本申请是申请日为2019年08月30日、发明名称为“粘合剂组合物、粘合片和接合体”的中国发明专利申请No.201980057389.4(PCT申请号为PCT/JP2019/034143)的分案申请。This application is filed on August 30, 2019, and the title of the invention is "Adhesive Composition, Adhesive Sheet, and Jointed Body". Divisional application.
技术领域technical field
本发明涉及粘合剂组合物、包含由该粘合剂组合物形成的粘合剂层的粘合片、及该粘合片与被粘物的接合体。The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, and a bonded body of the pressure-sensitive adhesive sheet and an adherend.
背景技术Background technique
在电子部件制造工序等中，与用于提高成品率的再加工、或在使用后将部件分解并回收的再利用等相关的要求正在增加。为了满足这种要求，有时在电子部件制造工序等中将构件间接合时，利用伴有一定粘接力并且还伴有一定剥离性的双面粘合片。In the manufacturing process of electronic components and the like, there are increasing demands for reprocessing to improve yields, and recycling in which components are disassembled and collected after use. In order to meet such demands, a double-sided PSA sheet having a certain amount of adhesive force and also a certain degree of releasability may be used when joining members in an electronic component manufacturing process or the like.
作为上述可实现粘接力和剥离性的双面粘合片，已知有在形成粘合剂组合物的成分中使用包含阳离子和阴离子的离子液体、并通过对粘合剂层施加电压而进行剥离的粘合片(电剥离型粘合片)(专利文献1～3)。As a double-sided adhesive sheet capable of achieving the above-mentioned adhesive force and peelability, it is known to use an ionic liquid containing cations and anions in the components forming the adhesive composition, and to apply a voltage to the adhesive layer. Peelable PSA sheet (electropeelable PSA sheet) (Patent Documents 1 to 3).
关于专利文献1～3的电剥离型粘合片，认为通过电压的施加，离子液体的阳离子在阴极侧移动而发生还原，离子液体的阴离子在阳极侧移动而发生氧化，粘接界面的粘接力变弱，变得容易剥离。Regarding the electro-peelable adhesive sheets of Patent Documents 1 to 3, it is considered that by the application of a voltage, the cations of the ionic liquid move to the cathode side and are reduced, and the anions of the ionic liquid move to the anode side and are oxidized. The force becomes weak and it becomes easy to peel off.
现有技术文献prior art literature
专利文献patent documents
专利文献1：日本特开2010-037354号公报Patent Document 1: Japanese Patent Laid-Open No. 2010-037354
专利文献2：日本专利第6097112号公报Patent Document 2: Japanese Patent No. 6097112
专利文献3：日本专利第4139851号公报Patent Document 3: Japanese Patent No. 4139851
发明内容Contents of the invention
发明所要解决的课题The problem to be solved by the invention
就电剥离型粘合片而言，优选的是，在不施加电压时将构件牢固地接合，且在施加电压时能够以小的力剥离。因此，在电剥离型粘合片中，优选的是，由电压施加导致的粘接力降低率大。然而，在例如冬季等湿度低的环境中，由电压施加导致的粘接力降低率变小成为问题。In the electro-peelable pressure-sensitive adhesive sheet, it is preferable that members are firmly bonded when no voltage is applied, and can be peeled with a small force when a voltage is applied. Therefore, in the electro-peelable pressure-sensitive adhesive sheet, it is preferable that the rate of decrease in the adhesive force by voltage application is large. However, in an environment with low humidity such as in winter, the decrease in the rate of decrease in adhesive force due to voltage application becomes a problem.
本发明是鉴于上述情况而完成的，其目的在于，提供即使在低湿度环境下也可通过电压的施加而使粘接力充分降低的粘合剂组合物、及具备由该粘合剂组合物形成的粘合剂层的粘合片。The present invention has been accomplished in view of the above circumstances, and its object is to provide an adhesive composition capable of sufficiently reducing the adhesive force by application of a voltage even in a low-humidity environment, and an adhesive comprising the adhesive composition. An adhesive sheet of the adhesive layer formed.
用于解决课题的手段means to solve the problem
根据本申请的发明人的研究，在低湿度环境下由电压施加导致的粘接力降低率变小是由在低湿度环境下粘合剂层的含水率降低、离子液体的阳离子及阴离子变得不易移动所引起的。According to the research of the inventors of the present application, the reduction in the rate of decrease in the adhesive force due to voltage application in a low-humidity environment is due to the decrease in the moisture content of the adhesive layer in a low-humidity environment, and the decrease in the cations and anions of the ionic liquid. Not easy to move caused.
本申请的发明人进一步反复进行了研究，结果获得以下的见解。The inventors of the present application further conducted repeated studies, and as a result obtained the following findings.
第一，发现粘合剂层的离子液体以外的成分的相对介电常数与由电压施加导致的粘接力降低率具有相关性，通过增大该相对介电常数，能够增大由电压施加导致的粘接力降低率。另外，发现即使在置于低湿度环境下粘合剂层的含水率降低的情况下，若该相对介电常数大，则电剥离性良好，即，由电压施加导致的粘接力降低率大。First, it was found that the relative permittivity of the components other than the ionic liquid in the adhesive layer has a correlation with the rate of decrease in the adhesive force caused by voltage application, and by increasing the relative permittivity, the rate of decrease in the adhesive force caused by voltage application can be increased. Adhesion reduction rate. In addition, it was found that even when the moisture content of the adhesive layer is lowered in a low-humidity environment, if the relative dielectric constant is large, the electrical peelability is good, that is, the rate of decrease in the adhesive force due to voltage application is large. .
第二，发现粘合剂层的离子传导率、及粘合剂层与被粘物的界面的每单位面积的电容与由电压施加导致的粘接力降低率具有相关性，通过增大该离子传导率、及粘合剂层与被粘物的界面的每单位面积的电容，能够增大由电压施加导致的粘接力降低率。另外，发现即使在置于低湿度环境下粘合剂层的含水率降低的情况下，若该离子传导率、及粘合剂层与被粘物的界面的每单位面积的电容大，则电剥离性良好，即，由电压施加导致的粘接力降低率大。Second, it was found that the ionic conductivity of the adhesive layer and the capacitance per unit area of the interface between the adhesive layer and the adherend have a correlation with the rate of decrease in the adhesive force caused by voltage application. The conductivity and the capacitance per unit area of the interface between the adhesive layer and the adherend can increase the rate of decrease in adhesive force due to voltage application. In addition, it was found that even when the moisture content of the adhesive layer is lowered in a low-humidity environment, if the ionic conductivity and the capacitance per unit area of the interface between the adhesive layer and the adherend are large, the electrical The peelability was good, that is, the rate of decrease in adhesive force by voltage application was large.
基于上述第1见解完成的本发明的一个粘合剂组合物是包含聚合物和离子液体的粘合剂组合物，其中，利用由粘合剂组合物所含的成分中的离子液体以外的成分形成的组合物来形成粘合剂层、并将该粘合剂层在22℃、20％RH的环境下放置3天后的、该粘合剂层在频率100Hz时的相对介电常数为5以上。One adhesive composition of the present invention completed based on the above-mentioned first finding is an adhesive composition comprising a polymer and an ionic liquid, wherein components other than the ionic liquid among the components contained in the adhesive composition are utilized Forming the composition to form an adhesive layer, and leaving the adhesive layer in an environment of 22° C. and 20% RH for 3 days, the relative dielectric constant of the adhesive layer at a frequency of 100 Hz is 5 or more .
基于上述第2见解完成的本发明的另一粘合剂组合物是包含聚合物和离子液体的粘合剂组合物，其中，利用粘合剂组合物来形成粘合剂层且将其贴附于由JIS H4000:2014中的A5052P H32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容为0.9μF/cm2以上，该粘合剂层的离子传导率为10μS/m以上。Another adhesive composition of the present invention based on the above-mentioned second finding is an adhesive composition comprising a polymer and an ionic liquid, wherein an adhesive layer is formed and attached using the adhesive composition The capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 μF/ cm2 or more, and the ionic conductivity of the adhesive layer is 10 μS/m or more.
在本发明的粘合剂组合物的一个方式中，利用粘合剂组合物来形成粘合剂层且将其贴附于由JIS H4000:2014中的A5052P H32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容可以为1.2μF/cm2以上，该粘合剂层的离子传导率可以为20μS/m以上。In one mode of the adhesive composition of the present invention, an adhesive layer is formed using the adhesive composition and attached to an aluminum plate formed by A5052P H32 in JIS H4000:2014, and the adhesive layer is formed at 22°C, The capacitance per unit area of the interface between the adhesive layer and the aluminum plate after being left for 7 days in an environment of 15% RH may be 1.2 μF/cm2 or more, and the ion conductivity of the adhesive layer may be 20 μS/m above.
在本发明的粘合剂组合物的一个方式中，粘合剂组合物可以还包含离子性固体。In one aspect of the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition may further contain an ionic solid.
在本发明的粘合剂组合物的一个方式中，聚合物可以包含离子性聚合物。In one aspect of the pressure-sensitive adhesive composition of the present invention, the polymer may contain an ionic polymer.
在本发明的粘合剂组合物的一个方式中，聚合物可以包含选自由聚酯系聚合物、氨基甲酸酯系聚合物、以及具有羧基、烷氧基、羟基和/或酰胺键的丙烯酸系聚合物组成的组中的至少1种。In one aspect of the adhesive composition of the present invention, the polymer may contain acrylic acid selected from polyester-based polymers, urethane-based polymers, and carboxyl, alkoxy, hydroxyl and/or amide bonds. It is at least 1 type in the group which consists of a polymer.
另外，本发明的另一粘合剂组合物包含聚合物和离子液体，相对于100质量份的聚合物，包含0.5～30质量份的离子液体和0.5～10质量份的离子性固体。Moreover, another adhesive composition of this invention contains a polymer and an ionic liquid, and contains 0.5-30 mass parts of ionic liquids and 0.5-10 mass parts of ionic solids with respect to 100 mass parts of polymers.
另外，本发明的另一粘合剂组合物包含聚合物和离子液体，相对于100质量份的聚合物，包含0.5～30质量份的离子液体，在聚合物中包含0.05～2质量份的离子性聚合物。In addition, another adhesive composition of the present invention includes a polymer and an ionic liquid, 0.5 to 30 parts by mass of an ionic liquid relative to 100 parts by mass of a polymer, and 0.05 to 2 parts by mass of an ionic liquid in the polymer. permanent polymer.
另外，本发明的另一粘合剂组合物是包含100质量份的丙烯酸系聚合物和0.5～30质量份的离子液体的粘合剂组合物，其中，含极性基团的单体相对于构成丙烯酸系聚合物的全部单体成分的比例为0.1～35质量％。In addition, another adhesive composition of the present invention is an adhesive composition comprising 100 parts by mass of an acrylic polymer and 0.5 to 30 parts by mass of an ionic liquid, wherein the polar group-containing monomer is The ratio of all the monomer components constituting the acrylic polymer is 0.1 to 35% by mass.
在本发明的一个方式中，粘合剂组合物用于电剥离。In one aspect of the present invention, the adhesive composition is used for electrical peeling.
另外，本发明的粘合片具备由本发明的粘合剂组合物形成的粘合剂层。Moreover, the adhesive sheet of this invention is equipped with the adhesive layer formed from the adhesive composition of this invention.
另外，本发明的接合体具备：具有金属被粘面的被粘物、和本发明的粘合片，本发明的粘合片的粘合剂层接合于金属被粘面。In addition, the bonded body of the present invention includes an adherend having a metal adherend surface, and the PSA sheet of the present invention, wherein the PSA layer of the PSA sheet of the present invention is bonded to the metal adherend surface.
本申请涉及下述的项：This application concerns the following items:
1、粘合剂组合物，其包含聚合物和离子液体，其中，利用由所述粘合剂组合物所含的成分中的所述离子液体以外的成分形成的组合物来形成粘合剂层、并将该粘合剂层在22℃、20％RH的环境下放置3天后的、该粘合剂层在频率100Hz时的相对介电常数为5以上。1. An adhesive composition comprising a polymer and an ionic liquid, wherein an adhesive layer is formed using a composition formed of components other than the ionic liquid among the components contained in the adhesive composition , and leave the adhesive layer in an environment of 22° C. and 20% RH for 3 days, the relative dielectric constant of the adhesive layer at a frequency of 100 Hz is 5 or more.
2、粘合剂组合物，其包含聚合物和离子液体，其中，利用所述粘合剂组合物来形成粘合剂层且将其贴附于由JIS H4000:2014中的A5052P H32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容为0.9μF/cm2以上，该粘合剂层的离子传导率为10μS/m以上。2. An adhesive composition comprising a polymer and an ionic liquid, wherein an adhesive layer is formed using the adhesive composition and attached to an aluminum plate formed by A5052P H32 in JIS H4000:2014 , and placed in an environment of 22° C. and 15% RH for 7 days, the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 μF/cm2 or more, and the ion conductivity of the adhesive layer is 10μS/m or more.
3、根据项2所述的粘合剂组合物，其中，利用所述粘合剂组合物来形成粘合剂层且将其贴附于由JIS H4000:2014中的A5052PH32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容为1.2μF/cm2以上，该粘合剂层的离子传导率为20μS/m以上。3. The adhesive composition according to item 2, wherein an adhesive layer is formed using the adhesive composition and attached to an aluminum plate formed of A5052PH32 in JIS H4000:2014, and After 7 days at 22°C and 15% RH, the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 1.2 μF/cm2 or more, and the ion conductivity of the adhesive layer is 20 μS/cm2. more than m.
4、根据项1～3中任一项所述的粘合剂组合物，其还包含离子性固体。4. The adhesive composition according to any one of items 1 to 3, further comprising an ionic solid.
5、根据项1～4中任一项所述的粘合剂组合物，其中，所述聚合物包含离子性聚合物。5. The adhesive composition according to any one of items 1 to 4, wherein the polymer comprises an ionic polymer.
6、根据项1～5中任一项所述的粘合剂组合物，其中，所述聚合物包含选自由聚酯系聚合物、氨基甲酸酯系聚合物、以及具有羧基、烷氧基、羟基和/或酰胺键的丙烯酸系聚合物组成的组中的至少1种。6. The adhesive composition according to any one of items 1 to 5, wherein the polymer comprises polyester polymers, urethane polymers, and polymers having carboxyl groups and alkoxy groups , hydroxyl and/or amide bonded acrylic polymers at least one of the group consisting of.
7、粘合剂组合物，其包含聚合物和离子液体，相对于100质量份的所述聚合物，包含0.5～30质量份的所述离子液体和0.5～10质量份的离子性固体。7. A binder composition comprising a polymer and an ionic liquid, comprising 0.5 to 30 parts by mass of the ionic liquid and 0.5 to 10 parts by mass of an ionic solid relative to 100 parts by mass of the polymer.
8、粘合剂组合物，其包含聚合物和离子液体，相对于100质量份的所述聚合物，包含0.5～30质量份的所述离子液体，在所述聚合物中包含0.05～2质量份的离子性聚合物。8. An adhesive composition comprising a polymer and an ionic liquid, 0.5 to 30 parts by mass of the ionic liquid relative to 100 parts by mass of the polymer, and 0.05 to 2 parts by mass in the polymer parts of ionic polymers.
9、粘合剂组合物，其包含100质量份的丙烯酸系聚合物和0.5～30质量份的离子液体，其中，含极性基团的单体相对于构成所述丙烯酸系聚合物的全部单体成分的比例为0.1～35质量％。9. An adhesive composition comprising 100 parts by mass of an acrylic polymer and 0.5 to 30 parts by mass of an ionic liquid, wherein the polar group-containing monomer is The proportion of the body composition is 0.1 to 35% by mass.
10、根据项1～9中任一项所述的粘合剂组合物，其用于电剥离。10. The adhesive composition according to any one of items 1 to 9, which is used for electro-disbonding.
11、粘合片，其具备由项1～10中任一项所述的粘合剂组合物形成的粘合剂层。11. A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition according to any one of items 1 to 10.
12、接合体，其具备：12. Conjugate, which has:
具有金属被粘面的被粘物；和an adherend having a metallic adherend surface; and
项11所述的粘合片，The adhesive sheet described in item 11,
所述粘合片的粘合剂层接合于所述金属被粘面。The adhesive layer of the adhesive sheet is bonded to the metal adherend surface.
发明的效果The effect of the invention
本发明的粘合剂组合物即使在低湿度环境下也可通过电压的施加而使粘接力充分降低。The pressure-sensitive adhesive composition of the present invention can sufficiently reduce the adhesive force by application of a voltage even in a low-humidity environment.
附图说明Description of drawings
[图1]为表示本发明的粘合片的一例的截面图。[ Fig. 1 ] is a cross-sectional view showing an example of the PSA sheet of the present invention.
[图2]为表示本发明的粘合片的层叠结构的一例的截面图。[ Fig. 2 ] is a cross-sectional view showing an example of the laminated structure of the pressure-sensitive adhesive sheet of the present invention.
[图3]为表示本发明的粘合片的层叠结构的另一例的截面图。[ Fig. 3 ] is a cross-sectional view showing another example of the laminated structure of the PSA sheet of the present invention.
[图4]为表示实施例中的180°剥离试验的方法的概要的截面图。[ Fig. 4] Fig. 4 is a cross-sectional view showing an outline of a method of a 180° peel test in Examples.
[图5]为电容及离子传导率测定用的复合体样品的侧视图。[ Fig. 5 ] is a side view of a composite sample for capacitance and ion conductivity measurement.
[图6]为电容及离子传导率测定用的复合体样品的俯视图。[ Fig. 6 ] is a plan view of a composite sample for capacitance and ion conductivity measurement.
[图7]为电容及离子传导率测定用的复合体样品的等效电路图。[ Fig. 7 ] is an equivalent circuit diagram of a composite sample for capacitance and ion conductivity measurement.
具体实施方式Detailed ways
以下，对用于实施本发明的方式详细地进行说明。需要说明的是，本发明并不限定于以下所说明的实施方式。Hereinafter, the form for carrying out this invention is demonstrated in detail. In addition, this invention is not limited to embodiment described below.
[粘合剂组合物][Adhesive composition]
本发明的第1及第2实施方式的粘合剂组合物均包含聚合物和离子液体。Both the adhesive compositions of the first and second embodiments of the present invention contain a polymer and an ionic liquid.
利用由第1实施方式的粘合剂组合物所含的成分中的离子液体以外的成分形成的组合物来形成粘合剂层、并将该粘合剂层在22℃、20％RH的环境下放置3天后的、该粘合剂层在频率100Hz时的相对介电常数为5以上。The pressure-sensitive adhesive layer is formed using a composition formed of components other than the ionic liquid among the components contained in the pressure-sensitive adhesive composition of the first embodiment, and the pressure-sensitive adhesive layer is placed in an environment of 22° C. and 20% RH. The relative permittivity of the pressure-sensitive adhesive layer at a frequency of 100 Hz after being left standing for 3 days was 5 or more.
另外，利用第2实施方式的粘合剂组合物来形成粘合剂层且将其贴附于由JISH4000:2014中的A5052P H32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容为0.9μF/cm2以上，该粘合剂层的离子传导率为10μS/m以上。In addition, an adhesive layer was formed using the adhesive composition of the second embodiment, attached to an aluminum plate formed of A5052P H32 in JISH4000:2014, and left in an environment of 22° C. and 15% RH for 7 days. In Tianhou, the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 μF/cm2 or more, and the ion conductivity of the adhesive layer is 10 μS/m or more.
这些粘合剂组合物具有通过电压施加而使粘接力降低的性质，适合作为电剥离用粘合剂组合物。These pressure-sensitive adhesive compositions have the property of reducing the adhesive force by voltage application, and are suitable as pressure-sensitive adhesive compositions for electrical peeling.
需要说明的是，上述第1及第2实施方式并不是排他的，存在第1及第2实施方式均符合的粘合剂组合物，也存在仅符合任一种的粘合剂组合物。只要为符合第1或第2实施方式中的任一种的粘合剂组合物，则可发挥出本发明的效果。In addition, the above-mentioned 1st and 2nd embodiment are not exclusive, and there exists an adhesive composition which conforms to both of 1st and 2nd embodiment, and there exists an adhesive composition which conforms to only any one. The effect of this invention can be exhibited as long as it is an adhesive composition according to any one of 1st or 2nd embodiment.
以下，对这些粘合剂组合物进行说明。Hereinafter, these adhesive compositions are demonstrated.
需要说明的是，在本说明书中，有时将本发明的第1及第2实施方式统称为“本实施方式”。In addition, in this specification, the 1st and 2nd embodiment of this invention are collectively called "this embodiment" sometimes.
