TW202130759A - Adhesive sheet, repeatedly bending laminated component and repeatedly bending device to provide an adhesive sheet having excellent durability against bending - Google Patents

Adhesive sheet, repeatedly bending laminated component and repeatedly bending device to provide an adhesive sheet having excellent durability against bending Download PDF

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TW202130759A
TW202130759A TW109143017A TW109143017A TW202130759A TW 202130759 A TW202130759 A TW 202130759A TW 109143017 A TW109143017 A TW 109143017A TW 109143017 A TW109143017 A TW 109143017A TW 202130759 A TW202130759 A TW 202130759A
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adhesive
adhesive layer
meth
less
adhesive sheet
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小鯖翔
髙橋洋一
七島祐
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日商琳得科股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides an adhesive sheet having excellent durability against bending, a repeatedly bending laminated component, and a repeatedly bending device. The solution of the invention is an adhesive sheet 1, which has an adhesive layer 11 for bonding the bending component 21 constituting the repeatedly bending device 3 with another bending component 22. For the adhesive layer 11 with thickness of 100 μm, the adhesive sheet 1 is sandwiched by two pieces of Tetoron mesh # 380. The water vapor transmission rate measured in accordance with JIS K7129 at 40 DEG C and 90% RH is 150 g/(m2-24h) or more, and the storage modulus G'(85) of the adhesive constituting the adhesive layer 11 at 85 DEG C is more than 0.02 MPa and less than 0.2 MPa.

Description

黏著片、反覆彎曲積層部件及反覆彎曲裝置Adhesive sheet, repetitive bending laminated component and repetitive bending device

本發明是關於一種反覆彎曲的裝置用的黏著片，以及反覆彎曲積層部件及反覆彎曲裝置。The invention relates to an adhesive sheet for a device that is repeatedly bent, as well as a repeatedly bent laminated component and a repeatedly bent device.

近年，作為裝置的一種，作為電子儀器的顯示體(顯示器)，提案一種可彎曲的彎曲性顯示器。作為彎曲性顯示器，在只有1次的曲面成形者外，提案一種反覆彎曲(折彎)用途的反覆彎曲顯示器。In recent years, as a kind of device, as a display body (display) of an electronic instrument, a bendable display has been proposed. As a flexible display, in addition to the one-time curved surface forming, a repetitive bending display for the use of repetitive bending (bending) is proposed.

在如上述的反覆彎曲顯示器中，考慮將構成該彎曲性顯示器的可彎曲的部件(彎曲性部件)與其他彎曲性部件，藉由黏著片的黏著劑層貼合。然而，在反覆彎曲顯示器中使用以往的黏著片時，由於反覆的彎曲，在彎曲部位中的黏著劑層與被附著物的界面發生剝離等，產生有關耐久性的問題。In the repetitively curved display as described above, it is considered that a bendable member (flexible member) constituting the curved display and another flexible member are bonded by an adhesive layer of an adhesive sheet. However, when a conventional adhesive sheet is used in a repetitively curved display, due to repeated bending, peeling occurs at the interface between the adhesive layer and the adherend in the curved portion, which causes problems related to durability.

作為上述以往的黏著片，可列舉，例如，專利文獻1中所揭示的黏著片。此黏著片為具有：含有來自具芳香族環構造的單體的構造單元的(甲基)丙烯酸系聚合物，以及含有聚輪烷的黏著劑組成物所構成的黏著劑層者，在光學用途中，以應力緩和性及耐久性佳為目的。 [先前技術文獻] [專利文獻]As the aforementioned conventional adhesive sheet, for example, the adhesive sheet disclosed in Patent Document 1 can be cited. This adhesive sheet has: a (meth)acrylic polymer containing structural units derived from a monomer having an aromatic ring structure, and an adhesive layer composed of an adhesive composition containing polyrotaxane, which is used in optical applications Among them, it aims at good stress relaxation and durability. [Prior Technical Literature] [Patent Literature]

專利文獻1：日本特開2016-155911號公報Patent Document 1: Japanese Patent Application Publication No. 2016-155911

[發明欲解決的問題][The problem to be solved by the invention]

然而，專利文獻1中所揭示的實施例，在丙烯酸系聚合物中作為交聯點的含羥基的單體的調配量比較少，交聯劑的使用量也較少。因此，推測交聯劑消耗在聚輪烷彼此的交聯，聚輪烷與丙烯酸系聚合物的交聯構造形成不充分。因此，當該黏著劑使用在反覆彎曲顯示器時，成為應力緩和性不足者。However, in the example disclosed in Patent Document 1, the compounding amount of the hydroxyl group-containing monomer as the crosslinking point in the acrylic polymer is relatively small, and the amount of the crosslinking agent used is also relatively small. Therefore, it is presumed that the crosslinking agent is consumed in the crosslinking of polyrotaxanes, and the formation of the crosslinked structure of the polyrotaxane and the acrylic polymer is insufficient. Therefore, when the adhesive is used in a repeatedly curved display, it becomes a person with insufficient stress relaxation.

本發明為鑒於上述情事而完成者，其目的為提供一種對於彎曲的耐久性佳的黏著片，反覆彎曲積層部件以及反覆彎曲裝置。 [解決問題的手段]The present invention was made in view of the above-mentioned circumstances, and its object is to provide an adhesive sheet, a repetitive bending laminated member, and a repetitive bending device that has good durability against bending. [Means to Solve the Problem]

為了達成上述目的，第一，本發明提供一種黏著片，為具有為用以將構成反覆彎曲的裝置的一彎曲性部件與其他彎曲性部件貼合的黏著劑層的黏著片，針對上述黏著劑層為厚度100μm者，以2片特多龍(Tetoron)網目#380夾持，在40℃，90%RH的條件，依JIS K7129為基準所測定的水蒸氣穿透度為150g/(m2 ．24h)以上，構成上述黏著劑層的黏著劑在85℃的儲存模數G’(85)為0.02MPa以上，0.2MPa以下(發明1)。In order to achieve the above-mentioned object, firstly, the present invention provides an adhesive sheet having an adhesive layer for bonding a flexible member and other flexible members that constitute a repetitive bending device, and is directed to the above-mentioned adhesive The layer is 100μm thick, sandwiched by two Tetoron mesh #380, at 40℃, 90%RH conditions, the water vapor permeability measured according to JIS K7129 is 150g/(m 2 .24h) or more, the storage modulus G'(85) of the adhesive constituting the above-mentioned adhesive layer at 85°C is 0.02 MPa or more and 0.2 MPa or less (Invention 1).

在上述發明(發明1)中，由於黏著劑層具有上述物性，藉由該黏著劑層將一彎曲性部件與其他彎曲性部件貼合而成的積層體，在高溫下使其反覆彎曲、或長時間處於彎曲狀態時，在彎曲部位的黏著劑層與被附著物的界面不易發生剝離，耐久性佳。此外，由於黏著劑層具有上述水蒸氣穿透度，耐濕熱白化性亦良好。In the above invention (Invention 1), since the adhesive layer has the above physical properties, a laminate formed by bonding a flexible member and another flexible member through the adhesive layer is repeatedly bent at a high temperature, or When it is in a bent state for a long time, the interface between the adhesive layer and the adherend at the bent part is not easy to peel off, and the durability is good. In addition, since the adhesive layer has the above-mentioned water vapor permeability, the heat and humidity resistance to whitening is also good.

在上述發明(發明1)中，構成上述黏著劑層的黏著劑的凝膠分率，以10%以上，90%以下為佳(發明2)。In the above invention (Invention 1), the gel fraction of the adhesive constituting the above adhesive layer is preferably 10% or more and 90% or less (Invention 2).

在上述發明(發明1、2)中，上述黏著劑層在23℃的霧度值為10%以下為佳(發明3)。In the above inventions (Inventions 1 and 2), the haze value of the adhesive layer at 23°C is preferably 10% or less (Invention 3).

在上述發明(發明1〜3)中，構成上述黏著劑層的黏著劑在23℃的儲存模數G’(23)，以0.02MPa以上，0.3MPa以下為佳(發明4)。In the above inventions (Inventions 1 to 3), the storage modulus G'(23) at 23°C of the adhesive constituting the adhesive layer is preferably 0.02 MPa or more and 0.3 MPa or less (Invention 4).

在上述發明(發明1〜4)中，構成上述黏著劑層的黏著劑，以含有聚輪烷化合物為佳(發明5)。In the above inventions (Inventions 1 to 4), the adhesive constituting the above adhesive layer preferably contains a polyrotaxane compound (Invention 5).

在上述發明(發明1〜5)中，構成上述黏著劑層的黏著劑，以丙烯酸系黏著劑為佳(發明6)。In the above inventions (Inventions 1 to 5), the adhesive constituting the above adhesive layer is preferably an acrylic adhesive (Invention 6).

在上述發明(發明1〜6)中，上述黏著片具備2片剝離片，以上述黏著劑層以與上述2片剝離片的剝離面接觸的方式，夾持於上述剝離片為佳(發明7)。In the above inventions (Inventions 1 to 6), the adhesive sheet includes two release sheets, and the adhesive layer is preferably sandwiched between the release sheets so that the adhesive layer is in contact with the release surfaces of the two release sheets (Invention 7 ).

第二，本發明提供一種反覆彎曲積層部件，為具備：構成反覆彎曲的裝置的彎曲性部件以及其他彎曲性部件，以及將上述一彎曲性部件與上述其他彎曲性部件彼此貼合的黏著劑層的反覆彎曲積層部件，上述黏著劑層為由上述黏著片(發明1〜7)的黏著劑層所構成(發明8)。Secondly, the present invention provides a repetitive bending laminated component, comprising: a flexible member constituting a repetitive bending device and other flexible members, and an adhesive layer for bonding the above-mentioned one flexible member and the above-mentioned other flexible member to each other In the repetitively curved laminated component, the adhesive layer is composed of the adhesive layer of the adhesive sheet (Inventions 1 to 7) (Invention 8).

第三，本發明提供一種反覆彎曲裝置，具備：上述反覆彎曲積層部件(發明8)(發明9)。 [發明的效果]Thirdly, the present invention provides a repetitive bending device including the above repetitive bending laminated member (Invention 8) (Invention 9). [Effects of the invention]

本發明相關的黏著片，反覆彎曲積層部件以及反覆彎曲裝置，為對於彎曲的耐久性良好。The adhesive sheet, the repetitive bending laminated member and the repetitive bending device related to the present invention have good durability against bending.

以下，說明有關於本發明的實施形態。 [黏著片] 本發明一實施形態相關的黏著片為具有用以將構成反覆彎曲裝置的一彎曲性部件與其他彎曲性部件貼合的黏著劑層，較佳為由在該黏著劑層的單面或雙面積層剝離片而形成。關於反覆彎曲裝置以及彎曲性部件，如下述。Hereinafter, embodiments related to the present invention will be described. [Adhesive Sheet] The adhesive sheet according to an embodiment of the present invention has an adhesive layer for bonding a flexible member constituting the repetitive bending device to other flexible members, and is preferably composed of one or both sides of the adhesive layer It is formed by laminating release sheets. The repetitive bending device and the flexible member are as follows.

在本實施形態相關的黏著片中，將上述黏著劑層調製成厚度100μm，以2片特多龍網目#380夾持，在40℃、90%RH的條件，依JIS K7129為基準所測定的水蒸氣穿透度為150g/(m2 ．24h)以上，構成上述黏著劑層的黏著劑在85℃的儲存模數G’(85)為0.02MPa以上，0.2MPa以下。且，在本說明書中的水蒸氣穿透度以及儲存模數的測定方法的詳情如下述試驗例中所示。In the adhesive sheet related to this embodiment, the above-mentioned adhesive layer is prepared to have a thickness of 100 μm, sandwiched between 2 sheets of Tetoron mesh #380, and measured under the conditions of 40°C and 90% RH in accordance with JIS K7129 The water vapor permeability is 150g/(m 2 .24h) or more, and the storage modulus G'(85) of the adhesive constituting the adhesive layer at 85°C is 0.02 MPa or more and 0.2 MPa or less. In addition, the details of the water vapor permeability and storage modulus measurement methods in this specification are shown in the following test examples.

本實施形態中的黏著劑層，由於具有上述物性，而成為對於彎曲的耐久性(以下，有時簡稱「耐久性」)良好者。具體而言，藉由該黏著劑層將一彎曲性部件與其他彎曲性部件貼合而形成的積層體，在高溫下使其反覆彎曲(以下，有時稱為「動態的耐久性」或「動態耐久性」)、或長時間處於彎曲狀態時(以下，有時稱為「靜態的耐久性」或「靜態耐久性」)，在彎曲部位的黏著劑層與被附著物的界面不易發生剝離。此外，本實施形態相關的黏著片，由於黏著劑層具有上述水蒸氣穿透度，即使反覆彎曲裝置置於高溫高濕條件下，滲入到黏著劑層中的水分，當回到常溫常濕時，易於從該黏著劑層脫落，不易產生水分的凝結，該黏著劑層的白化受到抑制。換言之，本實施形態相關的黏著片在耐久性以及耐混熱白化性兩者皆優。Since the adhesive layer in the present embodiment has the above-mentioned physical properties, it has good durability against bending (hereinafter, abbreviated as "durability" in some cases). Specifically, a laminate formed by bonding a flexible member and another flexible member through the adhesive layer is repeatedly bent at a high temperature (hereinafter, sometimes referred to as "dynamic durability" or " Dynamic durability”), or in a long-term bending state (hereinafter, sometimes referred to as “static durability” or “static durability”), the interface between the adhesive layer and the adherend at the bent part is not likely to peel off . In addition, in the adhesive sheet related to this embodiment, since the adhesive layer has the above-mentioned water vapor permeability, even if the repeated bending device is placed under high temperature and high humidity conditions, the water that penetrates into the adhesive layer will return to normal temperature and humidity. , It is easy to fall off from the adhesive layer, it is not easy to produce moisture condensation, and the whitening of the adhesive layer is suppressed. In other words, the pressure-sensitive adhesive sheet according to the present embodiment is excellent in both durability and resistance to whitening by mixing heat.

從上述耐久性以及耐混熱白化性的觀點而言，上述水蒸氣穿透度必須為150g/(m2 ．24h)以上，以160g/(m2 ．24h)以上為佳，特別是以170g/(m2 ．24h)以上為佳，進一步以190g/(m2 ．24h)以上為佳。另一方面，從上述耐久性的觀點而言，上述水蒸氣穿透度以500g/(m2 ．24h)以下為佳，以300g/(m2 ．24h)以下為更佳，當又加上隨著氫鍵增加使黏著劑層表面的硬度上升造成對耐久性的影響時，特別是以250g/(m2 ．24h)以下為佳，進一步以200g/(m2 ．24h)以下為佳。From the viewpoint of the durability and resistance to whitening by mixing heat, the water vapor permeability must be 150g/(m 2 .24h) or more, preferably 160g/(m 2 .24h) or more, especially 170g /(m 2 .24h) or more is preferable, and more preferably 190g/(m 2 .24h) or more. On the other hand, from the standpoint of the above durability, the above water vapor permeability is preferably 500g/(m 2 .24h) or less, more preferably 300g/(m 2 .24h) or less. When the hardness of the surface of the adhesive layer increases as the hydrogen bond increases, which affects durability, it is particularly preferably 250 g/(m 2 .24h) or less, and further preferably 200 g/(m 2 .24h) or less.

