistatic properties is used , dichroic dyes such as iodine adsorbed and oriented by polyvinyl alcohol (PVA), which is a constituent element of the polarizer, may be decolorized (deterioration of the polarizer).
因此，本发明人等进行了深入研究，其目的在于提供一种起偏镜用粘合剂组合物及粘合片，所述起偏镜用粘合剂组合物是具有防静电性能的粘合剂组合物，即使在直接附着于起偏镜的情况下，也不发生起偏镜的脱色或劣化。Therefore, the inventors of the present invention have conducted intensive research, and the purpose is to provide an adhesive composition for polarizers and an adhesive sheet, and the adhesive composition for polarizers is an adhesive with antistatic performance. The agent composition does not cause discoloration or deterioration of the polarizer even when it is directly attached to the polarizer.
因此，本发明人等持续研讨，目的在于提供一种起偏镜用粘合剂组合物及粘合片，其为具有防静电性能之粘合剂组合物，即使在直接附着于起偏镜的情况，仍不发生起偏镜之脱色或劣化。Therefore, the inventors of the present invention continue to study, and the purpose is to provide an adhesive composition for polarizers and an adhesive sheet, which is an adhesive composition with antistatic properties, even if it is directly attached to the polarizer. In this case, the decolorization or deterioration of the polarizer does not occur.
解决问题的技术方法technical approach to problem solving
本发明人等为了解决上述课题而调查了原因，其结果是判明了起偏镜的脱色原因在于粘合剂层所含有的用于赋予防静电性能的防静电剂。因此，本发明人等进一步潜心研究，结果发现，通过在粘合剂组合物中使用具有特定组成的防静电剂，可不损害防静电性能并抑制起偏镜脱色。具体而言，本发明人等发现，通过将在主链中含有聚醚基的增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的防静电性组合物稳定且均匀地分散于丙烯酸类粘合剂，将其使用于起偏镜与光学构件的贴合，则可不损害防静电性能并抑制起偏镜脱色。另外，本发明人等发现，通过使用这样的起偏镜用粘合剂组合物，可使偏振片薄型化，从而完成了本发明。As a result of investigating the cause in order to solve the above-mentioned problems, the inventors of the present invention found that the cause of the discoloration of the polarizer is the antistatic agent for imparting antistatic performance contained in the pressure-sensitive adhesive layer. Therefore, as a result of the present inventors' further earnest research, it was found that discoloration of the polarizer can be suppressed without impairing the antistatic performance by using an antistatic agent having a specific composition for the adhesive composition. Specifically, the inventors of the present invention have found that an antistatic composition in which a salt having an anion having a fluorine group and a sulfonyl group is dissolved in a plasticizer containing a polyether group in the main chain can be stably and uniformly dispersed in Acrylic adhesive, when used for laminating polarizers and optical members, prevents discoloration of polarizers without compromising antistatic properties. Moreover, the inventors of the present invention have found that a polarizing plate can be thinned by using such an adhesive composition for polarizers, and have completed the present invention.
具体而言，本发明具有以下构成。Specifically, the present invention has the following configurations.
[1]一种起偏镜用粘合剂组合物，其含有防静电性组合物，防静电性组合物是在主链中含有聚醚基的增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。[1] An adhesive composition for polarizers comprising an antistatic composition in which a plasticizer having a fluorine group and a sulfonate group is dissolved in a plasticizer containing a polyether group in the main chain. Compositions of salts of acyl anions.
[2]如[1]所述的起偏镜用粘合剂组合物，其中，防静电性组合物是在主链中含有聚醚基的聚醚酯类增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。[2] The adhesive composition for polarizers according to [1], wherein the antistatic composition is a polyether ester plasticizer having a polyether group in the main chain dissolved The composition of the salt of the anion of the group and the sulfonyl group.
[3]如[1]或[2]所述的起偏镜用粘合剂组合物，其中，聚醚酯类增塑剂含有下式(1)或(2)所示的至少1种聚醚酯类增塑剂，[3] The adhesive composition for polarizers according to [1] or [2], wherein the polyether ester plasticizer contains at least one kind of polymer represented by the following formula (1) or (2): ether ester plasticizer,
化学式1chemical formula 1
化学式2chemical formula 2
式(1)及式(2)中，m及n分别为整数，R表示烷基。In formula (1) and formula (2), m and n are respectively integers, and R represents an alkyl group.
[4]如[1]所述的起偏镜用粘合剂组合物，其中，防静电性组合物是在主链中含有聚醚基的聚醚类增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。[4] The adhesive composition for polarizers according to [1], wherein the antistatic composition is a polyether plasticizer having a fluorine group dissolved in a polyether plasticizer having a polyether group in the main chain. And the composition of the salt of the anion of the sulfonyl group.
[5]如[4]所述的起偏镜用粘合剂组合物，其中，聚醚类增塑剂包含具有下式(11)的聚醚类增塑剂，[5] The adhesive composition for polarizers according to [4], wherein the polyether plasticizer contains a polyether plasticizer having the following formula (11),
R1(OCH2CH2)nOR2 (11)R1 (OCH2 CH2 )n OR2 (11)
式中，R1表示碳原子数1～12的烷基，R2表示氢原子或碳原子数1～12的烷基，n表示3～6的整数。In the formula, R1 represents an alkyl group having1 to 12 carbon atoms, R2 represents ahydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 3 to 6.
[6]如[1]所述的起偏镜用粘合剂组合物，其中，防静电性组合物包含：在主链中含有聚醚基的聚醚酯类增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物、以及在主链中含有聚醚基的聚醚类增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。[6] The adhesive composition for polarizers according to [1], wherein the antistatic composition contains: a polyether ester plasticizer having a polyether group in the main chain dissolved with A composition of a salt of an anion having a fluorine group and a sulfonyl group, and a composition in which a salt having an anion having a fluorine group and a sulfonyl group is dissolved in a polyether plasticizer having a polyether group in the main chain.
[7]如[1]～[6]中任一项所述的起偏镜用粘合剂组合物，其中，起偏镜用粘合剂组合物的主成分是实质上不含有羧基的粘合剂组合物。[7] The adhesive composition for polarizers according to any one of [1] to [6], wherein the main component of the adhesive composition for polarizers is an adhesive substantially free of carboxyl groups. Mixture composition.
[8]如[1]～[7]中任一项所述的起偏镜用粘合剂组合物，其中，起偏镜用粘合剂组合物的主成分为丙烯酸类粘合剂组合物。[8] The adhesive composition for polarizers according to any one of [1] to [7], wherein the main component of the adhesive composition for polarizers is an acrylic adhesive composition .
[9]如[7]所述的起偏镜用粘合剂组合物，其中，丙烯酸类粘合剂组合物含有(甲基)丙烯酸类共聚物(A)与交联剂(B)，(甲基)丙烯酸类共聚物(A)至少使下述(i)与(ii)进行聚合而得到：[9] The adhesive composition for polarizers according to [7], wherein the acrylic adhesive composition contains a (meth)acrylic copolymer (A) and a crosslinking agent (B), ( The meth)acrylic copolymer (A) is obtained by polymerizing at least the following (i) and (ii):
(i)具有碳原子数1～18的烷基的(甲基)丙烯酸酯单体60～99.99质量％，(i) 60-99.99% by mass of a (meth)acrylate monomer having an alkyl group having 1 to 18 carbon atoms,
(ii)具有自由基聚合性不饱和基团、且具有至少1个反应性官能团的单体0.01～20质量％。(ii) 0.01 to 20% by mass of a monomer having a radically polymerizable unsaturated group and at least one reactive functional group.
[10]如[8]所述的起偏镜用粘合剂组合物，其中，反应性官能团选自羟基及氨基中的至少一者，具有反应性官能团的单体实质上不含有含羧基单体。[10] The adhesive composition for polarizers as described in [8], wherein the reactive functional group is selected from at least one of a hydroxyl group and an amino group, and the monomer having a reactive functional group does not substantially contain a carboxyl group-containing monomer. body.
[11]如[8]或[9]所述的起偏镜用粘合剂组合物，其中，交联剂(B)为选自异氰酸酯类交联剂、环氧类交联剂及金属螯合物类交联剂中的至少1种。[11] The adhesive composition for polarizers according to [8] or [9], wherein the crosslinking agent (B) is selected from isocyanate crosslinking agents, epoxy crosslinking agents and metal chelate At least one of compound crosslinking agents.
[12]如[8]～[10]中任一项所述的起偏镜用粘合剂组合物，其中，相对于(甲基)丙烯酸类共聚物(A)100重量份，防静电性组合物的含量为0.01～30质量份。[12] The adhesive composition for polarizers according to any one of [8] to [10], wherein the antistatic property is The content of the composition is 0.01 to 30 parts by mass.
[13]如[1]～[11]中任一项所述的起偏镜用粘合剂组合物，其中，具有氟基及磺酰基的阴离子是选自双(氟烷基磺酰基)酰亚胺离子、三(氟烷基磺酰基)甲基化物离子及氟烷基磺酸离子中的阴离子。[13] The adhesive composition for polarizers according to any one of [1] to [11], wherein the anion having a fluorine group and a sulfonyl group is selected from bis(fluoroalkylsulfonyl)acyl Anion in iminium ion, tris(fluoroalkylsulfonyl)methide ion and fluoroalkylsulfonate ion.
[14]如[1]～[12]中任一项所述的起偏镜用粘合剂组合物，其中，具备具有氟基及磺酰基的阴离子的盐是由选自碱金属、2族元素、过渡金属及两性金属的至少一种阳离子与具有氟基及磺酰基的阴离子所形成的盐。[14] The adhesive composition for polarizers according to any one of [1] to [12], wherein the salt having an anion having a fluorine group and a sulfonyl group is a compound selected from alkali metals, group 2 A salt formed of at least one cation of an element, a transition metal, and an amphoteric metal and an anion having a fluorine group and a sulfonyl group.
[15]如[1]～[13]中任一项所述的起偏镜用粘合剂组合物，其中，具备具有氟基及磺酰基的阴离子的盐是选自双(氟烷基磺酰基)酰亚胺的碱金属盐、三(氟烷基磺酰基)甲基化物的碱金属盐、以及三氟烷基磺酸的碱金属盐中的盐。[15] The adhesive composition for polarizers according to any one of [1] to [13], wherein the salt having an anion having a fluorine group and a sulfonyl group is selected from bis(fluoroalkylsulfonyl Salts of alkali metal salts of acyl)imides, alkali metal salts of tris(fluoroalkylsulfonyl)methides, and alkali metal salts of trifluoroalkylsulfonic acids.
[16]如[1]～[14]中任一项所述的起偏镜用粘合剂组合物，其中，起偏镜用粘合剂组合物用于贴合起偏镜与光学构件。[16] The adhesive composition for polarizers according to any one of [1] to [14], which is used for laminating a polarizer and an optical member.
[17]如[15]所述的起偏镜用粘合剂组合物，其中，光学构件为液晶单元或触摸面板。[17] The adhesive composition for polarizers according to [15], wherein the optical member is a liquid crystal cell or a touch panel.
[18]一种起偏镜用粘合片，其含有[1]～[16]中任一项所述的起偏镜用粘合剂组合物。[18] An adhesive sheet for polarizers containing the adhesive composition for polarizers according to any one of [1] to [16].
[19]一种图像显示装置，其具备至少一个[17]所述的粘合片。[19] An image display device comprising at least one adhesive sheet according to [17].
发明的效果The effect of the invention
根据本发明，可提供即使在起偏镜的至少一面直接附着或叠层粘合剂组合物的情况下，仍不损害防静电性能、且不发生起偏镜的脱色或劣化的起偏镜用粘合剂组合物及起偏镜用粘合片。这些起偏镜用粘合剂组合物或粘合片直接粘贴于起偏镜，经由起偏镜用粘合剂组合物或起偏镜用粘合片贴合起偏镜与光学构件。因此，可实现偏振片的薄型化。According to the present invention, even when at least one side of the polarizer is directly attached or laminated with an adhesive composition, it is possible to provide a polarizer that does not impair the antistatic performance and does not cause discoloration or deterioration of the polarizer. An adhesive composition and an adhesive sheet for polarizers. These adhesive compositions for polarizers or adhesive sheets are directly attached to polarizers, and polarizers and optical members are bonded via the adhesive compositions for polarizers or adhesive sheets for polarizers. Therefore, thinning of the polarizing plate can be achieved.
附图说明Description of drawings
图1为说明本发明所使用的防静电性组合物的作用效果的图。FIG. 1 is a diagram illustrating the effect of the antistatic composition used in the present invention.
图2为说明含有本发明的起偏镜用粘合剂组合物的偏振片的结构及现有的偏振片的结构的图。FIG. 2 is a diagram illustrating the structure of a polarizing plate containing the adhesive composition for polarizers of the present invention and the structure of a conventional polarizing plate.
图3为实施例所使用的防静电性组合物、含有防静电性组合物的粘合片的提取液、未加入防静电性组合物的粘合片的提取液的HPLC(高效液相色谱)的色谱图。Figure 3 is the HPLC (high performance liquid chromatography) of the antistatic composition used in the examples, the extract of the adhesive sheet containing the antistatic composition, and the extract of the adhesive sheet without the antistatic composition chromatograms.
符号说明Symbol Description
1 偏振片1 polarizer
10 起偏镜10 polarizer
12 保护膜12 protective film
20 粘合片(起偏镜用粘合剂组合物层)20 Adhesive sheet (adhesive composition layer for polarizer)
具体实施方式detailed description
以下详细说明本发明。以下记载的构成要件的说明基于代表性的实施形态或具体例，但本发明并不限定于这样的实施方式。另外，本说明书中，使用“～”表示的数值范围是指包括其前后记载的数值作为下限值及上限值的范围。The present invention will be described in detail below. The description of the constituent elements described below is based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after that as a lower limit and an upper limit.
(起偏镜用粘合剂组合物)(Adhesive composition for polarizer)
本发明之起偏镜用粘合剂组合物直接附着于起偏镜的至少一面，是用于将起偏镜与光学构件进行贴合的粘合剂组合物。本发明的起偏镜用粘合剂组合物含有防静电性组合物。这里，防静电性组合物是在主链中含有聚醚基的增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。本发明的起偏镜用粘合剂组合物为上述结构，因此可使起偏镜与粘合剂层柔软地密合。另外，本发明的起偏镜用粘合剂组合物由于可直接粘贴或叠层于起偏镜，因此可制作取消了透明保护膜或保护层的薄型偏振片。由此，即使是取消了保护膜等的偏振片，在高温或高温高湿环境下或反复加热与冷却的环境下的耐热性优异，另外，可抑制由激烈的温度变化或粘合剂成分(主要为防静电成分)的转移所造成的起偏镜脱色(劣化)。The adhesive composition for polarizers of this invention adheres directly to at least one surface of a polarizer, and is an adhesive composition for bonding a polarizer and an optical member. The adhesive composition for polarizers of this invention contains an antistatic composition. Here, the antistatic composition is a composition in which a salt having an anion having a fluorine group and a sulfonyl group is dissolved in a plasticizer containing a polyether group in the main chain. Since the adhesive composition for polarizers of this invention has the said structure, a polarizer and an adhesive layer can be adhere|attached softly. In addition, since the adhesive composition for polarizers of the present invention can be directly attached or laminated on a polarizer, it is possible to produce a thin polarizing plate without a transparent protective film or a protective layer. Thus, even a polarizing plate without a protective film or the like has excellent heat resistance in a high-temperature or high-temperature, high-humidity environment or in an environment of repeated heating and cooling. Discoloration (deterioration) of the polarizer caused by the transfer of (mainly antistatic components).
