TW201936823A - Method for peeling adhesive sheet - Google Patents

Method for peeling adhesive sheet Download PDF

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Publication number
TW201936823A
TW201936823A TW108103779A TW108103779A TW201936823A TW 201936823 A TW201936823 A TW 201936823A TW 108103779 A TW108103779 A TW 108103779A TW 108103779 A TW108103779 A TW 108103779A TW 201936823 A TW201936823 A TW 201936823A
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Taiwan
Prior art keywords
layer
adhesive
water
adhesive sheet
peeling
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TW108103779A
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Chinese (zh)
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TWI811296B (en
Inventor
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
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日商日東電工股份有限公司
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Priority claimed from JP2018126577A external-priority patent/JP7283867B2/en
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Publication of TW201936823A publication Critical patent/TW201936823A/en
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Publication of TWI811296B publication Critical patent/TWI811296B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

Provided is a method for peeling an adhesive sheet adhered to a polarization plate. The adhesive sheet is provided with an adhesive layer, wherein the adhesive layer includes a layer A that constitutes at least one surface of the adhesive layer. The polarization plate has an adhesive sheet-attached surface which is corona-treated or plasma-treated. The peeling method includes a water peeling step wherein, in a state in which an aqueous liquid is present at the interface between the polarization plate and the adhesive sheet at a peeling frontal line of the adhesive sheet from the polarization plate, the adhesive sheet is peeled from the polarization plate while causing the aqueous liquid to enter the interface along the movement of the peeling frontal line.

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 of peeling an adhesive sheet. The application is filed on the basis of Japanese Patent Application No. 2018-018621 filed on Feb. 5, 20, the Japanese Patent Application No. 2018-109385, filed on Jun. The priority of the Japanese Patent Application No. 2018-126577, the entire contents of each of which is incorporated herein 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]In general, an adhesive (also referred to as a pressure-sensitive adhesive. The same applies hereinafter) has a property of exhibiting a state of a soft solid (viscoelastic body) in a temperature region near room temperature, and simply follows by pressure. It is stuck to the body. By effectively utilizing such a property, the adhesive is widely used in various fields in the form of an adhesive sheet having an adhesive support layer on the support or an adhesive sheet having no support without an support.
[Previous Technical Literature]
[Patent Literature]

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][The problem that the invention wants to solve]

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。For the adhesive, various characteristics are required depending on the use. Among these characteristics, there is a tendency that the other characteristic is lowered if one characteristic is to be improved, and it is difficult to achieve a high level of consideration. An example of such a characteristic that the relationship is difficult to balance is the adhesion to the adherend and the secondary workability. The above secondary processing refers to a case where the adhesive sheet fails to adhere to the adherend (positional deviation, wrinkles or bubbles, foreign matter is caught, etc.), or after attaching the adhesive sheet. When the adhesive body is found to be in a bad condition, the adhesive sheet is peeled off from the adherend and reattached. Patent Document 1 discloses a method of peeling off an adhesive optical film from a substrate on which an optical film of an adhesive optical film is adhered from a surface of a substrate such as a glass substrate (adhered body), and discloses the above-mentioned adhesive optical film. A technique in which the adhesive optical film is peeled off from the substrate in a state where a liquid is present at a peeling interface between the adhesive layer of the film and the substrate. On the other hand, in Patent Document 1, 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, is not studied.

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 which can easily peel off 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 the present specification, there is provided a method of peeling off an adhesive sheet attached to a polarizing plate as an adherend. The surface of the polarizing plate to which the side of the above-mentioned adhesive sheet is attached is subjected to corona treatment or plasma treatment. The adhesive sheet has an adhesive layer containing 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 of causing the aqueous liquid to follow the state in which an aqueous liquid is present at an interface between the polarizing plate and the adhesive sheet from the peeling front line of the polarizing plate. The movement of the peeling front line enters the interface, and the adhesive sheet is peeled off from the polarizing plate. Here, the peeling front line refers to a portion where the adhesive sheet starts to separate from the polarizing plate when the adhesive sheet is peeled off from the polarizing plate. According to the water stripping step described above, the aqueous liquid can be effectively used to peel the adhesive sheet from the polarizing plate. In some aspects, the A layer is preferably composed of an adhesive comprising 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-described peeling method can be preferably carried out in a state in which the peeling front line is moved at a speed of 10 mm/min or more in the water peeling step. According to this aspect, the adhesive sheet can be peeled off efficiently 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。Hereinafter, preferred embodiments of the present invention will be described. In addition, matters necessary for the implementation of the present invention other than those specifically mentioned in the present specification can be understood based on the description of the implementation of the invention and the technical common sense at the time of filing the application. The present invention can be implemented based on the contents disclosed in the present specification and the technical common knowledge in the field. In the following description, members and portions that perform the same functions will be described with the same reference numerals, and overlapping descriptions may be omitted or simplified. Further, the embodiments described in the drawings are modeled to clearly illustrate the present invention, and do not necessarily accurately indicate the size or scale of the product actually 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 the present specification, the term "acrylic polymer" means a polymer derived from a monomer component containing more than 50% by weight of an acrylic monomer. The above acrylic monosystem refers to a monomer derived from a monomer having at least one (meth) acrylonitrile group in one molecule. In the present specification, the term "(meth)acryl fluorenyl" means a propylene group and a methacryl group. Similarly, the term "(meth)acrylate" means acrylate and methacrylate, and the term "(meth)acrylic" 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。<Configuration Example of Adhesive Sheet>
One of the adhesive sheets which can be used in the adhesive sheet peeling method disclosed herein is exemplified in Fig. 1. The adhesive sheet 1 is formed in the form of a single-sided adhesive sheet comprising a surface 10A as a bonding surface to a polarizing plate as an adherend (ie, a polarizing plate). The adhesive layer 10 on the side surface and the support 20 laminated on the other surface 10B of the adhesive layer 10. The adhesive layer 10 is fixedly joined to one surface 20A of the support body 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 layer of the adhesive layer 10 is constituted by the A layer constituting one surface (adhesive surface) 10A of the adhesive layer 10. The adhesive sheet 1 is used by attaching a surface 10A to a polarizing plate as an adherend. The adhesive sheet 1 before use (before being attached to the adherend) may be, for example, a protective liner 10A protected by a release liner 30 having at least the adhesive layer side as a peelable surface (peeling surface) as shown in FIG. The form of the adhesive sheet 50 with a release liner. Alternatively, the second surface 20B of the support body 20 (the surface opposite to the first surface 20A, also referred to as the back surface) may be a peeling surface, and may be abutted to the second surface by the adhesive surface 10A. The surface 20B is wound or laminated to protect the adhesive surface 10A.

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, and for example, a release liner having a surface of a liner substrate such as a resin film or paper, or a fluorine-based polymer (such as polytetrafluoroethylene) or a polyolefin resin may be used. (polyethylene, polypropylene, etc.) release liners of low adhesion materials, etc. In the above-mentioned peeling treatment, for example, a release treatment agent such as a polyfluorene-based or long-chain alkyl group can be used. In some aspects, a peel-treated resin film can be preferably used as the 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 configuration of an adhesive sheet which can be used in the adhesive sheet peeling method disclosed herein is shown in Fig. 2. The adhesive sheet 2 is formed in the form of a single-sided adhesive sheet comprising a surface 110A as an adhesive layer 110 to the adherend surface of the adherend, and a layer of adhesive. The support 20 of the other surface of the agent layer 110. The adhesive layer 110 has a two-layer structure including 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 adhered to the release liner 110A by a release liner (not shown) in the same manner as the adhesive sheet 1 shown in Fig. 1 . The form of the sheet. Alternatively, the second surface 20B of the support 20 may be a peeling surface, and the adhesive surface 110A may be wound or laminated so that the adhesive surface 110A abuts against the second surface 20B, whereby the adhesive surface 110A is protected.

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 which can be used in the adhesive sheet peeling method disclosed herein may also be a non-supported double-sided adhesive sheet comprising an adhesive layer. Such a non-supported double-sided adhesive sheet can be used, for example, by bonding a support to the other surface of the adhesive layer.

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 may be used to peel off the adhesive sheet from a member to which an adhesive sheet of a surface of one of the adhesive layers constituting the adhesive sheet (ie, the surface of the layer A) is attached to the member. It is preferably implemented in the aspect. Here, the above member is a polarizing plate, and more specifically, a polarizing plate to which a surface (attached surface) to which the side of the adhesive sheet is attached is subjected to corona treatment or plasma treatment. In general, the polarizing plate has a polarizing film composed of two sheets 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. The hard coat layer is preferably made of a urethane acrylate-based material. A polarizing plate having an antireflection layer further provided on the hard coat layer may be used.
For example, as shown in FIG. 3, the member to which the adhesive sheet is attached may be a surface (the surface on the side of the polarizing plate) 110A of the adhesive layer 110 which the adhesive sheet 2 shown in FIG. 2 has attached to the member ( The polarizing plate 70 is a member 200 to which an adhesive sheet is attached. Alternatively, instead of the adhesive sheet 2 shown in Fig. 2, the surface 10A of the adhesive sheet 1 shown in Fig. 1 may be attached to the member (polarizing plate) 70 to form a member to which the adhesive sheet is attached.

＜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 Sheets>
The adhesive sheet which can be used in the peeling method of the present invention preferably has a water-resistant adhesive reduction rate of 30% or less and a water peeling adhesion reduction rate of 40% or more. The water-resistant adhesion reduction rate [%] is defined as the normal adhesion N0 [N/10 mm] and the water-resistant adhesion N1 [N/10 mm] and calculated by (1-(N1/N0)) × 100. value. The water peeling adhesion reduction rate [%] is defined as a value calculated from the normal adhesion N0 [N/10 mm] and the water peeling force N2 by (1-(N2/N0)) × 100. The normal adhesion N0, the water-resistant adhesion N1, and the water peeling force N2 were measured by the following methods. The same measurement method can also be used in the examples below.

[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 N0]
The test piece was prepared by cutting the adhesive sheet of the measurement object into a rectangular shape having a width of 10 mm and a length of 120 mm. The layer A side of the test piece was bonded to the adherend by a hand roll to prepare a sample for evaluation, and the sample for evaluation was placed in an autoclave and treated at a pressure of 5 atm and a temperature of 50 ° C for 15 minutes. .
The sample for evaluation taken out from the autoclave was kept in an environment of 23 ° C and 50% RH for 1 day, and then the length of the test piece was inserted at the interface between the test piece and the adherend under the same environment. One of the directions was peeled off from the adherend, and the peel strength was measured in accordance with JIS Z0237 using a tensile tester at 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 resistance N1]
The test piece was prepared by cutting the adhesive sheet of the measurement object into a rectangular shape having a width of 10 mm and a length of 120 mm. The layer A side of the test piece was bonded to the adherend by a hand roll to prepare a sample for evaluation, and the sample for evaluation was placed in an autoclave and treated at a pressure of 5 atm and a temperature of 50 ° C for 15 minutes. .
The sample for evaluation taken out from the autoclave was kept 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 the water, ion-exchanged water or distilled water is used. In the water, the sample for evaluation was horizontally held in such a manner that the surface on which the test piece was attached was placed upward. The distance from the surface of the sample for evaluation to the water surface (dipping depth) is set to 10 mm or more (for example, 10 mm to 100 mm). Then, the sample for evaluation is lifted from the water, and the water adhering to the sample for evaluation is gently wiped, and then a cutting blade is inserted at the interface between the test piece and the adherend to peel off one end of the test piece in the longitudinal direction. In a 23 ° C, 50% RH environment, the peel strength was measured in accordance with JIS Z0237 using a tensile tester at a tensile speed of 300 mm/min and a peeling angle of 180 degrees. The time from when the sample for evaluation was lifted from the water to when the peel strength was measured was set to be 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]
The test piece was prepared by cutting the adhesive sheet of the measurement object into a rectangular shape having a width of 10 mm and a length of 120 mm. The layer A side of the test piece was bonded to the adherend by a hand roll to prepare a sample for evaluation, and the sample for evaluation was placed in an autoclave and treated at a pressure of 5 atm and a temperature of 50 ° C for 15 minutes. .
The sample for evaluation taken out from the autoclave was kept in an environment of 23° C. and 50% RH for one day, and then dripped on the surface of the adherend exposed from the one end in the same direction in the longitudinal direction of the test piece under the same environment. Add 1 drop (about 10 μl to about 40 μl) of distilled water. Then, after the cutting blade is inserted into the interface between the test piece and the adherend to allow the water to enter the interface, no new water supply is performed, and according to JIS Z0237, a tensile tester is used at a tensile speed of 300 mm/ The peel strength was measured under the conditions of a minute and a peeling angle of 180 degrees. Further, the water used for the measurement of the water peeling force N2 is only one drop of distilled water which is added dropwise to the adherend before the start of peeling.

