TW202020084A - Pressure-sensitive adhesive sheet, laminated body, and display - Google Patents

Pressure-sensitive adhesive sheet, laminated body, and display Download PDF

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TW202020084A
TW202020084A TW108141296A TW108141296A TW202020084A TW 202020084 A TW202020084 A TW 202020084A TW 108141296 A TW108141296 A TW 108141296A TW 108141296 A TW108141296 A TW 108141296A TW 202020084 A TW202020084 A TW 202020084A
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copolymer
adhesive layer
adhesive sheet
mass
acrylate
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TW108141296A
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Chinese (zh)
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福田克哲
小林孝行
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日商東洋油墨Ｓｃ控股股份有限公司
日商東洋科美股份有限公司
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Publication of TW202020084A publication Critical patent/TW202020084A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/02—Polyureas
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/005—Presence of polyester in the release coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention provides an adhesive sheet which is excellent in transparency and capable of having moist-heat resistance, heat resistance and flexibility, and a laminated body and a display using the adhesive sheet. The adhesive sheet of the present invention is an adhesive sheet for forming an adhesive layer (1) contained in a laminated body including a light-transmitting flexible substrate, an adhesive layer (1) and a polarizing plate. The adhesive layer (1) includes a copolymer (A) having a structural unit derived from a polymerizable compound (a) with a number average molecular weight of 1000 to 10000 and a hydroxyl group, and a cured product of a curing agent, wherein in a bending test under an atmosphere of a temperature of 25 DEG C and a relative humidity of 50% RH, the rate of HAZE change before and after bending 300,000 times is 20% or less.

Description

黏著片、積層體及顯示器Adhesive sheet, laminate and display

本申請主張以2018年11月16日提出申請的日本專利申請特願2018-215786號為基礎的優先權，將其公開的全部內容併入本文中。 本發明是有關於一種包括光透過性可撓性基材、黏著層及偏光板的積層體、以及所述積層體中所含的黏著層的形成用的黏著片（pressure-sensitive adhesive sheet）。所述積層體可較佳地用於顯示器。This application claims priority based on Japanese Patent Application No. 2018-215786 filed on November 16, 2018, and the entire contents of the disclosure are incorporated herein. The present invention relates to a laminate including a light-transmissive flexible substrate, an adhesive layer and a polarizing plate, and an adhesive sheet (pressure-sensitive adhesive sheet) for forming an adhesive layer included in the laminate. The laminate can be preferably used for displays.

近年來，將液晶顯示器（Liquid Crystal Display，LCD）及有機電致發光（有機EL）顯示器（organic light emitting display，OLED）等圖像顯示裝置與觸控螢幕組合而成的輸入裝置正在普及。觸控螢幕中所使用的透明導電性膜一般而言具有在包括塑膠等的基材上積層透明導電膜（氧化銦錫（Indium tin oxide，ITO））膜的構成，並經由黏著層而積層於其他構件上。In recent years, input devices that combine an image display device such as a liquid crystal display (LCD) and an organic light emitting display (organic light emitting display (OLED)) with a touch screen are becoming popular. The transparent conductive film used in the touch screen generally has a structure in which a transparent conductive film (Indium tin oxide (ITO)) film is laminated on a substrate including plastic, and is laminated on the substrate through an adhesive layer On other components.

作為圖像顯示裝置，以往，使用玻璃基板的平板顯示器是主流，但近年來，使用包括塑膠等的可撓性基板的可折疊顯示器（Foldable display）及可滾動顯示器（Rollable display）等柔性顯示器得到了開發。此種柔性顯示器與以往使用玻璃基板的平板顯示器相比，輕量性、薄度、可撓性及設計性等優異。As image display devices, flat-panel displays using glass substrates have been mainstream in the past, but in recent years, flexible displays such as foldable displays (Foldable display) and rollable displays (Rollable display) using flexible substrates including plastic have been obtained Development. Such a flexible display is superior in lightness, thinness, flexibility, design, etc. compared to the conventional flat panel display using a glass substrate.

黏著層一直以來需要在高溫環境或高溫高濕環境下不會產生起泡及剝離的性質。近年來還需要可應對彎折，以能夠用於可將顯示器自身彎曲的柔性顯示器。The adhesive layer has been required to have no foaming and peeling properties under high temperature environment or high temperature and high humidity environment. In recent years, there has also been a need for a flexible display that can handle bending so that it can be used to bend the display itself.

為了解決這些問題，專利文獻1中公開了一種包括可撓性基材、透明導電性膜及黏著層，黏著層的儲存彈性模量為0.1 MPa～0.4 MPa的積層體。專利文獻2中公開了一種包含基礎聚合物、紫外線吸收劑及色素化合物的黏著劑組合物。 [現有技術文獻] [專利文獻]In order to solve these problems, Patent Document 1 discloses a laminate including a flexible substrate, a transparent conductive film, and an adhesive layer, and the storage elastic modulus of the adhesive layer is 0.1 MPa to 0.4 MPa. Patent Document 2 discloses an adhesive composition containing a base polymer, an ultraviolet absorber, and a pigment compound. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2017-65217號公報 [專利文獻2]日本專利特開2018-28974號公報[Patent Document 1] Japanese Patent Laid-Open No. 2017-65217 [Patent Document 2] Japanese Patent Laid-Open No. 2018-28974

[發明所要解決的問題] 然而，以往的黏著片中，現狀是未能同時滿足實用上無問題的程度的耐熱性及耐濕熱性與彎曲性。[Problems to be solved by the invention] However, in the conventional adhesive sheet, the current situation is that it fails to satisfy both the heat resistance, the moisture resistance, and the bendability to a practically problem-free level.

本發明的目的在於提供一種透明性優異、能夠兼顧耐濕熱性及耐熱性與彎曲性的黏著片、以及使用所述黏著片的積層體。 [解決問題的技術手段]An object of the present invention is to provide an adhesive sheet excellent in transparency, capable of achieving both moisture resistance, heat resistance, and flexibility, and a laminate using the adhesive sheet. [Technical means to solve the problem]

本發明者們反覆進行了積極研究，發現以下的形態可解決本發明的課題，從而完成了本發明。 本發明的一形態為一種黏著片，其為包括光透過性可撓性基材、黏著層及偏光板的積層體中所含的所述黏著層的形成用的黏著片，其中， 所述黏著層包括具有源自數量平均分子量1000～10000的聚合性化合物（a）的構成單元與羥基的共聚物（A）及硬化劑的硬化物，溫度25℃、相對濕度50%RH環境下的彎曲試驗中30萬次彎曲前後的HAZE變化率為20%以下。 [發明的效果]The inventors have repeatedly conducted active research and found that the following forms can solve the problems of the present invention, and completed the present invention. An aspect of the present invention is an adhesive sheet, which is an adhesive sheet for forming the adhesive layer contained in a laminate including a light-transmissive flexible substrate, an adhesive layer and a polarizing plate, wherein, The adhesive layer includes a cured product of a copolymer (A) having a structural unit derived from a polymerizable compound (a) having a number average molecular weight of 1,000 to 10,000 and a hydroxyl group, and a hardener at a temperature of 25°C and a relative humidity of 50% RH The rate of HAZE change before and after 300,000 bends in the bending test was 20% or less. [Effect of invention]

根據本發明，可提供一種透明性優異，耐濕熱性、耐熱性及彎曲性良好的黏著片、以及使用所述黏著片的積層體。 通過使用本發明的黏著片及積層體，可提供一種可視性及對比度優異的顯示器。According to the present invention, it is possible to provide an adhesive sheet excellent in transparency, excellent in moisture and heat resistance, heat resistance, and flexibility, and a laminate using the adhesive sheet. By using the adhesive sheet and laminate of the present invention, a display with excellent visibility and contrast can be provided.

以下，針對本發明的黏著片、積層體及顯示器的構成例進行說明，但本發明並不限定於這些例子。 另外，本說明書中，重量平均分子量（Mw）及數量平均分子量（Mn）是通過凝膠滲透色譜法（Gel Permeation Chromatography，GPC）法而測定的聚苯乙烯換算值。測定法的細節記載於[實施例]的項中。Hereinafter, the configuration examples of the adhesive sheet, laminate, and display of the present invention will be described, but the present invention is not limited to these examples. In addition, in the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene conversion values measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) method. The details of the measurement method are described in the section of [Examples].

《黏著片》 本發明的黏著片是包括光透過性可撓性基材（也稱為蓋板（cover panel））、黏著層及偏光板的積層體中所含的黏著層的形成用的黏著片。本發明的黏著片用於將光透過性可撓性基材與偏光板接合。 圖1中示出本發明的一實施方式的黏著片的局部概略剖面圖的例子。圖1中，符號1為黏著層，符號2為剝離膜。"Adhesive Film" The adhesive sheet of the present invention is an adhesive sheet for forming an adhesive layer included in a laminate including a light-transmissive flexible substrate (also referred to as a cover panel), an adhesive layer, and a polarizing plate. The adhesive sheet of the present invention is used to join a light-transmitting flexible substrate to a polarizing plate. FIG. 1 shows an example of a partial schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention. In FIG. 1, symbol 1 is an adhesive layer, and symbol 2 is a release film.

本實施方式的黏著片如圖1中所示，具有在黏著層1的兩面積層有剝離膜2的構成。被夾持在兩個剝離膜2之間的黏著層1是使用具有羥基的共聚物（A）與硬化劑的混合物而形成的黏著層。 黏著片的構成能夠適當設計變更。As shown in FIG. 1, the adhesive sheet of this embodiment has a structure in which a release film 2 is formed on both areas of the adhesive layer 1. The adhesive layer 1 sandwiched between the two release films 2 is an adhesive layer formed using a mixture of a copolymer (A) having a hydroxyl group and a hardener. The configuration of the adhesive sheet can be appropriately designed and changed.

「黏著層」 黏著層是具有源自數量平均分子量（Mn）1000～10000的聚合性化合物（a）的構成單元與羥基的共聚物（A）及硬化劑的硬化物。所述黏著層中，溫度25℃、相對濕度50%RH氣氛下的彎曲試驗中30萬次彎曲前後的HAZE變化率為20%以下。"Sticky layer" The adhesive layer is a cured product having a copolymer (A) and a curing agent derived from a structural unit derived from a polymerizable compound (a) having a number average molecular weight (Mn) of 1,000 to 10,000 and a hydroxyl group. In the adhesive layer, the HAZE change rate before and after 300,000 bendings in a bending test at a temperature of 25° C. and a relative humidity of 50% RH was 20% or less.

通過使用具有源自高分子量的聚合性化合物的構成單元的共聚物（A），可在黏著層內局部地形成空間性密度高的部分與低的部分。由此可對黏著層賦予適度的柔軟性，結果能夠兼顧耐熱性與彎曲性。 而且，通過使用共聚物（A），可通過與後述的硬化劑的交聯反應而形成聚合物網路，從而可對黏著層賦予凝聚力。結果，黏著層變得耐熱性、耐濕熱性及彎曲性優異。By using the copolymer (A) having a structural unit derived from a high molecular weight polymerizable compound, a high spatial density portion and a low portion can be locally formed in the adhesive layer. As a result, moderate flexibility can be imparted to the adhesive layer, and as a result, both heat resistance and flexibility can be achieved. Furthermore, by using the copolymer (A), a polymer network can be formed by a cross-linking reaction with a hardener described below, and cohesive force can be imparted to the adhesive layer. As a result, the adhesive layer becomes excellent in heat resistance, moisture heat resistance, and flexibility.

進而，通過使彎曲試驗中30萬次彎曲前後的HAZE變化率為20%以下，即使在將黏著層應用作可折疊顯示器構件的情況下，也可不損害可視性地使用顯示器。Furthermore, by making the HAZE change rate before and after 300,000 bends in the bending test 20% or less, even when the adhesive layer is applied as a foldable display member, the display can be used without impairing visibility.

本說明書中，HAZE變化率可通過彎曲試驗來求出。彎曲試驗如下來進行。使用彎折試驗機（湯淺系統（yuasa-system）設備公司製造），將條件設定為彎折時的內徑為6 mm（彎曲半徑=3 mm）。將彎折與180°打開設為一個循環（cycle），並設定為1循環/1秒（彎曲速度=1次/1秒）。進行30萬循環（彎曲次數30萬次）反覆彎曲，通過下述式1求出HAZE變化率。 （式1） HAZE變化率（ΔHAZE）（%）： ΔHAZE（%）=[（HAZE（E）-HAZE（S））/HAZE（S）]×100 此處， HAZE（S）表示彎曲試驗前的黏著層的HAZE。 HAZE（E）表示彎曲試驗後的黏著層的HAZE。In this specification, the rate of change of HAZE can be obtained by a bending test. The bending test is performed as follows. Using a bending tester (manufactured by Yuasa-system), the condition was set to an inner diameter of 6 mm (bending radius = 3 mm) during bending. The bending and opening at 180° are set as one cycle, and set to 1 cycle/1 second (bending speed=1 time/1 second). 300,000 cycles (300,000 bending times) were repeatedly bent, and the HAZE change rate was determined by the following equation 1. (Formula 1) HAZE change rate (ΔHAZE) (%): ΔHAZE(%)=[(HAZE(E)-HAZE(S))/HAZE(S)]×100 Here, HAZE (S) represents the HAZE of the adhesive layer before the bending test. HAZE (E) represents the HAZE of the adhesive layer after the bending test.

HAZE變化率為20%以下，更優選為10%以下。通過使HAZE變化率為20%以下，即使在將黏著層應用作可折疊顯示器構件時，也不會損害可折疊顯示器的可視性。The HAZE change rate is 20% or less, and more preferably 10% or less. By making the HAZE change rate 20% or less, even when the adhesive layer is applied as a foldable display member, the visibility of the foldable display will not be impaired.

＜共聚物（A）＞ 共聚物（A）是對兩種以上的單體進行共聚而獲得，只要為具有羥基且具有源自數量平均分子量1000～10000的聚合性化合物（a）的構成單元的共聚物，則並無限制。例如可列舉：丙烯酸系共聚物、氨基甲酸酯系共聚物、氨基甲酸酯脲系共聚物、醯胺系共聚物及聚酯系聚合物等。其中，優選為丙烯酸系共聚物（A1）和/或氨基甲酸酯脲系共聚物（A2）。在使用丙烯酸系共聚物作為共聚物（A）的情況下，可尤其抑制耐熱試驗時HAZE變化率的上升，因此優選。在使用氨基甲酸酯脲系共聚物作為共聚物（A）的情況下，可尤其抑制耐濕熱試驗時HAZE變化率的上升，因此優選。<Copolymer (A)> The copolymer (A) is obtained by copolymerizing two or more monomers, and is not limited as long as it has a hydroxyl group and has a structural unit derived from the polymerizable compound (a) having a number average molecular weight of 1,000 to 10,000. . Examples include acrylic copolymers, urethane copolymers, urethane urea copolymers, amide copolymers, and polyester polymers. Among them, the acrylic copolymer (A1) and/or the urethane urea copolymer (A2) are preferred. When an acrylic copolymer is used as the copolymer (A), the increase in the HAZE change rate during the heat resistance test can be particularly suppressed, which is preferable. When a urethane urea-based copolymer is used as the copolymer (A), the increase in the HAZE change rate during the humid heat resistance test can be particularly suppressed, which is preferable.

另外，聚合性化合物是共聚反應後構成所獲得的共聚物的一部分的成分，可列舉單體及寡聚物等。在共聚物為氨基甲酸酯系樹脂的情況下，聚合性化合物中也包含多元醇及異氰酸酯。聚合性化合物中不包含起始劑等不構成共聚物的一部分的成分。In addition, the polymerizable compound is a component that constitutes a part of the obtained copolymer after the copolymerization reaction, and examples thereof include monomers and oligomers. When the copolymer is a urethane-based resin, the polymerizable compound also includes a polyol and an isocyanate. The polymerizable compound does not contain components such as an initiator that do not form part of the copolymer.

用於共聚物的製造的聚合性化合物的混合物是指聚合性化合物（a）、視需要的其他單體、及視需要的反應停止劑等、構成共聚物的所有成分的混合物。 具體而言，在丙烯酸系共聚物中，聚合性化合物的混合物是包含具有不飽和雙鍵的化合物等單體等的混合物。 在氨基甲酸酯系共聚物中，聚合性化合物的混合物是包含異氰酸酯化合物及多元醇的混合物。 在氨基甲酸酯脲系共聚物中，聚合性化合物的混合物是包含異氰酸酯化合物、多元醇、二氨基化合物及反應停止劑等的混合物。 在醯胺系共聚物中，聚合性化合物的混合物是包含多元氨基化合物及多元羧酸等的混合物。在聚酯系聚合物中，聚合性化合物的混合物是包含多元醇及多元羧酸等的混合物。The mixture of the polymerizable compounds used in the production of the copolymer refers to a mixture of all the components constituting the copolymer, such as the polymerizable compound (a), other monomers as needed, and reaction stoppers as needed. Specifically, in the acrylic copolymer, the mixture of polymerizable compounds is a mixture containing monomers such as a compound having an unsaturated double bond. In the urethane-based copolymer, the mixture of polymerizable compounds is a mixture containing an isocyanate compound and a polyol. In the urethane urea copolymer, the mixture of polymerizable compounds is a mixture containing an isocyanate compound, a polyol, a diamino compound, a reaction stopper, and the like. In the amide-based copolymer, the mixture of polymerizable compounds is a mixture containing a polyamino compound, a polycarboxylic acid, and the like. In the polyester-based polymer, the mixture of polymerizable compounds is a mixture containing a polyol, a polycarboxylic acid, and the like.

[丙烯酸系共聚物（A1）] 作為共聚物（A）而言優選的丙烯酸系共聚物（A1）（以下，有時簡單記述為「共聚物（A1）」）是具有源自數量平均分子量（Mn）1000～10000的聚合性化合物（a）的構成單元及羥基的丙烯酸系共聚物。丙烯酸系共聚物（A1）可通過對包含數量平均分子量（Mn）1000～10000的聚合性化合物（a）及具有羥基的單體的單體混合物進行共聚而獲得。[Acrylic copolymer (A1)] The acrylic copolymer (A1) preferred as the copolymer (A) (hereinafter, sometimes simply referred to as "copolymer (A1)") is a polymerizable compound having a number average molecular weight (Mn) of 1,000 to 10,000 (A) The acrylic copolymer of the structural unit and the hydroxyl group. The acrylic copolymer (A1) can be obtained by copolymerizing a monomer mixture containing a polymerizable compound (a) having a number average molecular weight (Mn) of 1,000 to 10,000 and a monomer having a hydroxyl group.

丙烯酸系共聚物（A1）的重量平均分子量（Mw）優選為20萬～200萬，更優選為50萬～180萬，特別優選為100萬～180萬。通過使丙烯酸系共聚物（A1）的Mw處於20萬～200萬的範圍，黏著層的凝聚力進一步提高，因此可進一步抑制高溫環境下及高溫高濕環境下黏著層的浮起及剝離，從而也使被接著體污染的抑制效果（也稱為耐污染性）進一步提高。The weight average molecular weight (Mw) of the acrylic copolymer (A1) is preferably 200,000 to 2 million, more preferably 500,000 to 1.8 million, and particularly preferably 1 million to 1.8 million. By setting the Mw of the acrylic copolymer (A1) to be in the range of 200,000 to 2 million, the cohesive force of the adhesive layer is further improved. Therefore, it is possible to further suppress the floating and peeling of the adhesive layer in a high-temperature environment and a high-temperature and high-humidity environment. The effect of suppressing contamination of the adherend (also referred to as contamination resistance) is further improved.

