TWI674304B - Pressure sensitive adhesive and pressure sensitive adhesive sheet - Google Patents
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Abstract
一種黏接劑，含有(甲基)丙烯酸系聚合物，該(甲基)丙烯酸系聚合物，包含： 相對於全部構成單元為35質量%以上的來自具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元；及 相對於全部構成單元為0.1質量%以上35質量%以下之來自具有羥基的單體的構成單元； 且玻璃化轉變溫度為-55℃~-10℃。An adhesive containing a (meth) acrylic polymer, the (meth) acrylic polymer comprising: a branched alkane having 5 to 9 carbon atoms with respect to a total of 35% by mass of all constituent units The constituent unit of the alkyl methacrylate group; and the constituent unit derived from the monomer having a hydroxyl group in an amount of 0.1% by mass or more and 35% by mass or less with respect to all the structural units; and the glass transition temperature is -55 ° C to -10 ° C .
Description
本發明之一實施型態係關於黏接劑及黏接片。One embodiment of the present invention relates to an adhesive and an adhesive sheet.
觸控面板現使用於行動電話及行動資訊終端等的電子機器的輸入裝置。一般來說，觸控面板是由玻璃基板、透明導電膜、設計膜等的多數構件構成。這些構件係介隔以黏接劑形成的黏接劑層疊層在一起。Touch panels are currently used as input devices for electronic devices such as mobile phones and mobile information terminals. Generally, a touch panel is composed of many members such as a glass substrate, a transparent conductive film, and a design film. These components are laminated together via an adhesive formed with an adhesive.
伴隨著近年來觸控面板的薄型化，黏接劑層也要求要薄型化。但是，將黏接劑層薄型化的話，因觸控面板內部的靜電容量會變大，會變得容易發生誤作動。為此，近年來尋求相對電容率(relative permittivity)低的黏接劑層以使得即使將黏接劑層薄型化也不會使靜電容量變大。With the reduction in thickness of touch panels in recent years, the thickness of the adhesive layer is also required to be reduced. However, if the thickness of the adhesive layer is reduced, the electrostatic capacity inside the touch panel becomes large, and malfunctions are liable to occur. For this reason, in recent years, an adhesive layer having a low relative permittivity has been sought so that even if the adhesive layer is thinned, the electrostatic capacity does not increase.
又，行動用的電子機器受到掉落等的衝擊會有構成觸控面板的構件剝落之虞。為此尋求高黏接力黏接劑層於作為觸控面板使用的黏接劑層以使即便受到衝擊也不易剝落。Furthermore, the electronic device for mobile use may be subject to peeling due to impact such as dropping. For this reason, a high-adhesion adhesive layer is sought for an adhesive layer used as a touch panel so that it is not easy to peel off even if it is impacted.
日本特開2013-129789號公報、日本特開2013-194170號公報，以及日本特開2013-32500 號公報中揭示一種黏接劑，含有將於酯末端具有分支鏈烷基的 (甲基)丙烯酸烷酯，與具有環狀結構的單體或於酯末端具有直鏈烷基的 (甲基)丙烯酸烷酯，以各自規定的比率聚合成的(甲基)丙烯酸系聚合物。黏接劑可滿足黏接性能，且可以實現低相對電容率的黏接劑層。Japanese Patent Laid-Open No. 2013-129789, Japanese Patent Laid-Open No. 2013-194170, and Japanese Patent Laid-Open No. 2013-32500 disclose an adhesive containing (meth) acrylic acid having a branched alkyl group at an ester terminal Alkyl ester is a (meth) acrylic polymer polymerized with a monomer having a cyclic structure or a (meth) acrylic acid alkyl ester having a linear alkyl group at the end of the ester at a predetermined ratio. The adhesive can satisfy the adhesive performance, and can realize an adhesive layer with a low relative permittivity.
［發明所欲解決之問題］[Problems to be solved by the invention]
觸控面板的製造中，疊層構成觸控面板的構件(以下稱為「觸控面板構成構件」)時，各構件的貼合多使用以切割刀刃切割出符合於前述構件大小的黏接片(有黏接劑層的片料)。切割黏接片時，黏接劑層附著於切割刀刃的話，黏接劑層會變形，將該黏接片使用於觸控面板構成構件之貼合的情況，會有黏接劑層超出觸控面板構成構件的情形。為此，尋求一種黏接劑層，於黏接片的切割時不會附著於切割刀片，能輕易地將黏接片加工(以下也稱為「加工性」)。 但是，以往對於具有低相對電容率的黏接劑層之黏接片尚未探討到加工性。In the manufacture of a touch panel, when the members constituting the touch panel are laminated (hereinafter referred to as "touch panel constituent members"), the bonding of each member is often used to cut an adhesive sheet in accordance with the size of the aforementioned member with a cutting blade. (Sheet with adhesive layer). When the adhesive sheet is cut, if the adhesive layer is attached to the cutting blade, the adhesive layer will be deformed. When the adhesive sheet is used for bonding the components of a touch panel, the adhesive layer may exceed the touch. The case where the panel constitutes a member. For this reason, an adhesive layer is sought, which does not adhere to the cutting blade during cutting of the adhesive sheet, and can easily process the adhesive sheet (hereinafter also referred to as "workability"). However, in the past, the workability has not been discussed for an adhesive sheet having an adhesive layer with a low relative permittivity.
本發明之一實施型態是鑑於上述情況。 即，本發明之一實施型態之課題為提供：形成相對電容率低、黏著力高、加工性優良的黏接劑層的黏接劑，及具有相對電容率低、黏著力高、加工性優良的黏接劑層的黏接片。 ［解決問題之方式］One embodiment of the present invention is based on the above situation. That is, the subject of one embodiment of the present invention is to provide an adhesive that forms an adhesive layer with low relative permittivity, high adhesion, and excellent processability, and has low relative permittivity, high adhesion, and processability. Adhesive sheet with excellent adhesive layer. [Method of Solving Problems]
解決上述問題的手段包含有以下態樣。 ＜1＞一種黏接劑，含有(甲基)丙烯酸系聚合物，該(甲基)丙烯酸系聚合物，包含： 相對於全部構成單元為35質量%以上的來自具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元；及 相對於全部構成單元為0.1質量%以上35質量%以下之來自具有羥基的單體的構成單元； 且玻璃化轉變溫度為-55℃~-10℃。The means to solve the above problems include the following aspects. <1> An adhesive containing a (meth) acrylic polymer, the (meth) acrylic polymer containing: 35% by mass or more of all constituent units derived from a group having 5 to 9 carbon atoms A constituent unit of a branched alkyl methacrylate; and a constituent unit derived from a monomer having a hydroxyl group in an amount of 0.1% by mass or more and 35% by mass or less with respect to all the constituent units; and the glass transition temperature is -55 ° C to -10 ° C.
＜2＞如＜1＞的黏接劑，前述(甲基)丙烯酸系聚合物中，前述來自具有羥基的單體的構成單元的含有率，相對於全部構成單元為 5質量%以上35質量%以下。 ＜3＞如＜1＞或＜2＞的黏接劑，前述(甲基)丙烯酸系聚合物更含有相對於全部構成單元為5質量%以上之來自具有碳原子數5~9之分支鏈烷基的丙烯酸烷酯得來的構成單元。 ＜4＞如＜3＞的黏接劑，前述(甲基)丙烯酸系聚合物中，前述來自具有羥基的單體的構成單元的含有率相對於全部構成單元為10質量%以上35質量%以下；前述(甲基)丙烯酸系聚合物中，前述來自丙烯酸烷酯的構成單元的含有率相對於全部構成單元為10質量%以上。 ＜5＞如＜1＞~＜4＞任一項的黏接劑，前述(甲基)丙烯酸系聚合物中，前述來自甲基丙烯酸烷酯的構成單元的含有率相對於全部構成單元為50質量%以上；前述(甲基)丙烯酸系聚合物中，前述來自具有羥基的單體的構成單元相對於前述來自甲基丙烯酸烷酯的構成單元的比率，按質量比，為1/2.5~1/7.5。 ＜6＞如＜1＞~＜5＞任一項的黏接劑，前述甲基丙烯酸烷酯的至少1種為甲基丙烯酸2-乙基己酯。 ＜7＞如＜1＞~＜6＞任一項的黏接劑，前述(甲基)丙烯酸系聚合物之來自具有環狀基的單體的構成單元的含有率相對於全部構成單元為5質量%以下。 ＜8＞如＜1＞~＜7＞任一項的黏接劑，係使用於貼合觸控面板構成構件。<2> The adhesive according to <1>, in the (meth) acrylic polymer, the content rate of the structural unit derived from the monomer having a hydroxyl group is 5% by mass or more and 35% by mass relative to all the structural units. the following. <3> An adhesive such as <1> or <2>, wherein the (meth) acrylic polymer further contains 5 to 9% by mass of all constituent units derived from a branched alkane having 5 to 9 carbon atoms. A structural unit derived from an alkyl acrylate. <4> The adhesive according to <3>, in the (meth) acrylic polymer, the content rate of the structural unit derived from the monomer having a hydroxyl group is 10% by mass or more and 35% by mass or less with respect to all the structural units. In the (meth) acrylic polymer, the content rate of the constituent units derived from the alkyl acrylate is 10% by mass or more based on the total constituent units. <5> The adhesive according to any one of <1> to <4>, in the (meth) acrylic polymer, the content rate of the constituent units derived from the alkyl methacrylate is 50 with respect to all the constituent units Mass% or more; in the (meth) acrylic polymer, the ratio of the structural unit derived from the monomer having a hydroxyl group to the structural unit derived from the alkyl methacrylate is 1 / 2.5 to 1 by mass ratio /7.5. <6> The adhesive according to any one of <1> to <5>, wherein at least one of the alkyl methacrylates is 2-ethylhexyl methacrylate. <7> The adhesive according to any one of <1> to <6>, wherein the content rate of the structural unit derived from the monomer having a cyclic group in the (meth) acrylic polymer is 5 with respect to all the structural units. Mass% or less. <8> The adhesive according to any one of <1> to <7> is used for bonding a touch panel constituent member.
＜9＞一種黏接片，具有黏接劑層，該黏接劑層含有如＜1＞~＜8＞項中任一項之黏接劑進行交聯反應而形成的交聯結構。 ［發明之效果］<9> An adhesive sheet having an adhesive layer, the adhesive layer containing a cross-linking structure formed by the cross-linking reaction of any one of the items <1> to <8>. [Effect of Invention]
根據本發明之一實施型態提供：形成相對電容率低、黏著力高、加工性優良的黏接劑層的黏接劑，及具有相對電容率低、黏著力高、加工性優良的黏接劑層的黏接片。According to one embodiment of the present invention, there is provided an adhesive for forming an adhesive layer with low relative permittivity, high adhesive force, and excellent processability, and an adhesive having low relative permittivity, high adhesive force, and excellent processability. Adhesive sheet.
以下說明關於本發明之一實施型態。 又，本說明書中使用「~」所表示的數值範圍係表示「~」的前後中記載的數值其各自的最大值及最小值所包含的範圍。 又，本說明書中，(甲基)丙烯酸基是指丙烯酸基及甲基丙烯酸基至少其中之一的意思，（甲基）丙烯酸酯是丙烯酸酯及甲基丙烯酸酯至少其中之一的意思。The following describes one embodiment of the present invention. In addition, the numerical range shown using "~" in this specification means the range included in the maximum and minimum value of the numerical value described before and after "~", respectively. In the present specification, (meth) acrylic group means at least one of an acrylic group and a methacrylic group, and (meth) acrylate means at least one of an acrylate and a methacrylate.
