TWI786232B - Temperature-sensitive adhesive sheet and laminate - Google Patents

Temperature-sensitive adhesive sheet and laminate Download PDF

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TWI786232B
TWI786232B TW107142200A TW107142200A TWI786232B TW I786232 B TWI786232 B TW I786232B TW 107142200 A TW107142200 A TW 107142200A TW 107142200 A TW107142200 A TW 107142200A TW I786232 B TWI786232 B TW I786232B
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temperature
adhesive
adhesive layer
sensitive adhesive
adhesive sheet
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TW107142200A
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TW201938734A (en
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小鯖翔
荒井隆行
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日商琳得科股份有限公司
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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J11/08—Macromolecular 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

〔課題〕提供一種即便應用在可撓性裝置，操作性亦優異之溫度敏感性黏著片、及使用該溫度敏感性黏著片之積層體。 〔解決手段〕提供一種溫度敏感性黏著片1，其為至少包括黏著劑層11之溫度敏感性黏著片1，在-20℃之對玻璃黏著力為小於1.5N/25mm，在80℃之對玻璃黏著力為2.0N/25mm以上，黏著劑層11在-20℃之儲存模數為1MPa以上且500MPa以下。[Problem] To provide a temperature-sensitive adhesive sheet excellent in handleability even when applied to a flexible device, and a laminate using the temperature-sensitive adhesive sheet. [Solution] A temperature-sensitive adhesive sheet 1 is provided, which is a temperature-sensitive adhesive sheet 1 including at least an adhesive layer 11, the adhesion to glass at -20°C is less than 1.5N/25mm, and the adhesion to glass at 80°C is The glass adhesive force is 2.0 N/25 mm or more, and the storage modulus of the adhesive layer 11 at -20° C. is 1 MPa or more and 500 MPa or less.

Description

溫度敏感性黏著片及積層體Temperature-sensitive adhesive sheet and laminate

本發明是有關於一種適合於工件的固定及剝離之溫度敏感性黏著片及使用該溫度敏感性黏著片之積層體。The present invention relates to a temperature-sensitive adhesive sheet suitable for fixing and peeling workpieces and a laminate using the temperature-sensitive adhesive sheet.

在作為被加工物(工件)之光學構件、電子構件等的裝置，在加工、裝配(層積)、檢查等的步驟中，透過黏著片的黏著劑層而進行將該裝置固定在基板(底座)。然後，步驟結束後，將上述工件從基板剝離。In devices such as optical components and electronic components that are workpieces (workpieces), in the steps of processing, assembly (lamination), inspection, etc., the device is fixed to the substrate (base) through the adhesive layer of the adhesive sheet. ). Then, after the step is completed, the above-mentioned workpiece is peeled off from the substrate.

作為被使用在如上述的黏著片之黏著劑，例如，專利文獻1揭示一種含有側鏈結晶性聚合物之溫度敏感性黏著劑，其由將金屬螯合化合物添加在使丙烯酸十八酯、丙烯酸甲酯及丙烯酸聚合而得到之共聚物、或使丙烯酸二十二酯、丙烯酸甲酯及丙烯酸聚合得到的共聚物中且進行交聯反應而得到的交聯聚合物所構成。As an adhesive used in the above-mentioned adhesive sheet, for example, Patent Document 1 discloses a temperature-sensitive adhesive containing a side-chain crystalline polymer, which consists of adding a metal chelate compound to stearyl acrylate, acrylic acid A copolymer obtained by polymerizing methyl ester and acrylic acid, or a cross-linked polymer obtained by polymerizing behenyl acrylate, methyl acrylate and acrylic acid and performing a cross-linking reaction.

又，專利文獻2揭示一種溫度敏感性黏著劑，其含有：使具有16~22的直鏈狀烷基之(甲基)丙烯酸酯、具有碳數1~6的烷基之(甲基)丙烯酸酯、具有羧基或羥基之乙烯不飽和單體、及反應性氟化合物聚合而得到的共聚物，使用金屬螯合化合物交聯而成之側鏈結晶體聚合物；及黏著賦予劑。In addition, Patent Document 2 discloses a temperature-sensitive adhesive containing (meth)acrylate having a linear alkyl group of 16 to 22, and (meth)acrylic acid having an alkyl group having 1 to 6 carbon atoms. Copolymer obtained by polymerization of ester, ethylenically unsaturated monomer with carboxyl group or hydroxyl group, and reactive fluorine compound, side chain crystalline polymer crosslinked by metal chelate compound; and adhesion imparting agent.

使用專利文獻1揭示之溫度敏感性黏著劑時，在高溫環境下，藉由該黏著劑發揮之黏著力而能夠將被黏著物固定，另一方面，藉由冷卻而黏著力降低且能夠將被黏著物剝離。而且，使用專利文獻2揭示之溫度敏感性黏著劑時，在通常的步驟中之環境溫度下，藉由該黏著劑發揮之黏著力而能夠將被黏著物固定，另一方面，藉由冷卻而黏著力降低且能夠將被黏著物剝離。 [先前技術文獻] [專利文獻]When the temperature-sensitive adhesive disclosed in Patent Document 1 is used, in a high-temperature environment, the adherend can be fixed by the adhesive force exerted by the adhesive. On the other hand, the adhesive force can be lowered by cooling and the adherend can be fixed. Adhesives peel off. Furthermore, when the temperature-sensitive adhesive disclosed in Patent Document 2 is used, the adherend can be fixed by the adhesive force exerted by the adhesive at the ambient temperature in the usual steps, and on the other hand, it can be fixed by cooling. The adhesive force is reduced and the adherend can be peeled off. [Prior Art Literature] [Patent Document]

[專利文獻1]日本特許第5600604號公報 [專利文獻2]日本特許第6109932號公報[Patent Document 1] Japanese Patent No. 5600604 [Patent Document 2] Japanese Patent No. 6109932

[發明欲解決之課題][Problem to be solved by the invention]

先前就上述裝置而言，以硬質物為多，但是近年來，出現可撓性裝置。例如，最近就光學構件而言，從硬質的液晶裝置過度至可撓性有機發光二極體(OLED；Organic Light-Emitting Diode)裝置之動態變得活躍。因而，即便作為黏著片亦需要對應此種可撓性裝置。In the past, the above-mentioned devices were mostly hard objects, but in recent years, flexible devices have appeared. For example, recently, in terms of optical components, the transition from rigid liquid crystal devices to flexible organic light-emitting diode (OLED; Organic Light-Emitting Diode) devices has become active. Therefore, it is necessary to correspond to such a flexible device even as an adhesive sheet.

但是將專利文獻1及2揭示的溫度敏感性黏著劑，應用在如上述的可撓性裝置時，針對固定及剝離之操作性，難以稱得上充分。However, when the temperature-sensitive adhesives disclosed in Patent Documents 1 and 2 are applied to the above-mentioned flexible device, it is difficult to say that the operability of fixing and peeling is sufficient.

本發明鑒於上述的情形而進行，其目的提供一種即便應用在可撓性裝置，操作性亦優異之溫度敏感性黏著片、及使用該溫度敏感性黏著片之積層體。 [用以解決課題之手段]The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a temperature-sensitive adhesive sheet excellent in handleability even when applied to a flexible device, and a laminate using the temperature-sensitive adhesive sheet. [Means to solve the problem]

為了達成上述目的，本發明第1提供一種溫度敏感性黏著片，其為至少包括黏著劑層之溫度敏感性黏著片，其特徵在於：在-20℃之對玻璃黏著力為小於1.5N/25mm，在80℃之對玻璃黏著力為2.0N/25mm以上，前述黏著劑層在-20℃之儲存模數為1MPa以上且500MPa以下(發明1)。In order to achieve the above object, the present invention firstly provides a temperature-sensitive adhesive sheet, which is a temperature-sensitive adhesive sheet including at least an adhesive layer, and is characterized in that: the adhesive force to glass at -20°C is less than 1.5N/25mm , the adhesion to glass at 80°C is above 2.0N/25mm, and the storage modulus of the adhesive layer at -20°C is above 1MPa and below 500MPa (Invention 1).

依照上述發明(發明1)，即便將該溫度敏感性黏著片應用在可撓性裝置時，針對固定及剝離的操作性亦優異。亦即，在常溫及高溫的步驟中，能夠將工件堅固地固定在基板，且能夠沒有問題地進行該步驟。又，將上述黏著劑層冷卻至低溫時，該黏著劑層的黏著力降低，藉此，能夠容易地將工件從基板剝離。According to the above invention (Invention 1), even when the temperature-sensitive adhesive sheet is applied to a flexible device, it is excellent in fixation and peeling operability. That is, in the normal-temperature and high-temperature steps, the workpiece can be firmly fixed to the substrate, and the steps can be performed without problems. In addition, when the above-mentioned adhesive layer is cooled to a low temperature, the adhesive force of the adhesive layer is lowered, whereby the workpiece can be easily peeled off from the substrate.

在上述發明(發明1)，其中在-20℃之對玻璃黏著力相對於在23℃之對玻璃黏著力之比，以1%以上且40%以下為佳(發明2)。In the above invention (Invention 1), the ratio of the adhesion to glass at -20°C to the adhesion to glass at 23°C is preferably 1% or more and 40% or less (Invention 2).

在上述發明(發明1、2)，其中在80℃之對玻璃黏著力相對於在23℃之對玻璃黏著力之比，以10%以上且300%以下為佳(發明3)。In the above inventions (Inventions 1 and 2), the ratio of the adhesion to glass at 80°C to the adhesion to glass at 23°C is preferably 10% or more and 300% or less (Invention 3).

在上述發明(發明1~3)，其中前述黏著劑層在80℃之儲存模數，以0.01MPa以上且1MPa以下為佳(發明4)。In the above inventions (Inventions 1 to 3), the storage modulus of the adhesive layer at 80°C is preferably 0.01 MPa or more and 1 MPa or less (Invention 4).

在上述發明(發明1~4)，較佳為其中前述黏著劑層由含有聚輪烷(polyrotaxane)化合物之黏著劑所構成(發明5)。In the above inventions (Inventions 1 to 4), preferably, the adhesive layer is formed of an adhesive containing a polyrotaxane compound (Invention 5).

在上述發明(發明5)，較佳為其中前述黏著劑由含有(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、及聚輪烷化合物(C)之黏著性組合物所形成(發明6)。In the above invention (Invention 5), it is preferable that the aforementioned adhesive is made of an adhesive composition containing a (meth)acrylate polymer (A), a crosslinking agent (B), and a polyrotaxane compound (C). Formation (Invention 6).

在上述發明(發明6)，較佳為其中前述(甲基)丙烯酸酯聚合物(A)含有在分子內具有羧基的單體作為構成該聚合物之單體單元(發明7)。In the above invention (Invention 6), it is preferable that the aforementioned (meth)acrylate polymer (A) contains a monomer having a carboxyl group in the molecule as a monomer unit constituting the polymer (Invention 7).

在上述發明(發明6、7)，其中前述交聯劑(B)以金屬螯合物系交聯劑為佳(發明8)。In the above inventions (Inventions 6 and 7), the aforementioned crosslinking agent (B) is preferably a metal chelate crosslinking agent (Invention 8).

在上述發明(發明1~8)之溫度敏感性黏著片，較佳為使用於步驟中透過前述黏著劑層而將工件固定在基板，且步驟結束後，將前述工件從前述黏著劑層剝離之用途(發明9)。The temperature-sensitive adhesive sheet of the above-mentioned inventions (Inventions 1-8) is preferably used in the step of fixing the workpiece on the substrate through the aforementioned adhesive layer, and after the step is completed, the aforementioned workpiece is peeled off from the aforementioned adhesive layer. Uses (Invention 9).

在上述發明(發明9)，其中在前述工件之前述黏著劑層側的面之表面粗糙度Ra，以0.01μm以上且80μm以下為佳(發明10)。In the above invention (Invention 9), the surface roughness Ra of the surface of the workpiece on the side of the adhesive layer is preferably 0.01 μm or more and 80 μm or less (Invention 10).

在上述發明(發明9、10)，其中在前述步驟中，工件亦可被加熱至40℃以上且200℃以下(發明11)。In the above inventions (Inventions 9, 10), wherein in the aforementioned step, the workpiece may also be heated to 40° C. or higher and 200° C. or lower (Invention 11).

在上述發明(發明9~11)，其中前述工件亦可為可撓性裝置(發明12)。In the above inventions (Inventions 9-11), the aforementioned workpiece can also be a flexible device (Invention 12).

在上述發明(發明1~12)，較佳為其中前述溫度敏感性黏著片包括2片剝離片，前述黏著劑層以與前述2片剝離片的剝離面接觸之方式而被前述剝離片挾持著(發明13)。In the above inventions (Inventions 1 to 12), preferably, the temperature-sensitive adhesive sheet includes two release sheets, and the adhesive layer is pinched by the release sheets so as to be in contact with the release surfaces of the two release sheets. (Invention 13).

本發明第2提供一種積層體，其係將可撓性裝置、前述溫度敏感性黏著片(發明1~13)的前述黏著劑層、及基板依此順序層積而成(發明14)。 [發明效果]The second aspect of the present invention provides a laminate, which is formed by laminating a flexible device, the aforementioned adhesive layer of the aforementioned temperature-sensitive adhesive sheet (Inventions 1 to 13), and a substrate in this order (Invention 14). [Invention effect]

本發明之溫度敏感性黏著片即便應用在可撓性裝置時，針對固定及剝離的操作性亦優異。又，本發明之積層體的操作性優異。Even when the temperature-sensitive adhesive sheet of the present invention is applied to a flexible device, it is excellent in fixation and peeling operability. In addition, the laminate of the present invention is excellent in handleability.

以下，說明本發明的實施形態。 本發明的一實施形態之溫度敏感性黏著片至少包括黏著劑層，較佳是將剝離片層積在黏著劑層的一面或兩面而成。Embodiments of the present invention will be described below. The temperature-sensitive adhesive sheet according to one embodiment of the present invention includes at least an adhesive layer, and is preferably formed by laminating a release sheet on one or both sides of the adhesive layer.

本實施形態之溫度敏感性黏著片，適合使用在加工、裝配(層積)、檢查等的步驟中，透過該溫度敏感性黏著片的黏著劑層而將作為被加工物(工件)之光學構件、電子構件等的裝置固定在基板。上述步驟結束後，將工件從基板剝離。又，上述基板是為了在步驟中支撐且固定工件之物，亦包含底座等的概念之物。The temperature-sensitive adhesive sheet of this embodiment is suitable for use in the steps of processing, assembly (lamination), inspection, etc., through the adhesive layer of the temperature-sensitive adhesive sheet, as the optical member of the workpiece (workpiece) , electronic components and other devices are fixed on the substrate. After the above steps are completed, the workpiece is peeled off from the substrate. In addition, the said board|substrate is what supports and fixes a workpiece|work in a process, and also includes concepts, such as a base.

