TWI811296B

TWI811296B - Adhesive sheet peeling method

Info

Publication number: TWI811296B
Application number: TW108103779A
Authority: TW
Inventors: 小坂尚史; 清水陽介; 本田哲士; 下栗大器; 寳田翔; 佐竹正之; 岡田研一; 高嶋淳; 水原銀次
Original assignee: 日商日東電工股份有限公司
Priority date: 2018-02-05
Filing date: 2019-01-31
Publication date: 2023-08-11
Also published as: WO2019151192A1; TW201936823A

Abstract

本發明提供一種貼附於偏光板之黏著片材之剝離方法。上述黏著片材具備黏著劑層，該黏著劑層包含構成該黏著劑層之至少一表面之A層。上述偏光板之貼附有上述黏著片材之側之表面經電暈處理或電漿處理。上述剝離方法包括水剝離步驟，其係於在上述黏著片材自上述偏光板之剝離前線處在上述偏光板與上述黏著片材之界面存在水性液體之狀態下，一面使上述水性液體追隨於上述剝離前線之移動而進入至上述界面，一面自上述偏光板剝離上述黏著片材。The invention provides a method for peeling off an adhesive sheet attached to a polarizing plate. The above-mentioned adhesive sheet has an adhesive layer, and the adhesive layer includes an A layer constituting at least one surface of the adhesive layer. The surface of the polarizing plate on the side where the adhesive sheet is attached is subjected to corona treatment or plasma treatment. The above-mentioned peeling method includes a water peeling step, which is to make the aqueous liquid follow the above-mentioned aqueous liquid while there is an aqueous liquid at the interface between the above-mentioned polarizing plate and the above-mentioned adhesive sheet at the peeling line of the above-mentioned adhesive sheet from the above-mentioned polarizing plate. The peeling front line moves to the interface and peels off the adhesive sheet from the polarizing plate.

Description

黏著片材剝離方法Adhesive sheet peeling method

本發明係關於一種黏著片材之剝離方法。本申請案主張基於2018年2月5日提出申請之日本專利申請案2018-018621號、2018年6月7日提出申請之日本專利申請案2018-109385號及2018年7月3日提出申請之日本專利申請案2018-126577號之優先權，且將該等申請案之全部內容作為參照而併入至本說明書中。The present invention relates to a method for peeling off adhesive sheets. The claims of this application are based on Japanese Patent Application No. 2018-018621 filed on February 5, 2018, Japanese Patent Application No. 2018-109385 filed on June 7, 2018, and Japanese Patent Application No. 2018-109385 filed on July 3, 2018. Priority is granted to Japanese Patent Application No. 2018-126577, and the entire contents of such application are incorporated into this specification by reference.

一般而言，黏著劑(亦稱為感壓接著劑。以下相同)具有如下性質：於室溫附近之溫度區域內呈現柔軟之固體(黏彈性體)之狀態，且藉由壓力而簡單地接著於被黏著體。有效利用此種性質，黏著劑以於支持體上具有黏著劑層之附支持體之黏著片材之形態、或者不具有支持體之無支持體之黏著片材之形態廣泛地用於各種領域。 [先前技術文獻] [專利文獻]Generally speaking, adhesives (also called pressure-sensitive adhesives. The same applies below) have the following properties: They assume the state of a soft solid (viscoelastic body) in a temperature range near room temperature and are easily adhered by pressure. on the adherend. By effectively utilizing this property, adhesives are widely used in various fields in the form of an adhesive sheet with a support having an adhesive layer on the support, or in the form of a support-less adhesive sheet without a support. [Prior technical literature] [Patent Document]

專利文獻1：日本專利申請案公開2005-148638號公報Patent Document 1: Japanese Patent Application Publication No. 2005-148638

[發明所欲解決之問題][Problem to be solved by the invention]

對於黏著劑，根據用途而要求各種特性。該等特性中，有存在若欲改善一特性則另一特性降低之傾向等難以以高水準兼顧者。如此處於難以兼顧之關係之特性之一例，可列舉對被黏著體之黏著力及二次加工性。上述二次加工係指於將黏著片材貼附於被黏著體時產生黏貼失敗(位置偏移、褶皺或氣泡之產生、異物之夾入等)之情形、或於貼附黏著片材後於被黏著體發現不良情況之情形等，將黏著片材自被黏著體剝離而重新黏貼。於專利文獻1中，關於自於玻璃基板等基板(被黏著體)之表面貼附有黏著型光學膜之附光學膜之基板剝離該黏著型光學膜之方法，揭示有於在上述黏著型光學膜之黏著劑層與上述基板之剝離界面存在液體之狀態下自上述基板剝離上述黏著型光學膜之技術。另一方面，於專利文獻1中，未對貼附於偏光板之黏著片材之剝離方法、即被黏著體為偏光板之情形時之黏著片材剝離方法進行研究。Adhesives are required to have various properties depending on their intended use. Among these characteristics, there is a tendency that if one characteristic is improved, another characteristic will be degraded, and it is difficult to achieve both at a high level. An example of characteristics that are in such a difficult-to-balance relationship is adhesion to the adherend and secondary processability. The above-mentioned secondary processing refers to the situation where adhesion failure (positional deviation, generation of wrinkles or bubbles, inclusion of foreign matter, etc.) occurs when the adhesive sheet is attached to the adherend, or when the adhesive sheet is attached. If any defect is found on the adherend, peel the adhesive sheet from the adherend and reattach it. Patent Document 1 discloses a method for peeling an adhesive optical film from a substrate with an adhesive optical film attached to the surface of a substrate (adherent) such as a glass substrate. A technique for peeling off the adhesive optical film from the substrate while a liquid exists at the peeling interface between the adhesive layer of the film and the substrate. On the other hand, Patent Document 1 does not examine the peeling method of the adhesive sheet attached to the polarizing plate, that is, the peeling method of the adhesive sheet when the adherend is a polarizing plate.

因此，本發明之目的在於提供一種可利用水等水性液體自作為被黏著體之偏光板容易地剝離黏著片材的黏著片材剝離方法。 [解決課題之技術手段]Therefore, an object of the present invention is to provide an adhesive sheet peeling method that can easily peel an adhesive sheet from a polarizing plate as an adherend using an aqueous liquid such as water. [Technical means to solve the problem]

根據本說明書，提供一種剝離貼附於作為被黏著體之偏光板之黏著片材之方法。上述偏光板之貼附有上述黏著片材之側之表面經電暈處理或電漿處理。上述黏著片材具備黏著劑層，該黏著劑層包含構成該黏著劑層之至少上述偏光板側之表面之A層。上述剝離方法可包括水剝離步驟，其係於在上述黏著片材自上述偏光板之剝離前線處在上述偏光板與上述黏著片材之界面存在水性液體之狀態下，一面使上述水性液體追隨於上述剝離前線之移動而進入至上述界面，一面自上述偏光板剝離上述黏著片材。此處，所謂剝離前線，係指於使黏著片材自偏光板之剝離進行時，上述黏著片材自上述偏光板開始分離之部位。根據上述水剝離步驟，可有效地利用上述水性液體自偏光板剝離黏著片材。於若干態樣中，上述A層較佳為由包含水親和劑之黏著劑構成。According to this specification, a method for peeling off an adhesive sheet attached to a polarizing plate as an adherend is provided. The surface of the polarizing plate on the side where the adhesive sheet is attached is subjected to corona treatment or plasma treatment. The above-mentioned adhesive sheet has an adhesive layer, and the adhesive layer includes an A layer constituting at least the surface of the adhesive layer on the side of the polarizing plate. The peeling method may include a water peeling step, which involves causing the aqueous liquid to follow the aqueous liquid at the interface between the polarizing plate and the adhesive sheet at the peeling line of the adhesive sheet from the polarizing plate. The peeling front line moves to the interface and peels off the adhesive sheet from the polarizing plate. Here, the peeling front line refers to the position where the adhesive sheet starts to separate from the polarizing plate when the adhesive sheet is peeled from the polarizing plate. According to the above water peeling step, the above aqueous liquid can be effectively used to peel off the adhesive sheet from the polarizing plate. In some aspects, the above-mentioned A layer is preferably composed of an adhesive containing a water affinity agent.

上述剝離方法可於在上述水剝離步驟中使上述剝離前線以10 mm/分鐘以上之速度移動之態樣中較佳地實施。根據該態樣，可將黏著片材自偏光板高效率地剝離。The above-mentioned peeling method can be preferably carried out in a state in which the above-mentioned peeling front line is moved at a speed of 10 mm/min or more in the above-mentioned water peeling step. According to this aspect, the adhesive sheet can be efficiently peeled off from the polarizing plate.

以下，說明本發明之較佳之實施形態。再者，對於本說明書中特別提及之事項以外之實施本發明所必需之事項，業者可基於本說明書中所記載之關於發明之實施之提示及提出申請時之技術常識而理解。本發明可基於本說明書中所揭示之內容及該領域中之技術常識而實施。又，以下之圖式中，對於發揮相同作用之構件、部位，有時標附相同符號而進行說明，且有時省略或簡化重複之說明。又，圖式中所記載之實施形態係為了清楚地說明本發明而進行模式化，未必正確地表示實際所提供之製品之尺寸或縮尺。Preferred embodiments of the present invention will be described below. Furthermore, those matters necessary for the implementation of the present invention other than those specifically mentioned in this specification can be understood by those skilled in the art based on the tips regarding the implementation of the invention described in this specification and the technical common sense at the time of filing the application. The present invention can be implemented based on the content disclosed in this specification and the technical common sense in this field. In addition, in the following drawings, members and parts that perform the same functions may be described with the same symbols attached, and repeated descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are schematic for the purpose of clearly explaining the present invention, and do not necessarily accurately represent the dimensions or scale of actual products provided.

於本說明書中，所謂「丙烯酸系聚合物」，係指源自包含多於50重量%之丙烯酸系單體之單體成分之聚合物。上述丙烯酸系單體係指源自於1分子中具有至少1個(甲基)丙烯醯基之單體之單體。又，於本說明書中，所謂「(甲基)丙烯醯基」，係指包括丙烯醯基及甲基丙烯醯基在內之含義。同樣地，所謂「(甲基)丙烯酸酯」，係指包括丙烯酸酯及甲基丙烯酸酯在內之含義，所謂「(甲基)丙烯酸」，係指包括丙烯酸及甲基丙烯酸在內之含義。In this specification, the so-called "acrylic polymer" refers to a polymer derived from a monomer component containing more than 50% by weight of acrylic monomers. The acrylic monomer refers to a monomer derived from a monomer having at least one (meth)acrylyl group per molecule. In addition, in this specification, the term "(meth)acrylyl group" refers to a meaning including an acrylyl group and a methacrylyl group. Similarly, "(meth)acrylate" means acrylate and methacrylate, and "(meth)acrylic acid" means acrylic acid and methacrylic acid.

＜黏著片材之構成例＞將本文所揭示之黏著片材剝離方法中可使用之黏著片材之一構成例示於圖1。該黏著片材1係以單面接著性之黏著片材之形式構成，該單面接著性之黏著片材包含一表面10A成為對作為被黏著體之偏光板之貼附面(即，偏光板側之表面)之黏著劑層10、及積層於黏著劑層10之另一表面10B之支持體20。黏著劑層10係固定地接合於支持體20之一表面20A。作為支持體20，例如可使用聚酯膜等塑膠膜。於圖1所示之例中，黏著劑層10為單層構造。即，由構成黏著劑層10之一表面(黏著面)10A之A層構成黏著劑層10之整體。黏著片材1係於作為被黏著體之偏光板貼附一表面10A而使用。使用前(貼附於被黏著體之前)之黏著片材1例如可為如圖1所示般黏著面10A由至少該黏著劑層側成為剝離性表面(剝離面)之剝離襯墊30保護的附剝離襯墊之黏著片材50之形態。或者，亦可為如下形態，即支持體20之第二面20B(與第一面20A為相反側之表面，亦稱為背面)成為剝離面，且藉由以黏著面10A抵接於第二面20B之方式進行捲繞或積層而黏著面10A得到保護。＜Construction example of adhesive sheet＞ An example of the structure of an adhesive sheet that can be used in the adhesive sheet peeling method disclosed herein is shown in FIG. 1 . The adhesive sheet 1 is constituted in the form of a single-sided adhesive sheet. The single-sided adhesive sheet includes a surface 10A that serves as an adhesion surface to a polarizing plate as an adherend (i.e., a polarizing plate). The adhesive layer 10 on one side of the adhesive layer 10 and the support 20 laminated on the other surface 10B of the adhesive layer 10 . The adhesive layer 10 is fixedly bonded to one surface 20A of the support 20 . As the support 20, for example, a plastic film such as a polyester film can be used. In the example shown in FIG. 1 , the adhesive layer 10 has a single-layer structure. That is, the entire adhesive layer 10 is composed of the A layer constituting one surface (adhesive surface) 10A of the adhesive layer 10 . The adhesive sheet 1 is used on a surface 10A on which a polarizing plate as an adherend is attached. The adhesive sheet 1 before use (before being attached to an adherend) may have an adhesive surface 10A protected by a release liner 30 with at least the adhesive layer side serving as a release surface (release surface) as shown in FIG. 1 . The form of the adhesive sheet 50 with a release liner. Alternatively, the second surface 20B of the support 20 (the surface opposite to the first surface 20A, also referred to as the back surface) may be a peeling surface, and the adhesive surface 10A may be in contact with the second surface. The adhesive surface 10A is protected by being wound or laminated in such a manner as to face 20B.

作為剝離襯墊，並無特別限定，例如可使用樹脂膜或紙等襯墊基材之表面經剝離處理之剝離襯墊、或包含氟系聚合物(聚四氟乙烯等)或聚烯烴系樹脂(聚乙烯、聚丙烯等)低接著性材料之剝離襯墊等。上述剝離處理中，例如可使用聚矽氧系、長鏈烷基系等之剝離處理劑。於若干態樣中，可較佳地採用經剝離處理之樹脂膜作為剝離襯墊。The release liner is not particularly limited. For example, a release liner whose surface is subjected to a release treatment of a liner base material such as a resin film or paper, or a release liner containing a fluorine-based polymer (polytetrafluoroethylene, etc.) or a polyolefin-based resin can be used. (Polyethylene, polypropylene, etc.) Release liners of low-adhesion materials, etc. In the above-mentioned peeling treatment, for example, a polysiloxane-based, long-chain alkyl-based, etc. peeling treatment agent can be used. In some aspects, a release-treated resin film may be preferably used as a release liner.

將本文所揭示之黏著片材剝離方法中可使用之黏著片材之另一構成例示於圖2。該黏著片材2以單面接著性之黏著片材之形式構成，該單面接著性之黏著片材包含一表面110A成為對被黏著體之貼附面之黏著劑層110、及積層於黏著劑層110之另一表面之支持體20。黏著劑層110具有兩層構造，該兩層構造包含構成一表面(黏著面)110A之A層112、及積層配置於A層112之背面側之B層114。使用前(貼附於被黏著體之前)之黏著片材2可與圖1所示之黏著片材1同樣地，為黏著面110A由未圖示之剝離襯墊保護之附剝離襯墊之黏著片材之形態。或者，亦可為如下形態，即支持體20之第二面20B成為剝離面，且藉由以黏著面110A抵接於第二面20B之方式進行捲繞或積層而黏著面110A得到保護。Another structural example of an adhesive sheet that can be used in the adhesive sheet peeling method disclosed herein is shown in FIG. 2 . The adhesive sheet 2 is constituted in the form of a single-sided adhesive sheet. The single-sided adhesive sheet includes an adhesive layer 110 with a surface 110A serving as an adhesion surface to the adherend, and an adhesive layer 110 laminated on the adherend. The other surface of the agent layer 110 is the support 20 . The adhesive layer 110 has a two-layer structure, and the two-layer structure includes an A layer 112 constituting a surface (adhesive surface) 110A, and a B layer 114 laminated on the back side of the A layer 112 . The adhesive sheet 2 before use (before being attached to the adherend) can be the same as the adhesive sheet 1 shown in FIG. 1 , with the adhesive surface 110A being protected by a release liner (not shown) with a release liner. The shape of the sheet. Alternatively, the second surface 20B of the support 20 may be a peeling surface, and the adhesive surface 110A may be protected by being wound or laminated so that the adhesive surface 110A is in contact with the second surface 20B.

本文所揭示之黏著片材剝離方法中可使用之黏著片材亦可為包含黏著劑層之無支持體之雙面黏著片材之態樣。此種無支持體之雙面黏著片材例如可於黏著劑層之另一表面接合支持體而使用。The adhesive sheet that can be used in the adhesive sheet peeling method disclosed herein can also be in the form of a double-sided adhesive sheet containing an adhesive layer without a support. This kind of double-sided adhesive sheet without a support can be used by bonding a support to the other surface of the adhesive layer, for example.

本文所揭示之黏著片材剝離方法可於自將構成黏著片材之黏著劑層之一表面(即，A層之表面)貼附於構件而成之附黏著片材之構件剝離上述黏著片材之態樣中較佳地實施。此處，上述構件為偏光板，更詳細而言，為貼附有黏著片材之側之表面(被貼附面)經電暈處理或電漿處理之偏光板。一般而言，偏光板具有偏光膜由兩片三乙醯纖維素(TAC)膜夾持之構成。較佳為上述兩片TAC膜中至少配置於貼附黏著片材之側之TAC膜之表面(被貼附面)由硬塗層保護。上述硬塗層較佳為由胺基甲酸酯丙烯酸酯系之材料構成。亦可為於上述硬塗層上進而設置有抗反射層之構成之偏光板。例如，如圖3所示，上述附黏著片材之構件可為將圖2所示之黏著片材2所具有之黏著劑層110之一表面(偏光板側之表面)110A貼附於構件(偏光板)70而成之附黏著片材之構件200。亦可為代替圖2所示之黏著片材2而將圖1所示之黏著片材1之一表面10A貼附於構件(偏光板)70而成之構成之附黏著片材之構件。The adhesive sheet peeling method disclosed herein can peel off the adhesive sheet from the member where one surface of the adhesive layer constituting the adhesive sheet (ie, the surface of the A layer) is attached to the member. Better implementation in this way. Here, the above-mentioned member is a polarizing plate, and more specifically, it is a polarizing plate in which the surface (attached surface) of the side to which the adhesive sheet is attached has been subjected to corona treatment or plasma treatment. Generally speaking, a polarizing plate has a polarizing film sandwiched between two pieces of triacetyl cellulose (TAC) film. It is preferable that at least the surface (attached surface) of the TAC film disposed on the side to which the adhesive sheet is attached is protected by a hard coat layer among the two TAC films. The above-mentioned hard coat layer is preferably composed of a urethane acrylate-based material. It may also be a polarizing plate in which an anti-reflection layer is further provided on the hard coat layer. For example, as shown in FIG. 3 , the above-mentioned member for attaching the adhesive sheet may be a surface 110A of the adhesive layer 110 of the adhesive sheet 2 shown in FIG. 2 (the surface on the polarizing plate side) attached to the member ( The component 200 of the adhesive sheet is made of a polarizing plate (70). It may also be an adhesive sheet member in which one surface 10A of the adhesive sheet 1 shown in FIG. 1 is attached to the member (polarizing plate) 70 instead of the adhesive sheet 2 shown in FIG. 2 .

＜黏著片材之特性＞本發明之剝離方法中可使用之黏著片材較佳為耐水黏著力降低率為30%以下，且水剝離黏著力降低率為40%以上。耐水黏著力降低率[%]係定義為根據常態黏著力N0[N/10 mm]及耐水黏著力N1[N/10 mm]並藉由(1－(N1/N0))×100所算出之值。水剝離黏著力降低率[%]係定義為根據常態黏著力N0[N/10 mm]及水剝離力N2並藉由(1－(N2/N0))×100所算出之值。常態黏著力N0、耐水黏著力N1及水剝離力N2係藉由以下之方法而測定。於下述之實施例中亦可使用相同之測定方法。＜Characteristics of adhesive sheet＞ The adhesive sheet that can be used in the peeling method of the present invention preferably has a water-resistant adhesive force reduction rate of less than 30%, and a water-repellent adhesive force reduction rate of more than 40%. The water-resistant adhesion reduction rate [%] is defined as the normal adhesion force N0 [N/10 mm] and the water-resistant adhesion force N1 [N/10 mm] and is calculated by (1-(N1/N0))×100 value. The water peel adhesion reduction rate [%] is defined as the value calculated based on the normal adhesion force N0 [N/10 mm] and the water peel force N2 by (1-(N2/N0))×100. The normal adhesion force N0, the water-resistant adhesion force N1 and the water peeling force N2 are measured by the following methods. The same measurement method can also be used in the following examples.

[常態黏著力N0之測定] 將測定對象之黏著片材切割成寬度10 mm、長度120 mm之長方形狀而製備試片。利用手壓輥將上述試片之A層側貼合於被黏著體而製成評價用樣品，將該評價用樣品投入至高壓釜中，於壓力5 atm、溫度50℃之條件下處理15分鐘。將自高壓釜中取出之評價用樣品於23℃、50%RH之環境中保持1天後，於相同環境下，於試片與被黏著體之界面***截切刀而使該試片之長度方向之一端自被黏著體剝離，依據JIS Z0237，使用拉伸試驗機於拉伸速度300 mm/分鐘、剝離角度180度之條件下測定剝離強度。[Measurement of normal adhesion force N0] Cut the adhesive sheet to be measured into a rectangular shape with a width of 10 mm and a length of 120 mm to prepare a test piece. Use a hand roller to attach the A layer side of the above test piece to the adherend to prepare an evaluation sample. Put the evaluation sample into an autoclave and process it for 15 minutes at a pressure of 5 atm and a temperature of 50°C. . After maintaining the evaluation sample taken out from the autoclave for 1 day in an environment of 23°C and 50% RH, under the same environment, insert a cutting knife into the interface between the test piece and the adherend to shorten the length of the test piece. One end of the direction is peeled off from the adherend. According to JIS Z0237, a tensile testing machine is used to measure the peel strength under the conditions of a tensile speed of 300 mm/min and a peeling angle of 180 degrees.

[耐水黏著力N1之測定] 將測定對象之黏著片材切割成寬度10 mm、長度120 mm之長方形狀而製備試片。利用手壓輥將上述試片之A層側貼合於被黏著體而製成評價用樣品，將該評價用樣品投入至高壓釜中，於壓力5 atm、溫度50℃之條件下處理15分鐘。將自高壓釜中取出之評價用樣品於23℃、50%RH之環境中保持1天後，於室溫(23℃～25℃)之水中浸漬30分鐘。作為水，使用離子交換水或蒸餾水。於水中，評價用樣品係以貼附有試片之面成為上方之朝向水平地保持。評價用樣品之上表面至水面之距離(浸漬深度)係設為10 mm以上(例如10 mm～100 mm左右)。繼而，將評價用樣品自水中提起，輕輕地擦拭附著於該評價用樣品之水後，於試片與被黏著體之界面***截切刀而將該試片之長度方向之一端剝離，於23℃、50%RH之環境下，依據JIS Z0237，使用拉伸試驗機於拉伸速度300 mm/分鐘、剝離角度180度之條件下測定剝離強度。將評價用樣品自水中提起後至測定剝離強度為止之時間係設為10分鐘以內。[Measurement of water-resistant adhesion N1] Cut the adhesive sheet to be measured into a rectangular shape with a width of 10 mm and a length of 120 mm to prepare a test piece. Use a hand roller to attach the A layer side of the above test piece to the adherend to prepare an evaluation sample. Put the evaluation sample into an autoclave and process it for 15 minutes at a pressure of 5 atm and a temperature of 50°C. . The evaluation sample taken out from the autoclave was maintained in an environment of 23°C and 50% RH for 1 day, and then immersed in water at room temperature (23°C to 25°C) for 30 minutes. As water, ion-exchanged water or distilled water is used. In water, the sample for evaluation is held horizontally with the surface with the test piece attached facing upward. The distance (immersion depth) from the upper surface of the evaluation sample to the water surface is set to 10 mm or more (for example, about 10 mm to 100 mm). Then, the evaluation sample was lifted out of the water, and after gently wiping off the water adhering to the evaluation sample, a cutting knife was inserted into the interface between the test piece and the adherend to peel off one end of the test piece in the length direction. In an environment of 23°C and 50% RH, according to JIS Z0237, use a tensile testing machine to measure the peel strength at a tensile speed of 300 mm/min and a peel angle of 180 degrees. The time from when the evaluation sample is lifted out of water to when the peel strength is measured is within 10 minutes.