需要说明的是，在本说明书中，有时将不施加电压时的粘接力称为“初始粘接力”。In addition, in this specification, the adhesive force when no voltage is applied may be called "initial adhesive force."
另外，有时将由粘合剂组合物所含的成分中的离子液体以外的成分形成的组合物称为“不含离子液体的粘合剂组合物”。Moreover, the composition which consists of components other than an ionic liquid among the components contained in an adhesive composition may be called "an ionic liquid-free adhesive composition."
另外，有时将通过不含离子液体的粘合剂组合物形成的粘合剂层称为“不含离子液体的粘合剂层”。In addition, an adhesive layer formed from an ionic liquid-free adhesive composition may be referred to as an "ionic liquid-free adhesive layer".
另外，有时将通过电压施加而使粘接力降低的性质称为“电剥离性”，有时将由电压施加导致的粘接力降低率大这一情况称为“电剥离性优异”等。In addition, the property of reducing the adhesive force by voltage application is sometimes referred to as "electric peelability", and the fact that the rate of decrease in adhesive force by voltage application is large is sometimes referred to as "excellent electric peelability".
<粘合剂组合物的成分><Ingredients of Adhesive Composition>
(聚合物)(polymer)
本实施方式的粘合剂组合物含有聚合物。在本实施方式中，聚合物只要为通常的有机高分子化合物，则并无特别限制，例如为单体的聚合物或部分聚合物。单体可以为1种单体，也可以为2种以上单体的混合物。需要说明的是，所谓部分聚合物，是指单体或单体混合物中的至少一部分部分地进行聚合的聚合物。The adhesive composition of this embodiment contains a polymer. In the present embodiment, the polymer is not particularly limited as long as it is a general organic polymer compound, for example, it is a polymer or a partial polymer of a monomer. The monomer may be one kind of monomer or a mixture of two or more kinds of monomers. In addition, the term "partial polymer" refers to a polymer in which at least a part of a monomer or a monomer mixture is partially polymerized.
本实施方式中的聚合物只要是通常用作粘合剂、具有粘合性的聚合物则并无特别限定，例如为丙烯酸系聚合物、橡胶系聚合物、乙烯基烷基醚系聚合物、有机硅系聚合物、聚酯系聚合物、聚酰胺系聚合物、氨基甲酸酯系聚合物、氟系聚合物及环氧系聚合物等。聚合物可单独使用或组合两种以上使用。The polymer in this embodiment is not particularly limited as long as it is usually used as an adhesive and has adhesive properties, for example, acrylic polymers, rubber polymers, vinyl alkyl ether polymers, Silicone-based polymers, polyester-based polymers, polyamide-based polymers, urethane-based polymers, fluorine-based polymers, epoxy-based polymers, etc. A polymer can be used individually or in combination of 2 or more types.
为了增大所获得的粘合剂层的除离子液体以外的成分的相对介电常数、并且增大所获得的粘合剂层的离子传导率及粘接界面的每单位面积的电容而提高电剥离性，聚合物的相对介电常数大是优选的，从该观点出发，尤其是优选本实施方式中的聚合物包含选自由聚酯系聚合物、氨基甲酸酯系聚合物、以及具有羧基、烷氧基、羟基和/或酰胺键的丙烯酸系聚合物组成的组中的至少1种。聚酯系聚合物及氨基甲酸酯系聚合物在末端具有容易极化的羟基，另外，就具有羧基、烷氧基、羟基和/或酰胺键的丙烯酸系聚合物而言，羧基、烷氧基、羟基和/或酰胺键容易极化，因此，通过使用这些聚合物，能够获得相对介电常数相对大的聚合物。本实施方式的聚合物中的聚酯系聚合物、以及具有羧基、烷氧基、羟基和/或酰胺键的丙烯酸系聚合物的含量合计优选为60质量％以上，更优选为80质量％以上。In order to increase the relative permittivity of the components other than the ionic liquid of the obtained adhesive layer, and increase the ion conductivity of the obtained adhesive layer and the capacitance per unit area of the bonding interface, the electric capacity is increased. In terms of peelability, it is preferable that the relative dielectric constant of the polymer is large. From this point of view, it is particularly preferable that the polymer in this embodiment includes a polymer selected from polyester-based polymers, urethane-based polymers, and polymers with carboxyl groups. , alkoxy, hydroxyl and/or amide bonded acrylic polymer at least one of the group consisting of. Polyester-based polymers and urethane-based polymers have easily polarized hydroxyl groups at their terminals. In addition, for acrylic polymers with carboxyl, alkoxy, hydroxyl and/or amide bonds, carboxyl, alkoxy groups, hydroxyl groups and/or amide bonds are easily polarized, and therefore, by using these polymers, a polymer having a relatively large relative permittivity can be obtained. The total content of the polyester polymer and the acrylic polymer having a carboxyl group, an alkoxy group, a hydroxyl group, and/or an amide bond in the polymer of this embodiment is preferably 60% by mass or more, more preferably 80% by mass or more .
另外，尤其是为了降低成本、提高生产率并且增大初始粘接力，本实施方式中的聚合物优选为丙烯酸系聚合物。In addition, the polymer in the present embodiment is preferably an acrylic polymer in order to reduce costs, improve productivity, and increase initial adhesion.
即，本实施方式的粘合剂组合物优选为包含丙烯酸系聚合物作为聚合物的丙烯酸系粘合剂组合物。That is, the adhesive composition of the present embodiment is preferably an acrylic adhesive composition containing an acrylic polymer as a polymer.
丙烯酸系聚合物优选包含源自具有碳原子数1～14的烷基的(甲基)丙烯酸烷基酯(下述式(1))的单体单元。这种单体单元适于获得大的初始粘接力。进而，为了增大粘合剂层的除离子液体以外的成分的相对介电常数、并且增大所获得的粘合剂层的离子传导率及粘接界面的每单位面积的电容而提高电剥离性，下述式(1)中的烷基Rb的碳原子数小是优选的，尤其是优选为8以下，更优选为4以下。The acrylic polymer preferably contains a monomer unit derived from an alkyl (meth)acrylate (the following formula (1)) having an alkyl group having 1 to 14 carbon atoms. Such a monomer unit is suitable for obtaining a large initial adhesion. Furthermore, in order to increase the relative dielectric constant of the components other than the ionic liquid in the adhesive layer, and increase the ionic conductivity of the obtained adhesive layer and the capacitance per unit area of the bonding interface to improve electrical peeling The number of carbon atoms in the alkyl group Rb in the following formula (1) is preferably small, especially preferably 8 or less, more preferably 4 or less.
CH2＝C(Ra)COORb (1)CH2 =C(Ra )COORb (1)
[式(1)中的Ra为氢原子或甲基，Rb为碳原子数1～14的烷基][Ra in the formula (1) is a hydrogen atom or a methyl group, and Rb is an alkyl group having 1 to 14 carbon atoms]
作为具有碳原子数1～14的烷基的(甲基)丙烯酸烷基酯，例如可列举(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)丙烯酸仲丁酯、丙烯酸1,3-二甲基丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基丁酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸2-乙基己酯、(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)丙烯酸正十二烷基酯、(甲基)丙烯酸正十三烷基酯及(甲基)丙烯酸正十四烷基酯等。其中，优选为丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸异壬酯。具有碳原子数1～14的烷基的(甲基)丙烯酸烷基酯可单独使用或组合两种以上使用。Examples of the alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate, Base) isopropyl acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, 1,3-dimethylbutyl acrylate, pentyl (meth)acrylate, iso(meth)acrylate Pentyl ester, hexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, ( 2-Ethylhexyl methacrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylate ) n-dodecyl acrylate, n-tridecyl (meth)acrylate and n-tetradecyl (meth)acrylate, etc. Among them, n-butyl acrylate, 2-ethylhexyl acrylate, and isononyl acrylate are preferable. The alkyl (meth)acrylates having an alkyl group having 1 to 14 carbon atoms can be used alone or in combination of two or more.
具有碳原子数1～14的烷基的(甲基)丙烯酸烷基酯相对于构成丙烯酸系聚合物的全部单体成分(100质量％)的比例并无特别限定，优选为70质量％以上，更优选为80质量％以上，进一步优选为85质量％以上。丙烯酸系聚合物的比例为70质量％以上时，容易获得大的初始粘接力。The ratio of the alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms to the total monomer components (100% by mass) constituting the acrylic polymer is not particularly limited, but is preferably 70% by mass or more. More preferably, it is 80 mass % or more, More preferably, it is 85 mass % or more. When the ratio of the acrylic polymer is 70% by mass or more, it is easy to obtain a large initial adhesive force.
作为丙烯酸系聚合物，为了改善凝聚力、耐热性、交联性等，优选除包含源自具有碳原子数1～14的烷基的(甲基)丙烯酸烷基酯的单体单元以外，还包含源自可与其共聚的含极性基团的单体的单体单元。单体单元能够赋予交联点，适于获得大的初始粘接力。进而，从增大粘合剂层的除离子液体以外的成分的相对介电常数、并且增大所获得的粘合剂层的离子传导率及粘接界面的每单位面积的电容而提高电剥离性的观点出发，也优选包含源自含极性基团的单体的单体单元。As an acrylic polymer, in order to improve cohesive force, heat resistance, crosslinkability, etc., it is preferable to contain a monomer unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms. Contains a monomer unit derived from a polar group-containing monomer copolymerizable therewith. The monomer unit can impart a crosslinking point, and is suitable for obtaining a large initial adhesive force. Furthermore, the electrical peeling is improved by increasing the relative permittivity of the components of the adhesive layer other than the ionic liquid, and increasing the ionic conductivity of the obtained adhesive layer and the capacitance per unit area of the bonding interface. From the viewpoint of polarity, it is also preferable to contain a monomer unit derived from a polar group-containing monomer.
作为含极性基团的单体，例如可列举含羧基的单体、含烷氧基的单体、含羟基的单体、含氰基的单体、含乙烯基的单体、芳香族乙烯基单体、含酰胺基的单体、含酰亚胺基的单体、含氨基的单体、含环氧基的单体、乙烯醚单体、N-丙烯酰基吗啉、含磺基的单体、含磷酸基的单体及含酸酐基的单体等。其中，从凝聚性优异方面出发，优选为含羧基的单体、含烷氧基的单体、含羟基的单体、含酰胺基的单体，尤其是优选为含羧基的单体。含羧基的单体尤其适于获得大的初始粘接力。含极性基团的单体可单独使用或组合两种以上使用。Examples of polar group-containing monomers include carboxyl group-containing monomers, alkoxy group-containing monomers, hydroxyl group-containing monomers, cyano group-containing monomers, vinyl group-containing monomers, aromatic vinyl Based monomers, amide-containing monomers, imide-containing monomers, amino-containing monomers, epoxy-containing monomers, vinyl ether monomers, N-acryloyl morpholine, sulfo-containing Monomers, monomers containing phosphoric acid groups, monomers containing acid anhydride groups, etc. Among these, carboxyl group-containing monomers, alkoxy group-containing monomers, hydroxyl group-containing monomers, and amide group-containing monomers are preferable, and carboxyl group-containing monomers are particularly preferable from the viewpoint of excellent cohesiveness. Carboxyl-containing monomers are especially suitable for obtaining high initial adhesion. The polar group-containing monomers can be used alone or in combination of two or more.
作为含羧基的单体，例如可列举丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、马来酸、富马酸、巴豆酸及异巴豆酸等。尤其是优选为丙烯酸。含羧基的单体可单独使用或组合两种以上使用。Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and iso Crotonic acid etc. In particular, acrylic acid is preferred. The carboxyl group-containing monomers can be used alone or in combination of two or more.
作为含烷氧基的单体，例如可列举含甲氧基的单体、含乙氧基的单体。作为含甲氧基的单体，例如可列举丙烯酸2-甲氧基乙酯。Examples of the alkoxy group-containing monomer include methoxy group-containing monomers and ethoxy group-containing monomers. As a methoxy group-containing monomer, 2-methoxyethyl acrylate is mentioned, for example.
作为含羟基的单体，例如可列举(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸6-羟基己酯、(甲基)丙烯酸8-羟基辛酯、(甲基)丙烯酸10-羟基癸酯、(甲基)丙烯酸12-羟基月桂酯、(甲基)丙烯酸(4-羟基甲基环己基)甲酯、N-羟甲基(甲基)丙烯酰胺、乙烯醇、烯丙醇、2-羟基乙基乙烯醚、4-羟基丁基乙烯醚及二乙二醇单乙烯醚等。尤其是优选为(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸4-羟基丁酯。含羟基的单体可单独使用或组合两种以上使用。Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxybutyl (meth)acrylate, Hydroxyhexyl, 8-Hydroxyoctyl (meth)acrylate, 10-Hydroxydecyl (meth)acrylate, 12-Hydroxylauryl (meth)acrylate, (4-Hydroxymethylcyclohexyl (meth)acrylate) ) methyl ester, N-methylol (meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and diethylene glycol monovinyl ether, etc. In particular, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferable. The hydroxyl group-containing monomers can be used alone or in combination of two or more.
作为含酰胺基的单体，例如可列举丙烯酰胺、甲基丙烯酰胺、N-乙烯基吡咯烷酮、N,N-二甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N,N-二乙基甲基丙烯酰胺、N,N’-亚甲基双丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺、N,N-二甲基氨基丙基甲基丙烯酰胺及双丙酮丙烯酰胺等。含酰胺基的单体可单独使用或组合两种以上使用。Examples of amide group-containing monomers include acrylamide, methacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N -Diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethyl Aminopropyl methacrylamide and diacetone acrylamide, etc. The amide group-containing monomers can be used alone or in combination of two or more.
作为含氰基的单体，例如可列举丙烯腈及甲基丙烯腈等。As a cyano group-containing monomer, acrylonitrile, methacrylonitrile, etc. are mentioned, for example.
作为含乙烯基的单体，例如可列举乙酸乙烯酯、丙酸乙烯酯及月桂酸乙烯酯等乙烯酯类等，尤其是优选为乙酸乙烯酯。Examples of vinyl group-containing monomers include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate, and vinyl acetate is particularly preferred.
作为芳香族乙烯基单体，例如可列举苯乙烯、氯苯乙烯、氯甲基苯乙烯、α-甲基苯乙烯及其他取代苯乙烯等。Examples of aromatic vinyl monomers include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and other substituted styrenes.
作为含酰亚胺基的单体，例如可列举环己基马来酰亚胺、异丙基马来酰亚胺、N-环己基马来酰亚胺及衣康酰亚胺等。As an imide group containing monomer, cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconimide, etc. are mentioned, for example.
作为含氨基的单体，例如可列举(甲基)丙烯酸氨基乙酯、(甲基)丙烯酸N,N-二甲基氨基乙酯及(甲基)丙烯酸N,N-二甲基氨基丙酯等。Examples of amino group-containing monomers include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate. wait.
作为含环氧基的单体，例如可列举(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸甲基缩水甘油酯及烯丙基缩水甘油醚等。Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, allyl glycidyl ether, and the like.
作为乙烯醚单体，例如可列举甲基乙烯醚、乙基乙烯醚及异丁基乙烯醚等。As a vinyl ether monomer, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc. are mentioned, for example.
含极性基团的单体相对于构成丙烯酸系聚合物的全部单体成分(100质量％)的比例优选为0.1质量％以上且35质量％以下。含极性基团的单体的比例的上限更优选为25质量％，进一步优选为20质量％，下限更优选为0.5质量％，进一步优选为1质量％，尤其优选为2质量％。含极性基团的单体的比例为0.1质量％以上时，容易获得凝聚力，因此，在剥离粘合剂层后的被粘物表面不易产生残胶，并且电剥离性提高。另外，含极性基团的单体的比例为35质量％以下时，容易防止粘合剂层过度密合于被粘物而发生重剥离化。尤其是为2质量％以上且20质量％以下时，容易谋求同时实现与被粘物的剥离性、及粘合剂层与其他层的密合性。The ratio of the polar group-containing monomer to all monomer components (100% by mass) constituting the acrylic polymer is preferably 0.1% by mass or more and 35% by mass or less. The upper limit of the ratio of the polar group-containing monomer is more preferably 25% by mass, still more preferably 20% by mass, and the lower limit is more preferably 0.5% by mass, still more preferably 1% by mass, and especially preferably 2% by mass. When the proportion of the polar group-containing monomer is 0.1% by mass or more, cohesive force is easily obtained, and therefore, adhesive residue is less likely to be generated on the surface of the adherend after the adhesive layer is peeled off, and the electro-peelability is improved. In addition, when the proportion of the polar group-containing monomer is 35% by mass or less, it is easy to prevent the pressure-sensitive adhesive layer from excessively sticking to the adherend and causing heavy peeling. Especially when it is 2 mass % or more and 20 mass % or less, it becomes easy to simultaneously realize the peelability with an adherend, and the adhesiveness of an adhesive layer and another layer.
另外，作为构成丙烯酸系聚合物的单体成分，为了向丙烯酸系聚合物中导入交联结构而容易获得所需的凝聚力，可以包含多官能单体。In addition, as a monomer component constituting the acrylic polymer, a polyfunctional monomer may be included in order to introduce a crosslinked structure into the acrylic polymer to easily obtain a desired cohesive force.
作为多官能单体，例如可列举乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二乙烯苯及N,N’-亚甲基双丙烯酰胺等。多官能单体可单独使用或组合两种以上使用。As a multifunctional monomer, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Acrylate, divinylbenzene and N,N'-methylenebisacrylamide, etc. A polyfunctional monomer can be used individually or in combination of 2 or more types.
多官能单体相对于构成丙烯酸系聚合物的全部单体成分(100质量％)的含量优选为0.1质量％以上且15质量％以下。多官能单体的含量的上限更优选为10质量％，下限更优选为3质量％。多官能单体的含量为0.1质量％以上时，粘合剂层的柔软性、粘接性容易提高而优选。多官能单体的含量为15质量％以下时，凝聚力不会变得过高，容易获得适度的粘接性。It is preferable that content of a polyfunctional monomer is 0.1 mass % or more and 15 mass % or less with respect to the whole monomer component (100 mass %) which comprises an acrylic-type polymer. The upper limit of the content of the polyfunctional monomer is more preferably 10% by mass, and the lower limit is more preferably 3% by mass. When the content of the polyfunctional monomer is 0.1% by mass or more, the flexibility and adhesiveness of the pressure-sensitive adhesive layer tend to be improved, which is preferable. When the content of the polyfunctional monomer is 15% by mass or less, the cohesive force does not become too high, and moderate adhesiveness is easily obtained.
聚酯系聚合物典型地是具有二羧酸等多元羧酸、其衍生物(以下也称为“多元羧酸单体”)与二醇等多元醇、其衍生物(以下称为“多元醇单体”)进行缩合而得的结构的聚合物。Polyester-based polymers typically have polycarboxylic acids such as dicarboxylic acids, their derivatives (hereinafter also referred to as "polycarboxylic acid monomers"), polyols such as diols, and their derivatives (hereinafter referred to as "polyols"). Monomer") is a polymer with a structure obtained by condensation.
作为多元羧酸单体，并无特别限定，例如可使用己二酸、壬二酸、二聚酸、癸二酸、1,4-环己烷二甲酸、1,3-环己烷二甲酸、1,2-环己烷二甲酸、4-甲基-1,2-环己烷二甲酸、十二碳烯基琥珀酸酐、富马酸、琥珀酸、十二烷二酸、六氢邻苯二甲酸酐、四氢邻苯二甲酸酐等、马来酸、马来酸酐、衣康酸、柠康酸、及它们的衍生物等。The polycarboxylic acid monomer is not particularly limited, and for example, adipic acid, azelaic acid, dimer acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid can be used , 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dodecenyl succinic anhydride, fumaric acid, succinic acid, dodecanedioic acid, hexahydro-ortho Phthalic anhydride, tetrahydrophthalic anhydride, etc., maleic acid, maleic anhydride, itaconic acid, citraconic acid, and their derivatives.
多元羧酸单体可单独使用或组合两种以上使用。The polyhydric carboxylic acid monomer can be used individually or in combination of 2 or more types.
作为多元醇单体，并无特别限定，例如可使用乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、新戊二醇、二乙二醇、二丙二醇、2,2,4-三甲基-1,5-戊二醇、2-乙基-2-丁基丙二醇、1,9-壬二醇、2-甲基辛二醇、1,10-癸二醇、及它们的衍生物等。The polyol monomer is not particularly limited, and for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1 ,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, di Ethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, 2-ethyl-2-butylpropanediol, 1,9-nonanediol, 2-methyloctanediol Alcohol, 1,10-decanediol, and their derivatives, etc.