＜黏接劑＞ 黏接劑含有(甲基)丙烯酸系聚合物，該(甲基)丙烯酸系聚合物，包含： 相對於全部構成單元為35質量%以上的來自具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元；相對於全部構成單元為0.1質量%以上35質量%以下之來自具有羥基的單體的構成單元；且玻璃化轉變溫度為-55℃~-10℃。 又，黏接劑也可以含有能與(甲基)丙烯酸系聚合物形成交聯結構的交聯劑。又，黏接劑含有交聯劑的情況，黏接劑可以也更含有交聯觸媒及螯合劑。 又，黏著劑若有必要，可以更含有上述以外的其他成分。<Adhesive> The adhesive contains a (meth) acrylic polymer, and the (meth) acrylic polymer contains: 35% by mass or more of all constituent units derived from those having 5 to 9 carbon atoms A constituent unit of a branched alkyl methacrylate; a constituent unit derived from a monomer having a hydroxyl group in an amount of 0.1% by mass or more and 35% by mass or less relative to all the constituent units; and the glass transition temperature is -55 ° C to- 10 ° C. The adhesive may contain a crosslinking agent capable of forming a crosslinking structure with the (meth) acrylic polymer. When the adhesive contains a crosslinking agent, the adhesive may further contain a crosslinking catalyst and a chelating agent. In addition, if necessary, the adhesive may further contain components other than the above.
藉由以上述構成黏接劑，可以形成相對電容率低，黏著力高且加工性優良的黏接劑層。 獲得本發明之一實施型態的效果之理由推測如下。 本發明之一實施型態中，製造(甲基)丙烯酸系聚合物時使用的甲基丙烯酸烷酯的烷基的碳原子數為5以上之大，且，因烷基是分支結構，莫耳體積大，偶極矩小。因此，可使含有前述來自甲基丙烯酸烷酯的構成單元的(甲基)丙烯酸系聚合物的莫耳體積大，偶極矩小。此結果，前述含有(甲基)丙烯酸系聚合物的黏接劑可形成相對電容率低的黏接劑層。 又，因甲基丙烯酸烷酯的烷基的碳原子數為9以下，比起烷基碳原子數10以上者，可以形成相對電容率較低的黏接劑層。此理由並不明確，但推測原因是：因烷基的碳原子數為9以下的甲基丙烯酸烷酯，比起烷基的碳原子數為10以上者，形成聚合物時的體積收縮率小，含有來自烷基的碳原子數為9以下的甲基丙烯酸烷酯的構成單元的(甲基)丙烯酸系聚合物，莫耳體積會變大。 如上所述，本發明之一實施型態的黏接劑，製造 (甲基)丙烯酸系聚合物時使用的甲基丙烯酸烷酯的莫耳體積大，偶極矩小。進而，因前述甲基丙烯酸烷酯形成聚合物時的體積收縮率小，故(甲基)丙烯酸系聚合物的莫耳體積變大。此結果，推測為可以形成相對電容率低的黏接劑層。 又，本發明之一實施型態的黏接劑因(甲基)丙烯酸系聚合物的玻璃化轉變溫度的下限為-55℃，故黏接劑層的凝聚力高，加工性優良。又，推測因(甲基)丙烯酸系聚合物的玻璃化轉變溫度的上限為-10℃，黏接劑層的黏接力高。By configuring the adhesive as described above, it is possible to form an adhesive layer having a low relative permittivity, high adhesion, and excellent processability. The reason for obtaining the effect of one embodiment of the present invention is presumed as follows. In one embodiment of the present invention, the number of carbon atoms in the alkyl group of the alkyl methacrylate used in the production of the (meth) acrylic polymer is 5 or more, and since the alkyl group has a branched structure, the mole Large volume and small dipole moment. Therefore, the molar volume of the (meth) acrylic polymer containing the structural unit derived from the alkyl methacrylate can be made large, and the dipole moment can be made small. As a result, the aforementioned (meth) acrylic polymer-containing adhesive can form an adhesive layer having a low relative permittivity. Further, since the number of carbon atoms in the alkyl group of the alkyl methacrylate is 9 or less, it is possible to form an adhesive layer having a relatively low relative permittivity as compared with the number of carbon atoms in the alkyl group of 10 or more. The reason for this is not clear, but it is presumed that the volume shrinkage of the alkyl group when the number of carbon atoms of the alkyl group is 9 or more is smaller than that of the alkyl group having 10 or more carbon atoms. A (meth) acrylic polymer containing a structural unit derived from an alkyl methacrylic acid alkyl group having 9 or less carbon atoms has a larger molar volume. As described above, the adhesive of one embodiment of the present invention has a large molar volume and a small dipole moment in the alkyl methacrylate used in the production of a (meth) acrylic polymer. Furthermore, since the volume shrinkage of the alkyl methacrylate when forming the polymer is small, the molar volume of the (meth) acrylic polymer is increased. As a result, it is estimated that an adhesive layer having a low relative permittivity can be formed. Moreover, since the lower limit of the glass transition temperature of a (meth) acrylic-type polymer is -55 degreeC in the adhesive of one Embodiment of this invention, the cohesive force of an adhesive layer is high and processability is excellent. In addition, it is presumed that the upper limit of the glass transition temperature of the (meth) acrylic polymer is -10 ° C, and the adhesive force of the adhesive layer is high.
本發明的一實施型態的黏接劑的用途，例如可列舉觸控面板構成構件的固定之用途。特別是本發明之一實施型態的黏接劑適合於製造觸控面板時，用以貼合玻璃基板、透明導電膜、設計膜等多數的觸控面板構成構件。又，更適合使用於製造觸控面板時，貼合透明導電膜與其之外的觸控面板構成構件。An application of the adhesive according to an embodiment of the present invention includes, for example, an application of fixing a touch panel constituent member. In particular, when the adhesive according to one embodiment of the present invention is suitable for manufacturing a touch panel, it is used for laminating most touch panel components such as a glass substrate, a transparent conductive film, and a design film. Moreover, it is more suitable for use in manufacturing a touch panel by laminating a transparent conductive film and other touch panel constituent members.
本發明之一實施型態的黏接劑中含有的 (甲基)丙烯酸系聚合物，包含： 相對於全部構成單元為35質量%以上的來自具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元；及相對於全部構成單元為0.1質量%以上35質量%以下之來自具有羥基的單體的構成單元；且玻璃化轉變溫度為-55℃~-10℃。此(甲基)丙烯酸系聚合物，更以含有來自丙烯酸烷酯的構成單元為佳，更可以含有既述的構成單元以外的構成單元。The (meth) acrylic polymer contained in the adhesive according to an embodiment of the present invention includes: a branched alkyl group having 5 to 9 carbon atoms and a branched alkyl group having 5 to 9 carbon atoms with respect to all constituent units; A structural unit of an alkyl methacrylate; and a structural unit derived from a monomer having a hydroxyl group in an amount of 0.1% by mass or more and 35% by mass or less with respect to all the structural units; and the glass transition temperature is -55 ° C to -10 ° C. The (meth) acrylic polymer preferably contains a constituent unit derived from an alkyl acrylate, and may further contain a constituent unit other than the aforementioned constituent unit.
製造(甲基)丙烯酸系聚合物時使用的甲基丙烯酸烷酯所具有的分支鏈烷基的碳原子數未達5的話，甲基丙烯酸烷酯的莫耳體積會變小，偶極矩會變大，黏接劑無法形成相對電容率低的黏接劑層。又，前述分支鏈烷基的碳原子數超過9的話，甲基丙烯酸烷酯形成聚合物時的體積收縮率大，(甲基)丙烯酸系聚合物的莫耳體積會有變小的傾向。因前述分支鏈烷基的碳原子數超過9，隨著碳原子數進一步增加，聚合物的聚合性變差，變得難以獲得分子量大的聚合物。此結果，聚合物的凝聚力變低，加工性變差。因此，前述分支鏈烷基的碳原子數超過9的話，黏接劑無法形成相對電容率低且加工性優良的黏接劑層。 又，由上述相對電容率的觀點及加工性的觀點，甲基丙烯酸烷酯的分支鏈烷基的碳原子數以7~9為佳。When the number of carbon atoms in the branched alkyl group of the alkyl methacrylate used in the production of the (meth) acrylic polymer is less than 5, the molar volume of the alkyl methacrylate will be reduced, and the dipole moment will be reduced. As the adhesive becomes larger, the adhesive cannot form an adhesive layer with a lower relative permittivity. When the number of carbon atoms in the branched alkyl group exceeds 9, the volume shrinkage rate of the alkyl methacrylate when forming the polymer is large, and the molar volume of the (meth) acrylic polymer tends to be small. Since the number of carbon atoms of the branched alkyl group exceeds 9, as the number of carbon atoms further increases, the polymerizability of the polymer deteriorates, and it becomes difficult to obtain a polymer having a large molecular weight. As a result, the cohesive force of the polymer is reduced, and the processability is deteriorated. Therefore, if the number of carbon atoms of the branched alkyl group exceeds 9, the adhesive cannot form an adhesive layer with a low relative permittivity and excellent processability. From the viewpoint of the relative permittivity and the viewpoint of processability, the number of carbon atoms in the branched alkyl group of the alkyl methacrylate is preferably 7 to 9.
(甲基)丙烯酸系聚合物中，來自具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元的含有率相對於全部構成單元為35質量%以上。該含有率，由相對電容率的觀點、加工性的觀點以及黏接力的觀點，相對於全部構成單元為50質量%以上為佳，60質量%以上更佳，70質量%以上最佳。 該含有率若未達35質量%的話，黏接劑無法形成相對電容率低的黏接劑層。In the (meth) acrylic polymer, the content rate of the structural unit derived from the alkyl methacrylate having a branched alkyl group having 5 to 9 carbon atoms is 35% by mass or more with respect to the entire structural unit. From the viewpoint of the relative permittivity, the viewpoint of workability, and the viewpoint of adhesive force, the content rate is preferably 50% by mass or more, more preferably 60% by mass or more, and most preferably 70% by mass or more based on the total constituent units. If the content is less than 35% by mass, the adhesive cannot form an adhesive layer with a low relative permittivity.
又，來自含有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元的含有率，由調整為即使於高溫高濕環境下也不會白化(以下也稱為「耐濕熱白化性」)的性質的觀點，以90質量%以下為佳，85質量%以下更佳，80質量%以下再更佳。In addition, the content rate of the constituent units derived from the alkyl methacrylate containing a branched alkyl group having 5 to 9 carbon atoms was adjusted so as not to whiten even in a high-temperature and high-humidity environment (hereinafter also referred to as "damp heat resistance" From the viewpoint of the properties of "whitening property"), it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.
進而，(甲基)丙烯酸系聚合物中，來自含有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元的含有率為50質量%以上，且來自含有羥基的單體的構成單元相對於前述來自甲基丙烯酸烷酯的構成單元的比率，按質量比以1/2.5~1/7.5為佳。藉由來自具有羥基的單體的構成單元相對於前述來自甲基丙烯酸烷酯的構成單元的比率滿足上述範圍，黏接劑可以形成相對電容率、加工性、耐濕熱白化性的平衡更優良的黏接劑層。Furthermore, in the (meth) acrylic polymer, the content rate of the structural unit derived from the alkyl methacrylate containing a branched alkyl group having 5 to 9 carbon atoms is 50% by mass or more, and the monomer is derived from a hydroxyl group-containing monomer. The ratio of the constituent units to the constituent units derived from the alkyl methacrylate is preferably 1 / 2.5 to 1 / 7.5 in terms of mass ratio. When the ratio of the structural unit derived from the monomer having a hydroxyl group to the aforementioned structural unit derived from the alkyl methacrylate satisfies the above range, the adhesive can form a more excellent balance of relative permittivity, processability, and heat and whitening resistance. Adhesive layer.