[水剝離力N2之測定] 將測定對象之黏著片材切割成寬度10 mm、長度120 mm之長方形狀而製備試片。利用手壓輥使上述試片之A層側貼合於被黏著體而製成評價用樣品，將該評價用樣品投入至高壓釜中，於壓力5 atm、溫度50℃之條件下處理15分鐘。將自高壓釜中取出之評價用樣品於23℃、50%RH之環境中保持1天後，於相同環境下，於試片之長度方向之一端附近於自該一端露出之被黏著體表面滴加1滴(約10 μl～約40 μl)之蒸餾水。然後，於試片與被黏著體之界面***截切刀而使上述水進入至上述界面後，不進行新的水之供給，而依據JIS Z0237，使用拉伸試驗機於拉伸速度300 mm/分鐘、剝離角度180度之條件下測定剝離強度。再者，水剝離力N2之測定中所使用之水僅為於剝離開始前滴加至被黏著體之1滴之蒸餾水。[Measurement of water peeling force N2] Cut the adhesive sheet to be measured into a rectangular shape with a width of 10 mm and a length of 120 mm to prepare a test piece. Use a hand roller to attach the A layer side of the above test piece to the adherend to prepare a sample for evaluation. Put the sample for evaluation into an autoclave and process it for 15 minutes at a pressure of 5 atm and a temperature of 50°C. . After maintaining the evaluation sample taken out from the autoclave for 1 day in an environment of 23°C and 50% RH, in the same environment, drop a drop on the surface of the adherend exposed from that end near one end of the length direction of the test piece. Add 1 drop (about 10 μl to about 40 μl) of distilled water. Then, after inserting a cutting knife into the interface between the test piece and the adherend to allow the above-mentioned water to enter the above-mentioned interface, a tensile testing machine was used according to JIS Z0237 at a tensile speed of 300 mm/ Minutes and a peeling angle of 180 degrees were used to measure the peel strength. Furthermore, the water used in the measurement of the water peel force N2 is only one drop of distilled water added to the adherend before peeling starts.

於上述之常態黏著力N0、耐水黏著力N1及水剝離力N2之測定中，作為被黏著體，使用偏光板，該偏光板具有偏光膜由兩片TAC膜夾持之構成，貼附黏著片材之側之表面(被貼附面)成為於上述TAC膜依序積層有作為保護層之硬塗層及抗反射層之表面，且於該表面(被貼附面)實施有電暈處理。被貼附面之電暈處理係藉由下述方式進行，即，於即將於被黏著體貼附試片之前(典型而言，貼附前30分鐘以內)，使該被黏著體於輸出設定3(顯示0.17 kW)、台速刻度20(相當於速度3 m/min)之條件下通過KASUGA製造之「AGF-012」(台式表面電暈處理裝置)1次。試片對被黏著體之貼附係以該試片之外周端至被黏著體之外周端之距離成為至少10 mm以上、較佳為15 mm以上之方式進行。又，作為拉伸試驗機，可使用萬能拉伸壓縮試驗機(裝置名「拉伸壓縮試驗機，TCM-1kNB」Minebea公司製造)或其相當品。剝離強度之測定係以貼附於被黏著體之試片之剝離自下而上地進行之方式進行。於測定時，視需要於黏著片材之背面(與A層之表面為相反側之表面)貼附適當之襯底材而對試片進行補強。作為襯底材，例如可使用厚度25 μm左右之聚對苯二甲酸乙二酯膜。再者，關於被黏著體，作為上述構成之偏光板之代用品，亦可使用模擬該偏光板之被貼附面側之構成之TAC膜、即具有依序積層有硬塗層及抗反射層之表面且於該表面於上述條件下實施有電暈處理的TAC膜。上述硬塗層及抗反射層可藉由下述之實施例中所記載之方法而形成。In the measurement of the above-mentioned normal adhesion force N0, water-resistant adhesion force N1 and water peeling force N2, as the adherend, a polarizing plate was used. The polarizing plate has a polarizing film sandwiched by two pieces of TAC film, and the adhesive sheet is attached. The surface on the side of the material (the surface to be attached) is a surface on which a hard coat layer and an anti-reflective layer as a protective layer are sequentially laminated on the TAC film, and corona treatment is performed on this surface (the surface to be attached). The corona treatment of the adherend surface is performed by placing the adherend at output setting 3 just before attaching the test piece to the adherend (typically, within 30 minutes before attachment). (Indicates 0.17 kW), passed through the "AGF-012" (desktop surface corona treatment device) manufactured by KASUGA once under the conditions of table speed scale 20 (equivalent to speed 3 m/min). The test piece is attached to the adherend in such a way that the distance from the outer peripheral end of the test piece to the outer peripheral end of the adherend is at least 10 mm or more, preferably 15 mm or more. In addition, as the tensile testing machine, a universal tensile and compression testing machine (device name "Tensile Compression Testing Machine, TCM-1kNB" manufactured by Minebea Co., Ltd.) or its equivalent can be used. The peel strength is measured by peeling off the test piece attached to the adherend from bottom to top. During measurement, if necessary, attach an appropriate substrate material to the back of the adhesive sheet (the surface opposite to the surface of layer A) to reinforce the test piece. As the substrate material, for example, a polyethylene terephthalate film with a thickness of about 25 μm can be used. Furthermore, regarding the adherend, as a substitute for the polarizing plate having the above structure, a TAC film that simulates the structure of the attached surface side of the polarizing plate, that is, having a hard coat layer and an anti-reflection layer laminated in sequence, can also be used. The surface is provided with a corona-treated TAC film under the above conditions. The above-mentioned hard coating layer and anti-reflection layer can be formed by the methods described in the following embodiments.

(水剝離黏著力降低率) 本發明之剝離方法較佳為應用於水剝離黏著力降低率為40%以上之黏著片材。顯示此種水剝離黏著力降低率之黏著片材可藉由使用水等水性液體而自偏光板容易地剝離。例如，對貼附有黏著片材之被黏著體(偏光板)供給少量之水性液體，藉由使該水性液體自黏著片材之一端進入至該黏著片材與上述被黏著體之界面而形成剝離之起點後將上述黏著片材剝離，藉此可使上述黏著片材自上述被黏著體之剝離強度大幅降低。利用該性質，可兼顧通常使用時之較高之黏著力及良好之二次加工性。於若干態樣中，水剝離黏著力降低率例如可為50%以上，亦可為65%以上，亦可為75%以上，亦可為85%以上，亦可為90%以上，亦可為95%以上，亦可為97%以上。水剝離黏著力降低率原理上為100%以下，典型而言未達100%。(Water peel adhesion reduction rate) The peeling method of the present invention is preferably applied to an adhesive sheet whose water peeling adhesive force reduction rate is more than 40%. An adhesive sheet showing such a water-peel adhesion reduction rate can be easily peeled from a polarizing plate by using an aqueous liquid such as water. For example, a small amount of aqueous liquid is supplied to an adherend (polarizing plate) to which an adhesive sheet is attached, and the aqueous liquid enters from one end of the adhesive sheet to the interface between the adhesive sheet and the adherend. By peeling off the adhesive sheet after the starting point of peeling, the peeling strength of the adhesive sheet from the adherend can be greatly reduced. This property can be used to achieve both high adhesion and good secondary processability during normal use. In certain aspects, the water peel adhesion reduction rate may be, for example, more than 50%, more than 65%, more than 75%, more than 85%, more than 90%, or more than Above 95%, it can also be above 97%. The water peel adhesion reduction rate is in principle less than 100%, but typically does not reach 100%.

(耐水黏著力降低率) 如上所述，應用本發明之剝離方法之黏著片材較佳為可使用水等水性液體而容易地剝離，且耐水黏著力降低率為30%以下。就獲得更高之耐水可靠性之觀點而言，耐水黏著力降低率例如較佳為20%以下，更佳為10%以下，亦可為7%以上。耐水黏著力降低率典型而言為0%以上。上述黏著片材可於水剝離黏著力降低率[%]與耐水黏著力降低率[%]之差為例如45%以上、或55%以上、或70%以上、或80%以上、或90%以上之態樣中較佳地實施。(Water-resistant adhesion reduction rate) As mentioned above, it is preferable that the adhesive sheet to which the peeling method of the present invention is applied can be easily peeled off using an aqueous liquid such as water, and that the water-resistant adhesive force reduction rate is 30% or less. From the viewpoint of obtaining higher water-resistant reliability, the water-resistant adhesion force reduction rate is, for example, preferably 20% or less, more preferably 10% or less, and may be 7% or more. The water-resistant adhesion reduction rate is typically 0% or more. The difference between the water peeling adhesive force reduction rate [%] and the water-resistant adhesive force reduction rate [%] of the above-mentioned adhesive sheet is, for example, 45% or more, or 55% or more, or 70% or more, or 80% or more, or 90% The above aspects are preferably implemented.

就接合之可靠性之觀點而言，應用本文所揭示之剝離方法之黏著片材較佳為常態黏著力N0為2.0 N/10 mm以上。於若干態樣中，常態黏著力N0例如可為2.5 N/10 mm以上，亦可為3.0 N/10 mm以上，亦可為3.5 N/10 mm以上，亦可為4.0 N/10 mm以上。常態黏著力N0之上限並無特別限定，例如可為30 N/10 mm以下。於若干態樣中，常態黏著力N0亦可為20 N/10 mm以下，亦可為15 N/10 mm以下。From the perspective of joint reliability, the adhesive sheet using the peeling method disclosed in this article preferably has a normal adhesive force N0 of 2.0 N/10 mm or more. In certain aspects, the normal adhesion force N0 may be, for example, 2.5 N/10 mm or more, 3.0 N/10 mm or more, 3.5 N/10 mm or more, or 4.0 N/10 mm or more. The upper limit of the normal adhesion force N0 is not particularly limited, for example, it can be 30 N/10 mm or less. In some aspects, the normal adhesion force N0 may be less than 20 N/10 mm or less than 15 N/10 mm.

水剝離力N2較佳為常態黏著力N0之60%以下，更佳為50%以下。雖無特別限定，但水剝離力N2例如可為10 N/10 mm以下，亦可為3.5 N/10 mm以下，亦可為2.5 N/10 mm以下，亦可為1.6 N/10 mm以下，亦可為1.2 N/10 mm以下，亦可為1.0 N/10 mm以下。根據水剝離力N2較低之黏著片材，可減輕剝離該黏著片材時對被黏著體所施加之負荷。該特性例如於自在表面具有硬塗層或抗反射層等薄膜之偏光板剝離黏著片材之態樣中特別有意義。上述黏著片材例如亦可於水剝離力N2為0.75 N/10 mm以下、或0.50 N/10 mm以下、或0.25 N/10 mm以下、或0.15 N/10 mm以下之態樣中較佳地實施。水剝離力N2之下限並無特別限制，亦可實質上為0 N/10 mm，亦可超過0 N/10 mm。再者，就二次加工性提高之觀點而言，較佳為於水剝離力N2之測定中，不於被黏著體上殘留黏著劑而自該被黏著體剝離之黏著片材。即，較佳為非糊劑殘留性優異之黏著片材。於被黏著體上有無殘留黏著劑例如可藉由利用目視觀察黏著片材剝離後之被黏著體而掌握。The water peeling force N2 is preferably 60% or less of the normal adhesion force N0, more preferably 50% or less. Although not particularly limited, the water peeling force N2 may be, for example, 10 N/10 mm or less, 3.5 N/10 mm or less, 2.5 N/10 mm or less, or 1.6 N/10 mm or less. It may be 1.2 N/10 mm or less, or it may be 1.0 N/10 mm or less. An adhesive sheet with a low water peeling force N2 can reduce the load exerted on the adherend when peeling off the adhesive sheet. This characteristic is particularly meaningful, for example, in the form of a polarizing plate peel-off adhesive sheet having a thin film such as a hard coat layer or an anti-reflective layer on its surface. For example, the adhesive sheet may preferably have a water peeling force N2 of 0.75 N/10 mm or less, or 0.50 N/10 mm or less, or 0.25 N/10 mm or less, or 0.15 N/10 mm or less. implementation. The lower limit of the water peeling force N2 is not particularly limited, and may be substantially 0 N/10 mm, or may exceed 0 N/10 mm. Furthermore, from the viewpoint of improving the secondary processability, an adhesive sheet that is peeled off from the adherend without leaving any adhesive on the adherend in the measurement of the water peeling force N2 is preferred. That is, an adhesive sheet excellent in non-paste residue is preferred. Whether there is any residual adhesive on the adherend can be determined, for example, by visually observing the adherend after peeling off the adhesive sheet.

水剝離力N2[N/10 mm]相對於常態黏著力N0[N/10 mm]之比(N2/N0)例如可為1/2.5以下，亦可為1/5以下，亦可為1/10以下。上述比(N2/N0)更小表示水剝離力N2相對於常態黏著力N0更顯著地降低。本文所揭示之剝離方法可於將比(N2/N0)為1/15以下、1/25以下或1/35以下之黏著片材自偏光板剝離之態樣中較佳地實施。比(N2/N0)之上限並無特別限制，例如可為1/200以上，亦可為1/150以上，亦可為1/100以上。The ratio of the water peeling force N2 [N/10 mm] to the normal adhesion force N0 [N/10 mm] (N2/N0) may be, for example, 1/2.5 or less, 1/5 or less, or 1/ Below 10. A smaller ratio (N2/N0) means that the water peeling force N2 is significantly lower than the normal adhesion force N0. The peeling method disclosed herein can be preferably implemented in the aspect of peeling off an adhesive sheet with a ratio (N2/N0) of 1/15 or less, 1/25 or less, or 1/35 or less from the polarizing plate. The upper limit of the ratio (N2/N0) is not particularly limited, but may be 1/200 or more, 1/150 or more, or 1/100 or more.

於上述黏著片材中，形成構成黏著劑層之至少偏光板側之表面之A層之黏著劑較佳為非水溶性。根據非水溶性之A層，容易獲得耐水黏著力N1較高，耐水黏著力降低率較低之黏著片材。A層為非水溶性就防止於使用水等水性液體之剝離中於被黏著體上殘留黏著劑之現象之觀點而言亦較佳。又，A層為非水溶性就防止因水浸漬或環境中之濕氣而導致黏著片材之透明性降低之現象之觀點而言亦可變得有利。In the above-mentioned adhesive sheet, the adhesive forming layer A constituting at least the surface on the polarizing plate side of the adhesive layer is preferably water-insoluble. Based on the water-insoluble A layer, it is easy to obtain an adhesive sheet with a high water-resistant adhesive force N1 and a low water-resistant adhesive force reduction rate. It is also preferable that the A layer is water-insoluble in order to prevent the adhesive from remaining on the adherend during peeling using an aqueous liquid such as water. In addition, it is advantageous that the A layer is water-insoluble in terms of preventing the transparency of the adhesive sheet from being reduced due to water immersion or moisture in the environment.

構成A層之黏著劑較佳為非水膨潤性。根據非水膨潤性之A層，容易獲得耐水黏著力N1較高，耐水黏著力降低率較低之黏著片材。又，於使用水等水性液體之剝離中，可有效地利用少量之水性液體而發揮良好之剝離性。A層為非水膨潤性就防止於使用水性液體之剝離中於被黏著體上殘留黏著劑之現象之觀點而言亦較佳。又，A層為非水膨潤性就防止因水浸漬或環境中之濕氣而導致黏著片材之透明性降低之現象之觀點而言亦可變得有利。The adhesive constituting layer A is preferably non-water-swellable. Based on the non-water-swellable A layer, it is easy to obtain an adhesive sheet with a high water-resistant adhesive force N1 and a low water-resistant adhesive force reduction rate. Furthermore, in peeling using an aqueous liquid such as water, a small amount of the aqueous liquid can be effectively utilized to exhibit good peeling properties. It is also preferable that layer A is non-water-swellable from the viewpoint of preventing adhesive from remaining on the adherend during peeling using an aqueous liquid. In addition, it is advantageous that the A layer is non-water-swellable in terms of preventing the transparency of the adhesive sheet from being reduced due to water immersion or moisture in the environment.

此處，於本說明書中，所謂黏著劑為非水溶性，係指利用以下之方法測定之凝膠分率為75%以上。又，所謂黏著劑為非水膨潤性，係指利用以下之方法測定之膨潤度為2以下。即，稱量測定對象之黏著劑0.5 g左右，將其重量設為W1。將該黏著劑於室溫(約23℃)下於蒸餾水500 ml中浸漬48小時後，利用尼龍篩網進行過濾，測定包含水之黏著劑之重量W2。其後，使黏著劑於130℃下乾燥5小時，測定不揮發分之重量W3。凝膠分率及膨潤度係藉由以下之式而算出。凝膠分率[%]＝(W3/W1)×100 膨潤度＝W2/W1Here, in this specification, the term "water-insoluble adhesive" means that the gel fraction measured by the following method is 75% or more. In addition, the term "the adhesive is non-water-swellable" means that the swelling degree measured by the following method is 2 or less. That is, weigh about 0.5 g of the adhesive to be measured, and let its weight be W1. The adhesive was immersed in 500 ml of distilled water at room temperature (about 23°C) for 48 hours, then filtered through a nylon mesh, and the weight W2 of the adhesive containing water was measured. Thereafter, the adhesive was dried at 130° C. for 5 hours, and the nonvolatile matter weight W3 was measured. The gel fraction and swelling degree are calculated by the following formulas. Gel fraction [%] = (W3/W1) × 100 Swelling degree=W2/W1

於若干態樣中，A層之凝膠分率例如可為80%以上，亦可為90%以上，亦可為95%以上，亦可為98%以上。A層之凝膠分率原理上為100%以下。又，於若干態樣中，A層之膨潤度例如可為1.7以下，亦可為1.5以下，亦可為1.2以下。A層之膨潤度通常為1.0以上，典型而言為超過1.0。In certain aspects, the gel fraction of layer A may be, for example, more than 80%, more than 90%, more than 95%, or more than 98%. The gel fraction of layer A is in principle less than 100%. Furthermore, in certain aspects, the swelling degree of layer A may be, for example, 1.7 or less, 1.5 or less, or 1.2 or less. The swelling degree of layer A is usually above 1.0, typically exceeding 1.0.

於黏著劑層包含A層及配置於該A層之背面側之B層之構成之黏著片材中，B層之凝膠分率並無特別限定。於若干態樣中，B層之凝膠分率較佳為A層之凝膠分率之同等以上，亦可高於A層之凝膠分率。B層之凝膠分率例如可為90%以上，亦可為95%以上，亦可為98%以上，亦可為99%以上。B層之凝膠分率原理上為100%以下。又，黏著劑層整體之凝膠分率例如可為85%以上，亦可為90%以上，亦可為95%以上，亦可為98%以上，亦可為99%以上。再者，於僅包含A層之黏著劑層中，該黏著劑層整體之凝膠分率意指A層之凝膠分率。In an adhesive sheet in which the adhesive layer includes layer A and layer B arranged on the back side of layer A, the gel fraction of layer B is not particularly limited. In some aspects, the gel fraction of layer B is preferably equal to or greater than the gel fraction of layer A, and may also be higher than the gel fraction of layer A. The gel fraction of layer B may be, for example, 90% or more, 95% or more, 98% or more, or 99% or more. The gel fraction of layer B is in principle less than 100%. Moreover, the gel fraction of the entire adhesive layer may be, for example, 85% or more, 90% or more, 95% or more, 98% or more, or 99% or more. Furthermore, in the adhesive layer including only layer A, the gel fraction of the entire adhesive layer means the gel fraction of layer A.

於黏著劑層包含A層及配置於該A層之背面側之B層之構成之黏著片材中，B層之膨潤度並無特別限定。於若干態樣中，B層之膨潤度較佳為A層之膨潤度之同等以下，亦可低於A層之膨潤度。B層之膨潤度例如可為1.5以下，亦可為1.3以下，亦可為1.1以下。B層之膨潤度通常為1.0以上，典型而言為超過1.0。又，黏著劑層整體之膨潤度例如可為1.6以下，亦可為1.4以下，亦可為1.2以下，亦可為1.1以下。再者，於僅包含A層之黏著劑層中，該黏著劑層整體之膨潤度意指A層之膨潤度。In an adhesive sheet in which the adhesive layer includes an A layer and a B layer disposed on the back side of the A layer, the swelling degree of the B layer is not particularly limited. In some aspects, the swelling degree of the B layer is preferably equal to or lower than the swelling degree of the A layer, and may also be lower than the swelling degree of the A layer. The swelling degree of layer B may be, for example, 1.5 or less, 1.3 or less, or 1.1 or less. The swelling degree of layer B is usually above 1.0, typically exceeding 1.0. Moreover, the swelling degree of the entire adhesive layer may be, for example, 1.6 or less, 1.4 or less, 1.2 or less, or 1.1 or less. Furthermore, in the adhesive layer including only the A layer, the swelling degree of the entire adhesive layer means the swelling degree of the A layer.

再者，黏著劑對水之凝膠分率或膨潤度可適宜採用例如單體成分之組成、聚合物之重量平均分子量、交聯劑或多官能單體之使用等對本案申請時之業者而言一般之方法而進行調節。Furthermore, the gel fraction or swelling degree of the adhesive to water can be appropriately determined by, for example, the composition of the monomer components, the weight average molecular weight of the polymer, the use of cross-linking agents or multifunctional monomers, etc. Make adjustments using general methods.

＜黏著劑層＞ (1)A層於藉由本文所揭示之剝離方法剝離之黏著片材中，構成黏著劑層之至少偏光板側之表面之A層例如可為包含選自丙烯酸系黏著劑、橡膠系黏著劑(天然橡膠系、合成橡膠系、該等之混合系等)、聚矽氧系黏著劑、聚酯系黏著劑、胺基甲酸酯系黏著劑、聚醚系黏著劑、聚醯胺系黏著劑、氟系黏著劑等公知之各種黏著劑中之一種或兩種以上之黏著劑而構成之黏著劑層。此處，所謂丙烯酸系黏著劑，係指以丙烯酸系聚合物作為主成分之黏著劑。橡膠系黏著劑及其他黏著劑亦為相同之含義。再者，此處所謂之聚合物之概念中亦包含有時一般被稱為低聚物之聚合度相對較低之聚合物。＜Adhesive layer＞ (1)A layer In the adhesive sheet peeled off by the peeling method disclosed herein, the A layer constituting at least the surface of the polarizing plate side of the adhesive layer may be selected from the group consisting of acrylic adhesives, rubber adhesives (natural rubber, Synthetic rubber systems, hybrid systems of these, etc.), polysilicone adhesives, polyester adhesives, urethane adhesives, polyether adhesives, polyamide adhesives, fluorine adhesives The adhesive layer is composed of one or two or more adhesives from various well-known adhesives. Here, the acrylic adhesive refers to an adhesive containing an acrylic polymer as a main component. Rubber adhesives and other adhesives also have the same meaning. Furthermore, the concept of polymers here also includes polymers with a relatively low degree of polymerization that are sometimes generally referred to as oligomers.

(丙烯酸系黏著劑) 就透明性或耐候性等觀點而言，於若干態樣中，可較佳地採用丙烯酸系黏著劑作為A層之構成材料。(Acrylic adhesive) From the viewpoint of transparency or weather resistance, in some aspects, an acrylic adhesive can be preferably used as the constituent material of the A layer.

作為丙烯酸系黏著劑，例如較佳為包含由包含多於50重量%之在酯末端具有碳原子數1以上且20以下之直鏈或支鏈狀之烷基之(甲基)丙烯酸烷基酯之單體成分構成之丙烯酸系聚合物者。以下，有時將在酯末端具有碳原子數為X以上且Y以下之烷基之(甲基)丙烯酸烷基酯表述為「(甲基)丙烯酸C_X-Y 烷基酯」。就容易獲取特性之平衡而言，單體成分整體中之(甲基)丙烯酸C_1-20 烷基酯之比率例如可為55重量%以上，亦可為60重量%以上，亦可為70重量%以上。就相同之理由而言，單體成分中之(甲基)丙烯酸C_1-20 烷基酯之比率例如可為99.9重量%以下，亦可為99.5重量%以下，亦可為99重量%以下。As the acrylic adhesive, for example, a (meth)acrylic acid alkyl ester containing more than 50% by weight of a linear or branched alkyl group having a carbon number of 1 to 20 at the ester terminal is preferred. Acrylic polymer composed of monomer components. Hereinafter, a (meth)acrylic acid alkyl ester having an alkyl group with a carbon number of X or more and Y or less at the ester terminal may be expressed as "(meth)acrylic acid C _XY alkyl ester". In order to easily obtain a balance of characteristics, the ratio of C _1-20 alkyl (meth)acrylate in the entire monomer component may be, for example, 55% by weight or more, 60% by weight or more, or 70% by weight. %above. For the same reason, the ratio of C _1-20 alkyl (meth)acrylate in the monomer component may be, for example, 99.9% by weight or less, 99.5% by weight or less, or 99% by weight or less.

作為(甲基)丙烯酸C_1-20 烷基酯之非限定性之具體例，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。Non-limiting specific examples of the C _1-20 alkyl (meth)acrylate include: (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (meth)propyl acrylate, (meth)acrylic acid propyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid propyl ester Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, (meth)acrylic acid Amyl ester, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Base) isooctyl acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate Ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, (meth) Cetyl acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, (meth)acrylate base) Eicosanyl acrylate, etc.