(防静电性组合物)(antistatic composition)
本发明的起偏镜用粘合剂组合物中所使用的防静电性组合物，是在主链中含有聚醚基的增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。即，防静电性组合物中，使具备具有氟基及磺酰基的阴离子的盐以溶解状态分散于主链中含有聚醚基的增塑剂中。The antistatic composition used in the adhesive composition for polarizers of the present invention has a salt having an anion having a fluorine group and a sulfonyl group dissolved in a plasticizer containing a polyether group in the main chain. combination. That is, in the antistatic composition, a salt having an anion having a fluorine group and a sulfonyl group is dispersed in a dissolved state in a plasticizer containing a polyether group in the main chain.
另外，本发明的起偏镜用粘合剂组合物中所使用的防静电性组合物，是在主链中含有聚醚基的增塑剂中溶解了具备选自碱金属、2族元素、过渡金属及两性金属中至少一种阳离子的盐的组合物。阳离子优选为选自碱金属及2族元素中的任一种阳离子，更优选为碱金属的阳离子。其中，阳离子优选为锂离子。In addition, the antistatic composition used in the adhesive composition for polarizers of the present invention is a plasticizer containing a polyether group in the main chain dissolved in a compound selected from alkali metals, group 2 elements, A composition of a transition metal and a salt of at least one cation of an amphoteric metal. The cation is preferably any cation selected from alkali metals and Group 2 elements, more preferably an alkali metal cation. Among them, the cation is preferably lithium ion.
这里，本发明的起偏镜用粘合剂组合物中，作为阴离子的抗衡离子的阳离子配位于增塑剂中的醚的氧原子，形成络合物。即，作为具有氟基及磺酰基的阴离子的抗衡离子的阳离子，与主链中含有聚醚基的增塑剂形成路易斯酸-碱型的络离子。本发明所使用的防静电性组合物的特征在于含有络合物，所述络合物由作为具有氟基及磺酰基的阴离子的抗衡离子的阳离子配位于主链中含有聚醚基的增塑剂中的醚的氧原子而形成。Here, in the adhesive composition for polarizers of this invention, the cation which is a counter ion of an anion coordinates with the oxygen atom of the ether in a plasticizer, and forms a complex. That is, the cation as the counter ion of the anion having the fluorine group and the sulfonyl group forms a Lewis acid-base type complex ion with the plasticizer containing the polyether group in the main chain. The antistatic composition used in the present invention is characterized by containing a complex in which a plasticizer containing a polyether group is coordinated in the main chain by a cation serving as a counter ion of an anion having a fluorine group and a sulfonyl group. formed by the oxygen atoms of the ether in the reagent.
与增塑剂形成络离子的阳离子优选为选自碱金属、2族元素、过渡金属及两性金属中至少一种阳离子，其中更优选为锂离子。即，所形成的络合物优选为锂聚醚络合物。The cation forming a complex ion with the plasticizer is preferably at least one cation selected from the group consisting of alkali metals, group 2 elements, transition metals and amphoteric metals, among which lithium ions are more preferred. That is, the formed complex is preferably a lithium polyether complex.
本发明的起偏镜用粘合剂组合物中所使用的防静电性组合物在用HPLC(高效液相色谱)进行分析时，可检测到源自络合物的峰。该峰在仅有盐的防静电性组合物或仅有主链中含有聚醚基的增塑剂时未被检测出，是源自络合物的峰。When the antistatic composition used for the adhesive composition for polarizers of this invention analyzes by HPLC (high performance liquid chromatography), the peak originating in a complex can be detected. This peak was not detected in the case of the antistatic composition containing only a salt or only a plasticizer containing a polyether group in its main chain, but it was a peak derived from a complex.
需要说明的是，HPLC条件如下所述。It should be noted that the HPLC conditions are as follows.
柱：XBridge C18，柱径4.6×250mm(WATERS公司制)Column: XBridge C18, column diameter 4.6×250mm (manufactured by WATERS Corporation)
柱温：30℃Column temperature: 30°C
流动相：乙腈/水Mobile phase: acetonitrile/water
流速：0.8mL/分Flow rate: 0.8mL/min
检测：225nmDetection: 225nm
本发明中，通过使用这样的防静电性组合物，即使在将粘合剂组合物直接附着于起偏镜的情况下，也可防止起偏镜脱色。另外，本说明书中，所谓“分散”是指具备具有氟基及磺酰基的阴离子的盐分散或溶入增塑剂中的状态。作为这样的防静电性组合物，可列举例如：Sankonol AD2326(三光化学工业公司制)、Sankonol AD2600(三光化学工业公司制)、Sankonol TGR(三光化学工业公司制)等。In this invention, by using such an antistatic composition, even when directly adhering an adhesive composition to a polarizer, discoloration of a polarizer can be prevented. In addition, in this specification, "dispersion" means the state in which the salt which has the anion which has a fluorine group and a sulfonyl group is dispersed or dissolved in a plasticizer. As such an antistatic composition, Sankonol AD2326 (made by Sanko Chemical Industry Co., Ltd.), Sankonol AD2600 (made by Sanko Chemical Industry Co., Ltd.), Sankonol TGR (made by Sanko Chemical Industry Co., Ltd.) etc. are mentioned, for example.
若将现有的含有离子性化合物的起偏镜用粘合剂组合物直接粘贴于起偏镜，则由于离子性化合物的流动性或与丙烯酸类粘合剂组合物的相容性差，因此阳离子发生渗出或辉散(blooming)，与起偏镜的碘离子(I3-、I5-)形成假性键，引起起偏镜的脱色。另一方面，本发明所使用的防静电性组合物由于以溶解于与丙烯酸类粘合剂组合物的亲和性高的增塑剂中的状态而分散，因此不引起渗出或辉散。进而，防静电性组合物的阳离子由于与增塑剂形成路易斯酸-碱型的络离子，因此不与起偏镜的碘离子形成化学键。If the conventional adhesive composition for polarizer containing an ionic compound is directly pasted on a polarizer, the ionic compound is poor in fluidity or compatibility with an acrylic adhesive composition, so the cationic Bleeding or blooming occurs, and a false bond is formed with iodine ions (I3- , I5- ) of the polarizer, causing decolorization of the polarizer. On the other hand, since the antistatic composition used in the present invention is dispersed in a state of being dissolved in a plasticizer having a high affinity with the acrylic pressure-sensitive adhesive composition, bleeding or scattering does not occur. Furthermore, since the cation of the antistatic composition forms a Lewis acid-base type complex ion with the plasticizer, it does not form a chemical bond with the iodide ion of the polarizer.
防静电性组合物的含量相对于起偏镜用粘合剂组合物所含的(甲基)丙烯酸类共聚物100质量份，优选为0.01～30质量份、更优选为0.1～10质量份。通过将防静电性组合物的含量设为上述范围内，可发挥充分的防静电性能，且于低温环境下可抑制防静电性组合物析出等不良情况。The content of the antistatic composition is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylic copolymer contained in the adhesive composition for polarizers. By making content of an antistatic composition into the said range, sufficient antistatic performance can be exhibited, and troubles, such as precipitation of an antistatic composition, can be suppressed in a low-temperature environment.
(聚醚酯类增塑剂)(polyether ester plasticizer)
防静电性组合物优选是在主链中含有聚醚基的聚醚酯类增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。聚醚酯类增塑剂含有聚醚基与酯键，通过进入树脂间隙而阻碍树脂的规则正确地取向。另外，聚醚酯类增塑剂是指即使在玻璃化转变温度以下仍保持非晶状态的聚醚酯类增塑剂。其中，聚醚酯类增塑剂优选为由下式(1)或(2)所示的聚醚酯类化合物。The antistatic composition is preferably a composition in which a salt having an anion having a fluorine group and a sulfonyl group is dissolved in a polyether ester plasticizer containing a polyether group in the main chain. Polyether ester plasticizers contain polyether groups and ester bonds, which hinder the regular and correct orientation of the resin by entering the resin gap. In addition, the polyether ester plasticizer refers to a polyether ester plasticizer that maintains an amorphous state even below the glass transition temperature. Among them, the polyether ester plasticizer is preferably a polyether ester compound represented by the following formula (1) or (2).
化学式3chemical formula 3
化学式4chemical formula 4
式(1)及(2)中，m及n分别为整数，R表示烷基。In formulas (1) and (2), m and n are each an integer, and R represents an alkyl group.
聚醚酯类增塑剂粘度低且操作性良好，具有低温柔软性，具有耐热老化性、柔软性与耐久性的平衡、非挥发性、非转移性、耐油性、安全性(符合PL)优异。Polyether ester plasticizer has low viscosity and good workability, low-temperature flexibility, heat aging resistance, balance of flexibility and durability, non-volatility, non-transferability, oil resistance, and safety (according to PL) excellent.
R优选为碳原子数1～14的烷基。例如优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正壬基、异壬基、正癸基、正月桂基等。R is preferably an alkyl group having 1 to 14 carbon atoms. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-nonyl, isononyl, n-decyl, n-lauryl, etc. are preferable.
式(1)及(2)中，m优选为1～40的整数，n优选为1～20的整数。m及n更优选为2以上的整数。m特别优选为2以上的整数。In formulas (1) and (2), m is preferably an integer of 1-40, and n is preferably an integer of 1-20. m and n are more preferably an integer of 2 or more. m is particularly preferably an integer of 2 or more.
在主链中含有聚醚基的聚醚酯类增塑剂的分子量优选为250～2000，更优选为500～1500。聚醚酯类增塑剂的粘度(25℃)优选为30～600mPa·s。The molecular weight of the polyether ester plasticizer containing a polyether group in the main chain is preferably 250-2000, more preferably 500-1500. The viscosity (25° C.) of the polyether ester plasticizer is preferably 30 to 600 mPa·s.
(聚醚类增塑剂)(polyether plasticizer)
防静电性组合物可以是在主链中含有聚醚基的聚醚类增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。另外，防静电性组合物可以包含：在主链中含有聚醚基的聚醚酯类增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物、在主链中含有聚醚基的聚醚类增塑剂中溶解有具备具有氟基及磺酰基的阴离子的盐的组合物。这里，所谓聚醚类增塑剂优选为下述通式(11)所示的聚亚烷基二醇二烷基醚化合物或聚亚烷基二醇单烷基醚化合物。The antistatic composition may be a composition in which a salt having an anion having a fluorine group and a sulfonyl group is dissolved in a polyether plasticizer having a polyether group in the main chain. In addition, the antistatic composition may include: a composition in which a salt having an anion having a fluorine group and a sulfonyl group is dissolved in a polyether ester plasticizer containing a polyether group in the main chain; A composition having a salt of an anion having a fluorine group and a sulfonyl group is dissolved in the ether group polyether plasticizer. Here, the polyether plasticizer is preferably a polyalkylene glycol dialkyl ether compound or a polyalkylene glycol monoalkyl ether compound represented by the following general formula (11).
化学式5chemical formula 5
R1(OCH2CH2)nOR2 (11)R1 (OCH2 CH2 )n OR2 (11)
式(11)中，R1表示碳原子数1～12的烷基，R2表示氢原子或碳原子数1～12的烷基，n表示3～6的整数。In formula (11), R1 represents an alkyl group having 1 to 12 carbon atoms, R2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 3 to 6.
该聚醚类增塑剂特别优选为聚亚烷基二醇烷基醚化合物。The polyether plasticizer is particularly preferably a polyalkylene glycol alkyl ether compound.
(其它增塑剂)(other plasticizers)
另外，防静电性组合物中除了上述聚醚酯类或聚醚类增塑剂以外，还可含有其它增塑剂。作为这样的增塑剂，可列举例如：由具有饱和或不饱和非环烃基的单或二羧酸与具有碳原子数1～20的非环烃基的醇所形成的酯，或者不饱和非环烃基中的不饱和基团被环氧化的酯所形成的增塑剂。通过使用这样的酯，可提高粘合剂层对被粘附物的润湿性，粘贴时不易发生气泡卷入，同时不易发生增塑剂从粘合剂层渗出，可适合降低被粘附物污染。In addition, the antistatic composition may contain other plasticizers in addition to the above-mentioned polyether ester or polyether plasticizers. Examples of such plasticizers include esters formed from mono- or dicarboxylic acids having saturated or unsaturated acyclic hydrocarbon groups and alcohols having acyclic hydrocarbon groups having 1 to 20 carbon atoms, or unsaturated acyclic hydrocarbon groups. A plasticizer formed by epoxidized esters of unsaturated groups in hydrocarbon groups. By using such an ester, the wettability of the adhesive layer to the adherend can be improved, air bubbles are less likely to be entangled during sticking, and at the same time, the plasticizer is less likely to bleed out from the adhesive layer, which can suitably reduce pollution.
作为构成酯的单或二羧酸成分中的饱和或不饱和的非环烃基，可列举例如：烷基或亚烷基，其中优选为碳原子数1～20的烷基或亚烷基，更优选为碳原子数4～18的烷基，特别优选为碳原子数4～14的烷基。对于这样的具有饱和或不饱和非环烃基的单或二羧酸而言，由于具有与构成起偏镜用粘合剂组合物所使用的丙烯酸类粘合剂组合物的丙烯酸类单体的碳原子数接近的碳原子数，因而与起偏镜用粘合剂组合物的相容性良好，适合保持于起偏镜用粘合剂组合物中，因此可抑制渗出。As the saturated or unsaturated acyclic hydrocarbon group in the mono- or dicarboxylic acid component constituting the ester, for example: an alkyl group or an alkylene group, an alkyl group or an alkylene group having 1 to 20 carbon atoms is preferred, and more It is preferably an alkyl group having 4 to 18 carbon atoms, particularly preferably an alkyl group having 4 to 14 carbon atoms. For such a mono- or dicarboxylic acid having a saturated or unsaturated acyclic hydrocarbon group, due to the presence of the carbon of the acrylic monomer constituting the acrylic adhesive composition used in the adhesive composition for polarizers, Since the number of carbon atoms close to each other has good compatibility with the adhesive composition for polarizers and is suitable for holding in the adhesive composition for polarizers, bleeding can be suppressed.