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 above-described measurement of the normal adhesion force N0, the water-resistant adhesion force N1, and the water-peeling force N2, a polarizing plate having a polarizing film sandwiched between two TAC films and attached with an adhesive sheet is used as the adherend. The surface (attached surface) on the side of the material is a surface on which the TAC film is sequentially laminated with a hard coat layer and an antireflection layer as a protective layer, and a corona treatment is performed on the surface (attached surface). The corona treatment of the attached surface is carried out by setting the adherend to the output 3 immediately before attaching the test piece to the adherend (typically within 30 minutes before attachment). "AGF-012" (desktop surface corona treatment device) manufactured by KASUGA was used once under the condition of (displaying 0.17 kW) and a table speed scale of 20 (corresponding to a speed of 3 m/min). The attachment of the test piece to the adherend is performed such 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. Further, as the tensile tester, a universal tensile compression tester (device name "tensile compression tester, TCM-1kNB" manufactured by Minebea Co., Ltd.) or its equivalent can be used. The peel strength was measured by peeling off the test piece attached to the adherend from bottom to top. At the time of measurement, the test piece is reinforced by attaching an appropriate substrate to the back surface of the adhesive sheet (the surface opposite to the surface of the A layer) as needed. As the substrate material, for example, a polyethylene terephthalate film having a thickness of about 25 μm can be used. Further, as the substitute for the polarizing plate having the above-described configuration, a TAC film which simulates the side of the surface to be attached of the polarizing plate, that is, a hard coat layer and an anti-reflection layer which are sequentially laminated may be used. The surface was subjected to a corona-treated TAC film under the above conditions. The hard coat layer and the antireflection layer can be formed by the methods described in the following examples.

(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 peeling adhesion reduction rate)
The peeling method of the present invention is preferably applied to an adhesive sheet having a water peeling adhesion reduction rate of 40% or more. The adhesive sheet showing such a water-repellent adhesion reduction rate can be easily peeled off from the polarizing plate by using an aqueous liquid such as water. For example, a small amount of an aqueous liquid is supplied to an adherend (polarizing plate) to which an adhesive sheet is attached, by forming the aqueous liquid from one end of the adhesive sheet to the interface between the adhesive sheet and the adherend. After the starting point of the peeling, the adhesive sheet is peeled off, whereby the peeling strength of the adhesive sheet from the adherend can be greatly reduced. By utilizing this property, it is possible to achieve both high adhesion in general use and good secondary workability. In some aspects, the water peeling adhesion reduction rate may be, for example, 50% or more, may be 65% or more, may be 75% or more, may be 85% or more, or may be 90% or more, or may be 95% or more, or 97% or more. The water peeling adhesion reduction rate is in principle 100% or less, typically less than 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 adhesion reduction rate)
As described above, the adhesive sheet to which the peeling method of the present invention is applied is preferably easily peeled off using an aqueous liquid such as water, and the water-resistant adhesive reduction rate is 30% or less. From the viewpoint of obtaining higher water resistance reliability, the water-resistant adhesive reduction rate is, for example, preferably 20% or less, more preferably 10% or less, or 7% or more. The water resistance reduction rate is typically 0% or more. The difference between the water-peeling adhesion reduction rate [%] and the water-resistant adhesion reduction rate [%] 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 viewpoint of the reliability of bonding, the adhesive sheet to which the peeling method disclosed herein is applied preferably has a normal adhesion force N0 of 2.0 N/10 mm or more. In some aspects, the normal adhesion N0 may be, for example, 2.5 N/10 mm or more, or 3.0 N/10 mm or more, or 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, and may be, for example, 30 N/10 mm or less. In some aspects, the normal adhesion N0 may be 20 N/10 mm or less, or 15 N/10 mm or less.

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 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, or may be 3.5 N/10 mm or less, or may be 2.5 N/10 mm or less, or 1.6 N/10 mm or less. It can also be 1.2 N/10 mm or less, or 1.0 N/10 mm or less. According to the adhesive sheet having a low water peeling force N2, the load applied to the adherend when the adhesive sheet is peeled off can be alleviated. This characteristic is particularly meaningful, for example, in the case of peeling an adhesive sheet from a polarizing plate having a film such as a hard coat layer or an antireflection layer on the surface. The adhesive sheet may preferably be, for example, preferably in a state where the water peeling force N2 is 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 more than 0 N/10 mm.
Further, from the viewpoint of improving the secondary workability, it is preferable that the adhesive sheet is peeled off from the adherend without adhering the adhesive to the adherend in the measurement of the water peeling force N2. That is, an adhesive sheet excellent in non-paste residual property is preferable. Whether or not the residual adhesive is adhered to the adherend can be grasped, for example, by visually observing the adherend after the adhesive sheet is peeled off.

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 (N2/N0) of the water peeling force N2 [N/10 mm] to the normal adhesion force N0 [N/10 mm] may be, for example, 1/2.5 or less, or 1/5 or less, or 1/1. 10 or less. The above ratio (N2/N0) is smaller, indicating that the water peeling force N2 is more significantly lowered with respect to the normal adhesion force N0. The peeling method disclosed herein can be preferably carried out in a state in which the adhesive sheet having a ratio of (N2/N0) of 1/15 or less, 1/25 or less, or 1/35 or less is peeled off from the polarizing plate. The upper limit of the ratio (N2/N0) is not particularly limited, and may be, for example, 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 adhesive sheet, the adhesive which forms the layer A of the surface of the adhesive layer which is at least on the side of the polarizing plate is preferably water-insoluble. According to the water-insoluble layer A, it is easy to obtain an adhesive sheet having a high water-resistant adhesion N1 and a low water-resistant adhesion reduction rate. The fact that the layer A is not water-soluble is also preferable from the viewpoint of the phenomenon that the adhesive is left on the adherend in the peeling of the aqueous liquid such as water. Further, it is also advantageous from the viewpoint that the layer A is water-insoluble and prevents the transparency of the adhesive sheet from being lowered 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 the layer A is preferably non-water swellable. According to the non-water-swellable layer A, it is easy to obtain an adhesive sheet having a high water-resistance adhesion N1 and a low water-resistant adhesion reduction rate. Further, in the peeling of an aqueous liquid such as water, it is possible to effectively utilize a small amount of an aqueous liquid to exhibit good peelability. The non-water swellability of the layer A is also preferable from the viewpoint of the phenomenon that the adhesive is left on the adherend in the peeling of the aqueous liquid. Further, the non-water swellability of the layer A can also be advantageous from the viewpoint of preventing the transparency of the adhesive sheet from being lowered by 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 the present specification, the adhesive is water-insoluble, and the gel fraction measured by the following method is 75% or more. In addition, the adhesive is non-water swellable, and the degree of swelling measured by the following method is 2 or less.
That is, the adhesive to be measured is weighed to about 0.5 g, and the weight is set to W1. The adhesive was immersed in 500 ml of distilled water at room temperature (about 23 ° C) for 48 hours, and then filtered through a nylon mesh to measure the weight W2 of the adhesive containing water. Thereafter, the adhesive was dried at 130 ° C for 5 hours, and the weight W3 of the nonvolatile matter was measured. The gel fraction and the degree of swelling were calculated by the following formula.
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 some aspects, the gel fraction of the layer A may be, for example, 80% or more, or 90% or more, or 95% or more, or 98% or more. The gel fraction of layer A is in principle 100% or less. Further, in some aspects, the degree of swelling of the layer A may be, for example, 1.7 or less, or may be 1.5 or less, or may be 1.2 or less. The degree of swelling of the layer A is usually 1.0 or more, and typically more than 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 the adhesive sheet comprising the layer A and the layer B disposed on the back side of the layer A, the gel fraction of the layer B is not particularly limited. In some aspects, the gel fraction of the B layer is preferably equal to or higher than the gel fraction of the A layer, and may also be higher than the gel fraction of the A layer. The gel fraction of the 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 100% or less. Further, 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. Further, in the adhesive layer containing only the A layer, the gel fraction of the entire adhesive layer means the gel fraction of the A layer.

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 the adhesive sheet comprising the layer A and the layer B disposed on the back side of the layer A, the degree of swelling of the layer B is not particularly limited. In some aspects, the swelling degree of the B layer is preferably equal to or less than the swelling degree of the A layer, and may be lower than the swelling degree of the A layer. The degree of swelling of the layer B may be, for example, 1.5 or less, or may be 1.3 or less, or may be 1.1 or less. The degree of swelling of the layer B is usually 1.0 or more, and typically exceeds 1.0. Further, the degree of swelling of the entire adhesive layer may be 1.6 or less, 1.4 or less, 1.2 or less, or 1.1 or less. Further, in the adhesive layer containing only the A layer, the degree of swelling of the entire adhesive layer means the degree of swelling 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 the degree of swelling of the adhesive to water may suitably be, for example, the composition of the monomer component, the weight average molecular weight of the polymer, the use of a crosslinking agent or a polyfunctional monomer, etc., for the applicant at the time of the application of the present application. Adjust in a general way.

＜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) Layer A In the adhesive sheet peeled off by the peeling method disclosed herein, the layer A constituting at least the surface of the adhesive layer on the side of the polarizing plate may be, for example, selected from the group consisting of an acrylic adhesive and a rubber adhesive. (natural rubber, synthetic rubber, mixed systems, etc.), polyoxygenated adhesives, polyester adhesives, urethane adhesives, polyether adhesives, polyamine adhesives An adhesive layer composed of one or two or more kinds of various known adhesives such as a fluorine-based adhesive and a fluorine-based adhesive. Here, the acrylic adhesive refers to an adhesive containing an acrylic polymer as a main component. Rubber adhesives and other adhesives have the same meaning. Further, the concept of the polymer referred to herein also includes a polymer which is sometimes referred to as a relatively low degree of polymerization of an oligomer.

(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 viewpoints of transparency, weather resistance, etc., in some aspects, an acrylic adhesive can be preferably used as a 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CX-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C1-20 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C1-20 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。The acrylic adhesive preferably contains, for example, an alkyl (meth)acrylate containing more than 50% by weight of a linear or branched alkyl group having 1 or more and 20 or less carbon atoms at the ester terminal. The acrylic polymer composed of the monomer components. Hereinafter, the number of carbon atoms in the ester end of X or more and Y or less of an alkyl acrylate, the alkyl (meth) acrylate is expressed as "(meth) acrylic acid alkyl ester C XY." The ratio of the C 1-20 alkyl (meth)acrylate in the entire monomer component may be, for example, 55% by weight or more, or 60% by weight or more, or 70% by weight. %the above. For the same reason, the ratio of the 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C1-20 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。Specific examples of non-limiting examples of the C 1-20 alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid Amyl ester, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (A) Isooctyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate Ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (methyl) Cetyl acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, pentadecyl (meth) acrylate, (a) Ethyl acrylate or the like.