該等之中，較佳為至少使用(甲基)丙烯酸C_4-20 烷基酯，更佳為至少使用(甲基)丙烯酸C_4-18 烷基酯。例如，較佳為包含丙烯酸正丁酯(BA)及丙烯酸2-乙基己酯(2EHA)之一者或兩者作為上述單體成分之丙烯酸系黏著劑，尤佳為至少包含2EHA之丙烯酸系黏著劑。作為可較佳地使用之(甲基)丙烯酸C_4-20 烷基酯之其他例，可列舉：丙烯酸異壬酯、甲基丙烯酸正丁酯(BMA)、甲基丙烯酸2-乙基己酯(2EHMA)、丙烯酸異硬脂酯(ISTA)等。Among these, it is preferable to use at least C _4-20 alkyl (meth)acrylate, and more preferably at least C _4-18 alkyl (meth)acrylate is used. For example, an acrylic adhesive containing one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) as the above-mentioned monomer components is preferred, and an acrylic adhesive containing at least 2EHA is particularly preferred. Adhesive. Other examples of the C _4-20 alkyl (meth)acrylate that can be preferably used include isononyl acrylate, n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate. (2EHMA), isostearyl acrylate (ISTA), etc.

於若干態樣中，構成丙烯酸系聚合物之單體成分可以40重量%以上之比率包含(甲基)丙烯酸C_4-18 烷基酯。根據如此包含相對較多之在酯末端具有碳原子數4以上之烷基之(甲基)丙烯酸烷基酯之單體成分，存在形成親油性較高之丙烯酸系聚合物之傾向。根據親油性較高之丙烯酸系聚合物，容易形成耐水黏著力降低率較低之黏著劑層。(甲基)丙烯酸C_4-18 烷基酯於單體成分中所占之比率例如可為60重量%以上，亦可為70重量%以上，亦可為75重量%以上，亦可為80重量%以上。亦可為以上述之任一下限值以上之比率包含(甲基)丙烯酸C_6-18 烷基酯之單體成分。又，就提高黏著劑層之凝聚性而防止凝聚破壞之觀點而言，(甲基)丙烯酸C_4-18 烷基酯於單體成分中所占之比率通常適當設為99.5重量%以下，亦可為99重量%以下，亦可為98重量%以下，亦可為97重量%以下。亦可為以上述之任一上限值以下之比率包含(甲基)丙烯酸C_6-18 烷基酯之單體成分。In some aspects, the monomer component constituting the acrylic polymer may include C _4-18 alkyl (meth)acrylate at a ratio of 40% by weight or more. Since the monomer component contains a relatively large amount of alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms at the ester terminal, there is a tendency to form an acrylic polymer with high lipophilicity. Acrylic polymers with higher lipophilicity can easily form an adhesive layer with a lower water-resistant adhesive strength reduction rate. The proportion of C _4-18 alkyl (meth)acrylate in the monomer component may be, for example, 60% by weight or more, 70% by weight or more, 75% by weight or more, or 80% by weight. %above. It may also be a monomer component containing C _6-18 alkyl (meth)acrylate at a ratio above any of the lower limits mentioned above. In addition, from the viewpoint of improving the cohesion of the adhesive layer and preventing cohesion failure, the proportion of C _4-18 alkyl (meth)acrylate in the monomer component is usually appropriately set to 99.5% by weight or less. It may be 99% by weight or less, it may be 98% by weight or less, or it may be 97% by weight or less. It may also be a monomer component containing C _6-18 alkyl (meth)acrylate in a ratio below any of the upper limits mentioned above.

構成丙烯酸系聚合物之單體成分亦可包含(甲基)丙烯酸烷基酯、以及視需要之可與(甲基)丙烯酸烷基酯共聚之其他單體(共聚性單體)。作為共聚性單體，可較佳地使用具有極性基(例如，羧基、羥基、含氮原子之環等)之單體。具有極性基之單體可有助於向丙烯酸系聚合物中導入交聯點，或提高黏著劑之凝聚力。共聚性單體可單獨使用一種或組合兩種以上而使用。The monomer components constituting the acrylic polymer may include alkyl (meth)acrylate and, if necessary, other monomers (copolymerizable monomers) that can be copolymerized with alkyl (meth)acrylate. As the copolymerizable monomer, a monomer having a polar group (for example, a carboxyl group, a hydroxyl group, a nitrogen atom-containing ring, etc.) can be preferably used. Monomers with polar groups can help introduce cross-linking points into acrylic polymers or improve the cohesion of adhesives. A copolymerizable monomer can be used individually by 1 type or in combination of 2 or more types.

作為共聚性單體之非限定性之具體例，可列舉以下者。含羧基之單體：例如丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸、異丁烯酸等。含酸酐基之單體：例如順丁烯二酸酐、伊康酸酐。含羥基之單體：例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥基甲基環己基)甲酯等(甲基)丙烯酸羥基烷基酯等。含有磺酸基或磷酸基之單體：例如苯乙烯磺酸、烯丙基磺酸、乙烯基磺酸鈉、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺基丙酯、(甲基)丙烯醯氧基萘磺酸、丙烯醯基磷酸2-羥基乙酯等。含環氧基之單體：例如(甲基)丙烯酸縮水甘油酯或(甲基)丙烯酸-2-乙基縮水甘油醚等含環氧基之丙烯酸酯、烯丙基縮水甘油醚、(甲基)丙烯酸縮水甘油醚等。含氰基之單體：例如丙烯腈、甲基丙烯腈等。含異氰酸基之單體：例如(甲基)丙烯酸2-異氰酸基乙酯等。含醯胺基之單體：例如(甲基)丙烯醯胺；N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N,N-二丙基(甲基)丙烯醯胺、N,N-二異丙基(甲基)丙烯醯胺、N,N-二(正丁基)(甲基)丙烯醯胺、N,N-二(第三丁基)(甲基)丙烯醯胺等N,N-二烷基(甲基)丙烯醯胺；N-乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺等N-烷基(甲基)丙烯醯胺；N-乙烯基乙醯胺等N-乙烯基羧酸醯胺類；具有羥基及醯胺基之單體，例如N-(2-羥基乙基)(甲基)丙烯醯胺、N-(2-羥基丙基)(甲基)丙烯醯胺、N-(1-羥基丙基)(甲基)丙烯醯胺、N-(3-羥基丙基)(甲基)丙烯醯胺、N-(2-羥基丁基)(甲基)丙烯醯胺、N-(3-羥基丁基)(甲基)丙烯醯胺、N-(4-羥基丁基)(甲基)丙烯醯胺等N-羥基烷基(甲基)丙烯醯胺；具有烷氧基及醯胺基之單體，例如N-甲氧基甲基(甲基)丙烯醯胺、N-甲氧基乙基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺等N-烷氧基烷基(甲基)丙烯醯胺；以及N,N-二甲基胺基丙基(甲基)丙烯醯胺、N-(甲基)丙烯醯基𠰌啉等。含胺基之單體：例如(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯。具有環氧基之單體：例如(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯、烯丙基縮水甘油醚。具有含氮原子之環之單體：例如N-乙烯基-2-吡咯啶酮、N-甲基乙烯基吡咯啶酮、N-乙烯基吡啶、N-乙烯基哌啶酮、N-乙烯基嘧啶、N-乙烯基哌𠯤、N-乙烯基吡𠯤、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基㗁唑、N-(甲基)丙烯醯基-2-吡咯啶酮、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶、N-乙烯基𠰌啉、N-乙烯基-3-𠰌啉酮、N-乙烯基-2-己內醯胺、N-乙烯基-1,3-㗁𠯤-2-酮、N-乙烯基-3,5-𠰌啉二酮、N-乙烯基吡唑、N-乙烯基異㗁唑、N-乙烯基噻唑、N-乙烯基異噻唑、N-乙烯基嗒𠯤等(例如N-乙烯基-2-己內醯胺等內醯胺類)。具有琥珀醯亞胺骨架之單體：例如N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基六亞甲基琥珀醯亞胺等。順丁烯二醯亞胺類：例如N-環己基順丁烯二醯亞胺、N-異丙基順丁烯二醯亞胺、N-月桂基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等。伊康醯亞胺類：例如N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等。 (甲基)丙烯酸胺基烷基酯類：例如(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二乙基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙基。含烷氧基之單體：例如(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸3-甲氧基丙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸丙氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基丙酯等(甲基)丙烯酸烷氧基烷基酯類；甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯等烷氧基伸烷基二醇(甲基)丙烯酸酯類。含烷氧基矽烷基之單體：例如3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷。乙烯酯類：例如乙酸乙烯酯、丙酸乙烯酯等。乙烯醚類：例如甲基乙烯醚或乙基乙烯醚等乙烯基烷基醚。芳香族乙烯基化合物：例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯等。烯烴類：例如乙烯、丁二烯、異戊二烯、異丁烯等。具有脂環式烴基之(甲基)丙烯酸酯：例如(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異𦯉基酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯等。具有芳香族烴基之(甲基)丙烯酸酯：例如(甲基)丙烯酸苯酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苄酯等。此外，(甲基)丙烯酸四氫糠酯等含雜環之(甲基)丙烯酸酯、氯乙烯或含氟原子之(甲基)丙烯酸酯等含鹵素原子之(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯等含矽原子之(甲基)丙烯酸酯、由萜烯化合物衍生物醇獲得之(甲基)丙烯酸酯等。Non-limiting specific examples of the copolymerizable monomer include the following. Monomers containing carboxyl groups: such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, etc. Monomers containing acid anhydride groups: such as maleic anhydride and itaconic anhydride. Hydroxyl-containing monomers: such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (meth)acrylic acid (meth)acrylic acid hydroxyalkyl esters such as 12-hydroxylauryl ester and (meth)acrylic acid (4-hydroxymethylcyclohexyl)methyl ester. Monomers containing sulfonic acid or phosphate groups: such as styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (methyl ) Acrylamide propanesulfonic acid, (meth)acrylic acid sulfopropyl ester, (meth)acryloxynaphthalene sulfonic acid, acrylyl phosphate 2-hydroxyethyl ester, etc. Epoxy group-containing monomers: such as glycidyl (meth)acrylate or (meth)acrylic acid-2-ethyl glycidyl ether and other epoxy group-containing acrylates, allyl glycidyl ether, (methyl ) Glycidyl acrylate, etc. Monomers containing cyano groups: such as acrylonitrile, methacrylonitrile, etc. Monomers containing isocyanato groups: such as 2-isocyanatoethyl (meth)acrylate, etc. Monomers containing amide groups: such as (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N -Dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N- Di(tert-butyl)(meth)acrylamide and other N,N-dialkyl(meth)acrylamide; N-ethyl(meth)acrylamide, N-isopropyl(methyl) ) Acrylamide, N-butyl(meth)acrylamide, N-n-butyl(meth)acrylamide, etc. N-alkyl(meth)acrylamide; N-vinyl acetamide, etc. N-vinyl carboxylic acid amides; monomers with hydroxyl and amide groups, such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(methyl) )Acrylamide, N-(1-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(methyl) N-hydroxyalkyl (meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, etc. Amides; monomers with alkoxy and amide groups, such as N-methoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-butoxy N-alkoxyalkyl (meth)acrylamide such as methyl(meth)acrylamide; and N,N-dimethylaminopropyl(meth)acrylamide, N-(meth)acrylamide, base) acrylyl 𠰌line, etc. Monomers containing amine groups: for example, aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate. Monomers with epoxy groups: for example, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and allyl glycidyl ether. Monomers with rings containing nitrogen atoms: such as N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinyl Pyrimidine, N-vinyl piperazole, N-vinylpyrrolidone, N-vinylpyrrole, N-vinylimidazole, N-vinylethazole, N-(meth)acrylyl-2-pyrrolidinone , N-(meth)acrylylpiperidine, N-(meth)acrylylpyrrolidine, N-vinyl𠰌line, N-vinyl-3-𠰌linone, N-vinyl-2- Caprolactam, N-vinyl-1,3-㗁𠯤-2-one, N-vinyl-3,5-𠰌lindione, N-vinylpyrazole, N-vinyliso㗁azole, N-vinylthiazole, N-vinylisothiazole, N-vinylpyridine, etc. (for example, N-vinyl-2-caprolactam and other lactams). Monomers with succinimide skeleton: such as N-(meth)acryloxymethylenesuccinimide, N-(meth)acryloxy-6-oxyhexamethylenesuccinimide Amine, N-(meth)acryl-8-oxyhexamethylenesuccinimide, etc. Maleimines: such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-benzene Maleic imide, etc. Iconidimines: such as N-methyl itonimide, N-ethyl itonimide, N-butyl itonimide, N-octyl itonimide, N- 2-Ethylhexyl Ikonimide, N-cyclohexyl Ikonimide, N-lauryl Ikonimide, etc. (Meth)acrylic acid aminoalkyl esters: such as (meth)acrylic acid aminoethyl ester, (meth)acrylic acid N,N-dimethylaminoethyl ester, (meth)acrylic acid N,N-dimethylaminoethyl Ethylaminoethyl, tert-butylaminoethyl (meth)acrylate. Monomers containing alkoxy groups: such as 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylate (meth)acrylic acid alkoxyalkyl esters such as propoxyethyl acrylate, butoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate, etc.; methoxyethylene glycol Alkoxyalkylene glycol (meth)acrylates such as (meth)acrylate and methoxypolypropylene glycol (meth)acrylate. Monomers containing alkoxysilyl groups: such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltriethoxysilane (Methyl)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane. Vinyl esters: such as vinyl acetate, vinyl propionate, etc. Vinyl ethers: vinyl alkyl ethers such as methyl vinyl ether or ethyl vinyl ether. Aromatic vinyl compounds: such as styrene, α-methylstyrene, vinyltoluene, etc. Olefins: such as ethylene, butadiene, isoprene, isobutylene, etc. (Meth)acrylates with alicyclic hydrocarbon groups: such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isopropyl (meth)acrylate, dicyclopentyl (meth)acrylate ester, adamantyl (meth)acrylate, etc. (Meth)acrylates with aromatic hydrocarbon groups: for example, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, etc. In addition, (meth)acrylates containing heterocycles such as tetrahydrofurfuryl (meth)acrylate, (meth)acrylates containing vinyl chloride or fluorine atoms, and (meth)acrylates containing halogen atoms such as polysilicon Oxy (meth)acrylate and other silicon atom-containing (meth)acrylate, (meth)acrylate obtained from terpene compound derivative alcohol, etc.

於使用此種共聚性單體之情形時，其使用量並無特別限定，通常適當設為單體成分整體之0.01重量%以上。就更良好地發揮共聚性單體之使用效果之觀點而言，亦可將共聚性單體之使用量設為單體成分整體之0.1重量%以上，亦可設為0.5重量%以上。又，就容易獲取黏著特性之平衡之觀點而言，共聚性單體之使用量通常適當設為單體成分整體之50重量%以下，較佳為設為40重量%以下。When such a copolymerizable monomer is used, the usage amount is not particularly limited, but is usually appropriately set to 0.01% by weight or more of the total monomer components. From the viewpoint of better exerting the use effect of the copolymerizable monomer, the usage amount of the copolymerizable monomer may be 0.1% by weight or more of the total monomer component, or may be 0.5% by weight or more. In addition, from the viewpoint of easily achieving a balance of adhesive properties, the usage amount of the copolymerizable monomer is usually appropriately set to 50% by weight or less of the total monomer components, and preferably 40% by weight or less.

於若干態樣中，單體成分較佳為包含含羧基之單體。作為含羧基之單體之較佳例，可列舉丙烯酸(AA)及甲基丙烯酸(MAA)。亦可將AA與MAA併用。於將AA與MAA併用之情形時，該等之重量比(AA/MAA)並無特別限定，例如可設為約0.1～10之範圍。於若干態樣中，上述重量比(AA/MAA)例如可為約0.3以上，亦可為約0.5以上。又，上述重量比(AA/MAA)例如可為約4以下，亦可為約3以下。In some aspects, the monomer component preferably includes a carboxyl-containing monomer. Preferable examples of the carboxyl group-containing monomer include acrylic acid (AA) and methacrylic acid (MAA). AA and MAA can also be used together. When AA and MAA are used together, the weight ratio (AA/MAA) is not particularly limited, but may be in the range of about 0.1 to 10, for example. In some aspects, the above weight ratio (AA/MAA) can be, for example, about 0.3 or more, or about 0.5 or more. Moreover, the said weight ratio (AA/MAA) may be about 4 or less, for example, or may be about 3 or less.

藉由使用含羧基之單體，可使水等水性液體快速地親和於A層之表面。該情況可有助於水剝離力N2之降低。含羧基之單體之使用量例如可為單體成分整體之0.05重量%以上，亦可為0.1重量%以上，亦可為0.3重量%以上，亦可為0.5重量%以上，亦可為0.8重量%以上。又，上述含羧基之單體之比率例如可為15重量%以下，亦可為10重量%以下，亦可為5重量%以下，亦可為4.5重量%以下，亦可為3.5重量%以下，亦可為3.0重量%以下，亦可為2.5重量%以下。含羧基之單體之使用量不過多就抑制水向A層之整體之擴散，抑制耐水黏著力N1之降低之觀點而言較佳。又，含羧基之單體之使用量不過多就防止用於測定水剝離力N2之水被A層吸收而於剝離中途水不足之情況之觀點而言亦可變得有利。By using carboxyl-containing monomers, aqueous liquids such as water can be quickly attached to the surface of layer A. This situation can contribute to the reduction of water peeling force N2. The usage amount of the carboxyl group-containing monomer may be, for example, 0.05% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, or 0.8% by weight of the total monomer components. %above. Furthermore, the ratio of the above-mentioned carboxyl group-containing monomer may be, for example, 15% by weight or less, 10% by weight or less, 5% by weight or less, 4.5% by weight or less, or 3.5% by weight or less. The content may be 3.0% by weight or less, or the content may be 2.5% by weight or less. It is preferable that the amount of the carboxyl group-containing monomer used is not too large from the viewpoint of suppressing the diffusion of water to the entire A layer and suppressing the decrease in the water-resistant adhesive force N1. In addition, it is advantageous that the amount of the carboxyl group-containing monomer used is not too large in order to prevent the water used for measuring the water peeling force N2 from being absorbed by the A layer and running out of water during peeling.

於若干態樣中，單體成分可包含含羥基之單體。藉由使用含羥基之單體，可調整黏著劑之凝聚力或交聯密度，而提高常態黏著力N0。使用含羥基之單體之情形時之使用量並無特別限制，例如可為單體成分整體之0.01重量%以上，亦可為0.1重量%以上，亦可為0.5重量%以上。又，就抑制向A層之整體之過度之水擴散之觀點而言，於若干態樣中，含羥基之單體之使用量適當設為單體成分整體之例如40重量%以下，亦可設為30重量%以下，亦可設為20重量%以下，亦可設為10重量%以下、5重量%以下或3重量%以下。本文所揭示之剝離方法亦可於藉由該剝離方法剝離之黏著片材實質上不使用含羥基之單體作為A層之單體成分之態樣中較佳地實施。In some aspects, the monomer component may include a hydroxyl-containing monomer. By using hydroxyl-containing monomers, the cohesion or cross-linking density of the adhesive can be adjusted to increase the normal adhesive force N0. When using a hydroxyl-containing monomer, the usage amount is not particularly limited. For example, it may be 0.01% by weight or more, 0.1% by weight or more, or 0.5% by weight or more of the total monomer component. In addition, from the viewpoint of suppressing excessive water diffusion into the entire A layer, in some aspects, the usage amount of the hydroxyl-containing monomer is appropriately set to, for example, 40% by weight or less of the total monomer component, or may be set to 40% by weight or less. The content may be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less. The peeling method disclosed herein can also be preferably implemented in an aspect where the adhesive sheet peeled off by the peeling method does not substantially use a hydroxyl-containing monomer as a monomer component of the A layer.

於若干態樣中，單體成分可包含含烷氧基矽烷基之單體。含烷氧基矽烷基之單體典型而言為於一分子內具有至少1個(較佳為2個以上、例如2個或3個)之烷氧基矽烷基之乙烯性不飽和單體，其具體例如上所述。上述含烷氧基矽烷基之單體可單獨使用一種或組合兩種以上而使用。藉由使用含烷氧基矽烷基之單體，可於黏著劑層中導入利用矽烷醇基之縮合反應(矽烷醇縮合)形成之交聯結構。再者，含烷氧基矽烷基之單體亦可理解為下述之矽烷偶合劑。In some aspects, the monomer component may include an alkoxysilyl group-containing monomer. The alkoxysilyl group-containing monomer is typically an ethylenically unsaturated monomer having at least 1 (preferably 2 or more, such as 2 or 3) alkoxysilyl groups in one molecule, Specific examples are as described above. The above-mentioned alkoxysilyl group-containing monomer may be used alone or in combination of two or more. By using a monomer containing an alkoxysilyl group, a cross-linked structure formed by the condensation reaction of the silanol group (silanol condensation) can be introduced into the adhesive layer. Furthermore, the alkoxysilyl group-containing monomer can also be understood as the following silane coupling agent.

於單體成分包含含烷氧基矽烷基之單體之態樣中，含烷氧基矽烷基之單體於該單體成分整體中所占之比率例如可設為0.005重量%以上，通常適當設為0.01重量%以上。又，就對被黏著體之密接性提高之觀點而言，上述含烷氧基矽烷基之單體之比率例如可為0.5重量%以下，亦可為0.1重量%以下，亦可為0.05重量%以下。In the case where the monomer component contains an alkoxysilyl group-containing monomer, the proportion of the alkoxysilyl group-containing monomer in the entire monomer component can be, for example, 0.005% by weight or more, which is usually appropriate. Let it be 0.01% by weight or more. Furthermore, from the viewpoint of improving the adhesiveness of the adherend, the ratio of the alkoxysilyl group-containing monomer may be, for example, 0.5% by weight or less, 0.1% by weight or less, or 0.05% by weight. the following.

單體成分之組成可以基於該單體成分之組成藉由Fox公式所求出之玻璃轉移溫度(以下，亦稱為「丙烯酸系聚合物之玻璃轉移溫度」)成為-75℃以上且-10℃以下之方式設定。於若干態樣中，上述丙烯酸系聚合物之玻璃轉移溫度(Tg)適當為-20℃以下，較佳為-30℃以下，更佳為-40℃以下，進而較佳為-50℃以下，例如亦可為-55℃以下。若丙烯酸系聚合物之Tg變低，則存在A層對被黏著體之密接性總體而言提高之傾向。根據對被黏著體之密接性較高之A層，容易抑制於未意圖黏著片材之剝離之狀況下水滲入至被黏著體與A層之界面。該特性就耐水黏著力N1之提高或耐水黏著力降低率之減小之觀點而言可變得有利。又，就容易提高常態黏著力N0之觀點而言，丙烯酸系聚合物之Tg例如可為-70℃以上，亦可為-65℃以上。The composition of the monomer component can be such that the glass transition temperature (hereinafter, also referred to as "the glass transition temperature of the acrylic polymer") calculated by the Fox formula is -75°C or more and -10°C Set as follows. In some aspects, the glass transition temperature (Tg) of the above-mentioned acrylic polymer is suitably -20°C or lower, preferably -30°C or lower, more preferably -40°C or lower, further preferably -50°C or lower, For example, it may be -55°C or lower. When the Tg of the acrylic polymer becomes low, the adhesiveness of the A layer to the adherend tends to improve as a whole. The A layer, which has a high adhesion to the adherend, can easily prevent water from penetrating into the interface between the adherend and the A layer without intending to peel off the adhesive sheet. This characteristic may become advantageous from the viewpoint of improvement of the water-resistant adhesive force N1 or reduction of the water-resistant adhesive force reduction rate. In addition, from the viewpoint of easily increasing the normal adhesion force N0, the Tg of the acrylic polymer may be -70°C or higher, or -65°C or higher, for example.

此處，如下所示，上述Fox公式係共聚物之Tg、與構成該共聚物之各單體單獨聚合而成之均聚物之玻璃轉移溫度Tgi之關係式。 1/Tg＝Σ(Wi/Tgi) 再者，於上述Fox公式中，Tg表示共聚物之玻璃轉移溫度(單位：K)，Wi表示該共聚物中之單體i之重量分率(重量基準之共聚比率)，Tgi表示單體i之均聚物之玻璃轉移溫度(單位：K)。Here, as shown below, the above-mentioned Fox formula is a relational formula between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer obtained by polymerizing each monomer constituting the copolymer individually. 1/Tg＝Σ(Wi/Tgi) Furthermore, in the above Fox formula, Tg represents the glass transition temperature of the copolymer (unit: K), Wi represents the weight fraction of monomer i in the copolymer (copolymerization ratio on a weight basis), and Tgi represents monomer i. The glass transition temperature of the homopolymer (unit: K).