作为具有饱和或不饱和的非环烃基的单羧酸及二羧酸，可列举例如：草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸等直链脂肪族二羧酸的单酯或多酯，乙酸、丙酸、丁酸、缬草酸、己酸、庚酸、辛酸、壬酸、癸酸、十一酸、月桂酸、十三酸、肉豆蔻酸、十五酸、软脂酸、十七酸、硬脂酸、十九酸、花生酸等饱和脂肪酸，巴豆酸、白芷酸、十二碳烯酸、肉豆蔻脑酸(myristoleic acid)、软脂油酸、油酸、异油酸、鳕油酸、二十碳烯酸、芥子酸、二十四碳烯酸、亚麻油酸、二十碳二烯酸、二十二碳二烯酸、十八碳三烯酸、松子油酸、桐酸、二十碳三烯酸、十八碳四烯酸、花生油酸、二十碳四烯酸、二十二碳四烯酸、反油酸、二十二碳六烯酸等不饱和脂肪酸等。Examples of monocarboxylic and dicarboxylic acids having a saturated or unsaturated acyclic hydrocarbon group include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. monoesters or polyesters of linear aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid, acetic acid, propionic acid, butyric acid, valerenic acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid , undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanic acid, arachidic acid and other saturated fatty acids, crotonic acid, angelica acid, lauryl acid Cenoic acid, myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, cod oleic acid, eicosenoic acid, erucic acid, tetracosenoic acid, linolenic acid, eicosanoid Carbadienoic acid, docosadienoic acid, octadecatrienoic acid, pinoleic acid, lyric acid, eicosatrienoic acid, stearidonic acid, arachidic acid, eicosatetraenoic acid , docosatetraenoic acid, elaidic acid, docosahexaenoic acid and other unsaturated fatty acids.
作为构成酯的醇中的碳原子数1～20的非环烃基，可适合使用碳原子数1～20的烷基或亚烷基、尤其是烷基，其中优选为碳原子数4～18的烷基、特别优选碳原子数4～14的烷基。这样的具有饱和或不饱和的非环烃基的醇，由于具有与构成起偏镜用粘合剂组合物所含的丙烯酸类粘合剂组合物的丙烯酸类单体的碳原子数接近的碳原子数，因而与起偏镜用粘合剂组合物的相容性良好，适合保持于起偏镜用粘合剂组合物中，因此可抑制渗出。与构成酯的羧酸成分相比，通过将该具有醇成分的烃基的碳原子数设为与构成起偏镜用粘合剂组合物之丙烯酸类粘合剂组合物的丙烯酸类单体的碳原子数接近的碳原子数，可以特别容易地抑制被粘附物污染。As the acyclic hydrocarbon group having 1 to 20 carbon atoms in the alcohol constituting the ester, an alkyl group or alkylene group having 1 to 20 carbon atoms, especially an alkyl group can be suitably used, and among them, an alkyl group having 4 to 18 carbon atoms is preferred. The alkyl group is particularly preferably an alkyl group having 4 to 14 carbon atoms. Such an alcohol having a saturated or unsaturated acyclic hydrocarbon group has carbon atoms close to those of the acrylic monomers constituting the acrylic adhesive composition contained in the adhesive composition for polarizers. Since the compatibility with the adhesive composition for polarizers is favorable and it is suitable for holding|maintenance in the adhesive composition for polarizers, bleeding can be suppressed. Compared with the carboxylic acid component constituting the ester, the number of carbon atoms of the hydrocarbon group having the alcohol component is equal to the carbon number of the acrylic monomer of the acrylic adhesive composition constituting the adhesive composition for polarizers. The number of carbon atoms having a close atomic number makes it particularly easy to suppress contamination by adherends.
作为这样的具有非环烃基的醇，可列举例如：甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、十一醇、十二醇、十三醇、十四醇、十五醇、鲸蜡醇、十七醇、十八醇、十九醇、花生醇的直链、支链醇。其中，特别优选使用丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇。Examples of alcohols having such an acyclic hydrocarbon group include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, Tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, arachidyl alcohol straight chain and branched alcohol. Among these, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol are particularly preferably used.
本发明中，除了上述聚醚酯类增塑剂和/或聚醚类增塑剂以外，还可将由上述单或二羧酸与醇所形成的酯用作增塑剂。作为该酯，可具有由饱和或不饱和烃基所形成的骨架，优选为不具有由不饱和烃基所形成的骨架的酯。另外，优选也可使用使具有由该不饱和烃基所构成的骨架的酯的不饱和键经环氧化而成的环氧化酯。在该酯当中，特别优选可使用己二酸单酯、癸二酸单酯、环氧化脂肪酸单酯。In the present invention, in addition to the above-mentioned polyether ester plasticizer and/or polyether plasticizer, esters formed of the above-mentioned mono- or dicarboxylic acids and alcohols can also be used as plasticizers. The ester may have a skeleton formed of a saturated or unsaturated hydrocarbon group, but is preferably an ester that does not have a skeleton formed of an unsaturated hydrocarbon group. Moreover, the epoxidized ester obtained by epoxidizing the unsaturated bond of the ester which has the skeleton which consists of this unsaturated hydrocarbon group can also be used preferably. Among these esters, adipate monoester, sebacate monoester, and epoxidized fatty acid monoester are particularly preferably used.
作为使用为增塑剂的酯，可为单酯或多酯中的任一种，从容易将溶解度参数(SP值)控制为适合范围、容易提高与起偏镜用粘合剂组合物的相容性的观点考虑，优选以PS换算计的重均分子量为1000以下的酯，特别优选为300～800的酯。As the ester used as a plasticizer, it can be either monoester or polyester, and it is easy to control the solubility parameter (SP value) to an appropriate range, and it is easy to improve the compatibility with the adhesive composition for polarizers. From the viewpoint of capacitive properties, esters having a weight average molecular weight of 1,000 or less in terms of PS are preferred, and esters of 300 to 800 are particularly preferred.
作为增塑剂，优选使用溶解度参数(SP值)为8.5以下的增塑剂。其中，优选为7.0～8.4。增塑剂的SP值为8.5以下时，与丙烯酸类粘合剂组合物的相容性优异，因此即使在以在起偏镜上粘贴有起偏镜用粘合剂组合物的状态在高温高湿环境下经长时间放置的情况下，在从起偏镜表面剥离时，仍不易在起偏镜表面发生起雾。作为增塑剂的SP值，可通用性地使用大于7.0的增塑剂。另外，上述SP值是根据J.Small所提倡的Small式[P.A.J.Small：J.Appl.Chem.,3,71(1953)]而得到的计算值。As the plasticizer, a plasticizer having a solubility parameter (SP value) of 8.5 or less is preferably used. Among them, 7.0 to 8.4 are preferable. When the SP value of the plasticizer is 8.5 or less, the compatibility with the acrylic adhesive composition is excellent, so even in the state where the adhesive composition for polarizer is attached to the polarizer at high temperature, high Even when it is left standing for a long time in a wet environment, fogging does not easily occur on the surface of the polarizer when it is peeled off from the surface of the polarizer. As the SP value of the plasticizer, a plasticizer larger than 7.0 can be commonly used. In addition, the said SP value is a calculated value based on the Small formula [P.A.J.Small: J.Appl.Chem., 3, 71 (1953)] advocated by J.Small.
相对于构成丙烯酸类粘合剂组合物的(甲基)丙烯酸类共聚物100质量份，上述增塑剂优选添加0.5～30质量份、更优选添加1～20质量份、特别优选添加1～10质量份。如果增塑剂的添加量多于0.5质量份，则在贴合时气泡容易排出。另外，如果少于30质量份，则即使在高温高湿环境下也不容易在显示器表面发生起雾。The plasticizer is preferably added in an amount of 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass, relative to 100 parts by mass of the (meth)acrylic copolymer constituting the acrylic pressure-sensitive adhesive composition. parts by mass. When the amount of the plasticizer added is more than 0.5 parts by mass, air bubbles are likely to be released during bonding. Moreover, if it is less than 30 mass parts, fogging will not generate|occur|produce easily on the surface of a display even in a high-temperature, high-humidity environment.
(具备具有氟基及磺酰基的阴离子的盐)(Salt with anion having fluorine group and sulfonyl group)
具备具有氟基及磺酰基的阴离子的盐容易溶解于聚醚酯类增塑剂及聚醚类增塑剂，可提高增塑剂中的盐浓度。通过将该溶液分散于起偏镜用粘合剂组合物，可使具备具有氟基及磺酰基的阴离子的盐大量且均匀地进入起偏镜用粘合剂组合物中。在起偏镜用粘合剂组合物中，作为阴离子的抗衡离子的阳离子与增塑剂中的醚的氧原子配位，形成络合物。A salt having an anion having a fluorine group and a sulfonyl group is easily dissolved in polyether ester plasticizers and polyether plasticizers, and the salt concentration in the plasticizer can be increased. By dispersing this solution in the adhesive composition for polarizers, the salt which has the anion which has a fluorine group and a sulfonyl group can be included in the adhesive composition for polarizers uniformly in large quantities. In the adhesive composition for polarizers, the cation which is the counter ion of an anion coordinates with the oxygen atom of the ether in a plasticizer, and forms a complex.
溶解了具备具有氟基及磺酰基的阴离子的盐的增塑剂溶液，在起偏镜用粘合剂组合物中与增塑剂的增塑性相配合，一边使防静电性能得到表现，一边赋予增塑性。另外，在主链中含有聚醚基的增塑剂，可接近起偏镜用粘合剂组合物的溶解度参数(SP值)，因此亲和性优异、不渗出。进而，可得到不发生转移污染、不依赖于湿度，速效性优异，且持续具有优异的防静电性的起偏镜用粘合剂组合物。需要说明的是，上述效果对于聚醚酯类增塑剂及聚醚类增塑剂而言也相同。A plasticizer solution in which a salt having an anion having a fluorine group and a sulfonyl group is dissolved is used in an adhesive composition for a polarizer in combination with the plasticizing properties of the plasticizer to impart antistatic performance while imparting Plasticity. In addition, since the plasticizer containing a polyether group in the main chain can approach the solubility parameter (SP value) of the adhesive composition for polarizers, it has excellent affinity and does not bleed out. Furthermore, the adhesive composition for polarizers which does not generate|occur|produce transfer contamination, does not depend on humidity, is excellent in quick-acting property, and has excellent antistatic property continuously can be obtained. In addition, the said effect is the same also about a polyether ester plasticizer and a polyether plasticizer.
溶解了具备具有氟基及磺酰基的阴离子的盐的增塑剂溶液，在起偏镜用粘合剂组合物中保持粘合物性、且发挥防静电性。另外，溶解了具备具有氟基及磺酰基的阴离子的盐之增塑剂溶液，与构成起偏镜用粘合剂组合物的分子的相容性优异，因此可得到不发生渗出、辉散及转移污染，不依存于湿度，速效性优异，且持续具有优异的防静电性的起偏镜用粘合剂组合物。The plasticizer solution in which the salt having an anion having a fluorine group and a sulfonyl group is dissolved maintains adhesive properties and exhibits antistatic properties in the adhesive composition for polarizers. In addition, a plasticizer solution in which a salt having an anion having a fluorine group and a sulfonyl group is dissolved has excellent compatibility with the molecules constituting the adhesive composition for polarizers, so it is possible to obtain It is an adhesive composition for polarizers which is independent of humidity, has excellent quick-acting properties, and continuously has excellent antistatic properties for transferring contamination.
具有氟基及磺酰基的阴离子优选为选自双(氟烷基磺酰基)酰亚胺离子、三(氟烷基磺酰基)甲基化物离子及氟烷基磺酸离子中的阴离子。The anion having a fluorine group and a sulfonyl group is preferably an anion selected from bis(fluoroalkylsulfonyl)imide ions, tris(fluoroalkylsulfonyl)methide ions, and fluoroalkylsulfonate ions.
具备具有氟基及磺酰基的阴离子的盐，优选为由选自碱金属、2族元素、过渡金属及两性金属中至少一种的阳离子与上述具有氟基及磺酰基的阴离子所形成的盐。另外，具备具有氟基及磺酰基的阴离子的盐特别优选为双(氟烷基磺酰基)酰亚胺离子的碱金属盐、三(氟烷基磺酰基)甲基化物离子的碱金属盐及氟烷基磺酸离子的碱金属盐。特别优选为锂盐。The salt having an anion having a fluorine group and a sulfonyl group is preferably a salt formed by at least one cation selected from the group consisting of alkali metals, group 2 elements, transition metals, and amphoteric metals and the above-mentioned anion having a fluorine group and a sulfonyl group. In addition, the salt having an anion having a fluorine group and a sulfonyl group is particularly preferably an alkali metal salt of a bis(fluoroalkylsulfonyl)imide ion, an alkali metal salt of a tris(fluoroalkylsulfonyl)methide ion, and Alkali metal salt of fluoroalkylsulfonate ion. Particular preference is given to lithium salts.
由上述阴离子及阳离子所形成的盐为数众多，其中，优选为由双(氟烷基磺酰基)酰亚胺离子、三(氟烷基磺酰基)甲基化物离子及氟烷基磺酸离子所构成，更优选为选自双(氟烷基磺酰基)酰亚胺的碱金属盐、三(氟烷基磺酰基)甲基化物的碱金属盐及氟烷基磺酸的碱金属盐中的盐。具体而言，优选为双(三氟甲烷磺酰基)酰亚胺锂Li(CF3SO2)2N、双(三氟甲烷磺酰基)酰亚胺钾K(CF3SO2)2N、双(三氟甲烷磺酰基)酰亚胺钠Na(CF3SO2)2N、三(三氟甲烷磺酰基)甲基化锂Li(CF3SO2)3C、三(三氟甲烷磺酰基)甲氧化钾K(CF3SO2)3C、三(三氟甲烷磺酰基)甲基化钠Na(CF2SO2)3C、三氟甲烷磺酸锂Li(CF3SO3)、三氟甲烷磺酸钾K(CF3SO3)、三氟甲烷磺酸钠Na(CF3SO3)。其中，可列举例如：双(三氟甲烷磺酰基)酰亚胺锂、及三(三氟甲烷磺酰基)甲基化锂、三氟甲烷磺酸锂。特别优选为双(三氟甲烷磺酰基)酰亚胺锂及三氟甲烷磺酸锂，通过少量添加这些化合物，可进一步加发挥上述效果。There are many salts formed by the above-mentioned anions and cations, among which, the salts formed by bis(fluoroalkylsulfonyl)imide ions, tris(fluoroalkylsulfonyl)methide ions and fluoroalkylsulfonate ions are preferred. Composition, more preferably selected from alkali metal salts of bis(fluoroalkylsulfonyl)imides, alkali metal salts of tris(fluoroalkylsulfonyl)methides, and alkali metal salts of fluoroalkylsulfonic acids Salt. Specifically, lithium bis(trifluoromethanesulfonyl)imide Li(CF3 SO2 )2 N, potassium bis(trifluoromethanesulfonyl)imide K(CF3 SO2 )2 N, Sodium bis(trifluoromethanesulfonyl)imide Na(CF3 SO2 )2 N, Lithium tris(trifluoromethanesulfonyl)methylide Li(CF3 SO2)3 C, Tris(trifluoromethanesulfonyl) ) potassium methoxide K(CF3 SO2 )3 C, sodium tris(trifluoromethanesulfonyl)methylate Na(CF2 SO2 )3 C, lithium trifluoromethanesulfonate Li(CF3 SO3 ), Potassium trifluoromethanesulfonate K(CF3 SO3 ), sodium trifluoromethanesulfonate Na(CF3 SO3 ). Among these, lithium bis(trifluoromethanesulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methyl, and lithium trifluoromethanesulfonate are exemplified. Lithium bis(trifluoromethanesulfonyl)imide and lithium trifluoromethanesulfonate are particularly preferable, and the above effects can be further exhibited by adding a small amount of these compounds.