該等之中，較佳為至少使用(甲基)丙烯酸C4-20 烷基酯，更佳為至少使用(甲基)丙烯酸C4-18 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C4-20 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 preferred to use at least a C 4-20 alkyl (meth)acrylate, and more preferably at least a C 4-18 alkyl (meth)acrylate. For example, an acrylic adhesive containing one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) or both as the monomer component is preferable, and an acrylic system containing at least 2EHA is particularly preferable. Adhesive. Other examples of the C 4-20 alkyl (meth)acrylate which can be preferably used include isodecyl acrylate, n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate. (2EHMA), isostearyl acrylate (ISTA), and the like.

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C4-18 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C4-18 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C6-18 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C4-18 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C6-18 烷基酯之單體成分。In some aspects, the monomer component constituting the acrylic polymer may contain a C 4-18 alkyl (meth)acrylate in a ratio of 40% by weight or more. The monomer component containing a relatively large alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms at the ester terminal as described above tends to form an acrylic polymer having a high lipophilicity. According to the acrylic polymer having a high lipophilic property, it is easy to form an adhesive layer having a low water-resistant adhesion reduction rate. The ratio of the C 4-18 alkyl (meth)acrylate to 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. %the above. The monomer component of the C 6-18 alkyl (meth)acrylate may be contained in a ratio equal to or higher than any of the above lower limits.
Further, from the viewpoint of improving the cohesiveness of the adhesive layer and preventing aggregation damage, the ratio of the C 4-18 alkyl (meth)acrylate to the monomer component is usually appropriately set to 99.5% by weight or less. It may be 99% by weight or less, 98% by weight or less, or 97% by weight or less. The monomer component of the C 6-18 alkyl (meth)acrylate may be contained in a ratio of any of the above upper limit values.

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 component constituting the acrylic polymer may also contain an alkyl (meth)acrylate and, if necessary, another monomer (copolymerizable monomer) copolymerizable with the alkyl (meth)acrylate. As the copolymerizable monomer, a monomer having a polar group (for example, a carboxyl group, a hydroxyl group, a ring containing a nitrogen atom, or the like) can be preferably used. The monomer having a polar group can contribute to the introduction of a crosslinking point into the acrylic polymer or increase the cohesive force of the adhesive. The copolymerizable monomers may be used alone or in combination of two or more.

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。Specific examples of non-limiting examples of the copolymerizable monomer include the following.
The carboxyl group-containing monomer: for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, and the like.
An acid anhydride group-containing monomer: for example, maleic anhydride, itaconic anhydride.
Hydroxyl-containing monomer: 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 A hydroxyalkyl (meth) acrylate such as 12-hydroxylauryl ester or (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
a monomer having a sulfonic acid group or a phosphoric acid group: for example, styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(methyl)acrylamido-2-methylpropanesulfonic acid, (methyl And acrylamide-propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid, 2-hydroxyethyl acryloylphosphoric acid, and the like.
The epoxy group-containing monomer: an epoxy group-containing acrylate such as glycidyl (meth)acrylate or 2-ethyl glycidyl (meth)acrylate, allyl glycidyl ether, (methyl ) glycidyl ether and the like.
A cyano group-containing monomer: for example, acrylonitrile, methacrylonitrile or the like.
The isocyanate group-containing monomer: for example, 2-isocyanatoethyl (meth)acrylate or the like.
Monoamine-containing monomer: for example, (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- N,N-dialkyl(meth)acrylamide such as bis(t-butyl)(methyl) acrylamide; N-ethyl(meth)acrylamide, N-isopropyl (methyl) N-alkyl (meth) acrylamide such as acrylamide, N-butyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-vinyl acetamide, etc. N-vinyl carboxylic acid amides; monomers having a hydroxyl group and a guanamine group, 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) (A) N-hydroxyalkyl (meth) propylene such as acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide Guanidine; a monomer having an alkoxy group and a guanamine group, such as N-methoxymethyl (meth) acrylamide, N-methoxy B N-alkoxyalkyl (meth) acrylamide such as (meth) acrylamide or N-butoxymethyl (meth) acrylamide; and N,N-dimethylaminopropyl (Meth) acrylamide, N-(methyl) propylene decyl porphyrin, and the like.
Amino group-containing monomer: for example, aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate.
Monomer having an epoxy group: for example, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, allyl glycidyl ether.
a monomer having a ring containing a nitrogen atom: for example, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinyl Pyrimidine, N-vinylpiperidin, N-vinylpyridinium, N-vinylpyrrole, N-vinylimidazole, N-vinylcarbazole, N-(methyl)propenyl-2-pyrrolidone , N-(methyl)acrylamidopiperidine, N-(methyl)propenylpyridylpyridinium, N-vinylporphyrin, N-vinyl-3-indolyl ketone, N-vinyl-2- Caprolactam, N-vinyl-1,3-indol-2-one, N-vinyl-3,5-porphyrindione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, N-vinyl anthracene or the like (for example, an indoleamine such as N-vinyl-2-caprolactam).
a monomer having an amber quinone imine skeleton: for example, N-(methyl)propenyloxymethylene succinimide, N-(methyl)propenyl-6-oxyhexamethylene amber Amine, N-(meth)acrylinyl-8-oxyhexamethylene succinimide, and the like.
Maleimide: for example, N-cyclohexylmethyleneimine, N-isopropyl maleimide, N-lauryl maleimide, N-benzene A cis-butenylene imine or the like.
Ikonium imines: for example, N-methyl Ikonide, N-ethyl Ikonide, N-butyl Ikonide, N-octyl Icinoimine, N- 2-ethylhexylkampwine imine, N-cyclohexylkkonium imine, N-lauryl Ikonide, and the like.
Aminoalkyl (meth)acrylates: for example, aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-di(meth)acrylate Ethylaminoethyl ester, tert-butylaminoethyl (meth)acrylate.
Alkoxy-containing monomers: for example, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (A) Alkoxyalkyl (meth)acrylates such as propoxyethyl acrylate, butoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate; methoxyethylene glycol An alkoxyalkylene glycol (meth) acrylate such as (meth) acrylate or methoxypolypropylene glycol (meth) acrylate.
Alkoxyalkylene-containing monomers: for example, 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3-(A Base) propylene methoxy propyl methyl dimethoxy decane, 3-(methyl) propylene methoxy propyl methyl diethoxy decane.
Vinyl esters: for example, vinyl acetate, vinyl propionate, and the like.
Vinyl ethers: vinyl vinyl ethers such as methyl vinyl ether or ethyl vinyl ether.
An aromatic vinyl compound: for example, styrene, α-methylstyrene, vinyltoluene or the like.
Olefins: for example, ethylene, butadiene, isoprene, isobutylene, and the like.
(meth) acrylate having an alicyclic hydrocarbon group: for example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, dicyclopentyl (meth) acrylate Ester, adamantyl (meth)acrylate, and the like.
The (meth) acrylate having an aromatic hydrocarbon group: for example, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate or the like.
Further, a halogen-containing (meth) acrylate such as a heterocyclic (meth) acrylate such as tetrahydrofurfuryl (meth) acrylate or a (meth) acrylate such as a vinyl chloride or a fluorine atom-containing (meth) acrylate A (meth) acrylate containing a halogen atom such as an oxygen (meth) acrylate, a (meth) acrylate obtained from a terpene compound derivative alcohol, or the like.

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。In the case of using such a copolymerizable monomer, the amount thereof to be used is not particularly limited, and is usually suitably 0.01% by weight or more based on the entire monomer component. The amount of the copolymerizable monomer used may be 0.1% by weight or more of the entire monomer component, or may be 0.5% by weight or more, from the viewpoint of more effectively exhibiting the use effect of the copolymerizable monomer. In addition, the amount of the copolymerizable monomer to be used is usually 50% by weight or less, preferably 40% by weight or less, based on the total amount of the monomer component.

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 comprises a carboxyl group-containing monomer. Preferable examples of the carboxyl group-containing monomer include acrylic acid (AA) and methacrylic acid (MAA). AA can also be used in combination with MAA. In the case where AA and MAA are used in combination, the weight ratio (AA/MAA) is not particularly limited, and may be, for example, in the range of about 0.1 to 10. In some aspects, the above weight ratio (AA/MAA) may be, for example, about 0.3 or more, or may be about 0.5 or more. Further, the above weight ratio (AA/MAA) may be, for example, about 4 or less, 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 a monomer having a carboxyl group, an aqueous liquid such as water can be quickly affinityd to the surface of the layer A. This condition can contribute to the reduction of the water peeling force N2. The amount of the carboxyl group-containing monomer may be, for example, 0.05% by weight or more based on the entire monomer component, or may be 0.1% by weight or more, may be 0.3% by weight or more, may be 0.5% by weight or more, or may be 0.8% by weight. %the above. Further, the ratio of the carboxyl group-containing monomer may be, for example, 15% by weight or less, may be 10% by weight or less, may be 5% by weight or less, may be 4.5% by weight or less, or may be 3.5% by weight or less. It may be 3.0% by weight or less, or 2.5% by weight or less. The use amount of the carboxyl group-containing monomer is preferably such that it suppresses the diffusion of water to the entire layer A and suppresses the decrease in the water-resistant adhesion N1. Further, the use amount of the carboxyl group-containing monomer is not particularly limited, and it is also advantageous from the viewpoint of preventing the water for measuring the water peeling force N2 from being absorbed by the layer A and the water being insufficient in the middle of the 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 several aspects, the monomer component can comprise a hydroxyl containing monomer. By using a hydroxyl group-containing monomer, the cohesive force or crosslink density of the adhesive can be adjusted to increase the normal adhesion N0. The amount of the monomer to be used in the case of using a hydroxyl group-containing monomer is not particularly limited. For example, the amount of the monomer component may be 0.01% by weight or more, or 0.1% by weight or more, or 0.5% by weight or more. Further, from the viewpoint of suppressing excessive water diffusion to the entire layer A, the amount of the hydroxyl group-containing monomer used in each of the plurality of aspects is appropriately set to, for example, 40% by weight or less based on the entire monomer component, and may be set. 30% by weight or less may be 20% by weight or less, or may be 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 carried out in a state in which the adhesive sheet peeled off by the peeling method does not substantially use a hydroxyl group-containing monomer as a monomer component of the layer A.

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 several aspects, the monomer component can comprise alkoxyalkylalkyl containing monomers. The alkoxyalkylene group-containing monomer is typically an ethylenically unsaturated monomer having at least one (preferably two or more, for example two or three) alkoxyalkylene groups in one molecule. This is specifically as described above. The alkoxyalkylene group-containing monomers may be used alone or in combination of two or more. By using a monomer containing an alkoxyalkylene group, a crosslinked structure formed by a condensation reaction (stanol condensation) of a stanol group can be introduced into the adhesive layer. Further, the alkoxyalkylene group-containing monomer can also be understood as the following decane 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 aspect in which the monomer component contains the alkoxyalkylene group-containing monomer, the ratio of the alkoxyalkyl group-containing monomer to the entire monomer component can be, for example, 0.005% by weight or more, usually appropriate It is set to 0.01% by weight or more. Moreover, the ratio of the alkoxyalkylene group-containing monomer may be 0.5% by weight or less, 0.1% by weight or less, or 0.05% by weight, from the viewpoint of improving the adhesion of the adherend. 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 -75 ° C or more and -10 ° C based on the glass transition temperature (hereinafter also referred to as "glass transition temperature of the acrylic polymer") determined by the Fox formula based on the composition of the monomer component. The following methods are set. In some aspects, the glass transition temperature (Tg) of the acrylic polymer is suitably -20 ° C or lower, preferably -30 ° C or lower, more preferably -40 ° C or lower, and still more preferably -50 ° C or lower. For example, it may be -55 ° C or less. When the Tg of the acrylic polymer is low, the adhesion of the layer A to the adherend tends to be improved as a whole. According to the layer A having a high adhesion to the adherend, it is easy to prevent the water from infiltrating into the interface between the adherend and the layer A in the case where the sheet is not intended to be peeled off. This property can be advantageous from the viewpoint of an improvement in the water-resistant adhesion N1 or a decrease in the water-resistant adhesion reduction rate. Further, from the viewpoint of easily increasing the normal adhesion N0, the Tg of the acrylic polymer may be, for example, -70 ° C or higher, or -65 ° C or higher.