多元醇单体可单独使用或组合两种以上使用。A polyol monomer can be used individually or in combination of 2 or more types.
另外，本实施方式的聚合物可以包含离子性聚合物。离子性聚合物是具有离子性官能团的聚合物。由于聚合物包含离子性聚合物，从而使得聚合物的相对介电常数增加，电剥离性提高。在聚合物包含离子性聚合物的情况下，离子性聚合物的含量优选相对于100质量份的聚合物而言为0.05质量份以上且2质量份以下。In addition, the polymer of this embodiment may contain an ionic polymer. Ionic polymers are polymers with ionic functional groups. Since the polymer contains an ionic polymer, the relative dielectric constant of the polymer is increased, and the electrolytic stripping property is improved. When the polymer contains an ionic polymer, the content of the ionic polymer is preferably not less than 0.05 parts by mass and not more than 2 parts by mass relative to 100 parts by mass of the polymer.
在本实施方式中，聚合物可通过使单体成分进行(共)聚合而获得。作为聚合方法，并无特别限定，可列举溶液聚合、乳液聚合、本体聚合、悬浮聚合、光聚合(活性能量射线聚合)法等。尤其是从成本、生产率的观点出发，优选为溶液聚合法。在共聚的情况下，聚合物为无规共聚物、嵌段共聚物、交替共聚物、接枝共聚物等均可。In the present embodiment, the polymer can be obtained by (co)polymerizing monomer components. Although it does not specifically limit as a polymerization method, Solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (active energy ray polymerization) method etc. are mentioned. In particular, the solution polymerization method is preferable from the viewpoint of cost and productivity. In the case of copolymerization, the polymer may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like.
作为溶液聚合法，并无特别限定，可列举：使单体成分、聚合引发剂等溶解于溶剂中，进行加热而进行聚合，从而获得包含聚合物的聚合物溶液的方法；等等。The solution polymerization method is not particularly limited, and examples thereof include a method in which a monomer component, a polymerization initiator, and the like are dissolved in a solvent, heated and polymerized to obtain a polymer solution containing a polymer, and the like.
作为溶液聚合法中使用的溶剂，可使用各种通常的溶剂。作为这种溶剂(聚合溶剂)，例如可列举甲苯、苯及二甲苯等芳香族烃类；乙酸乙酯及乙酸正丁酯等酯类；正己烷及正庚烷等脂肪族烃类；环己烷及甲基环己烷等脂环式烃类；甲基乙基酮及甲基异丁基酮等酮类等有机溶剂等。溶剂可单独使用或组合两种以上使用。As the solvent used in the solution polymerization method, various common solvents can be used. Examples of such solvents (polymerization solvents) include aromatic hydrocarbons such as toluene, benzene, and xylene; esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; Alicyclic hydrocarbons such as alkanes and methylcyclohexane; organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, etc. A solvent can be used individually or in combination of 2 or more types.
溶剂的用量并无特别限定，相对于构成聚合物的全部单体成分(100质量份)，优选为10质量份以上且1000质量份以下。溶剂的用量的上限更优选为500质量份，下限更优选为50质量份。The usage-amount of a solvent is not specifically limited, It is preferable that it is 10 mass parts or more and 1000 mass parts or less with respect to the whole monomer component (100 mass parts) which comprises a polymer. The upper limit of the amount of solvent used is more preferably 500 parts by mass, and the lower limit is more preferably 50 parts by mass.
作为溶液聚合法中使用的聚合引发剂，并无特别限定，可列举过氧化物系聚合引发剂、偶氮系聚合引发剂等。作为过氧化物系聚合引发剂，并无特别限定，可列举过氧化碳酸酯、过氧化酮、过氧化缩酮、过氧化氢、二烷基过氧化物、二酰基过氧化物及过氧化酯等，更具体而言，可列举过氧化苯甲酰、叔丁基过氧化氢、二叔丁基过氧化物、过氧化苯甲酸叔丁酯、二枯基过氧化物、1,1-双(叔丁基过氧化)-3,3,5-三甲基环己烷及1,1-双(叔丁基过氧化)环十二烷等。作为偶氮系聚合引发剂，并无特别限定，可列举2,2’-偶氮双异丁腈、2,2’-偶氮双-2-甲基丁腈、2,2’-偶氮双(2,4-二甲基戊腈)、2,2’-偶氮双(2-甲基丙酸)二甲酯、2,2’-偶氮双(4-甲氧基-2,4-二甲基戊腈)、1,1’-偶氮双(环己烷-1-甲腈)、2,2’-偶氮双(2,4,4-三甲基戊烷)、4,4’-偶氮双-4-氰基戊酸、2,2’-偶氮双(2-脒基丙烷)二盐酸盐、2,2’-偶氮双[2-(5-甲基-2-咪唑啉-2-基)丙烷]二盐酸盐、2,2’-偶氮双(2-甲基丙脒)二硫酸盐、2,2’-偶氮双(N,N’-二亚甲基异丁基脒)盐酸盐及2,2’-偶氮双[N-(2-羧基乙基)-2-甲基丙脒]水合物等。聚合引发剂可单独使用或组合两种以上使用。It does not specifically limit as a polymerization initiator used by the solution polymerization method, A peroxide type polymerization initiator, an azo type polymerization initiator, etc. are mentioned. The peroxide-based polymerization initiator is not particularly limited, and examples thereof include peroxycarbonates, peroxyketones, peroxyketals, hydrogen peroxide, dialkyl peroxides, diacyl peroxides, and peroxyesters. etc. More specifically, benzoyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis (tert-butyl peroxide)-3,3,5-trimethylcyclohexane and 1,1-bis(tert-butyl peroxide)cyclododecane, etc. The azo polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azo Bis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionate) dimethyl ester, 2,2'-azobis(4-methoxy-2, 4-Dimethylvaleronitrile), 1,1'-Azobis(cyclohexane-1-carbonitrile), 2,2'-Azobis(2,4,4-trimethylpentane), 4,4'-Azobis-4-cyanovaleric acid, 2,2'-Azobis(2-amidinopropane) dihydrochloride, 2,2'-Azobis[2-(5- Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N, N'-dimethyleneisobutylamidine) hydrochloride and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate, etc. A polymerization initiator can be used individually or in combination of 2 or more types.
聚合引发剂的用量并无特别限定，相对于构成聚合物的全部单体成分(100质量份)，优选为0.01质量份以上且5质量份以下。聚合引发剂的用量的上限更优选为3质量份，下限更优选为0.05质量份。The usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is 0.01 mass part or more and 5 mass parts or less with respect to the whole monomer component (100 mass parts) which comprises a polymer. The upper limit of the usage-amount of a polymerization initiator is more preferably 3 parts by mass, and the lower limit is more preferably 0.05 parts by mass.
利用溶液聚合法进行加热而聚合时的加热温度并无特别限定，例如为50℃以上且80℃以下。加热时间并无特别限定，例如为1小时以上且24小时以下。The heating temperature at the time of superposition|polymerization by heating by a solution polymerization method is not specifically limited, For example, it is 50 degreeC or more and 80 degreeC or less. The heating time is not particularly limited, and is, for example, not less than 1 hour and not more than 24 hours.
聚合物的重均分子量并无特别限定，优选为10万以上且500万以下。重均分子量的上限更优选为400万，进一步优选为300万，下限更优选为20万，进一步优选为30万。重均分子量为10万以上时，能够有效地抑制凝聚力变小、在剥离粘合剂层后的被粘物表面产生残胶这样的不良情况。另外，重均分子量为500万以下时，能够有效地抑制剥离粘合剂层后的被粘物表面的润湿性变得不充分这样的不良情况。The weight average molecular weight of the polymer is not particularly limited, but is preferably not less than 100,000 and not more than 5 million. The upper limit of the weight average molecular weight is more preferably 4 million, still more preferably 3 million, and the lower limit is more preferably 200,000, still more preferably 300,000. When the weight-average molecular weight is 100,000 or more, it is possible to effectively suppress defects such as a reduction in cohesive force and generation of residual adhesive on the surface of the adherend after peeling off the adhesive layer. Moreover, when the weight-average molecular weight is 5 million or less, it is possible to effectively suppress the inconvenience that the wettability of the surface of the adherend after peeling off the pressure-sensitive adhesive layer becomes insufficient.
重均分子量是通过凝胶渗透色谱(GPC)法进行测定而获得的，更具体而言，例如额使用商品名“HLC-8220GPC”(东曹公司制)作为GPC测定装置，在下述条件下进行测定，并利用标准聚苯乙烯换算值而算出。(重均分子量测定条件)The weight-average molecular weight is measured by gel permeation chromatography (GPC). More specifically, for example, the product name "HLC-8220GPC" (manufactured by Tosoh Corporation) is used as a GPC measurement device, and the measurement is carried out under the following conditions: Measured and calculated using standard polystyrene conversion values. (weight average molecular weight measurement conditions)
·样品浓度：0.2质量％(四氢呋喃溶液)・Sample concentration: 0.2% by mass (tetrahydrofuran solution)
·样品注入量：10μL・Sample injection volume: 10μL
·样品柱：TSKguardcolumn SuperHZ-H(1根)+TSKgel SuperHZM-H(2根)·Sample column: TSKguardcolumn SuperHZ-H (1 piece) + TSKgel SuperHZM-H (2 pieces)
·参照物柱：TSKgel SuperH-RC(1根)·Reference column: TSKgel SuperH-RC (1 piece)
·洗脱液：四氢呋喃(THF)Eluent: Tetrahydrofuran (THF)
·流量：0.6mL/min·Flow rate: 0.6mL/min
·检测器：差示折射计(RI)Detector: Differential refractometer (RI)
·柱温(测定温度)：40℃·Column temperature (measurement temperature): 40°C
聚合物的玻璃化转变温度(Tg)并无特别限定，为0℃以下时，能够抑制初始粘接力的降低，因此优选，更优选为-10℃以下，进一步优选为-20℃以下。另外，为-40℃以下时，由电压施加导致的粘接力降低率变得特别大，因此尤其优选，最优选为-50℃以下。The glass transition temperature (Tg) of the polymer is not particularly limited, but it is preferably 0°C or lower because it can suppress a decrease in initial adhesive force, more preferably -10°C or lower, and even more preferably -20°C or lower. In addition, when it is -40 degreeC or less, since the adhesive force reduction rate by voltage application becomes especially large, it is especially preferable, and it is most preferable that it is -50 degreeC or less.
玻璃化转变温度(Tg)例如可基于下述式(Y)(Fox式)进行计算。The glass transition temperature (Tg) can be calculated based on the following formula (Y) (Fox formula), for example.
1/Tg＝W1/Tg1+W2/Tg2+……+Wn/Tgn(Y)1/Tg＝W1/Tg1+W2/Tg2+...+Wn/Tgn(Y)
[式(Y)中，Tg表示聚合物的玻璃化转变温度(单位：K)，Tgi(i＝1、2、……n)表示单体i形成均聚物时的玻璃化转变温度(单位：K)，Wi(i＝1、2、……n)表示单体i在全部单体成分中的质量分数][In the formula (Y), Tg represents the glass transition temperature (unit: K) of polymer, and Tgi (i=1, 2, ... n) represents the glass transition temperature (unit: K) when monomer i forms a homopolymer : K), Wi (i=1, 2, ... n) represents the mass fraction of monomer i in all monomer components]
上述式(Y)为聚合物由单体1、单体2、……、单体n这n种单体成分构成时的计算式。The above formula (Y) is a calculation formula when the polymer is composed of n monomer components of monomer 1, monomer 2, . . . , monomer n.
需要说明的是，所谓形成均聚物时的玻璃化转变温度，是指该单体的均聚物的玻璃化转变温度，是指仅将某单体(有时称为“单体X”)作为单体成分而形成的聚合物的玻璃化转变温度(Tg)。具体而言，在“聚合物手册(Polymer Handbook)”(第3版，John Wiley&Sons，Inc，1989年)中列举了数值。需要说明的是，该文献中未记载的均聚物的玻璃化转变温度(Tg)例如是指通过以下的测定方法而获得的值。即，向具备温度计、搅拌机、氮气导入管及回流冷凝管的反应器中，投入100质量份的单体X、2,2’-偶氮双异丁腈0.2质量份及作为聚合溶剂的乙酸乙酯200质量份，一边导入氮气一边搅拌1小时。如此去除聚合体系内的氧后，升温至63℃并使其反应10小时。接下来，冷却至室温，获得固体成分浓度33质量％的均聚物溶液。接下来，将该均聚物溶液流延涂布于剥离衬垫上，进行干燥而制作厚度约2mm的试验样品(片状的均聚物)。然后，称量约1～2mg的该试验样品于铝制的敞开槽中，使用温度调制DSC(商品名“Q-2000”，TA Instruments公司制)，在50ml/min的氮气气氛下以5℃/min的升温速度获得均聚物的可逆热流(Reversing Heat Flow)(比热成分)行为。以JIS-K-7121为参考，将下述直线与玻璃化转变的阶梯状变化部分的曲线相交的点的温度作为制成均聚物时的玻璃化转变温度(Tg)，所述直线为与使所获得的可逆热流的低温侧的基线与高温侧的基线延长所得的直线在纵轴方向上成等距离的直线。It should be noted that the glass transition temperature at the time of forming a homopolymer refers to the glass transition temperature of the homopolymer of the monomer, and means that only a certain monomer (sometimes referred to as "monomer X") is used as The glass transition temperature (Tg) of a polymer formed from monomeric components. Specifically, numerical values are listed in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989). In addition, the glass transition temperature (Tg) of the homopolymer which is not described in this document means the value obtained by the following measuring method, for example. That is, 100 parts by mass of monomer X, 0.2 parts by mass of 2,2'-azobisisobutyronitrile, and ethyl acetate as a polymerization solvent were put into a reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction pipe, and a reflux condenser. 200 parts by mass of the ester were stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63° C., and the reaction was carried out for 10 hours. Next, it was cooled to room temperature, and a homopolymer solution having a solid content concentration of 33% by mass was obtained. Next, this homopolymer solution was cast-coated on a release liner, and dried to prepare a test sample (sheet-shaped homopolymer) having a thickness of about 2 mm. Then, weigh about 1 to 2 mg of the test sample in an aluminum open tank, use a temperature modulation DSC (trade name "Q-2000", manufactured by TA Instruments), and set the temperature at 5° C. under a nitrogen atmosphere of 50 ml/min. The heating rate of /min obtains the reversing heat flow (Reversing Heat Flow) (specific heat component) behavior of the homopolymer. Taking JIS-K-7121 as a reference, the temperature at the point where the following straight line intersects with the curve of the step-like change part of the glass transition is taken as the glass transition temperature (Tg) when making a homopolymer, and the straight line is the same as The straight line obtained by extending the base line on the low temperature side and the base line on the high temperature side of the obtained reversible heat flow is an equidistant straight line in the direction of the longitudinal axis.
关于本实施方式的粘合剂组合物中的聚合物的含量，相对于粘合剂组合物总量(100质量％)，优选为50质量％以上且99.9质量％以下，上限更优选为99.5质量％，进一步优选为99质量％，下限更优选为60质量％，进一步优选为70质量％。The content of the polymer in the adhesive composition of the present embodiment is preferably 50% by mass or more and 99.9% by mass or less with respect to the total amount of the adhesive composition (100% by mass), and the upper limit is more preferably 99.5% by mass. %, more preferably 99% by mass, the lower limit is more preferably 60% by mass, still more preferably 70% by mass.
(离子液体)(ionic liquid)
本实施方式中的离子液体由一对阴离子和阳离子构成，只要是于25℃为液体的熔融盐(常温熔融盐)则并无特别限定。以下列举阴离子及阳离子的例子，但在将它们组合而获得的离子性物质中，于25℃为液体的物质是离子液体，于25℃为固体的物质是后述的离子性固体，而不是离子液体。The ionic liquid in the present embodiment is composed of a pair of anion and cation, and is not particularly limited as long as it is a molten salt (ordinary temperature molten salt) that is liquid at 25°C. Examples of anions and cations are listed below, but among the ionic substances obtained by combining them, those that are liquid at 25°C are ionic liquids, and those that are solid at 25°C are ionic solids described later, not ions. liquid.
离子液体的阴离子例如可列举(FSO2)2N-、(CF3SO2)2N-、(CF3CF2SO2)2N-、(CF3SO2)3C-、Br-、AlCl4-、Al2Cl7-、NO3-、BF4-、PF6-、CH3COO-、CF3COO-、CF3CF2CF2COO-、CF3SO3-、CF3(CF2)3SO3-、AsF6-、SbF6-和F(HF)n-等。其中，作为阴离子，(FSO2)2N-[双(氟磺酰基)酰亚胺阴离子]及(CF3SO2)2N-[双(三氟甲磺酰基)酰亚胺阴离子]等磺酰基酰亚胺系化合物的阴离子从化学性稳定、适于使电剥离性变得良好的方面出发是优选的。Examples of anions of ionic liquids include (FSO2 )2 N- , (CF3 SO2 )2 N- , (CF3 CF2 SO2 )2 N- , (CF3 SO2 )3 C- , Br- , AlCl4- , Al2 Cl7- , NO3- , BF4- , PF6- , CH3 COO- , CF3 COO- , CF3 CF2 CF2 COO- , CF3 SO3- , CF3 ( CF2 )3 SO3- , AsF6- , SbF6- and F(HF)n- , etc. Among them, as the anion, sulfonic acid such as (FSO2 )2 N- [bis(fluorosulfonyl)imide anion] and (CF3 SO2 )2 N- [bis(trifluoromethanesulfonyl)imide anion], etc. The anion of the acyl imide compound is preferable from the viewpoint of being chemically stable and suitable for improving electro-disbonding properties.
关于离子液体中的阳离子，含氮的鎓、含硫的鎓及含磷的鎓阳离子从化学性稳定、适于使电剥离性变得良好的方面出发是优选的，更优选为咪唑鎓系、铵系、吡咯烷鎓系及吡啶鎓系阳离子。Regarding the cations in the ionic liquid, nitrogen-containing onium, sulfur-containing onium, and phosphorus-containing onium cations are preferred from the viewpoint of being chemically stable and suitable for making the electro-disbonding property good, more preferably imidazolium-based, Ammonium, pyrrolidinium and pyridinium cations.
作为咪唑鎓系阳离子，例如可列举1-甲基咪唑鎓阳离子、1-乙基-3-甲基咪唑鎓阳离子、1-丙基-3-甲基咪唑鎓阳离子、1-丁基-3-甲基咪唑鎓阳离子、1-戊基-3-甲基咪唑鎓阳离子、1-己基-3-甲基咪唑鎓阳离子、1-庚基-3-甲基咪唑鎓阳离子、1-辛基-3-甲基咪唑鎓阳离子、1-壬基-3-甲基咪唑鎓阳离子、1-十一烷基-3-甲基咪唑鎓阳离子、1-十二烷基-3-甲基咪唑鎓阳离子、1-十三烷基-3-甲基咪唑鎓阳离子、1-十四烷基-3-甲基咪唑鎓阳离子、1-十五烷基-3-甲基咪唑鎓阳离子、1-十六烷基-3-甲基咪唑鎓阳离子、1-十七烷基-3-甲基咪唑鎓阳离子、1-十八烷基-3-甲基咪唑鎓阳离子、1-十一烷基-3-甲基咪唑鎓阳离子、1-苄基-3-甲基咪唑鎓阳离子、1-丁基-2,3-二甲基咪唑鎓阳离子及1,3-双(十二烷基)咪唑鎓阳离子等。Examples of imidazolium cations include 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3- Methylimidazolium cation, 1-pentyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-heptyl-3-methylimidazolium cation, 1-octyl-3 -methylimidazolium cation, 1-nonyl-3-methylimidazolium cation, 1-undecyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tridecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1-pentadecyl-3-methylimidazolium cation, 1-hexadecane Base-3-methylimidazolium cation, 1-heptadecyl-3-methylimidazolium cation, 1-octadecyl-3-methylimidazolium cation, 1-undecyl-3-methyl imidazolium cation, 1-benzyl-3-methylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1,3-bis(dodecyl)imidazolium cation, etc.
作为吡啶鎓系阳离子，例如可列举1-丁基吡啶鎓阳离子、1-己基吡啶鎓阳离子、1-丁基-3-甲基吡啶鎓阳离子、1-丁基-4-甲基吡啶鎓阳离子及1-辛基-4-甲基吡啶鎓阳离子等。Examples of pyridinium-based cations include 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, and 1-octyl-4-methylpyridinium cation, etc.