作為工件，沒有特別限定，以具有柔軟性之光學構件、電子構件等的可撓性裝置為佳。又，作為工件，以在上述步驟中包含加熱步驟(例如，40℃以上且200℃以下的加熱步驟)之工件為佳。作為此種加熱步驟，可舉出，例如，用以形成透明電極的配線之金屬蒸鍍步驟、樹脂的硬化步驟等。從該等的觀點而言，作為工件，以，例如，可撓性有機發光二極體(OLED)裝置、可撓性液晶裝置等為佳，以可撓性OLED裝置為特佳。The workpiece is not particularly limited, but flexible devices such as optical members and electronic members having flexibility are preferable. In addition, as the workpiece, a workpiece including a heating step (for example, a heating step of 40° C. or higher and 200° C. or lower) among the above-mentioned steps is preferable. As such a heating process, the metal vapor deposition process for forming the wiring of a transparent electrode, the hardening process of resin, etc. are mentioned, for example. From these viewpoints, as a workpiece, for example, a flexible organic light emitting diode (OLED) device, a flexible liquid crystal device, etc. are preferable, and a flexible OLED device is particularly preferable.

又，作為基板，只要是工件能夠透過該溫度敏感性黏著片的黏著劑層而固定之物，就沒有特別限定，較佳為即便在上述步驟中亦包含金屬蒸鍍步驟、樹脂的硬化步驟等的加熱步驟，亦不產生變形或外觀變化之物。又，基板透過該溫度敏感性黏著片的黏著劑層而將工件貼合，在上述步驟中及將工件剝離之步驟，必須將黏著劑層與基板充分地固定。例如，基板表面粗糙時，基板與黏著劑層的密著性低落，在步驟中有產生黏著劑層從基板剝離掉的不良之情形。因此，基板的工件固定側之面以平滑為佳。從該等觀點而言，基板可舉出以玻璃基板為特佳。Also, the substrate is not particularly limited as long as the workpiece can be fixed through the adhesive layer of the temperature-sensitive adhesive sheet, and it is preferable to include a metal vapor deposition step, a resin hardening step, and the like even in the above-mentioned steps. The heating step does not produce deformation or change in appearance. In addition, since the substrate is attached to the workpiece through the adhesive layer of the temperature-sensitive adhesive sheet, the adhesive layer and the substrate must be sufficiently fixed in the above steps and the step of peeling off the workpiece. For example, when the surface of the substrate is rough, the adhesion between the substrate and the adhesive layer decreases, and the adhesive layer may be peeled off from the substrate during the process. Therefore, it is preferable that the surface of the substrate on the workpiece fixing side is smooth. From these viewpoints, a glass substrate is particularly preferable as the substrate.

本實施形態之溫度敏感性黏著片，在-20℃之對玻璃黏著力為小於1.5N/25mm，在80℃之對玻璃黏著力為2.0N/25mm以上。而且，本實施形態之溫度敏感性黏著片的黏著劑層，在-20℃之儲存模數(storage modulus)為1MPa以上且500MPa以下。藉由在-20℃及80℃之對玻璃黏著力以及在-20℃之儲存模數為上述之值，即便將該溫度敏感性黏著片應用在可撓性裝置時，針對固定及剝離的操作性亦優異。具體而言，在常溫及高溫步驟，藉由上述溫度敏感性黏著片之黏著劑層的黏著力，能夠將工件堅固地固定在基板，能夠沒有問題地進行該步驟。另一方面，將上述黏著劑層(或工件‧基板)冷卻至低溫(較佳為冷卻至-20℃附近)時，該黏著劑層的黏著力降低，藉此，能夠容易地將工件從基板剝離。The temperature-sensitive adhesive sheet of this embodiment has an adhesive force to glass of less than 1.5N/25mm at -20°C, and an adhesive force to glass of 2.0N/25mm or more at 80°C. Furthermore, the adhesive layer of the temperature-sensitive adhesive sheet of this embodiment has a storage modulus (storage modulus) at -20° C. of 1 MPa or more and 500 MPa or less. Since the adhesion to glass at -20°C and 80°C and the storage modulus at -20°C are the above values, even when this temperature-sensitive adhesive sheet is applied to a flexible device, it is suitable for fixing and peeling operations Sex is also excellent. Specifically, the work can be firmly fixed to the substrate by the adhesive force of the adhesive layer of the temperature-sensitive adhesive sheet in the normal temperature and high temperature steps, and this step can be performed without problems. On the other hand, when the above-mentioned adhesive layer (or workpiece‧substrate) is cooled to a low temperature (preferably cooled to around -20°C), the adhesive force of the adhesive layer is reduced, whereby the workpiece can be easily removed from the substrate. peel off.

在此，在本說明書之黏著力，基本上是指使用依據JIS Z0237：2009的180度剝下法所測定的黏著力，但是測定試樣設為25mm寬、100mm長，將該測定試樣貼附在被黏著物，於0.5MPa、50℃加壓20分鐘後，在常壓、所需要的溫度、50%RH的條件下放置24小時之後，以剝離速度2.0m/min進行測定。又，在本說明書之所謂「對玻璃黏著力」，是指對鈉鈣玻璃(soda lime glass)之黏著力。而且在本說明書之儲存模數的測定方法，如後述的試驗例所顯示。Here, the adhesive force in this specification basically refers to the adhesive force measured using the 180-degree peeling method in accordance with JIS Z0237:2009, but the measurement sample is set to 25mm wide and 100mm long, and the measurement sample is pasted Attached to the adherend, pressurize at 0.5MPa, 50°C for 20 minutes, leave it under the conditions of normal pressure, required temperature, and 50%RH for 24 hours, and measure it at a peeling speed of 2.0m/min. In addition, the "adhesion to glass" in this specification refers to the adhesion to soda lime glass. Furthermore, the method of measuring the storage modulus in this specification is as shown in the test examples described later.

作為應用本實施形態之溫度敏感性黏著片之工件，較佳為與該溫度敏感性黏著片的黏著劑層接觸之面為某種程度平滑之物。具體而言，在工件之上述黏著劑層側的面之表面粗糙度Ra，以80μm以下為佳，以40μm以下為特佳，進而以10μm以下為佳。如此工件的黏著劑層與接觸面為某種程度平滑時，前述工件固定時的密著性能夠更有效地發揮。As a workpiece to which the temperature-sensitive adhesive sheet of the present embodiment is applied, it is preferable that the surface in contact with the adhesive layer of the temperature-sensitive adhesive sheet is smooth to some extent. Specifically, the surface roughness Ra of the surface of the workpiece on the adhesive layer side is preferably 80 μm or less, particularly preferably 40 μm or less, and further preferably 10 μm or less. When the adhesive layer and the contact surface of the workpiece are smooth to some extent, the above-mentioned adhesiveness when fixing the workpiece can be more effectively exerted.

工件之上述黏著劑層側的面之表面粗糙度Ra的下限值，沒有特別限定，以0.01μm以上為佳，以0.1μm以上為佳，進而以1μm以上為佳。上述表面粗糙度Ra的下限值為上述時，前述工件固定時的密著性及工件剝離時易剝離性能夠更有效地發揮。而且，工件之上述黏著劑層側的面之表面粗糙度Ra，以比基板的表面粗糙度Ra更大為佳。藉此，工件剝離時能夠在黏著劑層堅固地固定在基板側之狀態下將工件剝離。The lower limit of the surface roughness Ra of the surface of the workpiece on the side of the adhesive layer is not particularly limited, but it is preferably 0.01 μm or more, more preferably 0.1 μm or more, and more preferably 1 μm or more. When the lower limit of the surface roughness Ra is the above, the adhesiveness at the time of fixing the work and the ease of peeling at the time of peeling the work can be exhibited more effectively. Furthermore, the surface roughness Ra of the surface of the workpiece on the side of the adhesive layer is preferably larger than the surface roughness Ra of the substrate. Thereby, when the workpiece is peeled off, the workpiece can be peeled off in a state where the adhesive layer is firmly fixed on the substrate side.

又，在本說明書之表面粗糙度Ra是依據JIS B0601：2001，且設為截止(cutoff)值λc=0.8mm、評價長度ln=10mm而所測得的值。In addition, the surface roughness Ra in this specification is based on JIS B0601:2001, and the value measured as cutoff (cutoff) value λc=0.8mm, evaluation length ln=10mm.

從上述的操作性，特別是工件的易剝離性之觀點而言，本實施形態之溫度敏感性黏著片在-20℃之對玻璃黏著力，以1.3N/25mm以下為佳，以1.0N/25mm以下為特佳。在-20℃之對玻璃黏著力的下限，從在將黏著劑層堅固地固定基板側之狀態下將工件剝離的觀點而言，以0.01N/25mm以上為佳，以0.1N/25mm以上為特佳。From the viewpoint of the above-mentioned operability, especially the ease of peeling of the workpiece, the temperature-sensitive adhesive sheet of this embodiment has an adhesive force to glass at -20°C, preferably 1.3N/25mm or less, and 1.0N/25mm or less. Below 25mm is especially good. The lower limit of the adhesion to glass at -20°C is preferably 0.01N/25mm or more, and 0.1N/25mm or more from the viewpoint of peeling off the workpiece with the adhesive layer firmly fixed to the substrate side. Excellent.

從上述操作性，特別是步驟中的工件固定之觀點而言，本實施形態之溫度敏感性黏著片在80℃之對玻璃黏著力為2.0N/25mm以上，以2.2N/25mm以上為佳，以2.8N/25mm以上為特佳。在80℃之對玻璃黏著力的下限值為上述時，即便在步驟中包含加熱步驟，亦能夠抑制在步驟中工件產生位置偏移或剝離等，且能夠將工件充分地固定。另一方面，在80℃之對玻璃黏著力的上限值，沒有特別限定，以70N/25mm以下為佳，以40N/25mm以下為特佳，進而以20N/25mm以下為佳。From the viewpoint of the above-mentioned operability, especially the fixation of the workpiece in the process, the temperature-sensitive adhesive sheet of this embodiment has an adhesive force to glass of 2.0N/25mm or more at 80°C, preferably 2.2N/25mm or more. Above 2.8N/25mm is especially good. When the lower limit of the adhesive force to glass at 80° C. is as above, even if a heating step is included in the process, it is possible to suppress the positional displacement or peeling of the workpiece during the process, and to sufficiently fix the workpiece. On the other hand, the upper limit of the adhesion to glass at 80°C is not particularly limited, but is preferably 70N/25mm or less, particularly preferably 40N/25mm or less, and more preferably 20N/25mm or less.

又，從上述操作性，特別是步驟中的工件固定之觀點而言，本實施形態之溫度敏感性黏著片在23℃之對玻璃黏著力，以2.0N/25mm以上為佳，以2.8N/25mm以上為特佳，進而以3.4N/25mm以上為佳。另一方面，在23℃之對玻璃黏著力之上限值，從再加工(rework)性的觀點而言，以30N/25mm以下為佳，以15N/25mm以下為特佳，進而以10N/25mm以下為佳。Also, from the viewpoint of the above-mentioned operability, especially the fixation of the workpiece in the process, the temperature-sensitive adhesive sheet of this embodiment preferably has an adhesive force to glass at 23°C of 2.0N/25mm or more, and preferably 2.8N/25mm. More than 25mm is particularly good, and more preferably 3.4N/25mm or more. On the other hand, the upper limit of the adhesion to glass at 23°C is preferably 30N/25mm or less, particularly preferably 15N/25mm or less, and 10N/25mm or less from the viewpoint of reworkability. Below 25mm is better.

在本實施形態之溫度敏感性黏著片，在-20℃之對玻璃黏著力相對於在23℃之對玻璃黏著力之比，以1%以上為佳，以5%以上為特佳，進而以10%以上為佳。若上述黏著力之比的下限值為上述，則冷卻至低溫而將工件剝離時，能夠防止在基板與黏著劑的界面產生浮起、剝落。又，上述黏著力之比，以40%以下為佳，以35%以下為特佳，進而以30%以下為佳。若上述黏著力之比的上限值為上述，則冷卻至低溫時，黏著力為充分地較低，且工件的剝離性更優異。因而，藉由上述黏著力之比在上述範圍內，工件固定時的密著性與工件易剝離性之並存變的更優異。In the temperature-sensitive adhesive sheet of this embodiment, the ratio of the adhesive force to glass at -20°C to the adhesive force to glass at 23°C is preferably 1% or more, particularly preferably 5% or more, and furthermore More than 10% is better. If the lower limit of the ratio of the adhesive force is the above, when the workpiece is cooled to a low temperature and the workpiece is peeled off, it is possible to prevent the occurrence of floating and peeling at the interface between the substrate and the adhesive. Moreover, the ratio of the above-mentioned adhesive force is preferably at most 40%, particularly preferably at most 35%, and further preferably at most 30%. If the upper limit value of the ratio of the said adhesive force is the above-mentioned, when cooling to low temperature, adhesive force will be sufficiently low, and the peelability of a workpiece|work will be more excellent. Therefore, when the ratio of the above-mentioned adhesive force is within the above-mentioned range, the coexistence of the adhesiveness at the time of fixing the workpiece and the ease of peeling the workpiece becomes more excellent.

又，在本實施形態之溫度敏感性黏著片，在80℃之對玻璃黏著力相對於在23℃之對玻璃黏著力之比，以10%以上為佳，以30%以上為特佳。進而50%以上為佳。上述黏著力之比的下限值為上述時，特別是即便在步驟中包含加熱步驟，因為黏著力不會過度降低，所以能夠防止步驟中工件產生位置偏移、剝離等，且能夠將工件更充分地固定。又，上述黏著力之比的上限值，沒有特別限定，以300%以下為佳，以200%以下為特佳，進而以100%以下為佳。因而，藉由上述黏著力之比在上述範圍內，在常溫的工件固定及在高溫的工件固定之任一者均能夠更良好地進行。In addition, in the temperature-sensitive adhesive sheet of this embodiment, the ratio of the adhesive force to glass at 80°C to the adhesive force to glass at 23°C is preferably at least 10%, particularly preferably at least 30%. Further more than 50% is preferred. When the lower limit of the ratio of the above-mentioned adhesive force is as above, especially even if a heating step is included in the process, since the adhesive force does not decrease excessively, it is possible to prevent the workpiece from being shifted, peeled off, etc. fully fixed. In addition, the upper limit of the above-mentioned adhesive force ratio is not particularly limited, but is preferably 300% or less, particularly preferably 200% or less, and further preferably 100% or less. Therefore, when the ratio of the above-mentioned adhesive force is within the above-mentioned range, either the work fixing at room temperature or the work fixing at high temperature can be performed more favorably.

本實施形態之溫度敏感性黏著片在-20℃之對表面粗糙度Ra為2.7μm(表面非常平滑)之聚對苯二甲酸乙二酯(PET)膜之黏著力，以1.2N/25mm以下為佳，以1.0N/25mm以下為特佳，進而以0.8N/25mm以下為佳。藉此，在工件的表面狀態與上述PET膜同等的情況，將上述黏著劑層(或工件‧基板)冷卻至低溫(較佳為冷卻至-20℃附近)時，能夠更容易地將工件從黏著劑層剝離。另一方面，上述黏著力的下限值，沒有特別限定，以0.01N/25mm以上為佳，以0.05N/25mm以上為特佳，進而以0.1N/25mm以上為佳。The temperature-sensitive adhesive sheet of this embodiment has an adhesive force of 1.2N/25mm or less to a polyethylene terephthalate (PET) film with a surface roughness Ra of 2.7μm (very smooth surface) at -20°C Preferably, it is especially preferably not more than 1.0N/25mm, and more preferably not more than 0.8N/25mm. Thereby, when the surface state of the workpiece is equal to the above-mentioned PET film, when the above-mentioned adhesive layer (or workpiece‧substrate) is cooled to a low temperature (preferably cooled to around -20°C), the workpiece can be more easily removed from the substrate. Adhesive layer peeled off. On the other hand, the lower limit of the adhesive force is not particularly limited, but it is preferably at least 0.01 N/25 mm, particularly preferably at least 0.05 N/25 mm, and more preferably at least 0.1 N/25 mm.