如图1所示，使用双(三氟甲烷磺酰基)酰亚胺锂作为盐溶解于由二乙二醇与己二酸所形成的聚醚酯类增塑剂后的状态，处于锂离子配位于聚乙二醇中的醚氧原子的状态。在使用起偏镜用粘合剂组合物形成粘合层时，以锂离子配位于醚氧原子的状态形成锂离子均匀分散的粘合层。而且，在粘合层中，锂离子处于由于醚氧的分子运动而容易移动的状态。若由外部对此施加电场，则在粘合层中，锂离子向对应的极移动(离子输送)而表现出离子传导性。As shown in Fig. 1, the lithium ion complex is in the state of dissolving lithium bis(trifluoromethanesulfonyl)imide as a salt in a polyether ester plasticizer composed of diethylene glycol and adipic acid. The state of the ether oxygen atom located in polyethylene glycol. When an adhesive layer is formed using the adhesive composition for polarizers, an adhesive layer in which lithium ions are uniformly dispersed is formed in a state where lithium ions are coordinated to ether oxygen atoms. Also, in the adhesive layer, lithium ions are in a state of being easily moved due to the molecular motion of ether oxygen. When an electric field is applied thereto from the outside, lithium ions move to the corresponding electrodes in the adhesive layer (ion transport) to exhibit ion conductivity.
所谓使用双(氟烷基磺酰基)酰亚胺锂Li(CF3SO2)2N溶解于四乙二醇二甲基醚的状态，是作为极性基团的醚基配位于Li+离子的状态，以此状态分散于组合物中。即，组合物中含有锂聚醚络合物。Li+离子被醚氧所包围，从(CF3SO2)2N-离子上脱离，处于裸露状态，大幅有助于防静电性。尤其是锂盐与在主链中含有聚醚基的增塑剂的混合物形成路易斯酸-碱型的络离子，该络合物作为一种离子性液体而发挥作用，特别有助于防静电性。另外，锂盐由于与主链中含有聚醚基的增塑剂形成路易斯酸-碱型的络离子，因此无法与起偏镜的碘离子形成化学键。因此，也不导致起偏镜的脱色。The state in which lithium bis(fluoroalkylsulfonyl)imide Li(CF3 SO2 )2 N is dissolved in tetraethylene glycol dimethyl ether is used because the ether group, which is a polar group, is coordinated to the Li+ ion state, dispersed in the composition in this state. That is, the lithium polyether complex is contained in the composition. Li+ ions are surrounded by ether oxygen, detached from (CF3 SO2 )2 N- ions, and are in a bare state, greatly contributing to antistatic properties. In particular, the mixture of lithium salt and plasticizer containing polyether group in the main chain forms a Lewis acid-base type complex ion, which functions as an ionic liquid and is especially helpful for antistatic properties . In addition, since the lithium salt forms a Lewis acid-base type complex ion with a plasticizer containing a polyether group in the main chain, it cannot form a chemical bond with the iodide ion of the polarizer. Therefore, discoloration of the polarizer is not caused, either.
相对于上述在主链中含有聚醚基的增塑剂100质量份，具备具有氟基及磺酰基的阴离子的盐优选含有0.1～200质量份、更优选为1～180质量份、进一步更优选为5～150质量份。The salt having an anion having a fluorine group and a sulfonyl group preferably contains 0.1 to 200 parts by mass, more preferably 1 to 180 parts by mass, and even more preferably It is 5-150 mass parts.
相对于(甲基)丙烯酸类共聚物100质量份，溶解了具备具有氟基及磺酰基的阴离子的盐的增塑剂溶液优选含有0.01～30质量份。通过将溶解了具备具有氟基及磺酰基的阴离子的盐的增塑剂溶液的含量设为上述范围内，可发挥充分的防静电性能。It is preferable that the plasticizer solution which melt|dissolved the salt which has the anion which has a fluorine group and a sulfonyl group contains 0.01-30 mass parts with respect to 100 mass parts of (meth)acryl-type copolymers. Sufficient antistatic performance can be exhibited by making content of the plasticizer solution which melt|dissolved the salt which has the anion which has a fluorine group and a sulfonyl group into the said range.
(聚合物型防静电剂)(polymer antistatic agent)
防静电性组合物还可进一步含有聚合物型防静电剂。聚合物型防静电剂可使具备阴离子的盐稳定化。另外，具备阴离子的盐由于以溶解于主链中含有聚醚基的增塑剂中的状态分散，因此可认为该盐集中在与主链中含有聚醚基的增塑剂具有亲和性的聚合物型防静电剂的存在处，利用两者的亲和力而稳定化。作为这样的聚合物型防静电剂，可列举例如：聚醚嵌段聚烯烃共聚物、聚氧亚烷基类共聚物或环氧乙烷-环氧丙烷-烯丙基环氧丙基共聚物。The antistatic composition may further contain a polymer type antistatic agent. Polymeric antistatic agents stabilize salts with anions. In addition, since the salt having an anion is dispersed in the state of being dissolved in the plasticizer containing a polyether group in the main chain, it is considered that the salt is concentrated in the plasticizer having an affinity with the plasticizer containing a polyether group in the main chain. Where the polymer antistatic agent exists, it is stabilized by utilizing the affinity between the two. Examples of such polymer antistatic agents include polyether block polyolefin copolymers, polyoxyalkylene copolymers, and ethylene oxide-propylene oxide-allylglycidyl copolymers. .
相对于(甲基)丙烯酸类共聚物100质量份，优选含有聚合物型防静电剂0.1～65质量份。It is preferable to contain 0.1-65 mass parts of polymer type antistatic agents with respect to 100 mass parts of (meth)acryl-type copolymers.
(防静电性组合物的制造方法)(Manufacturing method of antistatic composition)
本发明中使用的防静电性组合物的制造方法包括准备盐溶液的工序，所述盐处于作为具有氟基及磺酰基的阴离子的抗衡离子的阳离子配位于主链中含有聚醚基的增塑剂的醚氧原子的状态。在准备盐溶液的工序中，在主链中含有聚醚基的增塑剂将具备具有氟基及磺酰基的阴离子的盐一边散热一边迅速溶解。在本发明中，主链中含有聚醚基的增塑剂优选为聚醚酯类增塑剂和/或聚醚类增塑剂，盐溶液可以通过在这些增塑剂中添加具备具有氟基及磺酰基的阴离子的盐并进行搅拌等而得到。The production method of the antistatic composition used in the present invention includes the step of preparing a salt solution in which a cation as a counter ion of an anion having a fluorine group and a sulfonyl group is coordinated to a plasticizer containing a polyether group in the main chain. The state of the ether oxygen atom of the agent. In the step of preparing the salt solution, the plasticizer containing a polyether group in the main chain rapidly dissolves the salt having an anion having a fluorine group and a sulfonyl group while dissipating heat. In the present invention, the plasticizer containing polyether groups in the main chain is preferably polyether ester plasticizers and/or polyether plasticizers, and the salt solution can be added to these plasticizers with And the salt of the anion of the sulfonyl group and stirring etc. to obtain.
(粘合剂组合物)(adhesive composition)
起偏镜用粘合剂组合物优选的主成分优选为实质上不含有羧基的粘合剂组合物。这里，所谓实质上不含有羧基是指在根据JIS K0070(1992)测定粘合剂组合物的聚合所使用的单体的酸值时，其酸值小于0.1mgKOH/g。若酸值小于0.1mgKOH/g，则意味着不含有故意添加的含羧基单体。A preferable main component of the adhesive composition for polarizers is preferably an adhesive composition substantially not containing a carboxyl group. Here, "substantially not containing a carboxyl group" means that the acid value is less than 0.1 mgKOH/g when the acid value of the monomer used for the polymerization of the adhesive composition is measured according to JIS K0070 (1992). When the acid value is less than 0.1 mgKOH/g, it means that the intentionally added carboxyl group-containing monomer is not included.
(丙烯酸类粘合剂组合物)(acrylic adhesive composition)
起偏镜用粘合剂组合物优选的主成分为丙烯酸类粘合剂组合物。所谓丙烯酸类粘合剂组合物含有(甲基)丙烯酸类共聚物经由交联剂而交联得到的化合物。另外，所谓“主成分”指相对于粘合剂整体含有50质量％以上。A preferable main component of the adhesive composition for polarizers is an acrylic adhesive composition. The so-called acrylic pressure-sensitive adhesive composition contains a compound obtained by crosslinking a (meth)acrylic copolymer via a crosslinking agent. In addition, "main component" means containing 50 mass % or more with respect to the whole binder.
丙烯酸类粘合剂组合物含有(甲基)丙烯酸类共聚物(A)与交联剂(B)。“丙烯酸类粘合剂组合物”是具有(甲基)丙烯酰基的化合物。“(甲基)丙烯酰基”表示丙烯酰基或甲基丙烯酰基。The acrylic pressure-sensitive adhesive composition contains a (meth)acrylic copolymer (A) and a crosslinking agent (B). "Acrylic PSA composition" is a compound which has a (meth)acryloyl group. "(Meth)acryloyl" means acryloyl or methacryloyl.
(甲基)丙烯酸类共聚物(A)优选为至少使(i)与(ii)进行聚合而得到的聚合物：(i)具有碳原子数1～18的烷基的(甲基)丙烯酸酯单体60～99.99质量％，(ii)具有自由基聚合性不饱和基团、且具有至少1个反应性官能团的单体0.01～20质量％。The (meth)acrylic copolymer (A) is preferably a polymer obtained by polymerizing at least (i) and (ii): (i) (meth)acrylate having an alkyl group having 1 to 18 carbon atoms 60-99.99% by mass of the monomer, 0.01-20% by mass of (ii) a monomer having a radically polymerizable unsaturated group and at least one reactive functional group.
作为(i)具有碳原子数1～18的烷基的(甲基)丙烯酸酯单体(以下称为非交联性丙烯酸类单体)，可列举例如：将(甲基)丙烯酸的羧基的氢原子用烃基取代得到的(甲基)丙烯酸酯。该烃基的碳原子数优选为1～18、更优选为1～8。该烃基也可具有取代基。作为该取代基，只要不含交联性基团即可，没有特别限定，可列举例如：甲氧基、乙氧基等烷氧基。作为该(甲基)丙烯酸酯，具体可列举例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(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)丙烯酸正壬酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸正十一酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄酯。这些化合物可单独使用1种，也可组合使用2种以上。另外，在本发明中，“(甲基)丙烯酸”指包括“丙烯酸”及“甲基丙烯酸”两者。这些当中，从粘接性的观点考虑，优选为丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸甲酯。Examples of (i) (meth)acrylate monomers having an alkyl group having 1 to 18 carbon atoms (hereinafter referred to as non-crosslinkable acrylic monomers) include: A (meth)acrylate is obtained by substituting a hydrogen atom with a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1-18, more preferably 1-8. This hydrocarbon group may also have a substituent. As this substituent, it will not specifically limit if it does not contain a crosslinkable group, For example, alkoxy groups, such as a methoxy group and an ethoxy group, are mentioned. Specific examples of the (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate, ) n-butyl acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl (meth) acrylate Hexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylate Base) isodecyl acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, methoxyethyl (meth)acrylate, (meth) ) ethoxyethyl acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate. These compounds may be used alone or in combination of two or more. In addition, in this invention, "(meth)acryl" means including both "acryl" and "methacryl". Among these, n-butyl acrylate, 2-ethylhexyl acrylate, and methyl acrylate are preferable from the viewpoint of adhesiveness.
(甲基)丙烯酸类共聚物(A)的聚合所使用的非交联性丙烯酸类单体的量优选为60～99.99质量％、更优选为65～99.99质量％。如果聚合所使用的非交联性丙烯酸类单体的量为上述下限值以上，则可表现充分的粘合力，如果为上述上限值以下，则可充分进行交联。The quantity of the non-crosslinkable acrylic monomer used for superposition|polymerization of a (meth)acryl-type copolymer (A) becomes like this. Preferably it is 60-99.99 mass %, More preferably, it is 65-99.99 mass %. When the quantity of the non-crosslinkable acrylic monomer used for superposition|polymerization is more than the said lower limit, sufficient adhesive force can be expressed, and when it is below the said upper limit, crosslinking can fully progress.
(ii)具有自由基聚合性不饱和基团、且具有至少1个反应性官能团的单体(以下称为交联性单体)，若可与非交联性丙烯酸类单体进行聚合，则可以是丙烯酸类单体或非丙烯酸类单体，优选为丙烯酸类单体。作为反应性官能团，可列举例如：羧基、羟基、氨基、环氧基、环氧丙基等。(ii) A monomer having a radically polymerizable unsaturated group and at least one reactive functional group (hereinafter referred to as a crosslinkable monomer), if it can be polymerized with a non-crosslinkable acrylic monomer, It may be an acrylic monomer or a non-acrylic monomer, preferably an acrylic monomer. As a reactive functional group, a carboxyl group, a hydroxyl group, an amino group, an epoxy group, a glycidyl group etc. are mentioned, for example.
作为含羧基单体，可列举例如：丙烯酸、甲基丙烯酸、丁烯酸、顺丁烯二酸、反丁烯二酸、依康酸、柠康酸、戊烯二酸等α,β-不饱和羧酸或其酸酐等。Examples of carboxyl group-containing monomers include: acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, etc. Saturated carboxylic acid or its anhydride, etc.
作为含羟基单体，可列举例如：(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸2-羟基丙酯等(甲基)丙烯酸羟基烷酯，(甲基)丙烯酸单(二乙二醇)酯等(甲基)丙烯酸[(单、二或多)乙二醇]酯、(甲基)丙烯酸单己内酯等(甲基)丙烯酸内酯。Examples of hydroxyl-containing monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Esters, (meth)acrylates such as mono(diethylene glycol) (meth)acrylate [(mono-, di- or poly)ethylene glycol] esters, (meth)acrylates such as monocaprolactone (meth)acrylate Lactone.
作为含氨基单体，可列举例如：(甲基)丙烯酰胺、烯丙基酰胺、N,N-二甲基(甲基)丙烯酰胺、N-丁基(甲基)丙烯酰胺等。As an amino group-containing monomer, (meth)acrylamide, allylamide, N,N- dimethyl (meth)acrylamide, N-butyl (meth)acrylamide etc. are mentioned, for example.
作为含环氧丙基单体，可列举例如(甲基)丙烯酸环氧丙酯等。As a glycidyl group containing monomer, glycidyl (meth)acrylate etc. are mentioned, for example.