（數量平均分子量（Mw）1000～10000的聚合性化合物（a1）） 作為丙烯酸系共聚物（A1）的原料來使用的數量平均分子量（Mn）1000～10000的聚合性化合物（a1）只要為Mn為所述範圍的聚合性化合物，則並無限制。優選Mn為2000～6000。若使用此種高分子量的單體，則丙烯酸系共聚物（A1）由於具有高分子量的側鏈作為硬段（hard segment），因此丙烯酸系共聚物（A1）自身的凝聚力提高，獲得對於黏著層而言適度的硬度。而且，推測：因所述高分子量的側鏈的存在，共聚物（A）彼此的分子的絡合的形成或簇（cluster）的形成被抑制（絡合被緩和）。由此，在黏著層中獲得硬度與柔軟度的兼顧這一折衷的性質，耐熱性及彎曲性提高。 聚合性化合物（a1）中，就彎曲性及耐熱性的觀點而言，優選為大分子單體（a1-1）、或含有亞烷氧基的單體（a1-2）。特別優選為大分子單體（a1-1）。(Polymer compound (a1) with a number average molecular weight (Mw) of 1,000 to 10,000) The polymerizable compound (a1) having a number average molecular weight (Mn) of 1,000 to 10,000 used as the raw material of the acrylic copolymer (A1) is not limited as long as the Mn is a polymerizable compound in the above range. Preferably, Mn is 2000 to 6000. If such a high molecular weight monomer is used, the acrylic copolymer (A1) has a high molecular weight side chain as a hard segment, so the acrylic copolymer (A1) itself has improved cohesion and obtains an adhesive layer. In terms of moderate hardness. Furthermore, it is presumed that due to the presence of the high molecular weight side chains, the formation of the complex of molecules of the copolymer (A) or the formation of clusters is suppressed (the complex is alleviated). As a result, a compromise between hardness and softness is obtained in the adhesive layer, and heat resistance and flexibility are improved. The polymerizable compound (a1) is preferably a macromonomer (a1-1) or an alkyleneoxy group-containing monomer (a1-2) from the viewpoint of flexibility and heat resistance. Particularly preferred is the macromonomer (a1-1).

單體混合物100質量%中的分子量（Mn）1000～10000的聚合性化合物（a1）的含量優選為0.5質量%～10質量%，更優選為1質量%～10質量%，特別優選為1質量%～8質量%，最優選為1質量%～2質量%。若含量為1質量%～10質量%，則能夠以更高的程度兼顧黏著層的硬度與柔軟度，從而黏著層可高度地兼顧耐熱性與彎曲性。The content of the polymerizable compound (a1) having a molecular weight (Mn) of 1,000 to 10,000 in 100% by mass of the monomer mixture is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 10% by mass, and particularly preferably 1% by mass % To 8% by mass, most preferably 1% to 2% by mass. If the content is 1% by mass to 10% by mass, the hardness and flexibility of the adhesive layer can be balanced to a higher degree, and the adhesive layer can highly balance the heat resistance and the flexibility.

·大分子單體（a1-1） 大分子單體（a1-1）（以下，有時簡單記述為「單體（a1-1）」）具有聚合物單元及聚合性官能基單元（乙烯性不飽和基）。通過使用大分子單體（a1-1），可使黏著層在彎曲性及耐熱性方面優異，因此優選。·Macromonomer (a1-1) The macromonomer (a1-1) (hereinafter sometimes simply referred to as "monomer (a1-1)") has a polymer unit and a polymerizable functional group unit (ethylenically unsaturated group). By using the macromonomer (a1-1), the adhesive layer can be excellent in flexibility and heat resistance, which is preferable.

作為單體（a1-1）的聚合性官能基，例如優選為選自由乙烯基、烯丙基及(甲基)丙烯醯基所組成的群組中的至少一個官能基。作為構成大分子單體的聚合物鏈部分，優選為(甲基)丙烯酸烷基酯的聚合物。As the polymerizable functional group of the monomer (a1-1), for example, it is preferably at least one functional group selected from the group consisting of a vinyl group, an allyl group, and a (meth)acryloyl group. As the polymer chain portion constituting the macromonomer, a polymer of alkyl (meth)acrylate is preferred.

(甲基)丙烯酸烷基酯的聚合物例如可利用(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸2-乙基己酯、及(甲基)丙烯酸硬脂酯等(甲基)丙烯酸烷基酯的共聚來形成。共聚中也可使用能夠與(甲基)丙烯酸烷基酯進行共聚的丙烯酸系單體或乙烯基單體。As the polymer of alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth) It is formed by copolymerization of alkyl (meth)acrylates such as tert-butyl acrylate, 2-ethylhexyl (meth)acrylate, and stearyl (meth)acrylate. In the copolymerization, an acrylic monomer or a vinyl monomer that can be copolymerized with an alkyl (meth)acrylate can also be used.

作為單體（a1-1）的市售品，例如可列舉：分子末端為甲基丙烯醯基，聚合物鏈為聚甲基丙烯酸甲酯的大分子單體（製品名：AA-6、AA-6S、Mn6000；東亞合成公司製造）、聚合物鏈為聚苯乙烯的大分子單體（製品名：AS-6S、AS-6、Mn6000；東亞合成公司製造）、聚合物鏈為苯乙烯/丙烯腈的共聚物的大分子單體（製品名：AN-6S、Mn6000；東亞合成公司製造）、聚合物鏈為聚丙烯酸丁酯的大分子單體（製品名：AB-6、Mn6000；東亞合成公司製造）及聚合物鏈為聚丙烯酸丁酯的大分子單體（製品名：AB-8、Mn8000；東亞合成公司製造）等。 其中，在提高黏著層的耐熱性的方面，優選分子末端為甲基丙烯醯基，聚合物鏈為聚甲基丙烯酸甲酯的大分子單體（製品名：AA-6、Mn6000；東亞合成公司製造）、及聚合物鏈為聚丙烯酸丁酯的大分子單體（製品名：AB-6、Mn6000；東亞合成公司製造）。As a commercially available product of the monomer (a1-1), for example, a macromonomer (molecular name: AA-6, AA) whose molecular terminal is a methacryloyl group and whose polymer chain is polymethyl methacrylate is mentioned. -6S, Mn6000; manufactured by East Asia Synthetic Company), macromonomer with polystyrene polymer chain (product name: AS-6S, AS-6, Mn6000; manufactured by East Asia Synthetic Company), polymer chain styrene/ Macromonomer of acrylonitrile copolymer (product name: AN-6S, Mn6000; manufactured by East Asia Synthetic Corporation), macromonomer with polymer chain polybutyl acrylate (product name: AB-6, Mn6000; East Asia (Made by Synthetic Corporation) and a macromonomer with polymer chain polybutyl acrylate (product name: AB-8, Mn8000; manufactured by East Asia Synthetic Corporation), etc. Among them, in terms of improving the heat resistance of the adhesive layer, it is preferable that the molecular terminal is a methacryl group, and the polymer chain is a macromonomer of polymethyl methacrylate (product name: AA-6, Mn6000; East Asia Synthesizer) (Manufactured), and a macromonomer whose polymer chain is polybutyl acrylate (product name: AB-6, Mn6000; manufactured by East Asia Synthesizer).

·含有亞烷氧基的單體（a1-2） 含有亞烷氧基的單體（a1-2）（以下，有時簡單記述為「單體（a1-2）」）例如為下述一般式（2）所表示的、數量平均分子量（Mn）為1000～10000的單體。作為亞烷氧基，例如優選為乙烯氧基或丙烯氧基，更優選為乙烯氧基。 若使用單體（a1-2），則共聚物（A1）由於具有高分子量的側鏈作為硬段，因此共聚物（A1）自身的凝聚力提高，獲得對於黏著層而言適度的硬度。而且，推測：因高分子量的側鏈的存在，共聚物（A1）彼此的分子的絡合的形成或簇的形成被抑制（絡合被緩和）。由此，在黏著層中獲得硬度與柔軟度的兼顧這一折衷的性質，耐熱性及彎曲性提高。另外，單體（a1-2）的Mn更優選為1000～2000。·Monomer containing alkyleneoxy group (a1-2) The alkyleneoxy group-containing monomer (a1-2) (hereinafter sometimes simply referred to as "monomer (a1-2)") is, for example, the number average molecular weight (Mn) represented by the following general formula (2) It is a monomer of 1000～10000. As the alkyleneoxy group, for example, ethyleneoxy group or propyleneoxy group is preferable, and ethyleneoxy group is more preferable. If the monomer (a1-2) is used, the copolymer (A1) has a side chain with a high molecular weight as a hard segment, so the cohesion of the copolymer (A1) itself is improved, and an appropriate hardness for the adhesive layer is obtained. Furthermore, it is presumed that due to the presence of high molecular weight side chains, the formation of molecular complexes or cluster formation between the copolymers (A1) is suppressed (complexation is alleviated). As a result, a compromise between hardness and softness is obtained in the adhesive layer, and heat resistance and flexibility are improved. In addition, the Mn of the monomer (a1-2) is more preferably 1,000 to 2,000.

一般式（2）： [化1]

Figure 02_image001
所述式中，R1 為氫原子或甲基，n為表示重複單元的整數，1≦n≦25。General formula (2): [Chemical 1]
Figure 02_image001
In the above formula, R 1 is a hydrogen atom or a methyl group, n is an integer representing a repeating unit, and 1≦n≦25.

作為一般式（2）所表示的單體的市售品，例如可列舉：甲氧基聚乙二醇#1000丙烯酸酯（新中村化學工業公司製造：式（2）中，R1 為氫原子，n=23）及甲氧基聚乙二醇#1000甲基丙烯酸酯（新中村化學工業公司製造：式（2）中，R1 為氫原子，n=23）等。As a commercially available product of the monomer represented by general formula (2), for example, methoxypolyethylene glycol #1000 acrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.: in formula (2), R 1 is a hydrogen atom , N=23) and methoxypolyethylene glycol #1000 methacrylate (manufactured by Shin Nakamura Chemical Industry Company: in formula (2), R 1 is a hydrogen atom, n=23), etc.

其中，在可提高黏著層的耐熱性及耐濕熱性，從而可進一步抑制黏著層的浮起及剝離的方面，更優選為甲氧基聚乙二醇#1000丙烯酸酯。Among them, methoxypolyethylene glycol #1000 acrylate is more preferable in terms of improving the heat resistance and moisture heat resistance of the adhesive layer and further suppressing the floating and peeling of the adhesive layer.

單體（a1-1）、單體（a1-2）可單獨使用一種或將兩種以上組合來使用。The monomer (a1-1) and the monomer (a1-2) can be used alone or in combination of two or more.

丙烯酸系共聚物（A1）可通過對除了數量平均分子量（Mn）1000～10000的聚合性化合物（a）以外，還含有至少包括具有羥基的單體的一種以上的其他聚合性化合物的單體混合物進行共聚而獲得。另外，具有羥基的聚合性化合物在Mn為1000～10000的情況下，為聚合性化合物（a）。The acrylic copolymer (A1) can be used for a monomer mixture containing at least one polymerizable compound including at least one monomer having a hydroxyl group in addition to the polymerizable compound (a) having a number average molecular weight (Mn) of 1,000 to 10,000. Obtained by copolymerization. In addition, the polymerizable compound having a hydroxyl group is a polymerizable compound (a) when Mn is 1,000 to 10,000.

·具有羥基的單體 作為具有羥基的單體，可列舉在分子內具有羥基的(甲基)丙烯酸酯。 作為具有羥基的單體，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、及(甲基)丙烯酸4-羥基丁酯等。 其中，在可進一步提高黏著層的耐熱性及耐濕熱性的方面，更優選為(甲基)丙烯酸2-羥基乙酯及丙烯酸4-羥基丁酯等。 具有羥基的單體可單獨使用一種或將兩種以上組合來使用。·Monomer with hydroxyl group Examples of the monomer having a hydroxyl group include (meth)acrylates having a hydroxyl group in the molecule. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 2 -Hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Among them, from the viewpoint of further improving the heat resistance and the heat and humidity resistance of the adhesive layer, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl acrylate are more preferred. The monomer having a hydroxyl group may be used alone or in combination of two or more.

單體混合物100質量%中的具有羥基的單體的含量優選為0.1質量%～5質量%，更優選為0.2質量%～2質量%。若含量為0.1質量%～5質量%，則容易獲得對於黏著層而言充分的凝聚力，從而可高度地兼顧耐濕熱性與彎曲性，因此優選。The content of the monomer having a hydroxyl group in 100% by mass of the monomer mixture is preferably 0.1% by mass to 5% by mass, and more preferably 0.2% by mass to 2% by mass. If the content is 0.1% by mass to 5% by mass, it is easy to obtain sufficient cohesive force for the adhesive layer, and it is possible to achieve a high degree of balance between moisture resistance and flexibility, which is preferable.

·其他單體 作為丙烯酸系共聚物（A1）的原料，除了聚合性化合物（a）及具有羥基的單體以外，也可使用其他單體。其他單體是數量平均分子量（Mn）為1000～10000的範圍外的單體，可列舉：(甲基)丙烯酸烷基酯、含有羧基的單體、含有醯胺鍵的單體、含有環氧基的單體、含有氨基的單體及乙烯基單體等。·Other monomers As the raw material of the acrylic copolymer (A1), in addition to the polymerizable compound (a) and the monomer having a hydroxyl group, other monomers may be used. Other monomers are monomers having a number average molecular weight (Mn) outside the range of 1,000 to 10,000, and examples include: (meth)acrylic acid alkyl esters, carboxyl group-containing monomers, amide bond-containing monomers, and epoxy-containing monomers Group monomer, amino group-containing monomer, vinyl monomer, etc.

作為(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十六烷基酯、及(甲基)丙烯酸十八烷基酯等。其中，在進一步提高黏著層的黏著性能的方面，優選為(甲基)丙烯酸丁酯及(甲基)丙烯酸2-乙基己酯等。Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth) Amyl acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, Dodecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, octadecyl (meth)acrylate, etc. Among them, in terms of further improving the adhesive performance of the adhesive layer, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred.

作為含有羧基的單體，例如可列舉：(甲基)丙烯酸、丙烯酸對羧基苄酯、丙烯酸β-羧基乙酯、馬來酸、單乙基馬來酸、衣康酸、檸康酸及富馬酸等。Examples of carboxyl group-containing monomers include (meth)acrylic acid, p-carboxybenzyl acrylate, β-carboxyethyl acrylate, maleic acid, monoethylmaleic acid, itaconic acid, citraconic acid, and rich Horse acid and so on.

含有醯胺鍵的單體為具有醯胺鍵或醯胺基的單體。例如可列舉：(甲基)丙烯醯胺、N-甲基丙烯醯胺、N-異丙基丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二乙基丙烯醯胺、N,N-二甲基氨基丙基(甲基)丙烯醯胺、二丙酮丙烯醯胺、N-(羥基甲基)丙烯醯胺、及N-(丁氧基甲基)丙烯醯胺等(甲基)丙烯醯胺系化合物；N-乙烯基吡咯烷酮、N-乙烯基己內醯胺、及丙烯醯基嗎啉等含有雜環的化合物；N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基-N-甲基乙醯胺等。The monomer containing an amide bond is a monomer having an amide bond or an amide group. Examples include: (meth)acrylamide, N-methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide , N,N-dimethylaminopropyl (meth) acrylamide, diacetone acrylamide, N-(hydroxymethyl) acrylamide, and N-(butoxymethyl) acrylamide, etc. (Meth)acrylamide-based compounds; N-vinylpyrrolidone, N-vinylcaprolactam, and acryloylmorpholine-containing compounds such as heterocycles; N-vinylformamide, N-vinyl Acetamide, N-vinyl-N-methylacetamide, etc.

作為含有環氧基的單體，例如可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯、(甲基)丙烯酸3,4-環氧基環己基甲酯、及(甲基)丙烯酸6-甲基-3,4-環氧基環己基甲酯等。Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, And 6-methyl-3,4-epoxycyclohexyl methyl (meth)acrylate, etc.

作為含有氨基的單體，例如可列舉：(甲基)丙烯酸單甲基氨基乙酯、(甲基)丙烯酸單乙基氨基乙酯、(甲基)丙烯酸單甲基氨基丙酯、及(甲基)丙烯酸單乙基氨基丙酯等(甲基)丙烯酸單烷基氨基酯等。Examples of the amino group-containing monomer include monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, and (meth Group) Monoethylaminopropyl acrylate, etc. (Meth)acrylic acid monoalkylaminoester, etc.

作為乙烯基單體，例如可列舉：乙酸乙烯酯、丁烯酸乙烯酯、苯乙烯、及丙烯腈等。Examples of vinyl monomers include vinyl acetate, vinyl crotonate, styrene, and acrylonitrile.

這些其他單體可單獨使用一種或將兩種以上組合來使用。 單體混合物100質量%中的其他單體的含量優選為5質量%～99質量%，更優選為50質量%～99質量%。若含量為5質量%以上，則黏著層的密接性會進一步提高。若含量為90質量%以下，則容易兼顧黏著層的凝聚力與密接性，因此優選。These other monomers may be used alone or in combination of two or more. The content of other monomers in 100% by mass of the monomer mixture is preferably 5% by mass to 99% by mass, and more preferably 50% by mass to 99% by mass. If the content is 5 mass% or more, the adhesion of the adhesive layer will be further improved. If the content is 90% by mass or less, it is easy to reconcile the cohesive force and adhesion of the adhesive layer, which is preferable.

·丙烯酸系共聚物（A1）的製造方法 丙烯酸系共聚物（A1）可通過對單體混合物進行聚合而合成。作為聚合方法，可列舉溶液聚合、塊狀聚合、乳化聚合及懸浮聚合等公知的聚合方法，優選溶液聚合。作為溶液聚合中使用的溶媒，例如優選為丙酮、乙酸甲酯、乙酸乙酯、甲苯、二甲苯、苯甲醚、甲基乙基酮、及環己酮等。 聚合溫度優選為60℃～120℃，優選為沸點反應。聚合時間優選為5小時～12小時左右。·Production method of acrylic copolymer (A1) The acrylic copolymer (A1) can be synthesized by polymerizing the monomer mixture. Examples of the polymerization method include known polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization, and solution polymerization is preferred. As the solvent used in the solution polymerization, for example, acetone, methyl acetate, ethyl acetate, toluene, xylene, anisole, methyl ethyl ketone, cyclohexanone, etc. are preferable. The polymerization temperature is preferably 60°C to 120°C, preferably a boiling point reaction. The polymerization time is preferably about 5 hours to 12 hours.