又，本實施形態之溫度敏感性黏著片在-20℃之對表面粗糙度Ra為60μm(表面相對較平滑)之PET膜之黏著力，以1.0N/25mm以下為佳，以0.8N/25mm以下為特佳，進而以0.6N/25mm以下為佳。藉此，在工件的表面狀態與上述PET膜同等的情況，將上述黏著劑層(或工件‧基板)冷卻至低溫(較佳為冷卻至-20℃附近)時，能夠容易地將工件從黏著劑層剝離。另一方面，上述黏著力的下限值，沒有特別限定，以0.01N/25mm以上為佳，以0.05N/25mm以上為佳，進而以0.1N/25mm以上為佳。Also, the temperature-sensitive adhesive sheet of this embodiment has an adhesive force of 1.0N/25mm or less to a PET film with a surface roughness Ra of 60μm (the surface is relatively smooth) at -20°C, preferably 0.8N/25mm Less than or equal to 0.6N/25mm is more preferable. Thereby, when the surface state of the workpiece is equal to the above-mentioned PET film, when the above-mentioned adhesive layer (or workpiece‧substrate) is cooled to a low temperature (preferably cooled to around -20°C), the workpiece can be easily removed from the adhesive layer. Agent layer peeled off. On the other hand, the lower limit of the above-mentioned adhesive force is not particularly limited, but is preferably at least 0.01 N/25 mm, more preferably at least 0.05 N/25 mm, and more preferably at least 0.1 N/25 mm.

從上述操作性，特別是工件易剝離性的觀點而言，本實施形態之溫度敏感性黏著片的黏著劑層在-20℃之儲存模數為1MPa以上，以5MPa以上為佳，以10MPa以上為特佳。又，上述儲存模數為500MPa以下，以300MPa以下為佳，以100MPa以下為特佳。藉由上述儲存模數之上限值為上述，冷卻至低溫而將工件剝離時，能夠防止在基板與黏著劑層的界面產生浮起‧剝落。From the viewpoint of the above-mentioned workability, especially the ease of peeling of the workpiece, the storage modulus of the adhesive layer of the temperature-sensitive adhesive sheet of the present embodiment at -20°C is 1 MPa or more, preferably 5 MPa or more, and 10 MPa or more. For the best. In addition, the above-mentioned storage modulus is 500 MPa or less, preferably 300 MPa or less, particularly preferably 100 MPa or less. When the upper limit of the storage modulus is as above, when the workpiece is cooled to a low temperature and the workpiece is peeled off, it is possible to prevent the occurrence of floating and peeling at the interface between the substrate and the adhesive layer.

又，本實施形態之溫度敏感性黏著片的黏著劑層在80℃之儲存模數，以0.01MPa以上為佳，以0.02MPa以上為特佳，進而以0.03MPa以上為佳。又，上述儲存模數，以1MPa以下為佳，以0.6MPa以下為特佳，進而以0.2MPa以下為佳。藉由上述儲存模數為上述範圍內，在80℃之對玻璃黏著力(及在23℃之對玻璃黏著力)容易滿足前述的值。Also, the storage modulus at 80°C of the adhesive layer of the temperature-sensitive adhesive sheet of this embodiment is preferably at least 0.01 MPa, particularly preferably at least 0.02 MPa, and more preferably at least 0.03 MPa. In addition, the above-mentioned storage modulus is preferably at most 1 MPa, particularly preferably at most 0.6 MPa, and further preferably at most 0.2 MPa. When the above-mentioned storage modulus is within the above-mentioned range, the adhesion to glass at 80°C (and the adhesion to glass at 23°C) easily satisfies the above-mentioned value.

而且，本實施形態之溫度敏感性黏著片的黏著劑層在23℃之儲存模數，以0.05MPa以上為佳，以0.08MPa以上為特佳，進而以0.1MPa以上為佳。又，上述儲存模數，以3MPa以下為佳，以1MPa以下為特佳，進而以0.3MPa以下為佳。藉由上述儲存模數為上述範圍內，在23℃之對玻璃黏著力(及在80℃之對玻璃黏著力)容易滿足前述的值。Furthermore, the storage modulus at 23° C. of the adhesive layer of the temperature-sensitive adhesive sheet of this embodiment is preferably at least 0.05 MPa, particularly preferably at least 0.08 MPa, and further preferably at least 0.1 MPa. In addition, the above-mentioned storage modulus is preferably at most 3 MPa, particularly preferably at most 1 MPa, and further preferably at most 0.3 MPa. When the above-mentioned storage modulus is within the above-mentioned range, the adhesion to glass at 23°C (and the adhesion to glass at 80°C) easily satisfies the above-mentioned value.

本實施形態之溫度敏感性黏著片的黏著劑層，在-20℃之儲存模數相對於在23℃之儲存模數之比，以500%以上為佳，以1,000%以上為特佳，進而以5,000%以上為佳。如此，伴隨著從23℃冷卻至-20℃而儲存模數上升，因而工件的剝離性為更優異。又，上述儲存模數之比，以100,000%以下為佳，以50,0000%以下為特佳，進而以30,000%以下為佳。儲存模數之比的上限值為上述時，能夠防止伴隨著從23℃冷卻至-20℃而儲存模數過度上升致使工件從黏著劑層意外地剝離。因而，藉由儲存模數之比在上述範圍內，工件固定時的黏著性與工件的剝離性之並存變得更優異。The ratio of the storage modulus at -20°C to the storage modulus at 23°C of the adhesive layer of the temperature-sensitive adhesive sheet according to this embodiment is preferably 500% or more, particularly preferably 1,000% or more, and further More than 5,000% is preferred. In this way, the storage modulus increases with cooling from 23°C to -20°C, so the peelability of the workpiece is further excellent. In addition, the ratio of the above-mentioned storage modulus is preferably 100,000% or less, particularly preferably 50,0000% or less, and more preferably 30,000% or less. When the upper limit of the ratio of the storage modulus is as described above, it is possible to prevent the workpiece from being unintentionally peeled off from the adhesive layer due to an excessive increase in the storage modulus accompanying cooling from 23°C to -20°C. Therefore, when the ratio of the storage modulus is within the above-mentioned range, the coexistence of the adhesiveness at the time of fixing the workpiece and the detachability of the workpiece becomes more excellent.

又，本實施形態之溫度敏感性黏著片的黏著劑層，在80℃之儲存模數相對於在23℃之儲存模數之比，以15%以上為佳，20%以上為特佳，進而以25%以上為佳。藉由上述儲存模數之比的下限值為上述，特別是即便步驟中包含加熱步驟，亦能夠抑制黏著力過度降低，能夠防止在步驟中工件產生位置偏移，而將工件更充分地固定。又，上述儲存模數之比的上限值，沒有特別限定，以300%以下為佳，以150%以下為特佳，進而以80%以下為佳。藉由上述儲存模數之比為上述範圍內，在常溫的工件固定及在高溫的工件固定之任一者均能夠良好地進行。In addition, the ratio of the storage modulus at 80°C to the storage modulus at 23°C of the adhesive layer of the temperature-sensitive adhesive sheet of this embodiment is preferably 15% or more, particularly preferably 20% or more, and further More than 25% is better. Since the lower limit value of the storage modulus ratio is as above, especially even if the step includes a heating step, it is possible to suppress an excessive decrease in the adhesive force, prevent the workpiece from being displaced during the step, and fix the workpiece more fully. . In addition, the upper limit of the storage modulus ratio is not particularly limited, but is preferably 300% or less, particularly preferably 150% or less, and more preferably 80% or less. When the ratio of the storage modulus is within the above range, both the fixing of the workpiece at room temperature and the fixing of the workpiece at high temperature can be performed satisfactorily.

將作為本實施形態之溫度敏感性黏著片的一個例子之具體的構成顯示在第1圖。 如第1圖顯示，在一實施形態之溫度敏感性黏著片1，包含2片剝離片12a、12b及黏著劑層11，該黏著劑層11以與該等2片剝離片12a、12b的剝離面接觸之方式而被該2片剝離片12a、12b挾持。又，在本說明書之剝離片的剝離面，是指在剝離片之具有剝離性的面，包含經施行剝離處理之面以及即便未施行剝離處理亦顯示剝離性之面的任一者。The specific structure of an example of the temperature-sensitive adhesive sheet which is this embodiment is shown in FIG. 1. As shown in Figure 1, the temperature-sensitive adhesive sheet 1 in one embodiment includes two release sheets 12a, 12b and an adhesive layer 11, and the adhesive layer 11 is separated from the two release sheets 12a, 12b. The two release sheets 12a, 12b are pinched in a surface-to-face contact manner. In addition, the release surface of the release sheet in this specification refers to the release surface of the release sheet, including any of the surface subjected to release treatment and the surface that exhibits releasability even without release treatment.

1.各構件 1-1.黏著劑層 構成本實施形態之溫度敏感性黏著片1的黏著劑層11之黏著劑，只要滿足上述物性，就沒有特別限定，以含有聚輪烷化合物之黏著劑為佳。聚輪烷化合物具有將環狀分子與將其貫穿的直鏈狀分子之機械性的鍵結，環狀分子能夠自由地在直鏈狀分子上移動。藉由基於此種構造之滑動效果，所得到的黏著劑發揮較高的應力緩和性及可塑效果，在維持高黏著力之同時，能夠多量地調配後述交聯劑而使凝聚力提升。另一方面，容易將在低溫時結晶化之側鏈導入至聚輪烷化合物的環狀分子。如此經導入在低溫時結晶化之側鏈之聚輪烷化合物，在低溫時成為非黏著成分。又，聚輪烷化合物在低溫時非相容化，且有在黏著劑層的表面產生偏析之傾向。因此，將黏著劑層11冷卻至低溫時，非黏著成分之聚輪烷化合物在黏著劑層11表面產生偏析，藉此，該黏著劑層11的黏著力為顯著地降低。如此，含有聚輪烷化合物之黏著劑在室溫及高溫能夠發揮較高的黏著力，而且冷卻至低溫時其黏著力為顯著地降低。因此，由含有聚輪烷化合物的黏著劑所構成之黏著劑層11，容易滿足前述物性。1. Each component 1-1. Adhesive layer The adhesive constituting the adhesive layer 11 of the temperature-sensitive adhesive sheet 1 of this embodiment is not particularly limited as long as it satisfies the above physical properties, but an adhesive containing a polyrotaxane compound is preferable. A polyrotaxane compound has a mechanical bond between a cyclic molecule and a linear molecule passing through it, and the cyclic molecule can move freely on the linear molecule. Due to the sliding effect based on this structure, the obtained adhesive exhibits high stress relaxation and plasticity effects, and while maintaining high adhesive force, it is possible to mix a large amount of crosslinking agent described later to improve cohesion. On the other hand, it is easy to introduce a side chain crystallized at low temperature into the cyclic molecule of the polyrotaxane compound. Thus, the polyrotaxane compound introduced with a side chain that crystallizes at low temperature becomes a non-adhesive component at low temperature. Also, the polyrotaxane compound becomes incompatible at low temperature and tends to segregate on the surface of the adhesive layer. Therefore, when the adhesive layer 11 is cooled to a low temperature, the non-adhesive component polyrotaxane compounds segregate on the surface of the adhesive layer 11 , thereby significantly reducing the adhesive force of the adhesive layer 11 . In this way, the adhesive containing the polyrotaxane compound can exhibit high adhesive force at room temperature and high temperature, and its adhesive force is significantly reduced when cooled to low temperature. Therefore, the adhesive layer 11 composed of the adhesive containing the polyrotaxane compound can easily satisfy the aforementioned physical properties.

作為構成黏著劑層11之黏著劑的種類，例如，可為丙烯酸系黏著劑、聚酯系黏著劑、聚氨酯系黏著劑、橡膠系黏著劑、聚矽酮系黏著劑等的任一者。又，該黏著劑可為乳化液型、溶劑型或無溶劑型的任一者，可為交聯型或非交聯型的任一者。該等之中，以容易滿足前述物性且黏著物性亦優異之丙烯酸系黏著劑為佳。As the type of the adhesive constituting the adhesive layer 11 , for example, any of acrylic adhesive, polyester adhesive, polyurethane adhesive, rubber adhesive, silicone adhesive and the like may be used. In addition, the adhesive may be any of an emulsion type, a solvent type, or a solvent-free type, and may be any of a crosslinked type or a non-crosslinked type. Among them, an acrylic adhesive that easily satisfies the aforementioned physical properties and is also excellent in adhesive properties is preferable.

又，作為丙烯酸系黏著劑，可為活性能量線硬化性之物，亦可為活性能量線非硬化性之物，為了良好地發揮聚輪烷化合物的作用，以活性能量線非硬化性之物為佳。作為活性能量線非硬化性的丙烯酸系黏著劑，以交聯型之物為特佳，進而以熱交聯型之物為佳In addition, the acrylic adhesive may be active energy ray-curable or active energy ray non-curable. better. As an active energy ray non-hardening acrylic adhesive, a cross-linking type is particularly preferable, and a thermal cross-linking type is more preferable

本實施形態之黏著劑，以由含有(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、及聚輪烷化合物(C)之黏著性組合物(以下有稱為「黏著性組合物P」之情形)所形成之黏著劑(將黏著性組合物P交聯而成之黏著劑)為特佳。若為此種黏著劑，則容易滿足前述物性，而且因為發揮良好的黏著力及預定凝聚力，所以亦具有優異的耐久性。又，在本說明書，所謂(甲基)丙烯酸，意味著丙烯酸及甲基丙烯酸之雙方。其它類似用語亦同樣。又，「聚合物」是設定為亦包含「共聚物」的概念。The adhesive of this embodiment is composed of an adhesive composition (hereinafter referred to as "adhesive") containing a (meth)acrylate polymer (A), a crosslinking agent (B), and a polyrotaxane compound (C). In the case of the composition P"), an adhesive (an adhesive obtained by crosslinking the adhesive composition P) is particularly preferred. Such an adhesive is easy to satisfy the aforementioned physical properties, and also has excellent durability because it exhibits good adhesive force and predetermined cohesive force. In addition, in this specification, (meth)acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar expressions. In addition, "polymer" is assumed to also include the concept of "copolymer".