作為用於算出Tg之均聚物之玻璃轉移溫度，使用公知資料中所記載之值。例如，關於以下所列舉之單體，該單體之均聚物之玻璃轉移溫度使用以下之值。丙烯酸2-乙基己酯 -70℃ 丙烯酸正丁酯 -55℃ 甲基丙烯酸甲酯 105℃ 丙烯酸甲酯 8℃ 丙烯酸 106℃ 甲基丙烯酸 228℃As the glass transition temperature of the homopolymer for calculating Tg, the value described in publicly known documents is used. For example, regarding the monomers listed below, the following values are used for the glass transition temperature of the homopolymer of the monomer. 2-ethylhexyl acrylate -70℃ n-Butyl acrylate -55℃ Methyl methacrylate 105℃ Methyl acrylate 8℃ Acrylic 106℃ Methacrylic acid 228℃

關於上述例示以外之單體之均聚物之玻璃轉移溫度，使用「Polymer Handbook」(第3版，John Wiley & Sons, Inc., 1989)中所記載之數值。於在本文獻中記載有複數種值之情形時，採用最高值。Regarding the glass transition temperature of homopolymers of monomers other than those exemplified above, the values described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) are used. When multiple values are described in this document, the highest value is used.

關於上述Polymer Handbook中亦未記載均聚物之玻璃轉移溫度之單體，使用藉由以下之測定方法所獲得之值(參照日本專利申請案公開2007-51271號公報)。具體而言，於具備溫度計、攪拌機、氮氣導入管及回流冷卻管之反應器中，投入單體100重量份、偶氮雙異丁腈0.2重量份及作為聚合溶劑之乙酸乙酯200重量份，一面使氮氣流通一面攪拌1小時。如此去除聚合系內之氧後，升溫至63℃而反應10小時。繼而，冷卻至室溫，獲得固形物成分濃度33重量%之均聚物溶液。繼而，將該均聚物溶液流延塗佈於剝離襯墊上，進行乾燥而製作厚度約2 mm之試驗樣品(片狀之均聚物)。將該試驗樣品沖裁成直徑7.9 mm之圓盤狀，由平行板夾入，使用黏彈性試驗機(ARES，Rheometrics公司製造)，一面賦予頻率1 Hz之剪切應變，一面於溫度區域-70～150℃、5℃/分鐘之升溫速度下藉由剪切模式測定黏彈性，將tanδ之峰頂溫度設為均聚物之Tg。Regarding the monomers whose glass transition temperature of the homopolymer is not described in the above-mentioned Polymer Handbook, the value obtained by the following measurement method is used (see Japanese Patent Application Publication No. 2007-51271). Specifically, in a reactor equipped with a thermometer, a stirrer, a nitrogen introduction pipe and a reflux cooling pipe, 100 parts by weight of the monomer, 0.2 parts by weight of azobisisobutyronitrile and 200 parts by weight of ethyl acetate as the polymerization solvent were added. The mixture was stirred for 1 hour while flowing nitrogen gas. After removing the oxygen in the polymerization system in this way, the temperature was raised to 63°C and the reaction was carried out for 10 hours. Then, it was cooled to room temperature to obtain a homopolymer solution with a solid content concentration of 33% by weight. Then, the homopolymer solution was cast-coated on a release liner and dried to prepare a test sample (sheet-shaped homopolymer) with a thickness of about 2 mm. The test sample was punched into a disc shape with a diameter of 7.9 mm, clamped between parallel plates, and a viscoelastic testing machine (ARES, manufactured by Rheometrics) was used to impart shear strain with a frequency of 1 Hz on one side and in the temperature range of -70 The viscoelasticity was measured in shear mode at a temperature rise rate of ∼150°C and 5°C/min, and the peak temperature of tan δ was set as the Tg of the homopolymer.

黏著劑層可使用以聚合物、未聚合物(即，聚合性官能基為未反應之形態)、或者該等之混合物之形態包含如上所述之組成之單體成分之黏著劑組合物而形成。上述黏著劑組合物可為如下各種形態：黏著劑(黏著成分)分散於水中之形態之水分散型黏著劑組合物、於有機溶劑中包含黏著劑之形態之溶劑型黏著劑組合物、以藉由紫外線或放射線等活性能量線進行硬化而形成黏著劑之方式製備之活性能量線硬化型黏著劑組合物、於加熱熔融狀態下進行塗敷並冷卻至室溫附近時會形成黏著劑之熱熔型黏著劑組合物等。The adhesive layer can be formed using an adhesive composition containing monomer components having the composition described above in the form of a polymer, an unpolymer (that is, the polymerizable functional group is in an unreacted form), or a mixture thereof. . The above-mentioned adhesive composition can be in various forms as follows: a water-dispersed adhesive composition in which an adhesive (adhesive component) is dispersed in water; a solvent-based adhesive composition in which an adhesive is contained in an organic solvent. The active energy ray-curable adhesive composition prepared by hardening active energy rays such as ultraviolet rays or radiation to form an adhesive will form a hot melt of the adhesive when it is applied in a heated and molten state and cooled to near room temperature. Adhesive compositions, etc.

聚合時，根據聚合方法或聚合態樣等，可使用公知或慣用之熱聚合起始劑或光聚合起始劑。此種聚合起始劑可單獨使用一種或適宜組合兩種以上而使用。During polymerization, a known or commonly used thermal polymerization initiator or photopolymerization initiator may be used depending on the polymerization method or polymerization aspect. Such a polymerization initiator may be used alone or in combination of two or more thereof as appropriate.

作為熱聚合起始劑，並無特別限定，例如可使用偶氮系聚合起始劑、過氧化物系起始劑、利用過氧化物與還原劑之組合獲得之氧化還原系起始劑、取代乙烷系起始劑等。更具體而言，可例示：例如2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丙脒)二硫酸鹽、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2'-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2'-偶氮雙(N,N'-二亞甲基異丁基脒)、2,2'-偶氮雙[N-(2-羧基乙基)-2-甲基丙脒]水合物等偶氮系起始劑；例如過硫酸鉀、過硫酸銨等過硫酸鹽；過氧化苯甲醯、氫過氧化第三丁基、過氧化氫等過氧化物系起始劑；例如苯基取代乙烷等取代乙烷系起始劑；例如過硫酸鹽與亞硫酸氫鈉之組合、過氧化物與抗壞血酸鈉之組合等氧化還原系起始劑等，但並不限定於該等。再者，熱聚合可於例如20～100℃(典型而言40～80℃)左右之溫度下較佳地實施。The thermal polymerization initiator is not particularly limited. For example, azo-based polymerization initiators, peroxide-based initiators, redox-based initiators obtained by combining a peroxide and a reducing agent, and substituted polymerization initiators can be used. Ethane starter, etc. More specifically, examples include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis( 2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'- Azobis (N,N'-dimethyleneisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate and other azo series Starting agents; such as potassium persulfate, ammonium persulfate and other persulfates; peroxide-based starting agents such as benzyl peroxide, tert-butyl hydroperoxide, hydrogen peroxide; such as phenyl-substituted ethane, etc. Substituted ethane-based initiators; for example, redox-based initiators such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, etc., but are not limited to these. In addition, thermal polymerization can be preferably carried out at a temperature of about 20 to 100°C (typically 40 to 80°C).

作為光聚合起始劑，並無特別限定，例如可使用縮酮系光聚合起始劑、苯乙酮系光聚合起始劑、安息香醚系光聚合起始劑、醯基氧化膦系光聚合起始劑、α-酮醇系光聚合起始劑、芳香族磺醯氯系光聚合起始劑、光活性肟系光聚合起始劑、安息香系光聚合起始劑、苯偶醯系光聚合起始劑、二苯甲酮系光聚合起始劑、9-氧硫𠮿系光聚合起始劑等。The photopolymerization initiator is not particularly limited. For example, ketal-based photopolymerization initiators, acetophenone-based photopolymerization initiators, benzoin ether-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators can be used. Initiator, α-ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzoyl photopolymerization initiator Polymerization initiator, benzophenone photopolymerization initiator, 9-oxosulfide It is a photopolymerization initiator, etc.

此種熱聚合起始劑或光聚合起始劑之使用量可設為與聚合方法或聚合態樣等對應之通常之使用量，並無特別限定。例如，相對於聚合對象之單體100重量份，可使用聚合起始劑約0.001～5重量份(典型而言為約0.01～2重量份、例如約0.01～1重量份)。The usage amount of such thermal polymerization initiator or photopolymerization initiator can be a usual usage amount corresponding to the polymerization method, polymerization state, etc., and is not particularly limited. For example, the polymerization initiator can be used in about 0.001 to 5 parts by weight (typically about 0.01 to 2 parts by weight, for example, about 0.01 to 1 part by weight) relative to 100 parts by weight of the monomer to be polymerized.

上述聚合中，可視需要使用先前公知之各種鏈轉移劑(亦可理解為分子量調節劑或聚合度調節劑)。作為鏈轉移劑，可使用正十二烷基硫醇、第三-十二烷基硫醇、硫代乙醇酸等硫醇類。或者，亦可使用不含硫原子之鏈轉移劑(非硫繫鏈轉移劑)。作為非硫繫鏈轉移劑之具體例，可列舉：N,N-二甲基苯胺、N,N-二乙基苯胺等苯胺類；α-蒎烯、異松油烯等萜類；α-甲基苯乙烯、α-甲基苯乙烯二聚物等苯乙烯類；二亞苄基丙酮、肉桂醇、肉桂醛等具有亞苄基之化合物；對苯二酚、二羥基萘等對苯二酚類；苯醌、萘醌等醌類；2,3-二甲基-2-丁烯、1,5-環辛二烯等烯烴類；苯酚、苄醇、烯丙醇等醇類；二苯基苯、三苯基苯等苄基氫類等。鏈轉移劑可單獨使用一種或組合兩種以上而使用。於使用鏈轉移劑之情形時，其使用量相對於單體成分100重量份，可設為例如約0.01～1重量份左右。本文所揭示之技術亦可於不使用鏈轉移劑之態樣中較佳地實施。In the above-mentioned polymerization, various previously known chain transfer agents (which can also be understood as molecular weight regulators or polymerization degree regulators) may be used if necessary. As the chain transfer agent, thiols such as n-dodecylmercaptan, tertiary-dodecylmercaptan, and thioglycolic acid can be used. Alternatively, a chain transfer agent containing no sulfur atoms (non-sulfur chain transfer agent) may also be used. Specific examples of non-sulfur chain transfer agents include: anilines such as N,N-dimethylaniline and N,N-diethylaniline; terpenes such as α-pinene and terpinene; α- Styrenes such as methylstyrene and α-methylstyrene dimer; compounds with benzylidene groups such as dibenzylidene acetone, cinnamyl alcohol and cinnamaldehyde; paraphenyls such as hydroquinone and dihydroxynaphthalene Phenols; quinones such as benzoquinone and naphthoquinone; olefins such as 2,3-dimethyl-2-butene, 1,5-cyclooctadiene; alcohols such as phenol, benzyl alcohol, allyl alcohol; Benzyl hydrogens such as phenylbenzene and triphenylbenzene, etc. A chain transfer agent can be used individually by 1 type or in combination of 2 or more types. When a chain transfer agent is used, the usage amount can be, for example, about 0.01 to 1 part by weight relative to 100 parts by weight of the monomer component. The techniques disclosed herein may also be better implemented without the use of chain transfer agents.

於本文所揭示之剝離方法之若干較佳之態樣中，上述黏著片材具有由水分散型黏著劑組合物形成之A層。作為水分散型黏著劑組合物之代表例，可列舉乳液型黏著劑組合物。乳液型黏著劑組合物典型而言含有單體成分之聚合物、及視需要使用之添加劑。In some preferred aspects of the peeling method disclosed herein, the adhesive sheet has an A layer formed of a water-dispersed adhesive composition. Typical examples of water-dispersed adhesive compositions include emulsion-type adhesive compositions. The emulsion-type adhesive composition typically contains a polymer as a monomer component and optional additives.

單體成分之乳液聚合通常於乳化劑之存在下進行。作為乳液聚合用之乳化劑，並無特別限制，可使用公知之陰離子性乳化劑、非離子性乳化劑等。乳化劑可單獨使用一種或組合兩種以上而使用。Emulsion polymerization of monomer components is usually carried out in the presence of emulsifiers. The emulsifier for emulsion polymerization is not particularly limited, and known anionic emulsifiers, nonionic emulsifiers, etc. can be used. An emulsifier can be used individually by 1 type or in combination of 2 or more types.

作為陰離子性乳化劑之非限定性之例，可列舉：月桂基硫酸鈉、月桂基硫酸銨、十二烷基苯磺酸鈉、聚氧乙烯月桂基硫酸鈉、聚氧乙烯烷基醚硫酸鈉、聚氧乙烯烷基苯醚硫酸銨、聚氧乙烯烷基苯醚硫酸鈉、聚氧乙烯烷基磺基琥珀酸鈉等。作為非離子性乳化劑之非限定性之例，可列舉：聚氧乙烯烷基醚、聚氧乙烯烷基苯醚、聚氧乙烯脂肪酸酯、聚氧乙烯聚氧丙烯嵌段聚合物等。亦可使用具有反應性官能基之乳化劑(反應性乳化劑)。作為反應性乳化劑之例，可列舉於上述之陰離子性乳化劑或非離子性乳化劑中，導入有丙烯基或烯丙基醚基等自由基聚合性官能基之結構之自由基聚合性乳化劑。Non-limiting examples of anionic emulsifiers include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl benzene sulfonate, polyoxyethylene sodium lauryl sulfate, and polyoxyethylene sodium alkyl ether sulfate. , polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate, polyoxyethylene alkyl sodium sulfosuccinate, etc. Non-limiting examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyoxypropylene block polymers, and the like. Emulsifiers having reactive functional groups (reactive emulsifiers) can also be used. Examples of reactive emulsifiers include radically polymerizable emulsifiers in which a radically polymerizable functional group such as an acryl group or an allyl ether group is introduced into the above-mentioned anionic emulsifier or nonionic emulsifier. agent.

乳液聚合中之乳化劑之使用量相對於單體成分100重量份，例如可為0.2重量份以上，亦可為0.5重量份以上，亦可為1.0重量份以上，亦可為1.5重量份以上。又，就耐水黏著力N1之提高或耐水黏著力降低率之減小、或黏著劑層之透明性提高之觀點而言，於若干態樣中，乳化劑之使用量通常相對於單體成分100重量份適當設為10重量份以下，較佳為設為5重量份以下，亦可設為3重量份以下。再者，此處用於乳液聚合之乳化劑亦可作為A層之水親和劑發揮功能。The amount of emulsifier used in emulsion polymerization may be, for example, 0.2 parts by weight or more, 0.5 parts by weight or more, 1.0 parts by weight or more, or 1.5 parts by weight or more, based on 100 parts by weight of the monomer component. In addition, from the viewpoint of improving the water-resistant adhesive force N1, reducing the water-resistant adhesive force reduction rate, or improving the transparency of the adhesive layer, in some aspects, the usage amount of the emulsifier is usually 100% of the monomer component. The part by weight is suitably 10 parts by weight or less, preferably 5 parts by weight or less, and may be 3 parts by weight or less. Furthermore, the emulsifier used in the emulsion polymerization here can also function as the water affinity agent of the A layer.

根據乳液聚合，可獲得單體成分之聚合物分散於水中之乳液形態之聚合反應液。用於形成A層之水分散型黏著劑組合物可使用上述聚合反應液較佳地製造。Emulsion polymerization can obtain a polymerization reaction liquid in the form of an emulsion in which the polymer of the monomer component is dispersed in water. The water-dispersed adhesive composition used to form layer A can be preferably produced using the above-mentioned polymerization reaction liquid.

於若干態樣中，黏著片材可具有由溶劑型黏著劑組合物形成之A層。溶劑型黏著劑組合物典型而言含有單體成分之溶液聚合物、及視需要使用之添加劑。用於溶液聚合之溶劑(聚合溶劑)可自先前公知之有機溶劑中適宜選擇。例如，可使用選自甲苯等芳香族化合物類(典型而言為芳香族烴類)；乙酸乙酯或乙酸丁酯等酯類；己烷或環己烷等脂肪族或脂環式烴類；1,2-二氯乙烷等鹵化烷烴類；異丙醇等低級醇類(例如碳原子數1～4之一元醇類)；第三丁基甲醚等醚類；甲基乙基酮等酮類等中之任一種溶劑或兩種以上之混合溶劑。根據溶液聚合，可獲得單體成分之聚合物溶解於聚合溶劑中之形態之聚合反應液。用於形成A層之溶劑型黏著劑組合物可使用上述聚合反應液較佳地製造。In some aspects, the adhesive sheet may have an A layer formed from a solvent-based adhesive composition. Solvent-based adhesive compositions typically contain a solution polymer of monomer components and optional additives. The solvent (polymerization solvent) used for solution polymerization can be appropriately selected from previously known organic solvents. For example, aromatic compounds (typically aromatic hydrocarbons) selected from the group including toluene; esters such as ethyl acetate or butyl acetate; aliphatic or alicyclic hydrocarbons such as hexane or cyclohexane; Halogenated alkanes such as 1,2-dichloroethane; lower alcohols such as isopropyl alcohol (such as monohydric alcohols with 1 to 4 carbon atoms); ethers such as tert-butyl methyl ether; ketones such as methyl ethyl ketone Any one solvent or a mixture of two or more solvents. According to solution polymerization, a polymerization reaction liquid in a form in which a polymer of monomer components is dissolved in a polymerization solvent can be obtained. The solvent-based adhesive composition used to form layer A can be preferably produced using the above-mentioned polymerization reaction liquid.

於若干態樣中，黏著片材可具有由活性能量線硬化型黏著劑組合物形成之A層。此處，於本說明書中，所謂「活性能量線」，係指具有可引起聚合反應、交聯反應、起始劑之分解等化學反應之能量之能量線。此處所謂之活性能量線之例中包含如紫外線、可見光線、紅外線之類的光、或如α射線、β射線、γ射線、電子束、中子束、X射線之類的放射線等。作為活性能量線硬化型黏著劑組合物之一較佳例，可列舉光硬化型黏著劑組合物。光硬化型之黏著劑組合物具有即便為較厚之黏著劑層亦可容易地形成之優點。其中，較佳為紫外線硬化型黏著劑組合物。In some aspects, the adhesive sheet may have an A layer formed of an active energy ray curable adhesive composition. Here, in this specification, "active energy rays" refer to energy rays having energy that can cause chemical reactions such as polymerization reaction, cross-linking reaction, and decomposition of the initiator. Examples of active energy rays here include light such as ultraviolet rays, visible rays, infrared rays, or radiation such as alpha rays, beta rays, gamma rays, electron beams, neutron beams, and X-rays. A preferred example of the active energy ray curable adhesive composition is a photocurable adhesive composition. The photocurable adhesive composition has the advantage that even a thick adhesive layer can be easily formed. Among them, an ultraviolet curable adhesive composition is preferred.

光硬化型黏著劑組合物典型而言以聚合物之形態包含該組合物之單體成分中之至少一部分(可為單體之種類之一部分，亦可為分量之一部分)。形成上述聚合物時之聚合方法並無特別限定，可適宜採用先前公知之各種聚合方法。例如，可適宜採用溶液聚合、乳液聚合、塊狀聚合等熱聚合(典型而言，於熱聚合起始劑之存在下進行)；照射紫外線等光而進行之光聚合(典型而言，於光聚合起始劑之存在下進行)；照射β射線、γ射線等放射線而進行之放射線聚合等。其中，較佳為光聚合。The photocurable adhesive composition typically contains at least a part of the monomer components of the composition in the form of a polymer (it may be part of the type of monomer or part of the component). The polymerization method for forming the above-mentioned polymer is not particularly limited, and various conventionally known polymerization methods can be suitably used. For example, thermal polymerization such as solution polymerization, emulsion polymerization, and block polymerization (typically carried out in the presence of a thermal polymerization initiator); photopolymerization carried out by irradiation with light such as ultraviolet rays (typically carried out in the presence of light) can be suitably used. in the presence of a polymerization initiator); radiation polymerization by irradiating β-rays, γ-rays and other radiation. Among them, photopolymerization is preferred.

較佳之一態樣之光硬化型黏著劑組合物包含單體成分之部分聚合物。此種部分聚合物典型而言為源自單體成分之聚合物與未反應之單體之混合物，較佳為呈現漿液狀(具有黏性之液狀)。以下，有時將上述性狀之部分聚合物稱為「單體漿液」或簡稱為「漿液」。使單體成分部分聚合時之聚合方法並無特別限制，可適宜選擇如上所述之各種聚合方法而使用。就效率或簡便性之觀點而言，可較佳地採用光聚合法。根據光聚合，藉由光之照射量(光量)等聚合條件，可容易地控制單體成分之聚合轉化率(單體轉化率)。A preferred aspect of the photocurable adhesive composition includes a partial polymer of monomer components. Such a partial polymer is typically a mixture of a polymer derived from monomer components and unreacted monomers, and is preferably in the form of a slurry (viscous liquid). Hereinafter, some polymers with the above properties may be referred to as "monomer slurry" or simply "slurry". The polymerization method when partially polymerizing the monomer component is not particularly limited, and various polymerization methods as described above can be appropriately selected and used. From the viewpoint of efficiency or simplicity, the photopolymerization method may be preferably used. According to photopolymerization, the polymerization conversion rate (monomer conversion rate) of the monomer component can be easily controlled by polymerization conditions such as the amount of light irradiation (light quantity).

上述部分聚合物中之單體混合物之聚合轉化率並無特別限定。上述聚合轉化率可設為例如約70重量%以下，較佳為設為約60重量%以下。就包含上述部分聚合物之黏著劑組合物之製備容易性或塗敷性等觀點而言，通常上述聚合轉化率適當為約50重量%以下，較佳為約40重量%以下(例如約35重量%以下)。聚合轉化率之下限並無特別限定，典型而言為約1重量%以上，通常適當設為約5重量%以上。The polymerization conversion rate of the monomer mixture in the above-mentioned partial polymer is not particularly limited. The polymerization conversion rate can be, for example, about 70% by weight or less, preferably about 60% by weight or less. From the viewpoint of ease of preparation or coating properties of the adhesive composition containing the above-mentioned partial polymer, the polymerization conversion rate is generally about 50% by weight or less, preferably about 40% by weight or less (for example, about 35% by weight). %the following). The lower limit of the polymerization conversion rate is not particularly limited, but is typically about 1% by weight or more, and is usually appropriately set to about 5% by weight or more.

包含單體成分之部分聚合物之黏著劑組合物例如可藉由利用適當之聚合方法(例如光聚合法)使包含用於製備該黏著劑組合物之單體成分之全部量之單體混合物進行部分聚合而獲得。又，包含單體成分之部分聚合物之黏著劑組合物亦可為包含用於製備該黏著劑組合物之單體成分中之一部分之單體混合物之部分聚合物或完全聚合物、與剩餘之單體成分或其部分聚合物之混合物。再者，於本說明書中，所謂「完全聚合物」，係指聚合轉化率超過95重量%。The adhesive composition containing a partial polymer of the monomer component can be prepared, for example, by using a suitable polymerization method (such as a photopolymerization method) to make a monomer mixture containing the entire amount of the monomer component used to prepare the adhesive composition. Obtained by partial aggregation. Furthermore, the adhesive composition containing a partial polymer of the monomer component may also be a partial polymer or a complete polymer containing a monomer mixture of a part of the monomer components used to prepare the adhesive composition, and the remaining A mixture of monomer components or partial polymers thereof. In addition, in this specification, the so-called "complete polymer" means that the polymerization conversion rate exceeds 95% by weight.

包含上述部分聚合物之黏著劑組合物中可調配視需要使用之其他成分(例如光聚合起始劑、多官能單體、交聯劑、水親和劑等)。調配此種其他成分之方法並無特別限定，例如可使其預先含有於上述單體混合物中，亦可添加至上述部分聚合物中。The adhesive composition containing the above-mentioned partial polymers can be formulated with other components (such as photopolymerization initiator, multifunctional monomer, cross-linking agent, water affinity agent, etc.) used as needed. The method of preparing such other components is not particularly limited. For example, they may be contained in the above-mentioned monomer mixture in advance, or may be added to the above-mentioned partial polymer.

(水親和劑) 本文所揭示之剝離方法中，黏著片材較佳為構成黏著劑層之一表面之A層除單體成分之聚合反應物以外包含水親和劑。例如，較佳為具備包含丙烯酸系聚合物作為上述聚合反應物，且進而包含水親和劑之A層之黏著片材。(water affinity agent) In the peeling method disclosed herein, the adhesive sheet is preferably such that the A layer constituting one surface of the adhesive layer contains a water affinity agent in addition to the polymerization reactant of the monomer component. For example, an adhesive sheet preferably includes an A layer containing an acrylic polymer as the polymerization reactant and further containing a water affinity agent.