作為聚合中使用的聚合起始劑，優選為自由基聚合起始劑。作為自由基聚合起始劑，一般為過氧化物及偶氮化合物。 作為過氧化物，例如可列舉：二-叔丁基過氧化物、二異丙苯基過氧化物、叔丁基異丙苯基過氧化物、α,α'-雙(叔丁基過氧化-間異丙基)苯、及2,5-二(叔丁基過氧基)己炔-3等二烷基過氧化物； 過氧化苯甲酸叔丁酯、過氧化乙酸叔丁酯、及2,5-二甲基-2,5-二(苯甲醯基過氧基)己烷等過氧化酯； 環己酮過氧化物、3,3,5-三甲基環己酮過氧化物、及甲基環己酮過氧化物等酮過氧化物； 2,2-雙(4,4-二-叔丁基過氧化環己基)丙烷、1,1-雙(叔丁基過氧基)3,3,5-三甲基環己烷、1,1-雙(叔丁基過氧基)環己烷、及正丁基-4,4-雙(叔丁基過氧基)戊酸酯等過氧化縮酮； 異丙苯氫過氧化物、二異丙基苯氫過氧化物、及2,5-二甲基環己烷-2,5-二氫過氧化物等氫過氧化物； 苯甲醯基過氧化物、癸醯基過氧化物、月桂醯基過氧化物、及2,4-二氯苯甲醯基過氧化物等二醯基過氧化物； 雙(叔丁基環己基)過氧化二碳酸酯等過氧化二碳酸酯等。As the polymerization initiator used in the polymerization, a radical polymerization initiator is preferred. As a radical polymerization initiator, it is generally a peroxide and an azo compound. Examples of the peroxide include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, and α,α′-bis(tert-butyl peroxide) -M-isopropyl) benzene, and dialkyl peroxides such as 2,5-di(tert-butylperoxy)hexyne-3; Peroxyesters such as tert-butyl peroxybenzoate, tert-butyl peroxyacetate, and 2,5-dimethyl-2,5-bis(benzylperoxy)hexane; Ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 2,2-bis(4,4-di-tert-butylperoxycyclohexyl peroxide) propane, 1,1-bis(tert-butylperoxy) 3,3,5-trimethylcyclohexane, 1, 1-bis(tert-butylperoxy)cyclohexane, and n-butyl-4,4-bis(tert-butylperoxy)valerate and other peroxide ketals; Hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and 2,5-dimethylcyclohexane-2,5-dihydroperoxide; Diacyl peroxides such as benzoyl peroxide, decyl peroxide, lauryl peroxide, and 2,4-dichlorobenzyl peroxide; Peroxydicarbonate such as bis(tert-butylcyclohexyl)peroxydicarbonate and the like.

作為偶氮化合物，例如可列舉：2,2'-偶氮雙異丁腈（簡稱：AIBN（2,2'-azobisisobutyronitrile））、及2,2'-偶氮雙(2-甲基丁腈)等2,2'-偶氮雙丁腈； 2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、及2,2'-偶氮雙(2,4-二甲基戊腈)等2,2'-偶氮雙戊腈； 2,2'-偶氮雙(2-羥基甲基丙腈)等2,2'-偶氮雙丙腈； 1,1'-偶氮雙(環己烷-1-碳腈)等1,1'-偶氮雙-1-烷腈（alkanenitrile）等。Examples of azo compounds include 2,2'-azobisisobutyronitrile (abbreviation: AIBN (2,2'-azobisisobutyronitrile)) and 2,2'-azobis(2-methylbutyronitrile) ) Wait for 2,2'-azobisbutyronitrile; 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile), etc. 2,2 '-Azobisvaleronitrile; 2,2'-azobis(2-hydroxymethylpropionitrile) and other 2,2'-azobispropionitrile; 1,1'-azobis (cyclohexane-1-carbonitrile), etc. 1,1'-azobis-1-alkanenitrile (alkanenitrile), etc.

聚合起始劑可單獨使用一種或將兩種以上組合來使用。 關於聚合起始劑，相對於單體混合物100質量份，優選使用0.01質量份～10質量份，更優選為0.1質量份～2質量份。The polymerization initiator may be used alone or in combination of two or more. The polymerization initiator is preferably used in an amount of 0.01 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the monomer mixture.

[氨基甲酸酯脲系共聚物（A2）] 作為共聚物（A）而優選的、具有羥基的氨基甲酸酯脲系共聚物（A2）（以下，有時簡單記述為「共聚物（A2）」）為具有源自數量平均分子量（Mn）1000～10000的聚合性化合物（a）的構成單元及羥基的氨基甲酸酯脲系共聚物。 氨基甲酸酯脲系共聚物（A2）可通過對異氰酸酯化合物、多元醇及二氨基化合物進行共聚而獲得。 其中，作為氨基甲酸酯脲系共聚物（A2），優選為通過對在分子內含有兩個異氰酸酯基的異氰酸酯化合物、在分子內具有羥基的Mn 2000～10000的多元醇（a2）及二氨基化合物的混合物進行共聚而獲得的共聚物。[Urethane urea copolymer (A2)] The urethane urea copolymer (A2) having a hydroxyl group, which is preferable as the copolymer (A) (hereinafter sometimes simply referred to as "copolymer (A2)"), has a number-average molecular weight (Mn) A urethane urea-based copolymer having 1000 to 10,000 polymerizable compounds (a) as a constituent unit and a hydroxyl group. The urethane urea copolymer (A2) can be obtained by copolymerizing an isocyanate compound, a polyol, and a diamino compound. Among them, the urethane urea copolymer (A2) is preferably an isocyanate compound containing two isocyanate groups in the molecule, a polyhydric alcohol (a2) having a hydroxyl group in the molecule of Mn 2000 to 10000, and a diamino group A copolymer obtained by copolymerizing a mixture of compounds.

氨基甲酸酯脲系共聚物（A2）的重量平均分子量（Mw）就確保黏著層的黏著力的觀點而言，優選為1萬～50萬，更優選為5萬～30萬。The weight average molecular weight (Mw) of the urethane urea copolymer (A2) is preferably 10,000 to 500,000, and more preferably 50,000 to 300,000 from the viewpoint of securing the adhesive force of the adhesive layer.

（數量平均分子量1000～10000的聚合性化合物（a2）） 作為氨基甲酸酯脲系共聚物（A2）的原料來使用的數量平均分子量（Mn）1000～10000的聚合性化合物（a2）是分子量為所述範圍的多元醇。Mn更優選為1000～2000。 聚合性化合物（a2）中，就黏著層的彎曲性及耐熱性的觀點而言，優選為Mn 1000～10000的三官能多元醇（a2-1）。(Polymer compound with a number average molecular weight of 1,000 to 10,000 (a2)) The polymerizable compound (a2) having a number average molecular weight (Mn) of 1,000 to 10,000 used as a raw material of the urethane urea copolymer (A2) is a polyol having a molecular weight in the above range. Mn is more preferably 1,000 to 2,000. Among the polymerizable compounds (a2), from the viewpoint of the flexibility and heat resistance of the adhesive layer, a trifunctional polyol (a2-1) having an Mn of 1,000 to 10,000 is preferred.

作為在分子內具有羥基的Mn 1000～10000的多元醇，可使用公知者，可列舉聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、它們的共聚物及其他二醇類等。以下敘述的具體的化合物可組合多種來使用。As polyols having Mn 1000 to 10000 having hydroxyl groups in the molecule, known ones can be used, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, copolymers thereof, and other glycols. The specific compounds described below can be used in combination.

多元醇的數量平均分子量（Mn）就確保黏著層的耐熱性的觀點而言，優選為2000～10000。若多元醇的Mn不足2000，則存在對黏著層賦予凝聚力的氨基甲酸酯鍵增加、黏著層損害彎曲性的可能性。若Mn大於10000，則存在對黏著層賦予凝聚力的氨基甲酸酯鍵減少、黏著層的耐熱性下降的可能性。The number average molecular weight (Mn) of the polyol is preferably 2,000 to 10,000 from the viewpoint of ensuring the heat resistance of the adhesive layer. If the Mn of the polyol is less than 2000, there is a possibility that the urethane bond that imparts cohesive force to the adhesive layer increases, and the adhesive layer may impair the flexibility. If Mn is more than 10000, the urethane bond which gives cohesive force to the adhesive layer may decrease, and the heat resistance of the adhesive layer may decrease.

作為聚醚多元醇，可使用公知的聚醚多元醇。例如，可使用：環氧丙烷、四氫呋喃、環氧乙烷、及環氧丁烷等環氧烷的聚合物、共聚物、或接枝共聚物；己烷二醇、甲基己烷二醇、庚烷二醇、辛烷二醇、或通過它們的混合物的縮合反應而獲得的聚醚多元醇等、具有兩個或三個羥基的聚醚多元醇。 除了所述以外，還可使用對雙酚A及雙酚F等雙酚類加成環氧乙烷等環氧烷而成的二醇類。As the polyether polyol, a known polyether polyol can be used. For example, polymers, copolymers, or graft copolymers of alkylene oxides such as propylene oxide, tetrahydrofuran, ethylene oxide, and butylene oxide; hexanediol, methylhexanediol, Polyether polyols having two or three hydroxyl groups, such as heptane diol, octane diol, or polyether polyol obtained by condensation reaction of a mixture thereof. In addition to the above, diols obtained by adding bisphenols such as bisphenol A and bisphenol F to alkylene oxides such as ethylene oxide can also be used.

作為聚酯多元醇，可使用公知的聚酯多元醇。作為聚酯多元醇，例如可列舉通過二官能或三官能的醇成分與二元酸成分的縮合反應而獲得的聚酯多元醇。 作為醇成分，例如可列舉：乙二醇、丙二醇、二丙二醇、二乙二醇、三乙二醇、丁二醇、1,6-己烷二醇、3-甲基-1,5-戊烷二醇、3,3'-二羥甲基庚烷、聚氧乙二醇、聚氧丙二醇、1,3-丁烷二醇、1,4-丁烷二醇、新戊二醇、辛烷二醇、丁基乙基戊烷二醇、2-乙基-1,3-己烷二醇、環己烷二醇、雙酚A、及雙酚F等具有兩個羥基的化合物；甘油及三羥甲基丙烷等具有三個羥基的化合物。As the polyester polyol, a known polyester polyol can be used. Examples of the polyester polyol include polyester polyols obtained by condensation reaction of a difunctional or trifunctional alcohol component and a dibasic acid component. Examples of the alcohol component include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, and 3-methyl-1,5-pentane. Alkanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octene Compounds with two hydroxyl groups such as alkanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, bisphenol A, and bisphenol F; And trimethylolpropane and other compounds with three hydroxyl groups.

作為二元酸成分，可列舉：對苯二甲酸、己二酸、壬二酸、癸二酸、鄰苯二甲酸酐、間苯二甲酸、及偏苯三甲酸等脂肪族或芳香族二元酸。Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. acid.

除了所述以外，也可使用通過環狀酯化合物的開環聚合而獲得的聚酯多元醇。作為具體例，可列舉：β-丁內酯、β-丙內酯、γ-丁內酯、γ-戊內酯、δ-戊內酯、ε-己內酯、γ-己內酯、γ-庚內酯、及α-甲基-β-丙內酯等內酯類等。In addition to the above, a polyester polyol obtained by ring-opening polymerization of a cyclic ester compound can also be used. Specific examples include β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ -Lactones such as enanthrolactone and α-methyl-β-propiolactone, etc.

聚碳酸酯多元醇在分子中具有下述一般式（3）所表示的結構，可使用公知的聚碳酸酯多元醇。 一般式（3）： -[-O-R1 -O-CO-]m - （一般式（3）中，R1 表示二價的有機殘基，m表示1以上的整數）The polycarbonate polyol has a structure represented by the following general formula (3) in the molecule, and a known polycarbonate polyol can be used. General formula (3): -[-OR 1 -O-CO-] m- (In general formula (3), R 1 represents a divalent organic residue, and m represents an integer of 1 or more)

聚碳酸酯多元醇例如是利用[i]二醇或雙酚與碳酸酯的反應、[ii]在鹼的存在下使光氣（phosgene）作用於二醇或雙酚的反應等而獲得。Polycarbonate polyols are obtained, for example, by the reaction of [i] a diol or bisphenol and a carbonate, [ii] a reaction in which phosgene acts on a diol or bisphenol in the presence of a base.

作為[i]的製法中所使用的碳酸酯，例如可列舉碳酸二甲酯、碳酸二乙酯、碳酸二苯酯、碳酸亞乙酯及碳酸亞丙酯等。Examples of the carbonate used in the production method of [i] include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

作為[i]及[ii]的製法中所使用的二醇或雙酚，例如可列舉：乙二醇、丙二醇、二丙二醇、二乙二醇、三乙二醇、丁二醇、3-甲基-1,5-戊烷二醇、2-甲基-1,8-辛烷二醇、3,3'-二羥甲基庚烷、聚氧乙二醇、聚氧丙二醇、丙烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、1,5-戊烷二醇、1,6-己烷二醇、1,9-壬烷二醇、新戊二醇、辛烷二醇、丁基乙基戊烷二醇、2-乙基-1,3-己烷二醇、環己烷二醇；雙酚A及雙酚F等雙酚類；對雙酚類加成環氧乙烷及環氧丙烷等環氧烷而成的雙酚類等。 這些化合物可單獨使用一種或將兩種以上組合來使用。Examples of the diol or bisphenol used in the production methods of [i] and [ii] include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, and 3-methyl 1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol , 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol , Octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol; bisphenols such as bisphenol A and bisphenol F; p-bisphenol Bisphenols formed by addition of alkylene oxides such as ethylene oxide and propylene oxide. These compounds may be used alone or in combination of two or more.

作為其他二醇類，可列舉：乙二醇、二乙二醇、三乙二醇、丁烷二醇、丙烷二醇、1,6-己烷二醇、新戊二醇及環己烷二甲醇等具有兩個羥基的化合物。Examples of other glycols include ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6-hexanediol, neopentyl glycol, and cyclohexanediol. Compounds with two hydroxyl groups such as methanol.

本發明中，作為多元醇，優選使用聚丙二醇和/或聚乙二醇，就黏著層的耐熱性及彎曲性的方面而言，更優選使用在分子內含有三個羥基的三官能多元醇（a2-1）。In the present invention, as the polyol, polypropylene glycol and/or polyethylene glycol are preferably used, and in terms of heat resistance and flexibility of the adhesive layer, a trifunctional polyol containing three hydroxyl groups in the molecule is more preferably used ( a2-1).

·異氰酸酯化合物 作為在分子內含有兩個異氰酸酯基的異氰酸酯化合物，可使用以往已知者。例如可列舉：芳香族聚異氰酸酯、脂肪族聚異氰酸酯、芳香脂肪族聚異氰酸酯、及脂環族聚異氰酸酯等。以下敘述的具體的化合物也可組合多種來使用。·Isocyanate compounds As the isocyanate compound containing two isocyanate groups in the molecule, conventionally known ones can be used. Examples include aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, and alicyclic polyisocyanate. The specific compounds described below can also be used in combination.

作為芳香族聚異氰酸酯，可列舉：1,3-亞苯基二異氰酸酯、4,4'-二苯基二異氰酸酯、1,4-亞苯基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-甲苯胺二異氰酸酯、及聯大茴香胺二異氰酸酯、4,4'-二苯基醚二異氰酸酯等。Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4′-diphenylmethane diisocyanate. Isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, dianesidine diisocyanate, 4,4'-diphenyl ether diisocyanate, etc.

作為脂肪族聚異氰酸酯，可列舉：三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯（別名：HDI（hexamethylene diisocyanate））、五亞甲基二異氰酸酯、1,2-亞丙基二異氰酸酯、2,3-亞丁基二異氰酸酯、1,3-亞丁基二異氰酸酯、十二亞甲基二異氰酸酯、及2,4,4-三甲基六亞甲基二異氰酸酯等。Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (alias: HDI (hexamethylene diisocyanate)), pentamethylene diisocyanate, 1,2-methylene Propyl diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

作為芳香脂肪族聚異氰酸酯，可列舉：ω,ω'-二異氰酸酯-1,3-二甲基苯、ω,ω'-二異氰酸酯-1,4-二甲基苯、ω,ω'-二異氰酸酯-1,4-二乙基苯、1,4-四甲基苯二甲基二異氰酸酯、及1,3-四甲基苯二甲基二異氰酸酯等。Examples of the aromatic aliphatic polyisocyanate include: ω,ω′-diisocyanate-1,3-dimethylbenzene, ω,ω′-diisocyanate-1,4-dimethylbenzene, ω,ω′-diisocyanate Isocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, etc.

作為脂環族聚異氰酸酯，可列舉：異佛爾酮二異氰酸酯（別名：IPDI（isophorone diisocyanate））、1,3-環戊烷二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基-2,4-環己烷二異氰酸酯、甲基-2,6-環己烷二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、及1,4-雙(異氰酸酯甲基)環己烷等。Examples of the alicyclic polyisocyanate include isophorone diisocyanate (alias: IPDI (isophorone diisocyanate)), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4- Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), and 1, 4-bis(isocyanate methyl) cyclohexane, etc.

異氰酸酯化合物中，就耐候性的方面而言，優選4,4'-二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯（別名：IPDI）、苯二甲基二異氰酸酯、及4,4'-亞甲基雙(環己基異氰酸酯)（別名：氫化MDI）等的無黃變型或難黃變型的聚異氰酸酯化合物。就黏著層的透明性及反應性的控制的觀點而言，優選異佛爾酮二異氰酸酯（別名：IPDI）。Among the isocyanate compounds, in terms of weather resistance, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate (alias: IPDI), xylylene diisocyanate are preferred , And 4,4'-methylene bis (cyclohexyl isocyanate) (alias: hydrogenated MDI) and other non-yellowing or non-yellowing polyisocyanate compounds. From the viewpoint of controlling the transparency and reactivity of the adhesive layer, isophorone diisocyanate (alias: IPDI) is preferred.

·二氨基化合物 作為二氨基化合物，可使用公知者。以下敘述的具體的化合物可組合多種來使用。·Diamino compound As the diamino compound, known ones can be used. The specific compounds described below can be used in combination.

具體而言，可例示：亞乙基二胺、三亞甲基二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、三亞乙基四胺、二亞乙基三胺、三氨基丙烷、2,2,4-三甲基六亞甲基二胺、2-羥基乙基亞乙基二胺、N-(2-羥基乙基)亞丙基二胺、(2-羥基乙基亞丙基)二胺、(二-2-羥基乙基亞乙基)二胺、(二-2-羥基乙基亞丙基)二胺、(2-羥基丙基亞乙基)二胺、(二-2-羥基丙基亞乙基)二胺、及哌嗪（piperazine）等脂肪族多胺； 異佛爾酮二胺、及二環己基甲烷-4,4'-二胺等脂環式多胺； 亞苯基二胺、苯二甲基二胺、2,4-甲苯二胺（2,4-tolylene diamine）、2,6-甲苯二胺、二乙基甲苯二胺（diethyl toluene diamine）、3,3'-二氯-4,4'-二氨基二苯基甲烷、及4,4'-雙-(仲丁基)二苯基甲烷等芳香族二胺； 將二聚酸的羧基轉化為氨基的二聚體二胺； 在末端具有一級或二級氨基的樹枝狀聚合物等。Specifically, it can be exemplified by ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, triethylene tetramine, diethylene Triamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, ( 2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) Aliphatic) diamine, (di-2-hydroxypropylethylene) diamine, and piperazine (piperazine) and other aliphatic polyamines; Alicyclic polyamines such as isophorone diamine and dicyclohexylmethane-4,4'-diamine; Phenylenediamine, xylylenediamine, 2,4-tolylene diamine (2,4-tolylene diamine), 2,6-toluene diamine, diethyl toluene diamine, 3 , 3'-dichloro-4,4'-diaminodiphenylmethane, and 4,4'-bis-(sec-butyl)diphenylmethane and other aromatic diamines; Dimer diamine that converts the carboxyl group of a dimer acid to an amino group; A dendrimer having a primary or secondary amino group at the end, etc.