(1)黏著性組合物P的成分 (1-1) (甲基)丙烯酸酯聚合物(A) (甲基)丙烯酸酯聚合物(A)之玻璃轉移溫度(Tg)，以0℃以下為佳，以-20℃以下為特佳，進而以-40℃以下為佳。又，該玻璃轉移溫度(Tg)，以-80℃以上為佳，以-70℃以上為特佳。進而以-60℃以上為佳。藉由(甲基)丙烯酸酯聚合物(A)的玻璃轉移溫度(Tg)為-20℃以下，所得到的黏著劑容易顯現適當的黏彈性，而且能夠使在常溫及高溫的黏著力及在低溫的易剝離性更優異。又，玻璃轉移溫度(Tg)的測定方法，如後述的試驗例所示。(1) Components of the adhesive composition P (1-1) (meth)acrylate polymer (A) The glass transition temperature (Tg) of the (meth)acrylate polymer (A) is preferably 0°C or lower, particularly preferably -20°C or lower, further preferably -40°C or lower. In addition, the glass transition temperature (Tg) is preferably -80°C or higher, particularly preferably -70°C or higher. Furthermore, it is preferably -60°C or higher. When the glass transition temperature (Tg) of the (meth)acrylate polymer (A) is -20°C or lower, the obtained adhesive can easily exhibit appropriate viscoelasticity, and can improve the adhesive force at room temperature and high temperature and the The low-temperature easy-peelability is more excellent. In addition, the measuring method of the glass transition temperature (Tg) is as shown in the test example mentioned later.

(甲基)丙烯酸酯聚合物(A)，以含有(甲基)丙烯酸烷酯、及在分子內具有反應性官能基之單體(含反應性官能基的單體)作為構成該聚合物之單體單元為佳。The (meth)acrylate polymer (A) is composed of a monomer (monomer containing a reactive functional group) containing an alkyl (meth)acrylate and a reactive functional group in the molecule (reactive functional group-containing monomer) Single unit is preferred.

(甲基)丙烯酸酯聚合物(A)，藉由含有(甲基)丙烯酸烷酯作為構成該聚合物之單體，而能夠顯現較佳的黏著性。作為(甲基)丙烯酸烷酯，以烷基的碳數為1~20的(甲基)丙烯酸烷酯為佳。烷基可為直鏈狀或分枝鏈狀，亦可為具有環狀結構之物。The (meth)acrylate polymer (A) can express preferable adhesiveness by containing an alkyl (meth)acrylate as a monomer which comprises this polymer. As the alkyl (meth)acrylate, an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group is preferable. The alkyl group may be linear or branched, and may have a cyclic structure.

作為烷基之碳數為1~20的(甲基)丙烯酸烷酯，以含有作為同元聚合物之玻璃轉移溫度(Tg)為30℃以下之物(以下有稱為「低Tg丙烯酸烷酯」之情形)為佳。藉由含有此種低Tg丙烯酸烷酯作為構成單體單元，容易將(甲基)丙烯酸酯聚合物(A)的玻璃轉移溫度(Tg)設定為前述範圍。As an alkyl (meth)acrylate with an alkyl group having 1 to 20 carbon atoms, a homopolymer with a glass transition temperature (Tg) of 30°C or less (hereinafter referred to as "low Tg alkyl acrylate) ” situation) is better. By containing such a low Tg alkyl acrylate as a structural monomer unit, it becomes easy to set the glass transition temperature (Tg) of a (meth)acrylate polymer (A) to the said range.

作為低Tg丙烯酸烷酯，較佳可舉出，例如，丙烯酸正丁酯(Tg-55℃)、丙烯酸正辛酯(Tg-65℃)、丙烯酸異辛酯(Tg-58℃)、丙烯酸2-乙基己酯(Tg-70℃)、丙烯酸異壬酯(Tg-58℃)、丙烯酸異癸酯(Tg-60℃)、甲基丙烯酸異癸酯(Tg-41℃)、甲基丙烯酸正十二酯(Tg-65℃)、丙烯酸正十三酯(Tg-55℃)、甲基丙烯酸正十三酯(-40℃)等。其中，從使在常溫及高溫的黏著力及在低溫的易剝離性更優異之觀點而言，作為低Tg丙烯酸烷酯，以同元聚合物的Tg為-45℃以下之物為較佳，以-50℃以下之物為特佳。具體而言，以丙烯酸正丁酯及丙烯酸2-乙基己酯為特佳。該等可單獨使用，亦可組合2種以上而使用。As the low Tg alkyl acrylate, preferably, for example, n-butyl acrylate (Tg-55°C), n-octyl acrylate (Tg-65°C), isooctyl acrylate (Tg-58°C), acrylic acid 2 -Ethylhexyl (Tg-70°C), isononyl acrylate (Tg-58°C), isodecyl acrylate (Tg-60°C), isodecyl methacrylate (Tg-41°C), methacrylate n-dodecyl (Tg-65°C), n-tridecyl acrylate (Tg-55°C), n-tridecyl methacrylate (-40°C), etc. Among them, from the viewpoint of making the adhesive force at room temperature and high temperature more excellent and the ease of peeling at low temperature, as the low Tg alkyl acrylate, the Tg of the homopolymer is -45°C or less. The temperature below -50°C is especially preferred. Specifically, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. These may be used individually or in combination of 2 or more types.

(甲基)丙烯酸酯聚合物(A)，以含有下限值為50質量%以上的低Tg丙烯酸烷酯作為構成該聚合物之單體單元為佳，以含有60質量%以上為特佳，進而以含有70質量%以上為佳。藉由上述含量的下限值為上述，更容易將(甲基)丙烯酸酯聚合物(A)的玻璃轉移溫度(Tg)設定成為前述範圍。The (meth)acrylate polymer (A) preferably contains a low Tg alkyl acrylate having a lower limit of 50% by mass or more as a monomer unit constituting the polymer, particularly preferably 60% by mass or more, Furthermore, it is preferable to contain 70 mass % or more. When the lower limit of the said content is mentioned above, it becomes easier to set the glass transition temperature (Tg) of a (meth)acrylate polymer (A) to the said range.

另一方面，(甲基)丙烯酸酯聚合物(A)，以含有上限值為99質量%以下的上述低Tg丙烯酸烷酯作為構成該聚合物之單體單元為佳，以含有97質量%以下為特佳，進而以含有95質量%以下為佳。藉由上述含量的上限值為上述，能夠將適合量的其它單體成分(特別是含反應性官能基的單體)導入至(甲基)丙烯酸酯聚合物(A)中。On the other hand, the (meth)acrylate polymer (A) preferably contains the above-mentioned low Tg alkyl acrylate as a monomer unit constituting the polymer with an upper limit value of 99 mass % or less, and preferably contains 97 mass % The following are particularly preferable, and it is more preferable to contain 95 mass % or less. When the upper limit of the said content is mentioned above, an appropriate amount of other monomer components (reactive functional group containing monomer) can be introduced into a (meth)acrylate polymer (A).

(甲基)丙烯酸酯聚合物(A)，亦可含有同元聚合物的玻璃轉移溫度(Tg)為大於0℃之單體(以下有稱為「高Tg丙烯酸烷酯」之情形)作為上述烷基的碳數為1~20的(甲基)丙烯酸烷酯。藉由含有此種高Tg丙烯酸烷酯作為構成單體單元，能夠使所得到的黏著劑之凝聚力提升，且能夠使在高溫的黏著力提升。The (meth)acrylate polymer (A) may also contain a monomer whose glass transition temperature (Tg) of the homopolymer is higher than 0°C (hereinafter referred to as "high Tg alkyl acrylate") as the above-mentioned Alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group. By including such a high Tg alkyl acrylate as a constituent monomer unit, the cohesive force of the adhesive obtained can be improved, and the adhesive force at high temperature can be improved.

作為上述高Tg丙烯酸烷酯，可舉出，例如，丙烯酸甲酯(Tg10℃)、甲基丙烯酸甲酯(Tg105℃)、甲基丙烯酸乙酯(Tg65℃)、甲基丙烯酸正丁酯(Tg20℃)、甲基丙烯酸異丁酯(Tg48℃)、甲基丙烯酸三級丁酯(Tg107℃)、丙烯酸正十八酯(Tg30℃)、甲基丙烯酸正十八酯(Tg38℃)、丙烯酸環己酯(Tg15℃)、甲基丙烯酸環己酯(Tg66℃)、甲基丙烯酸苄酯(Tg54℃)、丙烯酸異莰酯(Tg94℃)、甲基丙烯酸異莰酯(Tg180℃)、丙烯酸金剛烷酯(Tg115℃)、甲基丙烯酸金剛烷酯(Tg141℃)、丙烯酸嗎啉酯(Tg145℃)等。上述之中，從所得到的黏著劑之凝聚力及玻璃轉移溫度的觀點而言，以丙烯酸甲酯為佳。該等可單獨使用，亦可組合2種以上而使用。As the above-mentioned high Tg alkyl acrylate, for example, methyl acrylate (Tg10°C), methyl methacrylate (Tg105°C), ethyl methacrylate (Tg65°C), n-butyl methacrylate (Tg20 °C), isobutyl methacrylate (Tg48 °C), tertiary butyl methacrylate (Tg107 °C), n-octadecyl acrylate (Tg30 °C), n-octadecyl methacrylate (Tg38 °C), acrylic ring Hexyl ester (Tg15°C), cyclohexyl methacrylate (Tg66°C), benzyl methacrylate (Tg54°C), isocamphoryl acrylate (Tg94°C), isocamphoryl methacrylate (Tg180°C), adamantine acrylate Alkyl ester (Tg115°C), adamantyl methacrylate (Tg141°C), morpholine acrylate (Tg145°C), etc. Among the above, methyl acrylate is preferable from the viewpoint of the cohesive force and glass transition temperature of the obtained adhesive. These may be used individually or in combination of 2 or more types.

(甲基)丙烯酸酯聚合物(A)含有高Tg丙烯酸烷酯作為構成該聚合物之單體單元時，其含量以5質量%以上為佳，以10質量%以上為特佳，進而以15質量%以上為佳。又，該含量以30質量%以下為佳，以25質量%以下為特佳，進而以20質量%以下為佳。When the (meth)acrylate polymer (A) contains a high Tg alkyl acrylate as a monomer unit constituting the polymer, its content is preferably at least 5% by mass, particularly preferably at least 10% by mass, and further preferably at least 15% by mass. More than mass % is preferred. In addition, the content is preferably at most 30% by mass, particularly preferably at most 25% by mass, and further preferably at most 20% by mass.

(甲基)丙烯酸酯聚合物(A)，藉由含有高Tg丙烯酸烷酯作為構成該聚合物之單體單元，透過源自該含反應性官能基的單體的反應性官能基而與後述交聯劑(B)反應，藉此形成交聯結構(三維網狀結構)，而能夠得到具有所需要的凝聚力之黏著劑。The (meth)acrylate polymer (A) contains a high Tg alkyl acrylate as a monomer unit constituting the polymer, and through the reactive functional group derived from the reactive functional group-containing monomer, it can be combined with the following The cross-linking agent (B) reacts to form a cross-linking structure (three-dimensional network structure), and an adhesive having the desired cohesion can be obtained.

(甲基)丙烯酸酯聚合物(A)，含有含反應性官能基的單體作為構成該聚合物之單體單元，就含反應性官能基的單體而言，可舉出在分子內具有羥基之單體(含羥基單體)、在分子內具有羧基之單體(含羧基單體)、及分子內具有胺基之單體(含胺基單體)等。該等含反應性官能基的單體，可單獨使用1種，亦可併用2種以上。The (meth)acrylate polymer (A) contains a reactive functional group-containing monomer as a monomer unit constituting the polymer. As for the reactive functional group-containing monomer, there are Hydroxyl monomers (hydroxyl-containing monomers), monomers with carboxyl groups in the molecule (carboxyl-containing monomers), and monomers with amine groups in the molecule (amine-containing monomers), etc. These reactive functional group-containing monomers may be used alone or in combination of two or more.

在此，聚輪烷化合物(C)的環狀分子多半具有反應性羥基，如前述，為了在低溫時使聚輪烷化合物(C)在黏著劑層11表面產生偏析，以不使聚輪烷化合物(C)與交聯劑(B)反應為佳。因此，作為交聯劑(B)，以選擇與羥基的反應性較低之物為佳，具體而言，以選擇與羧基的反應性較高之物為佳。因此，上述含反應性官能基的單體之中、以含羧基單體為特佳。又，含羧基單體亦能夠提高所得到的黏著劑之黏著力。Here, most of the cyclic molecules of the polyrotaxane compound (C) have reactive hydroxyl groups. As mentioned above, in order to segregate the polyrotaxane compound (C) on the surface of the adhesive layer 11 at low temperature, so as not to segregate the polyrotaxane compound (C) Compound (C) preferably reacts with crosslinking agent (B). Therefore, as a crosslinking agent (B), it is preferable to select the thing with low reactivity with a hydroxyl group, Specifically, it is preferable to select the thing with high reactivity with a carboxyl group. Therefore, among the above-mentioned reactive functional group-containing monomers, carboxyl group-containing monomers are particularly preferred. Moreover, the carboxyl group-containing monomer can also improve the adhesive force of the obtained adhesive.

作為含羧基單體，可舉出，例如，丙烯酸、甲基丙烯酸、巴豆酸、順丁烯二酸、伊康酸、檸康酸等的乙烯性不飽和羧酸。其中，從所得到的黏著劑之黏著力的觀點而言，以丙烯酸為佳。該等可單獨使用，亦可組合2種以上而使用。Examples of carboxyl group-containing monomers include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Among these, acrylic acid is preferable from the viewpoint of the adhesive force of the obtained adhesive. These may be used individually or in combination of 2 or more types.

(甲基)丙烯酸酯聚合物(A)，以含有1質量%以上之含反應性官能基的單體作為構成該聚合物之單體單元為佳，以含有2質量%以上含有為特佳，進而以含有3質量%以上為佳。又，以含有30質量%以下之含反應性官能基的單體為佳，以含有21質量%以下為佳，進而以含有12質量%以下為佳。藉由含反應性官能基的單體之含量在上述範圍，所得到的黏著劑的凝聚力為較高，且黏著力，特別是，在高溫的黏著力為較高。The (meth)acrylate polymer (A) preferably contains 1% by mass or more of reactive functional group-containing monomers as monomer units constituting the polymer, particularly preferably 2% by mass or more, Furthermore, it is more preferable to contain 3 mass % or more. In addition, the reactive functional group-containing monomer is preferably contained in an amount of not more than 30% by mass, preferably not more than 21% by mass, and more preferably not more than 12% by mass. When the content of the monomer containing the reactive functional group is within the above range, the cohesive force of the obtained adhesive is relatively high, and the adhesive force, especially the adhesive force at high temperature is relatively high.

(甲基)丙烯酸酯聚合物(A)，亦可按照需要而含有其它單體作為構成該聚合物之單體單元。作為其它單體，為了不阻礙含反應性官能基的單體之前述作用，以不含有反應性官能基之單體為佳。The (meth)acrylate polymer (A) may contain other monomer as the monomer unit which comprises this polymer as needed. As other monomers, monomers not containing reactive functional groups are preferred in order not to hinder the aforementioned effects of monomers containing reactive functional groups.

(甲基)丙烯酸酯聚合物(A)，以使用溶液聚合法而得到的溶液聚合物為佳。藉由為溶液聚合物，容易得到高分子量的聚合物，且能夠得在高溫的黏著力更優異之黏著劑。The (meth)acrylate polymer (A) is preferably a solution polymer obtained by a solution polymerization method. By being a solution polymer, it is easy to obtain a high-molecular-weight polymer, and it is possible to obtain an adhesive having better adhesive force at high temperature.

(甲基)丙烯酸酯聚合物(A)的聚合態樣，可為隨機共聚物，亦可為嵌段共聚物。The polymerization form of (meth)acrylate polymer (A) may be a random copolymer or a block copolymer.