此外，從上述耐久性的觀點而言，構成上述黏著劑層的黏著劑的儲存模數G’(85)必須為0.02MPa以上，以0.03MPa以上為佳，特別是以0.04MPa以上為佳，進一步以0.05MPa以上為佳。此外，同樣從耐久性的觀點而言，上述儲存模數G’(85)必須為0.2MPa以下，以0.1MPa以下為佳，特別是以0.08MPa以下為佳，進一步以0.06MPa以下為佳。In addition, from the standpoint of the aforementioned durability, the storage modulus G'(85) of the adhesive constituting the aforementioned adhesive layer must be 0.02 MPa or more, preferably 0.03 MPa or more, and particularly preferably 0.04 MPa or more. More preferably, it is 0.05 MPa or more. In addition, from the standpoint of durability, the storage modulus G'(85) must be 0.2 MPa or less, preferably 0.1 MPa or less, especially 0.08 MPa or less, and further preferably 0.06 MPa or less.

此外，構成上述黏著劑層的黏著劑在23℃的儲存模數G’(23)，以0.02MPa以上為佳，以0.03MPa以上為更佳，特別是以0.04MPa以上為佳，進一步以0.07MPa以上為佳。如此一來，易於滿足儲存模數G’(85)的上述下限值。此外，該儲存模數G’(23)，以0.3MPa以下為佳，以0.15MPa以下為更佳，特別是以0.10MPa以下為佳，進一步以0.08MPa以下為佳。如此一來，易於滿足儲存模數G’(85)的上述上限值。In addition, the storage modulus G'(23) of the adhesive constituting the above-mentioned adhesive layer at 23°C is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, especially 0.04 MPa or more, and further 0.07 MPa or more is preferred. In this way, it is easy to meet the aforementioned lower limit of the storage modulus G'(85). In addition, the storage modulus G'(23) is preferably 0.3 MPa or less, more preferably 0.15 MPa or less, particularly preferably 0.10 MPa or less, and further preferably 0.08 MPa or less. In this way, it is easy to meet the above upper limit of the storage modulus G'(85).

構成上述黏著劑層的黏著劑的凝膠分率，以10%以上為佳，以20%以上為更佳，特別是以30%以上為佳，進一步以40%以上為佳。如此一來，黏著劑發揮能夠承受反覆彎曲的適當凝集力。其結果為成為耐久性更佳者。另一方面，本實施形態中的黏著劑的凝膠分率，以90%以下為佳，以75%以下為更佳，特別是以65%以下為佳，進一步以55%以下為佳，以47%以下為最佳。如此一來，推測因彎曲引起的黏著劑中的殘留應力被降低，而成為耐久性更佳者。且，本說明書中的凝膠分率的測定方法，如下述試驗例中所示。The gel fraction of the adhesive constituting the adhesive layer is preferably 10% or more, more preferably 20% or more, particularly preferably 30% or more, and further preferably 40% or more. In this way, the adhesive exerts an appropriate cohesive force capable of withstanding repeated bending. As a result, it becomes a more durable one. On the other hand, the gel fraction of the adhesive in this embodiment is preferably 90% or less, more preferably 75% or less, particularly preferably 65% or less, and further preferably 55% or less. 47% or less is the best. In this way, it is estimated that the residual stress in the adhesive caused by bending is reduced, and the durability is better. In addition, the method for measuring the gel fraction in this specification is as shown in the following test example.

上述黏著劑層在23℃的霧度值，以10%以下為佳，以5%以下為更佳，特別是以1%以下為佳，進一步以0.7%以下為佳。由於黏著劑層在23℃的霧度值為上述，光穿透性佳，而成為適合作為反覆彎曲顯示器用者。上述在23℃的霧度值的下限值，並無特別限定，以0%以上為佳，以0.1%以上為更佳。The haze value of the adhesive layer at 23°C is preferably 10% or less, more preferably 5% or less, particularly preferably 1% or less, and further preferably 0.7% or less. Since the haze value of the adhesive layer at 23°C is as mentioned above, the light penetration is good, and it is suitable for use as a recursive curved display. The lower limit of the above-mentioned haze value at 23°C is not particularly limited, but is preferably 0% or more, and more preferably 0.1% or more.

此外，上述黏著劑層在-40℃的霧度值，以10%以下為佳，以5%以下為更佳，特別是以1%以下為佳，進一步以0.7%以下為佳。藉由黏著劑層在-40℃的霧度值為上述，所得的可撓式顯示器在寒冷下的耐久性可成為良好者。上述在-40℃的霧度值的下限值，並無特別限定，以0%以上為佳，以0.1%以上為更佳。在此，在-40℃的霧度值為將黏著劑層置於-40℃的環境下240小時後，在23℃，50%RH的環境下靜置1小時之後，所測定的值。In addition, the haze value of the adhesive layer at -40°C is preferably 10% or less, more preferably 5% or less, particularly preferably 1% or less, and further preferably 0.7% or less. With the haze value of the adhesive layer at -40°C as described above, the resulting flexible display has good durability in the cold. The lower limit of the above-mentioned haze value at -40°C is not particularly limited, but is preferably 0% or more, and more preferably 0.1% or more. Here, the haze value at -40°C is the value measured after the adhesive layer is placed in an environment of -40°C for 240 hours, and then left to stand for 1 hour in an environment of 23°C and 50% RH.

且，上述霧度值為亦包括黏著劑層的厚度的特性值，不論黏著劑層的厚度，以滿足上述霧度值為佳。在此，本說明書中的霧度值為依JIS K7136：2000為基準所測定的值。Moreover, the above-mentioned haze value also includes the characteristic value of the thickness of the adhesive layer, and it is better to satisfy the above-mentioned haze value regardless of the thickness of the adhesive layer. Here, the haze value in this specification is a value measured based on JIS K7136:2000.

上述黏著劑層在23℃的全光線穿透率，從畫面、影像的辨識性的觀點而言，以70%以上為佳，以80%以上為更佳，特別是以90%以上為佳，進一步以95%以上為佳。上述在23℃的全光線穿透率的上限值，通常為100%。且，本說明書中的全光線穿透率為以JIS K7361-1：1997為基準所測定的值。The total light transmittance of the adhesive layer at 23°C is preferably 70% or more, more preferably 80% or more, especially 90% or more, from the standpoint of screen and image recognizability. More preferably, it is more than 95%. The upper limit of the above-mentioned total light transmittance at 23°C is usually 100%. In addition, the total light transmittance in this specification is a value measured based on JIS K7361-1:1997.

此外，上述黏著劑層在-40℃的全光線穿透率，以70%以上為佳，以80%以上為更佳，特別是以90%以上為佳，進一步以95%以上為佳。藉由黏著劑層在-40℃的全光線穿透率為如上述，所得的可撓式顯示器可成為在寒冷下的耐久性良好者。另一方面，上述在-40℃的全光線穿透率的上限值，通常為100%。在此，在-40℃的全光線穿透率為將黏著劑層置於-40℃的環境下240小時後，在23℃，50%RH的環境下靜置1小時之後，所測定的值。In addition, the total light transmittance of the adhesive layer at -40°C is preferably 70% or more, more preferably 80% or more, especially 90% or more, and more preferably 95% or more. With the total light transmittance of the adhesive layer at -40°C as described above, the resulting flexible display can have good durability in the cold. On the other hand, the upper limit of the above-mentioned total light transmittance at -40°C is usually 100%. Here, the total light transmittance at -40°C is the value measured after placing the adhesive layer in an environment of -40°C for 240 hours and then standing for 1 hour in an environment of 23°C and 50%RH .

作為本實施形態相關的黏著片一例的具體構成如圖1所示。 如圖1所示，一實施形態相關的黏著片1為由2片剝離片12a、12b，以及以與此2片剝離片12a、12b的剝離面接觸的方式，夾持於該2片剝離片12a、12b間的黏著劑層11所構成。且，在本說明書中的剝離片的剝離面，是指剝離片中具有剝離性的面，為包括實施剝離處理的面以及即使未實施剝離處理仍顯示剝離性的面的任一者。The specific structure of an example of an adhesive sheet according to this embodiment is shown in FIG. 1. As shown in FIG. 1, the adhesive sheet 1 according to one embodiment is composed of two release sheets 12a, 12b, and is sandwiched between the two release sheets 12a, 12b so as to be in contact with the release surfaces of the two release sheets 12a, 12b. The adhesive layer 11 between 12a and 12b is formed. In addition, the peeling surface of the peeling sheet in this specification means the surface which has peelability in a peeling sheet, and it includes any one of the surface which performed a peeling process and the surface which showed peelability even if a peeling process was not performed.

1.構成元件 1-1.黏著劑層 黏著劑層11為由具有上述物性的黏著劑所形成者。構成黏著劑層11的黏著劑的種類，只要滿足上述物性(特別是水蒸氣穿透度以及儲存模數G’(85))即可，並無特別限定，可以是例如，丙烯酸系黏著劑(主聚合物：丙烯酸系聚合物)、聚酯系黏著劑(主聚合物：聚酯系聚合物)、聚氨酯系黏著劑(主聚合物：聚氨酯系聚合物)、橡膠系黏著劑(主聚合物：橡膠系聚合物)、矽酮系黏著劑(主聚合物：矽酮系聚合物)等的任一者。此外，該黏著劑可以是乳劑型、溶劑型或無溶劑型的任一者，可以是交聯類型或非交聯類型的任一者。此等當中，以易於滿足上述物性，黏著物性、光學特性等皆良好的丙烯酸系黏著劑為佳，特別是以溶劑型的丙烯酸系黏著劑為佳。1. Components 1-1. Adhesive layer The adhesive layer 11 is formed of an adhesive having the above-mentioned physical properties. The type of adhesive constituting the adhesive layer 11 is not particularly limited as long as it satisfies the above physical properties (especially the water vapor permeability and the storage modulus G'(85)), and it may be, for example, an acrylic adhesive ( Main polymer: acrylic polymer), polyester adhesive (main polymer: polyester polymer), polyurethane adhesive (main polymer: polyurethane polymer), rubber adhesive (main polymer) : Rubber-based polymer), silicone-based adhesive (main polymer: silicone-based polymer), etc. In addition, the adhesive may be any of an emulsion type, a solvent type, or a solvent-free type, and may be either a cross-linked type or a non-cross-linked type. Among these, acrylic adhesives that easily satisfy the above-mentioned physical properties, adhesive properties, and optical properties are preferred, and solvent-based acrylic adhesives are particularly preferred.

本實施形態中的黏著劑，以含有聚輪烷化合物的黏著劑為佳，特別是以含有聚輪烷化合物的丙烯酸系黏著劑為佳。具體而言，以將含有(甲基)丙烯酸酯聚合物(A)(相當於在主聚合物)、聚輪烷化合物(B)，以及較佳為進一步含有交聯劑(C)的黏著性組合物(以下，有時稱為「黏著性組合物P」)進行交聯而成的黏著劑為佳。只要是相關黏著劑，可以滿足上述物性，此外，易於獲得良好的黏著力。且，在本說明書中，(甲基)丙烯酸是指丙烯酸及甲基丙烯酸兩者的意思。其他類似用語亦相同。此外，「聚合物」為亦包含「共聚物」的概念者。The adhesive in this embodiment is preferably an adhesive containing a polyrotaxane compound, and particularly preferably an acrylic adhesive containing a polyrotaxane compound. Specifically, the adhesiveness that contains the (meth)acrylate polymer (A) (corresponding to the main polymer), the polyrotaxane compound (B), and preferably further contains the crosslinking agent (C) The composition (hereinafter, sometimes referred to as "adhesive composition P") is preferably an adhesive obtained by crosslinking. As long as it is a related adhesive, it can satisfy the above-mentioned physical properties, and in addition, it is easy to obtain good adhesion. In addition, in this specification, (meth)acrylic acid means both acrylic acid and methacrylic acid. Other similar terms are also the same. In addition, "polymer" also includes the concept of "copolymer".

(1) 黏著性組合物P的成分 (1-1) (甲基)丙烯酸酯聚合物(A) (甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有用以表現良好黏著性的(甲基)丙烯酸烷基酯，以及具有成為交聯點的反應性官能基的單體(含反應性官能基的單體)者為佳。(1) Components of adhesive composition P (1-1) (Meth)acrylate polymer (A) The (meth)acrylate polymer (A), as a monomer unit constituting the polymer, contains an alkyl (meth)acrylate for expressing good adhesiveness, and has a reactive function that becomes a crosslinking point Monomers (monomers containing reactive functional groups) are preferred.

此外，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有含芳香環的單體者為佳。如此一來，(甲基)丙烯酸酯聚合物(A)與聚輪烷化合物(B)的相溶性變得良好，即使在低溫環境下仍可維持其相溶性。因此，特別是變得易於滿足在-40℃的霧度值以及在-40℃的全光線穿透率。In addition, the (meth)acrylate polymer (A) preferably contains an aromatic ring-containing monomer as a monomer unit constituting the polymer. In this way, the compatibility of the (meth)acrylate polymer (A) and the polyrotaxane compound (B) becomes good, and the compatibility can be maintained even in a low-temperature environment. Therefore, in particular, it becomes easy to satisfy the haze value at -40°C and the total light transmittance at -40°C.

再者，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有含氮原子的單體者為佳。如此一來，將來自含反應性官能基的單體的反應性官能基進行活性化，即使反應性官能基比較少，仍可有效地促進與聚輪烷化合物(B)的交聯。因此，所得的黏著劑的凝集力及柔軟性提升，變得更容易滿足上述儲存模數G’(85)(及儲存模數G’(23))。Furthermore, the (meth)acrylate polymer (A) is preferably one containing a nitrogen atom-containing monomer as the monomer unit constituting the polymer. In this way, the reactive functional group derived from the monomer containing the reactive functional group is activated, and even if the reactive functional group is relatively small, the crosslinking with the polyrotaxane compound (B) can be effectively promoted. Therefore, the cohesive force and flexibility of the obtained adhesive are improved, and it becomes easier to satisfy the aforementioned storage modulus G'(85) (and storage modulus G'(23)).

因此，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有(甲基)丙烯酸烷基酯，含芳香環的單體，以及含反應性官能基的單體者為更佳，以含有(甲基)丙烯酸烷基酯，含芳香環的單體，含氮原子的單體，以及含反應性官能基的單體者為特別佳。Therefore, the (meth)acrylate polymer (A), as the monomer unit constituting the polymer, contains an alkyl (meth)acrylate, an aromatic ring-containing monomer, and a reactive functional group-containing monomer unit. The individual is more preferable, and the monomer containing an alkyl (meth)acrylate, an aromatic ring-containing monomer, a nitrogen atom-containing monomer, and a reactive functional group-containing monomer is particularly preferable.