進而，也可使用二氨基化合物與乙烯性不飽和化合物的邁克爾加成反應（michael addition reaction）產物。Furthermore, the product of the Michael addition reaction of the diamino compound and the ethylenically unsaturated compound may also be used.

作為二氨基化合物，異佛爾酮二胺、2,2,4-三甲基六亞甲基二胺、及六亞甲基二胺中，邁克爾加成反應的控制容易，可通過邁克爾加成反應容易地獲得期望的化合物。As the diamino compound, isophorone diamine, 2,2,4-trimethylhexamethylenediamine, and hexamethylenediamine, the Michael addition reaction can be easily controlled by Michael addition The reaction easily obtains the desired compound.

作為乙烯性不飽和化合物，可列舉(甲基)丙烯酸烷基酯、及具有羥基的(甲基)丙烯酸酯等。Examples of the ethylenically unsaturated compound include alkyl (meth)acrylate and (meth)acrylate having a hydroxyl group.

作為(甲基)丙烯酸烷基酯，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯、(甲基)丙烯酸二十一烷基酯、及(甲基)丙烯酸二十二烷基酯等、碳數1～22的(甲基)丙烯酸烷基酯。在以極性的調節為目的的情況下，(甲基)丙烯酸烷基酯的碳數更優選為碳數2～12，特別優選為碳數2～8。Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid. Amyl ester, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, (meth) )Decyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, ( Pentadecyl meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nineteen (meth)acrylate Alkyl esters, eicosyl (meth)acrylate, eicosyl (meth)acrylate, and behenyl (meth)acrylate, etc. ) Alkyl acrylate. In the case of the purpose of adjusting the polarity, the carbon number of the alkyl (meth)acrylate is more preferably 2 to 12, and particularly preferably 2 to 8.

作為具有羥基的(甲基)丙烯酸酯，可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、及(甲基)丙烯酸4-羥基丁酯等。若考慮與後述的硬化劑的反應性，則優選丙烯酸2-羥基乙酯及丙烯酸4-羥基丁酯等。Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth) ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Considering the reactivity with the hardener described below, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferred.

在二氨基化合物與乙烯性不飽和化合物的邁克爾加成反應中，二氨基化合物中的氨基的活性氫1莫耳與乙烯性不飽和化合物中的乙烯性不飽和基1莫耳進行反應。二氨基化合物中的氨基容易邁克爾加成於具有電子吸引性的基的化合物的乙烯性不飽和基。因此，作為乙烯性不飽和化合物，優選為(甲基)丙烯酸系化合物，特別是就邁克爾加成反應的效率的方面而言，最優選為丙烯酸酯系化合物。In the Michael addition reaction of a diamino compound and an ethylenically unsaturated compound, 1 mole of active hydrogen of the amino group in the diamino compound reacts with 1 mole of the ethylenically unsaturated group in the ethylenically unsaturated compound. The amino group in the diamino compound is easily added by Michael to the ethylenically unsaturated group of the compound having an electron-attracting group. Therefore, the ethylenically unsaturated compound is preferably a (meth)acrylic compound, and particularly in terms of the efficiency of Michael addition reaction, it is most preferably an acrylate compound.

作為使乙烯性不飽和化合物與二氨基化合物進行邁克爾加成反應而獲得的化合物的合成方法，可直接利用與邁克爾加成反應相關的公知方法。在乙烯性不飽和化合物為(甲基)丙烯酸系化合物，特別是丙烯酸酯系化合物等的情況下，視需要在醇等的催化劑下在10℃～100℃下進行反應。雖也依存於使用的乙烯性不飽和化合物的種類，但反應溫度優選為40℃～80℃。 在乙烯性不飽和化合物不具有電子吸引性基的情況下，能夠在金屬催化劑的存在下進行反應，在此情況下，若一面在催化劑存在下進行加熱一面在60℃～100℃下進行反應，則會成為適度的反應速度，因此優選。 可使用也可不使用用於合成的溶劑，其種類並無特別限定，可使用甲基乙基酮、甲苯、丙酮及苯等公知的溶劑。使用溶劑時的溶液濃度優選為20質量%以上，更優選為50質量%以上。 反應時間因使用的乙烯性不飽和化合物的種類而異。大致30分鐘～5小時結束反應。As a method for synthesizing a compound obtained by subjecting an ethylenically unsaturated compound and a diamino compound to Michael addition reaction, a publicly known method related to Michael addition reaction can be directly used. In the case where the ethylenically unsaturated compound is a (meth)acrylic compound, particularly an acrylate compound, etc., the reaction is carried out at 10°C to 100°C under a catalyst such as alcohol as necessary. Although it also depends on the type of ethylenically unsaturated compound used, the reaction temperature is preferably 40°C to 80°C. When the ethylenically unsaturated compound does not have an electron-attracting group, the reaction can be carried out in the presence of a metal catalyst. In this case, the reaction can be carried out at 60°C to 100°C while heating in the presence of a catalyst. It will be a moderate reaction rate, so it is preferable. The solvent used for synthesis may or may not be used, and the type is not particularly limited, and known solvents such as methyl ethyl ketone, toluene, acetone, and benzene can be used. The concentration of the solution when using a solvent is preferably 20% by mass or more, and more preferably 50% by mass or more. The reaction time varies depending on the type of ethylenically unsaturated compound used. The reaction is completed in about 30 minutes to 5 hours.

相對於具有兩個以上的一級氨基的化合物而言的、加成於其的乙烯性不飽和化合物的比率並無特別限定。優選以使進行邁克爾加成反應而獲得的化合物中殘存至少兩個一級或二級的氨基的方式，以相對於具有兩個以上的一級氨基的化合物所具有的一級氨基1莫耳，優選為0.1莫耳～1.0莫耳、更優選為0.2莫耳～1.0莫耳的比例使乙烯性不飽和化合物中的乙烯性不飽和基反應。The ratio of the ethylenically unsaturated compound added to the compound having two or more primary amino groups is not particularly limited. Preferably, the compound obtained by performing the Michael addition reaction has at least two primary or secondary amino groups remaining, and preferably 1 mole relative to the primary amino group of the compound having two or more primary amino groups, preferably 0.1 The molar ratio of 1.0 mole to 1.0 mole, more preferably 0.2 mole to 1.0 mole, reacts the ethylenically unsaturated group in the ethylenically unsaturated compound.

氨基甲酸酯脲系共聚物（A2）是通過對異氰酸酯化合物、多元醇（a2）、及二氨基化合物進行共聚而獲得。進而視需要可使單氨基化合物作為反應停止劑來共聚。在合成共聚物（A2）時，出於控制分子量，或與共聚物（A2）末端中因未反應而殘留的異氰酸酯基進行反應而使樹脂的反應活性穩定化的目的，可使用反應停止劑。此情況下的共聚物（A2）是使反應停止劑與使異氰酸脂化合物、多元醇及二氨基化合物反應而獲得的氨基甲酸酯預聚物進行反應而獲得。The urethane urea copolymer (A2) is obtained by copolymerizing an isocyanate compound, a polyol (a2), and a diamino compound. Furthermore, if necessary, the monoamino compound can be copolymerized as a reaction stopper. When synthesizing the copolymer (A2), a reaction stopper may be used for the purpose of controlling the molecular weight or reacting with isocyanate groups remaining at the end of the copolymer (A2) due to unreacted reaction to stabilize the reactivity of the resin. The copolymer (A2) in this case is obtained by reacting a reaction stopper with a urethane prepolymer obtained by reacting an isocyanate compound, a polyol, and a diamino compound.

作為反應停止劑，例如可使用：二乙基胺、二-正丁基胺、二-正辛基胺、二環己基胺、及二異壬基胺等二烷基胺類； 單乙醇胺、二乙醇胺、2-氨基-2-甲基-1-丙醇、三（羥基甲基）氨基甲烷、及2-氨基-2-乙基-1,3-丙烷二醇等具有羥基的單胺。As the reaction stopper, for example, dialkylamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine, and diisononylamine can be used; Monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, and 2-amino-2-ethyl-1,3-propanediol have hydroxyl groups Monoamine.

所述反應停止劑中，若使用單乙醇胺、二乙醇胺、2-氨基-2-甲基-1-丙醇、三(羥基甲基)氨基甲烷、及2-氨基-2-乙基-1,3-丙烷二醇等具有羥基的單胺化合物，則可獲得末端為羥基的保存穩定性優異的氨基甲酸酯脲樹脂。末端為羥基的氨基甲酸酯脲樹脂可將其羥基作為與後述的硬化劑的反應點來使用，因此優選。另外，在為具有羥基的單胺的情況下，氨基與羥基這兩者能夠與氨基甲酸酯預聚物的末端異氰酸酯基進行反應，但氨基的反應性更高，會優先與異氰酸酯基反應。In the reaction stopper, if monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, and 2-amino-2-ethyl-1 are used, A monoamine compound having a hydroxyl group such as 3-propanediol can obtain a urethane urea resin having excellent hydroxyl-terminal storage stability. A urethane urea resin having a hydroxyl group at the end can be used as a reaction point with a hardener described below, which is preferable. In the case of a monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanate group of the urethane prepolymer, but the amino group has higher reactivity and preferentially reacts with the isocyanate group.

·氨基甲酸酯脲系共聚物（A2）的製造方法 其次，針對氨基甲酸酯脲系共聚物（A2）的製造方法進行說明。作為氨基甲酸酯脲系共聚物（A2）的合成方法，能夠利用各種方法，但大致分為以下兩種方法。 [方法I]將異氰酸脂化合物、數量平均分子量（Mn）1000～10000的多元醇及二氨基化合物的全部量一括裝入來進行共聚的方法（一括進行氨基甲酸酯化反應及脲化反應的方法）。 [方法II]通過將作為原料的一部分的異氰酸酯化合物與數量平均分子量（Mn）1000～10000的多元醇裝入並進行聚合，獲得具有至少一個異氰酸酯基的氨基甲酸酯預聚物，之後進一步對所獲得的氨基甲酸酯預聚物與二氨基化合物及視需要的反應停止劑進行共聚的方法（在進行氨基甲酸酯化反應後，對所獲的氨基甲酸酯預聚物進行脲化的方法）。 在精密地控制反應的情況下，更優選為[方法II]。·Manufacturing method of urethane urea copolymer (A2) Next, the method for producing the urethane urea copolymer (A2) will be described. As a method for synthesizing the urethane urea copolymer (A2), various methods can be used, but they are roughly classified into the following two methods. [Method I] A method in which the total amount of an isocyanate compound, a polyol having a number average molecular weight (Mn) of 1,000 to 10,000, and a diamino compound are charged and copolymerized (including carbamate reaction and ureaization) Reaction method). [Method II] A urethane prepolymer having at least one isocyanate group is obtained by charging and polymerizing an isocyanate compound as a part of the raw material and a polyol having a number average molecular weight (Mn) of 1,000 to 10,000, and then further Method for copolymerization of obtained urethane prepolymer with diamino compound and optional reaction stopper (after urethane reaction, ureaize obtained urethane prepolymer Methods). In the case of precisely controlling the reaction, [Method II] is more preferable.

[方法I]中的氨基甲酸酯化反應及脲化反應的反應溫度優選為30℃～120℃，更優選為40℃～90℃。The reaction temperature of the urethane reaction and the urea reaction in [Method I] is preferably 30°C to 120°C, and more preferably 40°C to 90°C.

[方法II]中的氨基甲酸酯化反應的反應溫度優選為50℃～150℃，更優選為70℃～120℃。The reaction temperature of the urethanization reaction in [Method II] is preferably 50°C to 150°C, and more preferably 70°C to 120°C.

[方法II]中的脲化反應的反應溫度優選為30℃～90℃，更優選為40℃～70℃。The reaction temperature of the ureaization reaction in [Method II] is preferably 30°C to 90°C, and more preferably 40°C to 70°C.

在氨基甲酸酯脲系共聚物（A2）的合成時，可使用公知的催化劑。例如可列舉三級胺系化合物及有機金屬系化合物等。 作為三級胺系化合物，例如可列舉：三乙基胺、三亞乙基二胺、N,N-二甲基苄基胺、N-甲基嗎啉及二氮雜二環十一烯（別名：DBU）等，可單獨使用一種或將兩種以上組合來使用。In the synthesis of the urethane urea copolymer (A2), a known catalyst can be used. Examples include tertiary amine compounds and organometallic compounds. Examples of tertiary amine compounds include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, and diazabicycloundecene (alias) : DBU), etc., can be used alone or in combination of two or more.

作為有機金屬系化合物，可列舉錫系化合物及非錫系化合物。 作為錫系化合物，例如可列舉：二丁基二氯化錫、二丁基氧化錫、二丁基二溴化錫、二丁基二馬來酸錫（dibutyltin dimaleate）、二丁基二月桂酸錫（別名：DBTDL（dibutyltin dilaurate））、二丁基二乙酸錫、二丁基硫化錫、三丁基硫化錫、三丁基氧化錫、三丁基乙酸錫、三乙基乙氧基錫（triethyltin ethoxide）、三丁基乙氧基錫（tributyltin ethoxide）、二辛基氧化錫、三丁基氯化錫、三丁基三氯乙酸錫、以及二辛基二月桂酸錫（別名：DOTDL（dioctyl tin dilaurate））、2-乙基己酸錫等。Examples of organometallic compounds include tin compounds and non-tin compounds. Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, and dibutyl dilaurate Tin (alias: DBTDL (dibutyltin dilaurate)), dibutyl tin diacetate, dibutyl tin sulfide, tributyl tin sulfide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide ( triethyltin ethoxide, tributyltin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate, and dioctyl tin dilaurate (alias: DOTDL ( dioctyl tin dilaurate)), 2-ethylhexanoic acid tin, etc.

作為非錫系化合物，例如可列舉：二丁基二氯化鈦、鈦酸四丁酯、及二丁氧基三氯化鈦等鈦系；油酸鉛、2-乙基己酸鉛、苯甲酸鉛、及二環烷酸鉛等鉛系；2-乙基己酸鐵及乙醯丙酮二鐵等鐵系；苯甲酸鈷及二2-乙基己酸鈷等鈷系；環烷酸鋅及二2-乙基己酸鋅等鋅系；環烷酸鋯等。Examples of non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and dibutoxy titanium trichloride; lead oleate, lead 2-ethylhexanoate, and benzene Lead systems such as lead formate and lead dinaphthenate; iron systems such as ferric 2-ethylhexanoate and diiron acetone; cobalt systems such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate And zinc series such as zinc di-2-ethylhexanoate; zirconium naphthenate, etc.

所述催化劑中，在反應性及衛生性的方面，優選二丁基二月桂酸錫（別名：DBTDL）、二辛基二月桂酸錫（別名：DOTDL）及2-乙基己酸錫等。Among the catalysts, dibutyltin dilaurate (alias: DBTDL), dioctyltin dilaurate (alias: DOTDL), tin 2-ethylhexanoate, and the like are preferred in terms of reactivity and hygiene.

三級胺系化合物及有機金屬系化合物等催化劑可單獨使用一種或使用兩種以上。特別是，在並用聚酯二醇類與聚醚二醇類作為多元醇成分的情況下，通過並用二丁基二月桂酸錫與2-乙基己酸錫，會穩定地獲得氨基甲酸酯脲系共聚物（A2），所以優選。The catalysts such as tertiary amine compounds and organometallic compounds can be used alone or in combination of two or more. In particular, when polyester diols and polyether diols are used in combination as a polyol component, urethane can be stably obtained by using dibutyl tin dilaurate and tin 2-ethylhexanoate together. Urea copolymer (A2) is preferred.

在氨基甲酸酯脲系共聚物（A2）的合成時，可較佳地使用公知的溶劑。溶劑起到使反應控制容易的作用。作為出於所述目的而使用的溶劑，例如可列舉：甲基乙基酮、乙酸乙酯、甲苯、二甲苯、丙酮、苯、二噁烷、乙腈、四氫呋喃、二甘醇二甲醚、二甲基亞碸、N-甲基吡咯烷酮、及二甲基甲醯胺等。就氨基甲酸酯脲系共聚物（A2）的溶解性及溶劑的沸點的方面而言，特別是優選為乙酸乙酯、甲苯、甲基乙基酮、及它們的混合溶劑。使用了溶劑的情況下反應結束後所獲得的樹脂溶液的濃度（樹脂固體成分）優選為50質量%～95質量%，更優選為60質量%～90質量%。In the synthesis of the urethane urea copolymer (A2), a known solvent can be preferably used. The solvent serves to make the reaction control easy. Examples of the solvent used for the purpose include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, and diethylene glycol. Methyl sulfoxide, N-methylpyrrolidone, dimethylformamide, etc. In terms of the solubility of the urethane urea copolymer (A2) and the boiling point of the solvent, particularly preferred are ethyl acetate, toluene, methyl ethyl ketone, and mixed solvents thereof. When a solvent is used, the concentration (resin solid content) of the resin solution obtained after the completion of the reaction is preferably 50% by mass to 95% by mass, and more preferably 60% by mass to 90% by mass.

異氰酸脂化合物的使用量在氨基甲酸酯脲系共聚物（A2）100質量%中，就維持黏著層的凝聚力對黏著劑賦予耐久性的觀點而言，優選為5質量%以上，就防止樹脂的柔軟性的下降而確保充分的接著力的觀點而言，優選為50質量%以下。更優選為10質量%～30質量%。 此處，「氨基甲酸酯脲系共聚物（A2）100質量%中」是「氨基甲酸酯脲系共聚物（A2）的除溶劑以外的合成原料的合計100質量%中」，是氨基甲酸酯脲系共聚物（A2）的合成中使用的異氰酸脂化合物、多元醇（a2-1）、二氨基化合物及視需要使用的反應停止劑的合計100質量%中這一意思（在以下的記載中也相同）。The amount of isocyanate compound used is 100% by mass of the urethane urea copolymer (A2). From the viewpoint of maintaining the cohesive force of the adhesive layer and imparting durability to the adhesive, it is preferably 5% by mass or more. From the viewpoint of preventing a decrease in the flexibility of the resin and ensuring a sufficient adhesive force, it is preferably 50% by mass or less. It is more preferably 10% by mass to 30% by mass. Here, "in 100% by mass of the urethane urea copolymer (A2)" means "in 100% by mass of the total synthetic raw materials other than the solvent of the urethane urea copolymer (A2)", which is an amino group This means the total 100% by mass of the isocyanate compound, polyol (a2-1), diamino compound, and reaction stopper used if necessary for the synthesis of the formate urea copolymer (A2) ( The same applies to the following description).

數量平均分子量（Mn）1000～10000的聚合性化合物（a2）即多元醇的使用量在氨基甲酸酯脲系共聚物（A2）100質量%中，就維持黏著層的凝聚力對黏著劑賦予耐久性的觀點而言，優選為60質量%～90質量%。若所述量為60質量%～90質量%，則可防止共聚物的柔軟性的下降而確保充分的接著力，從而可高度兼顧耐熱性及彎曲性，因此優選。更優選為75質量%～90質量%。Polymerizable compound (a2) with a number average molecular weight (Mn) of 1,000 to 10,000, that is, the amount of polyol used in 100% by mass of the urethane urea copolymer (A2), maintains the cohesive force of the adhesive layer and imparts durability to the adhesive From a sexual point of view, it is preferably 60% by mass to 90% by mass. If the amount is 60% by mass to 90% by mass, the decrease in the flexibility of the copolymer can be prevented and sufficient adhesion can be ensured, so that the heat resistance and the bendability can be highly balanced, which is preferable. More preferably, it is 75% by mass to 90% by mass.