作为吡咯烷鎓系阳离子，例如可列举1-乙基-1-甲基吡咯烷鎓阳离子及1-丁基-1-甲基吡咯烷鎓阳离子等。Examples of the pyrrolidinium-based cation include 1-ethyl-1-methylpyrrolidinium cation, 1-butyl-1-methylpyrrolidinium cation, and the like.
作为铵系阳离子，例如可列举四乙基铵阳离子、四丁基铵阳离子、甲基三辛基铵阳离子、十四烷基三己基铵阳离子、缩水甘油基三甲基铵阳离子及三甲基氨基乙基丙烯酸酯阳离子等。Examples of ammonium-based cations include tetraethylammonium cations, tetrabutylammonium cations, methyltrioctylammonium cations, tetradecyltrihexylammonium cations, glycidyltrimethylammonium cations, and trimethylamino Ethacrylate cations, etc.
作为离子液体，从增大电压施加时的粘接力降低率的观点出发，优选选择分子量160以下的阳离子作为构成的阳离子，尤其优选为包含上述(FSO2)2N-[双(氟磺酰基)酰亚胺阴离子]或(CF3SO2)2N-[双(三氟甲磺酰基)酰亚胺阴离子]、和分子量160以下的阳离子的离子液体。作为分子量160以下的阳离子，例如可列举1-甲基咪唑鎓阳离子、1-乙基-3-甲基咪唑鎓阳离子、1-丙基-3-甲基咪唑鎓阳离子、1-丁基-3-甲基咪唑鎓阳离子、1-戊基-3-甲基咪唑鎓阳离子、1-丁基吡啶鎓阳离子、1-己基吡啶鎓阳离子、1-丁基-3-甲基吡啶鎓阳离子、1-丁基-4-甲基吡啶鎓阳离子、1-乙基-1-甲基吡咯烷鎓阳离子、1-丁基-1-甲基吡咯烷鎓阳离子、四乙基铵阳离子、缩水甘油基三甲基铵阳离子及三甲基氨基乙基丙烯酸酯阳离子等。As the ionic liquid, it is preferable to select a cation having a molecular weight of 160 or less as the constituting cation from the viewpoint of increasing the rate of decrease in the adhesive force when a voltage is applied, and it is especially preferable to include the above-mentioned (FSO2 )2 N- [bis(fluorosulfonyl )imide anion] or (CF3 SO2 )2 N- [bis(trifluoromethanesulfonyl)imide anion], and an ionic liquid having a molecular weight of 160 or less cations. Examples of cations having a molecular weight of 160 or less include 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3 -Methylimidazolium cation, 1-pentyl-3-methylimidazolium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1- Butyl-4-methylpyridinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-butyl-1-methylpyrrolidinium cation, tetraethylammonium cation, glycidyl trimethyl ammonium cation and trimethylaminoethyl acrylate cation, etc.
另外，作为离子液体的阳离子，也优选为下述式(2-A)～(2-D)所表示的阳离子。In addition, the cations of the ionic liquid are also preferably cations represented by the following formulas (2-A) to (2-D).
[化学式1][chemical formula 1]
式(2-A)中的R1表示碳原子数4～10的烃基(优选为碳原子数4～8的烃基，更优选为碳原子数4～6的烃基)，可以包含杂原子，R2及R3相同或不同，表示氢原子或碳原子数1～12的烃基(优选为碳原子数1～8的烃基，更优选为碳原子数2～6的烃基，进一步优选为碳原子数2～4的烃基)，可以包含杂原子。其中，在氮原子与邻接的碳原子形成双键的情况下，不存在R3。R in the formula (2-A) represents a hydrocarbon group with 4 to 10 carbon atoms (preferably a hydrocarbon group with 4 to 8 carbon atoms, more preferably a hydrocarbon group with 4 to 6 carbon atoms), which may contain heteroatoms, and R2 andR3 are the same or different, and represent a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms (preferably a hydrocarbon group with 1 to 8 carbon atoms, more preferably a hydrocarbon group with 2 to 6 carbon atoms, and even more preferably a hydrocarbon group with 1 to 6 carbon atoms. 2 to 4 hydrocarbon groups), may contain heteroatoms. However, when a nitrogen atom forms a double bond with an adjacent carbon atom, R3 does not exist.
式(2-B)中的R4表示碳原子数2～10的烃基(优选为碳原子数2～8的烃基，更优选为碳原子数2～6的烃基)，可以包含杂原子，R5、R6及R7相同或不同，表示氢原子或碳原子数1～12的烃基(优选为碳原子数1～8的烃基，更优选为碳原子数2～6的烃基，进一步优选为碳原子数2～4的烃基)，可以包含杂原子。R in the formula (2-B)represents a hydrocarbon group with 2 to 10 carbon atoms (preferably a hydrocarbon group with 2 to 8 carbon atoms, more preferably a hydrocarbon group with 2 to 6 carbon atoms), which may contain heteroatoms, and R5.R6 andR7 are the same or different, and represent a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms (preferably a hydrocarbon group with 1 to 8 carbon atoms, more preferably a hydrocarbon group with 2 to 6 carbon atoms, and even more preferably A hydrocarbon group having 2 to 4 carbon atoms) may contain heteroatoms.
式(2-C)中的R8表示碳原子数2～10的烃基(优选为碳原子数2～8的烃基，更优选为碳原子数2～6的烃基)，可以包含杂原子，R9、R10及R11相同或不同，表示氢原子或碳原子数1～16的烃基(优选为碳原子数1～10的烃基，更优选为碳原子数1～8的烃基)，可以包含杂原子。R in the formula (2-C) represents a hydrocarbon group with 2 to 10 carbon atoms (preferablya hydrocarbon group with 2 to 8 carbon atoms, more preferably a hydrocarbon group with 2 to 6 carbon atoms), which may contain heteroatoms, and R9. R10 and R11 are the same or different, and represent a hydrogen atom or a hydrocarbon group with 1 to 16 carbon atoms (preferably a hydrocarbon group with 1 to 10 carbon atoms, more preferably a hydrocarbon group with 1 to 8 carbon atoms), which may include heteroatoms.
式(2-D)中的X表示氮、硫或磷原子，R12、R13、R14及R15相同或不同，表示碳原子数1～16的烃基(优选为碳原子数1～14的烃基，更优选为碳原子数1～10的烃基，进一步优选为碳原子数1～8的烃基，尤其优选为碳原子数1～6的烃基)，可以包含杂原子。其中，在X为硫原子的情况下，不存在R12。X in the formula (2-D) represents a nitrogen, sulfur or phosphorus atom, R12 , R13 , R14 and R15 are the same or different, and represent a hydrocarbon group with 1 to 16 carbon atoms (preferably 1 to 14 carbon atoms A hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 8 carbon atoms, especially preferably a hydrocarbon group having 1 to 6 carbon atoms), may contain heteroatoms. However, when X is a sulfur atom, R12 does not exist.
离子液体中的阳离子的分子量例如为500以下，优选为400以下，更优选为300以下，进一步优选为250以下，尤其优选为200以下，最优选为160以下。另外，通常为50以上。认为离子液体中的阳离子具有在粘合剂层中在电压施加时向阴极侧移动而偏在于粘合剂层与被粘物的界面附近的性质。因此，在本发明中，相对于初始粘接力而言，电压施加中的粘接力降低，产生电剥离性。就分子量为500以下这样的分子量小的阳离子而言，粘合剂层中的阳离子向阴极侧的移动变得更容易，在增大电压施加时的粘接力降低率的方面是适宜的。The molecular weight of the cations in the ionic liquid is, for example, 500 or less, preferably 400 or less, more preferably 300 or less, further preferably 250 or less, especially preferably 200 or less, and most preferably 160 or less. In addition, it is usually 50 or more. It is considered that the cations in the ionic liquid have the property of moving toward the cathode side in the pressure-sensitive adhesive layer when a voltage is applied, and localized near the interface between the pressure-sensitive adhesive layer and the adherend. Therefore, in the present invention, the adhesive force during voltage application decreases with respect to the initial adhesive force, and electrical peelability occurs. A cation with a small molecular weight of 500 or less facilitates movement of the cation in the adhesive layer to the cathode side, and is suitable for increasing the rate of decrease in adhesive force during voltage application.
作为离子液体的市售品，例如可列举第一工业制药公司制的“ELEXCEL AS-110”、“ELEXCEL MP-442”、“ELEXCEL IL-210”、“ELEXCEL MP-471”、“ELEXCEL MP-456”、“ELEXCELAS-804”、Mitsubishi Materials公司制的“HMI-FSI”、JAPAN CARLIT公司制的“CIL-312”及“CIL-313”等。Examples of commercially available ionic liquids include "ELEXCEL AS-110", "ELEXCEL MP-442", "ELEXCEL IL-210", "ELEXCEL MP-471", "ELEXCEL MP- 456", "ELEXCELAS-804", "HMI-FSI" manufactured by Mitsubishi Materials, "CIL-312" and "CIL-313" manufactured by JAPAN CARLIT, etc.
离子液体的离子传导率优选为0.1mS/cm以上且10mS/cm以下。离子传导率的上限更优选为5mS/cm，进一步优选为3mS/cm，下限更优选为0.3mS/cm，进一步优选为0.5mS/cm。通过具有该范围的离子传导率，即使为低电压也可使粘接力充分降低。需要说明的是，离子传导率例如可使用Solartron公司制1260频率响应分析仪，通过AC阻抗法而进行测定。The ion conductivity of the ionic liquid is preferably not less than 0.1 mS/cm and not more than 10 mS/cm. The upper limit of the ion conductivity is more preferably 5 mS/cm, still more preferably 3 mS/cm, and the lower limit is more preferably 0.3 mS/cm, still more preferably 0.5 mS/cm. By having the ion conductivity in this range, the adhesive force can be sufficiently reduced even at a low voltage. In addition, ion conductivity can be measured by AC impedance method using the 1260 frequency response analyzer manufactured by Solartron, for example.
关于本实施方式的粘合剂组合物中的离子液体的含量(配合量)，相对于100质量份的聚合物而言，从降低电压施加中的粘接力的观点出发优选为0.5质量份以上，从提高初始粘接力的观点出发优选为30质量份以下。从同样的观点出发更优选为20质量份以下，进一步优选为15质量份以下，尤其优选为10质量份以下，最优选为5质量份以下。另外，更优选为0.6质量份以上，进一步优选为0.8质量份以上，尤其优选为1.0质量份以上，最优选为1.5质量份以上。The content (blend amount) of the ionic liquid in the adhesive composition of the present embodiment is preferably 0.5 parts by mass or more from the viewpoint of reducing the adhesive force during voltage application with respect to 100 parts by mass of the polymer. , from the viewpoint of improving the initial adhesive force, it is preferably 30 parts by mass or less. From the same viewpoint, it is more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, especially preferably 10 parts by mass or less, and most preferably 5 parts by mass or less. Moreover, it is more preferably 0.6 mass parts or more, still more preferably 0.8 mass parts or more, especially preferably 1.0 mass parts or more, most preferably 1.5 mass parts or more.
(其他成分)(other ingredients)
本实施方式的粘合剂组合物可根据需要在不损害本发明的效果的范围内含有1种或2种以上的除聚合物及离子液体以外的成分(以下，有时称为“其他成分”)。以下，对本实施方式的粘合剂组合物中可含有的其他成分进行说明。The adhesive composition of the present embodiment may contain one or more components other than polymers and ionic liquids (hereinafter, sometimes referred to as "other components") as needed within a range that does not impair the effects of the present invention. . Hereinafter, other components that may be contained in the adhesive composition of the present embodiment will be described.
基于控制相对介电常数、离子传导率、电容的目的，本实施方式的粘合剂组合物可以含有离子性添加剂。作为离子性添加剂，例如可使用离子性固体。The adhesive composition of the present embodiment may contain ionic additives for the purpose of controlling relative permittivity, ionic conductivity, and capacitance. As the ionic additive, for example, an ionic solid can be used.
离子性固体是于25℃为固体的离子性物质。离子性固体并无特别限定，例如可使用将在上述离子性液体的说明栏中所例示的阴离子和阳离子组合而获得的离子性物质中为固体的物质。在粘合剂组合物含有离子性固体的情况下，离子性固体的含量相对于100质量份的聚合物而言优选为0.5质量份以上，更优选为1质量份以上，另外，优选为10质量份以下，更优选为5质量份以下，进一步优选为2.5质量份以下。Ionic solids are ionic substances that are solid at 25°C. The ionic solid is not particularly limited, and for example, solid ionic substances obtained by combining the anions and cations exemplified in the description of the above-mentioned ionic liquids can be used. When the adhesive composition contains an ionic solid, the content of the ionic solid is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the polymer. Parts or less, more preferably 5 parts by mass or less, even more preferably 2.5 parts by mass or less.
基于通过使聚合物交联而改善蠕变性、剪切性的目的，本实施方式的粘合剂组合物可根据需要含有交联剂。作为交联剂，例如可列举异氰酸酯系交联剂、环氧系交联剂、三聚氰胺系交联剂、过氧化物系交联剂、脲系交联剂、金属醇盐系交联剂、金属螯合物系交联剂、金属盐系交联剂、噁唑啉系交联剂、氮丙啶系交联剂及胺系交联剂等。作为异氰酸酯系交联剂，例如可列举甲苯二异氰酸酯及亚甲基双苯基异氰酸酯等。作为环氧系交联剂，例如可列举N,N,N’,N’-四缩水甘油基间苯二甲胺、二缩水甘油基苯胺、1,3-双(N,N-二缩水甘油基氨基甲基)环己烷及1,6-己二醇二缩水甘油醚等。关于含有交联剂时的含量，相对于100质量份的聚合物而言，优选为0.1质量份以上，更优选为0.7质量份以上，另外，优选为50质量份以下，更优选为10质量份以下，进一步优选为3质量份以下。需要说明的是，交联剂可单独使用或组合两种以上使用。The adhesive composition of this embodiment may contain a crosslinking agent as needed for the purpose of improving creep properties and shear properties by crosslinking the polymer. Examples of the crosslinking agent include isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal Chelate-based cross-linking agent, metal salt-based cross-linking agent, oxazoline-based cross-linking agent, aziridine-based cross-linking agent, amine-based cross-linking agent, etc. As an isocyanate crosslinking agent, tolylene diisocyanate, methylene bisphenyl isocyanate, etc. are mentioned, for example. Examples of epoxy-based crosslinking agents include N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidyl Aminomethyl) cyclohexane and 1,6-hexanediol diglycidyl ether, etc. The content when the crosslinking agent is contained is preferably 0.1 parts by mass or more, more preferably 0.7 parts by mass or more, and preferably 50 parts by mass or less, more preferably 10 parts by mass with respect to 100 parts by mass of the polymer or less, more preferably 3 parts by mass or less. In addition, a crosslinking agent can be used individually or in combination of 2 or more types.
基于帮助电压施加时的离子液体的移动的目的，本实施方式的粘合剂组合物可根据需要含有聚乙二醇、四乙二醇二甲醚。作为聚乙二醇、四乙二醇二甲醚，可使用具有100～6000的数均分子量的物质。关于含有这些成分时的含量，相对于100质量份的聚合物而言，优选为0.1质量份以上，更优选为0.5质量份以上，进一步优选为1质量份以上，另外，优选为30质量份以下，更优选为20质量份以下，进一步优选为15质量份以下。The adhesive composition of the present embodiment may contain polyethylene glycol and tetraethylene glycol dimethyl ether as necessary for the purpose of assisting the movement of the ionic liquid during voltage application. As polyethylene glycol and tetraethylene glycol dimethyl ether, those having a number average molecular weight of 100 to 6,000 can be used. The content when these components are contained is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and preferably 30 parts by mass or less with respect to 100 parts by mass of the polymer. , more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less.
基于对粘合剂组合物赋予导电性的目的，本实施方式的粘合剂组合物可根据需要含有导电性填料。作为导电性填料，并无特别限定，可使用通常已知或惯用的导电性填料，例如可使用石墨、碳黑、碳纤维、银或铜等金属粉末等。关于含有导电性填料时的含量，相对于100质量份的聚合物而言，优选为0.1质量份以上且200质量份以下。The adhesive composition of this embodiment may contain a conductive filler as needed for the purpose of imparting conductivity to the adhesive composition. The conductive filler is not particularly limited, and generally known or commonly used conductive fillers can be used, for example, graphite, carbon black, carbon fiber, metal powder such as silver or copper, and the like can be used. The content when the conductive filler is contained is preferably 0.1 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polymer.
基于抑制金属被粘物的腐蚀的目的，本实施方式的粘合剂组合物可根据需要含有防腐剂。作为防腐剂，并无特别限定，可使用通常已知或惯用的防腐剂，例如可使用碳二亚胺化合物、吸附型抑制剂、螯合物形成型金属钝化剂等。The adhesive composition of the present embodiment may contain a preservative as necessary for the purpose of suppressing corrosion of the metal adherend. The preservative is not particularly limited, and generally known or customary preservatives can be used, for example, carbodiimide compounds, adsorption inhibitors, chelate-forming metal deactivators, and the like can be used.
作为碳二亚胺化合物，例如可列举1-[3-(二甲基氨基)丙基]-3-乙基碳二亚胺、1-乙基-3-(3-二甲基氨基丙基)碳二亚胺、N,N’-二环己基碳二亚胺、N,N’-二异丙基碳二亚胺、1-乙基-3-叔丁基碳二亚胺、N-环己基-N’-(2-吗啉代乙基)碳二亚胺、N,N’-二叔丁基碳二亚胺、1,3-双(对甲苯基)碳二亚胺、及将这些化合物作为单体的聚碳二亚胺树脂等。这些碳二亚胺化合物可单独使用或组合两种以上使用。关于在本实施方式的粘合剂组合物中含有碳二亚胺化合物时下的含量，相对于100质量份的聚合物而言，优选为0.01质量份以上且10质量份以下。Examples of carbodiimide compounds include 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl ) carbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-tert-butylcarbodiimide, N- Cyclohexyl-N'-(2-morpholinoethyl)carbodiimide, N,N'-di-tert-butylcarbodiimide, 1,3-bis(p-tolyl)carbodiimide, and Polycarbodiimide resins etc. which use these compounds as monomers. These carbodiimide compounds can be used alone or in combination of two or more. The content when the carbodiimide compound is contained in the adhesive composition of the present embodiment is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer.
作为吸附型抑制剂，例如可列举烷基胺、羧酸盐、羧酸衍生物、烷基磷酸盐等。吸附型抑制剂可单独使用或组合两种以上使用。关于在本实施方式的粘合剂组合物中含有烷基胺作为吸附型抑制剂时下的含量，相对于100质量份的聚合物而言，优选为0.01质量份以上且20质量份以下。关于在本实施方式的粘合剂组合物中含有羧酸盐作为吸附型抑制剂时下的含量，相对于100质量份的聚合物而言，优选为0.01质量份以上且10质量份以下。关于在本实施方式的粘合剂组合物中含有羧酸衍生物作为吸附型抑制剂时下的含量，相对于100质量份的聚合物而言，优选为0.01质量份以上且10质量份以下。关于在本实施方式的粘合剂组合物中含有烷基磷酸盐作为吸附型抑制剂时下的含量，相对于100质量份的聚合物而言，优选为0.01质量份以上且10质量份以下。Examples of adsorption inhibitors include alkylamines, carboxylates, carboxylic acid derivatives, and alkylphosphates. The adsorption-type inhibitors can be used alone or in combination of two or more. The content when the alkylamine is contained in the adhesive composition of the present embodiment as an adsorption-type inhibitor is preferably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymer. The content when the carboxylate is contained as the adsorption-type inhibitor in the adhesive composition of the present embodiment is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer. The content when the carboxylic acid derivative is contained in the adhesive composition of the present embodiment as the adsorption inhibitor is preferably 0.01 parts by mass to 10 parts by mass relative to 100 parts by mass of the polymer. The content when the alkyl phosphate is contained as an adsorption-type inhibitor in the adhesive composition of the present embodiment is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer.