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 relationship between the Tg of the above-mentioned Fox formula copolymer and the glass transition temperature Tgi of the homopolymer obtained by polymerizing each monomer constituting the copolymer is as follows.
1/Tg=Σ(Wi/Tgi)
Further, in the above Fox formula, Tg represents the glass transition temperature (unit: K) of the copolymer, Wi represents the weight fraction of the monomer i in the copolymer (copolymer ratio of the weight basis), and Tgi represents the 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 for calculating the homopolymer of Tg, the values described in the publicly known materials are used. For example, regarding the monomers listed below, the glass transition temperature of the homopolymer of the monomer uses the following values.
2-ethylhexyl acrylate-70 ° C
N-butyl acrylate -55 ° C
Methyl methacrylate 105 ° C
Methyl acrylate 8 ° C
Acrylic acid 106 ° C
Methacrylic acid 228 ° C

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 the homopolymer of the monomer other than the above-described examples, the values described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) were used. When a plurality of values are described in this document, the highest value is employed.

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 monomer which does not describe the glass transition temperature of the homopolymer in the above Polymer Handbook, the value obtained by the following measurement method is used (refer to Japanese Patent Laid-Open Publication No. 2007-51271). Specifically, 100 parts by weight of a monomer, 0.2 parts by weight of azobisisobutyronitrile, and 200 parts by weight of ethyl acetate as a polymerization solvent are charged into a reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction tube, and a reflux cooling tube. The nitrogen gas was circulated while stirring for 1 hour. After removing oxygen in the polymerization system in this manner, the temperature was raised to 63 ° C and the reaction was carried out for 10 hours. Then, the mixture was cooled to room temperature to obtain a homopolymer solution having 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-like homopolymer) having a thickness of about 2 mm. The test sample was punched out into a disk shape of 7.9 mm in diameter, sandwiched by a parallel plate, and a shear strain of 1 Hz was applied to one side using a viscoelasticity tester (ARES, manufactured by Rheometrics Co., Ltd.), and the temperature region was -70. The viscoelasticity was measured by a shear mode at a temperature increase rate of -150 ° C and 5 ° C / min, and the peak top temperature of tan δ was defined 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 may be formed using an adhesive composition containing a monomer component having a composition as described above in the form of a polymer, an unpolymer (that is, a polymerizable functional group in an unreacted form), or a mixture of the above. . The pressure-sensitive adhesive composition may be in the form of a water-dispersible pressure-sensitive adhesive composition in which an adhesive (adhesive component) is dispersed in water, or a solvent-based adhesive composition in the form of an adhesive in an organic solvent. An active energy ray-curable adhesive composition prepared by curing an active energy ray such as ultraviolet rays or radiation to form an adhesive, which is applied in a heated and molten state and cooled to a temperature near room temperature to form an adhesive of the adhesive. Type adhesive composition and the like.

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。At the time of polymerization, a known or customary thermal polymerization initiator or photopolymerization initiator may be used depending on the polymerization method, the polymerization state, and the like. Such a polymerization initiator may be used singly or in combination of two or more.

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, and for example, an azo polymerization initiator, a peroxide initiator, a redox initiator obtained by a combination of a peroxide and a reducing agent, and a substitution can be used. An ethane-based initiator or the like. More specifically, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis ( 2-mercaptopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-couple Azo system such as nitrogen bis(N,N'-dimethylene isobutyl fluorene) or 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine hydrate Starting agent; for example, persulfate such as potassium persulfate or ammonium persulfate; peroxide-based initiator such as benzamidine peroxide, tert-butyl hydroperoxide or hydrogen peroxide; for example, phenyl-substituted ethane The ethane-based initiator is substituted, for example, a combination of a persulfate and a sodium hydrogen sulfite, a redox-based initiator such as a combination of a peroxide and sodium ascorbate, and the like, but is not limited thereto. Further, the thermal polymerization can be preferably carried out at a temperature of, for example, 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, and for example, a ketal photopolymerization initiator, an acetophenone photopolymerization initiator, a benzoin ether photopolymerization initiator, a mercaptophosphine oxide photopolymerization can be used. Starting agent, α-keto alcohol photopolymerization initiator, aromatic sulfonium chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzoin photoluminescence Polymerization initiator, benzophenone photopolymerization initiator, 9-oxopurine A photopolymerization initiator or the like.

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 amount of the thermal polymerization initiator or the photopolymerization initiator to be used is not particularly limited as long as it is used in accordance with a polymerization method, a polymerization state, or the like. For example, 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) of the polymerization initiator can be used with respect 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 polymerization, various previously known chain transfer agents (which may also be understood as molecular weight regulators or polymerization degree regulators) may be used as needed. As the chain transfer agent, mercaptans such as n-dodecyl mercaptan, tri-dodecyl mercaptan, or thioglycolic acid can be used. Alternatively, a chain transfer agent (non-sulfur chain transfer agent) containing no sulfur atom may be used. Specific examples of the non-sulfur-based chain transfer agent include anilines such as N,N-dimethylaniline and N,N-diethylaniline; anthracene such as α-pinene and terpinene; α- Styrenes such as methyl styrene and α-methylstyrene dimer; compounds having a benzylidene group such as dibenzylideneacetone, cinnamyl alcohol, and cinnamaldehyde; and terephthalic acid such as hydroquinone or dihydroxynaphthalene Phenols; hydrazines such as benzoquinone and naphthoquinone; olefins such as 2,3-dimethyl-2-butene and 1,5-cyclooctadiene; alcohols such as phenol, benzyl alcohol and allyl alcohol; Benzyl hydrogen such as phenylbenzene or triphenylbenzene.
The chain transfer agent may be used alone or in combination of two or more. In the case of using a chain transfer agent, the amount thereof to be used may be, for example, about 0.01 to 1 part by weight based on 100 parts by weight of the monomer component. The techniques disclosed herein can also be preferably practiced without the use of a chain transfer agent.

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 stripping method disclosed herein, the adhesive sheet has an A layer formed of a water-dispersible adhesive composition. A representative example of the water-dispersible pressure-sensitive adhesive composition is an emulsion type pressure-sensitive adhesive composition. The emulsion type adhesive composition typically contains a polymer of a monomer component and, if necessary, an additive.

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。The emulsion polymerization of the monomer components is usually carried out in the presence of an emulsifier. The emulsifier for emulsion polymerization is not particularly limited, and a known anionic emulsifier, nonionic emulsifier or the like can be used. The emulsifier may be used alone or in combination of two or more.

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 the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene lauryl sulfate, and sodium polyoxyethylene alkyl ether sulfate. , polyoxyethylene alkyl phenyl ether ammonium sulfate, sodium polyoxyethylene alkyl phenyl ether, sodium polyoxyethylene alkyl sulfosuccinate and the like. Non-limiting examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene polyoxypropylene block polymer. An emulsifier (reactive emulsifier) having a reactive functional group can also be used. Examples of the reactive emulsifier include a radical polymerizable emulsifier having a structure in which a radical polymerizable functional group such as a propylene group or an allyl ether group is introduced into the anionic emulsifier or the nonionic emulsifier described above. 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 the emulsifier used in the emulsion polymerization may be, for example, 0.2 parts by weight or more, or may be 0.5 parts by weight or more, or 1.0 part by weight or more, or 1.5 parts by weight or more, based on 100 parts by weight of the monomer component. Further, in terms of improvement in water-resistant adhesion N1 or reduction in water-resistant adhesion reduction rate, or improvement in transparency of the adhesive layer, in some aspects, the amount of the emulsifier used is usually relative to the monomer component 100. The weight part is suitably 10 parts by weight or less, preferably 5 parts by weight or less, or 3 parts by weight or less. Further, the emulsifier used herein for emulsion polymerization can also function as a water affinity agent of the layer A.

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。According to the emulsion polymerization, a polymerization reaction liquid in the form of an emulsion in which a polymer of a monomer component is dispersed in water can be obtained. The water-dispersible pressure-sensitive adhesive composition for forming the layer A can be preferably produced by using the above 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 several aspects, the adhesive sheet can have an A layer formed from a solvent-based adhesive composition. The solvent-based adhesive composition typically contains a solution polymer of a monomer component, and an additive as needed. The solvent (polymerization solvent) used for the solution polymerization can be appropriately selected from previously known organic solvents. For example, an aromatic compound selected from toluene (typically an aromatic hydrocarbon); an ester such as ethyl acetate or butyl acetate; an aliphatic or alicyclic hydrocarbon such as hexane or cyclohexane; a halogenated alkane such as 1,2-dichloroethane; a lower alcohol such as isopropyl alcohol (for example, a monohydric alcohol having 1 to 4 carbon atoms); an ether such as a third butyl methyl ether; or a ketone such as methyl ethyl ketone. Any one of solvents or a mixture of two or more. According to the solution polymerization, a polymerization reaction liquid in a form in which a polymer of a monomer component is dissolved in a polymerization solvent can be obtained. The solvent-type adhesive composition for forming the layer A can be preferably produced by using the above 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 several aspects, the adhesive sheet can have an A layer formed from an active energy ray-curable adhesive composition. Here, in the present specification, the "active energy ray" means an energy ray having energy capable of causing a chemical reaction such as a polymerization reaction, a crosslinking reaction, or decomposition of an initiator. Examples of the active energy ray herein include light such as ultraviolet rays, visible rays, infrared rays, or radiation such as α rays, β rays, γ 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 an advantage that it can be easily formed even with a thick adhesive layer. 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 comprises at least a portion of the monomer component of the composition in the form of a polymer (which may be part of the type of monomer or part of a component). The polymerization method in the case of forming the above polymer is not particularly limited, and various conventionally known polymerization methods can be suitably employed. For example, thermal polymerization such as solution polymerization, emulsion polymerization, or bulk polymerization (typically, in the presence of a thermal polymerization initiator) may be suitably employed; photopolymerization by irradiation of light such as ultraviolet rays (typically, light) Radiation polymerization by irradiation with radiation such as β-rays or γ-rays is carried out in the presence of a polymerization initiator. 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 embodiment of the photocurable adhesive composition comprises a partial polymer of a monomer component. Such a partial polymer is typically a mixture of a polymer derived from a monomer component and an unreacted monomer, preferably in the form of a slurry (having a viscous liquid). Hereinafter, a part of the polymer of the above properties may be referred to as a "monomer slurry" or simply as a "slurry". The polymerization method in the case where the monomer component is partially polymerized is not particularly limited, and various polymerization methods as described above can be suitably used and used. From the viewpoint of efficiency or simplicity, a photopolymerization method can be preferably employed. According to the photopolymerization, the polymerization conversion ratio (monomer conversion ratio) of the monomer component can be easily controlled by polymerization conditions such as the amount of light irradiation (light amount).