本發明之一實施型態的黏接劑中含有的(甲基)丙烯酸系聚合物，含有來自具有羥基的單體的構成單元。 (甲基)丙烯酸系聚合物藉由含有具羥基的單體，而能與後述的交聯劑進行交聯反應。因此，以含有(甲基)丙烯酸系聚合物的黏接劑所形成的黏接劑層凝聚力高使加工性良好。The (meth) acrylic polymer contained in the adhesive of one embodiment of the present invention contains a structural unit derived from a monomer having a hydroxyl group. The (meth) acrylic polymer is capable of undergoing a cross-linking reaction with a cross-linking agent described later by containing a monomer having a hydroxyl group. Therefore, the adhesive layer formed with the (meth) acrylic polymer-containing adhesive has high cohesiveness and good processability.
(甲基)丙烯酸系聚合物中，來自含有羥基的單體的構成單元的含有率相對於全部構成單元，為0.1質量%以上35質量%以下。該含有率未達0.1質量%的話，因與交聯劑的反應不充分，形成的黏接劑層的凝聚力低，黏接劑層的加工性差。又，該含有率超過35質量%的話，無法形成相對電容率低的黏接劑層。In a (meth) acrylic polymer, content rate of the structural unit derived from the monomer containing a hydroxyl group is 0.1 mass% or more and 35 mass% or less with respect to all the structural units. If the content is less than 0.1% by mass, the reaction with the crosslinking agent is insufficient, the cohesive force of the formed adhesive layer is low, and the workability of the adhesive layer is poor. If the content ratio exceeds 35% by mass, an adhesive layer having a low relative permittivity cannot be formed.
來自含有羥基單體的構成單元的含有率，相對於全部構成單元以5質量%以上為佳。含有率為5質量%以上的話，因所形成的黏接劑層之黏接劑層與水分的相溶性高，黏接劑層更不容易白化，可以使耐濕熱白化性更提升。 又，由上述提升耐濕熱白化性的觀點，該含有率以相對於全部構成單元為10質量%以上更佳，20質量%以上再更佳。The content rate of the structural unit derived from a hydroxyl-containing monomer is 5 mass% or more with respect to all the structural units. When the content rate is 5 mass% or more, the adhesive layer of the formed adhesive layer has high compatibility with water, and the adhesive layer is less likely to whiten, which can improve the moisture and heat whitening resistance. From the viewpoint of improving the moisture and heat whitening resistance, the content ratio is more preferably 10% by mass or more, and even more preferably 20% by mass or more with respect to all the constituent units.
來自含有羥基單體的構成單元的含有率，相對於全部構成單元以30質量%以下為佳。該含有率為30質量%以下的話，黏接劑可以形成相對電容率低的黏接劑層。 又，由降低上述相對電容率的觀點，該含有率，相對於全部構成單元，以25質量%以下為佳，20質量%以下更佳。The content rate of the structural unit derived from a hydroxyl-containing monomer is 30 mass% or less with respect to all the structural units. When the content is 30% by mass or less, the adhesive can form an adhesive layer having a low relative permittivity. From the viewpoint of reducing the relative permittivity, the content ratio is preferably 25% by mass or less, and more preferably 20% by mass or less with respect to all the constituent units.
(甲基)丙烯酸系聚合物除了既述的來自甲基丙烯酸烷酯的構成單元及既述的來自具有羥基的單體的構成單元以外，更可以含有來自丙烯酸烷酯的構成單元。 藉由含有來自丙烯酸烷酯的構成單元，(甲基)丙烯酸系聚合物的分子量容易為大。(甲基)丙烯酸系聚合物的分子量變大時，黏接劑層的凝聚力會變高， 能夠形成加工性優良的黏接劑層。The (meth) acrylic polymer may contain a structural unit derived from an alkyl acrylate in addition to the structural unit derived from an alkyl methacrylate and the structural unit derived from a monomer having a hydroxyl group. By containing the structural unit derived from an alkyl acrylate, the molecular weight of a (meth) acrylic-type polymer becomes large easily. When the molecular weight of the (meth) acrylic polymer is increased, the cohesive force of the adhesive layer is increased, and an adhesive layer having excellent processability can be formed.
作為來自丙烯酸烷酯的構成單元，由耐濕熱白化性的觀點，以有來自具有碳原子數5~9之烷基的丙烯酸烷酯的構成單元為佳。 又，作為來自丙烯酸烷酯的構成單元，由相對電容率的觀點，以有來自具有分支鏈烷基的丙烯酸烷酯的構成單元為佳。 又，作為來自丙烯酸烷酯的構成單元，由耐濕熱白化性的觀點以及相對電容率的觀點，以有來自具有碳原子數5~9之分支鏈烷基的丙烯酸烷酯的構成單元更佳。As a structural unit derived from an alkyl acrylate, from the viewpoint of moist heat whitening resistance, a structural unit derived from an alkyl acrylate having an alkyl group having 5 to 9 carbon atoms is preferred. Moreover, as a structural unit derived from an alkyl acrylate, it is preferable that it is a structural unit derived from an alkyl acrylate which has a branched alkyl group from a viewpoint of a relative permittivity. Moreover, as a structural unit derived from an alkyl acrylate, the structural unit derived from an alkyl acrylate which has a branched alkyl group having 5 to 9 carbon atoms is more preferable from the viewpoint of moist heat whitening resistance and the viewpoint of relative permittivity.
(甲基)丙烯酸系聚合物藉由含有來自具有碳原子數5~9之分支鏈烷基的丙烯酸烷酯的構成單元，使黏接劑能形成耐濕熱白化性及相對電容率優異的黏接劑層的理由並不明確，但可推測如下。 具有碳原子數5~9之烷基的丙烯酸烷酯，相較於具有碳原子數5~9之烷基的甲基丙烯酸烷酯，因當形成均聚物時的玻璃化轉變溫度低，故藉由將製造(甲基)丙烯酸系聚合物時使用之甲基丙烯酸烷酯的一部分變更為丙烯酸烷酯，能使(甲基)丙烯酸系聚合物的玻璃化轉變溫度變低，使黏接劑的潤濕性上升。因此，推測：以黏接劑形成黏接劑層，例如於觸控面板與構成構件彼此貼合時，觸控面板構成構件與黏接劑層的密接性改善，且抑制水分從前述構件與黏接劑層間之交界面滲入。進而，藉由丙烯酸烷酯的烷基的碳原子數為5以上且疏水性高，推測能夠抑制水分從黏接劑層與前述構件的交界面以外向黏接劑層內滲透。藉這些交互作用可抑制因水分導致黏接劑層的白化。藉此，可推測以含有前述(甲基)丙烯酸系聚合物的黏接劑形成的黏接劑層的耐濕熱白化性上升。 又，丙烯酸烷酯中的烷基是分支鏈烷基時，相較於具有相同碳原子數的直鏈烷基的丙烯酸烷酯，其莫耳體積較大。因此，可推測黏接劑層的相對電容率會減小。The (meth) acrylic polymer contains a constitutional unit derived from an alkyl acrylate having a branched alkyl group having 5 to 9 carbon atoms, so that the adhesive can form an adhesive with excellent moist heat whitening resistance and relative permittivity. The reason for the agent layer is not clear, but it can be estimated as follows. An alkyl acrylate having an alkyl group having 5 to 9 carbon atoms has a lower glass transition temperature when forming a homopolymer than an alkyl methacrylate having an alkyl group having 5 to 9 carbon atoms. By changing a part of the alkyl methacrylate used in the production of the (meth) acrylic polymer to an alkyl acrylate, the glass transition temperature of the (meth) acrylic polymer can be lowered and the adhesive can be made. Wettability increases. Therefore, it is speculated that when an adhesive layer is formed with an adhesive, for example, when the touch panel and the constituent members are bonded to each other, the adhesion between the constituent members of the touch panel and the adhesive layer is improved, and moisture is prevented from passing from the aforementioned members and the adhesive. The interface between the contact layers penetrates. Furthermore, since the number of carbon atoms in the alkyl group of the alkyl acrylate is 5 or more and the hydrophobicity is high, it is estimated that it is possible to suppress the penetration of moisture from outside the interface between the adhesive layer and the member into the adhesive layer. These interactions can suppress whitening of the adhesive layer due to moisture. Accordingly, it is presumed that the moisture and heat whitening resistance of the adhesive layer formed of the adhesive containing the (meth) acrylic polymer is increased. When the alkyl group in the alkyl acrylate is a branched alkyl group, the molar volume of the alkyl acrylate is larger than that of a linear alkyl acrylate having the same number of carbon atoms. Therefore, it is speculated that the relative permittivity of the adhesive layer will decrease.
如上所述，可以將製造(甲基)丙烯酸系聚合物時使用的甲基丙烯酸烷酯變更為丙烯酸烷酯，但因丙烯酸烷酯莫耳體積比甲基丙烯酸烷酯的莫耳體積小，將所有的甲基丙烯酸烷酯變更成丙烯酸烷酯的情況，黏接劑無法形成相對電容率低的黏接劑層。As described above, the alkyl methacrylate used in the production of a (meth) acrylic polymer can be changed to an alkyl acrylate. However, the molar volume of the alkyl acrylate is smaller than that of the alkyl methacrylate. When all alkyl methacrylates are changed to alkyl acrylates, the adhesive cannot form an adhesive layer with a low relative permittivity.
(甲基)丙烯酸系聚合物中，來自具有碳原子數5~9之分支鏈烷基的丙烯酸烷酯的構成單元的含有率，由相對電容率的觀點以及耐濕熱白化性的觀點，相對於全部構成單元為5質量%以上為佳，10質量%以上更佳。In the (meth) acrylic polymer, the content rate of the constituent unit derived from the alkyl acrylate having a branched alkyl group having 5 to 9 carbon atoms is relative to the viewpoint of relative permittivity and the viewpoint of moist-heat whitening resistance. All the constituent units are preferably 5 mass% or more, and more preferably 10 mass% or more.
前述來自丙烯酸烷酯的構成單元的含有率，相對於全部構成單元為64.9質量%以下為佳。含有率為64.9質量%以下時，可形成相對電容率與耐濕熱白化性的平衡良好的黏接劑層。 又，由上述相對電容率與耐濕熱白化性的平衡之觀點，該含有率為45質量%以下更佳，30質量%以下再更佳。It is preferable that the content rate of the said structural unit derived from the alkyl acrylate is 64.9 mass% or less with respect to all the structural units. When the content rate is 64.9% by mass or less, an adhesive layer having a good balance between relative permittivity and moisture and heat whitening resistance can be formed. From the viewpoint of the balance between the relative permittivity and the moist-heat whitening resistance, the content ratio is more preferably 45% by mass or less, and even more preferably 30% by mass or less.