作為水親和劑，可適宜選擇藉由含有於A層中而可發揮提高該A層之表面之水親和性之作用的各種材料而使用。藉由提高A層之水親和性，可使水等水性液體更快速地親和於A層之表面。藉此，例如於水剝離力N2之測定時，可使最初滴加之1滴水追隨於黏著片材自被黏著體之剝離前線之移動而遍及A層之表面，可有效地減小水剝離力N2。藉由相同之作用，於包括一面使水等水性液體進入至黏著片材與被黏著體之界面，一面使剝離前線移動的黏著片材剝離方法中，可提高該黏著片材自被黏著體之剝離性。As the water affinity agent, various materials that can play a role of improving the water affinity of the surface of the A layer when contained in the A layer can be appropriately selected and used. By increasing the water affinity of the A layer, aqueous liquids such as water can be more quickly affined with the surface of the A layer. By this, for example, when measuring the water peeling force N2, the first drop of water can be made to follow the movement of the peeling line of the adhesive sheet from the adherend and spread across the surface of the A layer, which can effectively reduce the water peeling force N2. . Through the same effect, in the adhesive sheet peeling method that involves allowing an aqueous liquid such as water to enter the interface between the adhesive sheet and the adherend and moving the peeling front line, the adhesive sheet can be improved from the adherend. Peelability.

作為水親和劑，可利用公知之陰離子性界面活性劑、非離子性界面活性劑、陽離子系界面活性劑、水溶性塑化劑、水溶性聚合物等。水親和劑可單獨使用或組合兩種以上而使用。As the water affinity agent, known anionic surfactants, nonionic surfactants, cationic surfactants, water-soluble plasticizers, water-soluble polymers, etc. can be used. The water affinity agent can be used alone or in combination of two or more types.

作為水溶性塑化劑，可使用各種多元醇(較佳為聚醚多元醇)。具體而言，例如可列舉：聚乙二醇、聚丙二醇、聚氧丙烯山梨糖醇醚、聚甘油等。該等可單獨使用一種或組合兩種以上而使用。作為水溶性聚合物，例如可列舉：聚乙烯基醇、聚乙烯基吡咯啶酮、聚丙烯酸等。As water-soluble plasticizers, various polyols (preferably polyether polyols) can be used. Specific examples thereof include polyethylene glycol, polypropylene glycol, polyoxypropylene sorbitol ether, polyglycerin, and the like. These can be used individually by 1 type or in combination of 2 or more types. Examples of the water-soluble polymer include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, and the like.

作為陰離子性界面活性劑，例如可列舉：十二烷基苯磺酸鈉等烷基苯磺酸鹽；月桂基硫酸鈉、月桂基硫酸銨等烷基硫酸鹽；聚氧乙烯月桂胺、聚氧乙烯硬脂胺等聚醚胺；聚氧乙烯烷基醚硫酸鈉、聚氧乙烯烷基苯醚硫酸銨、聚氧乙烯烷基苯醚硫酸鈉等聚醚硫酸鹽；聚氧乙烯硬脂醚磷酸酯、聚氧乙烯月桂醚磷酸酯等聚氧乙烯烷基醚磷酸酯；上述聚氧乙烯烷基醚磷酸酯之鈉鹽、鉀鹽等聚氧乙烯烷基醚磷酸酯鹽；聚氧乙烯烷基磺基琥珀酸鈉等。Examples of anionic surfactants include alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; polyoxyethylene laurylamine, polyoxyethylene lauryl sulfate, etc. Polyether amines such as ethylene stearylamine; polyether sulfates such as polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate; polyoxyethylene stearyl ether phosphate Polyoxyethylene alkyl ether phosphate esters such as polyoxyethylene lauryl ether phosphate ester; polyoxyethylene alkyl ether phosphate ester salts such as sodium salt and potassium salt of the above-mentioned polyoxyethylene alkyl ether phosphate ester; polyoxyethylene alkyl ether phosphate esters Sodium sulfosuccinate, etc.

作為非離子性界面活性劑，例如可列舉：聚氧乙烯烷基醚、聚氧乙烯烷基苯醚、聚氧乙烯甘油醚、聚氧丙烯甘油醚、聚氧乙烯雙酚A醚等聚氧伸烷基醚；聚氧乙烯脂肪酸酯、聚氧乙烯-聚氧丙烯嵌段聚合物等。Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene bisphenol A ether and other polyoxyethylene surfactants. Alkyl ether; polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, etc.

於若干態樣中，例如可較佳地使用具有-POH基、-COH基及-SOH基之至少一個之陰離子性界面活性劑。其中，較佳為具有-POH基之界面活性劑。此種界面活性劑典型而言包含磷酸酯結構，例如可為磷酸之單酯(ROP(=O)(OH)₂ ；此處，R為1價有機基)、二酯((RO)₂ P(=O)OH；此處，R為相同或不同之1價有機基)、包含單酯及二酯之兩者之混合物等。作為具有-POH基之界面活性劑之較佳例，可列舉聚氧乙烯烷基醚磷酸酯。聚氧乙烯烷基醚磷酸酯中之烷基之碳原子數例如可為6～20，亦可為8～20，亦可為10～20，亦可為12～20，亦可為14～20。In some aspects, for example, an anionic surfactant having at least one of -POH group, -COH group and -SOH group can be preferably used. Among them, surfactants having a -POH group are preferred. This kind of surfactant typically contains a phosphate ester structure, for example, it can be a monoester of phosphoric acid (ROP(=O)(OH) ₂ ; here, R is a monovalent organic group), a diester ((RO) ₂ P (=O)OH; here, R is the same or different monovalent organic group), a mixture of both monoester and diester, etc. Preferable examples of the surfactant having a -POH group include polyoxyethylene alkyl ether phosphate. The number of carbon atoms of the alkyl group in the polyoxyethylene alkyl ether phosphate ester can be, for example, 6 to 20, 8 to 20, 10 to 20, 12 to 20, or 14 to 20 .

A層中之水親和劑之含量並無特別限定。於若干態樣中，水親和劑之含量相對於構成A層中所含之聚合物之單體成分每100重量份，例如可為0.2重量份以上，就獲得更高之效果之觀點而言，亦可為0.5重量份以上，亦可為1.0重量份以上，亦可為1.5重量份以上。又，就抑制向A層之整體中之過度之水擴散之觀點而言，於若干態樣中，水親和劑之使用量相對於單體成分100重量份適當設為10重量份以下，較佳為設為5重量份以下，亦可設為3重量份以下。水親和劑之含量不多過就耐水黏著力N1之提高或耐水黏著力降低率之減小、或黏著劑層之透明性提高之觀點而言亦較佳。The content of the water affinity agent in layer A is not particularly limited. In some aspects, the content of the water affinity agent may be, for example, 0.2 parts by weight or more per 100 parts by weight of the monomer components constituting the polymer contained in the A layer. From the perspective of obtaining higher effects, The amount may be 0.5 parts by weight or more, the amount may be 1.0 parts by weight or more, or the amount may be 1.5 parts by weight or more. Furthermore, from the viewpoint of suppressing excessive water diffusion into the entire A layer, in some aspects, the usage amount of the water affinity agent is preferably 10 parts by weight or less based on 100 parts by weight of the monomer component. In order to set it to 5 parts by weight or less, you may set it to 3 parts by weight or less. It is also preferable that the content of the water affinity agent is not more than that of the water-resistant adhesive force N1 from the viewpoint of improving the water-resistant adhesive force N1, reducing the water-resistant adhesive force reduction rate, or improving the transparency of the adhesive layer.

(矽烷偶合劑) 於若干態樣中，可使A層中含有矽烷偶合劑。根據包含矽烷偶合劑之A層，可較佳地實現耐水黏著力降低率較低，且水剝離黏著力降低率較高之黏著片材。(silane coupling agent) In some aspects, layer A can contain a silane coupling agent. According to the A layer containing a silane coupling agent, an adhesive sheet with a low water-resistant adhesive force reduction rate and a high water peeling adhesive force reduction rate can be better realized.

作為矽烷偶合劑，可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等具有環氧結構之矽化合物；3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)3-胺基丙基甲基二甲氧基矽烷等含胺基之矽化合物；3-氯丙基三甲氧基矽烷；含乙醯乙醯基之三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等含(甲基)丙烯醯基之矽烷偶合劑；3-異氰酸基丙基三乙氧基矽烷等含異氰酸基之矽烷偶合劑等。其中，作為較佳例，可列舉3-縮水甘油氧基丙基三甲氧基矽烷及含乙醯乙醯基之三甲氧基矽烷。Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane and other silicon compounds with epoxy structure; 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, N-(2 -Aminoethyl) 3-aminopropylmethyldimethoxysilane and other amine-containing silicon compounds; 3-chloropropyltrimethoxysilane; acetylacetyl-containing trimethoxysilane, 3 - Silane coupling agents containing (meth)acrylyl groups such as acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane; 3-isocyanatopropyltriethoxysilane Ethoxysilane and other isocyanate-containing silane coupling agents. Among them, preferred examples include 3-glycidoxypropyltrimethoxysilane and acetoacetyl group-containing trimethoxysilane.

矽烷偶合劑之使用量可以獲得所期望之使用效果之方式設定，並無特別限定。於若干態樣中，矽烷偶合劑之使用量相對於構成A層中所含之聚合物之單體成分100重量份，例如可為0.001重量份以上，就獲得更高之效果之觀點而言，可為0.005重量份以上，亦可為0.01重量份以上，亦可為0.015重量份以上。又，就提高與被黏著體之密接性之觀點而言，於若干態樣中，矽烷偶合劑之使用量相對於構成A層之單體成分100重量份，例如可為3重量份以下，亦可為1重量份以下，亦可為0.5重量份以下。The usage amount of the silane coupling agent is set in such a way that the desired effect can be obtained and is not particularly limited. In some aspects, the usage amount of the silane coupling agent may be, for example, 0.001 parts by weight or more relative to 100 parts by weight of the monomer component constituting the polymer contained in the A layer. From the perspective of obtaining higher effects, The amount may be 0.005 parts by weight or more, the amount may be 0.01 parts by weight or more, or the amount may be 0.015 parts by weight or more. Furthermore, from the viewpoint of improving the adhesion with the adherend, in some aspects, the usage amount of the silane coupling agent may be, for example, 3 parts by weight or less based on 100 parts by weight of the monomer components constituting the layer A. It may be 1 part by weight or less, or it may be 0.5 part by weight or less.

再者，於單體成分包含含烷氧基矽烷基之單體之態樣中，亦可利用上述含烷氧基矽烷基之單體作為A層中所含之矽烷偶合劑之一部分或全部。Furthermore, in the case where the monomer component includes an alkoxysilyl group-containing monomer, the above-mentioned alkoxysilyl group-containing monomer can also be used as part or all of the silane coupling agent contained in the A layer.

(交聯劑) 於A層中可視需要含有交聯劑。交聯劑之種類並無特別限制，例如可使用自先前公知之交聯劑中適宜選擇之交聯劑。作為交聯劑之具體例，可列舉：異氰酸酯系交聯劑、環氧系交聯劑、㗁唑啉系交聯劑、氮丙啶系交聯劑、碳二醯亞胺系交聯劑、三聚氰胺系交聯劑、脲系交聯劑、金屬烷氧化物系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、肼系交聯劑、胺系交聯劑等。該等可單獨使用一種或組合兩種以上而使用。(cross-linking agent) The A layer may contain a cross-linking agent if necessary. The type of cross-linking agent is not particularly limited, and for example, an appropriately selected cross-linking agent from previously known cross-linking agents can be used. Specific examples of the cross-linking agent include: isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, carbodiimide-based cross-linking agents, Melamine cross-linking agents, urea cross-linking agents, metal alkoxide cross-linking agents, metal chelate cross-linking agents, metal salt cross-linking agents, hydrazine cross-linking agents, amine cross-linking agents, etc. These can be used individually by 1 type or in combination of 2 or more types.

作為異氰酸酯系交聯劑之例，可使用2官能以上之多官能異氰酸酯化合物。例如可列舉：甲苯二異氰酸酯、二甲苯二異氰酸酯、聚亞甲基聚苯基二異氰酸酯、硫代磷酸三(對異氰酸基苯基)酯、二苯基甲烷二異氰酸酯等芳香族異氰酸酯；異佛爾酮二異氰酸酯等脂環族異氰酸酯；六亞甲基二異氰酸酯等脂肪族異氰酸酯等。作為市售品，可例示：三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物(東曹公司製造，商品名「Coronate L」)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(東曹公司製造，商品名「Coronate HL」)、六亞甲基二異氰酸酯異氰尿酸酯體(東曹公司製造，商品名「Coronate HX」)等異氰酸酯加成物等。於水分散型之黏著劑組合物中，較佳為使用可溶解或分散於水中之異氰酸酯系交聯劑。例如，可較佳地採用水溶性、水分散性或自乳化型之異氰酸酯系交聯劑。可較佳地使用異氰酸基經封端之所謂封端異氰酸酯型之異氰酸酯系交聯劑。As an example of the isocyanate-based cross-linking agent, a polyfunctional isocyanate compound having two or more functions can be used. Examples include: aromatic isocyanates such as toluene diisocyanate, xylene diisocyanate, polymethylene polyphenyl diisocyanate, tris(p-isocyanatophenyl)thiophosphate, diphenylmethane diisocyanate; isocyanate; Alicyclic isocyanates such as phorone diisocyanate; aliphatic isocyanates such as hexamethylene diisocyanate. Examples of commercially available products include: trimethylolpropane/toluene diisocyanate trimer adduct (manufactured by Tosoh Corporation, trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct Polymer adducts (manufactured by Tosoh Corporation, trade name "Coronate HL"), isocyanate adducts such as hexamethylene diisocyanate isocyanurate (manufactured by Tosoh Corporation, trade name "Coronate HX"), etc. . In a water-dispersed adhesive composition, it is preferred to use an isocyanate cross-linking agent that is soluble or dispersed in water. For example, water-soluble, water-dispersible or self-emulsifying isocyanate cross-linking agents can be preferably used. It is preferable to use a so-called blocked isocyanate type isocyanate cross-linking agent in which the isocyanate group is blocked.

作為環氧系交聯劑，可無特別限制地使用於1分子中具有2個以上之環氧基者。較佳為於1分子中具有3～5個環氧基之環氧系交聯劑。作為環氧系交聯劑之具體例，可列舉：N,N,N',N'-四縮水甘油基間苯二甲胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、1,6-己二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、聚甘油聚縮水甘油醚等。作為環氧系交聯劑之市售品，可列舉：三菱瓦斯化學公司製造之商品名「TETRAD-X」、「TETRAD-C」、DIC公司製造之商品名「EPICLON CR-5L」、Nagase ChemteX公司製造之商品名「DENACOL EX-512」、日產化學工業公司製造之商品名「TEPIC-G」等。於水分散型黏著劑組合物中，較佳為使用可溶解或分散於水中之環氧系交聯劑。As the epoxy cross-linking agent, those having two or more epoxy groups per molecule can be used without particular limitation. An epoxy cross-linking agent having 3 to 5 epoxy groups per molecule is preferred. Specific examples of the epoxy cross-linking agent include: N,N,N',N'-tetraglycidyl m-xylylenediamine, 1,3-bis(N,N-diglycidylamine Methyl)cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, etc. Examples of commercially available epoxy cross-linking agents include: "TETRAD-X" and "TETRAD-C" manufactured by Mitsubishi Gas Chemical Company, trade names "EPICLON CR-5L" and Nagase ChemteX manufactured by DIC Corporation The product is manufactured under the trade name "DENACOL EX-512" by the company, and the product is manufactured under the trade name "TEPIC-G" by Nissan Chemical Industries, Ltd. In the water-dispersed adhesive composition, it is preferable to use an epoxy cross-linking agent that can be dissolved or dispersed in water.

作為㗁唑啉系交聯劑，可無特別限制地使用於1分子內具有1個以上之㗁唑啉基者。於水分散型黏著劑組合物中，較佳為使用可溶解或分散於水中之㗁唑啉系交聯劑。作為氮丙啶系交聯劑之例，可列舉：三羥甲基丙烷三[3-(1-氮丙啶基)丙酸酯]、三羥甲基丙烷三[3-(1-(2-甲基)氮丙啶基丙酸酯)]等。作為碳二醯亞胺系交聯劑，可使用具有2個以上之碳二醯亞胺基之低分子化合物或高分子化合物。於水分散型黏著劑組合物中，較佳為使用可溶解或分散於水中之碳二醯亞胺系交聯劑。As the tetrazoline cross-linking agent, those having one or more tetrazoline groups per molecule can be used without particular limitation. In the water-dispersed adhesive composition, it is preferred to use a tetrazoline-based cross-linking agent that is soluble or dispersed in water. Examples of aziridine-based crosslinking agents include: trimethylolpropane tris[3-(1-aziridinyl)propionate], trimethylolpropane tris[3-(1-(2 -Methyl)aziridinylpropionate)], etc. As the carbodiimide cross-linking agent, a low molecular compound or a high molecular compound having two or more carbodiimide groups can be used. In the water-dispersed adhesive composition, it is preferred to use a carbodiimide cross-linking agent that is soluble or dispersed in water.

於若干態樣中，亦可使用過氧化物作為交聯劑。作為過氧化物，可列舉：過氧化二碳酸二(2-乙基己基)酯、過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二碳酸二第二丁酯、過氧化新癸酸第三丁酯、過氧化特戊酸第三己酯、過氧化特戊酸第三丁酯、過氧化二月桂醯、過氧化二正辛醯、過氧化異丁酸1,1,3,3-四甲基丁酯、過氧化二苯甲醯等。該等之中，作為交聯反應效率特別優異之過氧化物，可列舉：過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二月桂醯、過氧化二苯甲醯等。再者，於使用過氧化物作為上述聚合起始劑之情形時，亦可將未用於聚合反應而殘存之過氧化物用於交聯反應。該情形時定量過氧化物之殘存量，於過氧化物之比率未達特定量之情形時，可視需要以成為特定量之方式添加過氧化物。過氧化物之定量可藉由日本專利4971517號公報中所記載之方法而進行。In some aspects, peroxides can also be used as cross-linking agents. Examples of the peroxide include di(2-ethylhexyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, dibutyl peroxydicarbonate, and peroxydicarbonate. Oxidized tert-butyl neodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, dilauryl peroxide, di-n-octyl peroxide, isobutyric peroxide 1,1 ,3,3-tetramethylbutyl ester, dibenzoyl peroxide, etc. Among them, examples of peroxides having particularly excellent crosslinking reaction efficiency include di(4-tert-butylcyclohexyl)peroxydicarbonate, dilauryl peroxide, dibenzoyl peroxide, etc. . Furthermore, when peroxide is used as the above-mentioned polymerization initiator, the remaining peroxide that has not been used for the polymerization reaction may be used for the cross-linking reaction. In this case, the remaining amount of peroxide is quantified, and when the ratio of peroxide does not reach a specific amount, peroxide may be added to achieve a specific amount if necessary. Quantification of peroxide can be performed by the method described in Japanese Patent No. 4971517.

交聯劑之含量(於包含兩種以上之交聯劑之情形時為其等之合計量)並無特別限定。就實現平衡良好地發揮接著力或凝聚力等黏著特性之黏著劑之觀點而言，相對於黏著劑組合物中所含之單體成分100重量份，交聯劑之含量通常適當設為約5重量份以下，較佳為設為約0.001～5重量份，更佳為設為約0.001～4重量份，進而較佳為設為約0.001～3重量份。或者，亦可為不含如上所述之交聯劑之黏著劑組合物。或者，亦可為不含如上所述之交聯劑之黏著劑組合物。The content of the cross-linking agent (the total amount of equal amounts when two or more cross-linking agents are included) is not particularly limited. From the viewpoint of realizing an adhesive that exhibits well-balanced adhesive properties such as adhesive force and cohesive force, the content of the cross-linking agent is usually appropriately set to about 5 parts by weight relative to 100 parts by weight of the monomer components contained in the adhesive composition. parts or less, preferably about 0.001 to 5 parts by weight, more preferably about 0.001 to 4 parts by weight, still more preferably about 0.001 to 3 parts by weight. Alternatively, it may be an adhesive composition that does not contain the cross-linking agent as described above. Alternatively, it may be an adhesive composition that does not contain the cross-linking agent as described above.

(黏著賦予樹脂) 亦可使A層中含有黏著賦予樹脂。作為黏著賦予樹脂，例如可列舉：包含松香系黏著賦予樹脂、松香衍生物黏著賦予樹脂之石油系黏著賦予樹脂、萜烯系黏著賦予樹脂、酚系黏著賦予樹脂、酮系黏著賦予樹脂等。該等可單獨使用一種或組合兩種以上而使用。(Tackiness imparting resin) The A layer may also contain an adhesion-imparting resin. Examples of the tackifier resin include petroleum-based tackifier resins including rosin-based tackifier resins and rosin derivative tackifier-imparting resins, terpene-based tackifier-imparting resins, phenol-based tackifier-imparting resins, ketone-based tackifier-imparting resins, and the like. These can be used individually by 1 type or in combination of 2 or more types.

作為上述松香系黏著賦予樹脂，例如可列舉：松香膠、木松香、妥爾油松香等松香、以及穩定化松香(例如，對上述松香進行歧化或氫化處理而成之穩定化松香)、聚合松香(例如，上述松香之多聚物、典型而言為二聚物)、改性松香(例如，藉由順丁烯二酸、反丁烯二酸、(甲基)丙烯酸等不飽和酸進行改性而成之不飽和酸改性松香等)等。作為上述松香衍生物黏著賦予樹脂，例如可列舉：上述松香系黏著賦予樹脂之酯化物(例如，穩定化松香酯或聚合松香酯等松香酯類)、上述松香系樹脂之酚改性物(酚改性松香)及其酯化物(酚改性松香酯)等。作為上述石油系黏著賦予樹脂，例如可列舉：脂肪族系石油樹脂、芳香族系石油樹脂、共聚系石油樹脂、脂環族系石油樹脂、該等之氫化物等。作為上述萜烯系黏著賦予樹脂，例如可列舉：α-蒎烯樹脂、β-蒎烯樹脂、芳香族改性萜烯系樹脂、萜烯酚樹脂等。作為上述酮系黏著賦予樹脂，例如可列舉：利用酮類(例如，甲基乙基酮、甲基異丁基酮、苯乙酮等脂肪族酮；環己酮、甲基環己酮等脂環式酮等)與甲醛之縮合獲得之酮系樹脂等。Examples of the rosin-based adhesion-imparting resin include rosins such as rosin gum, wood rosin, and tall oil rosin, as well as stabilized rosins (for example, stabilized rosins obtained by disproportionating or hydrogenating the above rosins), and polymerized rosins. (For example, the above-mentioned rosin polymer, typically dimer), modified rosin (for example, modified by unsaturated acids such as maleic acid, fumaric acid, (meth)acrylic acid, etc. Unsaturated acid modified rosin, etc.). Examples of the rosin derivative tackifier-imparting resin include esterified products of the rosin-based tackifier-imparting resin (for example, rosin esters such as stabilized rosin ester or polymerized rosin ester), and phenol-modified products of the above-mentioned rosin-based resin (phenol). Modified rosin) and its esterification products (phenol modified rosin ester), etc. Examples of the petroleum-based tackifier-imparting resin include aliphatic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins, alicyclic petroleum resins, and hydrogenated products thereof. Examples of the terpene-based tackifier-imparting resin include α-pinene resin, β-pinene resin, aromatic modified terpene-based resin, terpene phenol resin, and the like. Examples of the ketone-based tackifier-imparting resin include ketones (for example, aliphatic ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetophenone; esters such as cyclohexanone and methylcyclohexanone). Ketone resins, etc. obtained by the condensation of cyclic ketones, etc.) and formaldehyde.

於若干態樣中，作為黏著賦予樹脂，可較佳地使用選自松香系黏著賦予樹脂、松香衍生物黏著賦予樹脂及萜烯酚樹脂中之一種或兩種以上。其中，較佳為松香衍生物黏著賦予樹脂，作為較佳例，可列舉穩定化松香酯及聚合松香酯等松香酯類。In some aspects, as the tackifier-imparting resin, one or two or more types selected from the group consisting of rosin-based tackifier-imparting resins, rosin derivative tackifier-imparting resins, and terpene phenol resins can be preferably used. Among them, rosin derivative adhesion-imparting resins are preferred, and preferred examples include rosin esters such as stabilized rosin ester and polymerized rosin ester.

於水分散型之黏著劑組合物中，較佳為使用如上所述之黏著賦予樹脂分散於水性溶劑中之形態之水分散型黏著賦予樹脂。例如，藉由將丙烯酸系聚合物之水分散液與水分散型黏著賦予樹脂進行混合，可容易地製備以所期望之比率含有該等成分之黏著劑組合物。於若干態樣中，作為水分散型黏著賦予樹脂，就對環境衛生之考慮等觀點而言，可較佳地使用至少實質上不含芳香族烴系溶劑者。更佳為使用實質上不含芳香族烴系溶劑及其他有機溶劑之水分散型黏著賦予樹脂。In the water-dispersed adhesive composition, it is preferable to use a water-dispersed tackifying resin in a form in which the tackifying resin as described above is dispersed in an aqueous solvent. For example, by mixing an aqueous dispersion of an acrylic polymer and a water-dispersed tackifier resin, an adhesive composition containing these components at a desired ratio can be easily prepared. In some aspects, as the water-dispersed adhesive-imparting resin, from the viewpoint of environmental hygiene, etc., it is preferable to use one that at least substantially does not contain aromatic hydrocarbon solvents. It is more preferable to use a water-dispersed adhesive-imparting resin that does not substantially contain aromatic hydrocarbon solvents and other organic solvents.