二氨基化合物的使用量在氨基甲酸酯脲系共聚物（A2）100質量%中，就維持黏著層的凝聚力對黏著劑賦予耐久性的觀點而言，優選為0.5質量%～20質量%。若所述量為0.5質量%～20質量%，則可防止樹脂的柔軟性的下降而確保充分的接著力，從而可高度兼顧耐熱性及彎曲性，因此優選。更優選為1質量%～5質量%。The use amount of the diamino compound is 100% by mass of the urethane urea copolymer (A2). From the viewpoint of maintaining the cohesive force of the adhesive layer and imparting durability to the adhesive, it is preferably 0.5% by mass to 20% by mass. If the amount is 0.5% by mass to 20% by mass, the decrease in the flexibility of the resin can be prevented to ensure a sufficient adhesive force, and the heat resistance and the flexibility can be highly balanced, which is preferable. More preferably, it is 1% by mass to 5% by mass.

在使用反應停止劑的情況下，其使用量在氨基甲酸酯脲系共聚物（A2）100質量%中，就確保共聚物的反應穩定性的觀點而言，優選為0.05質量%以上，就恰當地控制樹脂的質量平均分子量（Mw）而確保黏著層的耐久性的觀點而言，優選為5質量%以下。When a reaction stopper is used, its use amount is 100% by mass of the urethane urea copolymer (A2). From the viewpoint of ensuring the reaction stability of the copolymer, it is preferably 0.05% by mass or more. From the viewpoint of appropriately controlling the mass average molecular weight (Mw) of the resin and ensuring the durability of the adhesive layer, it is preferably 5% by mass or less.

＜硬化劑＞ 硬化劑可與構成黏著層的共聚物（A）的羥基反應，提高黏著層的凝聚力，提高黏著層的耐熱性及耐濕熱性，從而抑制高溫氣氛下及高溫高濕氣氛下的浮起及剝離。<Hardener> The hardener can react with the hydroxyl group of the copolymer (A) constituting the adhesive layer, improve the cohesive force of the adhesive layer, improve the heat resistance and humidity resistance of the adhesive layer, thereby suppressing the floating and peeling under high temperature atmosphere and high temperature and high humidity atmosphere .

作為硬化劑，例如可列舉異氰酸脂化合物、環氧化合物、氮丙啶化合物、碳二醯亞胺化合物、及金屬螯合物等。Examples of the curing agent include isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, and metal chelate compounds.

異氰酸脂化合物是具有兩個以上的異氰酸酯基的異氰酸酯。作為異氰酸脂化合物，例如優選為芳香族聚異氰酸酯、脂肪族聚異氰酸酯、芳香脂肪族聚異氰酸酯、及脂環族聚異氰酸酯等異氰酸酯單體；它們的縮二脲體、脲酸酯（nurate）體及加合物體。The isocyanate compound is an isocyanate having two or more isocyanate groups. As the isocyanate compound, for example, preferred are isocyanate monomers such as aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, and alicyclic polyisocyanate; their biuret and ureate Body and adduct body.

作為芳香族聚異氰酸酯，例如可列舉：1,3-亞苯基二異氰酸酯、4,4'-二苯基二異氰酸酯、1,4-亞苯基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-甲苯胺二異氰酸酯、2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯、聯大茴香胺二異氰酸酯、4,4'-二苯基醚二異氰酸酯、以及4,4',4''-三苯基甲烷三異氰酸酯等。Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4′-diphenylmethane Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, biphenyl Anisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4',4''-triphenylmethane triisocyanate, etc.

作為脂肪族聚異氰酸酯，例如可列舉：三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯（別名：HMDI（hexamethylene diisocyanate））、五亞甲基二異氰酸酯、1,2-亞丙基二異氰酸酯、2,3-亞丁基二異氰酸酯、1,3-亞丁基二異氰酸酯、十二亞甲基二異氰酸酯、以及2,4,4-三甲基六亞甲基二異氰酸酯等。Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (alias: HMDI (hexamethylene diisocyanate)), pentamethylene diisocyanate, 1,2- Propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

作為芳香脂肪族聚異氰酸酯，例如可列舉：ω,ω'-二異氰酸酯-1,3-二甲基苯、ω,ω'-二異氰酸酯-1,4-二甲基苯、ω,ω'-二異氰酸酯-1,4-二乙基苯、1,4-四甲基苯二甲基二異氰酸酯、以及1,3-四甲基苯二甲基二異氰酸酯等。Examples of the aromatic aliphatic polyisocyanate include: ω,ω′-diisocyanate-1,3-dimethylbenzene, ω,ω′-diisocyanate-1,4-dimethylbenzene, ω,ω′- Diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, etc.

作為脂環族聚異氰酸酯，例如可列舉：3-異氰酸酯甲基-3,5,5-三甲基環己基異氰酸酯（別名：IPDI（isophorone diisocyanate），異佛爾酮二異氰酸酯）、1,3-環戊烷二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基-2,4-環己烷二異氰酸酯、甲基-2,6-環己烷二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、以及1,4-雙(異氰酸酯甲基)環己烷等。Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (alias: IPDI (isophorone diisocyanate), isophorone diisocyanate), 1,3- Cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate Isocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, etc.

縮二脲體是異氰酸酯單體自己縮合而成的具有縮二脲鍵的自縮合物。作為縮二脲體，例如可列舉六亞甲基二異氰酸酯的縮二脲體等。Biuret is a self-condensation product with biuret bond formed by condensation of isocyanate monomer itself. Examples of the biuret include biuret of hexamethylene diisocyanate.

脲尿酸酯體是異氰酸酯單體的三聚體。例如可列舉六亞甲基二異氰酸酯的三聚體、異佛爾酮二異氰酸酯的三聚體、及甲苯二異氰酸酯的三聚體等。Urea urate is a trimer of isocyanate monomer. For example, the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate, the trimer of toluene diisocyanate, etc. are mentioned.

加合物體是異氰酸酯單體與二官能以上的含有低分子活性氫的化合物進行反應而成的二官能以上的異氰酸脂化合物。作為加合物體，例如可列舉：三羥甲基丙烷與六亞甲基二異氰酸酯的反應產物、三羥甲基丙烷與甲苯二異氰酸酯的反應產物、三羥甲基丙烷與苯二甲基二異氰酸酯的反應產物、三羥甲基丙烷與異佛爾酮二異氰酸酯的反應產物、及1,6-己烷二醇與六亞甲基二異氰酸酯的反應產物等。The adduct body is a difunctional or higher isocyanate compound obtained by reacting an isocyanate monomer with a bifunctional or higher low molecular active hydrogen-containing compound. Examples of adducts include reaction products of trimethylolpropane and hexamethylene diisocyanate, reaction products of trimethylolpropane and toluene diisocyanate, and trimethylolpropane and xylylene diisocyanate. Reaction products, the reaction product of trimethylolpropane and isophorone diisocyanate, and the reaction product of 1,6-hexanediol and hexamethylene diisocyanate.

作為異氰酸脂化合物，就形成充分的交聯結構的觀點而言，優選為三官能的異氰酸脂化合物，更優選為作為異氰酸酯單體與三官能的含有低分子活性氫的化合物的反應產物的加合物體、及脲酸酯體。其中優選為六亞甲基二異氰酸酯的三羥甲基丙烷加合物體、六亞甲基二異氰酸酯的脲酸酯體、甲苯二異氰酸酯的三羥甲基丙烷加合物體、甲苯二異氰酸酯的脲酸酯體、異佛爾酮二異氰酸酯的三羥甲基丙烷加合物體、及異佛爾酮二異氰酸酯的脲酸酯體，更優選為六亞甲基二異氰酸酯的三羥甲基丙烷加合物體、六亞甲基二異氰酸酯的脲酸酯體、甲苯二異氰酸酯的脲酸酯體、及異佛爾酮二異氰酸酯的脲酸酯體。The isocyanate compound is preferably a trifunctional isocyanate compound from the viewpoint of forming a sufficient cross-linked structure, and is more preferably a reaction as an isocyanate monomer and a trifunctional low molecular active hydrogen-containing compound The adduct body and urate body of the product. Among them, trimethylolpropane adduct of hexamethylene diisocyanate, urea ester of hexamethylene diisocyanate, trimethylolpropane adduct of toluene diisocyanate, and ureic acid of toluene diisocyanate are preferred. The ester body, the trimethylolpropane adduct of isophorone diisocyanate, and the urea ester body of isophorone diisocyanate are more preferably the trimethylolpropane adduct of hexamethylene diisocyanate. , Urea body of hexamethylene diisocyanate, urea body of toluene diisocyanate, and urea body of isophorone diisocyanate.

作為環氧化合物，例如可列舉：甘油二縮水甘油基醚、1,6-己烷二醇二縮水甘油基醚、N,N,N',N'-四縮水甘油基-間苯二甲基二胺、1,3-雙（N,N'-二縮水甘油基氨基甲基）環己烷、及N,N,N',N'-四縮水甘油基氨基苯基甲烷等。Examples of the epoxy compound include glycerin diglycidyl ether, 1,6-hexanediol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylene Diamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidylaminophenylmethane, etc.

作為氮丙啶化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶羧醯胺)、三-2,4,6-(1-氮丙啶基)-1,3,5-三嗪、及4,4'-雙(亞甲基亞胺基羰基氨基)二苯基甲烷等。Examples of the aziridine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), tri-2,4,6-(1-aziridine Pyridyl)-1,3,5-triazine, and 4,4'-bis(methyleneiminocarbonylamino)diphenylmethane, etc.

作為碳二醯亞胺化合物，優選為通過在碳二醯亞胺化催化劑的存在下使二異氰酸酯化合物進行脫碳酸縮合反應而生成的高分子量聚碳二醯亞胺。作為市售品，優選為日清紡績公司的卡波迪樂系列（Carbodilite series）。其中，卡波迪樂（Carbodilite）V-03、07、09與有機溶劑的相容性優異，因此優選。The carbodiimide compound is preferably a high-molecular-weight polycarbodiimide produced by subjecting a diisocyanate compound to decarbonation condensation reaction in the presence of a carbodiimidation catalyst. As a commercially available product, it is preferably the Carbodilite series of Nisshinbo. Among them, Carbodilite (Carbodilite) V-03, 07, 09 is excellent in compatibility with organic solvents, so it is preferable.

作為金屬螯合物，例如優選為：鋁、鐵、銅、鋅、錫、鈦、鎳、銻、鎂、釩、鉻及鋯等多價金屬與乙醯丙酮或乙醯乙酸乙酯的配位化合物。作為金屬螯合物，例如可列舉：乙基乙醯乙酸鋁-二異丙醇酯、三乙醯基丙酮酸鋁、雙乙基乙醯乙酸鋁-單乙醯基丙酮酸酯、及烷基乙醯乙酸鋁-二異丙醇酯。As the metal chelate compound, for example, coordination of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium with acetone or ethyl acetate is preferable. Compound. Examples of the metal chelate compound include aluminum ethyl acetoacetate-diisopropanol, aluminum triethyl acetonate, bisethyl aluminum acetoacetate-monoethyl acetonate, and alkyl groups Aluminum acetyl acetate-diisopropanol ester.

硬化劑可單獨使用一種或者將兩種以上組合來使用。 硬化劑的使用量相對於具有羥基的共聚物（A）100質量份，優選為0.01質量份～20質量份，更優選為1質量份～15質量份。若使用量為0.01質量份以上，則黏著層的凝聚力進一步提高，若為20質量份以下，則容易兼顧黏著層的凝聚力與柔軟性，因此優選。One kind of hardener may be used alone, or two or more kinds may be used in combination. The use amount of the hardener is preferably 0.01 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the copolymer (A) having a hydroxyl group. If the amount used is 0.01 parts by mass or more, the cohesive force of the adhesive layer is further improved, and if it is 20 parts by mass or less, it is easy to reconcile the cohesive force and flexibility of the adhesive layer, which is preferable.

＜有機矽烷化合物＞ 黏著層視需要可還含有有機矽烷化合物。 作為有機矽烷化合物，例如可列舉：3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三丙氧基矽烷、3-(甲基)丙烯醯氧基丙基三丁氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、及3-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷等具有(甲基)丙烯醯氧基的烷氧基矽烷化合物； 乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三異丙氧基矽烷、乙烯基三丁氧基矽烷、乙烯基甲基二甲氧基矽烷、及乙烯基甲基二乙氧基矽烷等具有乙烯基的烷氧基矽烷化合物； 3-氨基丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、3-氨基丙基三丙氧基矽烷、3-氨基丙基甲基二甲氧基矽烷、3-氨基丙基甲基二乙氧基矽烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基矽烷、N-(2-氨基乙基)-3-氨基丙基三乙氧基矽烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基矽烷、N-(2-氨基乙基)-3-氨基丙基甲基二乙氧基矽烷、及N-苯基-3-氨基丙基三甲氧基矽烷等具有氨基的烷氧基矽烷化合物； 3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基三丙氧基矽烷、及3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基甲基二乙氧基矽烷等具有巰基的烷氧基矽烷化合物； 3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三丙氧基矽烷、3-縮水甘油氧基丙基三丁氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、及2-(3,4-環氧基環己基)乙基三甲氧基矽烷等具有環氧基的烷氧基矽烷化合物； 四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、及四丁氧基矽烷等四烷氧基矽烷化合物； 3-氯丙基三甲氧基矽烷、正己基三甲氧基矽烷、正己基三乙氧基矽烷、正癸基三甲氧基矽烷、正癸基三乙氧基矽烷、苯乙烯基三甲氧基矽烷、苯基三甲氧基矽烷、二苯基二甲氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基亞丁基)丙基胺、1,3,5-三(3-三甲氧基矽烷基丙基)異氰脲酸酯、3-異氰酸酯基丙基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷、六甲基二矽氮烷、及在分子內具有烷氧基矽烷基的矽酮樹脂等。<Organic Silane Compound> The adhesive layer may also contain organic silane compounds as needed. Examples of the organic silane compound include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(methyl) Acryloyloxypropyltripropoxysilane, 3-(meth)acryloyloxypropyltributoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, And 3-(meth)acryloyloxypropylmethyl diethoxysilane and other alkoxysilane compounds having (meth)acryloyloxy; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxy Alkoxysilane compounds with vinyl groups such as silanes; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyl Methyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N -(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, and N-phenyl Alkoxyaminosilane compounds with amino groups such as -3-aminopropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, and 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Alkoxysilane compounds with mercapto groups such as methyl methyl diethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltrisilane Butoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl ) Ethyl trimethoxy silane and other alkoxy silane compounds with epoxy groups; Tetramethoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; 3-chloropropyltrimethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, styryltrimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, 1,3,5-tri( 3-trimethoxysilylpropyl) isocyanurate, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, hexamethyldisilazane, and in-molecules Silicone resin with alkoxy silane group inside.

有機矽烷化合物的使用量相對於共聚物（A）100質量份，優選為0.01質量份～2質量份，更優選為0.05質量份～1質量份。The use amount of the organosilane compound is preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the copolymer (A).

黏著層只要為可解決課題的範圍，則可含有各種樹脂、油、軟化劑、染料、顏料、抗氧化劑、紫外線吸收劑、耐候穩定劑、塑化劑、填充劑、抗老化劑、及抗靜電劑等所述以外的任意成分。The adhesive layer can contain various resins, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weathering stabilizers, plasticizers, fillers, anti-aging agents, and antistatic agents as long as it can solve the problem Optional ingredients other than those mentioned above.

「剝離膜」 作為剝離膜，並無特別限制，可較佳地使用透明塑膠基材。作為透明塑膠基材的原材料，例如可列舉：聚對苯二甲酸乙二酯（PET）等聚酯；聚甲基丙烯酸甲酯（PMMA）等丙烯酸系樹脂；聚碳酸酯；三乙醯纖維素；聚碸；聚芳酯；聚環烯烴等。另外，塑膠材料可單獨使用一種或者將兩種以上組合來使用。"Release Film" The release film is not particularly limited, and a transparent plastic substrate can be preferably used. Examples of raw materials for transparent plastic substrates include polyesters such as polyethylene terephthalate (PET); acrylic resins such as polymethyl methacrylate (PMMA); polycarbonate; and triethyl cellulose ; Polyphenol; Polyarylate; Polycycloolefin and so on. In addition, plastic materials can be used alone or in combination of two or more.

作為剝離膜，所述中，可較佳地使用耐熱性優異的透明塑膠基材、即高溫或高溫高濕等苛刻的條件下變形得到抑制或防止的透明塑膠基材。作為透明塑膠基材，特別是PET膜或片材較佳。As the release film, a transparent plastic substrate excellent in heat resistance, that is, a transparent plastic substrate whose deformation is suppressed or prevented under severe conditions such as high temperature or high temperature and high humidity can be preferably used. As a transparent plastic substrate, PET film or sheet is particularly preferable.

透明塑膠基材的厚度並無特別限定，例如優選為10 μm～200 μm，更優選為25 μm～150 μm。The thickness of the transparent plastic substrate is not particularly limited, for example, it is preferably 10 μm to 200 μm, and more preferably 25 μm to 150 μm.

剝離膜可具有單層及多層中的任一形態。而且，可對透明基材的表面實施例如電暈放電處理及等離子體處理等物理性處理；塗布處理等化學性處理等表面處理。The release film may have any form of a single layer or multiple layers. In addition, the surface of the transparent substrate may be subjected to physical treatments such as corona discharge treatment and plasma treatment, and chemical treatments such as coating treatment.

「黏著片的製造方法」 本發明的黏著片可依據通常的黏著片的製造方法來製造。作為本發明的黏著片的製造方法，例如可列舉如下方法，即：在剝離膜的剝離處理面，以乾燥後的厚度成為規定的厚度的方式直接塗布共聚物（A）與硬化劑的混合物（以下，有時簡單記述為「黏著劑組合物」），形成黏著層，並貼附剝離膜的方法；在兩枚剝離膜的剝離處理面分別以乾燥後的厚度成為規定的厚度的方式塗敷黏著劑組合物，形成黏著層，之後對兩枚剝離膜上形成的黏著層彼此進行貼附的方法等。"Manufacturing method of adhesive sheet" The adhesive sheet of the present invention can be manufactured according to a general method of manufacturing an adhesive sheet. As a method for manufacturing the adhesive sheet of the present invention, for example, a method of directly applying a mixture of the copolymer (A) and a hardener (so that the thickness after drying becomes a predetermined thickness on the peeling treatment surface of the peeling film ( Hereinafter, it is sometimes simply described as "adhesive composition"), a method of forming an adhesive layer and attaching a peeling film; coating the peeling treatment surfaces of the two peeling films so that the thickness after drying becomes a predetermined thickness, respectively The adhesive composition forms an adhesive layer, and then a method of attaching the adhesive layers formed on the two release films to each other.