作為(甲基)丙烯酸烷基酯，以含有烷基的碳數為1〜20的(甲基)丙烯酸烷基酯者為佳。烷基以直鏈狀或分支鏈狀為佳。As the alkyl (meth)acrylate, those containing an alkyl group having 1 to 20 carbon atoms are preferred. The alkyl group is preferably linear or branched.

作為烷基的碳數為1〜20的(甲基)丙烯酸烷基酯，以含有：作為均聚物(homopolymer)的玻璃轉換溫度(Tg)為-40℃以下者(以下，有時稱為「低Tg丙烯酸烷基酯」)，及作為均聚物的玻璃轉換溫度(Tg)超過0℃的單體(以下，有時稱為「高Tg丙烯酸烷基酯」)為佳。藉由含有相關的低Tg丙烯酸烷基酯及高Tg丙烯酸烷基酯，作為構成單體單元，推測可防止(甲基)丙烯酸酯聚合物(A)的構形(conformation)變得過小。其結果為增加與聚輪烷化合物(B)的接觸點，推測即使(甲基)丙烯酸酯聚合物(A)僅有少數交聯點，仍可與聚輪烷化合物(B)形成充分的交聯構造。因此，所得的黏著劑層發揮良好的黏著力，並成為易於滿足同時上述儲存模數G’(85)者。Alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group include those whose glass transition temperature (Tg) as a homopolymer is below -40°C (hereinafter, sometimes referred to as "Low Tg alkyl acrylate"), and a homopolymer whose glass transition temperature (Tg) exceeds 0°C (hereinafter, sometimes referred to as "high Tg alkyl acrylate") is preferable. By containing the related low-Tg alkyl acrylate and high-Tg alkyl acrylate as constituent monomer units, it is speculated that the conformation of the (meth)acrylate polymer (A) can be prevented from becoming too small. The result is to increase the contact point with the polyrotaxane compound (B). It is speculated that even if the (meth)acrylate polymer (A) has only a few crosslinking points, it can still form sufficient crosslinks with the polyrotaxane compound (B).联结构。 Union structure. Therefore, the resultant adhesive layer exhibits good adhesive force and can easily satisfy the above-mentioned storage modulus G'(85) at the same time.

作為低Tg丙烯酸烷基酯，較佳可列舉，例如，丙烯酸正丁酯(Tg-55℃)、丙烯酸正辛酯(Tg-65℃)、丙烯酸異辛酯(Tg-58℃)、丙烯酸2-乙基己酯(Tg-70℃)、丙烯酸異壬酯(Tg-58℃)、丙烯酸異癸酯(Tg-60℃)、甲基丙烯酸異癸酯(Tg-41℃)、甲基丙烯酸正十二酯(Tg-65℃)、丙烯酸正十三酯(Tg-55℃)、甲基丙烯酸正十三酯(Tg-40℃)等。當中，從黏著力的觀點而言，作為低Tg丙烯酸烷基酯，以均聚物的Tg為-45℃以下者為更佳，以-50℃以下者為特別佳。具體而言，以丙烯酸正丁酯以及丙烯酸2-乙基己酯為特別佳。此等可單獨使用，亦可組合2種以上使用。Examples of low Tg alkyl acrylates preferably include n-butyl acrylate (Tg-55°C), n-octyl acrylate (Tg-65°C), isooctyl acrylate (Tg-58°C), acrylic acid 2 -Ethylhexyl ester (Tg-70°C), isononyl acrylate (Tg-58°C), isodecyl acrylate (Tg-60°C), isodecyl methacrylate (Tg-41°C), methacrylic acid N-dodecyl ester (Tg-65°C), n-tridecyl acrylate (Tg-55°C), n-tridecyl methacrylate (Tg-40°C), etc. Among them, from the viewpoint of adhesion, as the low Tg alkyl acrylate, the homopolymer having a Tg of -45°C or lower is more preferable, and the one having -50°C or lower is particularly preferable. Specifically, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. These can be used alone or in combination of two or more kinds.

作為上述高Tg丙烯酸烷基酯，可列舉，例如，丙烯酸甲酯(Tg10℃)、甲基丙烯酸甲酯(Tg105℃)、甲基丙烯酸乙酯(Tg65℃)、甲基丙烯酸正丁酯(Tg20℃)、甲基丙烯酸異丁酯(Tg48℃)、甲基丙烯酸三級丁酯(Tg107℃)、丙烯酸正十八酯(Tg30℃)、甲基丙烯酸正十八酯(Tg38℃)等。上述當中，從易於滿足儲存模數G’(85)的觀點而言，以丙烯酸甲酯以及甲基丙烯酸甲酯為佳。此等可單獨使用，亦可組合2種以上使用。且，上述高Tg丙烯酸烷基酯中，不包含下述含芳香環的單體以及含氮原子的單體。Examples of the high Tg alkyl acrylate include methyl acrylate (Tg10°C), methyl methacrylate (Tg105°C), ethyl methacrylate (Tg65°C), and n-butyl methacrylate (Tg20°C). ℃), isobutyl methacrylate (Tg48℃), tertiary butyl methacrylate (Tg107℃), n-octadecyl acrylate (Tg30℃), n-octadecyl methacrylate (Tg38℃), etc. Among the above, from the viewpoint of easily satisfying the storage modulus G'(85), methyl acrylate and methyl methacrylate are preferred. These can be used alone or in combination of two or more kinds. In addition, the above-mentioned high Tg alkyl acrylate does not include the following aromatic ring-containing monomers and nitrogen atom-containing monomers.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有低Tg丙烯酸烷基酯40質量%以上為佳，特別是以含有50質量%以上為佳，進一步以含有60質量%以上為佳。此外，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有低Tg丙烯酸烷基酯90質量%以下為佳，特別是以含有80質量%以下為佳，進一步以含有75質量%以下為佳。The (meth)acrylate polymer (A), as the monomer unit constituting the polymer, preferably contains 40% by mass or more of low Tg alkyl acrylate, particularly preferably 50% by mass or more, and further It is better to contain 60% by mass or more. In addition, the (meth)acrylate polymer (A), as the monomer unit constituting the polymer, preferably contains a low Tg alkyl acrylate of 90% by mass or less, and particularly preferably contains 80% by mass or less. Furthermore, it is preferable to contain 75 mass% or less.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有高Tg丙烯酸烷基酯1質量%以上為佳，特別是以含有4質量%以上為佳，進一步以含有8質量%以上為佳。此外，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有高Tg丙烯酸烷基酯24質量%以下為佳，特別是以含有18質量%以下為佳，進一步以含有13質量%以下為佳。The (meth)acrylate polymer (A), as the monomer unit constituting the polymer, preferably contains 1% by mass or more of high Tg alkyl acrylate, particularly preferably 4% by mass or more, and further It is better to contain 8% by mass or more. In addition, the (meth)acrylate polymer (A), as a monomer unit constituting the polymer, preferably contains a high Tg alkyl acrylate of 24% by mass or less, and particularly preferably contains 18% by mass or less. It is more preferable to contain 13% by mass or less.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有烷基的碳數為1〜20的(甲基)丙烯酸烷基酯45質量%以上為佳，以含有60質量%以上為更佳，特別是以含有70質量%以上為佳，進一步以含有75質量%以上為佳。此外，以含有該(甲基)丙烯酸烷基酯94質量%以下為佳，以含有90質量%以下為更佳，特別是以含有88質量%以下為佳，進一步以含有83質量%以下為佳。當以上述的量含有烷基的碳數為1〜20的(甲基)丙烯酸烷基酯時，可賦予(甲基)丙烯酸酯聚合物(A)適當的黏著性，同時變得易於滿足上述儲存模數G’。The (meth)acrylate polymer (A), as the monomer unit constituting the polymer, preferably contains at least 45% by mass of alkyl (meth)acrylate having an alkyl group with a carbon number of 1-20, and The content is more preferably 60% by mass or more, particularly preferably 70% by mass or more, and more preferably 75% by mass or more. In addition, the alkyl (meth)acrylate is preferably 94% by mass or less, more preferably 90% by mass or less, especially 88% by mass or less, and more preferably 83% by mass or less . When an alkyl (meth)acrylate having an alkyl group with a carbon number of 1 to 20 is contained in the above-mentioned amount, the (meth)acrylate polymer (A) can be imparted with appropriate adhesiveness, and at the same time it becomes easy to satisfy the above-mentioned Store the modulus G'.

作為含芳香環的單體，可列舉，例如，(甲基)丙烯酸苯酯、(甲基)丙烯酸2-苯基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸2-苯氧乙酯、(甲基)丙烯酸苯氧丁酯、乙氧化鄰苯基苯酚丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、聯苯基二(甲基)丙烯酸酯、五氟芐基(甲基)丙烯酸酯等。此等可單獨使用，亦可組合2種以上使用。As the aromatic ring-containing monomer, for example, phenyl (meth)acrylate, 2-phenylethyl (meth)acrylate, benzyl (meth)acrylate, naphthyl (meth)acrylate, ( 2-phenoxyethyl acrylate, phenoxybutyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy polyethylene Alcohol (meth)acrylate, biphenyl di(meth)acrylate, pentafluorobenzyl (meth)acrylate, etc. These can be used alone or in combination of two or more kinds.

(甲基)丙烯酸酯共聚物(A)，作為構成該聚合物的單體單元，以含有含芳香環的單體1質量%以上為佳，以含有4質量%以上為更佳，特別是以含有8質量%以上為佳，進一步以含有12質量以上%為佳。此外，以含有含芳香環的單體40質量%以下為佳，以含有30質量%以下為更佳，特別是以含有23質量%以下為佳，進一步以含有18質量%以下為佳。藉由含芳香環的單體的含量於上述的範圍中，變得易於滿足上述在-40℃的霧度值以及儲存模數G’。此外，黏著性也可良好地維持。The (meth)acrylate copolymer (A), as the monomer unit constituting the polymer, preferably contains 1% by mass or more of aromatic ring-containing monomers, more preferably 4% by mass or more, especially The content is preferably 8% by mass or more, and more preferably 12% by mass or more. In addition, the aromatic ring-containing monomer is preferably 40% by mass or less, more preferably 30% by mass or less, particularly 23% by mass or less, and more preferably 18% by mass or less. When the content of the aromatic ring-containing monomer is in the above range, it becomes easy to satisfy the above-mentioned haze value at -40°C and the storage modulus G'. In addition, the adhesion can be maintained well.

作為含氮原子的單體，可列舉，具有胺基的單體、具有醯胺基的單體、具有含氮雜環的單體等，當中，以具有胺基的單體為佳。此外，在所構成的黏著劑的高階構造中，從提高來自上述含氮原子的單體的部分的自由度的觀點而言，該含氮原子的單體，除了用以形成(甲基)丙烯酸酯聚合物(A)的聚合中所使用的1個聚合性基以外，以不含有反應性不飽和雙鍵基為佳。含氮原子的單體可單獨1種使用，亦可組合2種以上使用。Examples of the nitrogen atom-containing monomer include a monomer having an amine group, a monomer having an amide group, a monomer having a nitrogen-containing heterocyclic ring, and the like. Among them, a monomer having an amine group is preferred. In addition, in the high-level structure of the constituted adhesive, from the viewpoint of increasing the degree of freedom of the part derived from the nitrogen atom-containing monomer, the nitrogen atom-containing monomer is used to form (meth)acrylic acid. In addition to the one polymerizable group used in the polymerization of the ester polymer (A), it is preferable that the reactive unsaturated double bond group is not contained. The nitrogen atom-containing monomer may be used singly or in combination of two or more kinds.

作為具有胺基的單體，可列舉，例如，(甲基)丙烯酸單甲基胺基乙酯、(甲基)丙烯酸單乙基胺基乙酯、(甲基)丙烯酸單甲基胺基丙酯、(甲基)丙烯酸單乙基胺基丙酯、(甲基)丙烯酸二甲基胺基乙酯等。Examples of the monomer having an amino group include, for example, monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, and monomethylaminopropyl (meth)acrylate. Ester, monoethylaminopropyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, etc.

做為具有醯胺基的單體，可列舉，例如，(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-三級丁基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N,N-二甲基胺基丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-(正丁氧基甲基)(甲基)丙烯醯胺、二甲基胺基丙基(甲基)丙烯醯胺、N-乙烯基己內醯胺。As the monomer having an amide group, for example, (meth)acrylamide, N-methyl (meth)acrylamide, N-methylol (meth)acrylamide, N- Tertiary butyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-dimethylaminopropyl (Meth)acrylamide, N-isopropyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-(n-butoxymethyl)(meth)acrylamide , Dimethylaminopropyl (meth)acrylamide, N-vinylcaprolactam.

作為具有含氮雜環的單體，可列舉，例如，N-(甲基)丙烯醯嗎啉、N-乙烯基-2-吡咯烷酮、N-(甲基)丙烯醯吡咯烷酮、N-(甲基)丙烯醯哌啶、N-(甲基)丙烯醯吡咯啶、N-(甲基)丙烯醯氮丙啶、氮丙啶基乙基(甲基)丙烯酸酯、2-乙烯基吡啶、4-乙烯基吡啶、2-乙烯基吡嗪、1-乙烯基咪唑、N-乙烯基咔唑、N-乙烯基酞醯亞胺等。Examples of the monomer having a nitrogen-containing heterocyclic ring include, for example, N-(meth)acrylomorpholine, N-vinyl-2-pyrrolidone, N-(meth)acrylopyrrolidone, N-(methyl) )Acrylic piperidine, N-(meth)acrylic pyrrolidine, N-(meth)acrylic aziridine, aziridinyl ethyl (meth)acrylate, 2-vinylpyridine, 4- Vinylpyridine, 2-vinylpyrazine, 1-vinylimidazole, N-vinylcarbazole, N-vinylphthalimide, etc.

(甲基)丙烯酸酯共聚物(A)，作為構成該聚合物的單體單元，以含有含氮原子的單體0.01質量%以上為佳，以含有0.1質量%以上為更佳，特別是以含有0.3質量%以上為佳，進一步以含有0.8質量以上%為佳。此外，以含有含氮原子的單體14質量%以下為佳，以含有8質量%以下為更佳，特別是以含有4質量%以下為佳，進一步以含有2質量%以下為佳。藉由使含氮原子的單體的含量於上述的範圍中，變得易於滿足上述儲存模數G’。此外，黏著性亦良好地維持。The (meth)acrylate copolymer (A), as the monomer unit constituting the polymer, is preferably 0.01% by mass or more of nitrogen-containing monomers, more preferably 0.1% by mass or more, especially The content is preferably 0.3% by mass or more, and more preferably 0.8% by mass or more. In addition, the monomer containing nitrogen atoms is preferably 14% by mass or less, more preferably 8% by mass or less, particularly 4% by mass or less, and more preferably 2% by mass or less. By setting the content of the nitrogen atom-containing monomer within the above-mentioned range, it becomes easy to satisfy the above-mentioned storage modulus G'. In addition, the adhesiveness is also well maintained.