又，(甲基)丙烯酸系聚合物中，來自具有碳原子數5~9之分支鏈烷基的丙烯酸烷酯的構成單元的含有率，相對於全部構成單元為10質量%以上，且，來自具有羥基的單體的構成單元的含有率，相對於全部構成單元為10質量%以上為佳。 (甲基)丙烯酸系聚合物，藉由的來自具有羥基單體的構成單元與來自具有碳原子數5~9之分支鏈烷基的丙烯酸烷酯的構成單元的含量均為10質量%以上，能抑制水分向黏接劑形成的黏接劑層滲透，且同時因黏接劑層與水分的相溶性變高，可更進一步提升耐濕熱白化性。In the (meth) acrylic polymer, the content rate of the constituent units derived from the alkyl acrylate having a branched alkyl group having 5 to 9 carbon atoms is 10% by mass or more based on the total constituent units. The content rate of the structural unit of the monomer which has a hydroxyl group is preferably 10 mass% or more with respect to all the structural units. The content of the (meth) acrylic polymer based on the constitutional unit derived from the monomer having a hydroxy monomer and the constitutional unit derived from the alkyl acrylate having a branched alkyl group having 5 to 9 carbon atoms is 10% by mass or more. It can suppress the penetration of moisture into the adhesive layer formed by the adhesive, and at the same time, the compatibility between the adhesive layer and the moisture becomes higher, which can further improve the moisture and heat whitening resistance.
作為具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯，例如可以列舉甲基丙烯酸異戊酯、甲基丙烯酸異己酯、甲基丙烯酸異庚酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異辛酯、甲基丙烯酸異壬酯。其中，由相對電容率的觀點，以甲基丙烯酸2-乙基己酯為佳。 具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯，可以單獨使用1種，也可以2種以上合併使用。Examples of the alkyl methacrylate having a branched alkyl group having 5 to 9 carbon atoms include isoamyl methacrylate, isohexyl methacrylate, isoheptyl methacrylate, and 2-ethyl methacrylate. Hexyl ester, isooctyl methacrylate, isononyl methacrylate. Among them, from the viewpoint of relative permittivity, 2-ethylhexyl methacrylate is preferred. The alkyl methacrylate having a branched alkyl group having 5 to 9 carbon atoms may be used alone or in combination of two or more.
作為具有羥基的單體，例如可以列舉具有羥基及乙烯性不飽和鍵的單體。作為具有羥基的單體的具體例子，可以列舉 (甲基) 丙烯酸2-羥乙酯、 (甲基) 丙烯酸2-羥丙酯、 (甲基) 丙烯酸3-羥丙酯、 (甲基) 丙烯酸4-羥基丁酯、 (甲基) 丙烯酸3-甲基-3-羥基丁酯、 (甲基) 丙烯酸1,3-二甲基-3-羥基丁酯、 (甲基) 丙烯酸2,2,4-三甲基-3-羥基戊酯、 (甲基) 丙烯酸2-乙基-3-羥基己酯、單(甲基) 丙烯酸甘油酯、單(甲基) 丙烯酸聚丙二醇酯、單(甲基) 丙烯酸聚乙二醇酯、單(甲基) 丙烯酸聚(乙二醇-丙二醇)酯等的(甲基) 丙烯酸酯化合物、N-羥甲基(甲基) 丙烯醯胺、N-羥乙基(甲基) 丙烯醯胺等的具有羥基的(甲基) 丙烯醯胺化合物，和烯丙醇、甲基烯丙醇等的不飽和醇等。Examples of the monomer having a hydroxyl group include monomers having a hydroxyl group and an ethylenically unsaturated bond. Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. 4-hydroxybutyl, 3-methyl-3-hydroxybutyl (meth) acrylate, 1,3-dimethyl-3-hydroxybutyl (meth) acrylate, 2,2 (meth) acrylate, 4-trimethyl-3-hydroxypentyl ester, 2-ethyl-3-hydroxyhexyl (meth) acrylate, glyceryl mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, mono (methyl) (Meth) acrylates, (meth) acrylate compounds such as polyethylene glycol acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, N-hydroxymethyl (meth) acrylamidonium, N-hydroxy (Meth) acrylamide compounds having a hydroxyl group, such as ethyl (meth) acrylamide, and unsaturated alcohols, such as allyl alcohol and methallyl alcohol.
在這些中，由與碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的相溶性及共聚合性良好的觀點，及與交聯劑的交聯反應的良好的觀點，作為具有羥基的單體，以具有碳原子數1~5的羥烷基的 (甲基) 丙烯酸羥烷酯為佳，具有碳原子數2~4的羥烷基的 (甲基) 丙烯酸羥烷酯更佳， (甲基) 丙烯酸2-羥乙酯或 (甲基) 丙烯酸4-羥基丁酯特佳。 具有羥基的單體可以單獨使用1種，也可以2種以上合併使用。Among these, from the viewpoint of good compatibility and copolymerizability with alkyl methacrylate having branched alkyl groups having 5 to 9 carbon atoms, and from the viewpoint of good cross-linking reaction with a cross-linking agent, The hydroxy monomer is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 1 to 5 carbon atoms, and more preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms. Preferably, 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate is particularly preferred. The monomer having a hydroxyl group may be used singly or in combination of two or more kinds.
作為丙烯酸烷酯，例如可以列舉丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸正辛酯、丙烯酸異辛酯、丙烯酸2-乙基己酯、丙烯酸正壬酯、丙烯酸異壬酯、丙烯酸正癸酯、丙烯酸月桂酯、丙烯酸十八酯。 這些之中，由相對電容率的觀點以及耐濕熱白化性的觀點，以丙烯酸2-乙基己酯為佳。 丙烯酸烷酯可以單獨使用1種，也可以2種以上合併使用。Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, and acrylic acid. Isononyl acrylate, n-decyl acrylate, lauryl acrylate, stearyl acrylate. Among these, 2-ethylhexyl acrylate is preferable from a viewpoint of a relative permittivity and a viewpoint of moist-heat whitening resistance. The alkyl acrylate may be used individually by 1 type, and may use 2 or more types together.
(甲基)丙烯酸系聚合物中，作為除既述的構成單元以外也可以含有的構成單元，例如可列舉來自甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸正辛酯、甲基丙烯酸正壬酯、甲基丙烯酸正癸酯、甲基丙烯酸月桂酯、甲基丙烯酸十八酯等的具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯以外的甲基丙烯酸烷酯，(甲基) 丙烯酸環己酯、(甲基) 丙烯酸芐酯、N-乙烯基-ε- 己內醯胺、N-乙烯基-2-吡咯啶酮、苯乙烯、α-甲基苯乙烯、乙烯基甲苯等的具有環狀基的單體，(甲基) 丙烯酸、伊康酸、馬來酸、富馬酸等的具有酸性基的單體，飽和脂肪酸乙烯基酯，例如甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、「叔碳酸乙烯酯」(商品名，新癸酸乙烯酯)等的脂肪族乙烯酯單體，及丙烯腈、甲基丙烯腈等的氰乙烯基單體等的構成單元。Examples of the (meth) acrylic polymer that can be contained in addition to the above-mentioned constituent units include ethyl methacrylate, methyl methacrylate, n-butyl methacrylate, and methyl groups. Isobutyl acrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, lauryl methacrylate, octadecyl methacrylate and the like having branched chains having 5 to 9 carbon atoms Alkyl methacrylate other than alkyl methacrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, N-vinyl-ε-caprolactam, N-vinyl- Monocyclic monomers such as 2-pyrrolidone, styrene, α-methylstyrene, vinyltoluene, and (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. Based monomers, saturated fatty acid vinyl esters, such as aliphatic vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, "ethylene tert-carbonate" (trade name, vinyl neodecanoate), And structural units such as vinyl cyanide monomers such as acrylonitrile and methacrylonitrile.
(甲基)丙烯酸系聚合物中來自具有環狀基的單體的構成單元的含有率，由耐濕熱白化性及黏接力的觀點，相對於全部構成單元，以5質量%以下為佳，3質量%以下更佳。The content rate of the structural unit derived from the monomer having a cyclic group in the (meth) acrylic polymer is preferably 5% by mass or less with respect to all the structural units from the viewpoint of moist-heat whitening resistance and adhesion. It is more preferably less than mass%.
(甲基)丙烯酸系聚合物中來自具有酸性基的單體的構成單元的含有率，相對於全部構成單元，為0.5質量%以下為佳。 來自具有酸性基的單體的構成單元的含有率於上述範圍內的話，於黏接劑層例如與觸控面板的透明電極等的金屬接觸的情況時，可以抑制金屬的腐蝕。因此，含有前述(甲基)丙烯酸系聚合物的黏接劑，可以更適合使用於作為觸控面板的用途。 又，由上述的觀點，來自具有酸性基的單體的構成單元的含有率，相對於全部構成單元，於0.2質量%以下更佳，完全不含再更佳。The content rate of the structural unit derived from the monomer which has an acidic group in a (meth) acrylic-type polymer is 0.5 mass% or less with respect to all the structural units. When the content rate of the structural unit derived from the monomer having an acidic group is within the above range, when the adhesive layer is in contact with a metal such as a transparent electrode of a touch panel, the corrosion of the metal can be suppressed. Therefore, the adhesive containing the (meth) acrylic polymer can be more suitably used for a touch panel application. From the viewpoint described above, the content rate of the structural unit derived from the monomer having an acidic group is more preferably 0.2% by mass or less with respect to all the structural units, and it is more preferably not contained at all.
(甲基)丙烯酸系聚合物的玻璃化轉變溫度(Tg)為-55℃~-10℃。(甲基)丙烯酸系聚合物的Tg未達-55℃時，作為黏接劑層時的凝聚力會降低，黏接劑層的加工性劣化。又，(甲基)丙烯酸系聚合物的Tg超過-10℃時，作為黏接劑層時的黏接力會降低。 又，由上述的觀點，(甲基)丙烯酸系聚合物的Tg於-40℃~-15℃為佳，-35℃~-18℃更佳。The (meth) acrylic polymer has a glass transition temperature (Tg) of -55 ° C to -10 ° C. When the Tg of the (meth) acrylic polymer is less than -55 ° C, the cohesive force when used as an adhesive layer is reduced, and the workability of the adhesive layer is deteriorated. When the Tg of the (meth) acrylic polymer exceeds -10 ° C, the adhesive force when used as an adhesive layer is reduced. From the above viewpoint, the Tg of the (meth) acrylic polymer is preferably -40 ° C to -15 ° C, and more preferably -35 ° C to -18 ° C.
本說明書中，(甲基)丙烯酸系聚合物的玻璃化轉變溫度(Tg)係利用以下的計算所求得的莫耳平均玻璃化轉變溫度。 下列式中的Tg1 、Tg2 、…以及Tgn 為單體1、單體2、…以及單體n各自的均聚物的玻璃化轉變溫度，換算為絕對溫度(K)計算之。m1 、m2 、…以及mn 為各自的單體的莫耳分率。 又，計算玻璃化轉變溫度是使用絕對溫度(K)，但本說明書中記載玻璃化轉變溫度時是使用攝氏度(℃)。In this specification, the glass transition temperature (Tg) of a (meth) acrylic-type polymer is the Mohr average glass transition temperature calculated | required by the following calculation. Tg 1 , Tg 2 ,... And Tg n in the following formulae are the glass transition temperatures of the homopolymers of monomer 1, monomer 2,... And monomer n, and are calculated by converting to the absolute temperature (K). m 1 , m 2 ,... and m n are Mohr fractions of the respective monomers. The glass transition temperature is calculated using the absolute temperature (K). However, when the glass transition temperature is described in this specification, the temperature is in degrees Celsius (° C).