從在低溫的易剝離性之觀點而言，(甲基)丙烯酸酯聚合物(A)的重量平均分子量，以20萬以上為佳，以30萬以上為特佳，進而以35萬以上為佳。又，該重量平均分子量，以250萬以下為佳，以200萬以下為特佳，進而以160萬以下為佳。上述重量平均分子量的上限值為上述時，所得到的黏著劑之在常溫及高溫的黏著力較高。因而，(甲基)丙烯酸酯聚合物(A)的重量平均分子量在上述範圍時，所得到的黏著劑，能夠成為使在常溫及高溫的黏著性及在低溫的易剝離性更有效地並存之物。在本說明書之重量平均分子量，是使用凝膠滲透層析法(GPC)法所測得的標準聚苯乙烯換算之值。From the viewpoint of easy peelability at low temperature, the weight average molecular weight of the (meth)acrylate polymer (A) is preferably at least 200,000, particularly preferably at least 300,000, and more preferably at least 350,000. . In addition, the weight average molecular weight is preferably at most 2.5 million, particularly preferably at most 2 million, and further preferably at most 1.6 million. When the upper limit of the above-mentioned weight average molecular weight is the above-mentioned value, the obtained adhesive has high adhesive force at room temperature and high temperature. Therefore, when the weight-average molecular weight of the (meth)acrylate polymer (A) is within the above-mentioned range, the adhesive obtained can be more effectively compatible with adhesiveness at room temperature and high temperature and easy peelability at low temperature. thing. The weight average molecular weight in this specification is the value measured using the gel permeation chromatography (GPC) method in terms of standard polystyrene.

在黏著性組合物P，(甲基)丙烯酸酯聚合物(A)可單獨使用1種，亦可組合2種以上而使用。In the adhesive composition P, (meth)acrylate polymer (A) may be used individually by 1 type, and may use it in combination of 2 or more types.

(1-2)交聯劑(B) 交聯劑(B)，將含有該交聯劑(B)之黏著性組合物P的加熱等設為觸發，而將(甲基)丙烯酸酯聚合物(A)交聯，且形成三維網狀結構。藉此，所得到的黏著劑之凝聚力提升，且黏著力，特別是，在高溫的黏著力為較高。(1-2) Crosslinking agent (B) The cross-linking agent (B) is triggered by heating the adhesive composition P containing the cross-linking agent (B), and the (meth)acrylate polymer (A) is cross-linked to form a three-dimensional network structure. Thereby, the cohesive force of the obtained adhesive is improved, and the adhesive force, especially, the adhesive force at high temperature is higher.

作為交聯劑(B)，如前述，為了在低溫時使聚輪烷化合物(C)在黏著劑層11表面產生偏析，以不與聚輪烷化合物(C)反應之物為佳。因為聚輪烷化合物(C)的環狀分子多半具有反應性羥基，所以作為交聯劑(B)，以選擇與羥基的反應性較低且與羧基的反應性較高之物為佳。The crosslinking agent (B) is preferably one that does not react with the polyrotaxane compound (C) in order to segregate the polyrotaxane compound (C) on the surface of the adhesive layer 11 at low temperature as described above. Since most of the cyclic molecules of the polyrotaxane compound (C) have reactive hydroxyl groups, it is preferable to select a crosslinking agent (B) that has low reactivity with hydroxyl groups and high reactivity with carboxyl groups.

作為如上述的交聯劑(B)，可舉出金屬螯合物系交聯劑、環氧系交聯劑、氮丙啶(aziridine)系交聯劑等，尤其是以金屬螯合物系交聯劑為佳。又，交聯劑(B)能夠單獨1種或組合2種以上而使用。Examples of the above-mentioned crosslinking agent (B) include metal chelate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, and the like, especially metal chelate-based crosslinking agents. A crosslinking agent is preferred. Moreover, a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.

作為金屬螯合物系交聯劑，可以是金屬原子為鋁、鋯、鈦、鋅、鐵、錫等的螯合化合物，從與(甲基)丙烯酸酯聚合物(A)的反應性的觀點而言，以鋁螯合化合物為佳。As the metal chelate crosslinking agent, it can be a chelate compound whose metal atom is aluminum, zirconium, titanium, zinc, iron, tin, etc. From the viewpoint of reactivity with (meth)acrylate polymer (A) As far as aluminum chelate compounds are concerned, aluminum chelate compounds are preferred.

作為鋁螯合化合物，可舉出，例如，二異丙氧基鋁一油醯基乙醯乙酸酯、一異丙氧基鋁雙油醯基乙醯乙酸酯、一異丙氧基鋁一油酸酯一乙基乙醯乙酸酯、二異丙氧基鋁一月桂基乙醯乙酸酯、二異丙氧基鋁一硬脂醯基乙醯乙酸酯、二異丙氧基鋁一異硬脂醯基乙醯乙酸酯、一異丙氧基鋁一-N-月桂醯基-β-鋁氫化物一月桂基乙醯乙酸酯、三乙醯丙酮鋁、一乙醯丙酮鋁雙(異丁基乙醯乙酸酯)螯合物、一乙醯丙酮鋁雙(2-乙基己基乙醯乙酸酯)螯合物、一乙醯丙酮鋁雙(十二基乙醯乙酸酯)螯合物、一乙醯丙酮鋁雙(油醯基乙醯乙酸酯)螯合物等。上述之中，從反應性、所得到的黏著劑容易成為需要的黏著力等之觀點而言，以三乙醯丙酮鋁為特佳。As the aluminum chelate compound, for example, diisopropoxyaluminum monooleyl acetylacetate, monoisopropoxyaluminum bisoleylacetate, monoisopropoxyaluminum Monooleate Monoethyl Acetyl Acetate, Diisopropoxy Aluminum Monolauryl Acetyl Acetate, Diisopropoxy Aluminum Monostearyl Acetyl Acetate, Diisopropoxy Aluminum Aluminum-isostearyl acetylacetate, aluminum monoisopropoxide-N-lauroyl-β-aluminum hydride monolauryl acetylacetate, aluminum triacetylacetonate, monoacetyl Aluminum acetonate bis(isobutyl acetyl acetate) chelate, monoacetylacetonate aluminum bis(2-ethylhexyl acetyl acetate) chelate, monoacetylacetonate aluminum bis(dodecyl ethyl Acyl acetate) chelate, aluminum acetylacetonate bis(oleyl acetate) chelate, etc. Among the above, aluminum triacetylacetonate is particularly preferred from the viewpoints of reactivity and the ease with which the obtained adhesive becomes the required adhesive force.

相對於(甲基)丙烯酸酯聚合物(A) 100質量份，在黏著性組合物P中之交聯劑(B)的含量，以0.1質量份以上為佳，以0.5質量份以上為特佳，進而以0.8質量份以上為佳。又，該含量以10質量份以下為佳，以5質量份以下為特佳，進而以3質量份以下為佳。藉由交聯劑(B)含量為上述範圍，所得到的黏著劑凝聚力為適當地較高，且黏著力，特別是，在高溫的黏著力為較高。The content of the crosslinking agent (B) in the adhesive composition P is preferably at least 0.1 parts by mass, particularly preferably at least 0.5 parts by mass, based on 100 parts by mass of the (meth)acrylate polymer (A). , and more preferably at least 0.8 parts by mass. Moreover, the content is preferably at most 10 parts by mass, particularly preferably at most 5 parts by mass, and further preferably at most 3 parts by mass. When the content of the crosslinking agent (B) is in the above-mentioned range, the cohesive force of the obtained adhesive is suitably high, and the adhesive force, especially, the adhesive force at high temperature is high.

(1-3)聚輪烷化合物(C) 聚輪烷化合物(C)，是直鏈狀分子貫穿至少2個環狀分子的開口部且在直鏈狀分子的兩末端具有封端基而成之化合物。在該聚輪烷化合物(C)，環狀分子能夠在直鏈狀分子上自由地移動，而且藉由封端基而成為環狀分子不從直鏈狀分子脫離之結構。亦即，直鏈狀分子及環狀分子不是藉由共價鍵等的化學鍵，而是藉由所謂機械性的鍵結而發揮滑動效果，同時維持其形態之物。本實施形態之黏著劑(黏著性組合物P)，藉由含有具有此種機械性的鍵結之聚輪烷化合物(C)，所得到的黏著劑發揮較高的應力緩和性及可塑效果，在維持高黏著力之同時，能夠多量地調配交聯劑(B)而使凝聚力提升。(1-3) Polyrotaxane compound (C) The polyrotaxane compound (C) is a compound in which a linear molecule penetrates at least two openings of a cyclic molecule and has end-capping groups at both ends of the linear molecule. In this polyrotaxane compound (C), the cyclic molecule can move freely on the linear molecule, and the structure is such that the cyclic molecule does not detach from the linear molecule due to the capping group. That is, linear molecules and cyclic molecules are not chemical bonds such as covalent bonds but so-called mechanical bonds that exhibit a sliding effect while maintaining their shape. The adhesive (adhesive composition P) of this embodiment, by containing the polyrotaxane compound (C) having such a mechanical bond, the obtained adhesive exhibits high stress relaxation and plasticity effects, While maintaining high adhesive force, a large amount of crosslinking agent (B) can be formulated to improve cohesive force.

在本實施形態之聚輪烷化合物(C)，以包括具有在低溫時結晶化的側鏈之環狀寡糖作為環狀分子為佳。具有此種環狀寡糖作為環狀分子之聚輪烷化合物(C)，在低溫成為非黏著成分。如前述，因為聚輪烷化合物(C)在低溫有在黏著劑層11表面產生偏析之傾向，所以將黏著劑層11冷卻至低溫時，成為非黏著成分之聚輪烷化合物在黏著劑層11表面產生偏析，且該黏著劑層11的黏著力顯著地降低。又，在本說明書，「環狀分子」或「環狀寡糖」的「環狀」，意味著實質上為「環狀」。亦即，只要能夠在直鏈狀分子上移動，環狀分子亦可為不完全閉環，例如，亦可為螺旋結構。The polyrotaxane compound (C) in this embodiment preferably includes, as a cyclic molecule, a cyclic oligosaccharide having a side chain that crystallizes at low temperature. The polyrotaxane compound (C) having such a cyclic oligosaccharide as a cyclic molecule becomes a non-adhesive component at low temperature. As mentioned above, since the polyrotaxane compound (C) tends to segregate on the surface of the adhesive layer 11 at low temperatures, when the adhesive layer 11 is cooled to a low temperature, the polyrotaxane compound that becomes a non-adhesive component is deposited on the adhesive layer 11. Segregation occurs on the surface, and the adhesive force of the adhesive layer 11 is significantly lowered. In addition, in this specification, "cyclic" in "cyclic molecule" or "cyclic oligosaccharide" means substantially "cyclic". That is, as long as it can move on a linear molecule, the cyclic molecule may be incompletely closed, for example, may have a helical structure.

作為在上述在低溫時結晶化之側鏈(低溫結晶化側鏈)，可舉出己內酯鏈、聚乙二醇鏈、聚酯鏈、聚醯胺鏈、聚丁二烯鏈等。Examples of the side chains that crystallize at low temperatures (low-temperature crystallization side chains) include caprolactone chains, polyethylene glycol chains, polyester chains, polyamide chains, and polybutadiene chains.

作為環狀寡糖，較佳可舉出α-環糊精、β-環糊精、γ-環糊等的環糊精。該等環糊精具有反應性羥基，透過該羥基而容易將在低溫時結晶化之側鏈導入。上述之中，從在低溫的易剝離性之觀點而言，以α-環糊精為特佳。聚輪烷化合物(C)的環狀分子，可以在聚輪烷化合物(C)中或黏著劑(黏著性組合物P)中混合存在2種以上。As the cyclic oligosaccharide, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferably mentioned. These cyclodextrins have reactive hydroxyl groups, through which side chains that crystallize at low temperatures can be easily introduced. Among the above, α-cyclodextrin is particularly preferable from the viewpoint of easy peelability at low temperature. The cyclic molecule of the polyrotaxane compound (C) may be a mixture of two or more types in the polyrotaxane compound (C) or in the adhesive (adhesive composition P).

聚輪烷化合物(C)的直鏈狀分子被環狀分子包接，不是藉由共價鍵等的化學鍵而是藉由機械性的鍵結而能夠一體化之分子或物質，只要是直鏈狀之物，就沒有特別限定。而且，在本說明書，「直鏈狀分子」的「直鏈」意味著實質上為「直鏈」。亦即，只要環狀分子能夠在直鏈狀分子上移動，直鏈狀分子亦可具有分枝鏈。A polyrotaxane compound (C) is a molecule or substance that can be integrated by a mechanical bond instead of a chemical bond such as a covalent bond where the straight-chain molecule is surrounded by a ring-shaped molecule, as long as it is a straight chain There are no special restrictions on the shape of the object. In addition, in this specification, "straight chain" of "linear molecule" means substantially "straight chain". That is, as long as the cyclic molecule can move on the linear molecule, the linear molecule may also have branched chains.

作為聚輪烷化合物(C)的直鏈狀分子，例如，以聚乙二醇、聚丙二醇、聚異戊二烯、聚異丁烯、聚丁二烯、聚四氫呋喃、聚丙烯酸酯、聚二甲基矽氧烷、聚乙烯、聚丙烯等為佳，該等直鏈狀分子在黏著性組合物P中亦可混合存在2種以上。As linear molecules of the polyrotaxane compound (C), for example, polyethylene glycol, polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, polytetrahydrofuran, polyacrylate, polydimethyl Silicone, polyethylene, polypropylene, etc. are preferable, and these linear molecules may be present in the adhesive composition P in mixture of two or more kinds.

聚輪烷化合物(C)的直鏈狀分子之數量平均分子量，其下限值以3,000以上為佳，以10,000以上為特佳，進而以20,000以上為佳。數量平均分子量的下限值為上述以上時，能夠確保環狀分子在直鏈狀分子上的移動量，且能夠充分地得到黏著劑的應力緩和性。又，聚輪烷化合物(C)的直鏈狀分子之數量平均分子量，其上限值以300,000以下為佳，以200,000以下為特佳，進而以100,000以下為佳。數量平均分子量的上限值為上述以下時，聚輪烷化合物(C)在溶劑的溶解性、與(甲基)丙烯酸酯聚合物(A)的相容性等成為良好。The lower limit of the number average molecular weight of the straight-chain molecules of the polyrotaxane compound (C) is preferably 3,000 or more, particularly preferably 10,000 or more, further preferably 20,000 or more. When the lower limit of the number average molecular weight is above the above, the amount of migration of the cyclic molecule to the linear molecule can be ensured, and the stress relaxation property of the adhesive can be sufficiently obtained. Also, the upper limit of the number average molecular weight of the straight-chain molecules of the polyrotaxane compound (C) is preferably at most 300,000, particularly preferably at most 200,000, and further preferably at most 100,000. When the upper limit of the number average molecular weight is the above or less, the solubility of the polyrotaxane compound (C) in a solvent, the compatibility with the (meth)acrylate polymer (A), and the like become favorable.

聚輪烷化合物(C)的封端基，只要是能夠保持環狀分子藉由直鏈狀分子而成為竹籤串狀的形態之基團，就沒有特別限定。作為此種基團，可舉出體積較高的基團、離子性基團等。The end-blocking group of the polyrotaxane compound (C) is not particularly limited as long as it is a group capable of maintaining the shape of a bamboo stick through a linear molecule through a cyclic molecule. As such a group, a bulky group, an ionic group, etc. are mentioned.