作为螯合物形成型金属钝化剂，例如可使用含三唑基的化合物或含苯并三唑基的化合物。这些化合物使铝等金属的表面钝化的作用高，并且即使在粘合成分中含有也不易对粘接性造成影响，因此优选。螯合物形成型金属钝化剂可单独使用或组合两种以上使用。关于在本实施方式的粘合剂组合物中含有螯合物形成型金属钝化剂时下的含量，相对于100质量份的聚合物而言，优选为0.01质量份以上且20质量份以下。As a chelate forming type metal deactivator, for example, a triazole group-containing compound or a benzotriazole group-containing compound can be used. These compounds are highly effective in deactivating the surface of metals such as aluminum, and are less likely to affect the adhesiveness even if they are contained in the adhesive component, so they are preferable. The chelate forming type metal deactivator can be used individually or in combination of 2 or more types. It is preferable that it is 0.01 mass part or more and 20 mass parts or less with respect to 100 mass parts of polymers about content at the time of containing a chelate-formation type metal deactivator in the adhesive composition of this embodiment.
防腐剂的总含量(配合量)相对于100质量份的聚合物而言优选为0.01质量份以上且30质量份以下。The total content (compounding amount) of antiseptics is preferably 0.01 mass parts or more and 30 mass parts or less with respect to 100 mass parts of polymers.
除此之外，本实施方式的粘合剂组合物可以含有填充剂、增塑剂、抗老化剂、抗氧化剂、颜料(染料)、阻燃剂、溶剂、表面活性剂(流平剂)、防锈剂、增粘树脂及防静电剂等各种添加剂。关于这些成分的总含量，只要可发挥本发明的效果则并无特别限制，相对于100质量份的聚合物而言，优选为0.01质量份以上且20质量份以下，更优选为10质量份以下，进一步优选为5质量份以下。In addition, the adhesive composition of this embodiment may contain fillers, plasticizers, anti-aging agents, antioxidants, pigments (dye), flame retardants, solvents, surfactants (leveling agents), Various additives such as antirust agent, tackifying resin and antistatic agent. The total content of these components is not particularly limited as long as the effect of the present invention can be exerted, but is preferably 0.01 to 20 parts by mass, more preferably 10 parts by mass or less, based on 100 parts by mass of the polymer , and more preferably 5 parts by mass or less.
作为填充剂，例如可列举二氧化硅、氧化铁、氧化锌、氧化铝、氧化钛、氧化钡、氧化镁、碳酸钙、碳酸镁、碳酸锌、叶蜡石粘土、高岭粘土及煅烧粘土等。Examples of fillers include silica, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, pyrophyllite clay, kaolin clay, and calcined clay. .
增塑剂可使用通常的树脂组合物等中使用的已知惯用的增塑剂，例如可使用石蜡油、加工处理油等油、液状聚异戊二烯、液状聚丁二烯、液状乙烯-丙烯橡胶等液状橡胶、四氢邻苯二甲酸、壬二酸、苯甲酸、邻苯二甲酸、偏苯三酸、均苯四酸、己二酸、癸二酸、富马酸、马来酸、衣康酸、柠檬酸、及它们的衍生物、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、己二酸二辛酯、己二酸二异壬酯(DINA)及琥珀酸异癸酯等。As the plasticizer, known and commonly used plasticizers used in ordinary resin compositions can be used, for example, oils such as paraffin oil and processing oil, liquid polyisoprene, liquid polybutadiene, liquid ethylene- Liquid rubber such as propylene rubber, tetrahydrophthalic acid, azelaic acid, benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid , itaconic acid, citric acid, and their derivatives, dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate, diisononyl adipate (DINA) and isodecyl succinate, etc.
作为抗老化剂，例如可列举受阻酚系、脂肪族及芳香族的受阻胺系等化合物。Examples of anti-aging agents include compounds such as hindered phenols, aliphatic and aromatic hindered amines, and the like.
作为抗氧化剂，例如可列举丁基羟基甲苯(BHT)及丁基羟基茴香醚(BHA)等。As an antioxidant, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), etc. are mentioned, for example.
作为颜料，例如可列举二氧化钛、氧化锌、群青、铁丹、锌钡白、铅、镉、铁、钴、铝、盐酸盐、硫酸盐等无机颜料；偶氮颜料及铜酞菁颜料等有机颜料等。Examples of pigments include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, ferrite, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate; organic pigments such as azo pigments and copper phthalocyanine pigments; Pigments, etc.
作为防锈剂，例如可列举磷酸锌、丹宁酸衍生物、磷酸酯、碱性磺酸盐及各种防锈颜料等。Examples of the antirust agent include zinc phosphate, tannic acid derivatives, phosphoric acid esters, alkaline sulfonates, and various antirust pigments.
作为增粘剂，例如可列举钛偶联剂及锆偶联剂等。As a thickener, a titanium coupling agent, a zirconium coupling agent, etc. are mentioned, for example.
作为防静电剂，通常可列举季铵盐、或聚乙醇酸、环氧乙烷衍生物等亲水性化合物等。As an antistatic agent, a hydrophilic compound, such as a quaternary ammonium salt, polyglycolic acid, an ethylene oxide derivative, etc. are mentioned normally.
作为增粘树脂，例如除了松香系增粘树脂、萜烯系增粘树脂、酚系增粘树脂、烃系增粘树脂、酮系增粘树脂以外，还可列举聚酰胺系增粘树脂、环氧系增粘树脂及弹性体系增粘树脂等。需要说明的是，增粘树脂可单独使用或组合两种以上使用。As the tackifying resin, for example, in addition to rosin-based tackifying resins, terpene-based tackifying resins, phenol-based tackifying resins, hydrocarbon-based tackifying resins, and ketone-based tackifying resins, polyamide-based tackifying resins, cyclic Oxygen-based tackifying resins and elastic-based tackifying resins, etc. In addition, tackifier resin can be used individually or in combination of 2 or more types.
<不含离子液体的粘合剂层的相对介电常数><Relative dielectric constant of adhesive layer not containing ionic liquid>
就第1实施方式的粘合剂组合物而言，利用由该粘合剂组合物中所含的成分中的离子液体以外的成分形成的组合物(不含离子液体的粘合剂组合物)来形成粘合剂层(不含离子液体的粘合剂层)、并将该粘合剂层在22℃、20％RH的环境下放置3天后的、该粘合剂层在频率100Hz时的相对介电常数为5以上。In the adhesive composition of the first embodiment, a composition composed of components other than the ionic liquid among the components contained in the adhesive composition (an adhesive composition containing no ionic liquid) is used. to form an adhesive layer (an adhesive layer not containing an ionic liquid), and leave the adhesive layer in an environment of 22° C. and 20% RH for 3 days, the frequency of the adhesive layer at a frequency of 100 Hz The relative permittivity is 5 or more.
需要说明的是，上述相对介电常数是指以如下方式测定的相对介电常数。In addition, the said relative permittivity refers to the relative permittivity measured as follows.
首先，通过将不含离子液体的粘合剂组合物均匀地涂布于表面经剥离处理的隔离件的剥离表面上，于130℃进行加热干燥3分钟，从而获得厚度30μm的不含离子液体的粘合剂层。接下来，将所获得的不含离子液体的粘合剂层在22℃、20％RH的环境下放置3天。其后，在以下的条件下测定相对介电常数。First, the ionic liquid-free adhesive composition with a thickness of 30 μm was obtained by uniformly coating the peeled surface of the separator whose surface was peeled off, and heating and drying at 130° C. for 3 minutes. Adhesive layer. Next, the obtained ionic liquid-free pressure-sensitive adhesive layer was left to stand in an environment of 22° C. and 20% RH for 3 days. Thereafter, the relative permittivity was measured under the following conditions.
(相对介电常数的测定条件)(Measurement conditions of relative permittivity)
测定方法：电容法(装置：使用Agilent Technologies 4294APrecisionImpedance Analyzer)Measuring method: capacitive method (device: using Agilent Technologies 4294A Precision Impedance Analyzer)
电极构成：Φ12.1mm、0.5mm厚的铝板Electrode composition: Φ12.1mm, 0.5mm thick aluminum plate
对向电极：60μm厚的铝箔Counter electrode: 60μm thick aluminum foil
测定环境：23±1℃、52±1％RHMeasurement environment: 23±1℃, 52±1%RH
不含离子液体的粘合剂层的相对介电常数与通过包含离子液体的粘合剂组合物形成的粘合剂层中的离子液体的移动容易性具有关联。不含离子液体的粘合剂层的相对介电常数越大，离子液体越容易在通过包含离子液体的粘合剂组合物形成的粘合剂层中移动，因此，在施加电压时粘接力容易降低。The relative permittivity of the ionic liquid-free PSA layer has a relationship with the ease of movement of the ionic liquid in the PSA layer formed from the PSA composition containing the ionic liquid. The larger the relative permittivity of the adhesive layer not containing the ionic liquid, the easier the ionic liquid moves in the adhesive layer formed by the adhesive composition containing the ionic liquid, and therefore, the adhesive force is easier when a voltage is applied. reduce.
就第1实施方式的粘合剂组合物而言，由于将不含离子液体的粘合剂层在22℃、20％RH的环境下放置3天后的、该粘合剂层在频率100Hz时的相对介电常数为5以上，因此即使在低湿度环境下也能够形成通过电压的施加而使粘接力充分降低的粘接。In the adhesive composition of the first embodiment, since the adhesive layer containing no ionic liquid is left for 3 days in an environment of 22° C. and 20% RH, the frequency of the adhesive layer at a frequency of 100 Hz is Since the relative dielectric constant is 5 or more, even in a low-humidity environment, it is possible to form an adhesion in which the adhesive force is sufficiently reduced by the application of a voltage.
不含离子液体的粘合剂层的相对介电常数例如可通过在上述适宜的范围内适当调整粘合剂组合物中的聚合物的成分、离子性添加剂的种类、含量而加以控制。The relative permittivity of the ionic liquid-free pressure-sensitive adhesive layer can be controlled, for example, by appropriately adjusting the polymer components in the pressure-sensitive adhesive composition and the type and content of the ionic additive within the above-mentioned suitable range.
<粘合剂层的离子传导率及粘合剂层与被粘物的界面的每单位面积的电容><Ionic conductivity of the adhesive layer and capacitance per unit area of the interface between the adhesive layer and the adherend>
就第2实施方式的粘合剂组合物而言，利用该粘合剂组合物来形成粘合剂层且将其贴附于由JIS H4000:2014中的A5052P H32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容为0.9μF/cm2以上，该粘合剂层的离子传导率为10μS/m以上。Regarding the adhesive composition of the second embodiment, the adhesive layer is formed using the adhesive composition and attached to an aluminum plate formed of A5052P H32 in JIS H4000:2014, and the adhesive layer is heated at 22°C. After 7 days in an environment of 15% RH, the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 μF/cm2 or more, and the ion conductivity of the adhesive layer is 10 μS/m or more .
粘合剂层的离子传导率与粘合剂层中的离子液体的移动容易性具有关联，离子传导率越大，离子液体越容易移动。另外，粘合剂层与被粘物的界面的每单位面积的电容与离子液体在粘合剂层与被粘物的界面的存在容易性具有关联，该电容越大，离子液体越容易大量存在于粘合剂层与被粘物的界面。The ion conductivity of the adhesive layer is related to the ease of movement of the ionic liquid in the adhesive layer, and the greater the ion conductivity, the easier the movement of the ionic liquid. In addition, the capacitance per unit area of the interface between the adhesive layer and the adherend is related to the ease with which the ionic liquid exists at the interface between the adhesive layer and the adherend. The larger the capacitance, the easier it is for the ionic liquid to exist in a large amount. At the interface between the adhesive layer and the adherend.
就第2实施方式的粘合剂组合物而言，利用该粘合剂组合物来形成粘合剂层且将其贴附于由JIS H4000:2014中的A5052P H32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容为0.9μF/cm2以上，该粘合剂层的离子传导率为10μS/m以上，因此，即使在低湿度环境下也能够形成通过施加电压而使粘接力充分降低的粘接。另外，更优选的是，上述每单位面积的电容为1.2μF/cm2以上，该粘合剂层的离子传导率为20μS/m以上。Regarding the adhesive composition of the second embodiment, the adhesive layer is formed using the adhesive composition and attached to an aluminum plate formed of A5052P H32 in JIS H4000:2014, and the adhesive layer is heated at 22°C. After 7 days in an environment of 15% RH, the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 μF/cm2 or more, and the ion conductivity of the adhesive layer is 10 μS/m or more , Therefore, even in a low-humidity environment, it is possible to form a bond in which the adhesive force is sufficiently reduced by applying a voltage. In addition, it is more preferable that the capacitance per unit area is 1.2 μF/cm2 or more, and the ion conductivity of the pressure-sensitive adhesive layer is 20 μS/m or more.
上述离子传导率及电容例如可通过在上述适宜的范围内适当调整粘合剂组合物中的聚合物的成分、离子液体的种类、含量、离子性添加剂的种类、含量而加以控制。The above-mentioned ionic conductivity and capacitance can be controlled, for example, by appropriately adjusting the polymer components in the adhesive composition, the type and content of the ionic liquid, and the type and content of the ionic additive within the above-mentioned suitable range.
需要说明的是，上述离子传导率及电容是指以如下方式测定的离子传导率及电容。In addition, the said ionic conductivity and capacitance refer to the ionic conductivity and capacitance measured as follows.
(测定用样品(复合体样品)的制造)(Manufacture of measurement samples (composite samples))
首先，在铝蒸镀PET膜100(商品名“Metalumy TS”，TORAY ADVANCED FILM公司制)的铝蒸镀面侧均匀地涂布粘合剂组合物。需要说明的是，此时为了使电极与铝蒸镀面接触，局部设置未涂布粘合剂组合物的部分。接下来，于130℃加热干燥3分钟形成粘合剂层200，获得粘合片样品。First, an adhesive composition was uniformly applied to the aluminum-deposited surface side of an aluminum-deposited PET film 100 (trade name "Metalumy TS", manufactured by TORAY ADVANCED FILM). In this case, in order to bring the electrode into contact with the aluminum vapor-deposited surface, a portion not coated with the adhesive composition was partially provided. Next, the adhesive layer 200 was formed by heating and drying at 130° C. for 3 minutes, and an adhesive sheet sample was obtained.
其后，将所获得的粘合片样品的粘合面贴附于铝板300(A5052PH32(JIS H4000:2014))，获得如图5及6所示的形状的接合体样品400。需要说明的是，图5为侧视图，图6为俯视图。Thereafter, the adhesive surface of the obtained adhesive sheet sample was attached to an aluminum plate 300 (A5052PH32 (JIS H4000:2014)) to obtain a bonded body sample 400 having the shape shown in FIGS. 5 and 6 . It should be noted that FIG. 5 is a side view, and FIG. 6 is a top view.
(电容及离子传导率的测定)(Determination of capacitance and ionic conductivity)
在电容及离子传导率的测定时，使用LCR测量仪(例如，日置电机公司制的IM3533)。For the measurement of capacitance and ion conductivity, an LCR meter (for example, IM3533 manufactured by Hioki Electric Co., Ltd.) is used.
首先，使用LCR测量仪在铝板300与铝蒸镀PET膜100的铝蒸镀面之间施加0.5V的交流电压，使频率从0.5Hz变化至200kHz从而获得科尔-科尔(cole-cole)曲线图。First, an AC voltage of 0.5V is applied between the aluminum plate 300 and the aluminum-evaporated surface of the aluminum-evaporated PET film 100 using an LCR measuring instrument, and the frequency is changed from 0.5Hz to 200kHz to obtain a cole-cole Graph.
接下来，将粘合剂层200的块体视为电阻成分Radh与静电电容成分Cadh的并联电路，将粘合剂层200的界面视为电阻成分Rp与静电电容成分Cdl的并联电路，如图7所示那样地设定接合体样品的等效电路，通过下述式(A)对所获得的科尔-科尔曲线图进行拟合。需要说明的是，电阻成分R0为布线电阻。Next, consider the bulk of the adhesive layer 200 as a parallel circuit of the resistance component Radh and the capacitance component Cadh , and regard the interface of the adhesive layer 200 as a parallel circuit of the resistance component Rp and the capacitance component Cdl As for the circuit, the equivalent circuit of the junction sample was set as shown in FIG. 7 , and the obtained Cole-Cole curve was fitted by the following equation (A). It should be noted that the resistance component R0 is wiring resistance.
[数学式1][mathematical formula 1]
需要说明的是，式(A)中，ω为角频率。It should be noted that, in formula (A), ω is the angular frequency.
通过将所获得的Cdl除以粘合剂层200的粘合面的面积A，能够求出粘合剂层200与铝板300的界面的每单位面积的电容。The capacitance per unit area of the interface between the adhesive layer 200 and the aluminum plate 300 can be obtained by dividing the obtained Cdl by the area A of the adhesive surface of the adhesive layer 200 .
接下来，可使用根据式(A)求出的粘合剂层200的块体的电阻成分Radh，并使用下述式(B)求出粘合剂层的离子传导率σ。Next, using the resistance componentRadh of the bulk of the adhesive layer 200 obtained from the formula (A), the ion conductivity σ of the adhesive layer can be obtained using the following formula (B).
[数学式2][mathematical formula 2]
需要说明的是，式(B)中，l为粘合剂层的厚度，A为粘合剂层200的粘合面的面积。It should be noted that, in formula (B), l is the thickness of the adhesive layer, and A is the area of the adhesive surface of the adhesive layer 200 .
<初始粘接力、由电压施加导致的粘接力降低率><Initial Adhesion Strength, Adhesion Decrease Rate by Voltage Application>
本实施方式的粘合剂组合物的粘接力可通过各种方法进行评价，例如可通过实施例的栏中所记载的180°剥离试验来进行评价。The adhesive force of the adhesive composition of the present embodiment can be evaluated by various methods, for example, it can be evaluated by the 180° peel test described in the column of Examples.
就本实施方式的粘合剂组合物而言，如实施例的栏中记载地形成粘合片并进行180°剥离试验而测定的初始粘接力优选为1.0N/cm以上，更优选为1.5N/cm以上，进一步优选为2.0N/cm以上，尤其优选为2.5N/cm以上，最优选为3.0N/cm以上。初始粘接力为1.0N/cm以上时，与被粘物的粘接充分，被粘物不易剥离、偏移。For the adhesive composition of the present embodiment, the initial adhesive force measured by forming an adhesive sheet as described in the column of Examples and performing a 180° peel test is preferably 1.0 N/cm or more, and more preferably 1.5 N/cm. N/cm or more, more preferably 2.0 N/cm or more, especially preferably 2.5 N/cm or more, most preferably 3.0 N/cm or more. When the initial adhesive force is 1.0 N/cm or more, the adhesion to the adherend is sufficient, and the adherend is less likely to be peeled off or shifted.
另外，就本实施方式的粘合剂组合物而言，优选如实施例的栏中记载地形成粘合片，在规定的温度及湿度的环境下放置规定时间，在施加10V的电压30秒钟后一边施加10V的电压一边利用180°剥离试验测定的粘接力相对于初始粘接力而言足够小。In addition, for the adhesive composition of the present embodiment, it is preferable to form an adhesive sheet as described in the column of Examples, leave it for a predetermined time in an environment with a predetermined temperature and humidity, and apply a voltage of 10V for 30 seconds. The adhesive force measured by the 180° peel test while applying a voltage of 10 V was sufficiently small compared to the initial adhesive force.
即，根据通过上述方法测定的粘接力(在下式(C)中仅表述为“电压施加中的粘接力”)、及初始粘接力，通过下式(C)求出的粘接力降低率优选为60％以上，更优选为70％以上，进一步优选为80％以上。上述规定的温度及湿度以及时间优选为22℃20％RH3天，更优选为22℃15％RH7天。That is, the adhesive force obtained by the following formula (C) from the adhesive force measured by the above method (expressed simply as "adhesive force during voltage application" in the following formula (C)) and the initial adhesive force The reduction rate is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more. The above-mentioned predetermined temperature, humidity and time are preferably 22° C. 20% RH for 3 days, and more preferably 22° C. 15% RH for 7 days.
粘接力降低率(％)＝{1－(电压施加中的粘接力/初始粘接力)}×100(C)Adhesion reduction rate (%)={1-(adhesion during voltage application/initial adhesion)}×100(C)
需要说明的是，电剥离时的施加电压及电压施加时间并不限定于上述的电压和时间，只要能够进行粘合片的剥离则并无特别限定。以下示出它们的合适范围。In addition, the applied voltage and voltage application time at the time of electro-peeling are not limited to the said voltage and time, As long as the adhesive sheet can be peeled off, it will not specifically limit. These suitable ranges are shown below.
施加电压优选为1V以上，更优选为3V以上，进一步优选为6V以上。另外，优选为100V以下，更优选为50V以下，进一步优选为30V以下，尤其优选为15V以下。The applied voltage is preferably 1V or higher, more preferably 3V or higher, and still more preferably 6V or higher. In addition, it is preferably 100 V or less, more preferably 50 V or less, still more preferably 30 V or less, and particularly preferably 15 V or less.