【數1】 [Number 1]
又，此處所稱之「均聚物的玻璃化轉變溫度(Tg)」係，將該單體的均聚物使用差示掃描熱量分析儀(DSC)(精工電子有限公司製，EXSTAR6000)，於氮氣氣流中，以測定樣本10mg，升溫速度10℃/分的條件進行測定，所得到的DSC曲線的反曲點就定義為均聚物的Tg。The "glass transition temperature (Tg) of a homopolymer" referred to herein is a homopolymer of this monomer using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., EXSTAR6000). In a nitrogen gas flow, the measurement was performed under the conditions of 10 mg of a sample and a temperature increase rate of 10 ° C./min. The inflection point of the obtained DSC curve was defined as the Tg of the homopolymer.
代表性單體的「均聚物之玻璃化轉變溫度(Tg)」係，甲基丙烯酸2-乙基己酯-10℃，丙烯酸2-乙基己酯-76℃，甲基丙烯酸異丁酯48℃，甲基丙烯酸正丁酯21℃，甲基丙烯酸月桂酯-65℃，丙烯酸-2-羥乙酯-15℃，甲基丙烯酸異癸酯-41℃，甲基丙烯酸環己酯56℃。"Glass transition temperature (Tg)" of representative monomers, 2-ethylhexyl methacrylate -10 ° C, 2-ethylhexyl acrylate -76 ° C, isobutyl methacrylate 48 ° C, n-butyl methacrylate 21 ° C, lauryl methacrylate -65 ° C, 2-hydroxyethyl acrylate -15 ° C, isodecyl methacrylate -41 ° C, cyclohexyl methacrylate 56 ° C .
(甲基)丙烯酸系聚合物的重量平均分子量(Mw)並沒有特別的限制，但由黏接劑層的加工性的觀點以及高低差追隨的容易性（以下稱為「高低差追隨性」）的觀點，係20萬以上100萬以下為佳，30萬以上80萬以下更佳，40萬以上60萬以下最佳。The weight average molecular weight (Mw) of the (meth) acrylic polymer is not particularly limited, but from the viewpoint of the processability of the adhesive layer and the ease of following the step (hereinafter referred to as "step following") From a viewpoint of 200,000 to 1,000,000, more preferably 300,000 to 800,000, and 400,000 to 600,000 is the best.
又，為(甲基)丙烯酸系聚合物的重量平均分子量(Mw)與數量平均分子量(Mn)之比的分散度(Mw/Mn)，由高低差追隨性的觀點，為20以下為佳，3以上15以下的範圍更佳，4.5以上8以下最佳。In addition, the degree of dispersion (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (meth) acrylic polymer, is preferably 20 or less from the viewpoint of followability. A range of 3 to 15 is more preferable, and a range of 4.5 to 8 is most preferable.
又，(甲基)丙烯酸系聚合物的重量平均分子量(Mw)與數平均分子量(Mn)係使用凝膠滲透層析儀(GPC)，遵循下述(1)~(3)測定的值。The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic polymer are values measured using a gel permeation chromatography (GPC) in accordance with the following (1) to (3).
(1)塗佈(甲基)丙烯酸系聚合物的溶液於剝離紙，於100℃使其乾燥2分鐘，得到膜狀的(甲基)丙烯酸系聚合物。 (2)將由上述(1)所得之膜狀(甲基)丙烯酸系聚合物於四氫呋喃中溶解成固體成分成為0.2質量%。 (3)於下述條件，使用凝膠滲透層析儀(GPC)，以標準聚苯乙烯換算值的形式，測定(甲基)丙烯酸系聚合物的重量平均分子量(Mw)與數平均分子量(Mn)。(1) A solution of a (meth) acrylic polymer is applied to a release paper and dried at 100 ° C for 2 minutes to obtain a film-like (meth) acrylic polymer. (2) The film-like (meth) acrylic polymer obtained in the above (1) was dissolved in tetrahydrofuran to a solid content of 0.2% by mass. (3) The weight average molecular weight (Mw) and the number average molecular weight (Mw) of the (meth) acrylic polymer are measured using a gel permeation chromatography (GPC) as a standard polystyrene conversion value under the following conditions ( Mn).
(條件) GPC：HLC-8220 GPC (東曹有限公司製) 管柱：TSK-GEL GMHXL 使用4支 (東曹有限公司製) 流動相溶劑：四氫呋喃 流速：0.6mL/分 管柱溫度：40℃(Condition) GPC: HLC-8220 GPC (manufactured by Tosoh Co., Ltd.). Column: TSK-GEL GMHXL. Four (manufactured by Tosoh Co., Ltd.). Mobile phase solvent: tetrahydrofuran. Flow rate: 0.6mL / min. Column temperature: 40 ° C.
(甲基)丙烯酸系聚合物可藉由將能形成既述的構成單元的單體混合物進行聚合來製造。(甲基)丙烯酸系聚合物的聚合方法並沒有特別的限制，可以由通常使用的聚合方法中適當選擇。作為聚合方法可以列舉溶液聚合法、乳化聚合法、懸浮聚合法等。考慮其中能相對簡單地進行製造，溶液聚合法較理想。The (meth) acrylic polymer can be produced by polymerizing a monomer mixture capable of forming the aforementioned constituent units. The polymerization method of the (meth) acrylic polymer is not particularly limited, and can be appropriately selected from polymerization methods generally used. Examples of the polymerization method include a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. Considering that it can be produced relatively easily, a solution polymerization method is preferable.
溶液聚合法一般來說，可以使用於聚合槽內放入規定的有機溶劑、單體、聚合反應起始劑以及視需要的鏈轉移劑，於氮氣氣流中，於有機溶劑的回流溫度，邊攪拌邊進行數小時的加熱反應等的公眾所知悉的方法。In general, the solution polymerization method can be used in a polymerization tank to put a predetermined organic solvent, monomer, polymerization reaction initiator and optionally a chain transfer agent in a nitrogen gas stream at the reflux temperature of the organic solvent while stirring. A publicly known method such as performing a heating reaction for several hours.
又，(甲基)丙烯酸系聚合物的重量平均分子量(Mw)、數平均分子量(Mn)以及分散度(Mw/Mn)，可以簡單地利用聚合溫度、時間、溶劑量、觸媒的種類及量和聚合反應起始劑的種類及量調節。The weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (Mw / Mn) of the (meth) acrylic polymer can be used simply by polymerization temperature, time, solvent amount, type of catalyst, and The amount and the type and amount of the polymerization initiator are adjusted.
交聯劑只要是能與(甲基)丙烯酸系聚合物反應而形成交聯結構者即可，並沒有特別的限定，例如可以列舉多元異氰酸酯化合物、聚環氧化合物、聚氮丙啶化合物、三聚氰胺甲醛縮合物、金屬螯合化合物。這些的交聯劑可以各自單獨1種或將2種以上組合使用。The cross-linking agent is not particularly limited as long as it can react with a (meth) acrylic polymer to form a cross-linked structure. Examples include polyisocyanate compounds, polyepoxy compounds, polyaziridine compounds, and melamine. Formaldehyde condensate, metal chelate compound. These crosslinking agents can be used individually by 1 type or in combination of 2 or more types.
這些的交聯劑中，由交聯反應的反應性的觀點以及交聯後對於環境變化的安定性的觀點，以多元異氰酸酯化合物為佳。Among these crosslinking agents, polyisocyanate compounds are preferred from the viewpoint of the reactivity of the crosslinking reaction and the viewpoint of stability to environmental changes after crosslinking.
作為多元異氰酸酯化合物，例如可以列舉苯二甲基二異氰酸酯、二苯基甲烷二異氰酸酯、三苯甲烷三異氰酸酯、甲伸苯基二異氰酸酯等的芳香族多元異氰酸酯化合物，或六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯，芳香族多元異氰酸酯化合物的氫化物等的脂肪族或脂環族多元異氰酸酯化合物。 又，上述多元異氰酸酯化合物的二聚物或三聚物，或上述多元異氰酸酯化合物與三羥甲丙烷等多元醇化合物的加成物，或上述異氰酸酯化合物的雙脲體，也可以作為多元異氰酸酯化合物使用。 其中，由苯二甲基二異氰酸酯的二聚物及三聚物和加成物構成的群體中至少選出1種為佳，苯二甲基二異氰酸酯加成物特佳。這些多元異氰酸酯化合物可以單獨使用1種或將2種以上混合使用。Examples of the polyisocyanate compound include aromatic polyisocyanate compounds such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and methylenephenyl diisocyanate, or hexamethylene diisocyanate, Aliphatic or alicyclic polyisocyanate compounds such as isophorone diisocyanate and hydrogenated products of aromatic polyisocyanate compounds. The dimer or trimer of the polyisocyanate compound, or the adduct of the polyisocyanate compound and a polyhydric alcohol compound such as trimethylolpropane, or the diurea of the isocyanate compound may also be used as the polyisocyanate compound. . Among them, at least one kind is preferably selected from the group consisting of dimer, trimer, and adduct of xylylene diisocyanate, and xylylene diisocyanate adduct is particularly preferable. These polyisocyanate compounds can be used individually by 1 type or in mixture of 2 or more types.
多元異氰酸酯化合物適合使用以例如「CORONATE HX」、「CORONATE HL-S」、「CORONATE 2234」、「AQUANATE 200」、「AQUANATE 210」[以上為日本聚氨酯有限公司製]、「Desmodur N3300」、「Desmodur N3400」[以上為住友拜耳烏拉坦有限公司製]、「DURANATE E-405-80T」、「DURANATE 24A-100」、「DURANATE TSE-100」[以上為旭化成工業有限公司製]、「TAKENATE D-110N」、「TAKENATE D-120N」、「TAKENATE M-631N」、「MT-OLESTER-NP1200」[以上為三井化學有限公司製]等商品名於市面販售的物品。The polyisocyanate compound is suitably used, for example, "CORONATE HX", "CORONATE HL-S", "CORONATE 2234", "AQUANATE 200", "AQUANATE 210" [The above are manufactured by Japan Polyurethane Co., Ltd.], "Desmodur N3300", "Desmodur" "N3400" [The above are manufactured by Sumitomo Bayer Urata Co., Ltd.], "DURANATE E-405-80T", "DURANATE 24A-100", "DURANATE TSE-100" [The above are manufactured by Asahi Kasei Industrial Co., Ltd.], "TAKENATE D- "110N", "TAKENATE D-120N", "TAKENATE M-631N", "MT-OLESTER-NP1200" [The above is made by Mitsui Chemicals Co., Ltd.] and other items sold on the market.
黏接劑中交聯劑的摻合量由黏接劑層的加工性及高低差追隨性的觀點，相對於(甲基)丙烯酸系聚合物100質量份，含有0.05質量份以上1.0質量份以下為佳，含有0.1質量份以上0.5質量份以下更佳，含有0.15質量份以上0.3質量份以下再更佳。The blending amount of the cross-linking agent in the adhesive contains from 0.05 to 1.0 part by mass of the (meth) acrylic polymer based on 100 parts by mass of the (meth) acrylic polymer from the viewpoint of the processability of the adhesive layer and the followability of the step. It is more preferable that the content is more than 0.1 part by mass and less than 0.5 part by mass, and it is more preferable that the content is more than 0.15 part by mass and less than 0.3 part by mass.
黏接劑除了交聯劑以外，為了加快初始硬化速度，也可以進一步含有交聯觸媒。作為交聯觸媒可以列舉例如二月桂酸二丁基錫、二月桂酸二辛基錫等的有機錫化合物，二丁氧基雙(乙基乙醯乙酸)鋯等的有機鋯化合物。In addition to the cross-linking agent, the adhesive may further contain a cross-linking catalyst in order to accelerate the initial hardening speed. Examples of the crosslinking catalyst include organic tin compounds such as dibutyltin dilaurate and dioctyltin dilaurate; and organic zirconium compounds such as dibutoxybis (ethylacetoacetate) zirconium.