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 ratio of the monomer mixture in the above partial polymer is not particularly limited. The polymerization conversion ratio can be, for example, about 70% by weight or less, preferably about 60% by weight or less. The polymerization conversion ratio is usually suitably about 50% by weight or less, preferably about 40% by weight or less (for example, about 35 parts by weight) from the viewpoints of easiness of preparation or coating property of the adhesive composition containing the above partial polymer. %the following). The lower limit of the polymerization conversion ratio is not particularly limited, and is typically about 1% by weight or more, and usually 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 comprising a part of the polymer of the monomer component can be, for example, carried out by using a suitable polymerization method (for example, photopolymerization) to carry out the entire amount of the monomer mixture containing the monomer component for preparing the adhesive composition. Obtained by partial polymerization. Further, the adhesive composition comprising a part of the polymer of the monomer component may also be a partial polymer or a complete polymer comprising a monomer mixture for preparing a part of the monomer component of the adhesive composition, and the remaining a mixture of monomer components or a portion thereof. In the present specification, the term "complete polymer" means a polymerization conversion ratio of more than 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。Other components (for example, a photopolymerization initiator, a polyfunctional monomer, a crosslinking agent, a water affinity agent, etc.) which can be used as desired in the adhesive composition containing the above partial polymer can be used. The method of blending such other components is not particularly limited. For example, it may be contained in the above monomer mixture in advance, or may be added to the above 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 preferably contains a water affinity agent in addition to the polymerization reaction product of the monomer component of the layer A constituting one surface of the adhesive layer. For example, it is preferable to provide an adhesive sheet of the A layer containing an acrylic polymer as the above-mentioned polymerization reaction product 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 which can exhibit the effect of improving the water affinity of the surface of the layer A by being contained in the layer A can be suitably used. By increasing the water affinity of the layer A, an aqueous liquid such as water can be more quickly affinityd to the surface of the layer A. Therefore, for example, in the measurement of the water peeling force N2, the first drop of water can be caused to follow the movement of the adhesive sheet from the peeling front of the adherend to the surface of the layer A, thereby effectively reducing the water peeling force N2. . By the same action, the adhesive sheet exfoliating body can be improved by including an aqueous liquid such as water entering the interface between the adhesive sheet and the adherend, and moving the peeling front line. 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, a known anionic surfactant, a nonionic surfactant, a cationic surfactant, a water-soluble plasticizer, a water-soluble polymer, or the like can be used. The water affinity agents may be used singly or in combination of two or more.

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 the water-soluble plasticizer, various polyols (preferably polyether polyols) can be used. Specific examples thereof include polyethylene glycol, polypropylene glycol, polyoxypropylene sorbitol ether, and polyglycerin. These may be used alone or in combination of two or more.
Examples of the water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acid.

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 the anionic surfactant include alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate; alkylsulfate such as sodium lauryl sulfate and ammonium lauryl sulfate; polyoxyethylene laurylamine and polyoxygen Polyetheramine such as ethylene stearylamine; polyether sulfate such as sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate; polyoxyethylene stearyl ether phosphate a polyoxyethylene alkyl ether phosphate such as an ester or a polyoxyethylene lauryl ether phosphate; a polyoxyethylene alkyl ether phosphate such as a sodium salt or a potassium salt of the above polyoxyethylene alkyl ether phosphate; a polyoxyethylene alkyl group; Sodium sulfosuccinate and the like.

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, and polyoxyethylene bisphenol A ether. Alkyl ether; polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, and the like.

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 a -POH group, a -COH group, and a -SOH group can be preferably used. Among them, a surfactant having a -POH group is preferred. Such a surfactant typically comprises a phosphate structure, such as 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 comprising both a monoester and a diester, and the like. Preferable examples of the surfactant having a -POH group include polyoxyethylene alkyl ether phosphates. The alkyl group in the polyoxyethylene alkyl ether phosphate may have a carbon number of, for example, 6 to 20, may be 8 to 20, may be 10 to 20, may be 12 to 20, or may be 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 the layer A is not particularly limited. In some aspects, the content of the aqueous affinity agent is, for example, 0.2 parts by weight or more per 100 parts by weight of the monomer component constituting the polymer contained in the layer A, in terms of obtaining a higher effect. It may be 0.5 parts by weight or more, 1.0 part by weight or more, or 1.5 parts by weight or more. Further, from the viewpoint of suppressing excessive water diffusion into the entire A layer, the amount of the aqueous affinity agent used is appropriately set to 10 parts by weight or less based on 100 parts by weight of the monomer component. When it is 5 parts by weight or less, it may be 3 parts by weight or less. The content of the water affinity agent is preferably not more than the viewpoint of the improvement of the water resistance N1 or the reduction of the water adhesion resistance or the improvement of 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。(decane coupling agent)
In several aspects, the layer A may contain a decane coupling agent. According to the layer A containing the decane coupling agent, it is possible to preferably achieve an adhesive sheet having a low rate of reduction in water-resistant adhesion and a high rate of reduction in water-peeling adhesion.

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 the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 2-(3,4-epoxycyclohexyl)B. Anthracene compound having an epoxy structure such as trimethoxymethoxydecane; 3-aminopropyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropyltrimethoxydecane, N-(2) An amine group-containing oxime compound such as -aminoethyl)3-aminopropylmethyldimethoxydecane; 3-chloropropyltrimethoxydecane; trimethoxydecane containing ethyl acetonitrile; - (meth) acrylonitrile-containing decane coupling agent such as propylene methoxy propyl trimethoxy decane, 3-methyl propylene oxy propyl triethoxy decane; 3-isocyanatopropyl propyl An isocyanate-containing decane coupling agent such as ethoxysilane or the like. Among them, preferred examples thereof include 3-glycidoxypropyltrimethoxydecane and trimethoxydecane containing an ethyl acetonitrile group.

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 amount of the decane coupling agent to be used can be set in such a manner that the desired use effect can be obtained, and is not particularly limited. In some aspects, the amount of the decane coupling agent used may be, for example, 0.001 parts by weight or more based on 100 parts by weight of the monomer component constituting the polymer contained in the layer A, from the viewpoint of obtaining a higher effect. It may be 0.005 parts by weight or more, 0.01 parts by weight or more, or 0.015 parts by weight or more. Further, from the viewpoint of improving the adhesion to the adherend, the amount of the decane coupling agent used may be, for example, 3 parts by weight or less based on 100 parts by weight of the monomer component constituting the layer A, in some aspects, It may be 1 part by weight or less, or 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。Further, in the aspect in which the monomer component contains the alkoxyalkylene group-containing monomer, the alkoxyalkylene group-containing monomer may be used as a part or all of the decane coupling agent contained in the layer A.

(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。(crosslinking agent)
A crosslinking agent may optionally be included in the layer A. The kind of the crosslinking agent is not particularly limited, and for example, a crosslinking agent which is appropriately selected from previously known crosslinking agents can be used. Specific examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and a carbodiimide crosslinking agent. A melamine-based crosslinking agent, a urea-based crosslinking agent, a metal alkoxide-based crosslinking agent, a metal chelate-based crosslinking agent, a metal salt-based crosslinking agent, an anthraquinone-based crosslinking agent, and an amine-based crosslinking agent. These may be used alone or in combination of two or more.

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 an isocyanate type crosslinking agent, a bifunctional or more polyfunctional isocyanate compound can be used. Examples thereof include aromatic isocyanates such as toluene diisocyanate, xylene diisocyanate, polymethylene polyphenyl diisocyanate, tris(p-isocyanatophenyl) thiophosphate, and diphenylmethane diisocyanate; An alicyclic isocyanate such as phorone diisocyanate; an aliphatic isocyanate such as hexamethylene diisocyanate; and the like. Commercially available products include trimethylolpropane/toluene diisocyanate trimer adduct (manufactured by Tosoh Corporation, trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate III. Isocyanate adducts such as a polymer adduct (manufactured by Tosoh Corporation, trade name "Coronate HL"), hexamethylene diisocyanate isocyanurate (manufactured by Tosoh Corporation, trade name "Coronate HX"), etc. . In the water-dispersible adhesive composition, an isocyanate-based crosslinking agent which is soluble or dispersible in water is preferably used. For example, a water-soluble, water-dispersible or self-emulsifying isocyanate-based crosslinking agent can be preferably used. A so-called blocked isocyanate type isocyanate crosslinking agent which is blocked with an isocyanate group can be preferably used.

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。The epoxy-based crosslinking agent can be used without any particular limitation in the case of having two or more epoxy groups in one molecule. An epoxy-based crosslinking agent having 3 to 5 epoxy groups in one molecule is preferred. Specific examples of the epoxy-based crosslinking agent include N, N, N', N'-tetraglycidyl meta-xylylenediamine, and 1,3-bis(N,N-diglycidylamino group). Methyl)cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, and the like. As a commercial item of the epoxy-based crosslinking agent, the product name "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., "TETRAD-C", and the trade name "EPICLON CR-5L" manufactured by DIC Corporation, Nagase ChemteX The product name "DENACOL EX-512" manufactured by the company and the trade name "TEPIC-G" manufactured by Nissan Chemical Industries Co., Ltd., etc. In the water-dispersible pressure-sensitive adhesive composition, an epoxy-based crosslinking agent which is soluble or dispersible in water is preferably used.

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。The oxazoline-based crosslinking agent can be used without any particular limitation in one or more oxazoline groups in one molecule. In the water-dispersible pressure-sensitive adhesive composition, an oxazoline-based crosslinking agent which is soluble or dispersible in water is preferably used.
Examples of the aziridine-based crosslinking agent include trimethylolpropane tris[3-(1-aziridine)propionate], and trimethylolpropane tris[3-(1-(2) -Methyl)aziridine propionate)].
As the carbodiimide crosslinking agent, a low molecular compound or a polymer compound having two or more carbodiimide groups can be used. In the water-dispersible pressure-sensitive adhesive composition, a carbodiimide-based crosslinking agent which is soluble or dispersible in water is preferably used.

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, a peroxide can also be used as the crosslinking agent. Examples of the peroxide include di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, and dibutyl butyl peroxydicarbonate. Oxidized neodecanoic acid tert-butyl ester, peroxidic pivalic acid trihexyl ester, peroxidic pivalic acid tert-butyl ester, dilaurin peroxide, di-n-octyl peroxide, isobutyric acid peroxide 1,1 , 3,3-tetramethylbutyl ester, dibenzoic acid peroxide, and the like. Among these, examples of the peroxide which is particularly excellent in crosslinking reaction efficiency include di(4-tert-butylcyclohexyl)peroxydicarbonate, dilaurin peroxide, and dibenzoic acid peroxide. . Further, when a peroxide is used as the polymerization initiator, a peroxide which is not used in the polymerization reaction may be used for the crosslinking reaction. In this case, the residual amount of the peroxide is quantified, and when the ratio of the peroxide is less than a specific amount, the peroxide may be added in a specific amount as needed. The quantification of the peroxide can be carried out by the method described in Japanese Patent No. 4,917,517.

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 crosslinking agent (the total amount of the crosslinking agent when it is contained in the case of containing two or more kinds of crosslinking agents) is not particularly limited. The content of the crosslinking agent is usually appropriately set to about 5 weights per 100 parts by weight of the monomer component contained in the adhesive composition, from the viewpoint of achieving an adhesive having a bonding property such as adhesion or cohesive force in a balanced manner. The amount is preferably 0.001 to 5 parts by weight, more preferably 0.001 to 4 parts by weight, still more preferably 0.001 to 3 parts by weight. Alternatively, it may be an adhesive composition which does not contain a crosslinking agent as described above. Alternatively, it may be an adhesive composition which does not contain a crosslinking 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。(adhesive to resin)
It is also possible to provide an adhesion-imparting resin in the layer A. Examples of the adhesion-imparting resin include a rosin-based adhesion-imparting resin, a rosin-based adhesion-imparting resin-based petroleum-based adhesion-imparting resin, a terpene-based adhesion-imparting resin, a phenol-based adhesion-imparting resin, and a ketone-based adhesion-imparting resin. These may be used alone or in combination of two or more.