电压施加时间优选为60秒以下，更优选为40秒以下，进一步优选为20秒以下，尤其优选为10秒以下。在这种情况下，作业性优异。另外，施加时间越短越好，但通常为1秒以上。The voltage application time is preferably 60 seconds or less, more preferably 40 seconds or less, further preferably 20 seconds or less, and particularly preferably 10 seconds or less. In this case, workability is excellent. In addition, the shorter the application time, the better, but it is usually 1 second or more.
<粘合剂组合物的制造方法><Manufacturing method of adhesive composition>
就本发明的粘合剂组合物而言，并无特别限制，可通过适当搅拌聚合物、离子液体、添加剂及根据需要配合的交联剂、聚乙二醇、导电性填料等进行混合来制造。The adhesive composition of the present invention is not particularly limited, and it can be produced by appropriately stirring polymers, ionic liquids, additives, and optionally blended crosslinking agents, polyethylene glycol, conductive fillers, etc. .
[粘合片][adhesive sheet]
(粘合片的构成)(composition of adhesive sheet)
本实施方式的粘合片只要具有至少一层由上述本实施方式的粘合剂组合物形成的粘合剂层(以下也称为“电剥离型粘合剂层”)，则并无特别限制。本实施方式的粘合片可以具有除电剥离型粘合剂层以外的、不含离子液体的粘合剂层(以下，有时称为“其他粘合剂层”)。本实施方式的粘合片除上述以外，还可以具有基材、导电层、通电用基材、中间层及底涂层等。本实施方式的粘合片例如可以是卷绕为卷状的形态、片状的形态。需要说明的是，“粘合片”中也包含“粘合带”的含义。即，本实施方式的粘合片可以为具有带状形态的粘合带。The PSA sheet of this embodiment is not particularly limited as long as it has at least one PSA layer (hereinafter also referred to as "electropeelable PSA layer") formed from the above-mentioned PSA composition of this embodiment. . The pressure-sensitive adhesive sheet according to the present embodiment may have a pressure-sensitive adhesive layer (hereinafter, may be referred to as "another pressure-sensitive adhesive layer") not containing an ionic liquid other than the electro-peelable pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet of the present embodiment may have a base material, a conductive layer, a base material for conduction, an intermediate layer, an undercoat layer, and the like in addition to the above. The pressure-sensitive adhesive sheet of the present embodiment may be, for example, a roll-shaped form or a sheet-like form. In addition, "adhesive tape" is also included in "adhesive sheet". That is, the pressure-sensitive adhesive sheet of the present embodiment may be a pressure-sensitive adhesive tape having a belt-like form.
本实施方式的粘合片可以为不具有基材而仅包含电剥离型粘合剂层、即不含基材层(无基材)的双面粘合片。本实施方式的粘合片可以为具有基材、且该基材的双面为粘合剂层(电剥离型粘合剂层、或其他粘合剂层)的双面粘合片。另外，本实施方式的粘合片可以为具有基材、且仅该基材的单面为粘合剂层(电剥离型粘合剂层、或其他粘合剂层)的单面粘合片。需要说明的是，本实施方式的粘合片可以具有用于保护粘合剂层表面的隔离件(剥离衬垫)，但该隔离件并不包括在本实施方式的粘合片中。The pressure-sensitive adhesive sheet of this embodiment may be a double-sided pressure-sensitive adhesive sheet including only an electro-peelable pressure-sensitive adhesive layer without a base material, that is, without a base material layer (no base material). The pressure-sensitive adhesive sheet of this embodiment may be a double-sided pressure-sensitive adhesive sheet having a substrate, and both sides of the substrate are pressure-sensitive adhesive layers (electropeelable pressure-sensitive adhesive layers or other pressure-sensitive adhesive layers). In addition, the PSA sheet according to the present embodiment may be a single-sided PSA sheet having a substrate and only one side of the substrate is an PSA layer (electropeelable PSA layer or other PSA layer). . In addition, although the adhesive sheet of this embodiment may have the separator (release liner) for protecting the surface of an adhesive layer, this separator is not included in the adhesive sheet of this embodiment.
作为本实施方式的粘合片的结构，并无特别限制，可优选地列举图1中所示的粘合片X1、图2中示出层叠结构的粘合片X2、图3中示出层叠结构的粘合片X3。粘合片X1是仅包含电剥离型粘合剂层1的无基材的双面粘合片。粘合片X2是具有粘合剂层2、通电用基材5(基材3及导电层4)、电剥离型粘合剂层1的层结构的带有基材的双面粘合片。粘合片X3是具有粘合剂层2、通电用基材5(基材3及导电层4)、电剥离型粘合剂层1、通电用基材5(基材3及导电层4)、粘合剂层2的层结构的带有基材的双面粘合片。在图2及3中所示的粘合片X2及X3的通电用基材5中，基材3不是必须的，可以仅为导电层4。另外，在图2的粘合片X2中，可以为未设置粘合剂层2的单面粘合片。The structure of the PSA sheet according to this embodiment is not particularly limited, and preferred examples include PSA sheet X1 shown in FIG. 1 , PSA sheet X2 with a laminated structure shown in FIG. Structural adhesive sheet X3. The PSA sheet X1 is a substrate-less double-sided PSA sheet including only the electro-peelable PSA layer 1 . The pressure-sensitive adhesive sheet X2 is a double-sided pressure-sensitive adhesive sheet with a base material having a layer structure of the pressure-sensitive adhesive layer 2 , the base material 5 for conduction (the base material 3 and the conductive layer 4 ), and the electric peelable pressure-sensitive adhesive layer 1 . The adhesive sheet X3 has an adhesive layer 2, a base material 5 for conducting electricity (a base material 3 and a conductive layer 4), an electrically peelable adhesive layer 1, and a base material 5 for conducting electricity (a base material 3 and a conductive layer 4). 1. A double-sided adhesive sheet with a substrate having a layer structure of the adhesive layer 2 . In the current-carrying base material 5 of the adhesive sheets X2 and X3 shown in FIGS. 2 and 3 , the base material 3 is not essential, and only the conductive layer 4 may be used. In addition, in the adhesive sheet X2 of FIG. 2, the single-sided adhesive sheet which does not provide the adhesive layer 2 may be sufficient.
作为基材3，并无特别限定，可列举纸等纸系基材、布、无纺布等纤维系基材、由各种塑料(聚乙烯、聚丙烯等聚烯烃系树脂、聚对苯二甲酸乙二醇酯等聚酯系树脂、聚甲基丙烯酸甲酯等丙烯酸系树脂等)制成的膜、片材等塑料系基材、它们的层叠体等。基材可以具有单层的形态，另外，也可以具有多层的形态。需要说明的是，可以根据需要对基材实施背面处理、防静电处理、底涂处理等各种处理。The substrate 3 is not particularly limited, and examples include paper-based substrates such as paper, fiber-based substrates such as cloth and non-woven fabrics, and materials made of various plastics (polyolefin-based resins such as polyethylene and polypropylene, polyethylene terephthalate, etc.). Polyester-based resins such as ethylene glycol formate, acrylic resins such as polymethyl methacrylate, etc.), plastic-based substrates such as films and sheets, laminates thereof, and the like. The substrate may have a single-layer form, or may have a multi-layer form. In addition, various treatments, such as a back surface treatment, an antistatic treatment, and a primer treatment, can be given to a base material as needed.
作为导电层4，只要为具有导电性的层，则并无特别限定，可以为金属(例如铝、镁、铜、铁、锡、金等)箔、金属板(例如铝、镁、铜、铁、锡、银等)等金属系基材、导电性聚合物等，另外，可以为设置于基材3上的金属蒸镀膜等。The conductive layer 4 is not particularly limited as long as it is a conductive layer, and may be a metal (such as aluminum, magnesium, copper, iron, tin, gold, etc.) foil, a metal plate (such as aluminum, magnesium, copper, iron, etc.) , tin, silver, etc.), a conductive polymer, etc., and a metal vapor-deposited film or the like provided on the base material 3 may be used.
作为通电用基材5，只要为具有导电层的(通电的)基材，则并无特别限定，可列举在基材的表面形成有金属层的基材等，例如可列举利用镀覆法、化学蒸镀法、溅射等方法在上述中所例示的基材的表面形成有金属层的基材。作为金属层，可列举上述中所例示的金属、金属板、导电性聚合物等。As the base material 5 for conduction, it is not particularly limited as long as it is a base material having a conductive layer (conduction of current), and examples include base materials in which a metal layer is formed on the surface of the base material. A base material in which a metal layer is formed on the surface of the base material exemplified above by methods such as chemical vapor deposition and sputtering. Examples of the metal layer include metals, metal plates, conductive polymers, and the like exemplified above.
在粘合片X1中，双面的被粘物优选为具有金属被粘面的被粘物。在粘合片X2中，电剥离型粘合剂层1侧的被粘物优选为具有金属被粘面的被粘物。In the PSA sheet X1, the double-sided adherend is preferably an adherend having a metal adherend surface. In the adhesive sheet X2, the adherend on the side of the electro-peelable adhesive layer 1 is preferably an adherend having a metal adherend surface.
作为金属被粘面，可列举具有导电性、且例如由以铝、铜、铁、镁、锡、金、银及铅等作为主成分的金属形成的面，其中，优选为由含有铝的金属形成的面。作为具有金属被粘面的被粘物，例如可列举由以铝、铜、铁、镁、锡、金、银及铅等作为主成分的金属形成的片材、部件及板等。作为除具有金属被粘面的被粘物以外的被粘物，并无特别限定，可列举纸、布及无纺布等纤维片材、各种塑料的膜或片材等。Examples of the metal to-be-adhered surface include conductive surfaces made of metals mainly composed of aluminum, copper, iron, magnesium, tin, gold, silver, and lead, among which metals containing aluminum are preferable. formed face. Examples of the adherend having a metal adherend surface include sheets, members, and plates made of metals mainly composed of aluminum, copper, iron, magnesium, tin, gold, silver, lead, and the like. The adherend other than the adherend having a metal adherend surface is not particularly limited, and examples thereof include fibrous sheets such as paper, cloth, and nonwoven fabric, films or sheets of various plastics, and the like.
从初始粘接力的观点出发，电剥离型粘合剂层1的厚度优选为1μm以上且1000μm以下。电剥离型粘合剂层1的厚度的上限更优选为500μm，进一步优选为100μm，尤其优选为30μm，下限更优选为3μm，进一步优选为5μm，尤其优选为8μm。需要说明的是，在粘合片为仅包含1个电剥离型粘合剂层的无基材的双面粘合片(图1所示的粘合片X1)的情况下，电剥离型粘合剂层的厚度为粘合片的厚度。From the viewpoint of initial adhesive force, the thickness of the electro-peelable adhesive layer 1 is preferably 1 μm or more and 1000 μm or less. The upper limit of the thickness of the electro-peelable adhesive layer 1 is more preferably 500 μm, still more preferably 100 μm, especially preferably 30 μm, and the lower limit is more preferably 3 μm, still more preferably 5 μm, and especially preferably 8 μm. It should be noted that, when the adhesive sheet is a double-sided adhesive sheet without a base material (adhesive sheet X1 shown in FIG. The thickness of the mixture layer is the thickness of the adhesive sheet.
从粘接力的观点出发，粘合剂层2的厚度优选为1μm以上且2000μm以下。粘合剂层2的厚度的上限更优选为1000μm，进一步优选为500μm，尤其优选为100μm，下限更优选为3μm，进一步优选为5μm，尤其优选为8μm。From the viewpoint of adhesive force, the thickness of the adhesive layer 2 is preferably not less than 1 μm and not more than 2000 μm. The upper limit of the thickness of the adhesive layer 2 is more preferably 1000 μm, still more preferably 500 μm, especially preferably 100 μm, and the lower limit is more preferably 3 μm, still more preferably 5 μm, especially preferably 8 μm.
基材3的厚度优选为10μm以上且1000μm以下。厚度的上限更优选为500μm，进一步优选为300μm，尤其优选为100μm，下限更优选为12μm，进一步优选为25μm。The thickness of the substrate 3 is preferably not less than 10 μm and not more than 1000 μm. The upper limit of the thickness is more preferably 500 μm, still more preferably 300 μm, especially preferably 100 μm, and the lower limit is more preferably 12 μm, still more preferably 25 μm.
导电层4的厚度优选为0.001μm以上且1000μm以下。厚度的上限更优选为500μm，进一步优选为300μm，进一步优选为50μm，进一步优选为10μm，下限更优选为0.01μm，更优选为0.03μm，进一步优选为0.05μm。The thickness of the conductive layer 4 is preferably not less than 0.001 μm and not more than 1000 μm. The upper limit of the thickness is more preferably 500 μm, still more preferably 300 μm, still more preferably 50 μm, still more preferably 10 μm, and the lower limit is more preferably 0.01 μm, more preferably 0.03 μm, still more preferably 0.05 μm.
通电用基材5的厚度优选为10μm以上且1000μm以下。厚度的上限更优选为500μm，进一步优选为300μm，尤其优选为100μm，下限更优选为12μm，进一步优选为25μm。The thickness of the current-carrying base material 5 is preferably not less than 10 μm and not more than 1000 μm. The upper limit of the thickness is more preferably 500 μm, still more preferably 300 μm, especially preferably 100 μm, and the lower limit is more preferably 12 μm, still more preferably 25 μm.
本实施方式的粘合片的电剥离型粘合剂层、及其他粘合剂层的表面可以利用隔离件(剥离衬垫)进行保护。作为隔离件，并无特别限定，可列举纸或塑料膜等基材(衬垫基材)的表面经有机硅处理而得的剥离衬垫、利用聚烯烃系树脂对纸或塑料膜等基材(衬垫基材)的表面进行层压而成的剥离衬垫等。隔离件的厚度并无特别限定，优选为10μm以上且100μm以下。The surface of the electro-peelable pressure-sensitive adhesive layer and other pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheet according to this embodiment can be protected with a separator (release liner). The separator is not particularly limited, and examples include release liners obtained by treating the surface of substrates such as paper or plastic films (liner substrates) with silicone, and substrates such as paper or plastic films coated with polyolefin-based resins. A release liner, etc., in which the surface of the (lining substrate) is laminated. The thickness of the separator is not particularly limited, but is preferably not less than 10 μm and not more than 100 μm.
本实施方式的粘合片的厚度优选为20μm以上且3000μm以下。厚度的上限更优选为1000μm，进一步优选为300μm，尤其优选为200μm，下限更优选为30μm，进一步优选为50μm。The thickness of the pressure-sensitive adhesive sheet according to the present embodiment is preferably not less than 20 μm and not more than 3000 μm. The upper limit of the thickness is more preferably 1000 μm, still more preferably 300 μm, especially preferably 200 μm, and the lower limit is more preferably 30 μm, still more preferably 50 μm.
尤其是在为图2所示的粘合片X2的情况下，粘合片的厚度优选为50μm以上且2000μm以下。厚度的上限更优选为1000μm，进一步优选为200μm，下限更优选为80μm，进一步优选为100μm。In particular, in the case of the PSA sheet X2 shown in FIG. 2 , the thickness of the PSA sheet is preferably not less than 50 μm and not more than 2000 μm. The upper limit of the thickness is more preferably 1000 μm, still more preferably 200 μm, and the lower limit is more preferably 80 μm, still more preferably 100 μm.
尤其是在为图3所示的粘合片X3的情况下，粘合片的厚度优选为100μm以上且3000μm以下。厚度的上限更优选为1000μm，进一步优选为300μm，下限更优选为150μm，进一步优选为200μm。In particular, in the case of the PSA sheet X3 shown in FIG. 3 , the thickness of the PSA sheet is preferably not less than 100 μm and not more than 3000 μm. The upper limit of the thickness is more preferably 1000 μm, still more preferably 300 μm, and the lower limit is more preferably 150 μm, still more preferably 200 μm.
(粘合片的制造方法)(Manufacturing method of adhesive sheet)
本实施方式的粘合片的制造方法可使用已知或惯用的制造方法。就本实施方式的粘合片中的电剥离型粘合剂层而言，可列举将使本实施方式的粘合剂组合物根据需要溶解于溶剂中所得的溶液涂布于隔离件、并进行干燥和/或固化的方法等。另外，就其他粘合剂层而言，可列举将使不含离子液体及添加剂的粘合剂组合物根据需要溶解于溶剂中所得的溶液涂布于隔离件、并进行干燥和/或固化的方法等。需要说明的是，溶剂及隔离件可使用上述中所列举的物质。A known or usual production method can be used for the production method of the PSA sheet of this embodiment. As the electro-peelable adhesive layer in the adhesive sheet of the present embodiment, a solution obtained by dissolving the adhesive composition of the present embodiment in a solvent is applied to a separator, and then Methods of drying and/or curing, etc. In addition, as another adhesive layer, a solution obtained by dissolving an adhesive composition containing no ionic liquid and additives in a solvent as needed is applied to a separator and dried and/or cured. method etc. In addition, the solvent and spacer can use the thing listed above.
在涂布时，可使用惯用的涂布机(例如凹版辊式涂布机、逆向辊式涂布机、接触辊式涂布机、浸渍辊式涂布机、棒式涂布机、刮刀涂布机、喷雾辊式涂布机等)。When coating, a conventional coating machine (such as gravure roll coater, reverse roll coater, contact roll coater, dip roll coater, rod coater, knife coater, etc.) can be used. cloth machine, spray roll coater, etc.).
通过上述方法，能够制造电剥离型粘合剂层及其他粘合剂层，通过适当地在基材、导电层、通电用基材层叠电剥离型粘合剂层及其他粘合剂层，能够制造本实施方式的粘合片。需要说明的是，可以代替隔离件而使用基材、导电层、通电用基材来涂布粘合剂组合物而制造粘合片。By the method described above, an electric peelable adhesive layer and other adhesive layers can be produced, and by appropriately laminating an electric peelable adhesive layer and other adhesive layers on a base material, a conductive layer, and a base material for conduction, it is possible to The adhesive sheet of this embodiment is manufactured. In addition, instead of a spacer, an adhesive composition can be coated using a base material, a conductive layer, and a base material for conduction, and an adhesive sheet can be manufactured.
(粘合片的电剥离方法)(Electric peeling method of adhesive sheet)
本实施方式的粘合片从被粘物的剥离可通过如下方式进行：通过向电剥离型粘合剂层施加电压，从而在电剥离型粘合剂层的厚度方向上产生电位差。例如，在粘合片X1中双面为具有金属被粘面的被粘物的情况下，可通过对双面的金属被粘面通电，对电剥离型粘合剂层施加电压而进行剥离。在粘合片X2中电剥离型粘合剂层侧为具有金属被粘面的被粘物的情况下，可通过对该导电性被粘物和导电层4通电，对电剥离型粘合剂层施加电压而进行剥离。在粘合片X3的情况下，可通过对双面的导电层4通电，对电剥离型粘合剂层施加电压而进行剥离。通电优选为使端子与粘合片的一端及另一端连接从而对电剥离型粘合剂层整体施加电压的方式进行。需要说明的是，在被粘物具有金属被粘面的情况下，上述一端及另一端可以为具有金属被粘面的被粘物的一部分。需要说明的是，在剥离时，可以在金属被粘面与电剥离型粘合剂层的界面处添加水后再施加电压。The peeling of the pressure-sensitive adhesive sheet according to the present embodiment from the adherend can be performed by applying a voltage to the electro-peelable pressure-sensitive adhesive layer to generate a potential difference in the thickness direction of the electro-peelable pressure-sensitive adhesive layer. For example, when both sides of the PSA sheet X1 are adherends having metal to-be-adhered surfaces, the metal to-be-adhered surfaces on both sides are energized to apply a voltage to the electro-peelable pressure-sensitive adhesive layer to perform peeling. In the adhesive sheet X2, in the case where the side of the electric peelable adhesive layer is an adherend having a metal adherend, the electric peelable adhesive can be bonded by passing electricity to the conductive adherend and the conductive layer 4. The layer is peeled off by applying a voltage. In the case of the pressure-sensitive adhesive sheet X3, it can be peeled by applying a voltage to the electro-peelable pressure-sensitive adhesive layer by energizing the conductive layers 4 on both sides. Conduction of electricity is preferably performed by connecting terminals to one end and the other end of the pressure-sensitive adhesive sheet to apply a voltage to the entire electro-peelable pressure-sensitive adhesive layer. In addition, when the to-be-adhered body has a metal to-be-adhered surface, the said one end and the other end may be a part of the to-be-adhered body which has a metal to-be-adhered surface. It should be noted that, at the time of peeling, voltage may be applied after adding water to the interface between the metal to-be-adhered surface and the electric peeling adhesive layer.