(甲基)丙烯酸类共聚物(A)的聚合所使用的交联性单体的量优选为0.01～20质量％、更优选为0.03～10质量％、进一步更优选为0.05～10质量％。若聚合所使用的交联性单体的量为上述下限值以上，则可充分交联；若为上述上限值以下，则容易控制粘合力，进行再剥离而再利用玻璃的返工性也良好。The quantity of the crosslinkable monomer used for superposition|polymerization of a (meth)acryl-type copolymer (A) becomes like this. Preferably it is 0.01-20 mass %, More preferably, it is 0.03-10 mass %, More preferably, it is 0.05-10 mass %. When the amount of the cross-linkable monomer used for polymerization is more than the above-mentioned lower limit, cross-linking is sufficient; if it is below the above-mentioned upper limit, it is easy to control the adhesive force, and the reworkability of glass can be reused by peeling off again. Also good.
从粘合性、交联性、聚合性及耐久性、以及进行再剥离而可再利用玻璃的返工性良好的观点考虑，交联性单体优选为含羟基单体或含氨基单体。也可将含羟基单体与含氨基单体组合使用。作为含羟基单体，优选为(甲基)丙烯酸羟基烷酯，特别优选为(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸4-羟基丁酯。作为含氨基单体，优选为(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N-丁基(甲基)丙烯酰胺。The crosslinkable monomer is preferably a hydroxyl group-containing monomer or an amino group-containing monomer from the viewpoint of adhesiveness, crosslinkability, polymerizability, durability, and reworkability of the reusable glass after re-peeling. It is also possible to use hydroxyl group-containing monomers in combination with amino group-containing monomers. As the hydroxyl group-containing monomer, hydroxyalkyl (meth)acrylate is preferable, and 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are particularly preferable. As the amino group-containing monomer, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N-butyl(meth)acrylamide are preferable.
在交联性单体为含羧基单体的情况下，由于酸性变强，因此在与锡掺杂氧化铟膜或金属膜等具有腐蚀性的膜接触时，有时使这些膜腐蚀。因此，从防止腐蚀性的观点考虑，(甲基)丙烯酸类共聚物(A)的聚合所使用的含羧基单体的量优选\小于0.5质量％、更优选小于0.05质量％。另外，具有反应性官能团的单体优选实质上不含有含羧基单体。这里，所谓具有反应性官能团的单体实质上不含有含羧基单体，是指在根据JIS K0070(1992)测定(甲基)丙烯酸类共聚物(A)的聚合所使用的具有反应性官能团的单体的酸值时，其酸值小于0.1mgKOH/g。若具有反应性官能团的单体的酸值小于0.1mgKOH/g，则可认为其并不含有故意添加的含羧基单体；若为0.1～1.0mgKOH/g，可认为其微量含有故意添加的含羧基单体。需要说明的是，所谓故意添加，是指使用了含羧基单体作为交联性单体。在使用作为非交联性丙烯酸单体的丙烯酸酯(来自丙烯酸的衍生物)时，虽然有时以杂质的形式含有微量的未反应丙烯酸，但这样的情况并不视为故意添加。When the crosslinkable monomer is a carboxyl group-containing monomer, since the acidity becomes stronger, when it comes into contact with a corrosive film such as a tin-doped indium oxide film or a metal film, these films may be corroded. Therefore, from the viewpoint of corrosion prevention, the amount of the carboxyl group-containing monomer used for the polymerization of the (meth)acrylic copolymer (A) is preferably \ less than 0.5% by mass, more preferably less than 0.05% by mass. Moreover, it is preferable that the monomer which has a reactive functional group does not contain a carboxyl group containing monomer substantially. Here, the monomer having a reactive functional group that does not substantially contain a carboxyl group-containing monomer refers to a monomer having a reactive functional group used for the polymerization of the (meth)acrylic copolymer (A) measured in accordance with JIS K0070 (1992). The acid value of the monomer is less than 0.1mgKOH/g. If the acid value of the monomer with reactive functional groups is less than 0.1mgKOH/g, it can be considered that it does not contain intentionally added carboxyl-containing monomers; carboxyl monomer. In addition, intentional addition means using a carboxyl group-containing monomer as a crosslinkable monomer. When using acrylate (derivative derived from acrylic acid) which is a non-crosslinkable acrylic monomer, a trace amount of unreacted acrylic acid may be contained as an impurity, but such a case is not regarded as intentional addition.
在根据JIS K0070(1992)测定酸值时，例如如下所述进行测定。When measuring an acid value based on JISK0070 (1992), it measures, for example as follows.
用精密天平在100ml三角烧瓶中精密称量试样约2g左右，向其中加入乙醇/乙醚＝1/1(重量比)的混合溶剂10ml并溶解。再在该容器中添加酚酞乙醇溶液1～3滴作为指示剂，充分搅拌至试样均匀为止。对其以0.1N氢氧化钾-乙醇溶液进行滴定，以指示剂持续淡红色30秒时作为中和终点。将根据由该结果使用下述计算式(1)所得的值作为试样的酸值。About 2 g of the sample was precisely weighed in a 100 ml Erlenmeyer flask with a precision balance, and 10 ml of a mixed solvent of ethanol/ether=1/1 (weight ratio) was added thereto and dissolved. Then add 1 to 3 drops of phenolphthalein ethanol solution in the container as an indicator, and stir well until the sample is uniform. It is titrated with 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization is when the indicator remains light red for 30 seconds. From this result, the value obtained using the following calculation formula (1) was made into the acid value of a sample.
酸值(mgKOH/g)＝[B×f×5.611]/S (1)Acid value (mgKOH/g)=[B×f×5.611]/S (1)
在计算式(1)中，B为0.1N氢氧化钾-乙醇溶液的用量(ml)，f为0.1N氢氧化钾-乙醇溶液的因子，S为试样的采集量(g)。In calculation formula (1), B is the consumption (ml) of 0.1N potassium hydroxide-ethanol solution, f is the factor of 0.1N potassium hydroxide-ethanol solution, S is the collection amount (g) of sample.
(甲基)丙烯酸类共聚物(A)也可具有非交联性丙烯酸类单体及交联性单体以外的其它单体。作为其它单体，可列举例如：(甲基)丙烯腈、乙酸乙烯酯、苯乙烯、氯乙烯、乙烯基吡咯烷酮、乙烯基吡啶等。The (meth)acrylic copolymer (A) may have other monomers other than a non-crosslinkable acrylic monomer and a crosslinkable monomer. As another monomer, (meth)acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinylpyrrolidone, vinylpyridine etc. are mentioned, for example.
(甲基)丙烯酸类共聚物(A)的聚合所使用的其它单体的量优选为0.1～20质量％、更优选为0.5～10质量％。若聚合所使用的其它单体的量为上述下限值以上，则可容易调整物性，若为上述上限值以下，可防止因经时劣化所造成的黄变。The quantity of the other monomer used for superposition|polymerization of a (meth)acrylic-type copolymer (A) becomes like this. Preferably it is 0.1-20 mass %, More preferably, it is 0.5-10 mass %. When the amount of the other monomer used for polymerization is more than the said lower limit, physical property can be adjusted easily, and when it is below the said upper limit, yellowing by aging deterioration can be prevented.
((甲基)丙烯酸类共聚物的重均分子量)(Weight average molecular weight of (meth)acrylic copolymer)
(甲基)丙烯酸类共聚物(A)的重均分子量优选为40万～250万、更优选为50万～200万、进一步更优选为100万～200万、特别优选150万～200万。通过将重均分子量设为上述范围内，可使其发挥充分的凝集力，可提高耐久性。另外，可抑制含有起偏镜用粘合剂组合物的涂布液的粘度增高，容易通过涂布而形成粘合剂层。另外，重均分子量可使用凝胶渗透色谱(GPC)进行测定，是换算为标准聚苯乙烯(PS)的重均分子量。The weight average molecular weight of the (meth)acrylic copolymer (A) is preferably 400,000 to 2,500,000, more preferably 500,000 to 2 million, still more preferably 1 million to 2 million, particularly preferably 1,500,000 to 2 million. By making weight average molecular weight into the said range, sufficient cohesive force can be exhibited, and durability can be improved. Moreover, an increase in the viscosity of the coating liquid containing the adhesive composition for polarizers can be suppressed, and it becomes easy to form an adhesive layer by coating. In addition, the weight average molecular weight can be measured using gel permeation chromatography (GPC), and is the weight average molecular weight converted into standard polystyrene (PS).
(丙烯酸类粘合剂组合物所使用的交联剂)(Crosslinking agent used in acrylic adhesive composition)
作为丙烯酸类粘合剂组合物所使用的交联剂(B)，优选为使用可与作为具有反应性官能团的单体的交联性单体进行反应的交联剂。可列举例如：异氰酸酯类交联剂、环氧类交联剂、唑啉类交联剂、氮丙啶类交联剂、金属螯合物类交联剂、丁基化三聚氰胺类交联剂等。这些交联剂中，由于可使(甲基)丙烯酸类共聚物(A)容易交联，因此优选异氰酸酯类交联剂、环氧类交联剂、金属螯合剂类交联剂。尤其是在(甲基)丙烯酸类共聚物(A)仅含有含羟基单体作为交联性单体的情况下，从羟基的反应性的观点考虑，优选使用异氰酸酯类交联剂。As a crosslinking agent (B) used for an acrylic pressure-sensitive adhesive composition, it is preferable to use the crosslinking agent which can react with the crosslinkable monomer which is a monomer which has a reactive functional group. Examples include: isocyanate-based crosslinking agents, epoxy-based crosslinking agents, Azoline cross-linking agent, aziridine cross-linking agent, metal chelate cross-linking agent, butylated melamine cross-linking agent, etc. Among these crosslinking agents, isocyanate crosslinking agents, epoxy crosslinking agents, and metal chelating agent crosslinking agents are preferable because they can easily crosslink the (meth)acrylic copolymer (A). In particular, when the (meth)acrylic copolymer (A) contains only a hydroxyl group-containing monomer as a crosslinkable monomer, it is preferable to use an isocyanate crosslinking agent from the viewpoint of the reactivity of the hydroxyl group.
作为异氰酸酯类交联剂，可列举例如：二异氰酸甲苯酯、二异氰酸二甲苯酯、二异氰酸六亚甲酯、二异氰酸异佛酮等。作为环氧类交联剂，可列举例如乙二醇二环氧丙基醚、聚乙二醇二环氧丙基醚、丙二醇二环氧丙基醚、聚丙二醇二环氧丙基醚、甘油二环氧丙基醚、新戊二醇二环氧丙基醚、1,6-己二醇二环氧丙基醚、四环氧丙基二甲苯二胺、1,3-双(N,N-二环氧丙基胺基甲基)环己酮、三羟甲基丙烷聚环氧丙基醚、二甘油聚环氧丙基醚、聚甘油聚环氧丙基醚、山梨醇聚环氧丙基醚等。交联剂的含量优选根据所需的粘合物性而适当选择。另外，这些交联剂可单独使用或使用2种以上。As an isocyanate crosslinking agent, cresyl diisocyanate, xylyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. Examples of epoxy-based crosslinking agents include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, tetraglycidyl xylylenediamine, 1,3-bis(N, N-Diglycidylaminomethyl) cyclohexanone, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polycyclo Oxypropyl ether etc. The content of the crosslinking agent is preferably appropriately selected according to the required physical properties of the adhesive. In addition, these crosslinking agents may be used alone or in combination of two or more.
相对于(甲基)丙烯酸类共聚物(A)100质量份，丙烯酸类粘合剂组合物所使用的交联剂(B)的含量优选为0.001～10质量份，更优选为0.01～5质量份。若为上述下限值以上，可抑制发泡，若为上述上限值以下，则可使其具有充分的应力缓和性能。The content of the crosslinking agent (B) used in the acrylic adhesive composition is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the (meth)acrylic copolymer (A). share. When it is more than the said lower limit, foaming can be suppressed, and when it is below the said upper limit, sufficient stress relaxation performance can be given.
(添加剂)(additive)
在本发明的起偏镜用粘合剂组合物中，还可以含有丙烯酸类粘合剂组合物与防静电性组合物以外的成分。例如，在丙烯酸类粘合剂组合物以外，也可组合使用聚酯树脂、氨基树脂、环氧树脂、聚氨酯树脂。The adhesive composition for polarizers of this invention may contain components other than an acrylic adhesive composition and an antistatic composition. For example, polyester resins, amino resins, epoxy resins, and polyurethane resins may be used in combination in addition to the acrylic pressure-sensitive adhesive composition.
另外，在本发明的起偏镜用粘合剂组合物中，视需要也可含有抗氧化剂、金属腐蚀防止剂、增粘剂、硅烷偶联剂、紫外线吸收剂、受阻胺类化合物等光稳定剂、填充剂等添加剂。作为抗氧化剂，可列举例如：酚类抗氧化剂、胺类抗氧化剂、内酯类抗氧化剂、磷类抗氧化剂、硫类抗氧化剂等。这些抗氧化剂可单独1种使用，也可组合使用2种以上。作为金属腐蚀防止剂，从粘合剂的相容性或效果的提高的观点考虑，优选为苯并三唑类树脂。作为增粘剂，可列举例如松香类树脂、萜类树脂、萜酚类树脂、苯并呋喃茚类树脂、苯乙烯类树脂、二甲苯类树脂、酚类树脂、石油树脂等。作为硅烷偶联剂，可列举例如巯基烷氧基硅烷化合物(例如巯基取代烷氧基低聚物等)等。作为紫外线吸收剂，可列举例如：苯并三唑类化合物、二苯基酮类化合物、三嗪类化合物等。In addition, in the adhesive composition for polarizers of the present invention, photostabilizing agents such as antioxidants, metal corrosion inhibitors, tackifiers, silane coupling agents, ultraviolet absorbers, hindered amine compounds, etc. may be contained as needed. Additives such as agents and fillers. Examples of antioxidants include phenolic antioxidants, amine antioxidants, lactone antioxidants, phosphorus antioxidants, and sulfur antioxidants. These antioxidants may be used alone or in combination of two or more. The metal corrosion inhibitor is preferably a benzotriazole-based resin from the viewpoint of improving the compatibility of the binder or the effect. Examples of the tackifier include rosin-based resins, terpene-based resins, terpene-phenol-based resins, coumarone-based resins, styrene-based resins, xylene-based resins, phenol-based resins, and petroleum resins. As a silane coupling agent, a mercaptoalkoxysilane compound (for example, a mercapto-substituted alkoxy oligomer etc.) etc. are mentioned, for example. As a ultraviolet absorber, a benzotriazole type compound, a benzophenone type compound, a triazine type compound, etc. are mentioned, for example.
相对于起偏镜用粘合剂组合物的固体成分100质量份，这些添加剂的含量通常优选为0.01～10质量份、更优选为0.05～5质量份、特别优选0.1～3质量份。The content of these additives is usually preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass relative to 100 parts by mass of solid content of the adhesive composition for polarizers.