具體而言，聚輪烷化合物(C)的封端基，以二硝苯基類、環糊精類、金剛烷基類、三苯甲基(trityl)類、螢光素(fluorescein)類、芘(pyrene)類、蒽(anthracene)類等、或數量平均分子量1,000~1,000,000之高分子的主鏈或側鏈等為佳，該等封端基亦可在聚輪烷化合物(C)中或黏著性組合物P中混合存在2種以上。Specifically, the end-capping group of the polyrotaxane compound (C) is based on dinitrophenyls, cyclodextrins, adamantyls, trityls, fluoresceins, Pyrene (pyrene) type, anthracene (anthracene) type, etc., or the main chain or side chain of a polymer with a number average molecular weight of 1,000~1,000,000 is preferred. In the adhesive composition P, 2 or more types are mixed and exist.

以上說明的聚輪烷化合物(C)，能夠使用先前習知的方法(例如，特開2005-154675記載的方法)而得到。The polyrotaxane compound (C) described above can be obtained by a conventionally known method (for example, the method described in JP-A-2005-154675).

在本實施形態之黏著性組合物P中之聚輪烷化合物(C)的含量，相對於(甲基)丙烯酸酯聚合物(A) 100質量份，其下限值以9質量份以上為佳，以18質量份以上為特佳，進而以27質量份以上為佳。聚輪烷化合物(C)的含量之下限值為上述時，黏著劑層11之在低溫時的易剝離性更優異。又，聚輪烷化合物(C)的含量之上限值，以70質量份以下為佳，以60質量份以下為較佳，以55質量份以下為特佳。聚輪烷化合物(C)的含量之上限值為上述時，黏著劑層11之在常溫及高溫的黏著力更優異。The lower limit of the content of the polyrotaxane compound (C) in the adhesive composition P of this embodiment is preferably 9 parts by mass or more relative to 100 parts by mass of the (meth)acrylate polymer (A) , it is particularly preferably 18 parts by mass or more, and more preferably 27 parts by mass or more. When the lower limit of the content of the polyrotaxane compound (C) is the above-mentioned value, the easy-peelability of the adhesive layer 11 at low temperature is more excellent. Moreover, the upper limit of the content of the polyrotaxane compound (C) is preferably not more than 70 parts by mass, more preferably not more than 60 parts by mass, and particularly preferably not more than 55 parts by mass. When the upper limit of the content of the polyrotaxane compound (C) is as described above, the adhesive force of the adhesive layer 11 at room temperature and high temperature is more excellent.

(1-4)各種添加劑 黏著性組合物P，能夠按照需要而添加在丙烯酸系黏著劑通常使用的各種添加劑，例如，黏著賦予劑、抗氧化劑、紫外線吸收劑、光安定劑、軟化劑、填充劑等。又，後述的聚合溶劑和稀釋溶劑，不包括在構成黏著性組合物P之添加劑中。(1-4) Various additives Adhesive composition P can add various additives generally used for acrylic adhesives, for example, an adhesive imparting agent, an antioxidant, a ultraviolet absorber, a light stabilizer, a softener, a filler, etc. as needed. In addition, the polymerization solvent and diluting solvent described later are not included in the additives constituting the adhesive composition P.

(2)黏著性組合物P的製造 黏著性組合物P，能夠藉由製造(甲基)丙烯酸酯聚合物(A)，將所得到的(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、及聚輪烷化合物(C)混合，同時按照需要而添加添加劑而製造。(2) Production of Adhesive Composition P Adhesive composition P can be prepared by producing (meth)acrylate polymer (A), and the obtained (meth)acrylate polymer (A), crosslinking agent (B), and polyrotaxane compound (C) Mixing and adding additives as necessary to manufacture.

(甲基)丙烯酸酯聚合物(A)，能夠藉由將構成聚合物之單體的混合物使用通常的自由基聚合法而聚合來製造。(甲基)丙烯酸酯聚合物(A)的聚合，較佳為按照需要而使用聚合起始劑且使用溶液聚合法來進行。作為聚合溶劑，可舉出，例如，乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲苯、丙酮、己烷、甲基乙基酮等，亦可併用2種以上。The (meth)acrylate polymer (A) can be manufactured by superposing|polymerizing the mixture of the monomer which comprises a polymer, using a normal radical polymerization method. The polymerization of the (meth)acrylate polymer (A) is preferably performed using a polymerization initiator as necessary and using a solution polymerization method. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, and the like, and two or more of them may be used in combination.

作為聚合起始劑，可舉出偶氮系化合物、有機過氧化物等，亦可併用2種以上。作為偶氮系化合物，例如可舉出2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷1-腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基2,2’-偶氮雙(2-甲基丙酸酯)、4,4’-偶氮雙(4-氰基戊酸)、2,2’-偶氮雙(2-羥甲基丙腈)、2,2’偶氮雙[2-(2-咪唑啉-2-基)丙烷]等。As a polymerization initiator, an azo compound, an organic peroxide, etc. are mentioned, and 2 or more types may be used together. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane alkane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile ), dimethyl 2,2'-azobis(2-methyl propionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2 -Hydroxymethylpropionitrile), 2,2'azobis[2-(2-imidazolin-2-yl)propane], etc.

作為有機過氧化物，可舉出，例如，過氧化苯甲醯基、過氧苯甲酸三級丁酯、異丙苯過氧化氫、過氧二碳酸二異丙酯、過氧二碳酸二正丙酯、過氧二碳酸二(2-乙氧基乙基)酯、過氧新癸酸三級丁酯、過氧化三甲基乙酸三級丁酯、過氧化(3,5,5-三甲基己醯)、過氧化二丙醯、過氧化二乙醯等。Examples of organic peroxides include benzoyl peroxide, tertiary butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-normal peroxydicarbonate Propyl ester, bis(2-ethoxyethyl) peroxydicarbonate, tertiary butyl peroxyneodecanoate, tertiary butyl peroxytrimethylacetate, peroxide (3,5,5-tri methylhexyl), diacryl peroxide, diacetyl peroxide, etc.

而且，在上述聚合步驟，藉由調配2-氫硫基乙醇等的鏈轉移劑而能夠調節所得到的聚合物之重量平均分子量。Furthermore, in the above-mentioned polymerization step, by preparing a chain transfer agent such as 2-mercaptoethanol, the weight average molecular weight of the polymer obtained can be adjusted.

得到(甲基)丙烯酸酯聚合物(A)之後，藉由將交聯劑(B)、聚輪烷化合物(C)、以及按照需要之添加劑及稀釋溶劑添加在(甲基)丙烯酸酯聚合物(A)的溶液且充分地混合，而得到經溶劑稀釋之黏著性組合物P(塗佈溶液)。After obtaining the (meth)acrylate polymer (A), by adding the crosslinking agent (B), the polyrotaxane compound (C), and additives and diluting solvents as required to the (meth)acrylate polymer (A) and fully mixed to obtain an adhesive composition P (coating solution) diluted with a solvent.

又，在上述各成分的任一者，是使用固體狀物之情況，或是以未經稀釋的狀態與其它成分混合時產生析出之情況，亦可將該成分單獨預先在稀釋溶劑溶解或稀釋之後，才與其它成分混合。In addition, when any of the above-mentioned components is used as a solid, or when it is mixed with other components in an undiluted state and precipitates, the components can also be dissolved or diluted in a diluent alone in advance. Afterwards, it is mixed with other ingredients.

作為上述稀釋溶劑，能夠使用，例如，己烷、庚烷、環己烷等的脂肪族烴、甲苯、二甲苯等的芳香族烴、二氯甲烷、二氯乙烷等的鹵化烴、甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等的醇類、丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等的酮、乙酸乙酯、乙酸丁酯等的酯、乙基賽路蘇等的賽路蘇系溶劑等。As the diluting solvent, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, methanol, Alcohols such as ethanol, propanol, butanol, and 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone, ethyl acetate esters, esters such as butyl acetate, and celuso-based solvents such as ethyl celuso, etc.

如此進行而調製的塗佈溶液之濃度‧黏度，只要是能夠塗佈的範圍即可，而沒有特別限制，能夠按照狀況而適當地選定。例如，以黏著性組合物P的濃度成為10~60質量%之方式進行稀釋。又，在得到塗佈溶液時，稀釋溶劑等的添加不是必要條件，若黏著性組合物P為能夠塗佈的黏度等，亦可不添加稀釋溶劑。此時，黏著性組合物P是將(甲基)丙烯酸酯聚合物(A)的聚合溶劑直接作為稀釋溶劑之塗佈溶液。The concentration and viscosity of the coating solution prepared in this way are not particularly limited as long as they are within the range that can be coated, and can be appropriately selected according to the situation. For example, it dilutes so that the density|concentration of the adhesive composition P may become 10-60 mass %. In addition, when obtaining a coating solution, addition of a diluent solvent etc. is not an essential requirement, If the adhesive composition P has the viscosity etc. which can be applied, a diluent solvent may not be added. At this time, the adhesive composition P is the coating solution which used the polymerization solvent of the (meth)acrylate polymer (A) as a dilution solvent as it is.

(3)黏著劑層的形成 黏著劑層11，能夠藉由將所塗佈的黏著性組合物P交聯而形成。黏著性組合物P的交聯，以藉由加熱處理而進行為佳。又，該加熱處理亦能夠兼作黏著性組合物P之塗佈後的乾燥處理。(3) Formation of adhesive layer The adhesive layer 11 can be formed by crosslinking the applied adhesive composition P. The crosslinking of the adhesive composition P is preferably performed by heat treatment. Moreover, this heating process can also be used also as the drying process after application|coating of the adhesive composition P.

加熱處理的加熱溫度，以50~150℃為佳，以70~120℃為特佳。又，加熱時間，以10秒~10分鐘為佳，以50秒~2分鐘為特佳。又，加熱處理後，設置在常溫(例如23℃、50%RH)下1~2星期左右的熟化期間亦佳。The heating temperature of the heat treatment is preferably 50~150°C, especially preferably 70~120°C. Also, the heating time is preferably 10 seconds to 10 minutes, and particularly preferably 50 seconds to 2 minutes. In addition, after the heat treatment, it is also preferable to set an aging period of about 1 to 2 weeks at normal temperature (for example, 23° C., 50% RH).

藉由上述的加熱處理(及熟化)，能夠透過交聯劑(B)而將(甲基)丙烯酸酯聚合物(A)良好地交聯。By the above heat treatment (and aging), the (meth)acrylate polymer (A) can be favorably crosslinked through the crosslinking agent (B).

(4)黏著劑層的厚度 在本實施形態之溫度敏感性黏著片1之黏著劑層11的厚度(依據JIS K7130而測得的值)，其下限值以5μm以上為佳，以10μm以上為特佳，進而以15μm以上為佳。黏著劑層11的厚度之下限值為上述時，在常溫及高溫的黏著力更優異。又，黏著劑層11的厚度之上限值，以50μm以下為佳，以40μm以下為特佳，進而以30μm以下為佳。黏著劑層11的厚度之上限值為上述時，在低溫的易剝離性更優異。而且，黏著劑層11能夠以單層而形成，亦可層積複數層而形成。(4) The thickness of the adhesive layer The lower limit of the thickness of the adhesive layer 11 of the temperature-sensitive adhesive sheet 1 of the present embodiment (measured in accordance with JIS K7130) is preferably 5 μm or more, particularly preferably 10 μm or more, and further preferably 15 μm or more. better. When the lower limit of the thickness of the adhesive layer 11 is as described above, the adhesive force at room temperature and high temperature is more excellent. Also, the upper limit of the thickness of the adhesive layer 11 is preferably 50 μm or less, particularly preferably 40 μm or less, and further preferably 30 μm or less. When the upper limit of the thickness of the adhesive layer 11 is as described above, it is more excellent in easy-peelability at a low temperature. Furthermore, the adhesive layer 11 may be formed as a single layer, or may be formed by laminating a plurality of layers.

1-2.剝離片 剝離片12a、12b是保護黏著劑層11至溫度敏感性黏著片1的使用時為止之物，且在使用溫度敏感性黏著片1 (黏著劑層11)時被剝離。在本實施形態之溫度敏感性黏著片1，剝離片12a、12b的一方或雙方未必為必要之物。1-2. Peeling sheet The release sheets 12a and 12b protect the adhesive layer 11 until the temperature-sensitive adhesive sheet 1 is used, and are peeled off when the temperature-sensitive adhesive sheet 1 (adhesive layer 11) is used. In the temperature-sensitive adhesive sheet 1 of this embodiment, one or both of the release sheets 12a and 12b are not necessarily essential.

作為剝離片12a、12b，能夠使用，例如，聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、聚氨酯膜、乙烯乙酸乙烯酯膜、離子聚合物樹脂膜、乙烯‧(甲基)丙烯酸共聚物膜、乙烯‧(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚醯亞胺膜、氟樹脂膜等。又，亦能夠使用該等的交聯膜。而且，亦可為該等的積層膜。As the release sheets 12a, 12b, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, poly Ethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene‧(meth)acrylic acid Copolymer film, ethylene‧(meth)acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. Moreover, these crosslinked films can also be used. Furthermore, these laminated films may also be used.

在上述剝離片12a、12b的剝離面(特別是與黏著劑層11接觸之面)，較佳為經施行剝離處理。作為剝離處理所使用的剝離劑，可舉出，例如，醇酸系、聚矽酮系、氟系、不飽和聚酯系、聚烯烴系、蠟系的剝離劑。又，剝離片12a、12b之中，較佳為將一方的剝離片設為剝離力較大的重剝離型剝離片，而將另一方的剝離片設為剝離力較小的輕剝離型剝離片。It is preferable to perform a peeling process on the peeling surface (particularly, the surface which contacts the adhesive layer 11) of the said peeling sheet 12a, 12b. Examples of the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents. Also, among the release sheets 12a, 12b, it is preferable to use one release sheet as a heavy release type release sheet with a higher release force, and use the other release sheet as a light release type release sheet with a smaller release force. .

針對剝離片12a、12b的厚度沒有特別限制，通常為20~150μm左右。The thickness of the release sheets 12a and 12b is not particularly limited, but is usually about 20 to 150 μm.

2.溫度敏感性黏著片的製造 作為溫度敏感性黏著片1的一製造例，針對使用上述黏著性組合物P之情況而說明。將黏著性組合物P的塗佈液塗佈在一方的剝離片12a (或12b)的剝離面，進行加熱處理而將黏著性組合物P熱交聯且形成塗佈層之後，將該塗佈層疊合另一方的剝離片12b (或12a)的剝離面。需要熟化期間時則放置熟化期間，不需要熟化期間時則使上述塗佈層直接成為黏著劑層11。藉此，能夠得到上述溫度敏感性黏著片1。針對加熱處理及熟化條件，如前述。2. Fabrication of Temperature Sensitive Adhesive Sheets As one manufacturing example of the temperature-sensitive adhesive sheet 1, the case where the said adhesive composition P is used is demonstrated. The coating solution of the adhesive composition P is applied to the release surface of one release sheet 12a (or 12b), and after heat treatment is performed to thermally crosslink the adhesive composition P to form a coating layer, the coating The release surface of the other release sheet 12b (or 12a) is laminated. If the curing period is required, the curing period is left, and when the curing period is not required, the above-mentioned coating layer is directly made into the adhesive layer 11 . Thereby, the above-mentioned temperature-sensitive adhesive sheet 1 can be obtained. For heat treatment and aging conditions, as mentioned above.