(粘合片的用途)(Application of adhesive sheet)
作为以往的再剥离技术，存在通过紫外线(UV)照射使其固化而剥离的粘合剂层、通过热而剥离的粘合剂层。关于使用了这种粘合剂层的粘合片，在难以进行紫外线(UV)照射的情况下、作为被粘物的构件因热而产生损伤的情况下等无法使用。具备上述电剥离型粘合剂层的本实施方式的粘合片由于不使用紫外线或热，因此不会使作为被粘物的构件受损，通过施加电压即可容易地剥离。因此，本实施方式的粘合片适于智能手机、移动电话、笔记本电脑、摄像机、数码相机等移动终端中使用的二次电池(例如锂离子电池组)在壳体上的固定的用途。Conventional re-peeling techniques include an adhesive layer that is cured and peeled by ultraviolet (UV) irradiation, and an adhesive layer that is peeled by heat. A PSA sheet using such a PSA layer cannot be used when ultraviolet (UV) irradiation is difficult or when a member to be adhered is damaged by heat. Since the pressure-sensitive adhesive sheet according to the present embodiment including the above-mentioned electro-peelable pressure-sensitive adhesive layer does not use ultraviolet light or heat, it can be easily peeled off by applying a voltage without damaging a member as an adherend. Therefore, the pressure-sensitive adhesive sheet of this embodiment is suitable for fixing secondary batteries (for example, lithium ion battery packs) used in mobile terminals such as smartphones, mobile phones, notebook computers, video cameras, and digital cameras to casings.
另外，关于作为利用本实施方式的粘合片进行接合的对象的刚性构件，例如可列举半导体晶片用途的硅基板、LED用的蓝宝石基板、SiC基板及金属基底基板、显示器用的TFT基板及滤光器基板、以及有机EL面板用的基底基板。关于作为利用双面粘合片进行接合的对象的脆弱构件，例如可列举化合物半导体基板等半导体基板、MEMS器件用途的硅基板、无源矩阵基板、智能手机用的表面覆盖玻璃、在该覆盖玻璃上附设触控面板传感器而成的OGS(One Glass Solution，单片玻璃解决方案)基板、以倍半硅氧烷等作为主成分的有机基板及有机无机混合基板、柔性显示器用的柔性玻璃基板以及石墨烯片材。In addition, examples of rigid members to be bonded using the adhesive sheet of this embodiment include silicon substrates for semiconductor wafers, sapphire substrates for LEDs, SiC substrates, and metal base substrates, TFT substrates for displays, and filter substrates. Optical device substrates, and base substrates for organic EL panels. As for fragile members to be bonded with a double-sided adhesive sheet, for example, semiconductor substrates such as compound semiconductor substrates, silicon substrates for MEMS devices, passive matrix substrates, surface cover glasses for smartphones, etc. OGS (One Glass Solution) substrates with touch panel sensors attached to them, organic substrates and organic-inorganic hybrid substrates with silsesquioxane as the main component, flexible glass substrates for flexible displays, and Graphene sheets.
[接合体][Joint body]
本实施方式的接合体具有层叠结构部，该层叠结构部包含：具有金属被粘面的被粘物、及电剥离型粘合剂层接合于金属被粘面的粘合片。作为具有金属被粘面的被粘物，例如可列举由以铝、铜、铁、镁、锡、金、银及铅等作为主成分的金属形成的被粘物，其中，优选为包含铝的金属。The bonded body according to the present embodiment has a laminated structure portion including an adherend having a metal adherend surface, and an adhesive sheet in which an electro-peelable adhesive layer is bonded to the metal adherend surface. As an adherend having a metal to-be-adhered surface, for example, an adherend formed of a metal mainly composed of aluminum, copper, iron, magnesium, tin, gold, silver, lead, etc., among them, those containing aluminum are preferred. Metal.
作为本实施方式的接合体，例如可列举：为粘合片X1、且在电剥离型粘合剂层1的双面具备具有金属被粘面的被粘物的接合体；为粘合片X2、且在电剥离型粘合剂层1侧具备具有金属被粘面的被粘物、在粘合剂层2侧具备被粘物的接合体；为粘合片X3、且在粘合剂层2的双面具备被粘物的接合体；等等。Examples of the bonded body of this embodiment include: a bonded body that is the PSA sheet X1 and has adherends having metal adherend surfaces on both sides of the electro-peelable pressure-sensitive adhesive layer 1 ; and the PSA sheet X2. , and an adherend having a metal adherend surface on the side of the electro-peelable adhesive layer 1, and a bonded body having an adherend on the side of the adhesive layer 2; it is an adhesive sheet X3, and the adhesive layer The two sides of 2 have a bonded body of an adherend; and so on.
实施例Example
以下，通过实施例更具体地说明本发明，但本发明并不受这些实施例限定。下述重均分子量是通过凝胶渗透色谱(GPC)法利用上述记载的方法进行测定而得的。Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples. The following weight average molecular weight is measured by the method described above by the gel permeation chromatography (GPC) method.
[实施例1-1～1-8、比较例1-1～1-5][Examples 1-1 to 1-8, Comparative Examples 1-1 to 1-5]
<聚合物溶液的制作><Preparation of polymer solution>
(丙烯酸系聚合物1溶液的制作)(Preparation of Acrylic Polymer 1 Solution)
将作为单体成分的丙烯酸正丁酯(BA)：95质量份、丙烯酸(AA)：5质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度40质量％的丙烯酸系聚合物1溶液。N-butyl acrylate (BA) as a monomer component: 95 parts by mass, acrylic acid (AA): 5 parts by mass, and ethyl acetate as a polymerization solvent: 150 parts by mass were put into a separable flask, and nitrogen gas was introduced , while stirring for 1 hour. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Then, ethyl acetate was added, and the acrylic polymer 1 solution of 40 mass % of solid content concentration was obtained.
(丙烯酸系聚合物2溶液的制作)(Preparation of acrylic polymer 2 solution)
将作为单体成分的丙烯酸正丁酯(BA)：90质量份、丙烯酸4-羟基丁酯(4HBA)：10质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度30质量％的丙烯酸系聚合物2溶液。Put n-butyl acrylate (BA): 90 parts by mass, 4-hydroxybutyl acrylate (4HBA): 10 parts by mass, and ethyl acetate as a polymerization solvent: 150 parts by mass as monomer components into a separable flask , stirring for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Then, ethyl acetate was added, and the acrylic polymer 2 solution of 30 mass % of solid content concentration was obtained.
(丙烯酸系聚合物3溶液的制作)(Preparation of acrylic polymer 3 solution)
将作为单体成分的丙烯酸正丁酯(BA)：67质量份、丙烯酸2-甲氧基乙酯(MEA)：30质量份、丙烯酸(AA)：3质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度40质量％的丙烯酸系聚合物3溶液。n-butyl acrylate (BA): 67 parts by mass, 2-methoxyethyl acrylate (MEA): 30 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate as a polymerization solvent Esters: 150 parts by mass were charged into a separable flask, and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Then, ethyl acetate was added, and the acrylic polymer 3 solution of 40 mass % of solid content concentration was obtained.
(丙烯酸系聚合物4溶液的制作)(Preparation of Acrylic Polymer 4 Solution)
将作为单体成分的丙烯酸正丁酯(BA)：67质量份、甲基丙烯酸甲酯(MMA)：33质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度40质量％的丙烯酸系聚合物4溶液。Put n-butyl acrylate (BA): 67 parts by mass, methyl methacrylate (MMA): 33 parts by mass, and ethyl acetate as a polymerization solvent: 150 parts by mass as monomer components into a separable flask , and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer 4 solution having a solid content concentration of 40% by mass.
(丙烯酸系聚合物5溶液的制作)(Preparation of Acrylic Polymer 5 Solution)
将作为单体成分的丙烯酸正丁酯(BA)：87质量份、丙烯酸4-羟基丁酯(4HBA)：10质量份、丙烯酸(AA)：3质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度30质量％的丙烯酸系聚合物5溶液。n-butyl acrylate (BA): 87 parts by mass, 4-hydroxybutyl acrylate (4HBA): 10 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate as a polymerization solvent: 150 parts by mass were charged into a separable flask, and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer 5 solution having a solid content concentration of 30% by mass.
<粘合剂组合物的制作><Preparation of Adhesive Composition>
添加上文中所获得的丙烯酸系聚合物溶液、如下所示的聚合物、交联剂、离子液体、添加剂并进行搅拌、混合，获得实施例1-1～1-8及比较例1-1～1-5的粘合剂组合物。在表1中示出各成分的配合量。Add the acrylic polymer solution obtained above, the following polymers, crosslinking agents, ionic liquids, additives, stir and mix, and obtain Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-5 adhesive compositions. Table 1 shows the compounding quantity of each component.
需要说明的是，表1中的各成分的值是指质量份。另外，聚合物的配合量(质量份)表示聚合物溶液中的固体成分的配合量(质量份)。In addition, the value of each component in Table 1 means a mass part. In addition, the compounding quantity (mass part) of a polymer shows the compounding quantity (mass part) of the solid content in a polymer solution.
表1中的聚合物、交联剂、离子液体及添加剂的简称如下所述。The abbreviations of the polymers, crosslinking agents, ionic liquids and additives in Table 1 are as follows.
(聚合物)(polymer)
VYLON UR-V8700：氨基甲酸酯改性聚酯树脂，商品名“VYLON UR-V8700”，东洋纺公司制VYLON UR-V8700: Urethane-modified polyester resin, trade name "VYLON UR-V8700", manufactured by Toyobo Co., Ltd.
VYLON BX1001：聚酯树脂，商品名“VYLON BX1001”，东洋纺公司制VYLON BX1001: Polyester resin, trade name "VYLON BX1001", manufactured by Toyobo Co., Ltd.
SOMAREX 530：阴离子性聚丙烯酰胺聚合物(离子性聚合物)，商品名“SOMAREX530”，SOMAR公司制SOMAREX 530: Anionic polyacrylamide polymer (ionic polymer), trade name "SOMAREX 530", manufactured by SOMAR Corporation
(离子液体)(ionic liquid)
AS-110：阳离子：1-乙基-3-甲基咪唑鎓阳离子，阴离子：双(氟磺酰基)酰亚胺阴离子，商品名“ELEXCEL AS-110”，第一工业制药公司制AS-110: cation: 1-ethyl-3-methylimidazolium cation, anion: bis(fluorosulfonyl)imide anion, trade name "ELEXCEL AS-110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.
(交联剂)(crosslinking agent)
V-05：聚碳二亚胺树脂，商品名“CARBODILITE V-05”，日清纺化学公司制V-05: Polycarbodiimide resin, trade name "CARBODILITE V-05", manufactured by Nisshinbo Chemical Co., Ltd.
TAKENATE D110：三羟甲基丙烷苯二甲撑二异氰酸酯，商品名“TAKENATE D110N”，三井化学公司制TAKENATE D110: Trimethylolpropane xylylene diisocyanate, trade name "TAKENATE D110N", manufactured by Mitsui Chemicals Corporation
(添加剂)(additive)
EMI-nitrate：1-乙基-3-甲基咪唑鎓硝酸盐，东京化成工业公司制EMI-nitrate: 1-ethyl-3-methylimidazolium nitrate, manufactured by Tokyo Chemical Industry Co., Ltd.
Zn-nitrate：硝酸锌六水合物，和光纯药工业公司制Zn-nitrate: Zinc nitrate hexahydrate, manufactured by Wako Pure Chemical Industries, Ltd.
BTC-5B：钛酸钡BTC-5B: barium titanate
No.27776：碳黑No.27776: Carbon black
<不含离子液体的粘合剂层的相对介电常数的测定><Measurement of Relative Permittivity of Adhesive Layer Not Containing Ionic Liquid>
除未添加离子液体这一点以外，与上述实施例1-1～1-8、比较例1-1～1-5同样地操作，对材料进行搅拌、混合，将所获得的不含离子液体的粘合剂组合物使用涂敷器以成为均匀厚度的方式涂布于表面经剥离处理的聚对苯二甲酸乙二醇酯隔离件(商品名“MRF38”，三菱树脂公司制)的剥离处理面上。接下来，于130℃进行3分钟的加热干燥，获得厚度30μm的不含离子液体的粘合剂层。接下来，将所获得的不含离子液体的粘合剂层在22℃、20％RH的环境下放置3天后，依据JIS K 6911，在下述条件下测定该粘合剂层在频率100kHz时的相对介电常数。Except for the fact that no ionic liquid was added, the same operation was performed as in the above-mentioned Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-5, and the materials were stirred and mixed, and the obtained ionic liquid-free The adhesive composition was applied to the release-treated surface of a polyethylene terephthalate spacer (trade name "MRF38", manufactured by Mitsubishi Plastics Corporation) with a release-treated surface using an applicator so as to have a uniform thickness. superior. Next, heat drying was performed at 130° C. for 3 minutes to obtain an ionic liquid-free pressure-sensitive adhesive layer having a thickness of 30 μm. Next, after leaving the obtained adhesive layer containing no ionic liquid in an environment of 22° C. and 20% RH for 3 days, according to JIS K 6911, the frequency of the adhesive layer at a frequency of 100 kHz was measured under the following conditions: Relative permittivity.
(测定条件)(measurement conditions)
测定方法：电容法(装置：使用Agilent Technologies 4294APrecisionImpedance Analyzer)Measuring method: capacitive method (device: using Agilent Technologies 4294A Precision Impedance Analyzer)
电极构成：Φ12.1mm、0.5mm厚的铝板Electrode composition: Φ12.1mm, 0.5mm thick aluminum plate
对向电极：3oz铜板Counter electrode: 3oz copper plate
测定环境：23±1℃、52±1％RHMeasurement environment: 23±1℃, 52±1%RH
<电剥离型粘合剂层的含水率的测定><Measurement of Moisture Content of Electropeelable Adhesive Layer>
使用各例的粘合剂组合物，将与上述同样地操作而获得的电剥离型粘合剂层在22℃20％RH的环境下放置3天后，利用卡尔费休水分气化-电量滴定法(JIS K 0113:2005)测定该粘合剂层的含水率。具体而言，使用平沼产业公司制的平沼微量水分测定装置AQ-2100，测定通过200℃、30分钟的加热气化而产生的水分量，将其相对于加热前的试样重量而言的比例作为含水率。即，通过下式求出含水率。需要说明的是，表1中的“-”是指未测定。Using the adhesive composition of each example, the electro-peelable adhesive layer obtained in the same manner as above was left to stand in an environment of 22°C and 20%RH for 3 days, and then was measured by the Karl Fischer moisture vaporization-coulometric titration method. (JIS K 0113:2005) measures the moisture content of the adhesive layer. Specifically, using the Hiranuma Sangyo Co., Ltd. Hiranuma Trace Moisture Meter AQ-2100, the amount of moisture generated by heating and vaporizing at 200°C for 30 minutes was measured, and its ratio to the weight of the sample before heating was measured. as moisture content. That is, the water content was obtained by the following formula. In addition, "-" in Table 1 means not measured.
含水率(％)＝(卡尔费休测定水分量/测定前的试样总重量)×100Moisture content (%) = (moisture content measured by Karl Fischer / total weight of the sample before measurement) × 100
<评价><Evaluation>
(初始粘接力)(initial adhesion)
将各例的粘合剂组合物使用涂敷器以成为均匀的厚度的方式涂布于表面经剥离处理的聚对苯二甲酸乙二醇酯隔离件(商品名“MRF38”、三菱树脂公司制)的剥离处理面上。接下来，于130℃进行3分钟的加热干燥，获得厚度30μm的电剥离型粘合剂层(粘合片)。The adhesive composition of each example was applied to a polyethylene terephthalate spacer (trade name "MRF38", manufactured by Mitsubishi Plastics Co., Ltd.) on the surface with a uniform thickness using an applicator. ) on the stripped surface. Next, it heat-dried at 130 degreeC for 3 minutes, and obtained the electro-peelable adhesive layer (adhesive sheet) of thickness 30 micrometers.
接下来，将所获得的电剥离型粘合剂层(粘合片)制成10mm×80mm尺寸的片材，在无隔离件的面贴合作为基材的带有金属层的膜(商品名“BR1075”，TORAY ADVANCED FILM公司制，厚度25μm，尺寸10mm×100mm)的金属层面，制成带有基材的单面粘合片。剥离带有基材的单面粘合片的隔离件，将作为被粘物的铝板(A5052P H32(JIS H4000:2014))以该粘合片的一端从被粘物伸出2mm左右的方式贴附于剥离的面，利用2kg的辊往返按压一次，在23℃的环境下放置30分钟，获得包含铝板6/电剥离型粘合剂层(粘合片)1’/带有金属层的膜(通电用基材)5’的接合体。将该接合体的概要示于图4。其后，利用剥离试验机(商品名“变角度剥离试验机YSP”，旭精工公司制)，以图4中的箭头方向进行剥离，测定180°剥离试验(拉伸速度：300mm/min，剥离温度23℃)中的粘接力。将测定结果示于表1。Next, the obtained electro-peelable adhesive layer (adhesive sheet) was made into a sheet of 10 mm x 80 mm in size, and a film with a metal layer (trade name "BR1075", manufactured by TORAY ADVANCED FILM Co., Ltd., has a thickness of 25 μm and a size of 10 mm×100 mm) as a single-sided adhesive sheet with a substrate. Peel off the separator of the single-sided adhesive sheet with the base material, and attach the aluminum plate (A5052P H32 (JIS H4000:2014)) as the adherend so that one end of the adhesive sheet protrudes about 2 mm from the adherend Attach to the peeled surface, press back and forth once with a 2kg roller, and place it in an environment of 23°C for 30 minutes to obtain a film comprising aluminum plate 6/electric peeling adhesive layer (adhesive sheet) 1'/metal layer (Base material for conduction) 5' bonded body. The outline of this joint body is shown in FIG. 4 . Thereafter, using a peel tester (trade name "Variable Angle Peel Tester YSP", manufactured by Asahi Seiko Co., Ltd.), peel in the direction of the arrow in Figure 4, and measure the 180° peel test (tensile speed: 300mm/min, peel Adhesive force in temperature 23°C). The measurement results are shown in Table 1.
(电压施加中的粘接力)(adhesion force during voltage application)
利用2kg的辊往返按压一次后，在22℃、20％RH的环境下放置3天，并且在剥离前分别在接合体的图4中的α和β处安装直流电流机的负极及正极的电极，以10V的电压施加电压30秒钟，在该状态下一边施加电压一边剥离，除这些方面以外，与上述测定初始粘接力同样地操作，测定电压施加中的粘接力。将测定结果示于表1。After pressing back and forth with a 2kg roller once, place it in an environment of 22°C and 20%RH for 3 days, and install the negative and positive electrodes of the DC current machine on the α and β positions in Figure 4 of the bonded body before peeling off. , a voltage of 10 V was applied for 30 seconds, and the voltage was applied while peeling in this state. Except for these points, the adhesive force during voltage application was measured in the same manner as the above-mentioned measurement of the initial adhesive force. The measurement results are shown in Table 1.
(粘接力降低率)(adhesion reduction rate)
使用利用上述方法测定的初始粘接力及电压施加中的粘接力，利用下述式(C)求出由电压施加导致的粘接力降低率。将结果示于表1。Using the initial adhesive force measured by the above-mentioned method and the adhesive force during voltage application, the adhesive force decrease rate by voltage application was calculated|required by the following formula (C). The results are shown in Table 1.
粘接力降低率(％)＝{1－(电压施加中的粘接力/初始粘接力)}×100(C)[表1]Adhesion reduction rate (%)={1-(adhesion during voltage application/initial adhesion)}×100(C)[Table 1]
就利用由粘合剂组合物所含的成分中的离子液体以外的成分形成的组合物来形成粘合剂层、并将该粘合剂层在22℃、20％RH的环境下放置3天后的、该粘合剂层在频率100Hz时的相对介电常数为5以上的实施例1-1～1-8的粘合剂组合物而言，由电压施加导致的粘接力降低率均大。After forming an adhesive layer using a composition composed of components other than the ionic liquid among the components contained in the adhesive composition, and leaving the adhesive layer in an environment of 22° C. and 20% RH for 3 days For the adhesive compositions of Examples 1-1 to 1-8 in which the relative dielectric constant of the adhesive layer at a frequency of 100 Hz was 5 or more, the rate of decrease in adhesive force due to voltage application was large. .