作為包含松香酯類之水分散型黏著賦予樹脂之市售品，例如可列舉：荒川化學股份有限公司製造之商品名「SUPER ESTER E-720」、「SUPER ESTER E-730-55」、「SUPER ESTER E-865NT」等、或哈利瑪化成股份有限公司製造之商品名「HARIESTER SK-90D」、「HARIESTER SK-70D」、「HARIESTER SK-70E」、「NEOTOL 115E」等。又，作為萜烯酚樹脂(可為水分散型萜烯酚樹脂之形態)之市售品，可列舉：荒川化學工業股份有限公司製造之商品名「TAMANOL E-100」、「TAMANOL E-200」、「TAMANOL E-200NT」等。Examples of commercially available water-dispersed tackifying resins containing rosin esters include: "SUPER ESTER E-720", "SUPER ESTER E-730-55", and "SUPER" manufactured by Arakawa Chemical Co., Ltd. ESTER E-865NT", etc., or the trade names "HARIESTER SK-90D", "HARIESTER SK-70D", "HARIESTER SK-70E", "NEOTOL 115E", etc. manufactured by Harima Chemical Co., Ltd. In addition, commercially available products of terpene phenol resin (which may be in the form of water-dispersed terpene phenol resin) include: "TAMANOL E-100" and "TAMANOL E-200" manufactured by Arakawa Chemical Industry Co., Ltd. ”, “TAMANOL E-200NT”, etc.

黏著賦予樹脂之軟化點並無特別限定。就抑制黏著劑層之凝聚力之降低之觀點而言，通常可較佳地使用軟化點為80℃以上之黏著賦予樹脂。黏著賦予樹脂之軟化點亦可為90℃以上，亦可為100℃以上，亦可為110℃以上，亦可為120℃以上。亦可使用軟化點130℃以上或140℃以上之黏著賦予樹脂。又，就透明性或對被黏著體之密接性之觀點而言，可較佳地使用軟化點為200℃以下或180℃以下之黏著賦予樹脂。再者，作為此處所謂之黏著賦予樹脂之軟化點，可採用文獻或目錄等中所記載之標稱值。於無標稱值之情形時，可基於JIS K5902或JIS K2207中所規定之軟化點試驗方法(環球法)測定黏著賦予樹脂之軟化點。The softening point of the adhesive imparting resin is not particularly limited. From the viewpoint of suppressing a decrease in the cohesive force of the adhesive layer, it is generally preferable to use an adhesive-imparting resin having a softening point of 80° C. or higher. The softening point of the adhesion imparting resin may be 90°C or higher, 100°C or higher, 110°C or higher, or 120°C or higher. Adhesion-imparting resins with softening points above 130°C or above 140°C can also be used. In addition, from the viewpoint of transparency or adhesion to an adherend, an adhesion-imparting resin having a softening point of 200° C. or lower or 180° C. or lower can be preferably used. In addition, as the softening point of the so-called tackifier-imparting resin here, the nominal value described in documents, catalogs, etc. can be used. When there is no nominal value, the softening point of the adhesion-imparting resin can be measured based on the softening point test method (ball and ball method) specified in JIS K5902 or JIS K2207.

就較佳地發揮其使用效果之觀點而言，黏著賦予樹脂之使用量通常相對於構成A層中所含之聚合物之單體成分100重量份，適當設為1重量份以上，亦可為5重量份以上，亦可為10重量份以上，亦可為15重量份以上，亦可為20重量份以上，亦可為25重量份以上。又，就平衡良好地兼顧對被黏著體之密接性與凝聚性之觀點而言，相對於單體成分100重量份之黏著賦予樹脂之使用量例如可為70重量份以下，亦可為50重量份以下，亦可為40重量份以下。或者，亦可為實質上不含黏著賦予樹脂之A層。From the viewpoint of better exerting its use effect, the usage amount of the tackifier resin is usually appropriately set to 1 part by weight or more based on 100 parts by weight of the monomer components constituting the polymer contained in the A layer, and may also be It may be 5 parts by weight or more, it may be 10 parts by weight or more, it may be 15 parts by weight or more, it may be 20 parts by weight or more, it may be 25 parts by weight or more. In addition, from the viewpoint of achieving a good balance between the adhesion to the adherend and the cohesiveness, the usage amount of the tackifying resin may be, for example, 70 parts by weight or less, or 50 parts by weight relative to 100 parts by weight of the monomer component. parts or less, or less than 40 parts by weight. Alternatively, the layer A may be substantially free of adhesion-imparting resin.

於本文所揭示之剝離方法之若干態樣中，黏著片材藉由於所期望之時間點進行使水剝離力上升之處理，可進一步提高耐水可靠性。顯示此種性質之黏著片材例如可於A層包含黏著賦予樹脂之構成中實現，但並不限定於該構成。使上述水剝離力上升之處理例如可為於對被黏著體貼附黏著片材之後，應用高於室溫區域之溫度之處理。所應用之溫度並無特別限定，可考慮作業性、經濟性、便利性、黏著片材或被黏著體之耐熱性等進行選擇。上述溫度例如可為45℃以上，亦可為55℃以上。又，上述溫度例如可未達150℃，亦可為120℃以下，亦可為100℃以下，亦可為80℃以下。應用上述溫度之時間並無特別限定，例如可為1小時以上，亦可為3小時以上，亦可為1天以上。或者，亦可於黏著片材或被黏著體不產生顯著之熱劣化之限度內，更長時間地應用上述溫度。於若干態樣中，就處理之效率化之觀點而言，應用上述溫度之時間例如可設為14天以內，亦可設為7天以內。上述溫度可一次應用，亦可分為複數次應用。In some aspects of the peeling method disclosed herein, the water-resistant reliability of the adhesive sheet can be further improved by subjecting the adhesive sheet to a treatment that increases the water peeling force at a desired time point. An adhesive sheet exhibiting such properties can be realized in a structure in which layer A contains an adhesive imparting resin, for example, but is not limited to this structure. The treatment to increase the water peeling force may be, for example, a treatment in which a temperature higher than room temperature is applied after the adhesive sheet is attached to the adherend. The applied temperature is not particularly limited and can be selected considering workability, economy, convenience, heat resistance of the adhesive sheet or adherend, etc. The temperature may be, for example, 45°C or higher, or 55°C or higher. In addition, the temperature may be less than 150°C, may be 120°C or lower, may be 100°C or lower, or may be 80°C or lower, for example. The time for applying the above temperature is not particularly limited. For example, it can be more than 1 hour, more than 3 hours, or more than 1 day. Alternatively, the above-mentioned temperature can be applied for a longer period of time as long as the adhesive sheet or adherend does not undergo significant thermal deterioration. In some aspects, from the perspective of processing efficiency, the time for applying the above temperature can be set to within 14 days, or within 7 days, for example. The above temperature can be applied once or divided into multiple applications.

使上述水剝離力上升之處理之後的黏著片材之水剝離力N3相對於針對該黏著片材利用上述之方法測定之水剝離力N2，例如可為2倍以上，亦可為5倍以上，亦可為10倍以上，亦可為20倍以上，亦可為30倍以上。水剝離力N3例如可為2.0 N/10 mm以上，亦可為3.0 N/10 mm以上，亦可為4.0 N/10 mm以上。再者，水剝離力N3之測定除對自高壓釜中取出之評價用樣品進行使水剝離力上升之處理以外，與上述之水剝離力N2之測定同樣地進行。The water peeling force N3 of the adhesive sheet after the treatment to increase the water peeling force may be, for example, 2 times or more or 5 times or more relative to the water peeling force N2 measured by the above method for the adhesive sheet. It may be 10 times or more, 20 times or more, or 30 times or more. The water peeling force N3 may be, for example, 2.0 N/10 mm or more, 3.0 N/10 mm or more, or 4.0 N/10 mm or more. In addition, the water peeling force N3 was measured in the same manner as the water peeling force N2 described above, except that the evaluation sample taken out from the autoclave was treated to increase the water peeling force.

用於形成A層之黏著劑組合物可為視需要含有以pH值調整等為目的而使用之酸或鹼(氨水等)者。作為該組合物中可含有之其他任意成分，可例示：黏度調整劑(例如增黏劑)、調平劑、塑化劑、填充劑、顏料或染料等著色劑、穩定劑、防腐劑、防老化劑等黏著劑組合物之領域中一般之各種添加劑。關於此種各種添加劑，可藉由常規方法使用先前公知者，由於並非特別對本發明賦予特徵者，故而省略詳細之說明。The adhesive composition used to form the A layer may contain acid or alkali (ammonia, etc.) used for the purpose of pH adjustment or the like, if necessary. Examples of other optional ingredients that may be included in the composition include viscosity adjusters (such as thickeners), leveling agents, plasticizers, fillers, colorants such as pigments or dyes, stabilizers, preservatives, and preservatives. Various additives commonly used in the field of adhesive compositions such as aging agents. As for such various additives, conventionally known ones can be used by conventional methods. Since they do not particularly characterize the present invention, detailed descriptions are omitted.

(2)B層藉由本文所揭示之剝離方法剝離之黏著片材之黏著劑層中，除構成黏著劑層之至少偏光板側之表面之A層以外，亦可進而包含配置於該A層之背面側之B層。根據如此包含A層及B層之構成，例如可藉由A層賦予良好之水剝離性，並且藉由B層調節黏著劑層之整體特性(例如，耐水性、凝聚性、耐熱性等)。因此，根據包含A層及B層之構成之黏著劑層，容易獲得水剝離性良好，且耐水可靠性優異之黏著片材。例如，可較佳地實現耐水黏著力降低率較低，且水剝離黏著力降低率較高之黏著片材。又，例如可較佳地實現以高水準兼顧強黏著性與良好之水剝離性之黏著片材。(2)B layer The adhesive layer of the adhesive sheet peeled off by the peeling method disclosed herein may further include, in addition to the A layer constituting at least the surface of the polarizing plate side of the adhesive layer, the B disposed on the back side of the A layer. layer. According to the structure including the A layer and the B layer, for example, the A layer can provide good water releasability, and the B layer can adjust the overall properties of the adhesive layer (for example, water resistance, cohesion, heat resistance, etc.). Therefore, according to the adhesive layer composed of the A layer and the B layer, it is easy to obtain an adhesive sheet with good water removability and excellent water resistance reliability. For example, an adhesive sheet with a low water-resistant adhesive force reduction rate and a high water peeling adhesive force reduction rate can be preferably realized. Furthermore, for example, it is possible to preferably realize an adhesive sheet that has both strong adhesiveness and good water releasability at a high level.

B層可直接接觸於A層之背面而配置，亦可於與A層之背面之間隔著其他層而配置。上述其他層(以下，亦稱為中間層)典型而言為非黏著性之層，例如可利用與下述之支持體相同之塑膠膜、發泡體片材、織布或織布、紙類、金屬箔等。就黏著片材之柔軟性或對被黏著體之表面形狀之追隨性之觀點而言，於若干態樣中，可較佳地採用A層與B層直接接觸(即，未隔著中間層)而積層之構成之黏著劑層。Layer B can be disposed in direct contact with the back surface of layer A, or can be disposed with other layers between it and the back surface of layer A. The above-mentioned other layer (hereinafter, also referred to as the middle layer) is typically a non-adhesive layer. For example, the same plastic film, foam sheet, woven fabric, or paper as the support described below can be used. , metal foil, etc. From the perspective of the flexibility of the adhesive sheet or its ability to follow the surface shape of the adherend, in some aspects, it is better to use layer A and layer B to be in direct contact (that is, without an intermediate layer) And the adhesive layer composed of laminates.

B層例如可為包含選自丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑、聚酯系黏著劑、胺基甲酸酯系黏著劑、聚醚系黏著劑、聚醯胺系黏著劑、氟系黏著劑等公知之各種黏著劑中之一種或兩種以上之黏著劑而構成之黏著劑層。就透明性或耐候性等觀點而言，於若干態樣中，可較佳地採用丙烯酸系黏著劑作為B層之構成材料。構成B層之丙烯酸系黏著劑例如可自作為可用於A層之丙烯酸系黏著劑所例示者中，以於與A層之組合中發揮出所期望之特性之方式選擇。B層可為包含一層之單層構造，亦可為包含組成不同之兩層以上之層之多層構造。The B layer may be selected from the group consisting of acrylic adhesives, rubber adhesives, polysiloxane adhesives, polyester adhesives, urethane adhesives, polyether adhesives, and polyamide adhesives. The adhesive layer is composed of one or more than two kinds of well-known adhesives such as adhesives and fluorine-based adhesives. From the viewpoint of transparency or weather resistance, in some aspects, an acrylic adhesive can be preferably used as the constituent material of the B layer. The acrylic adhesive constituting the B layer can be selected from those exemplified as the acrylic adhesives that can be used for the A layer, for example, so that desired characteristics can be exerted in combination with the A layer. Layer B may be a single-layer structure including one layer, or may be a multi-layer structure including two or more layers with different compositions.

於若干態樣中，構成B層中所含之聚合物(例如丙烯酸系聚合物)之單體成分可以該單體成分整體之40重量%以上之比率包含(甲基)丙烯酸C_1-20 烷基酯。(甲基)丙烯酸C_1-20 烷基酯於B層之單體成分整體中所占之比率例如可為98重量%以下，就B層之凝聚性提高之觀點而言，亦可為95重量%以下，亦可為85重量%以下，亦可為70重量%以下，亦可為60重量%以下。構成B層之單體成分可包含(甲基)丙烯酸烷基酯、以及共聚性單體。共聚性單體可自作為可用於A層之共聚性單體所例示者中適宜選擇。共聚性單體之使用量可為構成B層之單體成分整體之例如5重量%以上，亦可為15重量%以上，亦可為30重量%以上，亦可為40重量%以上。In some aspects, the monomer component constituting the polymer (for example, an acrylic polymer) contained in the B layer may contain (meth)acrylic acid C _1-20 alkane at a ratio of 40% by weight or more of the total monomer component. base ester. The proportion of C _1-20 alkyl (meth)acrylate in the total monomer component of the B layer may be, for example, 98% by weight or less. From the perspective of improving the cohesiveness of the B layer, it may also be 95% by weight. % or less, it may be 85% by weight or less, it may be 70% by weight or less, or it may be 60% by weight or less. The monomer component constituting layer B may include alkyl (meth)acrylate and copolymerizable monomers. The copolymerizable monomer can be appropriately selected from those exemplified as copolymerizable monomers that can be used for the A layer. The usage amount of the copolymerizable monomer may be, for example, 5% by weight or more, 15% by weight or more, 30% by weight or more, or 40% by weight or more of the total monomer components constituting layer B.

於若干態樣中，含羧基之單體於構成B層之單體成分中所占之比率例如可為2重量%以下，亦可為1重量%以下，亦可為0.5重量%以下。亦可實質上不使用含羧基之單體作為構成B層之單體成分。此處，所謂實質上不使用含羧基之單體，係指至少不刻意地使用含羧基之單體。具有此種組成之B層之黏著片材容易成為耐水可靠性較高者，故而較佳。In certain aspects, the proportion of the carboxyl group-containing monomer in the monomer components constituting the B layer may be, for example, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less. It is also possible to substantially not use a carboxyl group-containing monomer as the monomer component constituting the B layer. Here, the term "substantially not using a carboxyl group-containing monomer" means that a carboxyl group-containing monomer is not used at least intentionally. The adhesive sheet having the B layer having this composition is more likely to have higher water resistance reliability, so it is preferable.

作為具備A層及B層之黏著片材之一較佳例，可列舉具備滿足B層之凝膠分率高於A層之凝膠分率及B層之膨潤度低於A層之膨潤度之一者或兩者之黏著劑層之黏著片材。根據此種構成，容易獲得耐水黏著力降低率較低，且水剝離黏著力降低率較高之黏著片材。As a preferred example of an adhesive sheet having an A layer and a B layer, the gel fraction of the B layer is higher than that of the A layer and the swelling degree of the B layer is lower than that of the A layer. Adhesive sheet with one or both adhesive layers. According to this structure, it is easy to obtain an adhesive sheet with a low water-resistant adhesive force reduction rate and a high water peeling adhesive force reduction rate.

於若干態樣中，B層可為由光硬化型黏著劑組合物或溶劑型黏著劑組合物形成之層。根據由此種組合物形成之B層，容易獲得耐水可靠性良好之黏著片材。例如，於由水分散型黏著劑組合物形成之A層與由光硬化型黏著劑組合物形成之B層之組合、或由水分散型黏著劑組合物形成之A層與由溶劑型黏著劑組合物形成之B層之組合中，可較佳地實現耐水黏著力降低率較低，且水剝離黏著力降低率較高之黏著片材。於若干態樣中，就耐水性提高之觀點而言，可較佳地採用實質上不含水親和劑之B層。In some aspects, layer B may be a layer formed of a photocurable adhesive composition or a solvent-based adhesive composition. According to the B layer formed from such a composition, an adhesive sheet with excellent water resistance and reliability can be easily obtained. For example, a combination of layer A formed of a water-dispersed adhesive composition and layer B formed of a photocurable adhesive composition, or layer A formed of a water-dispersed adhesive composition and a solvent-based adhesive In the combination of the B layer formed by the composition, an adhesive sheet with a low water-resistant adhesive force reduction rate and a high water peeling adhesive force reduction rate can be better realized. In some aspects, from the viewpoint of improving water resistance, it may be preferable to use a B layer that does not substantially contain a water affinity agent.

＜支持體＞藉由本文所揭示之剝離方法剝離之黏著片材可為包含接合於黏著劑層之另一背面之支持體的附支持體之黏著片材之形態。支持體之材質並無特別限定，可根據黏著片材之使用目的或使用態樣等適宜選擇。作為可使用之支持體之非限定性之例，可列舉：以聚丙烯或乙烯-丙烯共聚物等聚烯烴作為主成分之聚烯烴膜、以聚對苯二甲酸乙二酯或聚對苯二甲酸丁二酯等聚酯作為主成分之聚酯膜、以聚氯乙烯作為主成分之聚氯乙烯膜等塑膠膜；包含聚胺基甲酸酯泡沫、聚乙烯泡沫、聚氯丁二烯泡沫等發泡體之發泡體片材；利用各種纖維狀物質(可為麻、棉等天然纖維、聚酯、維尼綸等合成纖維、乙酸酯等半合成纖維等)之單獨或混紡等獲得之織布及不織布；日本紙、道林紙、牛皮紙、皺紋紙等紙類；鋁箔、銅箔等金屬箔等。亦可為將該等複合而成之構成之支持體。作為此種複合結構之支持體之例，例如可列舉：金屬箔與上述塑膠膜積層之結構之支持體、藉由玻璃布等無機纖維強化之塑膠片材等。＜Support＞ The adhesive sheet peeled off by the peeling method disclosed herein may be in the form of an adhesive sheet with a support attached to a support joined to the other back side of the adhesive layer. The material of the support is not particularly limited and can be appropriately selected according to the purpose of use or usage pattern of the adhesive sheet. Non-limiting examples of supports that can be used include polyolefin films containing polyolefins such as polypropylene and ethylene-propylene copolymers as the main component, polyethylene terephthalate or polyterephthalate films. Polyester film with polyester as the main component such as butylene formate, polyvinyl chloride film with polyvinyl chloride as the main component and other plastic films; including polyurethane foam, polyethylene foam, polychloroprene foam Foam sheets of other foams; obtained by spinning various fibrous materials (which can be natural fibers such as linen and cotton, synthetic fibers such as polyester and vinylon, semi-synthetic fibers such as acetate, etc.) alone or in blends Woven and non-woven fabrics; Japanese paper, Dowling paper, kraft paper, crepe paper and other papers; aluminum foil, copper foil and other metal foils, etc. It can also be a support body composed of a composite of these. Examples of the support of such a composite structure include a support having a structure in which a metal foil and the above-mentioned plastic film are laminated, a plastic sheet reinforced with inorganic fibers such as glass cloth, and the like.

作為支持體，可較佳地使用各種膜(以下，亦稱為支持膜)。上述支持膜可為如發泡體膜或不織布片材等般多孔質之膜，亦可為非多孔質之膜，亦可為多孔質之層與非多孔質之層積層之結構之膜。於若干態樣中，作為上述支持膜，可較佳地使用包含可獨立地維持形狀之(自立型之或非依賴性之)樹脂膜作為基底膜者。此處，所謂「樹脂膜」，意指為非多孔質之結構，典型而言實質上不含氣泡之(無空隙之)樹脂膜。因此，上述樹脂膜係與發泡體膜或不織布區別之概念。上述樹脂膜可為單層構造，亦可為兩層以上之多層構造(例如三層構造)。As the support, various films (hereinafter also referred to as support films) can be preferably used. The above-mentioned supporting film may be a porous film such as a foam film or a non-woven sheet, or may be a non-porous film, or may be a film having a structure in which a porous layer and a non-porous layer are laminated. In some aspects, as the above-mentioned support film, one including a resin film that can independently maintain its shape (either self-standing or independent) as a base film can be preferably used. Here, the term "resin film" means a non-porous structure, typically a resin film that does not contain substantially bubbles (no voids). Therefore, the above-mentioned resin film is a concept that is different from a foam film or a nonwoven fabric. The above-mentioned resin film may have a single-layer structure, or may have a multi-layer structure of two or more layers (for example, a three-layer structure).

作為構成樹脂膜之樹脂材料，例如可使用聚酯、聚烯烴、源自具有降𦯉烯結構等脂肪族環結構之單體之聚環烯烴、尼龍6、尼龍66、部分芳香族聚醯胺等聚醯胺(PA)、聚醯亞胺(PI)、聚醯胺醯亞胺(PAI)、聚醚醚酮(PEEK)、聚醚碸(PES)、聚苯硫醚(PPS)、聚碳酸酯(PC)、聚胺基甲酸酯(PU)、乙烯-乙酸乙烯酯共聚物(EVA)、聚苯乙烯、聚氯乙烯、聚偏二氯乙烯、聚四氟乙烯(PTFE)等氟樹脂、聚甲基丙烯酸甲酯等丙烯酸系樹脂、二乙醯纖維素或三乙醯纖維素等纖維素系聚合物、乙烯基丁醛系聚合物、芳酯系聚合物、聚甲醛系聚合物、環氧系聚合物等樹脂。上述樹脂膜可為使用單獨包含此種樹脂之一種之樹脂材料所形成者，亦可為使用摻合有兩種以上之樹脂材料所形成者。上述樹脂膜可為未經延伸，亦可為經延伸(例如單軸延伸或雙軸延伸)者。As the resin material constituting the resin film, for example, polyester, polyolefin, polycyclic olefin derived from a monomer having an aliphatic ring structure such as a norvinyl structure, nylon 6, nylon 66, partially aromatic polyamide, etc. Polyamide (PA), polyimide (PI), polyamide imide (PAI), polyether ether ketone (PEEK), polyether sulfide (PES), polyphenylene sulfide (PPS), polycarbonate ester (PC), polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polystyrene, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene (PTFE) and other fluororesins , acrylic resins such as polymethyl methacrylate, cellulose polymers such as diacetyl cellulose or triacetyl cellulose, vinyl butyraldehyde polymers, aryl ester polymers, polyoxymethylene polymers, Resins such as epoxy polymers. The above-mentioned resin film may be formed using a resin material containing one type of resin alone, or may be formed using a blend of two or more resin materials. The above-mentioned resin film may be unstretched or stretched (eg, uniaxially stretched or biaxially stretched).

作為構成樹脂膜之樹脂材料之較佳例，可列舉聚酯系樹脂、PPS樹脂及聚烯烴系樹脂。此處，所謂聚酯系樹脂，係指以超過50重量%之比率含有聚酯之樹脂。同樣地，所謂PPS樹脂，係指以超過50重量%之比率含有PPS之樹脂，所謂聚烯烴系樹脂，係指以超過50重量%之比率含有聚烯烴之樹脂。Preferable examples of the resin material constituting the resin film include polyester resin, PPS resin and polyolefin resin. Here, the polyester-based resin refers to a resin containing polyester in a ratio exceeding 50% by weight. Similarly, PPS resin refers to a resin containing PPS in a ratio exceeding 50% by weight, and polyolefin-based resin refers to a resin containing polyolefin in a ratio exceeding 50% by weight.

作為聚酯系樹脂，典型而言，使用包含使二羧酸與二醇縮聚而獲得之聚酯作為主成分之聚酯系樹脂。作為聚酯系樹脂之具體例，可列舉聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚萘二甲酸乙二酯(PEN)、聚萘二甲酸丁二酯等。As the polyester-based resin, typically, a polyester-based resin containing a polyester obtained by polycondensing a dicarboxylic acid and a glycol as a main component is used. Specific examples of the polyester-based resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polynaphthalenedicarboxylic acid. Butylene glycol, etc.