作為塗佈上述黏著性組合物P的塗佈液之方法，能夠利用，例如，棒塗佈法、刮刀塗佈法、輥塗佈法、刀片塗佈法、模塗佈法、凹版塗佈法等。As a method of applying the coating liquid of the above-mentioned adhesive composition P, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method can be used. Wait.

3.溫度敏感性黏著片的使用 如前述，本實施形態之溫度敏感性黏著片1，能夠適合使用於將作為工件之光學構件、電子構件等的裝置、較佳是可撓性裝置、特佳是與溫度敏感性黏著片1的黏著劑層11之接觸面為平滑之可撓性裝置，在加工、層積、檢查等的步驟中固定在基板。又，上述的步驟結束後，工件從基板被剝離。3. Use of temperature-sensitive adhesive sheets As mentioned above, the temperature-sensitive adhesive sheet 1 of this embodiment can be suitably used in devices such as optical components and electronic components as workpieces, preferably flexible devices, and particularly preferably in conjunction with the temperature-sensitive adhesive sheet 1 The contact surface of the adhesive layer 11 is a smooth flexible device, which is fixed on the substrate during the steps of processing, lamination, and inspection. Also, after the above steps are completed, the workpiece is peeled off from the substrate.

第2圖是顯示表示溫度敏感性黏著片1的使用狀態之積層體4的剖面圖。本實施形態之積層體4，是將作為工件之可撓性裝置2、溫度敏感性黏著片1的黏著劑層11、及基板3依此順序層積而成。在此積層體4，因為在常溫及高溫的步驟，可撓性裝置2是透過黏著劑層11而被堅固地固定在基板3，所以能夠沒有問題地進行該步驟。FIG. 2 is a cross-sectional view showing the laminate 4 showing the temperature-sensitive adhesive sheet 1 in use. The laminated body 4 of this embodiment is formed by laminating the flexible device 2 as a workpiece, the adhesive layer 11 of the temperature-sensitive adhesive sheet 1, and the substrate 3 in this order. In the laminated body 4 , since the flexible device 2 is firmly fixed to the substrate 3 through the adhesive layer 11 in the normal-temperature and high-temperature steps, the steps can be performed without problems.

上述步驟結束之後，將黏著劑層11 (或可撓性裝置2、基板3)冷卻至低溫。冷卻溫度以-70℃以上且-20℃以下為佳，以-60℃以上且-25℃以下為特佳，進而以-50℃以上且-30℃以下為佳。藉由冷卻至所述溫度，黏著劑層11的黏著力顯著地降低，藉此，能夠容易地將可撓性裝置2從基板3剝離。After the above steps are completed, the adhesive layer 11 (or the flexible device 2, the substrate 3) is cooled to a low temperature. The cooling temperature is preferably not less than -70°C and not more than -20°C, particularly preferably not less than -60°C and not more than -25°C, and more preferably not less than -50°C and not more than -30°C. By cooling to the above temperature, the adhesive force of the adhesive layer 11 is significantly reduced, whereby the flexible device 2 can be easily peeled off from the substrate 3 .

以上說明的實施形態，是為了容易理解本發明而記載，不是用以限定本發明而記載。因而，在上述實施形態所揭示的各要素，亦包含屬於本發明技術的範圍之全部的設計變更和均等物之宗旨。The embodiments described above are described in order to facilitate understanding of the present invention, and are not described in order to limit the present invention. Therefore, each element disclosed in the above-mentioned embodiments includes all design changes and equivalents within the technical scope of the present invention.

例如，在溫度敏感性黏著片1之剝離片12a、12b的任一者或雙方亦可被省略。 [實施例]For example, either or both of the release sheets 12a and 12b of the temperature-sensitive adhesive sheet 1 may be omitted. [Example]

以下，藉由實施例等而進一步具體地說明本發明，但是本發明的範圍不被該等實施例等限定。Hereinafter, although an Example etc. demonstrate this invention more concretely, the scope of the present invention is not limited by these Examples etc.

[實施例1] 1.(甲基)丙烯酸酯聚合物(A)的調製 將丙烯酸正丁酯77質量份、丙烯酸甲酯20質量份及丙烯酸3質量份使用溶液聚合法而使其共聚合，而調製(甲基)丙烯酸酯聚合物(A)。使用後述方法而測定該(甲基)丙烯酸酯聚合物(A)的分子量時，為重量平均分子量(Mw) 80萬。[Example 1] 1. Preparation of (meth)acrylate polymer (A) 77 mass parts of n-butyl acrylates, 20 mass parts of methyl acrylates, and 3 mass parts of acrylic acid were copolymerized using the solution polymerization method, and the (meth)acrylate polymer (A) was prepared. When the molecular weight of this (meth)acrylate polymer (A) was measured using the method mentioned later, it was a weight average molecular weight (Mw) 800,000.

2.黏著性組合物的調製 將上述步驟1所得到的(甲基)丙烯酸酯聚合物(A) 100質量份(固體成分換算值；以下相同)、作為交聯劑(B)之三乙醯丙酮鋁1.0質量份、及聚輪烷化合物(C) (直鏈狀分子：聚乙二醇，環狀分子：具有羥丙基及己內酯鏈(低溫結晶化側鏈)之α-環糊精；封端基：金剛烷基，重量平均分子量(Mw) 70萬) 20質量份進行混合，充分地攪拌，使用甲基乙基酮稀釋，藉此而得到黏著性組合物的塗佈溶液。2. Preparation of adhesive composition 100 parts by mass of the (meth)acrylate polymer (A) obtained in the above step 1 (solid content conversion value; the same applies hereinafter), 1.0 parts by mass of aluminum triacetylacetonate as a crosslinking agent (B), and poly Rotaxane compound (C) (linear molecule: polyethylene glycol, cyclic molecule: α-cyclodextrin with hydroxypropyl and caprolactone chain (low temperature crystallization side chain); end-capping group: adamantane Base, weight average molecular weight (Mw) 700,000) 20 parts by mass were mixed, stirred sufficiently, and diluted with methyl ethyl ketone to obtain a coating solution of an adhesive composition.

3.黏著片的製造 將所得到的黏著性組合物之塗佈溶液，使用刮刀塗佈器塗佈在將聚對苯二甲酸乙二酯膜的一面使用聚矽酮系剝離劑進行剝離處理而成之重剝離型剝離片(LINTEC公司製，製品名「SP-PET752150」)的剝離處理面。而且，對塗佈層在90℃進行加熱處理1分鐘而形成塗佈層。3. Manufacture of adhesive sheet Heavy-duty peel-off type peeling in which the obtained coating solution of the adhesive composition is coated on one side of a polyethylene terephthalate film with a silicone-based peeling agent. The peeling-treated surface of the sheet (manufactured by Lintec Corporation, product name "SP-PET752150"). And the coating layer was heat-processed at 90 degreeC for 1 minute, and the coating layer was formed.

接著，將上述所得到的重剝離型剝離片上之塗佈層、與將聚對苯二甲酸乙二酯膜的一面使用聚矽酮系剝離劑進行剝離處理之輕剝離型剝離片(LINTEC公司製、製品名「SP-PET382120」)，以將該輕剝離型剝離片的剝離處理面接觸塗佈層之方式進行貼合，藉由在23℃、50%RH的條件下熟化7天，而製造具有厚度20μm的黏著劑層之黏著片，亦即，由重剝離型剝離片/黏著劑層(厚度：20μm)/輕剝離型剝離片的構成所構成之黏著片。又，黏劑層的厚度，是依據JIS K7130且使用定壓厚度測定器(Teclock公司製，製品名「PG-02」)而測定之值。Next, the coating layer on the heavy release type release sheet obtained above and the light release type release sheet (manufactured by Lintec Co., Ltd. , product name "SP-PET382120"), the release treatment surface of the light release type release sheet is bonded in such a way that it contacts the coating layer, and it is manufactured by aging at 23°C and 50%RH for 7 days An adhesive sheet having an adhesive layer with a thickness of 20 μm, that is, an adhesive sheet composed of a heavy release type release sheet/adhesive layer (thickness: 20 μm)/light release type release sheet. In addition, the thickness of the adhesive layer is a value measured using a constant pressure thickness measuring device (manufactured by Teclock Corporation, product name "PG-02") in accordance with JIS K7130.

在此，將(甲基)丙烯酸酯聚合物(A)設為100質量份(固體成分換算值)時之黏著性組合物的各組成(固體成分換算值)顯示在表1。又，表1記載的略號等之細節，如以下。 [(甲基)丙烯酸酯聚合物(A)] BA：丙烯酸正丁酯 2EHA：丙烯酸2-乙基己酯 MA：丙烯酸甲酯 AA：丙烯酸Here, Table 1 shows each composition (solid content conversion value) of the adhesive composition when the (meth)acrylate polymer (A) was 100 mass parts (solid content conversion value). In addition, details such as abbreviations described in Table 1 are as follows. [(Meth)acrylate polymer (A)] BA: n-butyl acrylate 2EHA: 2-Ethylhexyl Acrylate MA: methyl acrylate AA: Acrylic

[實施例2~6、比較例1~4] 將構成(甲基)丙烯酸酯聚合物(A)之各單體的種類及比例、(甲基)丙烯酸酯聚合物(A)的重量平均分子量(Mw)、交聯劑(B)的調配量、以及聚輪烷化合物(C)的調配量如表1顯示而變更，除此之外，與實施例1同樣地進行而製造黏著片。[Examples 2~6, Comparative Examples 1~4] The type and ratio of each monomer constituting the (meth)acrylate polymer (A), the weight average molecular weight (Mw) of the (meth)acrylate polymer (A), and the compounding amount of the crosslinking agent (B) , and the compounding quantity of the polyrotaxane compound (C) were changed as shown in Table 1, and it carried out similarly to Example 1, and produced the adhesive sheet.

在此，前述重量平均分子量(Mw)是使用凝膠滲透層析法(GPC)且在以下的條件下測定(GPC測定)之聚苯乙烯換算的重量平均分子量。 ＜測定條件＞ ‧GPC測定裝置：TOSOH公司製，HLC-8020 ‧GPC管柱(依照以下的順序通過)：TOSOH公司製 TSK guard column HXL-H TSK gel GMHXL(×2) TSK gel G2000HXL ‧測定溶劑：四氫呋喃 ‧測定溫度：40℃Here, the said weight average molecular weight (Mw) is the polystyrene conversion weight average molecular weight measured (GPC measurement) under the following conditions using gel permeation chromatography (GPC). ＜Measurement conditions＞ ‧GPC measurement device: HLC-8020 manufactured by TOSOH ‧GPC column (pass through in the following order): manufactured by TOSOH TSK guard column HXL-H TSK gel GMHXL (×2) TSK gel G2000HXL ‧Measurement solvent: tetrahydrofuran ‧Measurement temperature: 40℃

[試驗例1] (玻璃轉移溫度的測定) 將實施例及比較例所調製之(甲基)丙烯酸酯聚合物(A)的玻璃轉移溫度(Tg)，使用示差掃描熱量測定裝置(TA Instruments Japan公司製，製品名「DSC Q2000」)且以升溫‧降溫速度20℃/分鐘進行測定。將結果顯示在表1。[Test Example 1] (Measurement of Glass Transition Temperature) The glass transition temperature (Tg) of the (meth)acrylate polymer (A) prepared in Examples and Comparative Examples was measured using a differential scanning calorimeter (manufactured by TA Instruments Japan, product name "DSC Q2000") and expressed as The heating and cooling rate is 20°C/min for measurement. The results are shown in Table 1.

[試驗例2] (儲存模數的測定) 將實施例及比較例所製造的黏著片的黏著劑層層積複數層，而成為厚度3mm的積層體。從所得到的黏著劑層之積層體，沖切直徑8mm的圓柱體(高度3mm)，將其作為試樣。[Test Example 2] (Measurement of storage modulus) The adhesive layer of the adhesive sheet manufactured in the Example and the comparative example was laminated|stacked several layers, and it became the laminated body of thickness 3mm. A cylinder (3 mm in height) with a diameter of 8 mm was punched out from the obtained laminate of the adhesive layer, and this was used as a sample.

針對上述試樣，依JIS K7244-6且使用黏彈性測定器(REOMETRIC公司製，DYNAMIC ANALAYZER)而藉由扭轉剪切法，在以下的條件下測定儲存模數(MPa)。將結果顯示在表2。 測定頻率：1Hz 測定溫度：-20℃、23℃、80℃About the said sample, storage modulus (MPa) was measured under the following conditions by the torsional shear method using the viscoelasticity measuring device (DYNAMIC ANALAYZER manufactured by REOMETRIC company) according to JISK7244-6. The results are shown in Table 2. Measurement frequency: 1Hz Measuring temperature: -20°C, 23°C, 80°C

從上述所得到的結果，算出在-20℃之儲存模數相對於在23℃之儲存模數之比(%)、及在80℃之儲存模數相對於在23℃之儲存模數之比(%)。將結果顯示在表2。From the results obtained above, calculate the ratio (%) of the storage modulus at -20°C to the storage modulus at 23°C, and the ratio (%) of the storage modulus at 80°C to the storage modulus at 23°C (%). The results are shown in Table 2.

[試驗例3] (黏著力的測定) 從在實施例及比較例所製造的黏著片將輕剝離型剝離片剝離，將露出的黏著劑層貼合在具有易接著層之聚對苯二甲酸乙二酯(PET)膜(東洋紡公司製，製品名「PET A4300」，厚度：100μm)的易接著層，而得到剝離片/黏著劑層/PET膜的積層體。將所得到的積層體裁斷成為25mm寬、100mm長，將其作為試樣。[Test Example 3] (Measurement of Adhesive Force) The easy-release type release sheet was peeled off from the adhesive sheet produced in Examples and Comparative Examples, and the exposed adhesive layer was attached to a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd.) with an easy-adhesive layer. , Product name "PET A4300", thickness: 100μm) easy-adhesive layer to obtain a laminate of release sheet/adhesive layer/PET film. The obtained laminate was cut into a width of 25 mm and a length of 100 mm, and this was used as a sample.