(甲基)丙烯酸酯聚合物(A)，藉由含有含反應性官能基的單體作為構成該聚合物的單體單元，透過該來自含反應性官能基的單體的反應性官能基，與下述交聯劑(C)反應，形成交聯構造(三維網目構造)。如此一來，具有期望的凝集力，可獲得易於滿足上述物性的黏著劑。The (meth)acrylate polymer (A) contains a reactive functional group-containing monomer as a monomer unit constituting the polymer, and permeates the reactive functional group derived from the reactive functional group-containing monomer, It reacts with the following crosslinking agent (C) to form a crosslinked structure (three-dimensional mesh structure). In this way, it has a desired cohesive force, and an adhesive that easily meets the above-mentioned physical properties can be obtained.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元所含有的含反應性官能基的單體，較佳可列舉，在分子內具有羥基的單體(含羥基的單體)，在分子內具有羧基的單體(含羧基的單體)等。此等含反應性官能基的單體，可單獨1種使用，亦可併用2種以上。The (meth)acrylate polymer (A), as the reactive functional group-containing monomer contained in the monomer unit constituting the polymer, preferably, a monomer having a hydroxyl group in the molecule (hydroxyl-containing Monomer), a monomer having a carboxyl group in the molecule (a carboxyl group-containing monomer), and the like. These reactive functional group-containing monomers may be used alone or in combination of two or more.

上述含反應性官能基的單體當中，以含羥基的單體或含羧基的單體為佳，特別是以含羥基的單體為佳。含羥基的單體易於滿足上述物性。Among the above-mentioned reactive functional group-containing monomers, hydroxyl-containing monomers or carboxyl-containing monomers are preferred, and hydroxyl-containing monomers are particularly preferred. The hydroxyl-containing monomer easily satisfies the above-mentioned physical properties.

作為含羥基的單體，可列舉，例如，(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸3-羥丁酯、(甲基)丙烯酸4-羥丁酯等的(甲基)丙烯酸羥烷基酯等。上述當中，從易於滿足上述物性的觀點而言，以具有碳數為1〜4的羥烷基的(甲基)丙烯酸羥烷基酯為佳。此等可單獨使用，亦可組合2種以上使用。Examples of hydroxyl-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like. Among the above, from the viewpoint of easily satisfying the above physical properties, a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group having 1 to 4 carbon atoms is preferred. These can be used alone or in combination of two or more kinds.

作為含羧基的單體，可列舉，例如，丙烯酸、甲基丙烯酸、丁烯酸、順丁烯二酸、伊康酸、檸康酸等的乙烯性不飽和羧酸。當中，從所獲得的(甲基)丙烯酸酯聚合物(A)的黏著力的觀點而言，以丙烯酸為佳。此等可單獨使用，亦可組合2種以上使用。Examples of carboxyl group-containing monomers include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Among them, from the viewpoint of the adhesive force of the obtained (meth)acrylate polymer (A), acrylic acid is preferred. These can be used alone or in combination of two or more kinds.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有含反應性官能基的單體，1質量%以上為佳，特別是以含有2質量%以上為佳，進一步以含有3質量%以上為佳。此外，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以含有含反應性官能基的單體，13質量%以下為佳，特別是以含有8質量%以下為佳，進一步以含有5質量%以下為佳。當(甲基)丙烯酸酯聚合物(A)作為單體單元，以上述的量含有含反應性官能基的單體時，藉由與交聯劑(C)的交聯反應，所得的黏著劑的凝集力成為適當者，而成為變得易於滿足上述儲存模數G’者。此外，亦變得易於滿足上述水蒸氣穿透度。The (meth)acrylate polymer (A), as the monomer unit constituting the polymer, contains a reactive functional group-containing monomer, preferably at least 1% by mass, particularly preferably at least 2% by mass It is more preferable to contain 3% by mass or more. In addition, the (meth)acrylate polymer (A), as the monomer unit constituting the polymer, contains a reactive functional group-containing monomer, preferably 13% by mass or less, especially 8% by mass or less Preferably, it is more preferable to contain 5% by mass or less. When the (meth)acrylate polymer (A) as a monomer unit contains a monomer containing a reactive functional group in the above-mentioned amount, the resulting adhesive will be obtained by the cross-linking reaction with the cross-linking agent (C) If the cohesive force of is appropriate, it becomes easy to satisfy the above-mentioned storage modulus G'. In addition, it becomes easy to satisfy the above-mentioned water vapor permeability.

且，從耐濕熱白化性的觀點以及確實與聚輪烷化合物(B)交聯且使儲存模數G’降低的觀點而言，推斷以(甲基)丙烯酸酯聚合物(A)中的含羥基的單體的比例變大為較有利。然而，當含羥基的單體的比例變過大時，推測水蒸氣穿透度過度上升，黏著劑中的氫鍵變得非常多，到達無法顯示彈性率的程度，使黏著劑層表面變硬，如此一來，有時耐彎曲性會降低。In addition, from the viewpoint of heat and humidity resistance and from the viewpoint of crosslinking with the polyrotaxane compound (B) and lowering the storage modulus G', it is inferred that the content of the (meth)acrylate polymer (A) It is advantageous to increase the ratio of hydroxyl monomers. However, when the ratio of the hydroxyl group-containing monomer becomes too large, it is estimated that the water vapor permeability increases excessively, and the hydrogen bonds in the adhesive become too much to the extent that the elasticity cannot be displayed, and the surface of the adhesive layer becomes hard. As a result, the bending resistance may decrease.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，以不含有含羧基的單體為佳。由於羧基為酸成分，藉由不含有含羧基的單體，對於黏著劑的貼附對象，可抑制因酸而產生的不良，例如，在摻錫氧化銦(ITO)等的透明導電膜、金屬膜、金屬篩網等存在時，因酸引起的其不良(腐蝕、電阻值變化等)。The (meth)acrylate polymer (A) preferably does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. Since the carboxyl group is an acid component, by not containing a carboxyl group-containing monomer, it is possible to suppress the defects caused by the acid for the object of the adhesive. For example, in the transparent conductive film such as tin-doped indium oxide (ITO), metal When membranes, metal meshes, etc. are present, the defects (corrosion, resistance value changes, etc.) caused by acid.

(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的含反應性官能基的單體，不是含羧基的單體，而是含有含羥基的單體，透過交聯劑(C)(特別是異氰酸酯系交聯劑)，更有效率地進行(甲基)丙烯酸酯聚合物(A)與聚輪烷化合物(B)的交聯。其結果為更易於滿足上述儲存模數G’。The (meth)acrylate polymer (A), as the reactive functional group-containing monomer constituting the polymer, is not a carboxyl group-containing monomer, but a hydroxyl-containing monomer through the crosslinking agent (C) (In particular, an isocyanate-based crosslinking agent), the (meth)acrylate polymer (A) and the polyrotaxane compound (B) are crosslinked more efficiently. As a result, it is easier to satisfy the aforementioned storage modulus G'.

在此，所謂「不含有含羧基的單體」，是指實際上不含有含羧基的單體，在完全不含有含羧基的單體之外，容許以不產生因羧基引起的透明導電膜、金屬配線等的腐蝕的程度，含有含羧基的單體。具體而言，在(甲基)丙烯酸酯聚合物(A)中，作為單體單元，容許以0.1質量%以下，較佳為0.01質量%以下，進一步更佳為0.001質量%以下的量，含有含羧基的單體。Here, "does not contain a carboxyl group-containing monomer" means that it does not actually contain a carboxyl group-containing monomer. In addition to not containing a carboxyl group-containing monomer at all, it is allowed to not produce a transparent conductive film caused by a carboxyl group, The degree of corrosion of metal wiring and the like contains a carboxyl group-containing monomer. Specifically, in the (meth)acrylate polymer (A), as a monomer unit, the allowable amount is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001% by mass or less. Monomers containing carboxyl groups.

(甲基)丙烯酸酯聚合物(A)，根據需要，作為構成該聚合物的單體單元，亦可含有其他單體。作為其他單體，為了不妨礙含反應性官能基的單體的上述作用，以不含有反應性官能基的單體為佳。作為相關單體，可列舉，例如，(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等的(甲基)丙烯酸烷氧基烷基酯、醋酸乙烯酯、苯乙烯等。此等可單獨使用，亦可組合2種以上使用。The (meth)acrylate polymer (A) may contain other monomers as a monomer unit constituting the polymer as necessary. As other monomers, in order not to hinder the above-mentioned effects of the reactive functional group-containing monomer, a monomer that does not contain a reactive functional group is preferred. As related monomers, for example, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and other alkoxyalkyl (meth)acrylates, vinyl acetate, benzene Ethylene and so on. These can be used alone or in combination of two or more kinds.

(甲基)丙烯酸酯聚合物(A)的聚合態樣，可以是隨機共聚物，也可以是嵌段共聚物。The polymerization state of the (meth)acrylate polymer (A) may be a random copolymer or a block copolymer.

(甲基)丙烯酸酯聚合物(A)的重量平均分子量，以10萬以上為佳，以40萬以上為更佳，特別是以90萬以上為佳，進一步以140萬以上為佳。此外，(甲基)丙烯酸酯聚合物(A)的重量平均分子量，以300萬以下為佳，以230萬以下為更佳，特別是以180萬以下為佳，進一步以160萬以下為佳。當(甲基)丙烯酸酯聚合物(A)的重量平均分子量於上述範圍內時，成為易於滿足上述物性者。且，在本說明書中的重量平均分子量，為藉由凝膠滲透層析(GPC)法所測定的換算標準聚苯乙烯的值。The weight average molecular weight of the (meth)acrylate polymer (A) is preferably 100,000 or more, more preferably 400,000 or more, particularly preferably 900,000 or more, and further preferably 1.4 million or more. In addition, the weight average molecular weight of the (meth)acrylate polymer (A) is preferably 3 million or less, more preferably 2.3 million or less, particularly preferably 1.8 million or less, and further preferably 1.6 million or less. When the weight average molecular weight of the (meth)acrylate polymer (A) is within the above-mentioned range, it is easy to satisfy the above-mentioned physical properties. In addition, the weight average molecular weight in this specification is a value measured by a gel permeation chromatography (GPC) method in terms of standard polystyrene conversion.

(甲基)丙烯酸酯聚合物(A)的玻璃轉換溫度(Tg)，以-80℃以上為佳，以-60℃以上為更佳，特別是以-50℃以上為佳，進一步以-40℃以上為佳。此外，(甲基)丙烯酸酯聚合物(A)的玻璃轉換溫度(Tg)，以10℃以下為佳，以0℃以下為更佳，特別是以-10℃以下為佳，進一步以-20℃以下為佳。當(甲基)丙烯酸酯聚合物(A)的玻璃轉換溫度(Tg)於上述範圍時，變得易於滿足上述儲存模數G’。且，在本說明書中的(甲基)丙烯酸酯聚合物(A)的玻璃轉換溫度(Tg)，為以作為構成該(甲基)丙烯酸酯聚合物(A)的各單體的均聚物的玻璃轉換溫度(Tg)為基準，藉由FOX的算式所算出者。The glass transition temperature (Tg) of the (meth)acrylate polymer (A) is preferably -80°C or higher, more preferably -60°C or higher, especially -50°C or higher, and further preferably -40 Above ℃ is better. In addition, the glass transition temperature (Tg) of the (meth)acrylate polymer (A) is preferably 10°C or less, more preferably 0°C or less, especially -10°C or less, and further preferably -20°C or less. Below ℃ is better. When the glass transition temperature (Tg) of the (meth)acrylate polymer (A) is within the above range, it becomes easy to satisfy the above storage modulus G'. In addition, the glass transition temperature (Tg) of the (meth)acrylate polymer (A) in this specification is a homopolymer of each monomer constituting the (meth)acrylate polymer (A) The glass transition temperature (Tg) is calculated based on the formula of FOX.

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

(1-2) 聚輪烷化合物(B) 聚輪烷化合物(B)為在至少2個環狀分子的開口部有直鏈狀分子貫穿，且，在直鏈狀分子的兩末端具有阻斷基(blocking group)而成的化合物。在此聚輪烷化合物(B)中，雖然環狀分子可在直鏈狀分子上自由地移動(滑動)，但藉由阻斷基，成為環狀分子不會從直鏈狀分子脫出的構造。換言之，直鏈狀分子以及環狀分子成為不是以共價鍵結等的化學鍵結，而是藉由所謂機械性結合維持其形態者。(1-2) Polyrotaxane compound (B) The polyrotaxane compound (B) is a compound having linear molecules penetrating through the openings of at least two cyclic molecules, and having blocking groups at both ends of the linear molecules. In this polyrotaxane compound (B), although the cyclic molecule can move (slide) freely on the linear molecule, the blocking group makes the cyclic molecule not detached from the linear molecule. structure. In other words, linear molecules and cyclic molecules are not chemical bonds such as covalent bonds, but are maintained by so-called mechanical bonds.

由黏著性組合物P所獲得的黏著劑，藉由含有相關聚輪烷化合物(B)，應力緩和性變高，成為易於滿足上述儲存模數G’者。特別是當黏著性組合物P含有交聯劑(C)，使黏著性組合物P交聯時，交聯劑(C)的反應性基與聚輪烷化合物(B)所具有的環狀分子的反應性基反應，形成交聯劑加成物。此外，(甲基)丙烯酸酯聚合物(A)，藉由該聚合物所具有的來自含反應性官能基的單體的反應性官能基，透過交聯劑加成物中的交聯劑(C)，與聚輪烷化合物(B)的1個環狀分子鍵結，同樣地，推定另外的(甲基)丙烯酸酯聚合物(A)也與該聚輪烷化合物(B)另外的環狀分子鍵結。其結果為，複數個(甲基)丙烯酸酯聚合物(A)們，透過具有上述可滑動的機械性結合的聚輪烷化合物(B)，形成經過交聯的構造(交聯構造)。藉由含有相關交聯構造，所得的黏著劑，其應力緩和性更佳，成為更容易滿足上述儲存模數G’者。The adhesive obtained from the adhesive composition P contains the related polyrotaxane compound (B), so that the stress relaxation properties become high, and the adhesive can easily satisfy the above-mentioned storage modulus G'. Especially when the adhesive composition P contains a cross-linking agent (C), and the adhesive composition P is cross-linked, the reactive group of the cross-linking agent (C) and the cyclic molecule of the polyrotaxane compound (B) The reactive groups react to form crosslinker adducts. In addition, the (meth)acrylate polymer (A) has a reactive functional group derived from a monomer containing a reactive functional group through the crosslinking agent ( C) is bonded to one cyclic molecule of the polyrotaxane compound (B). Similarly, it is presumed that another (meth)acrylate polymer (A) is also bonded to another ring of the polyrotaxane compound (B). Like molecular bonding. As a result, the plurality of (meth)acrylate polymers (A) form a cross-linked structure (cross-linked structure) through the polyrotaxane compound (B) having the above-mentioned slidable mechanical bond. By containing the relevant cross-linked structure, the resulting adhesive has better stress relaxation properties, and is easier to meet the aforementioned storage modulus G'.