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-providing resin include rosin such as rosin gum, wood rosin, and tall oil rosin, and stabilized rosin (for example, stabilized rosin obtained by disproportionation or hydrogenation of the rosin), and polymerized rosin. (for example, the above rosin polymer, typically a dimer), modified rosin (for example, by unsaturated acid such as maleic acid, fumaric acid, (meth)acrylic acid, etc. Sexually unsaturated acid-modified rosin, etc.).
Examples of the rosin-based adhesion-imparting resin include an esterified product of the rosin-based adhesion-imparting resin (for example, a rosin ester such as a stabilized rosin ester or a polymerized rosin ester), and a phenol-modified product of the rosin-based resin (phenol). Modified rosin) and its esterified product (phenol-modified rosin ester) and the like.
Examples of the petroleum-based adhesion-imparting resin include an aliphatic petroleum resin, an aromatic petroleum resin, a copolymerized petroleum resin, an alicyclic petroleum resin, and the like.
Examples of the terpene-based adhesion-imparting resin include an α-pinene resin, a β-pinene resin, an aromatic modified terpene resin, and a terpene phenol resin.
Examples of the ketone-based adhesion-imparting resin include ketones (for example, aliphatic ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetophenone; and lipids such as cyclohexanone and methylcyclohexanone; A ketone resin obtained by condensation of a cyclic ketone or the like with 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 a certain aspect, one or two or more selected from the group consisting of a rosin-based adhesion-imparting resin, a rosin-derivative adhesion-imparting resin, and a terpene phenol resin can be preferably used as the adhesion-imparting resin. Among them, a rosin derivative is preferably added to the resin, and preferred examples thereof include rosin esters such as a stabilized rosin ester and a 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-dispersible pressure-sensitive adhesive composition, a water-dispersible pressure-imparting resin in a form in which the adhesion-imparting resin as described above is dispersed in an aqueous solvent is preferably used. For example, by mixing an aqueous dispersion of an acrylic polymer with a water-dispersible adhesion-imparting resin, an adhesive composition containing the components in a desired ratio can be easily prepared. In the case of the water-dispersion type adhesion-imparting resin, it is preferable to use at least substantially no aromatic hydrocarbon-based solvent from the viewpoint of environmental hygiene. More preferably, a water-dispersible adhesion-imparting resin which does not substantially contain an aromatic hydrocarbon solvent and another organic solvent is used.

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。For example, the product name "SUPER ESTER E-720", "SUPER ESTER E-730-55", "SUPER" manufactured by Arakawa Chemical Co., Ltd., as a commercially available product of the water-dispersion type adhesion-providing resin containing a rosin ester. ESTER E-865NT, etc., or the trade names "HARIESTER SK-90D", "HARIESTER SK-70D", "HARIESTER SK-70E", "NEOTOL 115E" manufactured by Halima Chemicals Co., Ltd., etc. In addition, as a commercial item of a terpene phenol resin (a form of a water-dispersible terpene phenol resin), the brand name "TAMANOL E-100" and "TAMANOL E-200" manufactured by Arakawa Chemical Industry Co., Ltd. ", "TAMANOL E-200NT" and so on.

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 the decrease in the cohesive force of the pressure-sensitive adhesive layer, an adhesion-imparting resin having a softening point of 80 ° C or higher is usually preferably used. The softening point of the adhesive imparting resin may be 90 ° C or more, 100 ° C or more, 110 ° C or more, or 120 ° C or more. It is also possible to use an adhesion-imparting resin having a softening point of 130 ° C or more or 140 ° C or more. Further, from the viewpoint of transparency or adhesion to the adherend, an adhesion-imparting resin having a softening point of 200 ° C or less or 180 ° C or less can be preferably used. In addition, as the softening point of the adhesive-imparting resin here, the nominal value as described in literature, catalog, etc. can be used. In the case of no nominal value, the softening point of the adhesion-imparting resin can be measured based on the softening point test method (ring and ball method) prescribed 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。The amount of the adhesive-imparting resin to be used is usually 1 part by weight or more, and may be appropriately 1 part by weight or more, based on 100 parts by weight of the monomer component constituting the polymer contained in the layer A. It may be 10 parts by weight or more, may be 15 parts by weight or more, may be 20 parts by weight or more, or may be 25 parts by weight or more. In addition, the amount of the adhesion-imparting resin to be used for 100 parts by weight of the monomer component can be, for example, 70 parts by weight or less, or 50 parts by weight, from the viewpoint of the adhesion to the adherend and the cohesiveness of the adherend. The amount may be 40 parts by weight or less or less. Alternatively, it may be an A layer which does not substantially contain an adhesive-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 adhesive sheet can further improve the water resistance reliability by performing the treatment for increasing the water peeling force at a desired time point. The adhesive sheet exhibiting such a property can be realized, for example, in the configuration in which the layer A contains the adhesion-imparting resin, but is not limited to this configuration. The treatment for increasing the water peeling force may be, for example, a treatment of applying a temperature higher than a room temperature region after attaching the adhesive sheet to the adherend. The temperature to be applied is not particularly limited, and can be selected in consideration of workability, economy, convenience, heat resistance of an adhesive sheet or an adherend. The temperature may be, for example, 45 ° C or higher, or 55 ° C or higher. Further, the temperature may be, for example, less than 150 ° C, may be 120 ° C or less, may be 100 ° C or less, or may be 80 ° C or less. The time for applying the above temperature is not particularly limited, and may be, for example, 1 hour or longer, 3 hours or longer, or 1 day or longer. Alternatively, the above temperature may be applied for a longer period of time within the limits of the adhesive sheet or the adherend without causing significant thermal deterioration. In some aspects, the time for applying the above temperature may be, for example, 14 days or less, or 7 days or less, from the viewpoint of efficiency of processing. The above temperature can be applied at one time, and can also be 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 for increasing the water-repellent force can be, for example, twice or more, or five times or more, with respect to the water-peeling force N2 measured by the above method. It can also be 10 times or more, 20 times or more, or 30 times or more. The water peeling force N3 can 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 measurement of the water-peeling force N3 is performed in the same manner as the above-described measurement of the water-peeling force N2, except that the sample for evaluation taken out from the autoclave is subjected to a treatment for increasing 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 for forming the layer A may be an acid or a base (ammonia water or the like) which is used for the purpose of pH adjustment or the like as needed. As other optional components which may be contained in the composition, a viscosity adjusting agent (for example, a tackifier), a leveling agent, a plasticizer, a filler, a coloring agent such as a pigment or a dye, a stabilizer, a preservative, and an anti-corrosion agent may be exemplified. Various additives generally in the field of adhesive compositions such as aging agents. Regarding such various additives, those previously known can be used by a conventional method, and the detailed description is omitted since the features of the present invention are not specifically described.

(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) Layer B The adhesive layer of the adhesive sheet peeled off by the peeling method disclosed herein may further include a layer A in addition to the layer A constituting at least the surface of the adhesive layer on the side of the polarizing plate. The B layer on the back side. According to the configuration including the A layer and the B layer as described above, for example, the A layer can impart good water releasability, and the B layer can adjust the overall properties (for example, water resistance, cohesiveness, heat resistance, etc.) of the adhesive layer. Therefore, according to the adhesive layer which consists of A layer and B layer, it is easy to obtain the adhesive sheet which is excellent in water-peelability, and it is excellent in water-resistant reliability. For example, an adhesive sheet having a low rate of reduction in water-resistant adhesion and a high rate of reduction in water-peeling adhesion can be preferably achieved. Further, for example, an adhesive sheet which is excellent in both high adhesion and good water releasability can be preferably obtained.

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。The layer B may be disposed in direct contact with the back surface of the layer A, or may be disposed on the back side of the layer A with other layers interposed therebetween. The other layer (hereinafter also referred to as an intermediate layer) is typically a non-adhesive layer, and for example, a plastic film, a foam sheet, a woven or woven fabric, or a paper sheet which is the same as the support described below can be used. , metal foil, etc. From the viewpoint of the softness of the adhesive sheet or the followability to the shape of the surface of the adherend, in some aspects, it is preferred to directly contact the A layer and the B layer (ie, without interposing the intermediate layer). And the adhesive layer formed by the laminate.

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 layer B may be, for example, selected from the group consisting of an acrylic adhesive, a rubber adhesive, a polyoxygen adhesive, a polyester adhesive, a urethane adhesive, a polyether adhesive, and a polyamide. An adhesive layer composed of one or two or more kinds of adhesives of various known adhesives such as an adhesive and a fluorine-based adhesive. From the viewpoints of transparency, weather resistance, and the like, in some aspects, an acrylic adhesive can be preferably used as a constituent material of the B layer. The acrylic adhesive constituting the layer B can be selected, for example, from the examples of the acrylic adhesive which can be used for the layer A, and exhibits desired characteristics in combination with the layer A. The B layer may be a single layer structure including one layer, or may be a multilayer structure including two or more layers having 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C1-20 烷基酯。(甲基)丙烯酸C1-20 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, the acrylic polymer) contained in the layer B may contain (meth)acrylic acid C 1-20 alkane in a ratio of 40% by weight or more of the entire monomer component. Base ester. The ratio of the C 1-20 alkyl (meth)acrylate to the monomer component of the layer B may be, for example, 98% by weight or less, and may be 95% from the viewpoint of improving the cohesiveness of the layer B. % or less may be 85% by weight or less, 70% by weight or less, or 60% by weight or less.
The monomer component constituting the layer B may contain an alkyl (meth)acrylate and a copolymerizable monomer. The copolymerizable monomer can be suitably selected from those exemplified as the copolymerizable monomer usable for the layer A. The amount of the copolymerizable monomer to be used may be, for example, 5% by weight or more, or 15% by weight or more, or may be 30% by weight or more, or 40% by weight or more, based on the entire monomer component constituting the 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 some aspects, the ratio of the carboxyl group-containing monomer to the monomer component constituting the layer B may be, for example, 2% by weight or less, or 1% by weight or less, or 0.5% by weight or less. It is also possible to use substantially no carboxyl group-containing monomer as the monomer component constituting the layer B. Here, the term "substantially not using a carboxyl group-containing monomer" means using a carboxyl group-containing monomer at least inadvertently. The adhesive sheet having the B layer having such a composition is preferable because it is likely to have high water resistance reliability.

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 the adhesive sheet having the A layer and the B layer, a gel fraction which satisfies the B layer is higher than the gel fraction of the A layer, and a swelling degree of the B layer is lower than the swelling degree of the A layer. Adhesive sheet of one or both of the adhesive layers. According to such a configuration, it is easy to obtain an adhesive sheet having a low rate of reduction in water-resistant adhesion and a high rate of reduction in water-peeling adhesion.

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 can be a layer formed from a photocurable adhesive composition or a solvent-based adhesive composition. According to the layer B formed of such a composition, an adhesive sheet having good water resistance reliability can be easily obtained. For example, a combination of the layer A formed of the water-dispersible pressure-sensitive adhesive composition and the layer B formed of the photo-curable pressure-sensitive adhesive composition, or the layer A formed of the water-dispersible pressure-sensitive adhesive composition and the solvent-based adhesive In the combination of the B layers formed by the composition, an adhesive sheet having a low rate of reduction in water-resistant adhesion and a high rate of reduction in water-peeling adhesion can be preferably achieved. In some aspects, the B layer which is substantially free of the aqueous affinity agent can be preferably used from the viewpoint of improvement in water resistance.