作為聚烯烴樹脂，可單獨使用一種聚烯烴或組合兩種以上之聚烯烴而使用。該聚烯烴例如可為α-烯烴之均聚物、兩種以上之α-烯烴之共聚物、一種或兩種以上之α-烯烴與其他乙烯基單體之共聚物等。作為具體例，可列舉：聚乙烯(PE)、聚丙烯(PP)、聚-1-丁烯、聚-4-甲基-1-戊烯、乙烯丙烯橡膠(EPR)等乙烯-丙烯共聚物、乙烯-丙烯-丁烯共聚物、乙烯-丁烯共聚物、乙烯-乙烯醇共聚物、乙烯-丙烯酸乙酯共聚物等。可使用低密度(LD)聚烯烴及高密度(HD)聚烯烴之任一者。作為聚烯烴樹脂膜之例，可列舉：未經延伸之聚丙烯(CPP)膜、雙軸延伸聚丙烯(OPP)膜、低密度聚乙烯(LDPE)膜、直鏈狀低密度聚乙烯(LLDPE)膜、中密度聚乙烯(MDPE)膜、高密度聚乙烯(HDPE)膜、摻合有兩種以上之聚乙烯(PE)之聚乙烯(PE)膜、摻合有聚丙烯(PP)與聚乙烯(PE)之PP/PE摻合膜等。As the polyolefin resin, one type of polyolefin can be used alone or two or more types of polyolefin can be used in combination. The polyolefin may be, for example, a homopolymer of α-olefin, a copolymer of two or more α-olefins, a copolymer of one or more α-olefins and other vinyl monomers, etc. Specific examples include ethylene-propylene copolymers such as polyethylene (PE), polypropylene (PP), poly-1-butene, poly-4-methyl-1-pentene, and ethylene propylene rubber (EPR). , ethylene-propylene-butylene copolymer, ethylene-butylene copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, etc. Either low density (LD) polyolefin or high density (HD) polyolefin can be used. Examples of polyolefin resin films include unstretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low-density polyethylene (LDPE) film, and linear low-density polyethylene (LLDPE). ) film, medium density polyethylene (MDPE) film, high density polyethylene (HDPE) film, polyethylene (PE) film blended with two or more polyethylene (PE), polypropylene (PP) and Polyethylene (PE) PP/PE blended film, etc.

作為可較佳地用作支持體之樹脂膜之具體例，可列舉：PET膜、PEN膜、PPS膜、PEEK膜、CPP膜及OPP膜。就強度之方面而言，作為較佳例，可列舉：PET膜、PEN膜、PPS膜及PEEK膜。就獲取容易性、尺寸穩定性、光學特性等觀點而言，作為較佳例，可列舉PET膜。Specific examples of resin films that can be preferably used as supports include PET films, PEN films, PPS films, PEEK films, CPP films, and OPP films. In terms of strength, preferred examples include PET film, PEN film, PPS film and PEEK film. From the viewpoints of ease of acquisition, dimensional stability, optical properties, etc., a PET film is a preferable example.

於樹脂膜中，可視需要調配光穩定劑、抗氧化劑、抗靜電劑、著色劑(染料、顏料等)、填充材料、潤滑劑、抗黏連劑等公知之添加劑。添加劑之調配量並無特別限定，可根據黏著片材之用途等而適宜設定。In the resin film, known additives such as light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, lubricants, and anti-adhesive agents may be blended as needed. The compounding amount of the additive is not particularly limited and can be appropriately set according to the use of the adhesive sheet.

樹脂膜之製造方法並無特別限定。例如可適宜採用擠出成形、吹脹成形、T模澆鑄成形、砑光輥成形等先前公知之一般之樹脂膜成形方法。The manufacturing method of the resin film is not particularly limited. For example, conventionally known general resin film forming methods such as extrusion molding, inflation molding, T-die casting, and calender roll molding can be suitably used.

上述支持體可為實質上由此種樹脂膜構成者。或者，上述支持體亦可為除上述樹脂膜以外，包含輔助層者。作為上述輔助層之例，可列舉：用以對光學特性調整層(例如著色層、抗反射層)、支持體或黏著片材賦予所期望之外觀之印刷層或層壓層、抗靜電層、底塗層、剝離層等表面處理層。又，上述支持材亦可為下述之光學構件。The support may be substantially composed of such a resin film. Alternatively, the support may include an auxiliary layer in addition to the resin film. Examples of the above-mentioned auxiliary layer include: a printing layer or a laminated layer, an antistatic layer, and a layer for imparting a desired appearance to an optical property adjustment layer (such as a colored layer, an antireflection layer), a support, or an adhesive sheet; Surface treatment layers such as base coat and peeling layer. Moreover, the said support material may be the following optical member.

支持體之厚度並無特別限定，可根據黏著片材之使用目的或使用態樣等而選擇。支持體之厚度例如可為1000 μm以下，亦可為500 μm以下，亦可為100 μm以下，亦可為70 μm以下，亦可為50 μm以下，亦可為25 μm以下，亦可為10 μm以下，亦可為5 μm以下。若支持體之厚度變小，則存在黏著片材之柔軟性或對被黏著體之表面形狀之追隨性提高之傾向。又，就操作性或加工性等觀點而言，支持體之厚度例如可為2 μm以上，亦可為超過5 μm或超過10 μm。於若干態樣中，支持體之厚度例如可為20 μm以上，亦可為35 μm以上，亦可為55 μm以上。The thickness of the support is not particularly limited and can be selected according to the purpose of use or usage pattern of the adhesive sheet. The thickness of the support may be, for example, 1000 μm or less, 500 μm or less, 100 μm or less, 70 μm or less, 50 μm or less, 25 μm or less, or 10 μm or less. μm or less, and may be 5 μm or less. When the thickness of the support becomes smaller, the flexibility of the adhesive sheet and its ability to follow the surface shape of the adherend tend to increase. In addition, from the viewpoint of operability, processability, etc., the thickness of the support may be, for example, 2 μm or more, may be more than 5 μm, or may be more than 10 μm. In some aspects, the thickness of the support may be, for example, 20 μm or more, 35 μm or more, or 55 μm or more.

於支持體中接合於黏著劑層之側之面，亦可視需要實施電暈放電處理、電漿處理、紫外線照射處理、酸處理、鹼處理、底塗劑(primer)之塗佈、抗靜電處理等先前公知之表面處理。此種表面處理可為用以提高支持體與黏著劑層之密接性、換言之黏著劑層對支持體之抓固性之處理。底塗劑之組成並無特別限定，可自公知者中適宜選擇。底塗層之厚度並無特別限制，通常適當為0.01 μm～1 μm左右，較佳為0.1 μm～1 μm左右。The side that is bonded to the adhesive layer in the support can also be subjected to corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, primer coating, and antistatic treatment if necessary. and other previously known surface treatments. This kind of surface treatment can be a treatment used to improve the adhesion between the support and the adhesive layer, in other words, the adhesive layer's grip on the support. The composition of the primer is not particularly limited and can be appropriately selected from known ones. The thickness of the primer layer is not particularly limited, but is usually about 0.01 μm to 1 μm, preferably about 0.1 μm to 1 μm.

於支持體中與接合於黏著劑層之側為相反側之面(以下，亦稱為背面)，亦可視需要實施剝離處理、接著性或黏著性提高處理、抗靜電處理等先前公知之表面處理。例如，藉由利用剝離處理劑對支持體之背面進行表面處理，可減小捲繞成卷狀之形態之黏著片材之解卷力。作為剝離處理劑，可使用聚矽氧系剝離處理劑、長鏈烷基系剝離處理劑、烯烴系剝離處理劑、氟系剝離處理劑、脂肪酸醯胺系剝離處理劑、硫化鉬、二氧化矽粉等。The surface of the support that is opposite to the side bonded to the adhesive layer (hereinafter also referred to as the back surface) may be subjected to previously known surface treatments such as peeling treatment, adhesion or adhesion improvement treatment, and antistatic treatment if necessary. . For example, by surface-treating the back surface of the support with a release treatment agent, the unwinding force of the adhesive sheet wound into a roll can be reduced. As the release treatment agent, polysiloxane-based release treatment agents, long-chain alkyl-based release treatment agents, olefin-based release treatment agents, fluorine-based release treatment agents, fatty acid amide-based release treatment agents, molybdenum sulfide, and silicon dioxide can be used. Powder etc.

＜黏著片材＞構成黏著片材之黏著劑層可為黏著劑組合物之硬化層。即，該黏著劑層可藉由將黏著劑組合物賦予(例如塗佈)至適當之表面後，適宜實施硬化處理而形成。於進行兩種以上之硬化處理(乾燥、交聯、聚合等)之情形時，該等可同時或歷經多階段而進行。於使用單體成分之部分聚合物(丙烯酸系聚合物漿液)之黏著劑組合物中，典型而言，作為上述硬化處理，進行最終之共聚反應。即，將部分聚合物供至進一步之共聚反應而形成完全聚合物。例如，若為光硬化性之黏著劑組合物，則實施光照射。亦可視需要實施交聯、乾燥等硬化處理。例如，於必須以光硬化性黏著劑組合物進行乾燥之情形時，可於乾燥後進行光硬化。於使用完全聚合物之黏著劑組合物中，典型而言，作為上述硬化處理，視需要實施乾燥(加熱乾燥)、交聯等處理。兩層以上之多層構造之黏著劑層可藉由貼合預先形成之黏著劑層而製作。或者，亦可於預先形成之第一黏著劑層上塗佈黏著劑組合物，使該黏著劑組合物硬化而形成第二黏著劑層。＜Adhesive sheet＞ The adhesive layer constituting the adhesive sheet may be a hardened layer of the adhesive composition. That is, the adhesive layer can be formed by applying (for example, coating) the adhesive composition to an appropriate surface and then performing a hardening treatment as appropriate. When two or more hardening treatments (drying, cross-linking, polymerization, etc.) are performed, they can be performed simultaneously or through multiple stages. In an adhesive composition using a partial polymer (acrylic polymer slurry) as a monomer component, a final copolymerization reaction is typically performed as the above-mentioned hardening treatment. That is, part of the polymer is subjected to further copolymerization to form a complete polymer. For example, in the case of a photocurable adhesive composition, light irradiation is performed. Hardening treatments such as cross-linking and drying can also be carried out as needed. For example, when it is necessary to dry the photocurable adhesive composition, photohardening can be performed after drying. In an adhesive composition using a complete polymer, typically, as the above-mentioned hardening treatment, drying (heat drying), cross-linking and other treatments are performed as necessary. The adhesive layer of a multi-layer structure of two or more layers can be produced by laminating pre-formed adhesive layers. Alternatively, the adhesive composition may be coated on the preformed first adhesive layer, and the adhesive composition may be hardened to form the second adhesive layer.

黏著劑組合物之塗佈例如可使用凹版輥式塗佈機、逆輥塗佈機、接觸輥塗佈機、浸漬輥塗佈機、棒式塗佈機、刮刀塗佈機、噴霧塗佈機等慣用之塗佈機而實施。於具有支持體之形態之黏著片材中，作為於支持體上設置黏著劑層之方法，可使用對該支持體直接賦予黏著劑組合物而形成黏著劑層之直接法，亦可使用將形成於剝離面上之黏著劑層轉印至支持體之轉印法。The adhesive composition can be coated using, for example, a gravure roll coater, a reverse roll coater, a contact roll coater, a dip roll coater, a rod coater, a blade coater, or a spray coater. Wait for the usual coating machine to be implemented. In an adhesive sheet having the form of a support, as a method of providing an adhesive layer on the support, a direct method of directly applying an adhesive composition to the support to form an adhesive layer can be used, or a method of forming an adhesive layer can be used. A transfer method in which the adhesive layer on the peeling surface is transferred to the support.

黏著劑層之厚度並無特別限定，例如可為3 μm～1000 μm左右。就使黏著劑層密接於被黏著體而提高耐水可靠性之觀點而言，於若干態樣中，黏著劑層之厚度例如可為5 μm以上，亦可為10 μm以上，亦可為20 μm以上，亦可為30 μm以上，亦可為50 μm以上，亦可為超過50 μm，亦可為70 μm以上，亦可為100 μm以上，亦可為120 μm以上。又，就防止因黏著劑層之凝聚破壞而產生糊劑殘留之觀點而言，於若干態樣中，黏著劑層之厚度例如可為500 μm以下，亦可為300 μm以下，亦可為200 μm以下，亦可為170 μm以下。本文所揭示之技術亦可較佳地應用於黏著劑層之厚度為130 μm以下、90 μm以下、60 μm以下或40 μm以下之黏著片材。再者，於由A層構成之黏著劑層中，黏著劑層之厚度意指A層之厚度。The thickness of the adhesive layer is not particularly limited, but may be about 3 μm to 1000 μm, for example. From the perspective of making the adhesive layer closely adhere to the adherend to improve water resistance reliability, in some aspects, the thickness of the adhesive layer may be, for example, 5 μm or more, 10 μm or more, or 20 μm. It may be 30 μm or more, it may be 50 μm or more, it may be more than 50 μm, it may be 70 μm or more, it may be 100 μm or more, it may be 120 μm or more. Furthermore, from the viewpoint of preventing paste residue due to cohesion and destruction of the adhesive layer, in some aspects, the thickness of the adhesive layer may be, for example, 500 μm or less, 300 μm or less, or 200 μm. μm or less, and may be 170 μm or less. The technology disclosed in this article can also be preferably applied to adhesive sheets with an adhesive layer thickness of less than 130 μm, less than 90 μm, less than 60 μm, or less than 40 μm. Furthermore, in the adhesive layer composed of the A layer, the thickness of the adhesive layer means the thickness of the A layer.

若黏著劑層變厚，則總體而言存在難以兼顧水剝離性與耐水可靠性之傾向。就該觀點而言，於該黏著劑層之厚度例如超過50 μm之態樣中，可較佳地採用黏著劑層包含A層及B層之構成。根據此種構成之黏著劑層，即便該黏著劑層變厚，亦容易獲得以高水準兼顧水剝離性與耐水可靠性之黏著片材。When the adhesive layer becomes thicker, it tends to be difficult to achieve both water-removability and water-resistant reliability in general. From this point of view, when the thickness of the adhesive layer exceeds 50 μm, for example, the adhesive layer may preferably be composed of layer A and layer B. According to the adhesive layer having this structure, even if the adhesive layer becomes thick, it is easy to obtain an adhesive sheet that has both water-removability and water-resistant reliability at a high level.

於黏著劑層包含A層及B層之態樣中，A層之厚度例如可為1 μm以上，亦可為2 μm以上，亦可為4 μm以上，亦可為5 μm以上，亦可為10 μm以上，亦可為15 μm以上。又，A層之厚度例如可為50 μm以下，亦可為45 μm以下，亦可為35 μm以下，亦可為25 μm以下。尤其是，於具備由水分散型黏著劑組成部形成之A層之態樣、或A層包含水親和劑之態樣中，A層之厚度不過大就黏著片材之耐水可靠性提高、黏著劑層之透明性提高等觀點而言較佳。In the case where the adhesive layer includes layer A and layer B, the thickness of layer A may be, for example, 1 μm or more, 2 μm or more, 4 μm or more, 5 μm or more, or 5 μm or more. 10 μm or more, or 15 μm or more. Moreover, the thickness of the A layer may be, for example, 50 μm or less, 45 μm or less, 35 μm or less, or 25 μm or less. In particular, in the case where the A layer is formed of a water-dispersible adhesive component or the A layer contains a water affinity agent, if the thickness of the A layer is not too large, the water resistance reliability of the adhesive sheet will be improved and the adhesion will be improved. It is preferable from the viewpoint of improving the transparency of the agent layer.

於黏著劑層包含A層及B層之態樣中，B層之厚度例如可為5 μm以上，亦可為10 μm以上。就更良好地發揮由在A層之背面側設置B層所帶來之效果之觀點而言，於若干態樣中，B層之厚度例如可為20 μm以上，亦可為30 μm以上，亦可為50 μm以上，亦可為70 μm以上，亦可為100 μm以上。In the case where the adhesive layer includes layer A and layer B, the thickness of layer B can be, for example, 5 μm or more, or 10 μm or more. From the viewpoint of better exerting the effect of providing the B layer on the back side of the A layer, in some aspects, the thickness of the B layer may be, for example, 20 μm or more, or 30 μm or more, or It may be 50 μm or more, 70 μm or more, or 100 μm or more.

於黏著劑層包含A層及B層之態樣中，於黏著劑層整體之厚度中所占之A層之厚度例如可為90%以下，通常較佳為70%以下，亦可為50%以下，亦可為30%以下，亦可為20%以下，亦可為15%以下。又，就A層之形成容易性或黏著片材之水剝離性之觀點而言，於若干態樣中，於黏著劑層整體之厚度中所占之A層之厚度例如可為3%以上，亦可為5%以上，亦可為7%以上，亦可為10%以上。In the case where the adhesive layer includes layer A and layer B, the thickness of layer A accounting for the entire thickness of the adhesive layer may be, for example, 90% or less, usually preferably 70% or less, and may also be 50%. It can be less than 30%, 20% or less, or 15% or less. Furthermore, from the viewpoint of the ease of formation of the A layer or the water releasability of the adhesive sheet, in some aspects, the thickness of the A layer in the entire thickness of the adhesive layer may be, for example, 3% or more. It may be more than 5%, more than 7%, or more than 10%.

＜剝離方法＞根據本說明書，提供一種貼附於作為被黏著體之偏光板之黏著片材之剝離方法。上述剝離方法包括水剝離步驟，其係於在上述黏著片材自上述被黏著體之剝離前線處在上述被黏著體與上述黏著片材之界面存在水性液體之狀態下，一面使上述水性液體追隨於上述剝離前線之移動而進入至上述界面，一面將上述黏著片材自上述被黏著體剝離。根據上述水剝離步驟，可有效地利用上述水性液體而將黏著片材自作為被黏著體之偏光板剝離。作為水性液體，可使用於水或以水作為主成分之混合溶劑中視需要含有少量之添加劑者。作為構成上述混合溶劑之水以外之溶劑，可使用可與水均勻地混合之低級醇(例如乙醇)或低級酮(例如丙酮)等。作為上述添加劑，可使用公知之界面活性劑等。就避免被黏著體之污染之觀點而言，於若干態樣中，可較佳地使用實質上不含添加劑之水性液體。就環境衛生之觀點而言，尤佳為使用水作為水性液體。作為水，並無特別限制，考慮根據用途所要求之純度或獲取容易性等，例如可使用蒸餾水、離子交換水、自來水等。＜Peel-off method＞ According to this specification, a method for peeling off an adhesive sheet attached to a polarizing plate as an adherend is provided. The peeling method includes a water peeling step, which is to make the aqueous liquid follow the state where an aqueous liquid exists at the interface between the adherend and the adhesive sheet at the peeling line of the adhesive sheet from the adherend. As the peeling front line moves to the interface, the adhesive sheet is peeled off from the adherend. According to the water peeling step, the aqueous liquid can be effectively used to peel the adhesive sheet from the polarizing plate as the adherend. As an aqueous liquid, water or a mixed solvent containing water as the main component and optionally a small amount of additives can be used. As a solvent other than water constituting the above mixed solvent, lower alcohol (for example, ethanol) or lower ketone (for example, acetone) that can be uniformly mixed with water can be used. As the above-mentioned additives, known surfactants and the like can be used. From the viewpoint of avoiding contamination of the adherend, in some aspects, it is preferable to use an aqueous liquid that does not substantially contain additives. From an environmental hygiene point of view, it is particularly preferred to use water as the aqueous liquid. The water is not particularly limited. For example, distilled water, ion-exchanged water, tap water, etc. can be used, taking into consideration the purity required according to the use, ease of acquisition, etc.

於若干態樣中，上述剝離方法例如可以如下態樣較佳地進行，即，與水剝離力N2之測定時同樣地，對貼附於被黏著體之黏著片材之外緣附近之被黏著體上供給水性液體，使該水性液體自上述黏著片材之外緣進入至該黏著片材與上述被黏著體之界面後，不進行新的水之供給(即，僅利用於剝離開始前供給至被黏著體上之水性液體)而進行黏著片材之剝離。再者，若於水剝離步驟之中途，追隨於剝離前線之移動而進入至黏著片材與被黏著體之界面之水於中途枯竭，則亦可於該水剝離步驟之開始後，斷續地或連續地追加供給水。例如，於被黏著體具有吸水性之情形、或於剝離後之被黏著體表面或黏著面容易殘留水性液體之情形等，可較佳地採用於水剝離步驟之開始後追加供給水之態樣。In some aspects, the above-mentioned peeling method can be preferably carried out in the following aspect, that is, in the same manner as in the measurement of the water peeling force N2, the adherend near the outer edge of the adhesive sheet attached to the adherend is The aqueous liquid is supplied onto the body so that the aqueous liquid enters from the outer edge of the adhesive sheet to the interface between the adhesive sheet and the adherend, and no new water is supplied (that is, it is only used to supply water before peeling off). to the aqueous liquid on the adherend) to peel off the adhesive sheet. Furthermore, if the water that follows the movement of the peeling front line and enters the interface between the adhesive sheet and the adherend is exhausted in the middle of the water peeling step, it is also possible to intermittently start the water peeling step. Or supply water continuously. For example, when the adherend is water-absorbent, or when an aqueous liquid is likely to remain on the surface of the adherend or the adhesive surface after peeling off, it may be preferable to additionally supply water after the start of the water-stripping step. .

於剝離開始前所供給之水性液體之量只要為可自黏著片材之貼附範圍外將上述水性液體導入至該黏著片材與被黏著體之界面之量即可，並無特別限定。上述水性液體之量例如可為5 μl以上，通常適當為10 μl以上，亦可為20 μl以上。又，關於上述水性液體之量之上限，並無特別限制。於若干態樣中，就作業性提高等觀點而言，上述水性液體之量例如可為10 ml以下，亦可為5 ml以下，亦可為1 ml以下，亦可為0.5 ml以下，亦可為0.1 ml以下，亦可為0.05 ml以下。藉由減少上述水性液體之量，可省略或簡化於黏著片材之剝離後藉由乾燥或擦拭等去除上述水性液體之操作。The amount of aqueous liquid supplied before peeling is started is not particularly limited as long as it is an amount that can introduce the aqueous liquid from outside the attachment range of the adhesive sheet to the interface between the adhesive sheet and the adherend. The amount of the aqueous liquid may be, for example, 5 μl or more, usually 10 μl or more, or 20 μl or more. In addition, there is no particular restriction on the upper limit of the amount of the aqueous liquid. In some aspects, from the viewpoint of improving workability, the amount of the aqueous liquid may be, for example, 10 ml or less, 5 ml or less, 1 ml or less, 0.5 ml or less, or It is 0.1 ml or less, or it can be 0.05 ml or less. By reducing the amount of the aqueous liquid, the operation of removing the aqueous liquid by drying or wiping after peeling off the adhesive sheet can be omitted or simplified.

於剝離開始時使水性液體自上述黏著片材之外緣進入至該黏著片材與上述被黏著體之界面之操作例如可以如下態樣進行：於黏著片材之外緣於上述界面***截切刀或針等治具之尖端、利用鉤子或指甲等刮撓黏著片材之外緣並提起、使強黏著性之黏著帶或吸盤等附著於黏著片材之外緣附近之背面而提起該黏著片材之端等。藉由如此般使水性液體自黏著片材之外緣強制地進入至上述界面，可高效率地形成於被黏著體與上述黏著片材之界面存在水性液體之狀態。又，可較佳地兼顧進行使水性液體強制地進入至界面之操作而形成剝離之起點後之良好之水剝離性、及未進行該操作之情形時之較高之耐水可靠性。At the beginning of peeling, the operation of causing the aqueous liquid to enter from the outer edge of the adhesive sheet to the interface between the adhesive sheet and the adherend can be performed, for example, as follows: inserting a cut at the outer edge of the adhesive sheet at the interface Using the tip of a jig such as a knife or needle, use a hook or fingernail to scratch the outer edge of the adhesive sheet and lift it up, so that a strong adhesive tape or suction cup can be attached to the back surface near the outer edge of the adhesive sheet to lift up the adhesive sheet. The end of the sheet etc. By forcing the aqueous liquid from the outer edge of the adhesive sheet to the interface, a state in which the aqueous liquid exists at the interface between the adherend and the adhesive sheet can be efficiently formed. Furthermore, it is possible to achieve a better balance between good water-removability after the operation of forcibly entering the aqueous liquid into the interface to form a starting point of peeling, and high water-resistant reliability when this operation is not performed.