且，所得的黏著劑不必要全部為上述構造，亦可含有2個(甲基)丙烯酸酯聚合物(A)未透過聚輪烷化合物(B)，藉由交聯劑(C)直接鍵結的構造等。Moreover, the resulting adhesive does not necessarily have the above structure, and it may contain two (meth)acrylate polymers (A) impermeable to the polyrotaxane compound (B) and directly bonded by the crosslinking agent (C) The structure and so on.

本實施形態中的聚輪烷化合物(B)，以具有含有可與交聯劑(C)的反應性基反應的反應性基的環狀分子為佳。此外，該反應性基以具有親水性的官能基為佳。藉由聚輪烷化合物(B)的環狀分子具有相關的反應性基，變得易於滿足上述水蒸氣穿透度。作為該反應性基，可列舉，例如，羥基、羧基等，當中尤以羥基為佳。The polyrotaxane compound (B) in this embodiment preferably has a cyclic molecule containing a reactive group capable of reacting with the reactive group of the crosslinking agent (C). In addition, the reactive group is preferably a functional group having hydrophilicity. Since the cyclic molecules of the polyrotaxane compound (B) have related reactive groups, it becomes easy to satisfy the above-mentioned water vapor permeability. As the reactive group, for example, a hydroxyl group, a carboxyl group, etc. can be cited, and among them, a hydroxyl group is particularly preferred.

本實施形態中的聚輪烷化合物(B)，以具有作為環狀分子的環狀寡醣者為佳。環狀寡醣在未修飾狀態，具有作為反應性基的羥基。此外，藉由使用環狀寡醣作為聚輪烷化合物(B)的環狀分子，變得可選擇適當的環徑，如此一來，在直鏈狀分子上環狀分子移動引起的效果容易顯現。再者，各種的取代基等的導入也比較容易，如此一來，變得可調整所得的黏著劑的物性。再者，以環狀寡醣而言，也有易於取得等的優點。且，在本說明書中，所謂「環狀分子」或「環狀寡醣」的「環狀」，是指實質上為「環狀」的意思。換言之，只要在直鏈狀分子上可移動的話，環狀分子可以不是完全的閉環，也可以是例如，螺旋構造。The polyrotaxane compound (B) in this embodiment preferably has a cyclic oligosaccharide as a cyclic molecule. The cyclic oligosaccharide has a hydroxyl group as a reactive group in an unmodified state. In addition, by using a cyclic oligosaccharide as the cyclic molecule of the polyrotaxane compound (B), it becomes possible to select an appropriate ring diameter, so that the effect caused by the movement of the cyclic molecule on the linear molecule is easily displayed . Furthermore, the introduction of various substituents and the like is relatively easy, so that the physical properties of the resulting adhesive can be adjusted. Furthermore, cyclic oligosaccharides also have advantages such as easy availability. In addition, in this specification, the "cyclic" of the "cyclic molecule" or "cyclic oligosaccharide" means that it is substantially "cyclic". In other words, as long as it is movable on a linear molecule, the cyclic molecule may not be a completely closed loop, but may have, for example, a spiral structure.

作為環狀寡醣，較佳可列舉，α-環糊精、β-環糊精、γ-環糊精等的環糊精，當中特別是以α-環糊精為佳。聚輪烷化合物(B)的環狀分子在聚輪烷化合物(B)中或在黏著性組合物P中，亦可混合存在2種以上。Preferred examples of cyclic oligosaccharides include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Among them, α-cyclodextrin is particularly preferred. Two or more types of cyclic molecules of the polyrotaxane compound (B) may be mixed in the polyrotaxane compound (B) or in the adhesive composition P.

上述環狀寡醣作為反應性基所具有的羥基，環狀寡醣可以是原本(所謂修飾前的狀態)所具有的羥基，也可以是在環狀寡醣上導入作為取代基的羥基。The above-mentioned cyclic oligosaccharide is the hydroxyl group possessed by the reactive group. The cyclic oligosaccharide may have the hydroxyl group originally (the state before modification), or the cyclic oligosaccharide may have a hydroxyl group as a substituent introduced into the cyclic oligosaccharide.

上述環狀分子的羥基值，作為下限值，以10mgKOH/g以上為佳，以30mgKOH/g以上為更佳，以50mgKOH/g以上為特別佳。羥基值的下限值為上述時，聚輪烷化合物(B)與交聯劑(C)可充分反應，且，殘存特定量的羥基，變得易於滿足上述水蒸氣穿透度。此外，上述環狀分子的羥基值，作為上限值，以1000mgKOH/g以下為佳，以200mgKOH/g以下為更佳，以100mgKOH/g以下為特別佳。當羥基值得上限值超過上述值時，由於在同一環狀分子上產生多數的交聯，該環狀分子本身變成交聯點，變得無法發揮作為聚輪烷化合物(B)全體的交聯點的效果，其結果恐怕變得在所得的黏著劑中無法確保充分的柔軟性。The lower limit of the hydroxyl value of the cyclic molecule is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, and particularly preferably 50 mgKOH/g or more. When the lower limit of the hydroxyl value is the above, the polyrotaxane compound (B) and the crosslinking agent (C) can be sufficiently reacted, and a specific amount of hydroxyl groups remain, making it easy to satisfy the above-mentioned water vapor permeability. In addition, as the upper limit of the hydroxyl value of the cyclic molecule, 1000 mgKOH/g or less is preferable, 200 mgKOH/g or less is more preferable, and 100 mgKOH/g or less is particularly preferable. When the upper limit of the hydroxyl value exceeds the above value, since many cross-links occur on the same cyclic molecule, the cyclic molecule itself becomes a cross-linking point, and it becomes impossible to perform cross-linking as the entire polyrotaxane compound (B). As a result, it may become impossible to ensure sufficient flexibility in the obtained adhesive.

聚輪烷化合物(B)的直鏈狀分子為被包容於環狀分子中，不是以共價鍵結等的化學鍵結而是能夠以機械性的結合而一體化的分子或物質，只要是直鏈狀者即可，並無特限定。且，在本說明書中，所謂「直鏈狀分子」的「直鏈」，是指實質上「直鏈」的意思。換言之，只要在直鏈狀分子上環狀分子可移動的話，直鏈狀分子亦可具有分支鏈。The linear molecule of the polyrotaxane compound (B) is a molecule or substance that is contained in a cyclic molecule and is not chemically bonded by covalent bonding but can be integrated by mechanical bonding, as long as it is straight The chain shape is sufficient, and there is no special limitation. In addition, in this specification, the "straight chain" of the "straight-chain molecule" means substantially "straight chain". In other words, as long as the cyclic molecule can move on the linear molecule, the linear molecule may have a branched chain.

作為聚輪烷化合物(B)的直鏈狀分子，較佳為例如，聚乙二醇、聚丙二醇、聚異戊二烯、聚異丁烯、聚丁二烯、聚四氫呋喃、聚丙烯酸酯、聚二甲基矽氧烷、聚乙烯、聚丙烯等，此等直鏈狀分子在黏著性組合物P中，亦可混合存在2種以上。The linear molecule of the polyrotaxane compound (B) is preferably, for example, polyethylene glycol, polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, polytetrahydrofuran, polyacrylate, polydiene In the adhesive composition P, two or more kinds of linear molecules such as methylsiloxane, polyethylene, polypropylene, etc., may be mixed.

聚輪烷化合物(B)的直鏈狀分子的數平均分子量，作為下限值，以3,000以上為佳，特別是以10,000以上為佳，進一步以20,000以上為佳。當數平均分子量的下限值為上述時，環狀分子在直鏈狀分子上的移動量受到確保，可充分獲得因聚輪烷化合物(B)所引起的交聯構造的柔軟性。此外，聚輪烷化合物(B)的直鏈狀分子的數平均分子量，作為上限值，以300,000以下為佳，特別是以200,000以下為佳，進一步以100,000以下為佳。當數平均分子量的上限值為上述時，聚輪烷化合物(B)對溶媒的溶解性變得良好。The lower limit of the number average molecular weight of the linear molecules of the polyrotaxane compound (B) is preferably 3,000 or more, particularly 10,000 or more, and more preferably 20,000 or more. When the lower limit of the number average molecular weight is the above, the amount of movement of the cyclic molecule on the linear molecule is ensured, and the flexibility of the crosslinked structure due to the polyrotaxane compound (B) can be sufficiently obtained. In addition, the upper limit of the number average molecular weight of the linear molecules of the polyrotaxane compound (B) is preferably 300,000 or less, particularly 200,000 or less, and more preferably 100,000 or less. When the upper limit of the number average molecular weight is the above, the solubility of the polyrotaxane compound (B) in the solvent becomes good.

聚輪烷化合物(B)的阻斷基，只要是可將環狀分子維持在藉由直鏈狀分子而成為串刺狀的形態的基即可，並無特限定。作為此類基，可列舉，巨大基團、離子基等。The blocking group of the polyrotaxane compound (B) is not particularly limited as long as it can maintain the cyclic molecule in the form of a thorn-like shape by the linear molecule. Examples of such groups include giant groups and ionic groups.

具體而言，聚輪烷化合物(B)的阻斷基，以二硝苯基類、環糊精類、金剛烷基類、三苯甲基(trityl)類、螢光素類、芘類、蒽類等，或是，數平均分子量1,000~1,000,000的高分子的主鏈或側鏈等為佳，此等阻斷基在聚輪烷化合物(B)中或在黏著性組合物P中，可混合存在2種以上。Specifically, the blocking group of the polyrotaxane compound (B) includes dinitrophenyls, cyclodextrins, adamantyls, trityls, luciferins, pyrenes, Anthracene, etc., or the main chain or side chain of a polymer with a number average molecular weight of 1,000 to 1,000,000 is preferable. These blocking groups are in the polyrotaxane compound (B) or in the adhesive composition P, Two or more types are mixed.

以上所說明的聚輪烷化合物(B)，可藉由過往習知的方法(例如，日本特開2005-154675中所記載的方法)而獲得。The polyrotaxane compound (B) described above can be obtained by a conventionally known method (for example, the method described in JP 2005-154675).

本實施形態相關的黏著性組合物P中的聚輪烷化合物(B)的含量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，以1質量份以上為佳，以4質量份以上為更佳，特別是以6質量份以上為佳，進一步以7質量份以上為佳。此外，聚輪烷化合物(B)的含量，以30質量份以下為佳，以24質量份以下為更佳，以17質量份以下為特別佳，以12質量份以下為進一步更佳。藉由聚輪烷化合物(B)的含量於上述範圍中，變得易於滿足上述水蒸氣穿透度以及儲存模數G’兩者。The content of the polyrotaxane compound (B) in the adhesive composition P according to this embodiment is preferably 1 part by mass or more, and 4 parts by mass relative to 100 parts by mass of the (meth)acrylate polymer (A) Part or more is more preferable, especially 6 parts by mass or more, and more preferably 7 parts by mass or more. In addition, the content of the polyrotaxane compound (B) is preferably 30 parts by mass or less, more preferably 24 parts by mass or less, particularly preferably 17 parts by mass or less, and even more preferably 12 parts by mass or less. When the content of the polyrotaxane compound (B) is in the above range, it becomes easy to satisfy both the above water vapor permeability and the storage modulus G'.

(1-3) 交聯劑(C) 交聯劑(C)具有反應性基。此反應性基以可與(甲基)丙烯酸酯聚合物(A)所具有的反應性官能基，以及聚輪烷化合物(B)的環狀分子所具有的反應性基反應者為佳。相關的交聯劑(C)與聚輪烷化合物(B)，形成交聯劑加成物。然後，該交聯劑加成物將(甲基)丙烯酸酯聚合物(A)彼此進行交聯，形成三維網目構造。如此一來，所得的黏著劑的凝集力提升，變得易於滿足上述物性。(1-3) Crosslinking agent (C) The crosslinking agent (C) has a reactive group. This reactive group is preferably one that can react with the reactive functional group possessed by the (meth)acrylate polymer (A) and the reactive group possessed by the cyclic molecule of the polyrotaxane compound (B). The related crosslinking agent (C) and the polyrotaxane compound (B) form a crosslinking agent adduct. Then, this crosslinking agent adduct crosslinks (meth)acrylate polymers (A) to each other to form a three-dimensional network structure. In this way, the cohesive force of the obtained adhesive increases, and it becomes easier to satisfy the above-mentioned physical properties.

作為上述交聯劑(C)，可列舉，例如，異氰酸酯系交聯劑、環氧系交聯劑、胺系交聯劑、三聚氰胺系交聯劑、氮丙啶系交聯劑、肼系交聯劑、醛系交聯劑、噁唑啉系交聯劑、金屬醇鹽系交聯劑、金屬螫合系交聯劑、金屬鹽系交聯劑、銨鹽系交聯劑等。此等當中，以與羥基的反應性高的異氰酸酯系交聯劑為佳。依照異氰酸酯系交聯劑，可充分進行具有羥基作為反應性基的聚輪烷化合物(B)的交聯劑加成，藉此，變得易於滿足上述水蒸氣穿透度以及儲存模數G’。且，交聯劑(C)可單獨1種，或組合2種以上使用。Examples of the above-mentioned crosslinking agent (C) include, for example, isocyanate-based crosslinking agents, epoxy-based crosslinking agents, amine-based crosslinking agents, melamine-based crosslinking agents, aziridine-based crosslinking agents, and hydrazine-based crosslinking agents. Linking agents, aldehyde-based cross-linking agents, oxazoline-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelating-based cross-linking agents, metal salt-based cross-linking agents, ammonium salt-based cross-linking agents, etc. Among these, an isocyanate-based crosslinking agent having high reactivity with a hydroxyl group is preferred. According to the isocyanate-based crosslinking agent, the addition of the crosslinking agent of the polyrotaxane compound (B) having a hydroxyl group as a reactive group can be sufficiently performed, thereby making it easier to satisfy the above-mentioned water vapor permeability and storage modulus G' . Moreover, the crosslinking agent (C) can be used individually by 1 type or in combination of 2 or more types.

異氰酸酯系交聯劑為至少含有聚異氰酸酯化合物者。作為聚異氰酸酯化合物，可列舉，例如，甲苯二異氰酸酯、二苯基甲烷二異氰酸酯(Diphenylmethane diisocyanate)、二甲苯二異氰酸酯(xylylene diisocyanate)等的芳香族聚異氰酸酯；六亞甲基二異氰酸酯等的脂肪族聚異氰酸酯；異佛爾酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯等的脂環式聚異氰酸酯等；以及其雙縮脲產物、異氰脲酸酯體、再者作為與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等的含低分子活性氫化合物的反應產物的加成產物等。The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatics such as hexamethylene diisocyanate. Polyisocyanate; alicyclic polyisocyanate such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.; and its biuret products, isocyanurate esters, and as a combination with ethylene glycol, propylene glycol, Addition products of reaction products containing low molecular active hydrogen compounds such as neopentyl glycol, trimethylolpropane, castor oil, etc.