＜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 comprising a support attached to the support of the other back side of the adhesive layer. The material of the support is not particularly limited, and may be appropriately selected depending on the purpose of use of the adhesive sheet or the manner of use. As a non-limiting example of a support which can be used, a polyolefin film containing a polyolefin such as polypropylene or an ethylene-propylene copolymer as a main component, polyethylene terephthalate or polyparaphenylene is exemplified. a polyester film such as a polyester film having a polyester such as butadiene dicarboxylate as a main component or a polyvinyl chloride film containing polyvinyl chloride as a main component; and comprising a polyurethane foam, a polyethylene foam, and a polychloroprene foam. A foam sheet of a foamed material; obtained by using various fibrous materials (may be natural fibers such as hemp, cotton, polyester, synthetic fibers such as vinylon, semi-synthetic fibers such as acetate, etc.) alone or in a blend. Weaving and non-woven fabrics; papers such as Japanese paper, Daolin paper, kraft paper, and crepe paper; metal foils such as aluminum foil and copper foil. It can also be a support composed of these composites. Examples of the support of the composite structure include a support in which a metal foil is laminated with the plastic film, 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 support film may be a porous film such as a foam film or a non-woven sheet, or may be a non-porous film or 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, a resin film containing a (self-standing or non-dependent) resin film which can independently maintain the shape can be preferably used as the base film. Here, the "resin film" means a non-porous structure, and typically a bubble-free (voidless) resin film. Therefore, the above resin film is different from the concept of a foam film or a non-woven fabric. The resin film may have a single layer structure or a multilayer 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, a polyester, a polyolefin, a polycycloolefin derived from a monomer having an aliphatic ring structure such as a norbornene structure, nylon 6, nylon 66, a partially aromatic polyamine, or the like can be used. Polyamide (PA), polyimine (PI), polyamidimide (PAI), polyetheretherketone (PEEK), polyether oxime (PES), polyphenylene sulfide (PPS), polycarbonate Fluorine resins such as ester (PC), polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polystyrene, polyvinyl chloride, polyvinylidene chloride, and polytetrafluoroethylene (PTFE) , an acrylic resin such as polymethyl methacrylate, a cellulose polymer such as diethyl phthalocyanine or triacetyl cellulose, a vinyl butyral polymer, an aryl ester polymer, or a polyoxymethylene polymer; A resin such as an epoxy polymer. The resin film may be formed by using a resin material containing one of such resins alone, or may be formed by using two or more kinds of resin materials. The above resin film may be unextended or may be extended (for example, 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 a polyester resin, a PPS resin, and a polyolefin resin. Here, the term "polyester-based resin" means a resin containing a polyester in a ratio of more than 50% by weight. Similarly, the PPS resin refers to a resin containing PPS in a ratio of more than 50% by weight, and the polyolefin resin refers to a resin containing polyolefin in a ratio of more than 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, a polyester-based resin containing a polyester obtained by polycondensing a dicarboxylic acid and a diol as a main component is typically used. Specific examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polynaphthalene dicarboxylic acid. Butadiene ester and the like.

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 or a combination of two or more types of polyolefins can be used alone. The polyolefin may be, for example, a homopolymer of an α-olefin, a copolymer of two or more kinds of α-olefins, a copolymer of one or two or more α-olefins and another vinyl monomer, or the like. Specific examples thereof include ethylene-propylene copolymers such as polyethylene (PE), polypropylene (PP), poly-1-butene, poly-4-methyl-1-pentene, and ethylene propylene rubber (EPR). An ethylene-propylene-butene copolymer, an ethylene-butene copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-ethyl acrylate copolymer, or the like. Any of low density (LD) polyolefins and high density (HD) polyolefins can be used. Examples of the polyolefin resin film include an unstretched polypropylene (CPP) film, a biaxially oriented polypropylene (OPP) film, a low density polyethylene (LDPE) film, and a linear low density polyethylene (LLDPE). Film, medium density polyethylene (MDPE) film, high density polyethylene (HDPE) film, polyethylene (PE) film blended with two or more kinds of polyethylene (PE), blended with 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 the resin film which can be preferably used as the support include a PET film, a PEN film, a PPS film, a PEEK film, a CPP film, and an OPP film. In terms of strength, preferred examples thereof include a PET film, a PEN film, a PPS film, and a PEEK film. From the viewpoints of availability, dimensional stability, optical properties, and the like, a PET film is exemplified as a preferred 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, a known additive such as a light stabilizer, an antioxidant, an antistatic agent, a colorant (dye, pigment, etc.), a filler, a lubricant, an anti-blocking agent, or the like may be blended as needed. The amount of the additive to be added is not particularly limited, and can be appropriately set depending on the use of the adhesive sheet or the like.

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 method for producing the resin film is not particularly limited. For example, a conventionally known general resin film forming method such as extrusion molding, inflation molding, T-die casting, and calender roll molding can be suitably employed.

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 be an auxiliary layer other than the resin film. Examples of the auxiliary layer include a printing layer or a laminate layer for imparting a desired appearance to an optical property adjustment layer (for example, a coloring layer or an antireflection layer), a support or an adhesive sheet, and an antistatic layer. A surface treatment layer such as an undercoat layer or a release layer. Further, the support member may be an optical member described below.

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 may be selected depending on the purpose of use of the adhesive sheet or the state of use. 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 Below μm, it may be 5 μm or less. When the thickness of the support is small, the flexibility of the adhesive sheet or the followability to the surface shape of the adherend tends to increase. Further, the thickness of the support may be, for example, 2 μm or more, or may exceed 5 μm or exceed 10 μm from the viewpoints of workability and workability. In some aspects, the thickness of the support may be, for example, 20 μm or more, or may be 35 μm or more, or may be 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。Corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, primer coating, antistatic treatment may be performed on the side of the support bonded to the side of the adhesive layer. Such as previously known surface treatments. Such a surface treatment may be a treatment for improving the adhesion between the support and the adhesive layer, in other words, the adhesion of the adhesive layer to the support. The composition of the primer is not particularly limited and may be appropriately selected from those skilled in the art. The thickness of the undercoat 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 opposite to the side to which the adhesive layer is bonded (hereinafter, also referred to as the back surface) may be subjected to a conventionally known surface treatment such as a peeling treatment, an adhesion property, an adhesion improving treatment, or an antistatic treatment. . For example, by subjecting the back surface of the support to a surface treatment by a release treatment agent, the unwinding force of the adhesive sheet wound in a roll form can be reduced. As the release treatment agent, a polyfluorene-based release treatment agent, a long-chain alkyl release treatment agent, an olefin-based release treatment agent, a fluorine-based release treatment agent, a fatty acid amide-based release treatment agent, molybdenum sulfide, and cerium oxide can be used. Powder and so on.

＜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) an adhesive composition to a suitable surface and then performing a curing treatment. In the case where two or more kinds of hardening treatments (drying, crosslinking, polymerization, etc.) are carried out, these may be carried out simultaneously or in multiple stages. In the adhesive composition using a partial polymer (acrylic polymer slurry) of a monomer component, the final copolymerization reaction is typically carried out as the above-mentioned hardening treatment. That is, a portion of the polymer is supplied to a further copolymerization reaction to form a complete polymer. For example, in the case of a photocurable adhesive composition, light irradiation is performed. Hardening treatment such as cross-linking and drying may also be carried out as needed. For example, when it is necessary to dry with a photocurable adhesive composition, photocuring can be performed after drying. In the adhesive composition using a complete polymer, for example, drying (heat drying), crosslinking, or the like is performed as the above-described hardening treatment. Two or more layers of the adhesive layer of the multilayer construction can be produced by laminating a preformed adhesive layer. Alternatively, the adhesive composition may be applied to the preformed first adhesive layer to harden the adhesive composition to form a 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。For the application of the adhesive composition, for example, a gravure roll coater, a reverse roll coater, a contact roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater can be used. It is implemented by a conventional coating machine. In the adhesive sheet having the form of the support, as a method of providing the adhesive layer on the support, a direct method in which the adhesive composition is directly applied to the support to form an adhesive layer can be used, and the adhesive layer can be formed. The transfer method of transferring the adhesive layer on the release surface 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, and may be, for example, about 3 μm to 1000 μm. From the viewpoint of adhering the adhesive layer to the adherend to improve water resistance reliability, the thickness of the adhesive layer may be, for example, 5 μm or more, or 10 μm or more, or 20 μm in some aspects. The above may be 30 μm or more, 50 μm or more, or may be more than 50 μm, 70 μm or more, 100 μm or more, or 120 μm or more. Further, from the viewpoint of preventing the occurrence of the paste residue due to the aggregation failure of the adhesive layer, the thickness of the adhesive layer may be, for example, 500 μm or less, or 300 μm or less, or 200. Below μm, it can be 170 μm or less. The technique disclosed herein can also be preferably applied to an adhesive sheet having a thickness of the adhesive layer of 130 μm or less, 90 μm or less, 60 μm or less, or 40 μm or less. Further, 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 pressure-sensitive adhesive layer is thick, it is generally difficult to achieve both water repellency and water resistance reliability. From this point of view, in the case where the thickness of the adhesive layer is, for example, more than 50 μm, it is preferable to use a structure in which the adhesive layer contains the A layer and the B layer. According to the adhesive layer having such a configuration, even if the pressure-sensitive adhesive layer is thick, it is easy to obtain an adhesive sheet which has a high level of water-repellent property and water-resistant reliability.

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 aspect in which the adhesive layer includes the A layer and the B layer, the thickness of the A layer may be, for example, 1 μm or more, or 2 μm or more, or 4 μm or more, or 5 μm or more. 10 μm or more, or 15 μm or more. Further, the thickness of the layer A may be, for example, 50 μm or less, or 45 μm or less, or 35 μm or less, or 25 μm or less. In particular, in the case of having the layer A formed of the water-dispersed adhesive component or the layer A containing the water affinity agent, the thickness of the layer A is not excessively large, and the water resistance reliability of the adhesive sheet is improved and adhered. 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 aspect in which the adhesive layer includes the A layer and the B layer, the thickness of the B layer may be, for example, 5 μm or more, or 10 μm or more. In view of the effect of providing the B layer on the back side of the layer A, the thickness of the layer B may be, for example, 20 μm or more, or 30 μm or more. It can 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 aspect in which the adhesive layer includes the A layer and the B layer, the thickness of the A layer occupied by the entire thickness of the adhesive layer may be, for example, 90% or less, usually preferably 70% or less, or 50%. Hereinafter, it may be 30% or less, 20% or less, or 15% or less. Further, in view of the ease of formation of the A layer or the water releasability of the adhesive sheet, the thickness of the A layer occupied by the thickness of the entire adhesive layer may be, for example, 3% or more in some aspects. It may be 5% or more, or may be 7% or more, or may be 10% or more.

＜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。<Peeling method>
According to the present specification, there is provided a peeling method of an adhesive sheet attached to a polarizing plate as an adherend. The peeling method includes a water peeling step of causing the aqueous liquid to follow while the adhesive sheet is in an aqueous liquid at the interface between the adherend and the adhesive sheet from the peeling front line of the adherend. The adhesive sheet is peeled off from the adherend while the movement of the peeling front line enters the interface. According to the water stripping step described above, the adhesive sheet can be effectively peeled off from the polarizing plate as the adherend by the aqueous liquid. As the aqueous liquid, those which are used in water or a mixed solvent containing water as a main component may optionally contain a small amount of an additive. As the solvent other than the water constituting the mixed solvent, a lower alcohol (for example, ethanol) or a lower ketone (for example, acetone) which can be uniformly mixed with water can be used. As the above additive, a known surfactant or the like can be used. From the standpoint of avoiding contamination by the adherend, in some aspects, an aqueous liquid substantially free of additives can be preferably used. In terms of environmental sanitation, it is especially preferred to use water as the aqueous liquid. The water is not particularly limited, and for example, distilled water, ion-exchanged water, tap water, or the like can be used depending on the purity required for use, availability, and the like.