作為黏著層的厚度，並無特別限制，例如優選為10 μm～500 μm，更優選為50 μm～200 μm。若黏著層的厚度為10 μm～500 μm，則容易獲得充分的凝聚力，可高度地兼顧耐熱性、耐濕熱性及彎曲性，因此優選。The thickness of the adhesive layer is not particularly limited. For example, it is preferably 10 μm to 500 μm, and more preferably 50 μm to 200 μm. If the thickness of the adhesive layer is 10 μm to 500 μm, sufficient cohesion is easily obtained, and heat resistance, moist heat resistance, and bendability can be highly balanced, which is preferable.

在黏著劑組合物的塗敷時，例如可使用凹版式輥塗機、反式輥塗機、吻合式輥塗機、浸漬式輥塗機、棒塗機、刮刀塗布機及噴塗機等公知的塗布機。In the application of the adhesive composition, for example, known gravure roll coaters, reverse roll coaters, stapling roll coaters, dip roll coaters, bar coaters, blade coaters, spray coaters, etc. can be used. Coating machine.

黏著片可利用所謂輥對輥（Roll to Roll）製程來製造。例如，連續地製造在剝離膜上形成有黏著層的黏著片或在兩枚剝離膜之間形成有黏著層的黏著片，裁剪為適當的寬度，並捲繞成卷狀，由此可製造捲繞成卷狀的黏著帶。The adhesive sheet can be manufactured using a so-called roll-to-roll process. For example, an adhesive sheet with an adhesive layer formed on a release film or an adhesive sheet with an adhesive layer formed between two release films can be continuously manufactured, cut to an appropriate width, and wound into a roll to produce a roll Adhesive tape wound into a roll.

《積層體》 本發明的積層體包括光透過性可撓性基材、黏著層及偏光板，黏著層是使用所述本發明的黏著片而形成。"Laminate" The laminate of the present invention includes a light-transmissive flexible substrate, an adhesive layer, and a polarizing plate. The adhesive layer is formed using the adhesive sheet of the present invention.

本發明的積層體是使用耐濕熱性、耐熱性及彎曲性優異的所述本發明的黏著片而形成，因此耐濕熱性、耐熱性及彎曲性優異。The laminate of the present invention is formed using the adhesive sheet of the present invention excellent in moisture and heat resistance, heat resistance and flexibility, and therefore is excellent in moisture and heat resistance, heat resistance and flexibility.

圖2中示出本發明的一實施方式的積層體的局部概略剖面圖。圖2中，符號3為光透過性可撓性基材（蓋板），符號4為黏著層，符號5為偏光板。FIG. 2 shows a partial schematic cross-sectional view of a laminate according to an embodiment of the present invention. In FIG. 2, symbol 3 is a light-transmissive flexible substrate (cover plate), symbol 4 is an adhesive layer, and symbol 5 is a polarizing plate.

在圖2中所示的積層體中，光透過性可撓性基材（蓋板）3經由本發明的黏著片中所含的黏著層4而貼附於偏光板5。如此，使用本發明的黏著片中所含的透明黏著層將光透過性可撓性基材（蓋板）與偏光板貼合，可獲得積層體。In the laminate shown in FIG. 2, the light-transmitting flexible base material (cover plate) 3 is attached to the polarizing plate 5 via the adhesive layer 4 included in the adhesive sheet of the present invention. In this way, the transparent adhesive layer contained in the adhesive sheet of the present invention is used to bond the light-transmissive flexible substrate (cover plate) and the polarizing plate, and a laminate can be obtained.

作為光透過性可撓性基材（蓋板），並無特別限制，可較佳地使用透明塑膠基材。作為透明塑膠基材的原材料，例如可列舉：聚對苯二甲酸乙二酯（PET）；聚甲基丙烯酸甲酯（PMMA）等丙烯酸系樹脂；聚碳酸酯；聚環烯烴等。另外，塑膠材料可單獨使用一種或將兩種以上組合來使用。The light-transmitting flexible substrate (cover plate) is not particularly limited, and a transparent plastic substrate can be preferably used. Examples of the raw material of the transparent plastic substrate include: polyethylene terephthalate (PET); acrylic resins such as polymethyl methacrylate (PMMA); polycarbonate; polycycloolefin and the like. In addition, plastic materials can be used alone or in combination of two or more.

作為光透過性可撓性基材（蓋板），所述中，可較佳地使用耐熱性優異的透明塑膠基材、即高溫或高溫高濕等苛刻的條件下變形得到抑制或防止的透明塑膠基材。作為透明塑膠基材的原材料，特別是聚對苯二甲酸乙二酯（PET）及聚環烯烴等較佳。As the light-transmitting flexible substrate (cover plate), among the above, a transparent plastic substrate excellent in heat resistance, that is, a transparent whose deformation is suppressed or prevented under severe conditions such as high temperature or high temperature and high humidity can be preferably used Plastic substrate. As the raw material of the transparent plastic substrate, especially polyethylene terephthalate (PET) and polycycloolefin are preferred.

光透過性可撓性基材（蓋板）的厚度並無特別限定，例如優選為100 μm～2000 μm，更優選為200 μm～1000 μm。The thickness of the light-transmitting flexible base material (cover plate) is not particularly limited, and for example, it is preferably 100 μm to 2000 μm, and more preferably 200 μm to 1000 μm.

《顯示器》 本發明的顯示器包括所述本發明的積層體及光學元件。作為光學元件，並無特別限定，例如可列舉液晶元件及有機EL元件等。"monitor" The display of the present invention includes the laminate and optical element of the present invention. The optical element is not particularly limited, and examples thereof include liquid crystal elements and organic EL elements.

本發明的顯示器具有耐濕熱性、耐熱性及彎曲性優異的所述本發明的積層體，因此耐濕熱性、耐熱性及彎曲性優異。The display of the present invention has the laminate of the present invention that is excellent in moisture and heat resistance, heat resistance, and flexibility, and therefore is excellent in moisture and heat resistance, heat resistance, and flexibility.

圖3中示出本發明的一實施方式的顯示器的局部概略剖面圖。圖3中，符號3為光透過性可撓性基材（蓋板）、符號4為黏著層，符號5為偏光板，符號6為偏光板用黏著層，符號7為包含氮化矽等的障壁層（barrier layer），符號8為有機EL層，符號9為包含聚醯亞胺等的支撐體，符號10為有機EL單元。另外，顯示器的構成能夠適當設計變更。FIG. 3 shows a partial schematic cross-sectional view of a display according to an embodiment of the present invention. In FIG. 3, symbol 3 is a light-transmissive flexible substrate (cover plate), symbol 4 is an adhesive layer, symbol 5 is a polarizing plate, symbol 6 is a polarizing plate adhesive layer, and symbol 7 is a material containing silicon nitride, etc. A barrier layer (barrier layer), symbol 8 is an organic EL layer, symbol 9 is a support including polyimide, etc., symbol 10 is an organic EL unit. In addition, the configuration of the display can be appropriately changed in design.

在圖3中所示的顯示器中，將圖2中所示的積層體進而經由偏光板用黏著層6而貼附於有機EL單元10，所述圖2中所示的積層體是將光透過性可撓性基材（蓋板）3經由本發明的黏著片中所含的黏著層4貼附於偏光板5而成。如此，使用本發明的黏著片中所含的黏著層將光透過性可撓性基材（蓋板）與偏光板予以貼附，獲得積層體，進而使用偏光板用黏著層將所述積層體貼附於有機EL，可獲得顯示器。 偏光板用黏著層可使用以往公知的黏著劑組合物來形成。In the display shown in FIG. 3, the laminate shown in FIG. 2 is further attached to the organic EL unit 10 via the polarizing plate adhesive layer 6, and the laminate shown in FIG. 2 transmits light The flexible substrate (cover plate) 3 is formed by attaching the polarizing plate 5 via the adhesive layer 4 contained in the adhesive sheet of the present invention. In this way, the light-transmitting flexible substrate (cover plate) and the polarizing plate are attached using the adhesive layer contained in the adhesive sheet of the present invention to obtain a laminate, and the laminate is then adhered using an adhesive layer for polarizing plate Attached to organic EL, a display can be obtained. The adhesive layer for polarizing plates can be formed using a conventionally well-known adhesive composition.

作為顯示器的使用用途，並無特別限制，可列舉：有機EL電視、有機EL智慧型手機、有機EL平板電腦及有機EL智慧型手錶等。 [實施例]The use of the display is not particularly limited, and examples include organic EL TVs, organic EL smartphones, organic EL tablets, and organic EL smart watches. [Example]

其次，示出實施例進而對細節進行說明，但本發明並不受這些的限定。例中，只要無特別說明，則「份」表示「質量份」，「%」表示「質量%」，「RH」是指相對濕度。而且，表中的調配量只要無特別說明，則為「質量份」。Next, the embodiments are shown to explain the details, but the present invention is not limited to these. In the example, unless otherwise specified, "parts" means "mass parts", "%" means "mass %", and "RH" means relative humidity. In addition, the compounding amount in the table is "parts by mass" unless otherwise specified.

＜重量平均分子量（Mw）及數量平均分子量（Mn）的測定方法＞ 聚合性化合物及共聚物的重量平均分子量（Mw）及數量平均分子量（Mn）是通過GPC法而求出。測定裝置及測定條件如下。Mw及Mn是根據將分子量已知的聚苯乙烯作為標準物質的換算而決定。 裝置名：島津制作所公司製造，LC-GPC系統「Prominence」、 管柱：東曹（Tosoh）公司製造的GMHXL 4根與東曹（Tosoh）公司製造的HXL-H 1根連結而成、 移動相溶媒：四氫呋喃、 流量：1.0 ml/分、 管柱溫度：40℃。<Measurement method of weight average molecular weight (Mw) and number average molecular weight (Mn)> The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymerizable compound and the copolymer are determined by the GPC method. The measuring device and measuring conditions are as follows. Mw and Mn are determined based on the conversion of polystyrene whose molecular weight is known as a standard substance. Device name: Made by Shimadzu Corporation, LC-GPC system "Prominence", Tubing: 4 pieces of GMHXL manufactured by Tosoh and 1 piece of HXL-H manufactured by Tosoh Mobile phase solvent: tetrahydrofuran, Flow rate: 1.0 ml/min, Column temperature: 40°C.

＜丙烯酸系共聚物的製造例＞ （丙烯酸系共聚物（A1-1）） 在具有攪拌機、溫度計、回流冷卻管、滴加裝置及氮導入管的反應容器（以下，有時簡單記述為「反應容器」）內裝入大分子單體AB-6（東亞合成公司製造，單末端甲基丙烯醯基丙烯酸丁酯）（AB-6）10份、4-羥基丁基丙烯酸酯（HBA）1份、丙烯酸2-乙基己酯（EHA）89份及2,2'-偶氮雙異丁腈（以下，簡單記述為「AIBN」）0.2份。利用氮氣對此反應容器內的氣氛進行置換。其後，在氮氣氛下對反應溶液一面進行攪拌一面加熱至50℃而開始反應，在所述溫度下反應4小時。反應結束後，進行冷卻，利用乙酸乙酯進行稀釋，獲得不揮發成分30%、黏度3000 mPa·s的共聚物（A1-1）溶液。所獲得的共聚物（A1-1）的Mw為140萬。<Production example of acrylic copolymer> (Acrylic copolymer (A1-1)) A macromonomer AB-6 (manufactured by East Asia Synthetic Co., Ltd.) is placed in a reaction vessel (hereinafter, sometimes simply referred to as "reaction vessel") equipped with a stirrer, thermometer, reflux cooling tube, dropping device, and nitrogen introduction tube. Terminal methacrylic butyl acrylate) (AB-6) 10 parts, 4-hydroxybutyl acrylate (HBA) 1 part, 2-ethylhexyl acrylate (EHA) 89 parts and 2,2'-couple Nitrobisisobutyronitrile (hereinafter, simply described as "AIBN") 0.2 parts. The atmosphere in this reaction vessel was replaced with nitrogen. Thereafter, the reaction solution was heated to 50°C while stirring under a nitrogen atmosphere, and the reaction was started, and the reaction was performed at the temperature for 4 hours. After the reaction was completed, it was cooled and diluted with ethyl acetate to obtain a copolymer (A1-1) solution with a nonvolatile content of 30% and a viscosity of 3000 mPa·s. The Mw of the obtained copolymer (A1-1) was 1.4 million.

（丙烯酸系共聚物（A1-2）～丙烯酸系共聚物（A1-12）、丙烯酸系共聚物（AC-1）～丙烯酸系共聚物（AC-4）） 除變更為表1中記載的組成及調配量（質量份）以外，利用與丙烯酸系共聚物（A1-1）的製造同樣的方法，合成共聚物（A1-2）～共聚物（A1-12）及共聚物（AC-1）～共聚物（AC-4）。將所獲得的共聚物（A1）及共聚物（AC）的Mw示於表1。表中的空欄表示不使用原料。(Acrylic copolymer (A1-2) to acrylic copolymer (A1-12), acrylic copolymer (AC-1) to acrylic copolymer (AC-4)) A copolymer (A1-2) to a copolymer (A1-12) were synthesized by the same method as the production of the acrylic copolymer (A1-1) except changing to the composition and blending amount (parts by mass) described in Table 1. ) And copolymer (AC-1) ~ copolymer (AC-4). Table 1 shows the Mw of the obtained copolymer (A1) and copolymer (AC). The empty column in the table indicates that no raw materials are used.

[表1]

Figure 108141296-A0304-0001
[Table 1]
Figure 108141296-A0304-0001

表中的各簡稱如下。 AB-6：分子末端為甲基丙烯醯基，聚合物鏈為聚丙烯酸丁酯的大分子單體（Mn=6000）、 AA-6：分子末端為甲基丙烯醯基，聚合物鏈為聚甲基丙烯酸甲酯的大分子單體（Mn=6000）、 APEG23：甲氧基聚乙二醇#1000丙烯酸酯（式（2）中，R1 為氫原子、n為23的單體）（Mn=1099）、 MPEG23：甲氧基聚乙二醇#1000甲基丙烯酸酯（式（2）中，R1 為甲基、n為23的單體）（Mn=1113）、 HEA：丙烯酸2-羥基乙酯（Mn=116）、 HBA：丙烯酸4-羥基丁酯（Mn=144）、 APEG14：甲氧基聚乙二醇#1000丙烯酸酯（式（2）中，R1 為氫原子、n為14的單體）（Mn=672）、 BA：正丁基丙烯酸酯（Mn=128）、 EHA：丙烯酸2-乙基己酯（Mn=184）。The abbreviations in the table are as follows. AB-6: The molecular end is a methacrylic group, the polymer chain is a polybutyl acrylate macromonomer (Mn=6000), AA-6: The molecular end is a methacryl group, and the polymer chain is a poly Macromonomer of methyl methacrylate (Mn=6000), APEG23: methoxypolyethylene glycol #1000 acrylate (in formula (2), R 1 is a hydrogen atom, n is 23 monomer) ( Mn=1099), MPEG23: methoxypolyethylene glycol #1000 methacrylate (in formula (2), R 1 is methyl and n is 23 monomer) (Mn=1113), HEA: acrylic 2 -Hydroxyethyl ester (Mn=116), HBA: 4-hydroxybutyl acrylate (Mn=144), APEG14: methoxypolyethylene glycol #1000 acrylate (In formula (2), R 1 is a hydrogen atom, n is a monomer of 14) (Mn=672), BA: n-butyl acrylate (Mn=128), EHA: 2-ethylhexyl acrylate (Mn=184).

＜氨基甲酸酯脲系共聚物的製造例＞ （二氨基化合物的合成） 在具有攪拌機、回流冷卻管、氮導入管、溫度計及滴加漏斗的四口燒瓶中裝入異佛爾酮二胺（IPDA）39.9份及甲苯39.9份，並在室溫下滴加丙烯酸丁酯（BA）60.1份。滴加結束後，在80℃下反應2小時，之後，加入甲苯60.1份。進而加入乙酸乙酯將固體成分調整為25%，獲得二氨基化合物（b-1）溶液。<Production example of urethane urea copolymer> (Synthesis of diamino compounds) In a four-necked flask equipped with a stirrer, reflux cooling tube, nitrogen introduction tube, thermometer and dropping funnel, 39.9 parts of isophorone diamine (IPDA) and 39.9 parts of toluene were added, and butyl acrylate was added dropwise at room temperature (BA) 60.1 copies. After the dropwise addition, the reaction was carried out at 80°C for 2 hours, and then, 60.1 parts of toluene was added. Further, ethyl acetate was added to adjust the solid content to 25% to obtain a diamino compound (b-1) solution.

[方法I] 將異氰酸脂化合物、多元醇及二氨基化合物的全部量一括裝入來進行共聚的方法（一括進行氨基甲酸酯化反應及脲化反應的方法） （氨基甲酸酯脲系共聚物（A2-1）） 在具有攪拌機、回流冷卻管、氮導入管及溫度計的四口燒瓶中裝入異佛爾酮二異氰酸酯（商品名：IPDI，贏創（EVONIK）製造）（IPDI）10.6份、可樂麗多元醇（Kuraray Polyol）P-2010（脂肪族聚酯多元醇，Mn=2000，可樂麗（Kuraray）股份有限公司製造）（PE2-2000）84.2份、異佛爾酮二胺（商品名：維斯塔明（VESTAMIN），贏創（EVONIK）製造）（IPDA）5.2份及甲苯100份。緩緩升溫至100℃，在所述溫度下進行4小時反應，獲得氨基甲酸酯脲系共聚物（A2-1）溶液。所獲得的共聚物的Mw為8萬。[Method I] Method for carrying out copolymerization by charging all amounts of isocyanate compound, polyol and diamino compound (including method for carrying out urethane reaction and urea reaction) (Urethane urea copolymer (A2-1)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen inlet tube and a thermometer, isophorone diisocyanate (trade name: IPDI, manufactured by EVONIK) (IPDI) 10.6 parts, Kuraray polyol ( Kuraray Polyol) P-2010 (aliphatic polyester polyol, Mn=2000, manufactured by Kuraray Co., Ltd.) (PE2-2000) 84.2 parts, isophorone diamine (trade name: Vestamin (VESTAMIN), manufactured by EVONIK (IPDA) 5.2 parts and 100 parts toluene. The temperature was gradually raised to 100°C, and the reaction was carried out at the temperature for 4 hours to obtain a urethane urea copolymer (A2-1) solution. The Mw of the obtained copolymer was 80,000.

（氨基甲酸酯脲系共聚物（A2-2）～氨基甲酸酯脲系共聚物（A2～6）、氨基甲酸酯脲系共聚物（AC-5）～氨基甲酸酯脲系共聚物（AC-6）） 除變更為表2記載的組成及調配量（質量份）以外，利用與氨基甲酸酯脲系共聚物（A2-1）的製造相同的方法合成共聚物（A2-2）～共聚物（A2-6）及共聚物（AC-5）～共聚物（AC-6）。將所獲得的共聚物（A2）及共聚物（AC）的Mw示於表2。表中的空欄表示不使用原料。(Urethane urea copolymer (A2-2) to urethane urea copolymer (A2 to 6), urethane urea copolymer (AC-5) to urethane urea copolymer Thing (AC-6)) The copolymer (A2-2) to copolymer (A2) were synthesized by the same method as the production of the urethane urea copolymer (A2-1) except that the composition and the blending amount (parts by mass) described in Table 2 were changed. -6) and copolymer (AC-5) ~ copolymer (AC-6). Table 2 shows the Mw of the obtained copolymer (A2) and copolymer (AC). The empty column in the table indicates that no raw materials are used.