藉由上述剝離方法剝離之黏著片材較佳為包含黏著劑層，且上述黏著劑層中至少構成偏光板側之表面之A層由包含水親和劑之黏著劑構成。上述黏著片材例如較佳為本文所揭示之任一黏著片材。因此，上述剝離方法適合作為本文所揭示之任一黏著片材之剝離方法。The adhesive sheet peeled off by the above-mentioned peeling method preferably includes an adhesive layer, and in the above-mentioned adhesive layer, at least the A layer constituting the surface on the polarizing plate side is composed of an adhesive containing a water affinity agent. The above-mentioned adhesive sheet is preferably any adhesive sheet disclosed herein. Therefore, the above peeling method is suitable as a peeling method for any adhesive sheet disclosed herein.

若干態樣之水剝離步驟可於使上述剝離前線以10 mm/分鐘以上之速度移動之態樣中較佳地實施。使剝離前線以10 mm/分鐘以上之速度移動之情況相當於例如於剝離角度180度之條件下將黏著片材以20 mm/分鐘以上之拉伸速度剝離之情況。使上述剝離前線移動之速度例如可為50 mm/分鐘以上，亦可為150 mm/分鐘以上，亦可為300 mm/分鐘以上，亦可為500 mm/分鐘以上。根據本文所揭示之剝離方法，藉由一面使上述水性液體進入至上述界面，一面將上述黏著片材自上述被黏著體剝離，即便為如此般相對較快之剝離速度，亦可發揮良好之水剝離性。使剝離前線移動之速度之上限並無特別限制。使上述剝離前線移動之速度例如可為1000 mm/分鐘以下。Some aspects of the water peeling step can be preferably implemented in an aspect in which the above-mentioned peeling front line is moved at a speed of 10 mm/min or more. Moving the peeling front line at a speed of 10 mm/min or more is equivalent to peeling the adhesive sheet at a stretching speed of 20 mm/min or more at a peeling angle of 180 degrees. The speed at which the peeling front line is moved may be, for example, 50 mm/min or more, 150 mm/min or more, 300 mm/min or more, or 500 mm/min or more. According to the peeling method disclosed in this article, by allowing the aqueous liquid to enter the interface while peeling the adhesive sheet from the adherend, good water can be exerted even at such a relatively fast peeling speed. Peelability. There is no particular limit on the speed at which the stripping front can move. The speed at which the peeling front line is moved can be, for example, 1000 mm/min or less.

本文所揭示之剝離方法例如可於該方法中所使用之水性液體(例如水)之體積每10 μl之黏著片材之剝離面積例如成為50 cm² 以上、較佳為100 cm² 以上之態樣中實施。 [實施例]The peeling method disclosed herein can be such that the peeling area of the adhesive sheet per 10 μl of the aqueous liquid (such as water) used in the method is, for example, 50 cm ² or more, preferably 100 cm ² or more. implemented in. [Example]

以下，說明與本發明相關之若干實施例，但並未意圖將本發明限定於該實施例中所示者。再者，於以下之說明中，只要無特別說明，則「份」及「%」為重量基準。Below, several embodiments related to the present invention are described, but the present invention is not intended to be limited to those shown in the embodiments. Furthermore, in the following description, unless otherwise stated, "parts" and "%" are based on weight.

＜例1＞ (黏著劑組合物U-1之製備) 將以80/35/5/30之重量比包含丙烯酸2-乙基己酯(2EHA)、N-乙烯基-2-吡咯啶酮(NVP)、丙烯酸2-羥基乙酯(HEA)及丙烯酸異𦯉基酯(IBXA)之單體混合物100份，與作為光聚合起始劑之商品名：Irgacure 651(汽巴精化公司製造)0.05份及商品名：Irgacure 184(汽巴精化公司製造)0.05份一起投入至四口燒瓶中，於氮氣氛圍下照射紫外線直至黏度(BH黏度計，No.5轉子，10 rpm，測定溫度30℃)成為約15 Pa・s為止進行光聚合，藉此製備包含上述單體混合物之部分聚合物之單體漿液。於該單體漿液100份中，添加1,6-己二醇二丙烯酸酯(HDDA)0.13份及光聚合起始劑(商品名：Irgacure 651，汽巴精化公司製造)0.33份，並均勻地混合，製備紫外線硬化型黏著劑組合物U-1。＜Example 1＞ (Preparation of adhesive composition U-1) It will contain 2-ethylhexyl acrylate (2EHA), N-vinyl-2-pyrrolidone (NVP), 2-hydroxyethyl acrylate (HEA) and isoacrylate in a weight ratio of 80/35/5/30. 100 parts of the monomer mixture of IBXA, and 0.05 parts of the trade name: Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator and the trade name: Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.05 parts were put into a four-necked flask together, and photopolymerized by irradiating ultraviolet rays under a nitrogen atmosphere until the viscosity (BH viscometer, No. 5 spindle, 10 rpm, measurement temperature 30°C) became about 15 Pa·s, to prepare A monomer slurry containing part of the polymer of the above monomer mixture. To 100 parts of the monomer slurry, add 0.13 parts of 1,6-hexanediol diacrylate (HDDA) and 0.33 parts of photopolymerization initiator (trade name: Irgacure 651, manufactured by Ciba Refining Chemicals Co., Ltd.), and mix evenly Mix thoroughly to prepare ultraviolet curable adhesive composition U-1.

(黏著劑組合物E-1之製備) 將2EHA 85份、丙烯酸甲酯(MA)13份、AA 1.2份、MAA 0.8份、3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業公司製造，KBM-503)0.02份、作為鏈轉移劑之第三-十二烷基硫醇0.048份及乳化劑(花王公司製造，Latemul E-118B)2.0份，於離子交換水100份中進行混合而乳化，藉此製備單體混合物之水性乳液(單體乳液)。於具備冷卻管、氮氣導入管、溫度計及攪拌裝置之反應容器中加入上述單體乳液，一面導入氮氣一面於室溫下攪拌1小時以上。繼而，將系統升溫至60℃，投入作為聚合起始劑之2,2'-偶氮雙[N-(2-羧基乙基)-2-甲基丙脒]水合物(和光純藥工業公司製造，VA-057)0.1份，於60℃下反應6小時，獲得丙烯酸系聚合物之水分散液。將系統冷卻至常溫後，上述丙烯酸系聚合物之水分散液之固形物成分每100份，添加以固形物成分基準為30份之黏著賦予樹脂乳液(荒川化學製造，SUPER ESTER E-865NT，軟化點160℃之聚合松香酯之水分散液)。進而，使用作為pH值調整劑之10%氨水及作為增黏劑之聚丙烯酸(不揮發分36%之水溶液)而調整至pH值約7.5、黏度約9 Pa・s，藉此製備乳液型黏著劑組合物E-1。(Preparation of adhesive composition E-1) 85 parts of 2EHA, 13 parts of methyl acrylate (MA), 1.2 parts of AA, 0.8 parts of MAA, 0.02 parts of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), A monomer mixture was prepared by mixing and emulsifying 0.048 parts of tertiary dodecylmercaptan as a chain transfer agent and 2.0 parts of an emulsifier (Latemul E-118B manufactured by Kao Corporation) in 100 parts of ion-exchange water. Aqueous emulsion (monomer emulsion). The above-mentioned monomer emulsion was added to a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer and a stirring device, and the mixture was stirred at room temperature for more than 1 hour while introducing nitrogen gas. Then, the system was heated to 60° C., and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (Wako Pure Chemical Industries, Ltd.) was added as a polymerization initiator. (manufactured by VA-057) 0.1 part, reacted at 60°C for 6 hours, and obtained an aqueous dispersion of acrylic polymer. After the system is cooled to normal temperature, 30 parts of adhesion-imparting resin emulsion (Super Ester E-865NT manufactured by Arakawa Chemical Co., Ltd. manufactured by Arakawa Chemical Co., Ltd., softened) is added to every 100 parts of the solid content of the aqueous dispersion of the acrylic polymer, based on the solid content. aqueous dispersion of polymerized rosin ester at 160°C). Furthermore, 10% ammonia as a pH adjuster and polyacrylic acid (36% non-volatile aqueous solution) as a tackifier were used to adjust the pH to about 7.5 and the viscosity to about 9 Pa·s to prepare an emulsion-type adhesive. Agent composition E-1.

(黏著片材之製作) 於聚酯膜之單面成為剝離面之厚度38 μm之剝離膜R1(三菱樹脂股份有限公司，MRF#38)塗佈黏著劑組合物U-1，被覆聚酯膜之單面成為剝離面之厚度38 μm之剝離膜R2(三菱樹脂股份有限公司，MRE#38)以遮斷空氣，照射紫外線而使之硬化，藉此形成厚度130 μm之黏著劑層B1。繼而，將覆蓋黏著劑層B1之剝離膜R2剝離，貼合經電暈處理之厚度75 μm之聚對苯二甲酸乙二酯(PET)膜，藉此獲得PET膜(支持體)、黏著劑層B1、及剝離膜R1依序積層而成之積層片材。於剝離膜R1(三菱樹脂股份有限公司，MRF#38)塗佈黏著劑組合物E-1，於120℃下乾燥3分鐘，形成厚度20 μm之黏著劑層A1。將覆蓋上述積層片材之黏著劑層B1之剝離膜R1剝離，此處貼合黏著劑層A1，藉此獲得包含黏著劑層B1及黏著劑層A1直接接觸而積層之兩層構造之黏著劑層，且於該黏著劑層之B1層側之表面接合有PET膜(支持體)之構成的黏著片材S1。該黏著片材之A1層側之表面由用於形成黏著劑層A1之剝離膜R1所保護。(Production of adhesive sheets) Adhesive composition U-1 was applied to a 38 μm-thick release film R1 (Mitsubishi Plastics Co., Ltd., MRF#38) that became the peeling surface on one side of the polyester film, and the one side of the polyester film became the peeling surface. The release film R2 (Mitsubishi Plastics Co., Ltd., MRE#38) with a thickness of 38 μm blocks the air and is irradiated with ultraviolet rays to harden it, thereby forming an adhesive layer B1 with a thickness of 130 μm. Then, the release film R2 covering the adhesive layer B1 is peeled off and laminated to a corona-treated polyethylene terephthalate (PET) film with a thickness of 75 μm, thereby obtaining a PET film (support) and an adhesive. A laminated sheet in which layer B1 and release film R1 are laminated in this order. The adhesive composition E-1 was applied to the release film R1 (Mitsubishi Plastics Co., Ltd., MRF#38) and dried at 120°C for 3 minutes to form an adhesive layer A1 with a thickness of 20 μm. The release film R1 covering the adhesive layer B1 of the above-mentioned laminated sheet is peeled off, and the adhesive layer A1 is bonded here, thereby obtaining an adhesive having a two-layer structure in which the adhesive layer B1 and the adhesive layer A1 are in direct contact and laminated. layer, and an adhesive sheet S1 composed of a PET film (support) bonded to the surface of the B1 layer side of the adhesive layer. The surface of the adhesive sheet on the A1 layer side is protected by the release film R1 for forming the adhesive layer A1.

(被黏著體之製作) 於以胺基甲酸酯丙烯酸酯作為主成分之紫外線硬化型樹脂單體或低聚物溶解於乙酸丁酯中而成之溶液(DIC(股)製造，商品名「UNIDIC 17-806」，固形物成分濃度80%)中，相對於該溶液之固形物成分每100份，添加光聚合起始劑(Ciba Japan(股)製造，製品名「IRGACURE906」)5份、調平劑(DIC(股)製造，製品名「GRANDIC PC4100」)0.03份。其後，於上述溶液中添加乙酸丁酯而將固形物成分濃度調整為75%，進而添加環戊酮(以下，記為「CPN」)而將固形物成分濃度調整為50%。以此方式製作用以形成硬塗層之硬塗層形成材料。於將上述硬塗層形成材料之總量設為1之情形時，該硬塗層形成材料中之良溶劑(CPN)之含有比(質量比)為0.33。該硬塗層形成材料中所含之紫外線硬化型樹脂單體或低聚物為各種分子量之胺基甲酸酯丙烯酸酯之混合物，於將上述紫外線硬化型樹脂單體或低聚物之總量設為1之情形時，低分子量成分(此處係指分子量800以下之紫外線硬化型樹脂單體或低聚物)之含有比(質量比)為0.482。使用模嘴塗佈機將上述硬塗層形成材料塗敷於透明之TAC膜(Fuji Film(股)製造，製品名「TD80UL」，厚度80 μm，折射率1.49)上而形成塗膜。硬塗層形成材料之塗敷厚度係設為13.8 μm。即，關於硬塗層形成材料，於假定溶劑未滲透至膜中之情形時，以硬化後之塗膜(硬塗層)之厚度成為7.5 μm之方式塗敷。將上述塗膜於80℃下乾燥2分鐘。其後，對上述塗膜，使用高壓水銀燈，照射累計光量300 mJ/cm² 之紫外線，藉此使樹脂單體聚合。以此方式於TAC膜上製作硬塗層。該硬塗層之固有之折射率為1.53。繼而，使用模嘴塗佈機將下述所示之抗反射層之形成材料均勻地塗佈於上述硬塗層之整個表面。將該塗膜於90℃下加熱2分鐘，進行紫外線照射而使之硬化，藉此於硬塗層之整個表面形成厚度0.1 μm之抗反射層。該抗反射層之折射率為1.38。上述抗反射層之形成材料係於低折射材料(JSR(股)製造，商品名「JUA204」。固形物成分濃度9.5%)中，添加甲基異丁基酮(MIBK)與第三丁醇(TBA)之混合溶劑(MIBK：TBA＝50：50)進行稀釋，調整為固形物成分濃度2.0%者。上述低折射材料係包含具有乙烯性不飽和基之氟化合物、丙烯酸酯、聚合起始劑、及相對於有效成分為約50%之中空奈米二氧化矽之紫外線硬化型樹脂。以此方式獲得具有依序積層有硬塗層及抗反射層之表面之TAC膜F1。將於該TAC膜F1之表面(被貼附面)於上述之條件下實施有電暈處理者設為例1中之被黏著體。(Preparation of adherend) A solution (manufactured by DIC Co., Ltd., trade name " UNIDIC 17-806", solid content concentration 80%), add 5 parts of photopolymerization initiator (manufactured by Ciba Japan Co., Ltd., product name "IRGACURE906") per 100 parts of the solid content of the solution, Leveling agent (manufactured by DIC Co., Ltd., product name "GRANDIC PC4100") 0.03 parts. Thereafter, butyl acetate was added to the above solution to adjust the solid content concentration to 75%, and cyclopentanone (hereinafter, referred to as "CPN") was further added to adjust the solid content concentration to 50%. In this way, a hard coat layer forming material for forming a hard coat layer is produced. When the total amount of the hard-coat-forming material is 1, the content ratio (mass ratio) of the good solvent (CPN) in the hard-coat-forming material is 0.33. The ultraviolet curable resin monomer or oligomer contained in the hard coat forming material is a mixture of urethane acrylates of various molecular weights, and the total amount of the ultraviolet curable resin monomer or oligomer is When it is set to 1, the content ratio (mass ratio) of low molecular weight components (here refers to ultraviolet curable resin monomers or oligomers with a molecular weight of 800 or less) is 0.482. The above-mentioned hard-coat layer forming material was coated on a transparent TAC film (manufactured by Fuji Film Co., Ltd., product name "TD80UL", thickness 80 μm, refractive index 1.49) using a die nozzle coater to form a coating film. The coating thickness of the hard coat forming material was set to 13.8 μm. That is, the hard coat layer forming material was applied so that the thickness of the cured coating film (hard coat layer) became 7.5 μm, assuming that the solvent did not penetrate into the film. The above coating film was dried at 80° C. for 2 minutes. Thereafter, the above-mentioned coating film was irradiated with ultraviolet rays with a cumulative light intensity of 300 mJ/cm ² using a high-pressure mercury lamp to polymerize the resin monomer. In this way, a hard coating layer is formed on the TAC film. The hard coat layer has an intrinsic refractive index of 1.53. Then, the antireflection layer forming material shown below is evenly coated on the entire surface of the hard coat layer using a die nozzle coater. The coating film was heated at 90° C. for 2 minutes and irradiated with ultraviolet rays to harden it, thereby forming an antireflection layer with a thickness of 0.1 μm on the entire surface of the hard coat layer. The refractive index of the anti-reflective layer is 1.38. The material for forming the above-mentioned anti-reflective layer is a low-refractive material (manufactured by JSR Co., Ltd., trade name "JUA204". Solid content concentration: 9.5%), to which methyl isobutyl ketone (MIBK) and tertiary butanol ( TBA) mixed solvent (MIBK: TBA = 50:50), and adjust to a solid content concentration of 2.0%. The low-refractive material includes a fluorine compound having an ethylenically unsaturated group, an acrylate, a polymerization initiator, and an ultraviolet curable resin containing approximately 50% hollow nanosilica based on the active ingredient. In this way, a TAC film F1 having a surface on which a hard coat layer and an anti-reflection layer are sequentially laminated is obtained. The surface (adhered surface) of the TAC film F1 that was corona treated under the above conditions was set as the adherend in Example 1.

(性能評價) 使用上述被黏著體，藉由上述之方法測定黏著片材S1之A層側之常態黏著力N0、耐水黏著力N1及水剝離力N2。被貼附面之電暈處理至黏著片材S1之貼附為止之時間係設為30分鐘以內。根據所獲得之測定值，算出耐水黏著力降低率及水剝離黏著力降低率。將結果示於表1。(Performance evaluation) Using the above-mentioned adherend, measure the normal adhesion force N0, water-resistant adhesion force N1 and water peeling force N2 of the A-layer side of the adhesive sheet S1 by the above-mentioned method. The time from corona treatment of the adhered surface to attachment of the adhesive sheet S1 is set to within 30 minutes. Based on the measured values obtained, the water-resistant adhesive force reduction rate and the water peeling adhesive force reduction rate were calculated. The results are shown in Table 1.

＜例2＞於本例中，作為被黏著體，將上述TAC膜F1不對其表面(被貼附面)進行電暈處理而使用。其他方面與例1相同，測定黏著片材S1之A層側之常態黏著力N0、耐水黏著力N1及水剝離力N2，算出耐水黏著力降低率及水剝離黏著力降低率。將結果示於表1。＜Example 2＞ In this example, as the adherend, the above-mentioned TAC film F1 was used without corona treatment on its surface (adhered surface). In other respects, it is the same as Example 1. The normal adhesion force N0, water-resistant adhesion force N1 and water-peel strength N2 of the A-layer side of the adhesive sheet S1 are measured, and the water-resistant adhesion force reduction rate and the water-peel adhesion force reduction rate are calculated. The results are shown in Table 1.

[表1] [Table 1]

如表1所示，於使用經電暈處理之被黏著體之例1中，針對耐水黏著力降低率較低之黏著片材S1，可使用少量之水將黏著片材S1自被黏著體容易地剝離。另一方面，於使用未經電暈處理之被黏著體之例2中，黏著片材S1之水剝離黏著力降低率較低，難以利用水進行剝離。As shown in Table 1, in Example 1 using a corona-treated adherend, for the adhesive sheet S1 with a low water-resistant adhesion reduction rate, a small amount of water can be used to easily remove the adhesive sheet S1 from the adherend. Ground peeling. On the other hand, in Example 2 in which an adherend without corona treatment was used, the adhesive sheet S1 had a low water peeling adhesive force reduction rate and was difficult to peel off with water.

以上詳細說明了本發明之具體例，但該等僅為例示，並不對申請專利範圍進行限定。申請專利範圍中記載之技術包括將以上例示之具體例進行各種變化、變更而成者。Specific examples of the present invention have been described in detail above, but these are only examples and do not limit the scope of the patent application. The technology described in the scope of the patent application includes various changes and modifications of the specific examples illustrated above.

1、2‧‧‧黏著片材 10‧‧‧黏著劑層(A層) 10A‧‧‧一表面(黏著面、偏光板側之表面) 10B‧‧‧另一表面 20‧‧‧支持體 20A‧‧‧第一面 20B‧‧‧第二面(背面) 30‧‧‧剝離襯墊 50‧‧‧附剝離襯墊之黏著片材 70‧‧‧構件(偏光板) 110‧‧‧黏著劑層 110A‧‧‧一表面(黏著面、偏光板側之表面) 112‧‧‧A層 114‧‧‧B層 200‧‧‧附黏著片材之構件1. 2‧‧‧Adhesive sheet 10‧‧‧Adhesive layer (A layer) 10A‧‧‧One surface (adhesive surface, polarizing plate side surface) 10B‧‧‧Another surface 20‧‧‧Support 20A‧‧‧Side 1 20B‧‧‧Second side (back) 30‧‧‧Release liner 50‧‧‧Adhesive sheet with release liner 70‧‧‧Component (polarizing plate) 110‧‧‧Adhesive layer 110A‧‧‧One surface (adhesive surface, polarizing plate side surface) 112‧‧‧A Floor 114‧‧‧B Floor 200‧‧‧Components with adhesive sheets

圖1係模式性地表示黏著片材之構成之剖視圖。圖2係模式性地表示另一黏著片材之構成之剖視圖。圖3係模式性地表示將另一黏著片材貼附於構件而成之附黏著片材之構件之剖視圖。FIG. 1 is a cross-sectional view schematically showing the structure of an adhesive sheet. FIG. 2 is a cross-sectional view schematically showing the structure of another adhesive sheet. FIG. 3 is a cross-sectional view schematically showing an adhesive sheet-attached member in which another adhesive sheet is attached to the member.

1‧‧‧黏著片材 1‧‧‧Adhesive sheet

10‧‧‧黏著劑層(A層) 10‧‧‧Adhesive layer (A layer)

10A‧‧‧一表面(黏著面、偏光板側之表面) 10A‧‧‧One surface (adhesive surface, polarizing plate side surface)

10B‧‧‧另一表面 10B‧‧‧Another surface

20‧‧‧支持體 20‧‧‧Support

20A‧‧‧第一面 20A‧‧‧Side 1

20B‧‧‧第二面(背面) 20B‧‧‧Second side (back)

30‧‧‧剝離襯墊 30‧‧‧Release liner

50‧‧‧附剝離襯墊之黏著片材 50‧‧‧Adhesive sheet with release liner

Claims

一種黏著片材剝離方法，其係剝離貼附於偏光板之黏著片材之方法，且上述黏著片材具備黏著劑層，該黏著劑層包含構成該黏著劑層之至少上述偏光板側之表面之A層，上述A層包含水親和劑，上述偏光板之貼附有上述黏著片材之側之表面經電暈處理或電漿處理，上述黏著片材剝離方法包括水剝離步驟，其係於在上述黏著片材自上述偏光板之剝離前線處在上述偏光板與上述黏著片材之界面存在水性液體之狀態下，一面使上述水性液體追隨於上述剝離前線之移動而進入至上述界面，一面自上述偏光板剝離上述黏著片材。 An adhesive sheet peeling method, which is a method of peeling off an adhesive sheet attached to a polarizing plate, and the adhesive sheet has an adhesive layer, and the adhesive layer includes at least the surface of the polarizing plate side that constitutes the adhesive layer The A layer of the above-mentioned A layer contains a water affinity agent, and the surface of the side of the above-mentioned polarizing plate on which the above-mentioned adhesive sheet is attached is subjected to corona treatment or plasma treatment. The above-mentioned adhesive sheet stripping method includes a water stripping step, which is based on When the peeling line of the adhesive sheet from the polarizing plate is in a state where an aqueous liquid exists at the interface between the polarizing plate and the adhesive sheet, the aqueous liquid follows the movement of the peeling line and enters the interface. The adhesive sheet is peeled off from the polarizing plate.

如請求項1之黏著片材剝離方法，其中於上述水剝離步驟中，使上述剝離前線以10mm/分鐘以上之速度移動。 The adhesive sheet peeling method of claim 1, wherein in the water peeling step, the peeling front line is moved at a speed of 10 mm/min or more.

如請求項1或2之黏著片材剝離方法，其中上述A層為非水溶性且非水膨潤性，非水溶性係指利用以下方法測定之凝膠分率為75%以上，非水膨潤性係指利用以下方法測定之膨潤度為2以下：稱量測定對象之黏著劑0.5g左右，將其重量設為W1，將該黏著劑於室溫下於蒸餾水500ml中浸漬48小時後，利用尼龍篩網進行過濾，測定包含水之黏著劑之重量W2，其後，使黏著劑於130℃下乾燥5小時，測定不揮發分之重量W3，凝膠分率及膨潤度係藉由以下之式而算出，凝膠分率[%]=(W3/W1)×100 膨潤度=W2/W1。 For example, the adhesive sheet peeling method of claim 1 or 2, wherein the above-mentioned layer A is water-insoluble and non-water-swellable. Non-water-soluble means that the gel fraction measured by the following method is more than 75% and non-water-swellable. It means that the swelling degree measured by the following method is less than 2: Weigh about 0.5g of the adhesive to be measured, set its weight as W1, immerse the adhesive in 500ml of distilled water at room temperature for 48 hours, and then use nylon Filter through a sieve, measure the weight W2 of the adhesive containing water, and then dry the adhesive at 130°C for 5 hours. The weight of volatile matter W3, gel fraction and swelling degree are calculated by the following formulas: gel fraction [%] = (W3/W1) × 100 and swelling degree = W2/W1.