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 peeling method can be preferably carried out, for example, in the same manner as in the measurement of the water peeling force N2, in the vicinity of the outer edge of the adhesive sheet attached to the adherend. The aqueous liquid is supplied to the body so that the aqueous liquid enters the interface between the adhesive sheet and the adherend after the outer edge of the adhesive sheet, and no new water supply is performed (that is, only the supply before the peeling starts) Peeling of the adhesive sheet is carried out to the aqueous liquid on the adherend. Further, if the water entering the interface between the adhesive sheet and the adherend is depleted in the middle of the water stripping step, the water entering the interface between the adhesive sheet and the adherend may be intermittently stopped after the start of the water stripping step. Or continuously supply water. For example, in the case where the adherend has water absorbing property, or the case where the aqueous liquid is easily left on the surface or the adhesive surface of the adherend after peeling, it is preferable to additionally apply the water supply 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 the aqueous liquid to be supplied before the start of the peeling is not particularly limited as long as the aqueous liquid is introduced into the interface between the adhesive sheet and the adherend in addition to the adhesion range of the self-adhesive sheet. The amount of the aqueous liquid may be, for example, 5 μl or more, and usually 10 μl or more, or 20 μl or more. Further, the upper limit of the amount of the above aqueous liquid is not particularly limited. In some aspects, the amount of the aqueous liquid may be, for example, 10 ml or less, or 5 ml or less, or 1 ml or less, or 0.5 ml or less, from the viewpoint of improvement in workability, and the like. It is 0.1 ml or less, and may be 0.05 ml or less. By reducing the amount of the above aqueous liquid, the operation of removing the aqueous liquid by drying or wiping or the like after peeling of 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。The operation of allowing the aqueous liquid to enter the interface between the adhesive sheet and the adherend at the beginning of the peeling may be performed, for example, by inserting a cut at the outer edge of the adhesive sheet. The tip of the jig, such as a knife or a needle, is scraped by a hook or a nail, and the outer edge of the sheet is scraped and lifted, and a strong adhesive tape or a suction cup is attached to the back surface near the outer edge of the adhesive sheet to lift the adhesive. The end of the sheet, etc. By for example, the aqueous liquid is forcibly introduced into the interface from the outer edge of the adhesive sheet, and the aqueous liquid can be efficiently formed in the interface between the adherend and the adhesive sheet. Further, it is preferable to achieve both good water releasability after the start of peeling from the operation of forcibly entering the aqueous liquid, and high water resistance reliability when the 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 contains an adhesive layer, and the layer A of at least the surface constituting the polarizing plate side of the adhesive layer is composed of an adhesive containing a water affinity agent. The above adhesive sheet is preferably, for example, any of the adhesive sheets disclosed herein. Therefore, the above peeling method is suitable as a peeling method for any of the adhesive sheets 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。The water stripping step of several aspects can be preferably carried out in a state in which the peeling front line is moved at a speed of 10 mm/min or more. The case where the peeling front thread is moved at a speed of 10 mm/min or more corresponds to, for example, the peeling of the adhesive sheet at a stretching speed of 20 mm/min or more under the condition of 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 herein, the adhesive sheet is peeled off from the adherend while allowing the aqueous liquid to enter the interface, and a good water can be exhibited even at such a relatively high peeling speed. Peelability. The upper limit of the speed at which the peeling front line is moved is not particularly limited. 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, for example, the peeling area of the adhesive sheet per 10 μl of the volume of the aqueous liquid (for example, water) used in the method is, for example, 50 cm 2 or more, preferably 100 cm 2 or more. Implemented in the middle.
[Examples]

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。In the following, several embodiments relating to the invention are described, but are not intended to limit the invention to those shown in this embodiment. In the following description, "parts" and "%" are based on weight unless otherwise specified.

＜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 acrylic acid in a weight ratio of 80/35/5/30. 100 parts of a monomer mixture of decyl ester (IBXA), and a trade name of a photopolymerization initiator: Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.05 parts and trade name: Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.05 parts were placed in a four-necked flask, and ultraviolet rays were irradiated under a nitrogen atmosphere until the viscosity (BH viscosity meter, No. 5 rotor, 10 rpm, measurement temperature: 30° C.) was about 15 Pa·s, and photopolymerization was carried out. A monomer slurry comprising a portion of the polymer of the above monomer mixture.
To 100 parts of the monomer slurry, 0.13 parts of 1,6-hexanediol diacrylate (HDDA) and 0.33 parts of a photopolymerization initiator (trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added and uniformly The mixture was mixed to prepare an 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, 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503), 0.02 parts, 0.048 parts of a third-dodecyl mercaptan as a chain transfer agent and 2.0 parts of an emulsifier (manufactured by Kao Corporation, Latemul E-118B) were mixed and emulsified in 100 parts of ion-exchanged water to prepare a monomer mixture. Aqueous emulsion (monomer emulsion).
The monomer emulsion was placed in 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 1 hour or more while introducing nitrogen gas. Then, the system was heated to 60 ° C, and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate was added as a polymerization initiator (Wako Pure Chemical Industries Co., Ltd.) 0.1 part of VA-057) was produced and reacted at 60 ° C for 6 hours to obtain an aqueous dispersion of an acrylic polymer.
After the system was cooled to room temperature, the solid content of the aqueous dispersion of the acrylic polymer was added to the adhesive component of 30 parts by weight of the solid content component (April Chemical Co., Ltd., SUPER ESTER E-865NT, softened). An aqueous dispersion of a polymerized rosin ester at 160 ° C). Further, an emulsion type adhesive was prepared by using 10% aqueous ammonia as a pH adjuster and polyacrylic acid (an aqueous solution having a nonvolatile content of 36%) as a tackifier to adjust to a pH of about 7.5 and a viscosity of about 9 Pa·s. 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 sheet)
The release film R1 (Mitsubishi Resin Co., Ltd., MRF #38) having a thickness of 38 μm on the one side of the polyester film was applied with the adhesive composition U-1, and the one side of the coated polyester film was a release surface. The release film R2 (Mitsubishi Resin Co., Ltd., MRE #38) having a thickness of 38 μm was formed by blocking air and irradiating it with ultraviolet rays to form an adhesive layer B1 having a thickness of 130 μm. Then, the release film R2 covering the adhesive layer B1 was peeled off, and a corona-treated polyethylene terephthalate (PET) film having a thickness of 75 μm was attached thereto, thereby obtaining a PET film (support) and an adhesive. The layer B1 and the release film R1 are sequentially laminated to form a laminated sheet.
The adhesive composition E-1 was applied to the release film R1 (Mitsubishi Resin Co., Ltd., MRF #38), and dried at 120 ° C for 3 minutes to form an adhesive layer A1 having a thickness of 20 μm. The release film R1 covering the adhesive layer B1 of the laminated sheet is peeled off, and the adhesive layer A1 is bonded thereto, thereby obtaining an adhesive having a two-layer structure in which the adhesive layer B1 and the adhesive layer A1 are directly contacted and laminated. An adhesive sheet S1 composed of a PET film (support) is bonded to the surface of the adhesive layer in the B1 layer side. The surface of the A1 layer side of the adhesive sheet is protected by a 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。(made by the adhesive body)
A solution obtained by dissolving an ultraviolet curable resin monomer or oligomer having a urethane acrylate as a main component in butyl acetate (manufactured by DIC, trade name "UNIDIC 17-806", solid type) In the concentration of the component (80%), 5 parts of a photopolymerization initiator (manufactured by Ciba Japan Co., Ltd., product name "IRGACURE 906") and a leveling agent (DIC) were added per 100 parts of the solid content of the solution. ) Manufacturing, product name "GRANDIC PC4100") 0.03 parts. Thereafter, butyl acetate was added to the solution to adjust the solid content concentration to 75%, and further cyclopentanone (hereinafter referred to as "CPN") was added to adjust the solid content concentration to 50%. A hard coat forming material for forming a hard coat layer was produced in this manner. When the total amount of the hard coat layer forming material is set to 1, the content ratio (mass ratio) of the good solvent (CPN) in the hard coat layer forming material is 0.33. The ultraviolet curable resin monomer or oligomer contained in the hard coat layer forming material is a mixture of urethane acrylates of various molecular weights, and the total amount of the above ultraviolet curable resin monomers or oligomers In the case of 1st, the content ratio (mass ratio) of the low molecular weight component (herein, the ultraviolet curable resin monomer or oligomer having a molecular weight of 800 or less) is 0.482.
The hard coat layer forming material was applied to a transparent TAC film (manufactured by Fuji Film Co., Ltd., product name "TD80UL", thickness: 80 μm, refractive index: 1.49) using a die 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) was 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 coating film was irradiated with ultraviolet rays having a cumulative light amount of 300 mJ/cm 2 using a high-pressure mercury lamp to polymerize the resin monomer. A hard coat layer was formed on the TAC film in this manner. The inherent refractive index of the hard coat layer was 1.53.
Then, a material for forming an antireflection layer shown below was uniformly applied to the entire surface of the above hard coat layer using a die coater. The coating film was heated at 90 ° C for 2 minutes, and cured by ultraviolet irradiation to form an antireflection layer having a thickness of 0.1 μm on the entire surface of the hard coat layer. The antireflection layer has a refractive index of 1.38. The material for forming the antireflection layer is a low refractive material (manufactured by JSR Co., Ltd., trade name "JUA204". The solid content concentration is 9.5%), and methyl isobutyl ketone (MIBK) and third butanol are added. The mixed solvent of TBA) (MIBK: TBA = 50:50) was diluted and adjusted to a solid content 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 having a hollow nano-cerium oxide of about 50% with respect to the active ingredient.
In this way, the TAC film F1 having the surface of the hard coat layer and the antireflection layer laminated in this order was obtained. The surface of the TAC film F1 (attached surface) was subjected to corona treatment under the above conditions, and 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, the normal adhesion force N0, the water-resistant adhesion force N1, and the water peeling force N2 of the layer A side of the adhesive sheet S1 were measured by the above method. The time from the corona treatment of the attached surface to the attachment of the adhesive sheet S1 is set to be within 30 minutes. Based on the obtained measured values, the water-resistant adhesion reduction rate and the water-peeling adhesion 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 TAC film F1 was used without corona treatment on the surface (attached surface). In the same manner as in Example 1, the normal adhesion N0, the water-resistant adhesion N1, and the water-peeling force N2 of the layer A side of the adhesive sheet S1 were measured, and the water-resistant adhesion reduction rate and the water-peeling adhesion reduction rate were 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 the case of using the corona-treated adherend, the adhesive sheet S1 having a low water-resistant adhesive reduction rate can be easily adhered to the adhesive sheet S1 by using a small amount of water. Stripping. On the other hand, in Example 2 in which the adherend without corona treatment was used, the adhesive sheet S1 had a low rate of water peeling adhesion reduction, and it 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。The specific examples of the present invention have been described in detail above, but these are merely illustrative and are not intended to limit the scope of the application. The technology described in the patent application scope includes various changes and modifications of the specific examples described above.

1、2‧‧‧黏著片材1, 2‧‧‧Adhesive sheets

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‧‧‧ a surface (adhesive surface, surface on the polarizing plate side)

10B‧‧‧另一表面 10B‧‧‧Other surface

20‧‧‧支持體 20‧‧‧Support

20A‧‧‧第一面 20A‧‧‧ first side

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

70‧‧‧構件(偏光板) 70‧‧‧ components (polarizer)

110‧‧‧黏著劑層 110‧‧‧Adhesive layer

110A‧‧‧一表面(黏著面、偏光板側之表面) 110A‧‧‧ a surface (adhesive surface, surface on the polarizing plate side)

112‧‧‧A層 112‧‧‧A floor

114‧‧‧B層 114‧‧‧B layer

200‧‧‧附黏著片材之構件 200‧‧‧Members with adhesive sheets

圖1係模式性地表示黏著片材之構成之剖視圖。Fig. 1 is a cross-sectional view schematically showing the constitution of an adhesive sheet.

圖2係模式性地表示另一黏著片材之構成之剖視圖。 Fig. 2 is a cross-sectional view schematically showing the constitution of another adhesive sheet.

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. 3 is a cross-sectional view schematically showing a member to which an adhesive sheet is attached by attaching another adhesive sheet to a member.

Claims (4)

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 containing an A layer constituting at least the surface of the polarizer side of the adhesive layer. The surface of the polarizing plate to which the side of the adhesive sheet is attached is subjected to corona treatment or plasma treatment. The adhesive sheet peeling method includes a water peeling step of causing the aqueous liquid to be present while the adhesive sheet has an aqueous liquid at an interface between the polarizing plate and the adhesive sheet at a peeling front line of the polarizing plate. The adhesive sheet is peeled off from the polarizing plate while following the movement of the peeling front line and entering the interface. 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10 mm/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 thread 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層包含水親和劑。The adhesive sheet peeling method of claim 1 or 2, wherein the layer A comprises a water affinity agent. 如請求項1至3中任一項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。The adhesive sheet peeling method according to any one of claims 1 to 3, wherein the layer A is water-insoluble and non-water-swellable.
TW108103779A 2018-02-05 2019-01-31 Adhesive sheet peeling method TWI811296B (en)

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JP2018126577A JP7283867B2 (en) 2018-02-05 2018-07-03 Adhesive sheet peeling method
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