黏接劑含有交聯觸媒的情況以黏接劑更含有螯合劑為佳。作為螯合劑，例如可以列舉β-二酮類或β-酮酯類。作為β-二酮類及β-酮酯類，例如可以列舉乙醯丙酮、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸正丙酯、乙醯乙酸異丙酯。這些螯合劑中，由黏接劑的使用期與反應速度的良好平衡的觀點以乙醯丙酮為佳。In the case where the adhesive contains a crosslinking catalyst, it is preferable that the adhesive further contains a chelating agent. Examples of the chelating agent include β-diketones and β-ketoesters. Examples of the β-diketones and β-ketoesters include acetoacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, and isopropyl acetoacetate. Among these chelating agents, acetoacetone is preferred from the viewpoint of a good balance between the life of the adhesive and the reaction rate.
將黏接劑作為黏接劑層時的凝膠分率，由加工性的觀點、黏接力的觀點及高低差追隨性的觀點，以40質量%~90質量%為佳，45質量%~80質量%更佳，50質量%~65質量%再更佳。 本說明書中，黏接劑層的凝膠分率係使用乙酸乙酯作為萃取劑測定的溶劑不溶部分的比例。詳細的測定方法如以下所述。The gel fraction when the adhesive is used as the adhesive layer is preferably from 40% by mass to 90% by mass, from 45% by mass to 80% from the viewpoint of processability, the viewpoint of adhesion, and the viewpoint of followability of the height difference. Mass% is better, 50% to 65% by mass is even better. In this specification, the gel fraction of an adhesive layer is a ratio of the solvent-insoluble part measured using ethyl acetate as an extractant. The detailed measurement method is as follows.
—凝膠分率的測定方法— 凝膠分率是利用下述(1)~(4)所表示的方法測定的。 (1)於以精密天平正確地測定質量的250網孔的金屬絲網(100mm×100mm)黏貼約0.25g的黏接劑層，包好使凝膠成分使其不漏出。之後，於精密天平正確地測定質量，製作成樣品。 (2)將得到的樣品浸泡於80ml乙酸乙酯3天。 (3)取出樣品並用少量的乙酸乙酯洗淨，於120℃乾燥24小時。之後於精密天平正確地測定質量。 (4)利用下列算式算出凝膠分率。 凝膠分率(質量%)=(Z-X)/(Y-X) ×100 惟，X為金屬絲網的質量(g)，Y為已黏貼黏接劑層的金屬絲網浸泡前的質量(g)，Z為浸泡後已乾燥之已黏貼黏接劑層的金屬絲網的質量(g)。—Method for Measuring Gel Fraction— The gel fraction is measured by a method represented by the following (1) to (4). (1) Attach about 0.25 g of an adhesive layer to a 250-mesh wire mesh (100 mm x 100 mm) that accurately measures the mass with a precision balance, and wrap the gel component so that it does not leak out. After that, the mass was accurately measured on a precision balance to make a sample. (2) The obtained sample was immersed in 80 ml of ethyl acetate for 3 days. (3) The sample was taken out, washed with a small amount of ethyl acetate, and dried at 120 ° C for 24 hours. After that, the mass is accurately measured on a precision balance. (4) The gel fraction was calculated using the following formula. Gel fraction (% by mass) = (ZX) / (YX) × 100 However, X is the mass of the wire mesh (g), and Y is the mass of the wire mesh before the adhesive layer is dipped (g) , Z is the mass (g) of the metal wire mesh that has been dried and soaked after the adhesive layer has been pasted.
作為本發明的黏接劑也可以含有的其他成分，可以列舉紫外線吸收劑、增黏劑、塑化劑、軟化劑、助剝離劑、染料、顏料、無機充填劑、界面活性劑、抗氧化劑、金屬腐蝕抑制劑、矽烷偶合劑等。其他的成分於無損本發明之一實施型態的效果的範圍內之量摻合於黏接劑。Other components that may be contained in the adhesive of the present invention include ultraviolet absorbers, tackifiers, plasticizers, softeners, release aids, dyes, pigments, inorganic fillers, surfactants, antioxidants, Metal corrosion inhibitor, silane coupling agent, etc. The other components are blended in the adhesive in an amount that does not impair the effect of one embodiment of the present invention.
＜黏接片＞ 本發明的一實施型態的黏接片，具有以既述的本發明之一實施型態的黏接劑形成的黏接劑層。該黏接劑層含有既述的(甲基)丙烯酸系聚合物與交聯劑間所形成的交聯結構。該黏接劑層的相對電容率低，黏接力高，加工性優良。<Adhesive sheet> The adhesive sheet of one embodiment of the present invention has an adhesive layer formed of the adhesive of one embodiment of the present invention described above. This adhesive layer contains the crosslinked structure formed between the said (meth) acrylic-type polymer and a crosslinking agent. The relative permittivity of the adhesive layer is low, the adhesive force is high, and the processability is excellent.
黏接片可以是沒有基材的類型(無基材型)，也可以是有基材的類型(有基材型)。 作為基材可以列舉樹脂膜(例如聚對苯二甲酸乙二醇酯(PET)等的聚酯膜)。基材以透明為佳。基材的厚度並沒有特別的限制，但由耐久性的觀點以5μm~100μm為佳。 作為黏接片由透明性的觀點以無基材為佳。The adhesive sheet may be a type without a substrate (no substrate type), or may be a type with a substrate (type with a substrate). Examples of the substrate include a resin film (for example, a polyester film such as polyethylene terephthalate (PET)). The substrate is preferably transparent. The thickness of the substrate is not particularly limited, but it is preferably from 5 μm to 100 μm from the viewpoint of durability. From the viewpoint of transparency, the adhesive sheet is preferably a baseless material.
黏接片的黏接劑層的露出的面可利用剝離膜保護。 作為剝離膜，只要是可以從黏接劑層輕易地進行剝離即可，並沒有特別的限制，例如可以列舉於至少一面使用剝離處理劑實施易剝離處理的樹脂膜（例如PET等的聚酯膜）。作為剝離處理劑例如可以列舉氟系樹脂、石蠟、矽酮、長鏈烷基化合物。 剝離膜於黏接片提供實用之前的期間保護黏接劑層的表面，於使用時剝離。The exposed surface of the adhesive layer of the adhesive sheet can be protected by a release film. The release film is not particularly limited as long as it can be easily peeled from the adhesive layer, and examples thereof include a resin film (for example, a polyester film such as PET) that is easily peeled using a release treatment agent on at least one side. ). Examples of the peeling treatment agent include a fluorine-based resin, paraffin, silicone, and a long-chain alkyl compound. The release film protects the surface of the adhesive layer before the adhesive sheet is provided for practical use, and is peeled off during use.
黏接片的黏接劑層的厚度並沒有特別的限制，可依用途及要求的性能適當地選擇。黏接劑的厚度由高低差追隨性的觀點以及黏接片的生產性的觀點，例如可列舉20μm~300μm的範圍。The thickness of the adhesive layer of the adhesive sheet is not particularly limited, and may be appropriately selected according to the application and required performance. The thickness of the adhesive is, for example, in a range of 20 μm to 300 μm from the viewpoint of step-followability and the viewpoint of productivity of the adhesive sheet.
黏接劑層由作為觸控面板時的可見性之觀點，以透明性高者為佳，具體來說，例如可見光波長區之全光線透射率(JIS K 7361(1997年))為85%以上為佳，90%以上更佳。 黏接劑層的霧度(JIS K 7136(2000年))由作為觸控面板時的可見性的觀點，以未達2.0%為佳，未達1.0%更佳，0.5%以下再更佳。From the viewpoint of visibility when used as a touch panel, the adhesive layer is preferably a transparent one. Specifically, for example, the total light transmittance in the visible wavelength region (JIS K 7361 (1997)) is 85% or more. Better, more than 90%. From the viewpoint of visibility when used as a touch panel, the haze (JIS K 7136 (2000)) of the adhesive layer is preferably less than 2.0%, more preferably less than 1.0%, and even more preferably less than 0.5%.
黏接片例如可以將本發明之一實施型態的黏接劑塗佈於剝離膜等，使其乾燥，藉由發生交聯反應形成黏接劑層而製作。The pressure-sensitive adhesive sheet can be produced by, for example, applying a pressure-sensitive adhesive according to an embodiment of the present invention to a release film or the like, drying it, and forming a pressure-sensitive adhesive layer by a crosslinking reaction.
無基材類型的黏接片例如可以於剝離膜的剝離處理面塗佈黏接劑，發生交聯反應而形成黏接劑層，之後，於此黏接劑層上使另一剝離膜以剝離處理面以接觸的方式重疊以製作。The substrate-less type adhesive sheet can be coated with an adhesive on the release-treated surface of a release film, for example, to cause a cross-linking reaction to form an adhesive layer. Thereafter, another release film can be peeled off on this adhesive layer. The processing surfaces are overlapped in a contact manner to make.
有基材類型的黏接片例如可以於基材的兩面塗佈黏接劑，發生交聯反應形成黏接劑層，之後，於此兩面塗佈的黏接劑層上，各自使剝離膜之剝離處理面接觸的方式重疊以製作。又，也可以利用下列方法製作：於剝離膜的剝離處理面形成黏接劑層，將此附有剝離膜的黏接劑層重疊於基材的兩面。The adhesive sheet with a substrate type can be coated with an adhesive on both sides of the substrate, for example, and a cross-linking reaction occurs to form an adhesive layer. Then, on the adhesive layer coated on both sides, the release film The peeling treatment surfaces are superimposed so as to make contact. In addition, it can also be produced by forming an adhesive layer on the release-treated surface of the release film, and overlapping the adhesive layer with the release film on both surfaces of the substrate.
作為於剝離膜及基材塗佈黏接劑的方法可列舉使用輪轉凹輥塗佈機、逆轉輥式塗佈機、輥舐塗布機、浸漬輥塗布機、刮棒塗佈機、刀式塗佈機、噴塗機等為公眾所知悉的方法。Examples of a method for applying an adhesive to a release film and a substrate include a rotary gravure coater, a reverse roll coater, a roll coater, a dip roll coater, a bar coater, and a knife coater. Distributors, sprayers, etc. are known to the public.
作為本發明之一實施型態的黏接片的用途，例如可列舉觸控面板用途。特別是本發明之一實施型態的黏接片，適合使用於構成觸控面板時貼合玻璃基板、透明導電膜及設計膜等多數構件。又，更適合使用於構成觸控面板時，貼合透明導電膜與其他構件。Examples of the application of the adhesive sheet according to one embodiment of the present invention include touch panel applications. In particular, the adhesive sheet according to an embodiment of the present invention is suitable for bonding a plurality of members such as a glass substrate, a transparent conductive film, and a design film when forming a touch panel. Furthermore, it is more suitable for bonding a transparent conductive film and other members when forming a touch panel.