[方法II] 通過將作為原料的一部分的異氰酸酯化合物與多元醇裝入並進行聚合，獲得具有至少一個異氰酸酯基的氨基甲酸酯預聚物，之後進一步對所獲得的氨基甲酸酯預聚物、二氨基化合物及視需要的反應停止劑進行共聚的方法（在進行氨基甲酸酯化反應後，對所獲的氨基甲酸酯預聚物進行脲化的方法）。[Method II] The urethane prepolymer having at least one isocyanate group is obtained by charging and polymerizing the isocyanate compound and polyol as a part of the raw material, and then the obtained urethane prepolymer and diamino compound And a method of copolymerizing the reaction stopper as needed (method of ureaizing the obtained urethane prepolymer after the urethane reaction).

（氨基甲酸酯脲系共聚物（A2-7）） 在具有攪拌機、回流冷卻管、氮導入管及溫度計的四口燒瓶中裝入異佛爾酮二異氰酸酯（商品名：IPDI，贏創（EVONIK）製造）（IPDI）31.1份、可樂麗多元醇（Kuraray Polyol）P-2010（PE2-2000）61.2份、及甲苯100份。緩緩升溫至100℃，在所述溫度下進行4小時反應，獲得氨基甲酸酯預聚物溶液。其次將所獲得的溶液冷卻至40℃，花費30分鐘以均勻的速度滴加異佛爾酮二胺（商品名：維斯塔明（VESTAMIN），贏創（EVONIK）製造）（IPDA）7.2份、及甲苯50份，其後反應1小時。進而，加入氨基羥甲基丙烷（AMP）0.5份進行反應，由此獲得氨基甲酸酯脲系共聚物（A2-7）溶液。所獲得的共聚物的Mw為8萬。(Urethane urea copolymer (A2-7)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube and a thermometer, isophorone diisocyanate (trade name: IPDI, manufactured by EVONIK) (IPDI) 31.1 parts, Kuraray polyol ( Kuraray Polyol) P-2010 (PE2-2000) 61.2 parts, and 100 parts toluene. The temperature was gradually raised to 100°C, and the reaction was carried out at the temperature for 4 hours to obtain a urethane prepolymer solution. Secondly, the obtained solution was cooled to 40°C, and isophoronediamine (trade name: VESTAMIN, manufactured by EVONIK) (IPDA) 7.2 parts was added dropwise at a uniform rate over 30 minutes. , And 50 parts of toluene, followed by reaction for 1 hour. Furthermore, 0.5 part of aminomethylolpropane (AMP) was added and reacted, thereby obtaining a urethane urea copolymer (A2-7) solution. The Mw of the obtained copolymer was 80,000.

（氨基甲酸酯脲系共聚物（A2-8）～氨基甲酸酯脲系共聚物（A2-12）、氨基甲酸酯脲系共聚物（AC-7）～氨基甲酸酯脲系共聚物（AC-10）） 除變更為表3中記載的組成及調配量（質量份）以外，利用與氨基甲酸酯脲系共聚物（A2-7）的製造相同的方法合成共聚物（A2-8）～共聚物（A2-12）及共聚物（AC-7）～共聚物（AC-10）。將所獲得的共聚物（A2）及共聚物（AC）的Mw示於表3。表中的空欄表示不使用原料。 另外，氨基甲酸酯脲系共聚物（AC-7）、氨基甲酸酯脲系共聚物（AC-8）為不具有羥基的共聚物。(Urethane urea copolymer (A2-8) to urethane urea copolymer (A2-12), urethane urea copolymer (AC-7) to urethane urea copolymer Thing (AC-10)) The copolymer (A2-8) to the copolymer (A2-8) to copolymer ( A2-12) and copolymer (AC-7) ~ copolymer (AC-10). Table 3 shows the Mw of the obtained copolymer (A2) and copolymer (AC). The empty column in the table indicates that no raw materials are used. In addition, the urethane urea copolymer (AC-7) and the urethane urea copolymer (AC-8) are copolymers having no hydroxyl group.

[表2]

Figure 108141296-A0304-0002
[Table 2]
Figure 108141296-A0304-0002

[表3]

Figure 108141296-A0304-0003
[table 3]
Figure 108141296-A0304-0003

表中的各簡稱如下。 IPDI：異佛爾酮二異氰酸酯（Mn=222）、 HMDI：六亞甲基二異氰酸酯（Mn=168）、 PP3-5000：普萊姆保羅（PRIMEPOL） FF-3500（三官能聚丙二醇，Mn=5000，三洋化成工業製造）、 PE2-1000：可樂麗多元醇 P-1010（二官能脂肪族聚酯多元醇，Mn=1000，可樂麗股份有限公司製造）、 PE2-2000：可樂麗多元醇 P-2010（二官能脂肪族聚酯多元醇，Mn=2000，可樂麗股份有限公司製造）、 PP2-2000：桑尼庫斯（Sannix） PP-2000（二官能聚丙二醇，Mn=1000，三洋化成工業製造）、 PP2-500：桑尼庫斯（Sannix） PP-500（二官能聚丙二醇，Mn=500，三洋化成工業製造）、 IPDA：異佛爾酮二胺（Mn=170）、 DBA：二丁基胺（Mn=73）、 AMP：氨基羥甲基丙烷（Mn=89）、 PA：丙醇（Mn=60）。The abbreviations in the table are as follows. IPDI: isophorone diisocyanate (Mn=222), HMDI: hexamethylene diisocyanate (Mn=168), PP3-5000: PRIMEPOL (PRIMEPOL) FF-3500 (trifunctional polypropylene glycol, Mn=5000, manufactured by Sanyo Chemical Industry), PE2-1000: Kuraray Polyol P-1010 (difunctional aliphatic polyester polyol, Mn=1000, manufactured by Kuraray Co., Ltd.), PE2-2000: Kuraray Polyol P-2010 (difunctional aliphatic polyester polyol, Mn=2000, manufactured by Kuraray Co., Ltd.), PP2-2000: Sannix PP-2000 (difunctional polypropylene glycol, Mn=1000, manufactured by Sanyo Chemical Industry), PP2-500: Sannix PP-500 (bifunctional polypropylene glycol, Mn=500, manufactured by Sanyo Chemical Industry), IPDA: isophorone diamine (Mn=170), DBA: Dibutylamine (Mn=73), AMP: aminomethylolpropane (Mn=89), PA: Propanol (Mn=60).

（實施例1） ＜黏著劑組合物的製備＞ 針對丙烯酸系共聚物（A1-1）不揮發成分100份，調配作為硬化劑的甲苯二異氰酸酯的三羥甲基丙烷的加合物體（I-1）2.5份、作為有機矽烷化合物的3-縮水甘油氧基丙基三甲氧基矽烷（S-1）0.1份及不揮發成分成為20%的量的乙酸乙酯並進行攪拌，獲得黏著劑組合物。(Example 1) <Preparation of adhesive composition> For 100 parts of non-volatile component of acrylic copolymer (A1-1), 2.5 parts of trimethylolpropane adduct body (I-1) of toluene diisocyanate as a hardener is blended, and 3-shrinkage of organosilane compound 0.1 parts of glyceryloxypropyltrimethoxysilane (S-1) and ethyl acetate having a nonvolatile content of 20% were stirred, and an adhesive composition was obtained.

＜黏著片的製造＞ 在厚度50 μm的剝離膜（聚對苯二甲酸乙二酯（PET），「E7004」，矽酮系剝離層、東洋紡公司製造）上，以乾燥後的厚度成為50 μm的方式塗敷所獲得的黏著劑組合物，在110℃下乾燥3分鐘，由此形成黏著層。繼而，在此黏著層上，貼合厚度38 μm的剝離膜（聚對苯二甲酸乙二酯、「SP-PET3811」）、矽酮系剝離層、琳得科（Lintec）公司製造），製作「剝離性膜/黏著層/剝離性膜」的積層體。繼而，使所獲得的積層體在溫度25℃、相對濕度55%RH的條件下熟成1周，獲得黏著片。<Manufacture of adhesive sheet> A 50 μm thick release film (polyethylene terephthalate (PET), “E7004”, silicone-based release layer, manufactured by Toyobo Co., Ltd.) was applied so that the thickness after drying became 50 μm. The adhesive composition was dried at 110°C for 3 minutes, thereby forming an adhesive layer. Then, on this adhesive layer, a release film (polyethylene terephthalate, "SP-PET3811") with a thickness of 38 μm, a silicone-based release layer, and manufactured by Lintec Co., Ltd. were produced. The laminate of "Releasable Film/Adhesive Layer/Releasable Film". Then, the obtained laminate was aged for 1 week under the conditions of a temperature of 25° C. and a relative humidity of 55% RH to obtain an adhesive sheet.

（實施例2～實施例13、比較例1～比較例4） 除了如表4及表5中所示，變更共聚物、硬化劑及矽烷偶合劑的種類與調配量（質量份）以外，以與實施例1同樣的方式獲得黏著片。(Example 2 to Example 13, Comparative Example 1 to Comparative Example 4) An adhesive sheet was obtained in the same manner as in Example 1, except that the types and formulation amounts (parts by mass) of the copolymer, hardener, and silane coupling agent were changed as shown in Table 4 and Table 5.

（比較例5、比較例6） 作為比較例5、比較例6，使用下述專利文獻的實施例中記載的黏著劑，以與本說明書的實施例1的黏著片的製作方法同樣的方式，分別獲得黏著片。 比較例5：日本專利特開2017-65217號公報的實施例1的黏著劑、 比較例6：日本專利特開2018-28974號公報的實施例1的黏著劑。(Comparative example 5, comparative example 6) As Comparative Examples 5 and 6, the adhesives described in the examples of the following patent documents were used, and the adhesive sheets were obtained in the same manner as in the method for manufacturing the adhesive sheet of Example 1 of this specification. Comparative Example 5: The adhesive of Example 1 of Japanese Patent Laid-Open No. 2017-65217, Comparative Example 6: The adhesive of Example 1 of Japanese Patent Laid-Open No. 2018-28974.

（實施例14） ＜黏著劑組合物的製備＞ 針對氨基甲酸酯脲系共聚物（A2-1）不揮發成分100份，調配作為硬化劑的甲苯二異氰酸酯的三羥甲基丙烷的加合物體（I-1）2.5份、作為有機矽烷化合物的3-縮水甘油氧基丙基三甲氧基矽烷（S-1）0.1份及不揮發成分成為20%的量的乙酸乙酯並進行攪拌，獲得黏著劑組合物。(Example 14) <Preparation of adhesive composition> 2.5 parts of trimethylolpropane adduct body (I-1) of toluene diisocyanate as a hardener is formulated for 100 parts of the volatile component of the urethane urea copolymer (A2-1) as an organosilane compound 0.1 parts of 3-glycidoxypropyltrimethoxysilane (S-1) and 20% of the non-volatile content of ethyl acetate were stirred and stirred to obtain an adhesive composition.

＜黏著片的製造＞ 在厚度50 μm的剝離膜（聚對苯二甲酸乙二酯（PET）、「E7004」、矽酮系剝離層、東洋紡公司製造）上，以乾燥後的厚度成為50 μm的方式塗敷所獲得的黏著劑組合物，在110℃下乾燥3分鐘，由此形成黏著層。繼而，在此黏著層上，貼合厚度38 μm的剝離膜（聚對苯二甲酸乙二酯，「SP-PET3811」）、矽酮系剝離層、琳得科（Lintec）公司製造），製作「剝離性膜/黏著層/剝離性膜」的積層體。繼而，使所獲得的積層體在溫度25℃、相對濕度55%RH的條件下熟成1周，獲得黏著片。<Manufacture of adhesive sheet> A 50 μm thick release film (polyethylene terephthalate (PET), “E7004”, silicone-based release layer, manufactured by Toyobo Co., Ltd.) was applied so that the thickness after drying became 50 μm. The adhesive composition was dried at 110°C for 3 minutes, thereby forming an adhesive layer. Then, a peeling film (polyethylene terephthalate, "SP-PET3811") with a thickness of 38 μm, a silicone-based peeling layer, and manufactured by Lintec Co., Ltd. were laminated on this adhesive layer to produce The laminate of "Releasable Film/Adhesive Layer/Releasable Film". Then, the obtained laminate was aged for 1 week under the conditions of a temperature of 25° C. and a relative humidity of 55% RH to obtain an adhesive sheet.

（實施例15～實施例26、比較例7～比較例12） 除了如表6及表7中所示，變更共聚物、硬化劑及矽烷偶合劑的種類與調配量（質量份）以外，以與實施例14同樣的方式獲得黏著片。(Example 15 to Example 26, Comparative Example 7 to Comparative Example 12) An adhesive sheet was obtained in the same manner as in Example 14 except that as shown in Table 6 and Table 7, the types and formulation amounts (parts by mass) of the copolymer, hardener and silane coupling agent were changed.

[表4]

Figure 108141296-A0304-0004
[Table 4]
Figure 108141296-A0304-0004

[表5]

Figure 108141296-A0304-0005
[table 5]
Figure 108141296-A0304-0005

[表6]

Figure 108141296-A0304-0006
[Table 6]
Figure 108141296-A0304-0006

[表7]

Figure 108141296-A0304-0007
[Table 7]
Figure 108141296-A0304-0007

《黏著片的評價》 針對所獲得的黏著片，實施常態環境下/熱環境下/濕熱環境下的HAZE變化率的測定、與透明性、耐熱性、耐濕熱性及耐彎曲性的評價。將結果示於表4～表9。"Evaluation of Adhesive Tablets" With respect to the obtained adhesive sheet, the measurement of the HAZE change rate under normal environment/heat environment/humid heat environment, and evaluation of transparency, heat resistance, humidity resistance, and bending resistance were carried out. The results are shown in Table 4 to Table 9.

另外，「試驗用黏著片」是將所獲得的黏著片的其中一個剝離膜剝離，將露出的黏著層在25℃、相對濕度50%RH氣氛下，使用層壓機黏貼到厚度100 μm的PET膜（東洋紡績公司製造，A-4300）上而獲得的、包括PET膜/黏著層/剝離膜的黏著片。In addition, the "adhesive sheet for test" is one of the peeling films of the obtained adhesive sheet, and the exposed adhesive layer is adhered to PET with a thickness of 100 μm using a laminator under an atmosphere of 25°C and a relative humidity of 50%RH. Adhesive sheet including PET film/adhesive layer/release film obtained on film (manufactured by Toyobo, A-4300).

＜HAZE變化率（常態環境（溫度25℃、相對濕度50%RH）＞ 實施例及比較例中所獲得的黏著片的黏著層的、溫度25℃、相對濕度50%RH氣氛下的彎曲試驗中30萬次彎曲前後的HAZE變化率是利用下述的方法求出。 將所獲得的黏著片裁剪為寬度112 mm×長度200 mm的尺寸（9英寸型顯示器用的尺寸），製作包括剝離膜/黏著層/剝離膜的黏著片1。 繼而，針對黏著片1，在25℃、相對濕度50%RH氣氛的常態環境下，使用彎折試驗機（湯淺系統（yuasa-system）設備公司製造），實施反覆彎折與180°打開的彎曲試驗。以彎折時的內徑（直徑）成為6 mm的方式進行條件設定，將在彎折一次後、180°打開一次的操作設為一個循環，將此操作反覆進行30萬循環。 在彎曲試驗的前後分別從黏著片1中將其中一個剝離膜剝離，測定黏著層的HAZE，基於下述式（1）算出HAZE變化率（ΔHAZE）。將結果示於表4～表7。 另外，黏著層的HAZE是使用日本電色工業公司製造的Turbidimeter NDH5000W進行測定（以下的評價也相同）。 （式1） ΔHAZE（%）=[（HAZE（E）-HAZE（S））/HAZE（S）]×100 此處， HAZE（S）表示彎曲試驗前的黏著片1的黏著層的HAZE。 HAZE（E）表示彎曲試驗後的黏著片1的黏著層的HAZE。＜HAZE change rate (normal environment (temperature 25℃, relative humidity 50%RH)> The HAZE change rate before and after 300,000 bendings in the bending test of the adhesive layer of the adhesive sheet obtained in the Examples and Comparative Examples at a temperature of 25° C. and a relative humidity of 50% RH was obtained by the following method. The obtained adhesive sheet was cut into a size of 112 mm in width×200 mm in length (a size for 9-inch display) to prepare an adhesive sheet 1 including a release film/adhesive layer/release film. Then, for the adhesive sheet 1, a bending test machine (manufactured by Yuasa-system Equipment Co., Ltd.) was used in a normal environment of an atmosphere of 25°C and a relative humidity of 50% RH to perform repeated bending and bending at 180° opening. test. The condition was set so that the inner diameter (diameter) at the time of bending became 6 mm, and the operation of opening at 180° after bending once was set as one cycle, and this operation was repeated for 300,000 cycles. One of the release films was peeled from the adhesive sheet 1 before and after the bending test, the HAZE of the adhesive layer was measured, and the HAZE change rate (ΔHAZE) was calculated based on the following formula (1). The results are shown in Table 4 to Table 7. In addition, the HAZE of the adhesive layer was measured using Turbidimeter NDH5000W manufactured by Nippon Denshoku Industries Co., Ltd. (the following evaluations are also the same). (Formula 1) ΔHAZE(%)=[(HAZE(E)-HAZE(S))/HAZE(S)]×100 Here, HAZE (S) represents the HAZE of the adhesive layer of the adhesive sheet 1 before the bending test. HAZE (E) represents the HAZE of the adhesive layer of the adhesive sheet 1 after the bending test.

＜HAZE變化率（熱環境（85℃）或濕熱環境（溫度60℃、相對濕度95%RH）＞ 將實施例及比較例中所獲得的黏著片裁剪為寬度112 mm×長度200 mm的尺寸（9英寸型顯示器用的尺寸），製作包括剝離膜/黏著層/剝離膜的黏著片1。 繼而，針對黏著片1，在85℃氣氛下的熱環境、或60℃、相對濕度95%RH氣氛的濕熱環境下，實施與常態環境下的評價同樣的30萬循環的彎曲試驗。與常態環境下的評價同樣地，在彎曲試驗的前後分別測定黏著層的HAZE，算出HAZE變化率。＜HAZE change rate (thermal environment (85℃) or hot and humid environment (temperature 60℃, relative humidity 95%RH)> The adhesive sheet obtained in Examples and Comparative Examples was cut into a size of 112 mm in width×200 mm in length (a size for a 9-inch display) to prepare an adhesive sheet 1 including a release film/adhesive layer/release film. Next, the adhesive sheet 1 was subjected to a bending test of 300,000 cycles in the same manner as the evaluation in the normal environment under a hot environment of 85°C atmosphere or a hot and humid environment of 60°C and 95%RH relative humidity atmosphere. As in the evaluation under the normal environment, the HAZE of the adhesive layer was measured before and after the bending test, and the HAZE change rate was calculated.