(起偏镜用粘合剂组合物的制造方法)(Manufacturing method of adhesive composition for polarizers)
起偏镜用粘合剂组合物使具备具有氟基及磺酰基的阴离子的盐分散于含有丙烯酸类粘合剂组合物等粘合性树脂的组合物中而制造。制造方法包括：准备盐溶液的工序，所述盐溶液在主链中含有聚醚基的增塑剂中溶解具备具有氟基及磺酰基的阴离子的盐而成；将盐溶液(第1成分)与粘合性树脂(第2成分)混练，形成组合物的工序；将上述组合物进一步与粘合性树脂(第2成分)混练或混合的工序。通过第1成分与第2成分的混练，盐溶液在组合物中以微液滴状分散存在或溶入。然后，以盐溶入组合物中的状态，再与粘合性树脂(第2成分)混练或混合，因此盐在粘合性树脂(第2成分)中以更均匀的亲和状态分散。The adhesive composition for polarizers is produced by dispersing a salt having an anion having a fluorine group and a sulfonyl group in a composition containing an adhesive resin such as an acrylic adhesive composition. The production method includes the steps of preparing a salt solution prepared by dissolving a salt having an anion having a fluorine group and a sulfonyl group in a plasticizer containing a polyether group in the main chain; A step of kneading with an adhesive resin (second component) to form a composition; a step of kneading or mixing the above composition with an adhesive resin (second component). By kneading the first component and the second component, the salt solution is dispersed or dissolved in the composition in the form of fine droplets. Then, the salt is kneaded or mixed with the adhesive resin (second component) in a state where the salt is dissolved in the composition, so that the salt is dispersed in a more uniform affinity state in the adhesive resin (second component).
(起偏镜用粘合片)(Adhesive sheets for polarizers)
本发明的起偏镜用粘合剂组合物可形成片状而制成起偏镜用粘合片。起偏镜用粘合片例如可将粘合剂溶解于溶剂并涂布后通过去除溶剂而制造。作为涂布方法，可从刀涂机、微棒涂布机、气刀涂布机、反转辊涂布机、反转凹版涂布机、Vario凹版涂布机、模涂机、帘涂机等中适当选择。若使用本发明的粘合片，则不需要贴合阶段的粘合剂涂布、干燥工序，只要在光学薄膜与粘合对象物之间叠层起偏镜用粘合片并加压就可进行粘合，因此非常简便。The adhesive composition for polarizers of this invention can be formed into a sheet form, and can be used as an adhesive sheet for polarizers. The pressure-sensitive adhesive sheet for polarizers can be manufactured by removing a solvent, for example, after dissolving a pressure-sensitive adhesive in a solvent and applying it. As the coating method, from knife coater, micro bar coater, air knife coater, reverse roll coater, reverse gravure coater, Vario gravure coater, die coater, curtain coater Choose appropriately. If the pressure-sensitive adhesive sheet of the present invention is used, the pressure-sensitive adhesive coating and drying steps in the bonding stage are not required, and it is only necessary to laminate the pressure-sensitive adhesive sheet for polarizers between the optical film and the object to be bonded and pressurize. Glue it, so it's very easy.
(起偏镜用粘合片的厚度)(thickness of adhesive sheet for polarizer)
本发明的起偏镜用粘合片的粘合剂层的厚度优选为100μm以下、更优选为5～50μm。若为上述上限值以下，则可充分表现出粘合剂层的应力缓和性能。The thickness of the adhesive layer of the adhesive sheet for polarizers of this invention becomes like this. Preferably it is 100 micrometers or less, More preferably, it is 5-50 micrometers. The stress relaxation performance of an adhesive layer can fully express as it is below the said upper limit.
(起偏镜用带有剥离片的粘合片)(Adhesive sheet with release sheet for polarizer)
起偏镜用带有剥离片的粘合片优选具有将剥离膜设于粘合片的单面或两面的结构，所述剥离膜在基材上设有剥离剂。例如，在粘合剂层的两面设有剥离膜的带有剥离片的双面粘合片可以通过以下方式得到：将粘合剂涂布液涂布于高分子膜上设有剥离剂层的第1剥离膜的剥离层面，干燥后，将由剥离力与第1剥离膜不同的剥离剂层所形成的第2剥离膜的剥离层面贴合压粘于粘合剂层。若第1剥离膜与第2剥离膜的剥离力接近，则在将轻剥离力侧的剥离膜进行剥离时，发生粘合剂从重剥离力侧的剥离膜上浮起分离的现象。因此，重剥离力侧的剥离膜的剥离力优选为0.05N～0.15N，轻剥离力侧的剥离膜的剥离力优选为0.01～0.04N。The pressure-sensitive adhesive sheet with release sheet for polarizers preferably has a structure in which a release film provided with a release agent on a substrate is provided on one or both surfaces of the pressure-sensitive adhesive sheet. For example, a double-sided adhesive sheet with a release sheet provided with a release film on both sides of the adhesive layer can be obtained by applying an adhesive coating liquid to a polymer film provided with a release agent layer. After the release layer of the first release film is dried, the release layer of the second release film formed of a release agent layer having a release force different from that of the first release film is bonded and pressure-bonded to the adhesive layer. If the peeling force of the 1st release film and the 2nd release film are close, when the release film of the side of light release force is peeled off, the phenomenon that an adhesive agent floats and separates from the release film of the side of heavy release force occurs. Therefore, the peeling force of the peeling film on the heavy peeling force side is preferably 0.05N to 0.15N, and the peeling force of the peeling film on the light peeling force side is preferably 0.01 to 0.04N.
另外，此时，在保持二个剥离膜的剥离力之差时，也可在先将粘合剂涂布液涂布至第2剥离膜后，使第1剥离膜贴合压粘。粘合片的形状可为片状，也可卷起为卷状。In addition, at this time, when maintaining the difference in the peeling force of the two peeling films, the first peeling film may be pasted and pressure-bonded after the adhesive coating liquid is first applied to the second peeling film. The shape of the PSA sheet may be a sheet or rolled into a roll.
(偏振片)(polarizer)
本发明的起偏镜用粘合剂组合物及起偏镜用粘合片，可直接粘贴(叠层)于起偏镜。图2(a)表示使用本发明的起偏镜用粘合剂组合物及粘合片时的偏振片。如图2(a)所示，粘合片(起偏镜用粘合剂组合物层)20直接粘贴于起偏镜10。另外，粘合片(起偏镜用粘合剂组合物层)20也可粘贴于起偏镜10的两面。The pressure-sensitive adhesive composition for polarizers and the pressure-sensitive adhesive sheet for polarizers of this invention can be directly stuck (laminated) on a polarizer. Fig. 2(a) shows a polarizing plate when the adhesive composition for polarizers and the adhesive sheet of the present invention are used. As shown in FIG. 2( a ), an adhesive sheet (adhesive composition layer for polarizers) 20 is directly attached to the polarizer 10 . Moreover, the adhesive sheet (adhesive composition layer for polarizers) 20 may be stuck on both surfaces of the polarizer 10.
图2(b)表示现有的偏振片的结构。在现有的偏振片中，起偏镜被保护膜所挟持，粘合片(粘合层)粘贴于保护膜。本发明的起偏镜用粘合剂组合物及粘合片也可应用于这样的结构，在如图2(a)一样直接粘贴于起偏镜时可发挥本发明的效果。FIG. 2(b) shows the structure of a conventional polarizer. In a conventional polarizing plate, a polarizer is sandwiched by a protective film, and an adhesive sheet (adhesive layer) is attached to the protective film. The adhesive composition for polarizers of this invention, and an adhesive sheet can also be applied to such a structure, and when it sticks to a polarizer directly like FIG.2(a), the effect of this invention can be exhibited.
本发明的起偏镜用粘合剂组合物及起偏镜用粘合片用于贴合起偏镜与厚度100μm、优选1mm以上的构件。另外，本发明的起偏镜用粘合剂组合物及起偏镜用粘合片用于贴合起偏镜与光学构件。作为光学构件，可列举例如：液晶单元或触摸面板等，可制作具备本发明的粘合片的图像显示装置。The adhesive composition for polarizers and the adhesive sheet for polarizers of this invention are used for bonding a polarizer and a member with thickness 100 micrometers, Preferably it is 1 mm or more. Moreover, the adhesive composition for polarizers of this invention, and the adhesive sheet for polarizers are used for bonding a polarizer and an optical member. As an optical member, a liquid crystal cell, a touch panel, etc. are mentioned, for example, and the image display apparatus provided with the pressure-sensitive adhesive sheet of this invention can be produced.
作为偏振片所使用的起偏镜可使用例如，二色性色素吸附取向于聚乙烯醇类树脂膜或日本专利特开2012-159778号中记载的聚乙烯醇类树脂而成的起偏镜。构成起偏镜的聚乙烯醇类树脂通过将聚乙酸乙烯酯类树脂皂化而获得。作为聚乙酸乙烯酯类树脂，除了作为乙酸乙烯酯的均聚物的聚乙酸乙烯酯之外，可例示乙酸乙烯酯及可与其进行共聚的其它单体的共聚物等。作为可与乙酸乙烯酯进行共聚的其它单体，可列举例如：不饱和羧酸类、烯烃类、乙烯基醚类、不饱和磺酸类、具有铵基的丙烯酰胺类等。聚乙烯醇类树脂的皂化度，通常为85～100摩尔％左右、优选98摩尔％以上。该聚乙烯醇类树脂也可进一步改性，例如可使用由醛类所改性的聚乙烯基甲醛或聚乙烯基乙醛等。另外，聚乙烯醇类树脂的聚合度通常为1,000～10,000左右、优选1,500～5,000左右。As the polarizer used for the polarizing plate, for example, a polarizer in which a dichroic dye is adsorbed and aligned on a polyvinyl alcohol-based resin film or a polyvinyl alcohol-based resin described in JP-A-2012-159778 can be used. The polyvinyl alcohol-based resin constituting the polarizer is obtained by saponifying polyvinyl acetate-based resin. As the polyvinyl acetate resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith, and the like can be exemplified. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be further modified, for example, polyvinyl formaldehyde or polyvinyl acetaldehyde modified with aldehydes may be used. In addition, the degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably about 1,500 to 5,000.
将这样的聚乙烯醇类树脂进行成膜而得到的膜可以用作起偏镜的原料膜。对聚乙烯醇类树脂进行成膜的方法并无特别限定，可依公知方法进行成膜。由聚乙烯醇类树脂所构成的原料膜的膜厚并无特别限定，为例如1～150μm左右。若考虑拉伸容易度等，其膜厚优选为3μm以上。A film formed by forming such a polyvinyl alcohol-based resin can be used as a raw material film of a polarizer. The method of forming a film of the polyvinyl alcohol-based resin is not particularly limited, and it can be formed according to a known method. The film thickness of the raw material film which consists of polyvinyl-alcohol-type resin is not specifically limited, For example, it is about 1-150 micrometers. In consideration of easiness of stretching, etc., the film thickness is preferably 3 μm or more.
另外，起偏镜可以经过下述工序并最终干燥来制造：将上述这样的聚乙烯醇类树脂膜或日本专利特开2012-159778号中记载的聚乙烯醇类树脂进行单向拉伸的工序、将聚乙烯醇类树脂或膜用二色性色素进行染色而使该二色性色素吸附的工序、将吸附了二色性色素的聚乙烯醇类树脂或膜用硼酸水溶液进行处理的工序、以及在该硼酸水溶液的处理后进行水洗的工序。In addition, the polarizer can be manufactured through the process of uniaxially stretching the above-mentioned polyvinyl alcohol-based resin film or the polyvinyl alcohol-based resin described in Japanese Patent Laid-Open No. 2012-159778, followed by final drying. , a step of dyeing a polyvinyl alcohol-based resin or a film with a dichroic dye to adsorb the dichroic dye, a step of treating the polyvinyl alcohol-based resin or film on which the dichroic dye has been adsorbed with a boric acid aqueous solution, And a step of washing with water after the treatment of the boric acid aqueous solution.
另外，偏振片具有在上述所制造的起偏镜的至少一者叠层了透明保护膜的结构。作为该透明保护膜，可使用由适当的透明树脂所形成的保护膜。具体而言，优选使用由透明性或均匀的光学特性、机械强度、热稳定性等优异的聚合物所形成的保护膜。作为这样的透明树脂膜，可使用三乙酰纤维素及二乙酰纤维素等纤维素类膜，聚对苯二甲酸乙二醇酯、聚间苯二甲酸乙二醇酯及聚对苯二甲酸丁二醇酯等聚酯类膜，聚(甲基)丙烯酸甲酯及聚(甲基)丙烯酸乙酯等丙烯酸树脂类膜、聚碳酸酯类膜、聚醚砜类膜、聚砜类膜、聚酰亚胺类膜、聚烯烃类膜、聚降冰片烯类膜等，但并不限定于此。In addition, the polarizing plate has a structure in which a transparent protective film is laminated on at least one of the polarizers manufactured above. As the transparent protective film, a protective film formed of an appropriate transparent resin can be used. Specifically, it is preferable to use a protective film formed of a polymer excellent in transparency, uniform optical properties, mechanical strength, thermal stability, and the like. As such a transparent resin film, cellulose films such as triacetyl cellulose and diacetyl cellulose, polyethylene terephthalate, polyethylene isophthalate, and polybutylene terephthalate can be used. Polyester films such as glycol esters, acrylic resin films such as polymethyl (meth)acrylate and polyethyl (meth)acrylate, polycarbonate films, polyethersulfone films, polysulfone films, poly Imide-based films, polyolefin-based films, polynorbornene-based films, etc., but not limited thereto.
实施例Example
以下，列举实施例与比较例更具体说明本发明特征。以下实施例所示材料、用量、比例、处理内容、处理步骤等在不脱离本发明主旨的前提下可适当变更。因此，本发明范围并非被限定解释为以下所示的具体例。另外，例中的“份”及“％”在无特别说明的情况下，分别为“质量份”及“质量％”。Hereinafter, the characteristics of the present invention will be described in more detail by way of examples and comparative examples. Materials, dosages, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" in the examples are "parts by mass" and "% by mass", respectively, unless otherwise specified.
(制造例1)(Manufacturing example 1)
<(甲基)丙烯酸类共聚物(A-1)的制备><Preparation of (meth)acrylic copolymer (A-1)>
向具备冷却管、氮导入管、搅拌机及温度计的反应容器中添加乙酸乙酯80份，加入作为单体的丙烯酸丁酯65份、丙烯酸2-乙基己酯30份、丙烯酸2-羟基乙酯5份，封入氮气而使其不含氧，并将内温提高为55℃。然后，添加使偶氮二异丁腈(聚合引发剂)0.06份溶解于乙酸乙酯10份而得到的溶液的全部量。然后，一边保持温度一边进行搅拌，搅拌12小时后，进行冷却使聚合反应停止。得到的(甲基)丙烯酸类共聚物(A-1)的利用GPC测定的换算为聚苯乙烯的重均分子量Mw为150万。80 parts of ethyl acetate, 65 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 5 parts were filled with nitrogen gas so as not to contain oxygen, and the internal temperature was increased to 55°C. Then, the whole amount of the solution obtained by dissolving 0.06 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. Then, stirring was performed while maintaining the temperature, and after stirring for 12 hours, cooling was performed to stop the polymerization reaction. The obtained (meth)acrylic copolymer (A-1) had a polystyrene-equivalent weight average molecular weight Mw of 1,500,000 measured by GPC.