黏著性組合物P中的交聯劑(C)的含量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，以0.1質量份以上為佳，以0.5質量份以上為更佳，特別是以1.0質量份以上為佳，進一步以1.3質量份以上為佳。此外，該含量以10質量份以下為佳，以5質量份以下為更佳，特別是以2質量份以下為佳，進一步以1.8質量份以下為佳。交聯劑(C)的含量在上述範圍內時，易於滿足上述物性。The content of the crosslinking agent (C) in the adhesive composition P is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the (meth)acrylate polymer (A). In particular, it is preferably 1.0 part by mass or more, and more preferably 1.3 parts by mass or more. In addition, the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, particularly preferably 2 parts by mass or less, and further preferably 1.8 parts by mass or less. When the content of the crosslinking agent (C) is within the above range, the above physical properties are easily satisfied.

(1-4) 各種添加劑 在黏著性組合物P中，根據需要，可添加丙烯酸系黏著劑中通常使用的各種添加劑，例如，矽烷偶合劑、紫外線吸收劑、抗靜電劑、增黏劑、抗氧化劑、光穩定劑、軟化劑、填充劑、折射率調整劑等。且，下述聚合溶媒、稀釋溶媒為不包含於構成黏著性組合物P的添加劑。(1-4) Various additives In the adhesive composition P, various additives commonly used in acrylic adhesives, such as silane coupling agents, ultraviolet absorbers, antistatic agents, tackifiers, antioxidants, light stabilizers, and softening agents, can be added as needed. Agents, fillers, refractive index modifiers, etc. In addition, the following polymerization solvents and dilution solvents are additives that are not included in the adhesive composition P.

黏著性組合物P以含有上述矽烷偶合劑為佳。如此一來，在所得的黏著劑層中，與作為被附著物的彎曲性部件間的密附性提升，而成為黏著力更佳者。The adhesive composition P preferably contains the above-mentioned silane coupling agent. In this way, in the obtained adhesive layer, the adhesion with the bendable member as the adherend is improved, and the adhesion is better.

作為矽烷偶合劑，為在分子內具有至少1個烷氧基矽烷基的有機矽化合物，以與(甲基)丙烯酸酯聚合物(A)的相溶性良好，具有光穿透性者為佳。The silane coupling agent is an organosilicon compound having at least one alkoxysilyl group in the molecule, and is preferably compatible with the (meth)acrylate polymer (A) and has light permeability.

作為相關的矽烷偶合劑，可列舉，例如，乙烯三甲氧矽烷、乙烯三乙氧矽烷、甲基丙烯醯氧基丙基三甲氧矽烷等的含聚合性不飽和基的矽化合物；3-環氧丙基丙基三甲氧矽烷、3-環氧丙基丙基甲基二甲氧矽烷、2-(3,4-環氧基環己基)乙基三甲氧矽烷等的具有環氧構造的矽化合物；3-巰基丙基三甲氧矽烷、3-巰基丙基三乙氧矽烷、3-巰基丙基二甲氧甲基矽烷等的含巰基的矽化合物；3-胺基丙基三甲氧矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧矽烷等的含胺基的矽化合物；3-氯丙基三甲氧矽烷、3-異氰酸酯丙基三乙氧矽烷，或是其至少1者與甲基三乙氧矽烷、乙基三乙氧矽烷、甲基三甲氧矽烷、乙基三甲氧矽烷等的含烷基的矽化合物的縮合產物等。此等可單獨使用1種，亦可組合2種以上使用。Examples of related silane coupling agents include, for example, ethylene trimethoxysilane, ethylene triethoxysilane, methacryloxypropyltrimethoxysilane, and other polymerizable unsaturated group-containing silicon compounds; 3-epoxy Silicon compounds with epoxy structure, such as propyl propyl trimethoxy silane, 3-epoxypropyl propyl methyl dimethyl siloxane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, etc. ; 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl dimethoxymethyl silane and other mercapto group-containing silicon compounds; 3-aminopropyl trimethoxysilane, N -(2-Aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and other amino-containing silicon Compound; 3-chloropropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, or at least one of them and methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, ethyl Condensation products of alkyl-containing silicon compounds such as trimethoxysilane. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

黏著性組合物P中的矽烷偶合劑的含量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，以0.01質量份以上為佳，特別是以0.05質量份以上為佳，進一步以0.1質量份以上為佳。此外，該含量以1質量份以下為佳，特別是以0.5質量份以下為佳，進一步以0.3質量份以下為佳。藉由矽烷偶合劑的含量於上述的範圍內，所得的黏著劑層與作為被附著物的彎曲性部件的密附性提升，而成為黏著力更大者。The content of the silane coupling agent in the adhesive composition P is preferably 0.01 parts by mass or more, particularly preferably 0.05 parts by mass or more, relative to 100 parts by mass of the (meth)acrylate polymer (A), and further 0.1 part by mass or more is preferable. In addition, the content is preferably 1 part by mass or less, particularly preferably 0.5 parts by mass or less, and further preferably 0.3 parts by mass or less. When the content of the silane coupling agent is within the above-mentioned range, the adhesion between the resulting adhesive layer and the flexible member as the adherend is improved, and the adhesive force becomes greater.

(2) 黏著性組合物P的製造 黏著性組合物P可藉由製造(甲基)丙烯酸酯聚合物(A)，將所獲得的(甲基)丙烯酸酯聚合物(A)與聚輪烷化合物(B)，及根據需要而添加的交聯劑(C)以及添加劑而製造。(2) Production of adhesive composition P Adhesive composition P can be produced by manufacturing (meth)acrylate polymer (A), and the obtained (meth)acrylate polymer (A) and polyrotaxane compound (B) can be added as needed The crosslinking agent (C) and additives are manufactured.

(甲基)丙烯酸酯聚合物(A)可藉由將構成聚合物的單體的混合物，以一般的自由基聚合法進行聚合而製造。(甲基)丙烯酸酯聚合物(A)的聚合，可使用依需要的聚合起始劑，藉由溶液聚合法而進行較佳。藉由以溶液聚合法將(甲基)丙烯酸酯聚合物(A)聚合，所獲得的聚合物的高分子量化及分子量分佈的調整變得容易，再者，變得可減少低分子量產物的生成。因此，即使是凝膠分率比較小，交聯的程度平緩時，伴隨著反覆彎曲而來的黏著劑的偏離不易產生，易於獲得耐久性佳的黏著劑。The (meth)acrylate polymer (A) can be produced by polymerizing a mixture of monomers constituting the polymer by a general radical polymerization method. The polymerization of the (meth)acrylate polymer (A) can be carried out by a solution polymerization method using a polymerization initiator as required. By polymerizing the (meth)acrylate polymer (A) by the solution polymerization method, the high molecular weight and molecular weight distribution of the obtained polymer can be easily adjusted. Furthermore, the production of low molecular weight products can be reduced. . Therefore, even when the gel fraction is relatively small and the degree of crosslinking is gentle, the deviation of the adhesive accompanying repeated bending is not easy to occur, and it is easy to obtain an adhesive with good durability.

作為溶液聚合法所使用的聚合溶媒，可列舉，例如，醋酸乙酯、醋酸正丁酯、醋酸異丁酯、甲苯、丙酮、己烷、丁酮等，亦可併用2種以上。Examples of the polymerization solvent used in the solution polymerization method include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, etc., and two or more types may be used in combination.

作為聚合起始劑，可列舉，偶氮系化合物、有機過氧化物等，亦可併用2種以上。作為偶氮系化合物，可列舉，例如，2,2-偶氮雙異丁腈、2,2-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷1-甲腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基2,2’-偶氮雙(2-丙酸甲酯)、4,4’-偶氮雙(4-氰戊酸)、2,2’-偶氮雙(2-羥甲基丙腈)、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]等。As a polymerization initiator, an azo compound, an organic peroxide, etc. can be mentioned, You may use 2 or more types together. As the azo compound, for example, 2,2-azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , Dimethyl 2,2'-azobis(2-propionic acid methyl ester), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethyl) Base propionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] and the like.

作為有機過氧化物，可列舉，例如，過氧化苯甲醯、過苯甲酸三級丁酯、氫過氧化異丙苯、過氧化二碳酸二異丙酯、過氧化二碳酸二正丙酯、過氧化二碳酸二(2-乙氧基乙基)酯、過氧化新癸酸三級丁酯、過氧化異丁酸三級丁酯(tert-butyl peroxypivalate)、過氧化(3,5,5-三甲基己醯)、過氧化二丙醯、過氧化二乙醯等。Examples of organic peroxides include, for example, benzyl peroxide, tertiary butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, Di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, peroxide (3,5,5) -Trimethylhexyl), dipropylene peroxide, diacetyl peroxide, etc.

且，在上述聚合步驟中，藉由調配2-巰基乙醇等的鏈轉移劑，可調節所得的聚合物的重量平均分子量。In addition, in the above-mentioned polymerization step, the weight average molecular weight of the obtained polymer can be adjusted by formulating a chain transfer agent such as 2-mercaptoethanol.

獲得(甲基)丙烯酸酯聚合物(A)之後，藉由在(甲基)丙烯酸酯聚合物(A)的溶液中，添加聚輪烷化合物(B)，及根據需要的交聯劑(C)、添加劑以及稀釋溶劑，充分混合，獲得以溶劑稀釋過的黏著性組合物P(塗佈溶液)。After obtaining the (meth)acrylate polymer (A), by adding the polyrotaxane compound (B) to the solution of the (meth)acrylate polymer (A), and the crosslinking agent (C) as needed ), the additives and the dilution solvent are thoroughly mixed to obtain the adhesive composition P (coating solution) diluted with the solvent.

且，在上述各成分任一者中，使用固體狀者，或是，在未經稀釋的狀態與其他成分混合而發生析出時，可將該成分可單獨預先溶解於稀釋溶媒中或稀釋後，再與其他成分混合。In addition, among the above-mentioned components, a solid one is used, or when it is mixed with other components in an undiluted state and precipitates, the component can be separately pre-dissolved in a diluting solvent or after being diluted, Mix with other ingredients.

作為上述稀釋溶劑，可使用例如，己烷、庚烷、環己烷等的脂肪族烴；甲苯、二甲苯等的芳香族烴；二氯甲烷、二氯乙烷(ethylene chloride)等的鹵化烴；甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等的醇；丙酮、丁酮、2-戊酮、異佛爾酮、環己酮等的酮；醋酸乙酯、醋酸丁酯等的酯；乙基賽珞蘇等的賽珞蘇系溶劑等。As the above-mentioned dilution solvent, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and ethylene chloride can be used. ; Alcohols such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol; ketones such as acetone, butanone, 2-pentanone, isophorone, and cyclohexanone; ethyl acetate , Butyl acetate and other esters; ethyl serosol and other serosol-based solvents, etc.

作為如此所調製的塗佈溶液的濃度、黏度，只要是可塗佈的範圍即可，並無特別限制，可對應狀況而適當選擇。例如，以黏著性組合物P的濃度成為10〜60質量%的方式進行稀釋。且，在獲得塗佈溶液時，稀釋溶劑等的添加並非必要條件，只要是黏著性組合物P可塗佈的黏度等，亦可不添加稀釋溶劑。此時，黏著性組合物P成為將(甲基)丙烯酸酯聚合物(A)的聚合溶媒直接當作稀釋溶劑的塗佈溶液。The concentration and viscosity of the coating solution prepared in this way are not particularly limited as long as they are in the coatable range, and can be appropriately selected according to the situation. For example, it is diluted so that the concentration of the adhesive composition P may become 10-60 mass %. In addition, when the coating solution is obtained, the addition of a dilution solvent or the like is not a necessary condition, and as long as the adhesive composition P can be coated with a viscosity or the like, the dilution solvent may not be added. At this time, the adhesive composition P becomes a coating solution in which the polymerization solvent of the (meth)acrylate polymer (A) is directly used as a diluting solvent.

(3) 黏著劑的製造 本實施形態中構成黏著劑層11的黏著劑，較佳為黏著性組合物P進行交聯而形成者。黏著性組合物P的交聯可藉由一般的加熱處理而進行。且，此加熱處理可兼任藉由使稀釋溶劑從塗佈在期望的對象物上的黏著性組合物P的塗膜揮發時的乾燥處理。(3) Manufacturing of adhesive In this embodiment, the adhesive constituting the adhesive layer 11 is preferably formed by cross-linking the adhesive composition P. The crosslinking of the adhesive composition P can be performed by general heat treatment. In addition, this heat treatment can also serve as a drying treatment at the time of volatilizing the diluent solvent from the coating film of the adhesive composition P applied on the desired object.

加熱處理的加熱溫度，以50〜150℃為佳，特別是以70〜120℃為佳。此外，加熱時間以10秒〜10分鐘為佳，特別是以50秒〜2分鐘為佳。The heating temperature of the heat treatment is preferably 50 to 150°C, particularly 70 to 120°C. In addition, the heating time is preferably 10 seconds to 10 minutes, especially 50 seconds to 2 minutes.

加熱處理後，必要時，亦可在常溫(例如23℃，50%RH)設置1〜2週左右的熟成期間。當此熟成期間為必要時，在熟成期間過後，當熟成期間為非必要時，在加熱處理結束後，形成黏著劑。After the heat treatment, if necessary, an aging period of about 1 to 2 weeks may be set at normal temperature (for example, 23° C., 50% RH). When this aging period is necessary, after the aging period, when the aging period is not necessary, the adhesive is formed after the heat treatment is completed.

黏著性組合物P含有交聯劑(C)時，藉由上述加熱處理(及熟成)，透過交聯劑(C)，使(甲基)丙烯酸酯聚合物(A)及聚輪烷化合物(B)交聯，形成交聯構造，獲得黏著劑。When the adhesive composition P contains a cross-linking agent (C), the above-mentioned heat treatment (and aging) allows the (meth)acrylate polymer (A) and the polyrotaxane compound (C) to pass through the cross-linking agent (C). B) Cross-linking to form a cross-linked structure to obtain an adhesive.

(4) 黏著劑層的厚度 本實施形態相關的黏著片1中的黏著劑層11的厚度(以JIS K7130為基準所測定的值)，作為下限值以1μm以上為佳，以5μm以上為更佳，特別是以10μm以上為佳，進一步以15μm以上為佳。黏著劑層11的厚度的下限值為上述時，易於發揮期望的黏著力，成為耐久性更佳者。(4) The thickness of the adhesive layer The thickness of the adhesive layer 11 in the adhesive sheet 1 related to this embodiment (value measured based on JIS K7130) is preferably 1 μm or more as the lower limit, more preferably 5 μm or more, and particularly 10 μm or more Preferably, it is more preferably 15 μm or more. When the lower limit of the thickness of the adhesive layer 11 is the above, the desired adhesive force is easily exhibited, and the durability is better.