[实施例2-1～2-11、比较例2-1～2-3][Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-3]
<聚合物溶液的制作><Preparation of polymer solution>
(丙烯酸系聚合物6溶液的制作)(Preparation of acrylic polymer 6 solution)
将作为单体成分的丙烯酸正丁酯(BA)：90质量份、丙烯酸(AA)：10质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度40质量％的丙烯酸系聚合物6溶液。N-butyl acrylate (BA) as a monomer component: 90 parts by mass, acrylic acid (AA): 10 parts by mass, and ethyl acetate as a polymerization solvent: 150 parts by mass were put into a separable flask, and nitrogen gas was introduced , while stirring for 1 hour. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer 6 solution having a solid content concentration of 40% by mass.
(丙烯酸系聚合物7溶液的制作)(Preparation of Acrylic Polymer 7 Solution)
将作为单体成分的丙烯酸正丁酯(BA)：90质量份、丙烯酸4-羟基丁酯(4HBA)：7质量份、丙烯酸(AA)：3质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度30质量％的丙烯酸系聚合物7溶液。N-butyl acrylate (BA): 90 parts by mass, 4-hydroxybutyl acrylate (4HBA): 7 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate as a polymerization solvent: 150 parts by mass were charged into a separable flask, and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer 7 solution having a solid content concentration of 30% by mass.
(丙烯酸系聚合物8溶液的制作)(Preparation of acrylic polymer 8 solution)
将作为单体成分的丙烯酸正丁酯(BA)：94质量份、丙烯酸4-羟基丁酯(4HBA)：3质量份、丙烯酸(AA)：3质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度30质量％的丙烯酸系聚合物8溶液。N-butyl acrylate (BA): 94 parts by mass, 4-hydroxybutyl acrylate (4HBA): 3 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate as a polymerization solvent: 150 parts by mass were charged into a separable flask, and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer 8 solution having a solid content concentration of 30% by mass.
(丙烯酸系聚合物9溶液的制作)(Preparation of Acrylic Polymer 9 Solution)
将作为单体成分的丙烯酸正丁酯(BA)：77质量份、丙烯酸2-甲氧基乙酯(MEA)：20质量份、丙烯酸(AA)：3质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度40质量％的丙烯酸系聚合物9溶液。n-butyl acrylate (BA): 77 parts by mass, 2-methoxyethyl acrylate (MEA): 20 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate as a polymerization solvent Esters: 150 parts by mass were charged into a separable flask, and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer 9 solution having a solid content concentration of 40% by mass.
(丙烯酸系聚合物10溶液的制作)(Preparation of acrylic polymer 10 solution)
将作为单体成分的丙烯酸正丁酯(BA)：87质量份、丙烯酸2-甲氧基乙酯(MEA)：10质量份、丙烯酸(AA)：3质量份、及作为聚合溶剂的乙酸乙酯：150质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度40质量％的丙烯酸系聚合物10溶液。n-butyl acrylate (BA) as a monomer component: 87 parts by mass, 2-methoxyethyl acrylate (MEA): 10 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate as a polymerization solvent Esters: 150 parts by mass were charged into a separable flask, and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Then, ethyl acetate was added, and the acrylic polymer 10 solution of 40 mass % of solid content concentration was obtained.
<粘合剂组合物的制作><Preparation of Adhesive Composition>
添加上文中获得的丙烯酸系聚合物溶液、上述聚合物、交联剂、离子液体、添加剂、或下述离子液体、防腐剂并进行搅拌、混合，获得实施例2-1～2-11及比较例2-1～2-3的粘合剂组合物。表2中示出各成分的配合量。Add the acrylic polymer solution obtained above, the above-mentioned polymer, cross-linking agent, ionic liquid, additive, or the following ionic liquid, preservative and stir and mix to obtain Examples 2-1 to 2-11 and comparison Adhesive compositions of Examples 2-1 to 2-3. Table 2 shows the compounding quantity of each component.
(离子液体)(ionic liquid)
1-己基-吡啶鎓-双(三氟磺酰基)酰亚胺1-Hexyl-pyridinium-bis(trifluorosulfonyl)imide
(防腐剂，添加剂，交联剂)(preservatives, additives, crosslinking agents)
Irgamet30：N,N-双(2-乙基己基)-1,2,4-三唑-1-甲胺，商品名“Irgamet30”，BASF公司制Irgamet30: N,N-bis(2-ethylhexyl)-1,2,4-triazole-1-methylamine, trade name "Irgamet30", manufactured by BASF Corporation
IrgacorDSSG：癸二酸二钠，商品名“IrgacorDSSG”、BASF公司制IrgacorDSSG: disodium sebacate, trade name "IrgacorDSSG", manufactured by BASF Corporation
AminO：咪唑啉衍生物，商品名“Amin O”，BASF公司制AminO: imidazoline derivative, trade name "Amin O", manufactured by BASF Corporation
PEG400：聚乙二醇，商品名“PEG400”，东京化成工业公司制Coronate L：异氰酸酯化合物，商品名“Coronate L”，东曹公司制PEG400: Polyethylene glycol, trade name "PEG400", manufactured by Tokyo Chemical Industry Co., Ltd. Coronate L: Isocyanate compound, trade name "Coronate L", manufactured by Tosoh Corporation
<粘合剂层的离子传导率及每单位面积的电容的测定><Measurement of Ionic Conductivity and Capacitance per Unit Area of Adhesive Layer>
使用各例的粘合剂组合物以如下方式制作测定用样品(复合体样品)，并通过以下的方法求出粘接界面的电容及粘合剂层的离子传导率。将结果示于表2。Using the adhesive composition of each example, samples for measurement (composite samples) were produced as follows, and the capacitance of the adhesive interface and the ion conductivity of the adhesive layer were determined by the following method. The results are shown in Table 2.
(测定用样品(复合体样品)的制造)(Manufacture of measurement samples (composite samples))
首先，在铝蒸镀PET膜100(商品名“Metalumy TS”，TORAY ADVANCED FILM公司制)的铝蒸镀面侧均匀地涂布粘合剂组合物。需要说明的是，此时为了使电极与铝蒸镀面接触，局部设置未涂布粘合剂组合物的部分。接下来，于130℃进行加热干燥3分钟而形成粘合剂层200，获得粘合片样品。First, an adhesive composition was uniformly applied to the aluminum-deposited surface side of an aluminum-deposited PET film 100 (trade name "Metalumy TS", manufactured by TORAY ADVANCED FILM). In this case, in order to bring the electrode into contact with the aluminum vapor-deposited surface, a portion not coated with the adhesive composition was partially provided. Next, it heat-dried at 130 degreeC for 3 minutes, the adhesive layer 200 was formed, and the adhesive sheet sample was obtained.
其后，将所获得的粘合片样品的粘合面贴附于铝板300(A5052PH32(JIS H4000:2014))，获得如图5及6所示的形状的接合体样品400。需要说明的是，图5为侧视图，图6为俯视图。Thereafter, the adhesive surface of the obtained adhesive sheet sample was attached to an aluminum plate 300 (A5052PH32 (JIS H4000:2014)) to obtain a bonded body sample 400 having the shape shown in FIGS. 5 and 6 . It should be noted that FIG. 5 is a side view, and FIG. 6 is a top view.
(电容及离子传导率的测定)(Determination of capacitance and ionic conductivity)
在电容及离子传导率的测定中，使用LCR测量仪(例如，日置电机公司制的IM3533)。For the measurement of capacitance and ion conductivity, an LCR meter (for example, IM3533 manufactured by Hioki Electric Co., Ltd.) is used.
首先，使用LCR测量仪在铝板300与铝蒸镀PET膜100的铝蒸镀面之间施加0.5V的交流电压，使频率从0.5Hz变化至200kHz从而获得科尔-科尔曲线图。First, an AC voltage of 0.5 V was applied between the aluminum plate 300 and the aluminum-deposited surface of the aluminum-deposited PET film 100 using an LCR measuring instrument, and the frequency was changed from 0.5 Hz to 200 kHz to obtain a Cole-Cole curve.
接下来，将粘合剂层200的块体视为电阻成分Radh与静电电容成分Cadh的并联电路，将粘合剂层200的界面视为电阻成分Rp与静电电容成分Cdl的并联电路，如图7所示那样地设定接合体样品的等效电路，通过下述式(A)对所获得的科尔-科尔曲线图进行拟合。需要说明的是，电阻成分R0为布线电阻。Next, consider the bulk of the adhesive layer 200 as a parallel circuit of the resistance component Radh and the capacitance component Cadh , and regard the interface of the adhesive layer 200 as a parallel circuit of the resistance component Rp and the capacitance component Cdl As for the circuit, the equivalent circuit of the junction sample was set as shown in FIG. 7 , and the obtained Cole-Cole curve was fitted by the following equation (A). It should be noted that the resistance component R0 is wiring resistance.
[数学式3][mathematical formula 3]
需要说明的是，式(A)中，ω为角频率。It should be noted that, in formula (A), ω is the angular frequency.
通过将所获得的Cdl除以粘合剂层200的粘合面的面积A，从而求出粘合剂层200与铝板300的界面的每单位面积的电容。The capacitance per unit area of the interface between the adhesive layer 200 and the aluminum plate 300 was obtained by dividing the obtained Cdl by the area A of the adhesive surface of the adhesive layer 200 .
接下来，使用根据式(A)求出的粘合剂层200的块体的电阻成分Radh，并使用下述式(B)求出粘合剂层的离子传导率σ。Next, using the resistance componentRadh of the bulk body of the adhesive layer 200 obtained from the formula (A), the ion conductivity σ of the adhesive layer was obtained using the following formula (B).
[数学式4][mathematical formula 4]
需要说明的是，式(B)中，l为粘合剂层的厚度，A为粘合剂层200的粘合面的面积。It should be noted that, in formula (B), l is the thickness of the adhesive layer, and A is the area of the adhesive surface of the adhesive layer 200 .
<评价><Evaluation>
(初始粘接力)(initial adhesion)
针对各例的粘合剂组合物，使用铝蒸镀PET膜(商品名“Metalumy TS”，TORAYADVANCED FILM公司制)作为基材，在铝蒸镀面形成粘合剂层，除此以外，与实施例1-1～1-8及比较例1-1～1-5同样地操作，测定初始粘接力。将测定结果示于表2。Regarding the adhesive composition of each example, an aluminum vapor-deposited PET film (trade name "Metalumy TS", manufactured by TORAYADVANCED FILM Co., Ltd.) was used as a base material, and an adhesive layer was formed on the aluminum vapor-deposited surface. In the same manner as Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-5, the initial adhesive force was measured. The measurement results are shown in Table 2.
(在22℃、20％RH的环境下保存3天后的、电压施加中的粘接力)(Adhesive strength during voltage application after storage at 22°C, 20%RH for 3 days)
利用2kg的辊往返按压一次后，在22℃、20％RH的环境下放置3天，并且在剥离前分别在接合体的图4中的α和β处安装直流电流机的负极及正极的电极，以10V的电压施加电压30秒钟，在该状态下一边施加电压一边剥离，除这些方面以外，与上述测定初始粘接力同样地操作，测定电压施加中的粘接力，根据以下的基准来评价电剥离性。将测定结果示于表2。After pressing back and forth with a 2kg roller once, place it in an environment of 22°C and 20%RH for 3 days, and install the negative and positive electrodes of the DC current machine on the α and β positions in Figure 4 of the bonded body before peeling off. , a voltage of 10V was applied for 30 seconds, and the voltage was applied while peeling off in this state. Except for these points, the same operation as the above-mentioned measurement of the initial adhesive force was performed, and the adhesive force during voltage application was measured according to the following criteria To evaluate the electrical peelability. The measurement results are shown in Table 2.
○：粘接力降低率为60％以上。◯: Adhesive strength reduction rate is 60% or more.
×：粘接力降低率小于60％。×: Adhesive strength reduction rate is less than 60%.
(在22℃、15％RH的环境下保存7天后的、电压施加中的粘接力)(Adhesive force during voltage application after storage at 22°C, 15%RH for 7 days)
利用2kg的辊往返按压一次后，在22℃、15％RH的环境下放置7天，并且在剥离前分别在接合体的图4中的α和β处安装直流电流机的负极及正极的电极，以10V的电压施加电压10秒钟，在该状态下一边施加电压一边剥离，除这些方面以外，与上述测定初始粘接力同样地操作，测定电压施加中的粘接力。将测定结果示于表2。After pressing back and forth with a 2kg roller once, place it in an environment of 22°C and 15% RH for 7 days, and install the negative and positive electrodes of the DC current machine on the α and β positions in Figure 4 of the bonded body before peeling off. , a voltage of 10 V was applied for 10 seconds, and the voltage was applied while peeling in this state. Except for these points, the adhesive force during voltage application was measured in the same manner as the above-mentioned measurement of the initial adhesive force. The measurement results are shown in Table 2.
(粘接力降低率)(adhesion reduction rate)
使用通过上述方法测定的初始粘接力及在22℃、15％RH的环境下保存7天后的电压施加中的粘接力，利用下述式(C)求出由电压施加导致的粘接力降低率。Using the initial adhesive force measured by the above method and the adhesive force during voltage application after storage at 22°C and 15% RH for 7 days, the adhesive force due to voltage application was obtained by the following formula (C) reduce rate.
将结果示于表2。The results are shown in Table 2.
粘接力降低率(％)＝{1－(电压施加中的粘接力/初始粘接力)}×100(C)[表2]Adhesion reduction rate (%) = {1 - (adhesion during voltage application/initial adhesion)} x 100 (C) [Table 2]
关于利用粘合剂组合物来形成粘合剂层且将其贴附于由JIS H4000:2014中的A5052P H32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容为0.9μF/cm2以上、该粘合剂层的离子传导率为10μS/m以上的实施例2-1～2-11的粘合剂组合物，由电压施加导致的粘接力降低率均大。About using the adhesive composition to form the adhesive layer, attaching it to the aluminum plate formed by A5052P H32 in JIS H4000:2014, and leaving it for 7 days under the environment of 22 ° C and 15% RH, the adhesive The adhesive of Examples 2-1 to 2-11 in which the capacitance per unit area of the interface between the mixture layer and the aluminum plate is 0.9 μF/cm2 or more, and the ion conductivity of the adhesive layer is 10 μS/m or more All of the compositions had a large rate of decrease in adhesive force by voltage application.
[实施例3-1～3-5][Embodiments 3-1 to 3-5]
<聚合物溶液的制作><Preparation of polymer solution>
(丙烯酸系聚合物11溶液的制作)(Preparation of acrylic polymer 11 solution)
将作为单体成分的丙烯酸2-甲氧基乙酯(MEA)：95质量份、丙烯酸4-羟基丁酯(4HBA)：5质量份投入至可分离式烧瓶中，一边导入氮气，一边搅拌1小时。如此去除聚合体系内的氧后，添加作为聚合引发剂的2,2’-偶氮双异丁腈(AIBN)：0.2质量份，升温至63℃并反应6小时。其后，添加乙酸乙酯，获得固体成分浓度30质量％的丙烯酸系聚合物11溶液。2-Methoxyethyl acrylate (MEA): 95 parts by mass and 4-hydroxybutyl acrylate (4HBA): 5 parts by mass as monomer components were put into a separable flask and stirred for 1 Hour. After removing oxygen in the polymerization system in this way, 2,2'-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the mixture was heated to 63°C and reacted for 6 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer 11 solution having a solid content concentration of 30% by mass.
<粘合剂组合物的制作><Preparation of Adhesive Composition>
添加上文中获得的丙烯酸系聚合物溶液、上述聚合物、交联剂、离子液体、添加剂、或下述添加剂并进行搅拌、混合，获得实施例3-1～3-5的粘合剂组合物。表3中示出各成分的配合量。The acrylic polymer solution obtained above, the above polymer, crosslinking agent, ionic liquid, additives, or the following additives were added and stirred and mixed to obtain the adhesive compositions of Examples 3-1 to 3-5 . Table 3 shows the compounding quantity of each component.
(添加剂)(additive)
·EMIM-MeSO3：离子性添加剂，咪唑鎓盐，东京化成工业公司制。· EMIM-MeSO3 : ionic additive, imidazolium salt, manufactured by Tokyo Chemical Industry Co., Ltd.
·EPOMIN200：聚乙烯亚胺，日本触媒制。· EPOMIN200: polyethyleneimine, manufactured by Nippon Shokubai.
<粘合剂层的离子传导率及每单位面积的电容的测定及评价><Measurement and Evaluation of Ion Conductivity and Capacitance per Unit Area of Adhesive Layer>
与实施例2-1～2-11及比较例2-1～2-3同样地操作，测定初始粘接力、在22℃20％RH的环境下保存3天后的电压施加中的粘接力及粘接力降低率、在22℃15％RH的环境下保存7天后的电压施加中的粘接力及粘接力降低率。另外，与实施例2-1～2-11及比较例2-1～2-3同样地操作，制作测定用样品(复合体样品)，求出粘接界面的电容及粘合剂层的离子传导率。将结果示于表3。In the same manner as in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-3, the initial adhesive force and the adhesive force during voltage application after storage at 22°C and 20%RH for 3 days were measured. and the rate of decrease in the adhesive force, and the rate of decrease in the adhesive force and the rate of decrease in the adhesive force during voltage application after storage at 22° C. and 15% RH for 7 days. In addition, in the same manner as in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-3, samples for measurement (composite samples) were produced, and the capacitance at the bonding interface and the ion density of the adhesive layer were obtained. Conductivity. The results are shown in Table 3.
[表3][table 3]
关于利用粘合剂组合物来形成粘合剂层且将其贴附于由JIS H4000:2014中的A5052P H32形成的铝板、并在22℃、15％RH的环境下放置7天后的、该粘合剂层与该铝板的界面的每单位面积的电容为0.9μF/cm2以上、该粘合剂层的离子传导率为10μS/m以上的实施例3-1～3-5的粘合剂组合物，由电压施加导致的粘接力降低率均大。About using the adhesive composition to form the adhesive layer, attaching it to the aluminum plate formed by A5052P H32 in JIS H4000:2014, and leaving it for 7 days under the environment of 22 ° C and 15% RH, the adhesive The adhesives of Examples 3-1 to 3-5 in which the capacitance per unit area of the interface between the mixture layer and the aluminum plate is 0.9 μF/cm2 or more, and the ion conductivity of the adhesive layer is 10 μS/m or more All of the compositions had a large rate of decrease in adhesive force by voltage application.
以上对本发明的优选的实施方式进行了说明，但本发明并不限定于上述实施方式，可在不脱离本发明范围的范围内对上述实施方式实施各种变形及替换。Preferred embodiments of the present invention have been described above, but the present invention is not limited to the above-described embodiments, and various modifications and substitutions can be made to the above-described embodiments without departing from the scope of the present invention.
需要说明的是，本申请基于2018年9月3日提出的日本专利申请(特愿2018-164545)、2019年3月28日提出的日本专利申请(特愿2019-065065)及2019年8月29日提出的日本专利申请(特愿2019-157325)，其内容在本申请中作为参照而援引。It should be noted that this application is based on the Japanese patent application filed on September 3, 2018 (Japanese Patent Application No. 2018-164545), the Japanese patent application filed on March 28, 2019 (Japanese Patent Application No. 2019-065065), and the The content of the Japanese patent application (Japanese Patent Application No. 2019-157325) filed on the 29th is incorporated by reference in this application.
附图标记说明Explanation of reference signs
X1、X2、X3粘合片X1, X2, X3 adhesive sheet
1 电剥离型粘合剂层1 Electro-peelable adhesive layer
2 粘合剂层2 adhesive layers
3 基材3 Substrate
4 导电层4 conductive layer
5 通电用基材5 Substrate for electrification
100铝蒸镀PET膜100 aluminum evaporated PET film
200 粘合剂层200 adhesive layers
300 铝板300 aluminum sheet
400 接合体样品400 conjugation samples
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| JP2018-164545 | 2018-09-03 | ||
| JP2018164545 | 2018-09-03 | ||
| JP2019-065065 | 2019-03-28 | ||
| JP2019065065 | 2019-03-28 | ||
| JP2019157325AJP7651255B2 (en) | 2018-09-03 | 2019-08-29 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and bonded body |
| JP2019-157325 | 2019-08-29 | ||
| CN201980057389.4ACN112639045B (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet, and joined body |
| PCT/JP2019/034143WO2020050169A1 (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet and bonded body |
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| CN201980057389.4ADivisionCN112639045B (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet, and joined body |
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| CN116536005Atrue CN116536005A (en) | 2023-08-04 |
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| CN202310680383.0APendingCN116536005A (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet, and joined body |
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