((甲基)丙烯酸类共聚物的重均分子量的测定)(Measurement of weight average molecular weight of (meth)acrylic copolymer)
对于(甲基)丙烯酸类共聚物的重均分子量Mw而言，通过GPC(凝胶渗透色谱)测定溶解了THF(四氢呋喃)的试样。About the weight average molecular weight Mw of a (meth)acrylic-type copolymer, the sample which melt|dissolved THF (tetrahydrofuran) was measured by GPC (gel permeation chromatography).
(制造例2)(Manufacturing example 2)
<(甲基)丙烯酸类共聚物(A-2)的制备><Preparation of (meth)acrylic copolymer (A-2)>
向具备冷却管、氮导入管、搅拌机及温度计的反应容器中添加乙酸乙酯80份，加入作为单体的丙烯酸丁酯65份、丙烯酸2-乙基己酯30份、丙烯酸2-羟基乙酯5份，封入氮气而使其不含氧，并将内温提高为45℃。然后，添加使偶氮二异丁腈(聚合引发剂)0.04份溶解于乙酸乙酯10份而得到的溶液的全部量。然后，一边保持温度一边进行搅拌，搅拌16小时后，进行冷却使聚合反应停止。得到的(甲基)丙烯酸类共聚物(A-2)的利用GPC测定的换算为聚苯乙烯的重均分子量Mw为180万。80 parts of ethyl acetate, 65 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 5 parts were filled with nitrogen gas so as not to contain oxygen, and the internal temperature was increased to 45°C. Then, the whole amount of the solution obtained by dissolving 0.04 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. Then, stirring was performed while maintaining the temperature, and after stirring for 16 hours, cooling was performed to stop the polymerization reaction. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the obtained (meth)acryl-type copolymer (A-2) was 1,800,000.
(制造例3)(Manufacturing example 3)
<偏振片的制作><Production of Polarizer>
将厚75μm的聚乙烯醇膜(平均聚合度约2,400，皂化度99.9摩尔％以上)通过干式拉伸单向拉伸至约5倍，再在保持紧张状态下，浸渍于60℃纯水中1分钟，然后在碘/碘化钾/水的重量比为0.05/5/100之水溶液中于28℃浸渍60秒钟。然后，在碘化钾/硼酸/水的重量比为8.5/8.5/100的水溶液中于72℃浸渍300秒钟。接着以26℃纯水洗净20秒钟，然后于65℃下进行干燥，得到了碘吸附取向于聚乙烯醇膜的厚28μm的起偏镜。接着，在该起偏镜的一侧涂布环氧类粘接剂，制造了贴合厚40μm的三乙酰纤维素膜(TAC)[Konica Minolta公司制造，商品名“KC4UY”]作为透明保护膜的偏振片，所述环氧类粘接剂相对于水100份，溶解了羧基改性聚乙烯醇[由可乐丽股份有限公司获得，商品名“KL-318”]3份，并在该水溶液中添加了作为水溶性环氧树脂的聚酰胺环氧类添加剂[由田冈化学工业株式会社获得，商品名“Sumirez Resin 650(30)”，固体成分浓度30％的水溶液]1.5份。A polyvinyl alcohol film with a thickness of 75 μm (average degree of polymerization about 2,400, degree of saponification over 99.9 mol%) is uniaxially stretched to about 5 times by dry stretching, and then immersed in pure water at 60°C while maintaining tension 1 minute, and then immersed in an aqueous solution with a weight ratio of iodine/potassium iodide/water of 0.05/5/100 at 28° C. for 60 seconds. Then, it was immersed in the aqueous solution whose weight ratio of potassium iodide/boric acid/water was 8.5/8.5/100 at 72 degreeC for 300 second. Next, it was washed with 26° C. pure water for 20 seconds, and then dried at 65° C. to obtain a 28 μm thick polarizer in which iodine was adsorbed and aligned on the polyvinyl alcohol film. Next, an epoxy-based adhesive was applied to one side of the polarizer, and a 40 μm-thick triacetyl cellulose film (TAC) [manufactured by Konica Minolta, trade name "KC4UY"] was laminated as a transparent protective film. polarizer, the epoxy-based adhesive is dissolved in 3 parts of carboxy-modified polyvinyl alcohol [obtained by Kuraray Co., Ltd., trade name "KL-318"] with respect to 100 parts of water, and in the aqueous solution Added 1.5 parts of a polyamide epoxy additive as a water-soluble epoxy resin [obtained from Taoka Chemical Industry Co., Ltd., trade name "Sumirez Resin 650 (30)", an aqueous solution with a solid content concentration of 30%].
(实施例1)(Example 1)
<丙烯酸类粘合剂溶液的制备><Preparation of Acrylic Adhesive Solution>
相对于由制造例1得到的(甲基)丙烯酸类共聚物(A-1)的固体成分100份，添加作为交联剂的二甲苯二异氰酸酯(三井化学公司制：TAKENATE500)0.1份与3-环氧丙氧基丙基甲氧基硅烷(信越化学工业公司制：KBM-403)0.1份，再添加在聚醚酯类化合物50份(Monocizer(注册商标)W-262与Polycizer(注册商标)W-230-H的1︰1混合物)中溶解了双(三氟甲烷磺酰基)酰亚胺锂50份的组合物2.5份作为防静电性组合物，以乙酸乙酯稀释为固体成分浓度15％的溶液，制备了丙烯酸类粘合剂溶液。With respect to 100 parts of solid content of the (meth)acrylic copolymer (A-1) obtained in Production Example 1, 0.1 part of xylene diisocyanate (manufactured by Mitsui Chemicals: TAKENATE 500) and 3- 0.1 part of glycidoxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403), and 50 parts of polyether ester compound (Monocizer (registered trademark) W-262 and Polycizer (registered trademark) 2.5 parts of a composition in which 50 parts of lithium bis(trifluoromethanesulfonyl)imide was dissolved in W-230-H (1:1 mixture) was used as an antistatic composition, diluted with ethyl acetate to a solid content concentration of 15 % solution, an acrylic adhesive solution was prepared.
<粘合片的制作><Preparation of adhesive sheet>
用涂布器将如上述制作的粘合剂溶液均匀地涂布于具备经聚硅氧烷类剥离剂处理的剥离剂层的厚38μm的聚对苯二甲酸乙二醇酯膜(分离膜)(王子F-TEX公司制：38RL-07(2))的表面，使得干燥后的涂布量为20μm/m2，用100℃的空气循环式恒温烘箱干燥3分钟，在分离膜的表面形成粘合剂层。接着，在该粘合剂层表面贴合38μm的分离膜(王子F-TEX公司制：38RL-07(L))，得到了粘合片，所述粘合片由具有剥离力差的1对分离膜挟持粘合剂层而成的、具备分离膜/粘合剂层/分离膜的结构。该粘合片在23℃、相对湿度50％的条件下进行养护7天。The adhesive solution prepared as above was uniformly applied to a 38 μm thick polyethylene terephthalate film (separation film) provided with a release agent layer treated with a silicone release agent using an applicator. (manufactured by Oji F-TEX Co., Ltd.: 38RL-07(2)) so that the coating amount after drying is 20 μm/m2 , dry in an air-circulating constant temperature oven at 100°C for 3 minutes, and form on the surface of the separation membrane. Adhesive layer. Next, a 38 μm separation film (manufactured by Oji F-Tex Co., Ltd.: 38RL-07(L)) was bonded to the surface of the adhesive layer to obtain an adhesive sheet consisting of a pair of adhesives with poor peeling force. The separation film has a separation film/adhesive layer/separation film structure in which the pressure-sensitive adhesive layer is interposed. The adhesive sheet was cured for 7 days under the conditions of 23°C and 50% relative humidity.
<带有粘合剂层的偏振片的制作><Production of Polarizing Plate with Adhesive Layer>
将粘合片的具备较轻剥离力的剥离剂层的分离膜剥离，在制造例3所得到的偏振片的起偏镜的偏光层侧直接转印(附着)粘合剂层，制作了具有粘合剂层的偏振片。The separation film of the release agent layer having a relatively light peeling force of the adhesive sheet was peeled off, and the adhesive layer was directly transferred (attached) to the polarizing layer side of the polarizer of the polarizer obtained in Production Example 3 to produce a Polarizer with adhesive layer.
(实施例2)(Example 2)
<丙烯酸类粘合剂溶液的制备><Preparation of Acrylic Adhesive Solution>
相对于由制造例2得到的(甲基)丙烯酸类共聚物(A-2)的固体成分100份，添加作为交联剂的二甲苯二异氰酸酯(三井化学公司制：TAKENATE500)0.1份与3-环氧丙氧基丙基甲氧基硅烷(信越化学工业公司制：KBM-403)0.1份，再添加在聚醚酯类化合物50份(Monocizer(注册商标)W-262与Polycizer(注册商标)W-230-H的1︰1混合物)中溶解了双(三氟甲烷磺酰基)酰亚胺锂50份的组合物1.8份作为防静电性组合物，用乙酸乙酯稀释为固体成分浓度15％的溶液，制备了丙烯酸类粘合剂溶液。With respect to 100 parts of solid content of the (meth)acrylic copolymer (A-2) obtained in Production Example 2, 0.1 part of xylene diisocyanate (manufactured by Mitsui Chemicals: TAKENATE 500) and 3- 0.1 part of glycidoxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403), and 50 parts of polyether ester compound (Monocizer (registered trademark) W-262 and Polycizer (registered trademark) 1.8 parts of a composition in which 50 parts of lithium bis(trifluoromethanesulfonyl)imide was dissolved in W-230-H (1:1 mixture) was used as an antistatic composition, diluted with ethyl acetate to a solid content concentration of 15 % solution, an acrylic adhesive solution was prepared.
<粘合片的制作><Preparation of adhesive sheet>
与实施例1同样地制作了粘合片。A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
<带有粘合剂层的偏振片的制作><Production of Polarizing Plate with Adhesive Layer>
与实施例1同样地制作了带有粘合剂层的偏振片。A polarizing plate with an adhesive layer was produced in the same manner as in Example 1.
(实施例11)(Example 11)
<丙烯酸类粘合剂溶液的制备><Preparation of Acrylic Adhesive Solution>
相对于由制造例1得到的(甲基)丙烯酸类共聚物(A-1)的固体成分100份，添加作为交联剂的二甲苯二异氰酸酯(三井化学公司制：TAKENATE500)0.1份与3-环氧丙氧基丙基甲氧基硅烷(信越化学工业公司制：KBM-403)0.1份，再添加在聚亚烷基二醇(二/单)烷基醚化合物50份中溶解了双(三氟甲烷磺酰基)酰亚胺锂50份的组合物2.5份作为防静电性组合物，用乙酸乙酯稀释为固体成分浓度15％的溶液，制备了丙烯酸类粘合剂溶液。With respect to 100 parts of solid content of the (meth)acrylic copolymer (A-1) obtained in Production Example 1, 0.1 part of xylene diisocyanate (manufactured by Mitsui Chemicals: TAKENATE 500) and 3- Add 0.1 part of glycidoxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403), and then add bis( As an antistatic composition, 2.5 parts of a composition of 50 parts of lithium trifluoromethanesulfonyl)imide was diluted with ethyl acetate to a solution having a solid content concentration of 15%, to prepare an acrylic adhesive solution.
<粘合片的制作><Preparation of adhesive sheet>
用涂布器将如上述制作的粘合剂溶液均匀地涂布于具备经聚硅氧烷类剥离剂处理的剥离剂层的厚38μm的聚对苯二甲酸乙二醇酯膜(分离膜)(王子F-TEX公司制：38RL-07(2))的表面，用100℃的空气循环式恒温炉干燥3分钟，使得干燥后的涂布量为20μm/m2，在分离膜的表面形成粘合剂层。接着，在该粘合剂层表面贴合38μm的分离膜(王子F-TEX公司制：38RL-07(L))，得到了由具有剥离力差的1对分离膜挟持粘合剂层而成的、具备分离膜/粘合剂层/分离膜的结构的粘合片。该粘合片在23℃、相对湿度50％的条件下进行养护7天。The adhesive solution prepared as above was uniformly applied to a 38 μm thick polyethylene terephthalate film (separation film) provided with a release agent layer treated with a silicone release agent using an applicator. (manufactured by Oji F-TEX Co., Ltd.: 38RL-07(2)) was dried in an air-circulating constant temperature oven at 100°C for 3 minutes so that the coating amount after drying was 20 μm/m2 and formed on the surface of the separation membrane. Adhesive layer. Next, a 38 μm separation film (manufactured by Oji F-Tex Co., Ltd.: 38RL-07(L)) was bonded to the surface of the pressure-sensitive adhesive layer to obtain an adhesive layer sandwiched by a pair of separation films with poor peeling force. PSA sheet having a structure of separation film/adhesive layer/separation film. The adhesive sheet was cured for 7 days under the conditions of 23°C and 50% relative humidity.
<带有粘合剂层的偏振片的制作><Production of Polarizing Plate with Adhesive Layer>
将粘合片的具备较轻剥离力的剥离剂层的分离膜剥离，在制造例3所得到的偏振片的起偏镜的偏光层侧直接转印(附着)粘合剂层，制作了具有粘合剂层的偏振片。The separation film of the release agent layer having a relatively light peeling force of the adhesive sheet was peeled off, and the adhesive layer was directly transferred (attached) to the polarizing layer side of the polarizer of the polarizer obtained in Production Example 3 to produce a Polarizer with adhesive layer.
(比较例1)(comparative example 1)
<丙烯酸类粘合剂溶液的制备><Preparation of Acrylic Adhesive Solution>
除了使用作为离子性固体的N-己基-4-甲基吡啶六氟磷酸酯(25℃下为固体)来代替实施例1所使用的在聚醚酯类化合物50份(Monocizer(注册商标)W-262与Polycizer(注册商标)W-230-H的1︰1混合物)中溶解了双(三氟甲烷磺酰基)酰亚胺锂50份的组合物以外，与实施例1同样地得到了丙烯酸类粘合剂溶液。In addition to using N-hexyl-4-picoline as an ionic solid Hexafluorophosphate (solid at 25° C.) to replace 50 parts of polyether ester compounds used in Example 1 (1 of Monocizer (registered trademark) W-262 and Polycizer (registered trademark) W-230-H: 1 mixture), except that 50 parts of lithium bis(trifluoromethanesulfonyl)imide was dissolved, an acrylic adhesive solution was obtained in the same manner as in Example 1.
<粘合片的制作><Preparation of adhesive sheet>
与实施例1同样地制作了粘合片。A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
<带有粘合剂层的偏振片的制作><Production of Polarizing Plate with Adhesive Layer>
与实施例1同样地制作了带有粘合剂层的偏振片。A polarizing plate with an adhesive layer was produced in the same manner as in Example 1.