＜觸控面板＞ 使用本發明之一實施型態的黏接劑或黏接片的觸控面板，具有以既述的本發明之一實施型態之黏接劑所形成的黏接劑層。該黏接劑層因相對電容率低，即使黏接劑層的厚度薄，於觸控面板動作時，觸控面板內部的靜電容量仍可保持於適當的值，而可抑制起因於靜電容量的誤作動。 又，本發明之一實施型態的觸控面板因使用既述的本發明之一實施型態的黏接劑，作為黏接片情況的加工性優良，不容易發生黏接劑超出觸控面板構成構件等製造上的失敗。<Touch Panel> A touch panel using an adhesive or an adhesive sheet according to one embodiment of the present invention has an adhesive layer formed with the adhesive of one embodiment of the present invention described above. Due to the low relative permittivity of the adhesive layer, even if the thickness of the adhesive layer is thin, the electrostatic capacity inside the touch panel can be maintained at an appropriate value when the touch panel is operating, and the capacitance caused by the electrostatic capacity can be suppressed. Malfunction. In addition, the touch panel of one embodiment of the present invention uses the adhesive of one of the embodiments of the present invention described above, and has excellent processability as an adhesive sheet, and it is unlikely that the adhesive exceeds the touch panel. Failure in manufacturing of constituent members and the like.
使用本發明之一實施態樣的黏接劑或黏接片的電容式觸控面板，例如可為按設計膜、黏接劑層、透明導電膜、黏接劑層、透明導電膜的順序疊層的結構。 ［實施例］A capacitive touch panel using an adhesive or an adhesive sheet according to an embodiment of the present invention may be stacked in the order of a design film, an adhesive layer, a transparent conductive film, an adhesive layer, and a transparent conductive film. The structure of the layers. [Example]
以下利用實施例具體地說明本發明之一實施型態，但本發明並不限於這些實施例。Hereinafter, an embodiment of the present invention will be specifically described using examples, but the present invention is not limited to these examples.
(實施例1) [(甲基) 丙烯酸系聚合物的製造] 於具備攪拌機、回流冷凝器、連續滴加裝置及溫度計的反應裝置，放入乙酸乙酯147質量份及2,2'-偶氮雙(2,4-二甲基戊腈)0.05質量份。接著，於別的容器中準備由甲基丙烯酸-2-乙基己酯(2EHMA)210質量份(相對全部構成單元為35質量%)、丙烯酸 2-乙基己酯(2EHA)330質量份(相對全部構成單元為55質量%)、丙烯酸2-羥乙酯(2HEA)60質量份(相對全部構成單元為10質量%)構成的單體混合液600質量份，將其中150質量份放入反應裝置，加熱，並於回流溫度進行20分鐘的回流。接下來，於回流溫度條件下將剩下的單體混合液450質量份與乙酸乙酯33質量份及2,2'-偶氮雙(2,4-二甲基戊腈)0.03質量份於90分鐘內連續滴下，滴下結束後再進行90分鐘的聚合反應。之後將乙酸乙酯15質量份與過氧化新戊酸叔丁酯0.13質量份的混合液以30分鐘連續滴加，再進行150分鐘的聚合反應。 反應結束後於乙酸乙酯中稀釋成固體成分為45質量%，得到(甲基) 丙烯酸系聚合物1的溶液。(Example 1) [Production of (meth) acrylic polymer] In a reaction apparatus including a stirrer, a reflux condenser, a continuous dropping device, and a thermometer, 147 parts by mass of ethyl acetate and 2,2'-coupling were placed. 0.05 parts by mass of nitrogen bis (2,4-dimethylvaleronitrile). Next, 210 parts by mass of 2-ethylhexyl methacrylate (2EHMA) (35% by mass with respect to all constituent units) and 330 parts by mass of 2-ethylhexyl acrylate (2EHA) were prepared in another container ( 600 mass parts of monomer mixed liquid consisting of 60 mass parts of 2-hydroxyethyl acrylate (2HEA) relative to all constituent units) and 60 mass parts of 2-hydroxyethyl acrylate (2HEA), and 150 mass parts thereof were put into the reaction The apparatus was heated, and refluxed at the reflux temperature for 20 minutes. Next, 450 parts by mass of the remaining monomer mixed solution, 33 parts by mass of ethyl acetate, and 0.03 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) were mixed under reflux temperature conditions. The dripping was continued for 90 minutes, and the polymerization reaction was performed for another 90 minutes after the dripping was completed. Thereafter, a mixed solution of 15 parts by mass of ethyl acetate and 0.13 parts by mass of tert-butyl peroxypivalate was continuously added dropwise for 30 minutes, and a polymerization reaction was further performed for 150 minutes. After completion of the reaction, the solid content was diluted to 45% by mass in ethyl acetate to obtain a solution of the (meth) acrylic polymer 1.
得到的(甲基) 丙烯酸系聚合物1之重量平均分子量(Mw)為49萬，分散度(Mw/Mn)為6.2，玻璃化轉變溫度(Tg)為-50℃。又，重量平均分子量(Mw)、數平均分子量(Mn)及玻璃化轉變溫度(Tg)是利用既述的方法測定或算出。The weight average molecular weight (Mw) of the obtained (meth) acrylic polymer 1 was 490,000, the degree of dispersion (Mw / Mn) was 6.2, and the glass transition temperature (Tg) was -50 ° C. The weight average molecular weight (Mw), the number average molecular weight (Mn), and the glass transition temperature (Tg) are measured or calculated by the methods described above.
［黏接劑溶液的製備］ 相對於(甲基) 丙烯酸系聚合物1的溶液222.2質量份(固體成分為100質量份)，加入固體成分為0.2質量份的作為交聯劑的D-110N(三井化學有限公司製)並混合，製備成黏接劑溶液。[Preparation of Adhesive Solution] D-110N (as a cross-linking agent with a solid content of 0.2 parts by mass was added to 222.2 parts by mass of the (meth) acrylic polymer 1 solution (100 parts by mass of solid content) ( Mitsui Chemical Co., Ltd.) and mixed to prepare an adhesive solution.
［試驗用樣品的製作］ 將製備的黏接劑溶液以乾燥後的黏接劑層厚度成為50μm的方式塗佈於以矽酮系剝離處理劑進行易剝離處理的剝離膜(商品名：FILMBYNA 100E，藤森工業有限公司製)的剝離處理面，形成塗佈層。之後，將得到具有塗佈層的剝離膜以100℃、2分鐘的乾燥條件乾燥，於剝離膜上形成黏接劑層。將黏接劑層露出的面貼合於另外準備的剝離膜(商品名：FILMBYNA 100E，藤森工業有限公司製)，製作無基材類型的黏接片。之後，於溫度23℃、50%RH的環境下熟成4天進行交聯反應，得到具有含交聯結構的黏接劑層的試驗用樣品。製作的試驗用樣品的凝膠分率為58.0質量%。又，凝膠分率是利用既述之方法測定。[Production of test sample] The prepared adhesive solution was applied to a release film (trade name: FILMBYNA 100E) which was easily peeled with a silicone release treatment agent so that the thickness of the dried adhesive layer was 50 μm. , Manufactured by Fujimori Industry Co., Ltd.) to form a coating layer. Thereafter, the release film having the coating layer was dried under a drying condition at 100 ° C. for 2 minutes to form an adhesive layer on the release film. The exposed surface of the adhesive layer was bonded to a separately prepared release film (trade name: FILMBYNA 100E, manufactured by Fujimori Industry Co., Ltd.) to produce a substrate-less type adhesive sheet. Then, it was aged for 4 days under the environment of a temperature of 23 ° C. and 50% RH to perform a crosslinking reaction to obtain a test sample having an adhesive layer containing a crosslinked structure. The gel fraction of the produced test sample was 58.0% by mass. The gel fraction was measured by the method described above.
［評價］ 遵循下述，評價試驗用樣品中的黏接劑層的相對電容率、加工性、黏接力以及耐濕熱白化性。結果表示於表1。[Evaluation] The relative permittivity, processability, adhesion, and wet heat whitening resistance of the adhesive layer in the test sample were evaluated in accordance with the following. The results are shown in Table 1.
(相對電容率) 剝離製作的試驗用樣品的其中一剝離膜，貼合於電解銅箔(古河電氣工業股份有限公司製，10μm，NC-WC處理品)。之後，剝離試驗用樣品的另一剝離膜，於露出黏接層的面再貼合另一已剝離其中一邊一剝離膜的試驗用樣品的露出黏接劑層的面。重複此試驗用樣品貼合的順序，直到黏接劑層的厚度成為200μm。於黏接劑層厚度成為200μm的時點，剝離最後貼合的試驗用樣品的剝離膜，於黏接劑層露出的面貼合電解銅箔。將如此得到的兩張電解銅箔間疊層了200μm厚度的黏接劑層的樣品切割成50mm×50mm的尺寸，作為測定相對電容率的樣品。(Relative permittivity) One of the peeling films of the test sample produced was peeled and bonded to an electrolytic copper foil (manufactured by Furukawa Electric Industry Co., Ltd., 10 μm, NC-WC-treated product). Then, the other release film of the test sample is peeled, and the surface of the other test sample from which one of the release films has been peeled off is adhered to the surface on which the adhesive layer is exposed. The procedure for bonding the test samples was repeated until the thickness of the adhesive layer became 200 μm. When the thickness of the adhesive layer became 200 μm, the release film of the test sample that was last attached was peeled off, and an electrolytic copper foil was pasted on the exposed surface of the adhesive layer. A sample in which an adhesive layer having a thickness of 200 μm was laminated between the two electrolytic copper foils thus obtained was cut into a size of 50 mm × 50 mm as a sample for measuring a relative permittivity.
相對電容率的測定係使用Agilent Technologies製的Material Analyzer 4291B以下列條件進行。接著，以下列的基準評價黏接劑層的相對電容率。下列評價基準的A及B為實用上沒有問題的等級，C是實用上有問題的等級。The measurement of the relative permittivity was performed using a Material Analyzer 4291B manufactured by Agilent Technologies under the following conditions. Next, the relative permittivity of the adhesive layer was evaluated on the following criteria. A and B in the following evaluation criteria are grades without practical problems, and C is a grade with practical problems.
—測定條件— 測定工具：Agilent Technologies製的Dielectric Test Fixture 16453A 測定頻率：100kHz—Measurement conditions— Measurement tool: Dielectric Test Fixture 16453A manufactured by Agilent Technologies Measurement frequency: 100kHz
—評價基準— A：相對電容率為3.5以下。 B：相對電容率超過3.5，為4.0以下。 C：相對電容率超過4.0。—Evaluation Criteria— A: The relative permittivity is 3.5 or less. B: The relative permittivity exceeds 3.5 and is 4.0 or less. C: Relative permittivity exceeds 4.0.
(加工性) 黏接劑層的加工性是遵循JIS Z 0237(2009年)的保持力評價的。也就是說，是以下列記載的試驗評價。 剝離製作好的試驗用樣品的其中一邊剝離膜，貼合於經易黏接處理的PET膜(A-4100(東洋紡有限公司製)，厚度100μm)之易黏接處理的面。之後，切割成25mm×50mm的尺寸，切割後，剝離另一剝離膜，以試驗用樣品的端部開始至10mm處為止，以接觸不鏽鋼(SUS)板的方式進行壓接貼合(貼合面積25mm×10mm)於，作為加工性評價用樣品。將此加工性評價用樣品於23℃、50%RH的環境下保持，使 SUS板與地面呈法線方向，且黏接片的未貼合部分在下方，為施掛重物以對於黏接片增加1.0kg的負荷。測定從掛上負荷開始，1小時後的黏接片移動距離，遵循下列的評價基準評價加工性。又，加工性以移動距離越短者為優，下列評價基準的A及B為實用上沒有問題的等級，C是實用上有問題的等級。(Processability) The processability of the adhesive layer was evaluated in accordance with the retention of JIS Z 0237 (2009). That is, it was evaluated by the test described below. One of the prepared test samples was peeled, and the film was peeled off, and then bonded to the easily-adhesive treated PET film (A-4100 (manufactured by Toyobo Co., Ltd.), thickness 100 μm) on the easily-adhesive surface. After that, it was cut into a size of 25mm × 50mm. After cutting, another peeling film was peeled off, and the end of the test sample was started up to 10mm, and pressure-bonded and bonded (contact area) to a stainless steel (SUS) plate. 25 mm × 10 mm), and used as a sample for evaluation of processability. This sample for processability evaluation was held in an environment of 23 ° C and 50% RH, so that the SUS board and the ground were in a normal direction, and the non-adhered part of the adhesive sheet was below. The tablet increased the load by 1.0kg. The moving distance of the adhesive sheet 1 hour after the load was measured was measured, and the processability was evaluated according to the following evaluation criteria. In addition, the shorter the moving distance is, the better the processability is. The following evaluation criteria A and B are grades that are practically not problematic, and C is a grade that is practically problematic.