＜透明性[1]＞ 將試驗用黏著片裁剪為寬度112 mm×長度200 mm的尺寸（9英寸型顯示器用的尺寸），製作包括PET膜/黏著層/剝離膜的試驗用黏著片1。從所述試驗用黏著片1中將剝離膜剝離，將露出的黏著層在25℃、相對濕度50%RH氣氛下，使用層壓機黏貼到無鹼玻璃板（EN-A1：旭硝子公司製造）上，測定HAZE。評價基準如下。 ○：HAZE不足1.0（良好）。 ×：HAZE為1.0以上（不良）。<Transparency [1]> The test adhesive sheet was cut into a size of 112 mm width×200 mm length (the size for 9-inch display) to prepare an adhesive sheet 1 for testing including PET film/adhesive layer/release film. The peeling film was peeled from the test adhesive sheet 1, and the exposed adhesive layer was adhered to an alkali-free glass plate using a laminator at 25°C and a relative humidity of 50% RH (EN-A1: manufactured by Asahi Glass Co., Ltd.) On, measure HAZE. The evaluation criteria are as follows. ○: HAZE is less than 1.0 (good). ×: HAZE is 1.0 or more (bad).

＜透明性[2]（濕熱經時後的透明性）＞ 將試驗用黏著片裁剪為寬度112 mm×長度200 mm的尺寸（9英寸型顯示器用的尺寸），製作包括PET膜/黏著層/剝離膜的試驗用黏著片2。從所述試驗用黏著片2中將剝離膜剝離，將露出的黏著層在25℃、相對濕度50%RH氣氛下，使用層壓機黏貼到無鹼玻璃板（EN-A1：旭硝子公司製造）上，獲得包括PET膜/黏著層/玻璃的試驗用積層體。 繼而，將所述試驗用積層體在85℃、相對濕度85%RH氣氛下放置1000小時，並在25℃、相對濕度50%RH氣氛下進行自然冷卻，之後測定HAZE。評價基準如下。本試驗條件是比通常的耐久試驗的條件即溫度60℃、相對濕度95%RH更苛刻的試驗條件。 ○：HAZE不足2.0（良好）。 ×：HAZE為2.0以上（不良）。<Transparency [2] (Transparency over time with damp heat)> The test adhesive sheet was cut to a size of 112 mm width × 200 mm length (the size for a 9-inch display), and a test adhesive sheet 2 including a PET film/adhesive layer/release film was produced. The peeling film was peeled off from the test adhesive sheet 2, and the exposed adhesive layer was adhered to an alkali-free glass plate using a laminator under an atmosphere of 25°C and a relative humidity of 50% RH (EN-A1: manufactured by Asahi Glass Co., Ltd.) Above, a laminate for testing including PET film/adhesive layer/glass was obtained. Next, the test laminate was left in an atmosphere of 85°C and a relative humidity of 85%RH for 1000 hours, and was naturally cooled in an atmosphere of 25°C and a relative humidity of 50%RH, and then the HAZE was measured. The evaluation criteria are as follows. This test condition is a test condition that is more severe than the usual endurance test conditions, that is, a temperature of 60°C and a relative humidity of 95% RH. ○: HAZE is less than 2.0 (good). ×: HAZE is 2.0 or more (bad).

＜耐熱性/耐濕熱性（無鹼玻璃[X]）＞ 將試驗用黏著片裁剪為寬度112 mm×長度200 mm的尺寸（9英寸型顯示器用的尺寸），製作包括PET膜/黏著層/剝離膜的試驗用黏著片3。從所述試驗用黏著片3中將剝離膜剝離，將露出的黏著層在25℃、相對濕度50%RH氣氛下，使用層壓機黏貼到無鹼玻璃板（EN-A1：旭硝子公司製造）上，獲得包括PET膜/黏著層/玻璃的試驗用積層體。 繼而，作為耐熱性的評價，將所述試驗用積層體在105℃的條件下放置500小時，在25℃、相對濕度50%RH氣氛下進行自然冷卻，之後，在以下的條件下對試驗用積層體內有無發生氣泡、與有無黏著層的浮起或剝離進行目視評價。 而且，作為耐濕熱性的評價，將所述試驗用積層體在60℃、相對濕度95%RH氣氛下放置500小時，在25℃、相對濕度50%RH氣氛下進行自然冷卻，之後，在以下的條件下對試驗用積層體內有無發生氣泡、與有無黏著層的浮起或剝離進行目視評價。 ◎：完全確認不到試驗用積層體內發生氣泡、以及黏著層的浮起及剝離，實用上完全不存在問題。 ○：稍微確認到試驗用積層體內發生氣泡、和/或黏著層的浮起或剝離，實用上不存在問題。 ×：明顯確認到試驗用積層體內發生氣泡，和/或黏著層的浮起或剝離，實用上不可。<heat resistance/moisture resistance (alkali-free glass [X])> The test adhesive sheet was cut to a size of 112 mm width × 200 mm length (the size for a 9-inch display), and a test adhesive sheet 3 including a PET film/adhesive layer/release film was produced. The peeling film was peeled from the test adhesive sheet 3, and the exposed adhesive layer was adhered to an alkali-free glass plate using a laminator at 25°C and a relative humidity of 50% RH (EN-A1: manufactured by Asahi Glass Co., Ltd.) Above, a laminate for testing including PET film/adhesive layer/glass was obtained. Next, as an evaluation of heat resistance, the test laminate was left standing at 105°C for 500 hours, and was naturally cooled in an atmosphere of 25°C and a relative humidity of 50% RH. Thereafter, the test was conducted under the following conditions Visually evaluate the presence or absence of air bubbles in the layered body and the presence or absence of floating or peeling of the adhesive layer. Furthermore, as the evaluation of the heat and humidity resistance, the test laminate was left to stand in an atmosphere of 60°C and a relative humidity of 95% RH for 500 hours, and then naturally cooled in an atmosphere of 25°C and a relative humidity of 50% RH. Visually evaluate the presence or absence of air bubbles in the test laminate and the presence or absence of floating or peeling of the adhesive layer under the conditions. ⊚: No bubbles were generated in the test laminate, and the floating and peeling of the adhesive layer were not confirmed at all, and there was no practical problem at all. ○: It was slightly confirmed that bubbles were generated in the test laminate, and/or that the adhesive layer had floated or peeled off, and there was no practical problem. ×: It was clearly confirmed that bubbles were generated in the test laminate, and/or the floating or peeling of the adhesive layer was not practically acceptable.

＜耐熱性/耐濕熱性（偏光板[Y]）＞ 通過與所述耐熱性/耐濕熱性（無鹼玻璃[X]）的評價同樣的方法，新準備試驗用黏著片3。除了將試驗用黏著片3的被接著體從無鹼玻璃板變更為偏光板（層構成：三乙醯基纖維素膜/聚乙烯基醇膜/聚甲基丙烯酸甲酯膜）以外，通過與所述相同的方法，進行耐熱性及耐濕熱性的評價。本試驗條件是比無鹼玻璃[X]更苛刻的試驗條件。<Heat resistance/moisture resistance (polarizing plate [Y])> The adhesive sheet 3 for a test was newly prepared by the same method as the evaluation of the heat resistance/humid heat resistance (alkali-free glass [X]). In addition to changing the adherend of the test adhesive sheet 3 from an alkali-free glass plate to a polarizing plate (layer structure: triethyl acetyl cellulose film/polyvinyl alcohol film/polymethyl methacrylate film), by In the same manner as described above, the evaluation of heat resistance and moisture heat resistance was performed. This test condition is a more severe test condition than alkali-free glass [X].

＜耐彎曲性[1]、[2]、[3]＞ 將試驗用黏著片裁剪為寬度112 mm×長度200 mm的尺寸（9英寸型顯示器用的尺寸），製作包括PET膜/黏著層/剝離膜的試驗用黏著片5。從所述試驗用黏著片5中將剝離膜剝離，將露出的黏著層在25℃、相對濕度50%RH氣氛下，使用層壓機黏貼到偏光板（層構成：三乙醯基纖維素膜/聚乙烯基醇膜/聚甲基丙烯酸甲酯膜）上，獲得包括PET膜/黏著層/偏光板的試驗用積層體。 繼而，針對所述試驗用積層體，在下述3種環境下，使用彎折試驗機（湯淺系統（yuasa-system）設備公司製造），實施反覆彎折與180°打開的彎曲試驗。以彎折時的內徑（直徑）成為6 mm的方式進行條件設定，將在彎折一次後，180°打開一次的操作設為一個循環，將此操作反覆進行30萬循環。 常態環境（25℃、相對濕度50%RH氣氛）：耐彎曲性[1]、 熱環境（85℃氣氛）：耐彎曲性[2]、 濕熱環境（60℃、相對濕度95%RH氣氛）：耐彎曲性[3]。 耐彎曲性是對試驗結束後的試驗用積層體的外觀進行觀察，並利用以下的觀點進行評價。 外觀：在以下的條件下對試驗用積層體內有無發生氣泡、與有無黏著層的浮起或剝離進行目視評價。 ◎：完全確認不到試驗用積層體內發生氣泡、以及黏著層的浮起或剝離，實用上完全不存在問題。 ○：稍微確認到試驗用積層體內發生氣泡、和/或黏著層的浮起或剝離，實用上不存在問題。 ×：明顯確認到試驗用積層體內發生氣泡，和/或黏著層的浮起或剝離，實用上存在問題。<Bending resistance [1], [2], [3]> The test adhesive sheet was cut to a size of 112 mm in width×200 mm in length (the size for a 9-inch display), and a test adhesive sheet 5 including a PET film/adhesive layer/release film was produced. The peeling film was peeled off from the test adhesive sheet 5, and the exposed adhesive layer was adhered to the polarizing plate using a laminator at 25°C and a relative humidity of 50% RH (layer structure: triethyl acetyl cellulose film) /Polyvinyl alcohol film/polymethyl methacrylate film), a test laminate including a PET film/adhesive layer/polarizing plate was obtained. Then, with respect to the laminate for the test, a bending test machine (manufactured by Yuasa-system Equipment Co., Ltd.) was used under the following three environments to perform a bending test with repeated bending and 180° opening. The conditions were set so that the inner diameter (diameter) at the time of bending became 6 mm, and the operation of opening 180° after bending once was set as one cycle, and this operation was repeated for 300,000 cycles. Normal environment (25℃, relative humidity 50%RH atmosphere): bending resistance [1], Thermal environment (85℃ atmosphere): bending resistance [2], Hot and humid environment (60℃, relative humidity 95%RH atmosphere): bending resistance [3]. The bending resistance is to observe the appearance of the test laminate after the test and evaluate it from the following viewpoint. Appearance: Visually evaluate the presence or absence of bubbles in the test laminate and the presence or absence of floating or peeling of the adhesive layer under the following conditions. ⊚: No bubbles were generated in the test laminate, and the floating or peeling of the adhesive layer was not confirmed at all, and there was no practical problem at all. ○: It was slightly confirmed that bubbles were generated in the test laminate, and/or that the adhesive layer had floated or peeled off, and there was no practical problem. ×: It was clearly confirmed that bubbles were generated in the test laminate, and/or that the adhesive layer had floated or peeled off, which was a practical problem.

[表8]

Figure 108141296-A0304-0008
[Table 8]
Figure 108141296-A0304-0008

[表9]

Figure 108141296-A0304-0009
[Table 9]
Figure 108141296-A0304-0009

透明性[1]的評價條件：25℃、相對濕度50%RH氣氛、 透明性[2]的評價條件：85℃、相對濕度85%RH氣氛、1000小時、 耐彎曲性[1]的評價條件：25℃、相對濕度50%RH氣氛、 耐彎曲性[2]的評價條件：85℃氣氛、 耐彎曲性[3]的評價條件：60℃、相對濕度95%RH氣氛、 [X]：無鹼玻璃、 [Y]：偏光板。Evaluation conditions for transparency [1]: 25°C, relative humidity 50% RH atmosphere, Evaluation conditions for transparency [2]: 85°C, relative humidity 85%RH, 1000 hours, Evaluation conditions of bending resistance [1]: 25°C, relative humidity 50% RH atmosphere, Evaluation conditions of bending resistance [2]: 85°C atmosphere, Evaluation conditions of bending resistance [3]: 60°C, relative humidity 95% RH atmosphere, [X]: Alkali-free glass, [Y]: Polarizing plate.

根據表8及表9的結果，可確認到：實施例1～實施例26中所獲得的黏著片中，透明性、耐熱性、耐濕熱性及耐彎曲性的所有特性良好。根據這些結果，表示：使用本發明的黏著片的積層體及顯示器在透明性、耐熱性、耐濕熱性及耐彎曲性方面優異。進而，表示：使用本發明的黏著片的顯示器在可視性及對比度方面優異。 另一方面，比較例1～比較例12中所獲得的黏著片中，一個以上的特性不良。From the results in Tables 8 and 9, it was confirmed that all the characteristics of transparency, heat resistance, humidity resistance, and bending resistance of the adhesive sheets obtained in Examples 1 to 26 were good. From these results, it is shown that the laminate and the display using the adhesive sheet of the present invention are excellent in transparency, heat resistance, humidity resistance, and bending resistance. Furthermore, it shows that the display using the adhesive sheet of the present invention is excellent in visibility and contrast. On the other hand, in the adhesive sheets obtained in Comparative Examples 1 to 12, one or more of the characteristics were poor.

1:黏著層 2:剝離膜 3:光透過性可撓性基材（蓋板） 4:黏著層 5:偏光板 6:偏光板用黏著層 7:障壁層 8:有機EL層 9:支撐體 10:有機EL單元1: Adhesive layer 2: release film 3: Light transmissive flexible substrate (cover) 4: Adhesive layer 5: polarizer 6: Adhesive layer for polarizer 7: Barrier layer 8: Organic EL layer 9: Support 10: Organic EL unit

圖1是本發明的一實施方式的黏著片的局部概略剖面圖。 圖2是本發明的一實施方式的黏著片的使用例即積層體的局部概略剖面圖。 圖3是本發明的一實施方式的黏著片的使用例即顯示器的局部概略剖面圖。FIG. 1 is a partial schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention. 2 is a partial schematic cross-sectional view of a laminate as an example of use of an adhesive sheet according to an embodiment of the present invention. 3 is a partial schematic cross-sectional view of a display, which is an example of use of an adhesive sheet according to an embodiment of the present invention.

1:黏著層 1: Adhesive layer

2:剝離膜 2: release film

Claims (8)

一種黏著片，其為包括光透過性可撓性基材、黏著層及偏光板的積層體中所含的所述黏著層的形成用的黏著片， 所述黏著層包括具有源自數量平均分子量1000～10000的聚合性化合物（a）的構成單元與羥基的共聚物（A）及硬化劑的硬化物，溫度25℃、相對濕度50%RH氣氛下的彎曲試驗中30萬次彎曲前後的HAZE變化率為20%以下。An adhesive sheet is an adhesive sheet for forming the adhesive layer contained in a laminate including a light-transmissive flexible substrate, an adhesive layer and a polarizing plate, The adhesive layer includes a cured product of a copolymer (A) having a structural unit derived from a polymer compound (a) having a number average molecular weight of 1,000 to 10,000 and a hydroxyl group, and a hardener, at a temperature of 25°C and a relative humidity of 50%RH The rate of HAZE change before and after 300,000 bends in the bending test was 20% or less. 如申請專利範圍第1項所述的黏著片，其中所述共聚物（A）為丙烯酸系共聚物（A1）或氨基甲酸酯脲系共聚物（A2）。The adhesive sheet according to item 1 of the patent application scope, wherein the copolymer (A) is an acrylic copolymer (A1) or a urethane urea copolymer (A2). 如申請專利範圍第2項所述的黏著片，其中所述共聚物（A）是單體混合物100質量%中，包含數量平均分子量1000～10000的聚合性化合物（a）1質量%～10質量%的單體混合物的共聚物即丙烯酸系共聚物（A1）。The adhesive sheet as described in item 2 of the patent application range, wherein the copolymer (A) is a polymer compound (a) having a number average molecular weight of 1,000 to 10,000 in 100% by mass of the monomer mixture and containing 1 to 10 mass % Copolymer of monomer mixture is acrylic copolymer (A1). 如申請專利範圍第2項或第3項所述的黏著片，其中所述共聚物（A）為丙烯酸系共聚物（A1），數量平均分子量1000～10000的聚合性化合物（a）包含大分子單體（a1-1）。The adhesive sheet according to item 2 or item 3 of the patent application scope, wherein the copolymer (A) is an acrylic copolymer (A1), and the polymerizable compound (a) having a number average molecular weight of 1,000 to 10,000 contains macromolecules Monomer (a1-1). 如申請專利範圍第2項所述的黏著片，其中所述共聚物（A）是單體混合物100質量%中，包含數量平均分子量1000～10000的聚合性化合物（a）60質量%～90質量%的單體混合物的共聚物即氨基甲酸酯脲系共聚物（A2）。The adhesive sheet as described in item 2 of the patent application range, wherein the copolymer (A) is a polymer compound (a) having a number average molecular weight of 1,000 to 10,000 in 100% by mass of the monomer mixture and containing 60 to 90% by mass % Of the monomer mixture copolymer is the urethane urea copolymer (A2). 如申請專利範圍第2項或第5項所述的黏著片，其中所述共聚物（A）為氨基甲酸酯脲系共聚物（A2），數量平均分子量1000～10000的聚合性化合物（a）包含三官能多元醇（a2-1）。The adhesive sheet according to item 2 or item 5 of the patent application scope, wherein the copolymer (A) is a urethane urea copolymer (A2), a polymerizable compound with a number average molecular weight of 1,000 to 10,000 (a ) Contains trifunctional polyol (a2-1). 一種積層體，包括光透過性可撓性基材、黏著層及偏光板， 所述黏著層是使用如申請專利範圍第1項或第2項所述的黏著片而形成。A laminate including a light-transmissive flexible substrate, an adhesive layer and a polarizing plate, The adhesive layer is formed using the adhesive sheet as described in the first or second patent application. 一種顯示器，包括如申請專利範圍第7項所述的積層體、及光學元件。A display including the laminate as described in item 7 of the patent application scope and an optical element.
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TWI642740B (en) * 2015-08-06 2018-12-01 綜研化學股份有限公司 Adhesive composition for polarizing plate, adhesive layer, adhesive sheet and polarizing plate with adhesive layer
JP6830753B2 (en) 2015-10-02 2021-02-17 日東電工株式会社 Methods for improving bending resistance of laminates, touch panels, laminate formation kits, and transparent conductive films
JP6632350B2 (en) * 2015-11-27 2020-01-22 三星エスディアイ株式会社ＳＡＭＳＵＮＧ ＳＤＩ Ｃｏ．， ＬＴＤ． Pressure-sensitive adhesive for optical film, pressure-sensitive adhesive layer, optical member, and image display device
JP6269646B2 (en) * 2015-12-08 2018-01-31 東洋インキＳｃホールディングス株式会社 Adhesive and adhesive sheet using the same
JP6314336B2 (en) * 2016-03-17 2018-04-25 藤森工業株式会社 Electrical insulating pressure-sensitive adhesive layer, electrical insulating pressure-sensitive adhesive film, and optical member on which it is bonded
JP2018028974A (en) 2016-08-15 2018-02-22 日東電工株式会社 Adhesive composition for organic el display device, adhesive layer for organic el display device, polarizing film with adhesive layer for organic el display device, and organic el display device
JP7052298B2 (en) * 2017-11-06 2022-04-12 東洋インキＳｃホールディングス株式会社 Optical Adhesives and Optical Adhesive Sheets

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