(比较例2)(comparative example 2)
<丙烯酸类粘合剂溶液的制备><Preparation of Acrylic Adhesive Solution>
除了使用作为离子性固体的环氧丙基三甲基铵三氟甲烷磺酸酯(25℃下为液体)来代替实施例1所使用的在聚醚酯类化合物50份(Monocizer(注册商标)W-262与Polycizer(注册商标)W-230-H的1︰1混合物)中溶解了双(三氟甲烷磺酰基)酰亚胺锂50份的组合物以外，与实施例1同样地得到了丙烯酸类粘合剂溶液。In addition to using glycidyltrimethylammonium trifluoromethanesulfonate (liquid at 25° C.) as an ionic solid instead of 50 parts of the polyether ester compound used in Example 1 (Monocizer (registered trademark) 1:1 mixture of W-262 and Polycizer (registered trademark) W-230-H), except for dissolving 50 parts of lithium bis(trifluoromethanesulfonyl)imide, obtained in the same manner as in Example 1. Acrylic adhesive solution.
<粘合片的制作><Preparation of adhesive sheet>
与实施例1同样地制作了粘合片。A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
<带有粘合剂层的偏振片的制作><Production of Polarizing Plate with Adhesive Layer>
与实施例1同样地制作了带有粘合剂层的偏振片。A polarizing plate with an adhesive layer was produced in the same manner as in Example 1.
(参考例1)(reference example 1)
<丙烯酸类粘合剂溶液的制备><Preparation of Acrylic Adhesive Solution>
除了未添加实施例1所使用的在聚醚酯类化合物50份(Monocizer(注册商标)W-262与Polycizer(注册商标)W-230-H的1︰1混合物)中溶解了双(三氟甲烷磺酰基)酰亚胺锂50份的组合物以外，与实施例1同样地得到了丙烯酸类粘合剂溶液。Dissolved bis(trifluoro An acrylic adhesive solution was obtained in the same manner as in Example 1 except for a composition of 50 parts of lithium methanesulfonyl)imide.
<粘合片的制作><Preparation of adhesive sheet>
与实施例1同样地制作了粘合片。A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
<带有粘合剂层的偏振片的制作><Production of Polarizing Plate with Adhesive Layer>
与实施例1同样地制作了带有粘合剂层的偏振片。A polarizing plate with an adhesive layer was produced in the same manner as in Example 1.
(评价)(Evaluation)
<表面电阻值的测定><Measurement of Surface Resistance>
将裁断为100mm×100mm的带有粘合剂层的偏振片的分离膜剥离后，使用电阻值测定器(三菱化学公司制：Hiresta-UP，MCP-HT450)测定粘合剂表面的表面电阻值(Ω/□)。After peeling off the separation film of the polarizing plate with an adhesive layer cut into 100 mm × 100 mm, the surface resistance value of the adhesive surface was measured using a resistance value meter (manufactured by Mitsubishi Chemical Corporation: Hiresta-UP, MCP-HT450) (Ω/□).
<偏振片耐久性的评价><Evaluation of Polarizer Durability>
在将带有粘合剂层的偏振片的分离膜剥离后，将粘合剂面粘贴于厚0.7mm的无碱玻璃(康宁公司制：EAGLE XG)的一面，制作了光学叠层体。接着，进行50℃、0.5MPa、20分钟的高压釜处理，制作了使带有粘合剂层的偏振片完全密合于玻璃的光学叠层体。将上述制作的光学叠层体用恒温恒湿槽在85℃(耐热试验)下处理500小时，以肉眼观察试验后的光学叠层体。After peeling off the separation film of the polarizing plate with an adhesive layer, the adhesive surface was attached to one surface of an alkali-free glass (manufactured by Corning Incorporated: EAGLE XG) having a thickness of 0.7 mm to produce an optical laminate. Next, autoclave treatment was performed at 50° C. and 0.5 MPa for 20 minutes to prepare an optical laminate in which the polarizing plate with an adhesive layer was completely adhered to glass. The optical laminate produced above was treated at 85° C. (heat resistance test) for 500 hours in a constant temperature and humidity chamber, and the optical laminate after the test was observed with the naked eye.
(评价基准)(evaluation criteria)
○：完全未观察到浮起、剥离、发泡等的外观变化。◯: Changes in appearance such as floating, peeling, and foaming were not observed at all.
△：稍有浮起、剥离、发泡等外观变化。Δ: Slight changes in appearance such as floating, peeling, and foaming.
×：明显观察到浮起、剥离、发泡等外观变化。×: Appearance changes such as floating, peeling, and foaming were clearly observed.
<光学耐久性(透射色调)的评价><Evaluation of optical durability (transmission color tone)>
在将带有粘合剂层的偏振片的分离膜剥离后，将粘合剂面粘贴于厚0.7mm的无碱玻璃(康宁公司制：EAGLE XG)的一面，制作了光学叠层体。接着，进行50℃、0.5MPa、20分钟的高压釜处理，制作了将带有粘合剂层的偏振片完全密合于玻璃的光学叠层体。将上述制作的光学叠层体用恒温恒湿槽在60℃、相对湿度90％(耐湿热试验)下以初期、100小时、240小时、500小时进行处理并测定了各处理时间的透射色调b值。测定使用分光比色计(日本电色公司制：SE6000)。使用该测定值计算出试验前后的透射色调的变化量Δb值。After peeling off the separation film of the polarizing plate with an adhesive layer, the adhesive surface was attached to one surface of an alkali-free glass (manufactured by Corning Incorporated: EAGLE XG) having a thickness of 0.7 mm to produce an optical laminate. Next, autoclave treatment was performed at 50° C. and 0.5 MPa for 20 minutes to prepare an optical laminate in which the polarizing plate with an adhesive layer was completely adhered to glass. The optical laminate produced above was treated in a constant temperature and humidity chamber at 60°C and a relative humidity of 90% (moisture and heat resistance test) at the initial stage, 100 hours, 240 hours, and 500 hours, and the transmission color tone b was measured for each treatment time. value. For the measurement, a spectrocolorimeter (manufactured by Nippon Denshoku Co., Ltd.: SE6000) was used. The change amount Δb value of the transmission color tone before and after the test was calculated using the measured value.
Δb值＝试验后测定值－试验前初期值Δb value = measured value after test - initial value before test
<光学耐久性(780nm透射率)的评价><Evaluation of Optical Durability (780nm Transmittance)>
在将带有粘合剂层的偏振片的分离膜剥离后，将粘合剂面粘贴于厚0.7mm的无碱玻璃(康宁公司制：EAGLE XG)的一面，制作了光学叠层体。接着，进行50℃、0.5MPa、20分钟的高压釜处理，制作了将带有粘合剂层的偏振片完全密合于玻璃的光学叠层体。将上述制作的光学叠层体用恒温恒湿槽在60℃、相对湿度90％(耐湿热试验)下以初期、100小时、240小时、500小时进行处理，测定各处理时间的780nm的透射率T⊥。测定系使用分光光谱仪(岛津制作所公司制：Solidspec-3700)。使用该测定值计算出试验前后的780nm透射率的变化量ΔT⊥。After peeling off the separation film of the polarizing plate with an adhesive layer, the adhesive surface was attached to one surface of an alkali-free glass (manufactured by Corning Incorporated: EAGLE XG) having a thickness of 0.7 mm to produce an optical laminate. Next, autoclave treatment was performed at 50° C. and 0.5 MPa for 20 minutes to prepare an optical laminate in which the polarizing plate with an adhesive layer was completely adhered to glass. The optical laminate produced above was treated in a constant temperature and humidity chamber at 60°C and a relative humidity of 90% (moisture resistance test) at the initial stage, 100 hours, 240 hours, and 500 hours, and the transmittance at 780 nm was measured for each treatment time. T⊥. A spectrometer (manufactured by Shimadzu Corporation: Solidspec-3700) was used for the measurement. The amount of change ΔT⊥ in the 780 nm transmittance before and after the test was calculated using the measured value.
ΔT⊥＝(处理后测定值)－(初期值)ΔT⊥ = (measured value after treatment) - (initial value)
<偏振度的测定><Measurement of Polarization Degree>
在将带有粘合剂层的偏振片的分离膜剥离后，将粘合剂面粘贴于厚0.7mm的无碱玻璃(康宁公司制：EAGLE XG)的一面，制作了光学叠层体。接着，进行50℃、0.5MPa、20分钟的高压釜处理，制作了将带有粘合剂层的偏振片完全密合于玻璃的光学叠层体。将上述制作的光学叠层体在60℃、相对湿度90％(耐湿热试验)下以初期、100小时进行处理，使用分光光谱仪(日本分光公司制：V-7100)测定处理前与处理100小时后的偏振片的偏振度，计算出变化量ΔPy。After peeling off the separation film of the polarizing plate with an adhesive layer, the adhesive surface was attached to one surface of an alkali-free glass (manufactured by Corning Incorporated: EAGLE XG) having a thickness of 0.7 mm to produce an optical laminate. Next, autoclave treatment was performed at 50° C. and 0.5 MPa for 20 minutes to prepare an optical laminate in which the polarizing plate with an adhesive layer was completely adhered to glass. The optical laminate produced above was treated at 60°C and a relative humidity of 90% (moisture resistance test) for 100 hours at the initial stage, and a spectrometer (manufactured by JASCO Corporation: V-7100) was used to measure the time before treatment and after 100 hours of treatment. After the degree of polarization of the polarizer, calculate the amount of change ΔPy.
ΔPy＝(处理后测定值)－(初期值)ΔPy = (measured value after treatment) - (initial value)
(通过肉眼观察确认颜色变化)(Confirm the color change by visual observation)
在将带有粘合剂层的偏振片的分离膜剥离后，将粘合剂面粘贴于厚0.7mm的无碱玻璃(康宁公司制：EAGLE XG)的一面，制作了光学叠层体。接着，进行50℃、0.5MPa、20分钟的高压釜处理，制作了将带有粘合剂层的偏振片完全密合于玻璃的光学叠层体。将上述制作的光学叠层体用恒温恒湿槽在60℃、相对湿度90％(耐湿热试验)下处理500小时，通过肉眼观察确认有无颜色变化。After peeling off the separation film of the polarizing plate with an adhesive layer, the adhesive surface was stuck to one surface of an alkali-free glass (manufactured by Corning Incorporated: EAGLE XG) with a thickness of 0.7 mm to produce an optical laminate. Next, autoclave treatment was performed at 50° C. and 0.5 MPa for 20 minutes to prepare an optical laminate in which the polarizing plate with an adhesive layer was completely adhered to glass. The optical laminate produced above was treated for 500 hours in a constant temperature and humidity chamber at 60° C. and a relative humidity of 90% (moisture and heat resistance test), and the presence or absence of color change was confirmed by visual observation.
<粘合片中的防静电性组合物的分析(检测源自络合物的峰)><Analysis of Antistatic Composition in PSA Sheet (Detection of Peak Originating from Complex)>
对实施例等所制作的粘合片0.2g添加乙腈15ml，进行超音波处理30分钟，然后静置1天(前处理)。进行浓缩干固后，溶解于1ml乙腈并将用0.45μm过滤器过滤后的样品作为测定试样，进行HPLC(高效液相色谱)分析。HPLC(高效液相色谱)分析使用WATERS制造的系统：Separations Module2696，使用Photodiode Array Detector 996作为检测器。另外，HPLC分析的详细条件如下所述。15 ml of acetonitrile was added to 0.2 g of the pressure-sensitive adhesive sheet produced in Examples, and ultrasonic treatment was performed for 30 minutes, and then left to stand for 1 day (pretreatment). After concentrating to dryness, the sample was dissolved in 1 ml of acetonitrile and filtered through a 0.45 μm filter as a measurement sample, and analyzed by HPLC (high performance liquid chromatography). HPLC (High Performance Liquid Chromatography) analysis used a system manufactured by WATERS: Separations Module 2696, using Photodiode Array Detector 996 as a detector. In addition, detailed conditions of HPLC analysis are as follows.
柱：XBridge C18，柱径4.6×250mm(WATERS公司制)Column: XBridge C18, column diameter 4.6×250mm (manufactured by WATERS Corporation)
柱温：30℃Column temperature: 30°C
流动相：乙腈/水Mobile phase: acetonitrile/water
流速：0.8mL/分Flow rate: 0.8mL/min
检测：225nmDetection: 225nm
将以上评价结果示于表1。Table 1 shows the above evaluation results.
由表1可知，实施例中除了偏振片耐久性之外，光学耐久性也优异。即，对于实施例而言，即使在高温、高湿度环境下放置长时间，仍然着色少、光透射率高。As can be seen from Table 1, the Examples are excellent in optical durability in addition to polarizing plate durability. That is, even if the Example was left to stand for a long time in a high-temperature, high-humidity environment, there was little coloring and high light transmittance.
另一方面可知，对于比较例而言，光学耐久性差。特别是对于比较例1及2而言，偏振片耐久性也不好，作为偏振片的功能劣化。On the other hand, it can be seen that the optical durability is inferior to the comparative example. Especially in Comparative Examples 1 and 2, the durability of the polarizing plate was not good, and the function as a polarizing plate deteriorated.
另外，图3从由上方起为含络合物的防静电性组合物、实施例所得的含有防静电性组合物的粘合片的提取液、未加入防静电性组合物的粘合片的提取物(参考例1)的HPLC(高效液相色谱)分析结果。如中段的含有防静电性组合物的粘合片的提取液的色谱所示，从添加了防静电性组合物的粘合片的提取液中在保留时间15.0分钟检测到了络合物峰。In addition, Fig. 3 is the antistatic composition containing the complex, the extract of the PSA sheet containing the antistatic composition obtained in the examples, and the PSA sheet without the antistatic composition from the top. HPLC (High Performance Liquid Chromatography) analysis results of the extract (Reference Example 1). As shown in the chromatogram of the extract of the PSA sheet containing the antistatic composition in the middle stage, a complex peak was detected at a retention time of 15.0 minutes from the extract of the PSA sheet to which the antistatic composition was added.
| Application Number | Priority Date | Filing Date | Title |
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| JP2014-125310 | 2014-06-18 | ||
| JP2014-125311 | 2014-06-18 | ||
| JP2014125311 | 2014-06-18 | ||
| JP2014125310 | 2014-06-18 | ||
| PCT/JP2015/067257WO2015194532A1 (en) | 2014-06-18 | 2015-06-16 | Adhesive agent composition for polarizers and adhesive sheet for polarizers |
| Publication Number | Publication Date |
|---|---|
| CN106795416Atrue CN106795416A (en) | 2017-05-31 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580032667.2APendingCN106795416A (en) | 2014-06-18 | 2015-06-16 | Polarizer adhesive composition and polarizer bonding sheet |
| Country | Link |
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| JP (1) | JP6508204B2 (en) |
| KR (1) | KR101958680B1 (en) |
| CN (1) | CN106795416A (en) |
| TW (1) | TWI662099B (en) |
| WO (1) | WO2015194532A1 (en) |
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