在23℃、50%RH的環境下，將重剝離型剝離片從上述試樣剝離，將露出的黏著劑層貼附在鈉鈣玻璃(日本板硝子公司製)之後，藉由栗原製作所公司製高壓釜且在0.5MPa、50℃加壓20分鐘。隨後，在以下(a)~(c)的條件下放置24小時之後，使用拉伸試驗機(ORIENTEC公司製，TENSILON)，在剝離速度2.0m/min、剝離角度180度的條件下測定黏著力(對玻璃黏著力；N/25mm)。在此所記載以外的條件是依據JIS Z0237：2009而進行測定。將結果顯示在表2。 (a) -20℃、50%RH (b) 23℃、50%RH (c) 80℃、50%RHIn an environment of 23°C and 50% RH, the heavy-peeling release sheet was peeled from the above sample, and the exposed adhesive layer was attached to soda-lime glass (manufactured by Nippon Plate Glass Co., Ltd.), and then the product was removed by a high-pressure device manufactured by Kurihara Seisakusho Co., Ltd. The kettle was pressurized at 0.5MPa, 50°C for 20 minutes. Then, after standing for 24 hours under the following conditions (a) to (c), the adhesive force was measured under the conditions of a peeling speed of 2.0 m/min and a peeling angle of 180 degrees using a tensile tester (manufactured by Orientec Co., Ltd., TENSILON). (adhesion to glass; N/25mm). Conditions other than those described here were measured in accordance with JIS Z0237:2009. The results are shown in Table 2. (a) -20℃, 50%RH (b) 23°C, 50%RH (c) 80°C, 50%RH

從上述所得到的結果，算出在-20℃之對玻璃黏著力相對於在23℃之對玻璃黏著力之比(%)、及在80℃之對玻璃黏著力相對於在23℃之對玻璃黏著力之比(%)。將結果顯示在表2。From the results obtained above, calculate the ratio (%) of the adhesion to glass at -20°C to that at 23°C, and the ratio (%) of the adhesion to glass at 80°C to that at 23°C Adhesion ratio (%). The results are shown in Table 2.

又，在23℃、50%RH的環境下，將重剝離型剝離片從上述試樣剝離，將露出的黏著劑層貼附在作為被黏著物之一面的表面粗糙度Ra為2.7μm之PET膜(表面為非常平滑的PET膜A，厚度：100μm)的上述一面。而且，在栗原製作所公司製高壓釜於0.5MPa、50℃加壓20分鐘。隨後，在-20℃、50%RH的條件下放置24小時之後，與上述同樣地進行而測定黏著力(在-20℃之對PET黏著力A；N/25mm)。將結果顯示在表1。Also, in an environment of 23°C and 50%RH, the heavy release type release sheet was peeled off from the above sample, and the exposed adhesive layer was attached to a PET with a surface roughness Ra of 2.7 μm on one side of the adherend. The above-mentioned side of the film (the surface is very smooth PET film A, thickness: 100 μm). And it pressurized at 0.5 MPa and 50 degreeC for 20 minutes in the autoclave manufactured by Kurihara Seisakusho. Then, after leaving it to stand on the condition of -20 degreeC and 50%RH for 24 hours, it carried out similarly to the above, and measured the adhesive force (adhesion force A with respect to PET at -20 degreeC; N/25mm). The results are shown in Table 1.

而且，將一面的表面粗糙度Ra為60μm之PET膜(表面為相對較平滑的PET膜B，厚度：100μm)作為被黏著物。與上述同樣地進行而測定黏著力(在-20℃之對PET黏著力B；N/25mm)。將結果顯示在表2。And, the PET film (the surface is relatively smooth PET film B, thickness: 100 μm) whose surface roughness Ra of one side is 60 μm was used as an adherend. Adhesion was measured in the same manner as above (adhesion B to PET at -20°C; N/25mm). The results are shown in Table 2.

[試驗例4] (製程評價) (A)工件表面為非常平滑的情況 作為工件，準備一面的表面粗糙度Ra為2.7μm之聚對苯二甲酸乙二酯(PET)膜(厚度：100μm)，從實施例及比較例所製造的黏著片將輕剝離型剝離片剝離，將露出的黏著劑層貼合在上述工件的上述一面，而得到重剝離型剝離片/黏著劑層/PET膜的積層體。將所得到的積層體裁斷成為25mm寬、100mm長。[Test Example 4] (Process evaluation) (A) When the workpiece surface is very smooth As a workpiece, a polyethylene terephthalate (PET) film (thickness: 100 μm) with a surface roughness Ra of 2.7 μm on one side was prepared, and the light-peelable release sheet was peeled off from the adhesive sheet produced in the examples and comparative examples. , stick the exposed adhesive layer on the above-mentioned one side of the above-mentioned workpiece to obtain a laminate of heavy-release type release sheet/adhesive layer/PET film. The obtained laminate was cut into a width of 25 mm and a length of 100 mm.

在23℃、50%RH的環境下，從上述積層體將重剝離型剝離片剝離，將露出的黏著劑層貼附在鈉鈣玻璃(日本板硝子公司製)之後，在栗原製作所公司製高壓釜於0.5MPa、50℃加壓20分鐘，將其作為試樣。作為高溫製程，將所得到的試樣投入150℃、50%RH的高溫條件下30分鐘。隨後，作為低溫製程，投入-20℃、50%RH的低溫條件下1小時，然後將PET膜從黏著劑層剝離。In an environment of 23°C and 50% RH, after peeling off the heavy-release type release sheet from the above-mentioned laminate, and attaching the exposed adhesive layer to soda-lime glass (manufactured by Nippon Plate Glass Co., Ltd.), the product was placed in an autoclave manufactured by Kurihara Seisakusho Co., Ltd. It pressurized at 0.5 MPa and 50 degreeC for 20 minutes, and made this into a sample. As a high-temperature process, the obtained sample was placed under high-temperature conditions of 150° C. and 50% RH for 30 minutes. Then, as a low-temperature process, it was put into low-temperature conditions of -20°C and 50%RH for 1 hour, and then the PET film was peeled off from the adhesive layer.

在上述的高溫製程，針對PET膜與黏著劑層的界面、及黏著劑層與鈉鈣玻璃的界面之狀態進行確認，基於以下的基準而進行高溫的製程評價(A)。將結果顯示在表2。 ◎…高溫步驟中，在各界面不產生浮起‧剝落，且PET膜堅固地固定在鈉鈣玻璃。 ○...高溫步驟中，能夠在界面稍微觀察到浮起‧剝落。 ╳…高溫步驟中，在界面產生浮起‧剝落且產生剝離。In the above-mentioned high-temperature process, the state of the interface between the PET film and the adhesive layer and the interface between the adhesive layer and soda-lime glass was confirmed, and the high-temperature process evaluation (A) was performed based on the following criteria. The results are shown in Table 2. ◎...During the high temperature step, there is no floating and peeling at each interface, and the PET film is firmly fixed on the soda lime glass. ○...In the high-temperature step, floating and peeling were slightly observed at the interface. ╳...In the high-temperature step, floating and peeling occurred at the interface and peeling occurred.

又，在上述的低溫製程，針對剝離的容易性、及PET膜與黏著劑層的界面狀態進行確認，且基於以下的基準而進行低溫的製程評價(A)。將結果顯示在表2。 ◎…在黏著劑層與PET膜的界面之剝離為容易的，剝離後，黏著劑層亦附著在鈉鈣玻璃。 ○…在黏劑層與PET膜的界面之剝離為容易的，剝離後能夠觀察到在鈉鈣玻璃與黏著劑層的界面產生浮起。 ╳…在黏劑層與PET膜的界面之剝離為困難的。(PET膜與黏著劑層之積層體從鈉鈣玻璃剝落)。In addition, in the above-mentioned low-temperature process, the easiness of peeling and the state of the interface between the PET film and the adhesive layer were confirmed, and the low-temperature process evaluation (A) was performed based on the following criteria. The results are shown in Table 2. ◎...It is easy to peel off at the interface between the adhesive layer and the PET film, and after peeling off, the adhesive layer also adheres to the soda lime glass. ○...Peeling at the interface between the adhesive layer and the PET film was easy, and after peeling, it was observed that floating occurred at the interface between the soda lime glass and the adhesive layer. ╳...It was difficult to peel off at the interface between the adhesive layer and the PET film. (The laminate of the PET film and the adhesive layer peeled off from the soda-lime glass).

(B)工件的表面為相對較平滑的情況 準備一面的表面粗糙度Ra為60μm之PET膜(厚度：100μm)作為工件。使用該工件，與上述製程評價(A)同樣地進行評價高溫及低溫的製程評價(B)。將結果顯示在表2。(B) The surface of the workpiece is relatively smooth A PET film (thickness: 100 μm) having a surface roughness Ra of one side of 60 μm was prepared as a work. Using this workpiece, the process evaluation (B) for evaluating high temperature and low temperature was performed in the same manner as the above process evaluation (A). The results are shown in Table 2.

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

[表2]

Figure 02_image003
[Table 2]
Figure 02_image003

從表2能夠清楚明白，實施例所製造的溫度敏感性黏著片，在常溫及高溫可發揮優異的黏著力，而且在步驟中能夠將工件堅固地固定在基板。又，使用該溫度敏感性黏著片時，藉由在低溫冷卻而能夠從基板將工件容易地剝離。 [產業上之可利用能性]It can be clearly seen from Table 2 that the temperature-sensitive adhesive sheet produced in the embodiment can exhibit excellent adhesive force at room temperature and high temperature, and can firmly fix the workpiece on the substrate during the steps. In addition, when this temperature-sensitive adhesive sheet is used, the workpiece can be easily peeled off from the substrate by cooling at a low temperature. [Industrial availability]

本發明之溫度敏感性黏著片，特別是適合作為在可撓性裝置的加工、層積、檢查等的步驟所使用的步驟用黏著片。The temperature-sensitive adhesive sheet of the present invention is particularly suitable as an adhesive sheet for steps used in steps such as processing, lamination, and inspection of flexible devices.

1‧‧‧溫度敏感性黏著片 11‧‧‧黏著劑層 12a、12b‧‧‧剝離片 2‧‧‧工件(可撓性裝置) 3‧‧‧基板 4‧‧‧積層體1‧‧‧Temperature Sensitive Adhesive Sheet 11‧‧‧adhesive layer 12a, 12b‧‧‧Peeling sheet 2‧‧‧Workpiece (flexible device) 3‧‧‧substrate 4‧‧‧Laminated body

第1圖是本發明的一實施形態之溫度敏感性黏著片的剖面圖。 第2圖是本發明的一實施形態之積層體的剖面圖。Fig. 1 is a cross-sectional view of a temperature-sensitive adhesive sheet according to an embodiment of the present invention. Fig. 2 is a cross-sectional view of a laminate according to an embodiment of the present invention.

1‧‧‧溫度敏感性黏著片 1‧‧‧Temperature Sensitive Adhesive Sheet

11‧‧‧黏著劑層 11‧‧‧adhesive layer

12a、12b‧‧‧剝離片 12a, 12b‧‧‧Peeling sheet

Claims (11)

一種溫度敏感性黏著片，其為至少包括黏著劑層之溫度敏感性黏著片，其特徵在於：在-20℃之對玻璃黏著力為小於1.5N/25mm，在80℃之對玻璃黏著力為2.0N/25mm以上，前述黏著劑層在-20℃之儲存模數為1MPa以上且500MPa以下，前述黏著劑層是由含有(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、及聚輪烷化合物(C)之黏著性組合物形成的黏著劑所構成，其中前述交聯劑(B)為金屬螯合物系交聯劑，前述黏著性組合物中前述聚輪烷化合物(C)的含量為相對於前述(甲基)丙烯酸酯聚合物(A)100質量份為9質量份以上、70質量份以下。 A temperature-sensitive adhesive sheet, which is a temperature-sensitive adhesive sheet including at least an adhesive layer, characterized in that: the adhesive force to glass at -20°C is less than 1.5N/25mm, and the adhesive force to glass at 80°C is 2.0N/25mm or more, the storage modulus of the adhesive layer at -20°C is not less than 1 MPa and not more than 500 MPa, and the adhesive layer is made of (meth)acrylate polymer (A), crosslinking agent (B) , and an adhesive composed of an adhesive composition of a polyrotaxane compound (C), wherein the aforementioned crosslinking agent (B) is a metal chelate-based crosslinking agent, and the aforementioned polyrotaxane compound in the aforementioned adhesive composition Content of (C) is 9 mass parts or more and 70 mass parts or less with respect to 100 mass parts of said (meth)acrylate polymers (A). 如申請專利範圍第1項所述之溫度敏感性黏著片，其中在-20℃之對玻璃黏著力相對於在23℃之對玻璃黏著力之比，為1%以上且40%以下。 The temperature-sensitive adhesive sheet as described in claim 1, wherein the ratio of the adhesive force to glass at -20°C to the adhesive force to glass at 23°C is not less than 1% and not more than 40%. 如申請專利範圍第1項所述之溫度敏感性黏著片，其中在80℃之對玻璃黏著力相對於在23℃之對玻璃黏著力之比，為10%以上且300%以下。 The temperature-sensitive adhesive sheet described in claim 1, wherein the ratio of the adhesive force to glass at 80°C to the adhesive force to glass at 23°C is not less than 10% and not more than 300%. 如申請專利範圍第1項所述之溫度敏感性黏著片，其中前述黏著劑層在80℃之儲存模數為0.01MPa以上且1MPa以下。 The temperature-sensitive adhesive sheet as described in claim 1, wherein the storage modulus of the adhesive layer at 80° C. is not less than 0.01 MPa and not more than 1 MPa. 如申請專利範圍第1項所述之溫度敏感性黏著片，其中前述(甲基)丙烯酸酯聚合物(A)含有在分子內具有羧基的單體作為構成該聚合物之單體單元。 The temperature-sensitive adhesive sheet as described in claim 1, wherein the (meth)acrylate polymer (A) contains a monomer having a carboxyl group in the molecule as a monomer unit constituting the polymer. 如申請專利範圍第1項所述之溫度敏感性黏著片，其係使用於步驟中透過前述黏著劑層而將工件固定在基板，且步驟結束後，將前述工件從前 述黏著劑層剝離之用途。 The temperature-sensitive adhesive sheet described in item 1 of the scope of the patent application is used to fix the workpiece on the substrate through the aforementioned adhesive layer in the step, and after the step is completed, the aforementioned workpiece is removed from the previous step. The purpose of peeling off the adhesive layer is described above. 如申請專利範圍第6項所述之溫度敏感性黏著片，其中在前述工件之前述黏著劑層側的面之表面粗糙度Ra為0.01μm以上且80μm以下。 The temperature-sensitive adhesive sheet according to claim 6, wherein the surface roughness Ra of the surface of the workpiece on the side of the adhesive layer is 0.01 μm or more and 80 μm or less. 如申請專利範圍第6項所述之溫度敏感性黏著片，其中在前述步驟中，工件被加熱至40℃以上且200℃以下。 The temperature-sensitive adhesive sheet described in claim 6 of the patent application, wherein in the aforementioned step, the workpiece is heated to a temperature above 40°C and below 200°C. 如申請專利範圍第6項所述之溫度敏感性黏著片，其中前述工件為可撓性裝置。 The temperature-sensitive adhesive sheet as described in claim 6 of the patent application, wherein the aforementioned workpiece is a flexible device. 如申請專利範圍第1項所述之溫度敏感性黏著片，其中前述溫度敏感性黏著片包括2片剝離片，前述黏著劑層以與前述2片剝離片的剝離面接觸之方式而被前述剝離片挾持著。 The temperature-sensitive adhesive sheet as described in item 1 of the scope of patent application, wherein the aforementioned temperature-sensitive adhesive sheet includes two release sheets, and the aforementioned adhesive layer is peeled off by the aforementioned method in contact with the release surfaces of the aforementioned two release sheets. The film is held hostage. 一種積層體，其係將可撓性裝置、如申請專利範圍第1至10項中任一項所述之溫度敏感性黏著片的前述黏著劑層、及基板依此順序層積而成。 A laminated body formed by laminating a flexible device, the aforementioned adhesive layer of the temperature-sensitive adhesive sheet described in any one of claims 1 to 10, and a substrate in this order.
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