—評價基準— A：移動距離未達0.4mm。 B：移動距離為0.4mm以上，未達0.8mm。 C：移動距離為0.8mm以上。—Evaluation Criteria— A: The moving distance is less than 0.4mm. B: The moving distance is 0.4 mm or more and less than 0.8 mm. C: The moving distance is 0.8 mm or more.
(黏接力) 剝離製作好的實驗用樣品的其中一剝離膜，將露出黏接劑層的面貼合於經易黏接處理的PET膜(A-4100(東洋紡有限公司製)，厚度100μm)的經易黏接處理的面。將此試驗用樣品切割成25mm×150mm後，再剝離另一剝離膜，使用重2kg的橡膠輥以黏接劑層接觸玻璃板的方式壓接於玻璃板表面，作為評價黏接力的樣品。 將此黏接力評價用樣品於23℃、50%RH的環境下放置24小時後，以剝離速度300mm/min測定180゜剝離的黏接力(N/25mm)，並遵循下列評價基準評價。下列評價基準的A、B以及C為實用上沒有問題的等級，D是實用上有問題的等級。(Adhesive force) One of the prepared test samples was peeled off, and the surface exposing the adhesive layer was bonded to a PET film (A-4100 (manufactured by Toyobo Co., Ltd.) with a thickness of 100 μm) which was easily adhered. Easy-to-adhesive surface. This test sample was cut into 25 mm × 150 mm, and then the other peeling film was peeled off, and a 2 kg rubber roller was used to press-contact the glass plate surface with the adhesive layer contacting the glass plate as a sample for evaluating the adhesion. After the sample for adhesive force evaluation was left in an environment of 23 ° C. and 50% RH for 24 hours, the adhesive force (N / 25 mm) of peeling at 180 ° was measured at a peeling speed of 300 mm / min, and evaluated in accordance with the following evaluation criteria. A, B, and C of the following evaluation criteria are grades without practical problems, and D is a grade with practical problems.
—評價基準— A：黏接力為20N/25mm以上。 B：黏接力為15N/25mm以上，未達20N/25mm。 C：黏接力為10N/25mm以上，未達15N/25mm。 D：黏接力未達10N/25mm。—Evaluation Criteria— A: Adhesive force is 20N / 25mm or more. B: The adhesive force is 15N / 25mm or more and less than 20N / 25mm. C: The adhesive force is 10N / 25mm or more and less than 15N / 25mm. D: The adhesive force is less than 10N / 25mm.
(耐濕熱白化性) 將製作好的試驗用樣品切割成寬80mm×長60mm的尺寸。剝離試驗用樣品的其中一剝離膜，將露出黏接劑層的面重疊於1.8mm厚的玻璃板(松浪硝子工業股份有限公司製，光學鈉鈣玻璃，寬250mm×長200mm)，再用桌上型層合機壓接，作為耐濕熱白化性試驗用樣品，測定霧度(試驗進行前霧度)。之後，於85℃，90%RH的環境下放置250小時，再於23℃，50%RH的環境下冷卻10分鐘後，測定霧度(試驗進行後霧度)。又，霧度是使用日本電色有限公司製的NDH 5000SP測定。求出試驗進行後之霧度減去試驗進行前霧度的值(ΔH)，遵循下列基準評價耐濕熱白化性。又，ΔH越小，耐濕熱白化性越優良。(Moisture and whitening resistance) The prepared test sample was cut into a size of 80 mm in width × 60 mm in length. One of the peeling films of the peeling test sample, the surface on which the adhesive layer was exposed was superimposed on a 1.8 mm-thick glass plate (manufactured by Songlang Glass Industry Co., Ltd., optical soda-lime glass, width 250 mm × length 200 mm), and the table The upper-layer laminator was crimped, and a haze was measured as a sample for a moist-heat whitening resistance test (the haze before the test was performed). Then, it was left to stand in an environment of 85 ° C and 90% RH for 250 hours, and then cooled in an environment of 23 ° C and 50% RH for 10 minutes, and then the haze was measured (haze after the test was performed). The haze was measured using NDH 5000SP manufactured by Nippon Denshoku Co., Ltd. The value of the haze after the test was subtracted from the haze before the test (ΔH) was determined, and the moist heat whitening resistance was evaluated in accordance with the following criteria. The smaller the ΔH, the better the moist-heat whitening resistance.
—評價基準— A：ΔH未達1.0。 B：ΔH為1.0以上未達1.5。 C：ΔH為1.5以上未達2.0。 D：ΔH為2.0以上未達4.0。 E：ΔH為4.0以上。—Evaluation Criteria— A: ΔH did not reach 1.0. B: ΔH is 1.0 or more and less than 1.5. C: ΔH is 1.5 or more and less than 2.0. D: ΔH is 2.0 or more and less than 4.0. E: ΔH is 4.0 or more.
(實施例2~實施例9，比較例1~比較例8) 實施例2~實施例9，比較例1~比較例8如表1及表2所示，黏接劑中除變更(甲基)丙烯酸系聚合物的組成以外，其他與實施例1一樣，進行(甲基)丙烯酸系聚合物的製造、黏接劑的製備以及試驗用樣品的製作，評價試驗用樣品中黏接劑層的相對電容率、加工性、黏接力以及耐濕熱白化性。結果表示於表1或表2。(Example 2 to Example 9, Comparative Example 1 to Comparative Example 8) Example 2 to Example 9, Comparative Example 1 to Comparative Example 8 are shown in Tables 1 and 2, except that the adhesive was changed (methyl ) Except for the composition of the acrylic polymer, the production of the (meth) acrylic polymer, the preparation of the adhesive, and the preparation of the test sample were performed in the same manner as in Example 1. The evaluation of the adhesive layer in the test sample was performed. Relative permittivity, processability, adhesion and moist heat whitening resistance. The results are shown in Table 1 or Table 2.
【表1】
【表2】
又，表1及表2中所表示的簡稱如下所述。 ．2EHMA：甲基丙烯酸2-乙基己酯(具有碳原子數8的分支鏈烷基的甲基丙烯酸烷酯) ．2EHA：丙烯酸2-乙基己酯(具有碳原子數8的分支鏈烷基的丙烯酸烷酯) ．iBMA：甲基丙烯酸異丁酯(具有碳原子數4的分支鏈烷基的甲基丙烯酸烷酯) ．nBMA：甲基丙烯酸正丁酯(具有碳原子數4的直鏈烷基的甲基丙烯酸烷酯) ．IDMA：甲基丙烯酸異癸酯(具有碳原子數10的分支鏈烷基的甲基丙烯酸烷酯) ．LMA：甲基丙烯酸月桂酯 (具有碳原子數12的直鏈烷基的甲基丙烯酸烷酯) ．CHMA：甲基丙烯酸環己酯 (具有環狀基的單體) ．2HEA：丙烯酸2-羥乙酯(具有羥基的單體) ．D110N：異氰酸酯系交聯劑(商品名TAKENATE D-110N)The abbreviations shown in Tables 1 and 2 are as follows. ． 2EHMA: 2-ethylhexyl methacrylate (alkyl methacrylate having a branched alkyl group having 8 carbon atoms). 2EHA: 2-ethylhexyl acrylate (alkyl acrylate having a branched alkyl group having 8 carbon atoms). iBMA: isobutyl methacrylate (alkyl methacrylate with a branched alkyl group having 4 carbon atoms). nBMA: n-butyl methacrylate (alkyl methacrylate with a linear alkyl group having 4 carbon atoms). IDMA: isodecyl methacrylate (alkyl methacrylate having a branched alkyl group having 10 carbon atoms). LMA: lauryl methacrylate (alkyl methacrylate with a linear alkyl group having 12 carbon atoms). CHMA: cyclohexyl methacrylate (monomer with cyclic group). 2HEA: 2-hydroxyethyl acrylate (monomer with hydroxyl group). D110N: Isocyanate-based crosslinking agent (brand name TAKENATE D-110N)
由表1可知，實施例1～實施例9的相對電容率、加工性及黏接力均優良。 由表2可知，如比較例1般，來自具有羥基的單體的構成單元的含有率超過35質量%的話，相對電容率為高。 如比較例2，可知來自具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元的含有率未達35質量%的話，相對電容率為高。 如比較例3~比較例7，可知代替來自具有碳原子數5~9之分支鏈烷基的甲基丙烯酸烷酯的構成單元，而包含來自丙烯酸烷酯的構成單元，或來自具有碳原子數超過9的分支鏈烷基或直鏈烷基的甲基丙烯酸酯的構成單元的話，相對電容率與加工性不能兩全。 如比較例8，可知(甲基)丙烯酸系聚合物的Tg超過-10℃的話，黏接力會低，而不具作為黏接劑的功能。As can be seen from Table 1, the relative permittivity, workability, and adhesion of Examples 1 to 9 were all excellent. As can be seen from Table 2, as in Comparative Example 1, when the content rate of the structural unit derived from the monomer having a hydroxyl group exceeds 35% by mass, the relative permittivity is high. As shown in Comparative Example 2, when the content rate of the constituent unit derived from the alkyl methacrylate having a branched alkyl group having 5 to 9 carbon atoms is less than 35% by mass, the relative permittivity is high. As shown in Comparative Example 3 to Comparative Example 7, it can be seen that instead of the constitutional unit derived from an alkyl methacrylate having a branched alkyl group having 5 to 9 carbon atoms, the constitutional unit derived from an alkyl acrylate is included, or the constitutional unit is derived from an alkyl acrylate. When the constituent unit of a branched alkyl group or linear alkyl methacrylate exceeds 9, the relative permittivity and processability are not compatible. As can be seen from Comparative Example 8, if the Tg of the (meth) acrylic polymer exceeds -10 ° C, the adhesive force will be low, and it will not function as an adhesive.
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- 2015-09-30 CN CN201510640224.3A patent/CN105482744B/en active Active
- 2015-10-01 TW TW104132307A patent/TWI674304B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103582685A (en) * | 2011-06-14 | 2014-02-12 | 日东电工株式会社 | Adhesive composition, adhesive layer, and adhesive sheet |
| WO2014092186A1 (en) * | 2012-12-13 | 2014-06-19 | 東亞合成株式会社 | Active energy ray-curable adhesive composition |
Non-Patent Citations (1)
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Also Published As
| Publication number | Publication date |
|---|---|
| CN105482744B (en) | 2019-04-16 |
| KR20160040106A (en) | 2016-04-12 |
| JP6309422B2 (en) | 2018-04-11 |
| CN105482744A (en) | 2016-04-13 |
| KR102326888B1 (en) | 2021-11-16 |
| TW201619332A (en) | 2016-06-01 |
| JP2016074761A (en) | 2016-05-12 |
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