此外，黏著劑層11的厚度，作為上限值，以300μm以下為佳，以150μm以下為更佳，特別是以90μm以下為佳，從可獲得更薄的反覆彎曲裝置的觀點而言，進一步以40μm以下為佳。黏著劑層11的厚度的上限值為上述時，抑制因反覆彎曲發生在黏著劑層的應力過大，可成為耐久性更佳者。且，黏著劑層11可以單層形成，亦可將複數層進行積層而形成。In addition, the upper limit of the thickness of the adhesive layer 11 is preferably 300 μm or less, more preferably 150 μm or less, particularly preferably 90 μm or less. From the viewpoint of obtaining a thinner repeating bending device, further 40μm or less is preferred. When the upper limit of the thickness of the adhesive layer 11 is as described above, it is possible to suppress excessive stress that occurs in the adhesive layer due to repeated bending, and the durability is better. In addition, the adhesive layer 11 may be formed in a single layer, or may be formed by laminating a plurality of layers.

1-2.剝離片 剝離片12a、12b為至黏著片1使用時為止保護黏著劑層11者，當使用黏著片1(黏著劑層11)時，將其剝離。在本實施形態相關的黏著片1中，剝離片12a、12b的一者或兩者未必是必要者。1-2. Peeling sheet The peeling sheets 12a and 12b protect the adhesive layer 11 until the adhesive sheet 1 is used, and when the adhesive sheet 1 (adhesive layer 11) is used, it is peeled off. In the pressure-sensitive adhesive sheet 1 according to this embodiment, one or both of the release sheets 12a and 12b are not necessarily essential.

作為剝離片12a、12b，可使用例如，聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、聚氨酯膜、乙烯醋酸乙烯酯膜膜、離子聚合物樹脂膜、乙烯-(甲基)丙烯酸共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚醯亞胺膜、氟樹脂膜等。此外，亦可使用其交聯膜。再者，也可以是其積層膜。As the release sheets 12a, 12b, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, and polyvinyl chloride film can be used. Ethylene phthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene-(meth)acrylic acid Copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. In addition, its crosslinked film can also be used. Furthermore, it may be a laminated film.

上述剝離片12a、12b的剝離面(特別是與黏著劑層11接觸的面)，以實施剝離處理為佳。作為剝離處理中所使用的剝離劑，可列舉，例如，醇酸系、矽酮系、氟系、不飽和聚酯系、聚烯烴系、蠟系的剝離劑。且，剝離片12a、12b當中，以一側的剝離片作為剝離力大的重剝離型剝離片，另一側的剝離片作為剝離力小的輕剝離型剝離片為佳。The peeling surfaces of the peeling sheets 12a and 12b (especially the surfaces in contact with the adhesive layer 11) are preferably subjected to a peeling treatment. Examples of the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents. Among the release sheets 12a and 12b, one side of the release sheet is preferably a heavy release type release sheet with a large release force, and the other side release sheet is preferably a light release type release sheet with a small release force.

關於剝離片12a、12b的厚度雖然並無特別限制，但通常為20〜150μm左右。Although the thickness of the release sheets 12a and 12b is not particularly limited, it is usually about 20 to 150 μm.

2.物性(黏著力) 本實施形態相關的黏著片1對鈉鈣玻璃的黏著力，作為下限值，以0.1N/25mm以上為佳，以1N/25mm以上為更佳，特別是以3N/25mm以上為佳，進一步以4.5N/25mm以上為佳。當黏著片1對鈉鈣玻璃的黏著力的下限值為上述時，成為耐久性更佳者。另一方面，關於上述黏著力的上限值，雖然無特別限制，但有時重工性(rework)為必要。由此種觀點而言，上述黏著力，以60N/25mm以下為佳，以30N/25mm以下為更佳，以10N/25mm以下為特別佳。且，在本說明書中的黏著力，基本上是指藉由以JIS Z0237：2009為基準的180度拉剝法所測定的黏著力，具體的試驗方法如下述試驗例中所示。2. Physical properties (adhesion) The lower limit of the adhesive force of the adhesive sheet 1 related to this embodiment to the soda lime glass is preferably 0.1N/25mm or more, more preferably 1N/25mm or more, especially 3N/25mm or more, and further More than 4.5N/25mm is preferred. When the lower limit of the adhesive force of the adhesive sheet 1 to the soda lime glass is the above, the durability is better. On the other hand, although the upper limit of the adhesive force is not particularly limited, rework may be necessary. From this point of view, the above-mentioned adhesive strength is preferably 60N/25mm or less, more preferably 30N/25mm or less, and particularly preferably 10N/25mm or less. In addition, the adhesive force in this specification basically refers to the adhesive force measured by the 180-degree peel method based on JIS Z0237:2009, and the specific test method is shown in the following test examples.

(2) CIE1976L*a*b*表色系 本實施形態相關的黏著片1的黏著劑層11，根據CIE1976L*a*b*表色系所制訂的明度L*，以60以上為佳，以70以上為更佳，特別是以80以上為佳，進一步以90以上為佳。此外，該明度L*以100以下為佳，以99以下為更佳，特別是以98以下為佳。黏著劑層11的色度a*的絕對值，以0以上為佳，特別是以0.1以上為佳，進一步以0.2以上為佳。此外，該色度a*的絕對值，以0.8以下為佳，特別是以0.6以下為佳，進一步以0.4以下為佳。黏著劑層11的色度b*的絕對值，以0以上為佳，特別是以0.1以上為佳，進一步以0.2以上為佳。此外，該色度b*的絕對值，以0.8以下為佳，特別是以0.6以下為佳，進一步以0.4以下為佳。根據上述，黏著劑層11為具有作為反覆彎曲顯示器用合適的色調者。且，在本說明書中的明度L*、色度a*以及b*的測定方法，如下述試驗例中所示。(2) CIE1976L*a*b* color system The lightness L* of the adhesive layer 11 of the adhesive sheet 1 related to this embodiment is formulated according to the CIE1976L*a*b* color system, preferably 60 or more, more preferably 70 or more, especially 80 or more Better, more preferably 90 or more. In addition, the lightness L* is preferably 100 or less, more preferably 99 or less, and particularly preferably 98 or less. The absolute value of the chromaticity a* of the adhesive layer 11 is preferably 0 or more, particularly preferably 0.1 or more, and further preferably 0.2 or more. In addition, the absolute value of the chromaticity a* is preferably 0.8 or less, particularly preferably 0.6 or less, and further preferably 0.4 or less. The absolute value of the chromaticity b* of the adhesive layer 11 is preferably 0 or more, particularly preferably 0.1 or more, and further preferably 0.2 or more. In addition, the absolute value of the chromaticity b* is preferably 0.8 or less, particularly preferably 0.6 or less, and further preferably 0.4 or less. According to the above, the adhesive layer 11 has a suitable hue as a repetitive curved display. In addition, the measurement methods of lightness L*, chromaticity a*, and b* in this specification are as shown in the following test examples.

3.黏著片的製造 作為黏著片1的一製造例，針對使用上述黏著性組合物P的情形進行說明。在一側的剝離片12a(或12b)的剝離面上，塗佈黏著性組合物P的塗佈液，進行加熱處理將黏著性組合物P熱交聯，形成塗佈層後，在此塗佈層疊合另一剝離片12b(或12a)的剝離面。當熟成期間為必要時，藉由經過熟成期間，當熟成期間為不必要時，則依原樣，上述塗佈層成為黏著劑層11。如此一來，可獲得上述黏著片1。關於加熱處理以及熟成的條件如上述。3. Manufacture of Adhesive Sheet As a manufacturing example of the adhesive sheet 1, the case where the said adhesive composition P is used is demonstrated. On the peeling surface of the peeling sheet 12a (or 12b) on one side, apply a coating solution of the adhesive composition P, and perform a heat treatment to thermally crosslink the adhesive composition P to form a coating layer. The cloth is laminated on the peeling surface of the other peeling sheet 12b (or 12a). When the aging period is necessary, by passing the aging period, when the aging period is unnecessary, the above-mentioned coating layer becomes the adhesive layer 11 as it is. In this way, the above-mentioned adhesive sheet 1 can be obtained. The conditions for heat treatment and maturation are as described above.

作為黏著片1的其他製造例，在一側的剝離片12a的剝離面上，塗佈黏著性組合物P的塗佈液，進行加熱處理將黏著性組合物P熱交聯，形成塗佈層，獲得附塗佈層的剝離片12a。此外，在另一剝離片12b的剝離面上，塗佈上述黏著性組合物P的塗佈液，進行加熱處理將黏著性組合物P熱交聯，形成塗佈層，獲得附塗佈層的剝離片12b。然後，將附塗佈層的剝離片12a與附塗佈層的剝離片12b，以兩塗佈層互相接觸的方式貼合。當熟成期間為必要時，藉由經過熟成期間，當熟成期間為不必要時，則依原樣，上述經積層的塗佈層成為黏著劑層11。如此一來，可獲得上述黏著片1。根據此製造例，即使黏著劑層11為比較厚時，仍可穩定地製造。As another example of the production of the adhesive sheet 1, a coating liquid of the adhesive composition P is applied on the release surface of the release sheet 12a on one side, and the adhesive composition P is thermally crosslinked by heat treatment to form a coating layer , A release sheet 12a with a coating layer was obtained. In addition, on the release surface of the other release sheet 12b, the coating liquid of the adhesive composition P is applied, and the adhesive composition P is thermally crosslinked by heat treatment to form a coating layer to obtain a coating layer. The peeling sheet 12b. Then, the peeling sheet 12a with a coating layer and the peeling sheet 12b with a coating layer are bonded together so that the two coating layers may contact each other. When the aging period is necessary, by passing the aging period, when the aging period is unnecessary, the above-mentioned laminated coating layer becomes the adhesive layer 11 as it is. In this way, the above-mentioned adhesive sheet 1 can be obtained. According to this manufacturing example, even when the adhesive layer 11 is relatively thick, it can be manufactured stably.

作為塗佈上述黏著性組合物P的塗佈液的方法，可利用，例如，棒塗佈法、刀式塗佈法、輥塗佈法、翼片塗佈法、模具塗佈法、凹版塗佈法等。As a method of applying the coating liquid of the adhesive composition P, it is possible to use, for example, a bar coating method, a knife coating method, a roll coating method, a flap coating method, a die coating method, and a gravure coating method. Bufa and so on.

[反覆彎曲積層部件] 如圖2所示，本實施形態相關的反覆彎曲積層部件2由具備位在第1彎曲性部件21(一彎曲性部件)與第2彎曲性部件22(其他彎曲性部件)之間，將第1彎曲性部件21以及第2彎曲性部件22彼此貼合的黏著劑層11所構成。[Repetitive bending of laminated parts] As shown in FIG. 2, the repetitive bending laminate member 2 of this embodiment is provided with a first bending member 21 (a bending member) and a second bending member 22 (other bending members). The first flexible member 21 and the second flexible member 22 are composed of an adhesive layer 11 bonded to each other.

上述反覆彎曲積層部件2中的黏著劑層11為上述黏著片1的黏著劑層11。The adhesive layer 11 in the above-mentioned repeatedly curved laminated member 2 is the adhesive layer 11 of the above-mentioned adhesive sheet 1.

反覆彎曲積層部件2為反覆彎曲裝置本身，或是構成反覆彎曲裝置的一部分的部件。反覆彎曲裝置以可反覆彎曲(包含彎折)的顯示器(反覆彎曲顯示器)為佳，但不限於此等。作為相關的反覆彎曲裝置，可列舉，例如，有機電致發光(有機EL)顯示器、電泳方式的顯示器(電子紙)、使用塑膠基板(膜)作為基板的液晶顯示器、可摺式顯示器等，也可以是觸控面板。The repetitive bending laminated member 2 is the repetitive bending device itself, or a component constituting a part of the repetitive bending device. The repetitive bending device is preferably a display capable of repetitive bending (including bending) (repetitive bending display), but is not limited to this. Examples of related repetitive bending devices include, for example, organic electroluminescence (organic EL) displays, electrophoretic displays (electronic paper), liquid crystal displays using a plastic substrate (film) as the substrate, and foldable displays. It can be a touch panel.

第1彎曲性部件21以及第2彎曲性部件22為可反覆彎曲(包含彎折)的部件，可列舉，例如，覆蓋膜、阻氣膜、硬塗層膜、偏光膜(偏光板)、偏光片、相位差膜(相位差板)、視角補償膜、亮度提升膜、對比提升膜、擴散膜、半穿透反射膜、電極膜、透明導電性膜、金屬篩網膜、可撓式玻璃、薄膜感測(觸控感測膜)、液晶高分子膜、發光高分子膜、薄膜狀液晶模組、有機EL模組(有機EL膜、有機EL元件)、電子紙模組(膜狀電子紙)、TFT(Thin Film Transistor)基板等。The first flexible member 21 and the second flexible member 22 are members that can be repeatedly bent (including bending), and examples include cover films, gas barrier films, hard coat films, polarizing films (polarizing plates), and polarizing films. Film, retardation film (phase difference plate), viewing angle compensation film, brightness enhancement film, contrast enhancement film, diffusion film, transflective film, electrode film, transparent conductive film, metal mesh film, flexible glass, thin film Sensing (touch sensing film), liquid crystal polymer film, light-emitting polymer film, thin-film liquid crystal module, organic EL module (organic EL film, organic EL element), electronic paper module (film electronic paper) , TFT (Thin Film Transistor) substrate, etc.

第1彎曲性部件21以及第2彎曲性部件22的至少一者可為聚醯亞胺膜，或在黏著劑層11側具備聚醯亞胺膜的積層體。雖然聚醯亞胺膜通常與黏著劑層的密附性低，但只要依照本實施形態相關的黏著劑層11，即使聚醯亞胺膜為被附著物，仍可獲得優良的耐久性。At least one of the first flexible member 21 and the second flexible member 22 may be a polyimide film, or a laminate having a polyimide film on the adhesive layer 11 side. Although the polyimide film generally has low adhesion to the adhesive layer, as long as the adhesive layer 11 according to this embodiment is used, even if the polyimide film is an adherend, excellent durability can still be obtained.

第1彎曲性部件21以及第2彎曲性部件22的楊氏係數，分別以0.1〜10GPa為佳，特別是以0.5〜7GPa為佳，進一步以1.0〜5GPa為佳。藉由第1彎曲性部件21以及第2彎曲性部件22的楊氏係數於相關範圍中，針對各彎曲性部件，使其變得更容易反覆彎曲。The Young's coefficients of the first flexible member 21 and the second flexible member 22 are each preferably 0.1-10 GPa, particularly preferably 0.5-7 GPa, and further preferably 1.0-5 GPa. With the Young's coefficients of the first flexible member 21 and the second flexible member 22 in the relevant range, it becomes easier to repeatedly bend for each flexible member.

此外，第1彎曲性部件21以及第2彎曲性部件22，在其中心線彎折時，沒有破裂、不可逆的變形的可彎折角度(在彎曲性部件面所形成的銳角側的彎折角度)，分別以150°以下為佳，以90°以下為更佳，以60°以下為特別佳，以30°以下為進一步更佳，以10°以下為最佳。如此一來，更容易獲得下述反覆彎曲裝置。In addition, the first bending member 21 and the second bending member 22 have no breakage or irreversible deformation when their center lines are bent. ), respectively preferably 150° or less, more preferably 90° or less, particularly preferably 60° or less, more preferably 30° or less, and most preferably 10° or less. In this way, it is easier to obtain the following repeated bending device.

第1彎曲性部件21以及第2彎曲性部件22的厚度，分別以10〜3000μm為佳，特別是以25〜1000μm為佳，進一步以50〜500μm為佳。藉由第1彎曲性部件21以及第2彎曲性部件22的厚度於相關範圍內，對於各彎曲性部件，變得更容易使其反覆彎曲。The thickness of the first flexible member 21 and the second flexible member 22 is preferably 10 to 3000 μm, respectively, preferably 25 to 1000 μm, and further preferably 50 to 500 μm. When the thicknesses of the first flexible member 21 and the second flexible member 22 are within the relevant range, it becomes easier to repeatedly bend each flexible member.

製造上述反覆彎曲積層部件2時，作為一例，剝離黏著片1一側的剝離片12a，將黏著片1露出的黏著劑層11貼合於第1彎曲性部件21一側的面。When manufacturing the above-mentioned repetitively curved laminated member 2, as an example, the peeling sheet 12a on the adhesive sheet 1 side is peeled, and the exposed adhesive layer 11 of the adhesive sheet 1 is bonded to the surface on the first flexible member 21 side.

之後，從黏著片1的黏著劑層11將另一側的剝離片12b剝離，黏著片1露出的黏著劑層11與第2彎曲性部件22貼合，獲得反覆彎曲積層部件2。此外，作為其他例，亦可將第1彎曲性部件21以及第2彎曲性部件22的貼合順序替換。After that, the other release sheet 12b is peeled from the adhesive layer 11 of the adhesive sheet 1, and the adhesive layer 11 exposed from the adhesive sheet 1 is bonded to the second flexible member 22 to obtain the repetitively curved laminated member 2. In addition, as another example, the order of bonding the first flexible member 21 and the second flexible member 22 may be replaced.

[反覆彎曲裝置] 本實施形態相關的反覆彎曲裝置為具備上述反覆彎曲積層部件2者，可以是僅由反覆彎曲積層部件2所構成，也可以是由具備一個或複數個反覆彎曲積層部件2與其他彎曲性部件所構成。在將一反覆彎曲部件2與其他反覆彎曲部件積層時，或是反覆彎曲積層部件2與其他彎曲性部件積層時，以透過上述黏著片1的黏著劑層11積層為佳。[Repetitive Bending Device] The repetitive bending device according to this embodiment is provided with the above repetitive bending laminate member 2. It may be composed of only the repetitive bending laminate member 2, or it may be composed of one or more repetitive bending laminate members 2 and other flexible members. constitute. When laminating a repetitive bending part 2 with another recursive bending part, or when laminating a repetitive bending laminate part 2 and another flexible part, it is preferable to laminate the adhesive layer 11 through the adhesive sheet 1.

本實施形態相關的反覆彎曲裝置，由於黏著劑層為由上述黏著劑所構成，在使其反覆彎曲時，或處在長期彎曲狀態時，在彎曲部位的黏著劑層與被附著物間的界面不易發生剝離，且，因彎曲引起的漏光以及辨識性降低受到抑制。In the repetitive bending device related to this embodiment, since the adhesive layer is composed of the above-mentioned adhesive, when it is repeatedly bent or in a long-term bending state, the interface between the adhesive layer and the adherend at the bent portion Peeling is less likely to occur, and light leakage and reduced visibility due to bending are suppressed.

作為本實施形態中一例的反覆彎曲裝置如圖3所示。且，本發明相關的反覆彎曲裝置不限定於該反覆彎曲裝置。The repetitive bending device as an example of this embodiment is shown in FIG. 3. Moreover, the repetitive bending device related to the present invention is not limited to the repetitive bending device.

本實施形態相關的反覆彎曲裝置3，由上方起依序，積層覆蓋膜31、第1黏著劑層32、偏光膜33、第2黏著劑層34、觸控感測膜35、第3黏著劑層36、有機EL元件37、第4黏著劑層38、TFT基板39所構成。上述的覆蓋膜31、偏光膜33、觸控感測膜35、有機EL元件37以及TFT基板39相當於彎曲性部件。The repetitive bending device 3 related to this embodiment has a cover film 31, a first adhesive layer 32, a polarizing film 33, a second adhesive layer 34, a touch sensor film 35, and a third adhesive layer in order from above. The layer 36, the organic EL element 37, the fourth adhesive layer 38, and the TFT substrate 39 are constituted. The cover film 31, the polarizing film 33, the touch sensor film 35, the organic EL element 37, and the TFT substrate 39 mentioned above correspond to a flexible member.

第1黏著劑層32、第2黏著劑層34、第3黏著劑層36以及第4黏著劑層38的至少任1層為上述黏著片1的黏著劑層11。以第1黏著劑層32、第2黏著劑層34、第3黏著劑層36以及第4黏著劑層38的任2層以上為上述黏著片1的黏著劑層11為佳，以全部的黏著劑層32、34、36、38為黏著片1的黏著劑層11為最佳。At least any one of the first adhesive layer 32, the second adhesive layer 34, the third adhesive layer 36, and the fourth adhesive layer 38 is the adhesive layer 11 of the adhesive sheet 1 described above. It is preferable that any two or more of the first adhesive layer 32, the second adhesive layer 34, the third adhesive layer 36, and the fourth adhesive layer 38 are the adhesive layer 11 of the above-mentioned adhesive sheet 1. Preferably, the agent layers 32, 34, 36, and 38 are the adhesive layer 11 of the adhesive sheet 1.

在此，例如，TFT基板39為包含聚醯亞胺膜時，特別是在第4黏著劑層38側具備聚醯亞胺膜時，以至少第4黏著劑層38為上述黏著片1的黏著劑層11為佳。Here, for example, when the TFT substrate 39 includes a polyimide film, especially when a polyimide film is provided on the side of the fourth adhesive layer 38, at least the fourth adhesive layer 38 is used as the adhesive of the above-mentioned adhesive sheet 1. The agent layer 11 is preferred.

以上所說明的實施形態，為用以使本發明的理解變得容易所記載者，並非用以限定本發明而記載者。因此，上述實施形態所揭示的各元件也以包括本發明的技術所屬範圍的全部的設計變更、均等物為主旨。The embodiments described above are described in order to facilitate the understanding of the present invention, and are not described in order to limit the present invention. Therefore, each element disclosed in the above-mentioned embodiment also includes all design changes and equivalents in the technical scope of the present invention.

例如，黏著片1中的剝離片12a、12b的任一者或兩者可被省略，此外，亦可積層想要的彎曲性部件以取代剝離片12a及/或剝離片12b。 [實施例]For example, either or both of the release sheets 12a and 12b in the adhesive sheet 1 may be omitted, and a desired flexible member may be laminated instead of the release sheet 12a and/or the release sheet 12b. [Example]

以下，雖然藉由實施例等進一步具體說明本發明，但本發明的範圍不限於此等實施例等。Hereinafter, although the present invention will be described in further detail with examples and the like, the scope of the present invention is not limited to these examples and the like.

[實施例1] 1.(甲基)丙烯酸酯聚合物(A)的調製 將丙烯酸正丁酯70質量份、丙烯酸甲酯10質量份、丙烯酸2-苯氧乙酯15質量份、丙烯酸二甲基胺基乙酯1質量份以及丙烯酸2-羥乙酯4質量份，藉由溶液聚合法使其共聚合，調製(甲基)丙烯酸酯聚合物(A)。此(甲基)丙烯酸酯聚合物(A)的分子量以下述方法測定後，重量平均分子量(Mw)為150萬。此外，藉由FOX的算式所算出的(甲基)丙烯酸酯聚合物(A)的玻璃轉換溫度(Tg)為-35℃。[Example 1] 1. Preparation of (meth)acrylate polymer (A) 70 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 15 parts by mass of 2-phenoxyethyl acrylate, 1 part by mass of dimethylaminoethyl acrylate, and 4 parts by mass of 2-hydroxyethyl acrylate, It is copolymerized by a solution polymerization method to prepare a (meth)acrylate polymer (A). When the molecular weight of this (meth)acrylate polymer (A) was measured by the following method, the weight average molecular weight (Mw) was 1.5 million. In addition, the glass transition temperature (Tg) of the (meth)acrylate polymer (A) calculated by the formula of FOX was -35°C.

2.黏著性組合物的調製 藉由將在上述步驟1所獲得的(甲基)丙烯酸酯聚合物(A)100質量份(固形分換算值；以下相同)，聚輪烷化合物(B)(ASM Inc.製，製品名「SeRM Super Polymer SH3400P」，直鏈狀分子：聚乙二醇，環狀分子：具有羥丙基及己內酯鏈的α-環糊精，阻斷基：金剛烷基，重量平均分子量(Mw)70萬，羥基值72mgKOH/g)5.0質量份，作為交聯劑(C)的三羥甲基丙烷改質二甲苯二異氰酸酯(xylylene diisocyanate)(綜研化學公司製，製品名「TD-75」)1.5質量份，作為矽烷偶合劑的3-環氧丙基丙基三甲氧矽烷0.17質量份混合，充分攪拌，以丁酮進行稀釋，獲得黏著性組合物的塗佈溶液。2. Preparation of adhesive composition A polyrotaxane compound (B) (manufactured by ASM Inc., product name "100 parts by mass of the (meth)acrylate polymer (A)) obtained in step 1 above (solid content conversion value; the same below) SeRM Super Polymer SH3400P", linear molecule: polyethylene glycol, cyclic molecule: α-cyclodextrin with hydroxypropyl and caprolactone chains, blocking group: adamantyl, weight average molecular weight (Mw) 700,000, hydroxyl value 72mgKOH/g) 5.0 parts by mass, trimethylolpropane as a crosslinking agent (C) modified xylylene diisocyanate (manufactured by Soken Chemical Co., Ltd., product name "TD-75") 1.5 parts by mass and 0.17 parts by mass of 3-epoxypropylpropyltrimethoxysilane as a silane coupling agent were mixed, fully stirred, and diluted with methyl ethyl ketone to obtain a coating solution of the adhesive composition.

3.黏著片的製造 將所得的黏著性組合物的塗佈溶液，在聚對苯二甲酸丁二酯膜的單面，以矽酮系剝離劑進行剝離處理的重剝離型剝離片(Lintec公司製，製品名「SP-PET752150」)的剝離處理面，以刀式塗佈機進行塗佈。然後，對塗佈層，在90℃加熱處理1分鐘，形成塗佈層。3. Manufacture of Adhesive Sheet A heavy peeling type release sheet (manufactured by Lintec, product name "SP -PET752150") is coated with a knife coater. Then, the coating layer was heat-treated at 90°C for 1 minute to form the coating layer.

接著，將上述所得的重剝離型剝離片上的塗佈層，與聚對苯二甲酸乙二酯膜的單面以矽酮系剝離劑進行剝離處理的輕剝離型剝離片(Lintec公司製，製品名「SP-PET381130」)，以該輕剝離型剝離片的剝離處理面接觸塗佈層的方式進行貼合，藉由在23℃，50%RH的條件下，熟成7日，製作具有厚度25μm的黏著劑層的黏著片，換言之，由重剝離型剝離片/黏著劑層(厚度：25μm)/輕剝離型剝離片的構成所形成的黏著片。且，黏著劑層的厚度為依JIS K7130為基準，使用定壓厚度測定器(TECLOCK公司製，製品名「PG-02」)所測定的值。Next, the coating layer on the heavy peelable release sheet obtained above was peeled off with a silicone-based release agent on one side of the polyethylene terephthalate film (product made by Lintec) Name "SP-PET381130"), the light-peelable release sheet is bonded so that the release-treated surface of the light-peelable release sheet is in contact with the coating layer, and is aged for 7 days under the conditions of 23°C and 50%RH to produce a thickness of 25μm The adhesive sheet of the adhesive layer, in other words, is an adhesive sheet formed by the composition of a heavy peeling type release sheet/adhesive layer (thickness: 25 μm)/light peeling type release sheet. In addition, the thickness of the adhesive layer is a value measured using a constant-pressure thickness measuring device (manufactured by TECLOCK, product name "PG-02") based on JIS K7130.

在此，(甲基)丙烯酸酯聚合物(A)當作100質量份(固形分換算值)時的黏著性組合物的各調配(固形分換算值)如表1所示。且，表1中所記載的簡稱等的詳細內容如以下。 [(甲基)丙烯酸酯聚合物(A)] BA：丙烯酸正丁酯 MA：丙烯酸甲酯 PhEA：丙烯酸2-苯氧乙酯 DMAEA：丙烯酸二甲基胺基乙酯 HEA：丙烯酸2-羥乙酯。Here, each formulation (solid content conversion value) of the adhesive composition when the (meth)acrylate polymer (A) is regarded as 100 parts by mass (solid content conversion value) is shown in Table 1. In addition, the details of the abbreviations and the like described in Table 1 are as follows. [(Meth)acrylate polymer (A)] BA: n-butyl acrylate MA: methyl acrylate PhEA: 2-phenoxyethyl acrylate DMAEA: dimethylaminoethyl acrylate HEA: 2-hydroxyethyl acrylate.

[實施例2〜6、比較例1〜2] 除了將構成(甲基)丙烯酸酯聚合物(A)的各單體的種類以及比例，(甲基)丙烯酸酯聚合物(A)的重量平均分子量(Mw)，聚輪烷化合物(B)的調配量，交聯劑(C)的調配量，以及黏著劑層的厚度變更如表1所示以外，其餘與實施例1同樣地製造黏著片。各例中的(甲基)丙烯酸酯聚合物(A)，依照FOX的算式所算出的玻璃轉換溫度(Tg)記載於表1中。[Examples 2 to 6, Comparative Examples 1 to 2] In addition to the types and ratios of the monomers constituting the (meth)acrylate polymer (A), the weight average molecular weight (Mw) of the (meth)acrylate polymer (A), and the ratio of the polyrotaxane compound (B) Except that the compounding amount, the compounding amount of the crosslinking agent (C), and the thickness of the adhesive layer were changed as shown in Table 1, the pressure-sensitive adhesive sheet was produced in the same manner as in Example 1. The (meth)acrylate polymer (A) in each example has a glass transition temperature (Tg) calculated in accordance with the formula of FOX and is described in Table 1.

[試驗例1] (凝膠分率的測定) 將在實施例以及比較例所製作的黏著片，裁切成80mm×80mm的尺寸，此黏著劑層包裹在聚酯製篩網(品名：特多龍網目#200)中，其質量以精密天秤秤量，藉由扣除上述篩網單獨的質量，計算出僅黏著劑的質量。此時的質量作為M1。[Test Example 1] (Measurement of Gel Fraction) The adhesive sheets produced in the examples and comparative examples were cut into a size of 80mm×80mm, and the adhesive layer was wrapped in a polyester mesh (product name: Tetoron mesh #200), and its quality was measured by a precision balance Weighing, by subtracting the mass of the above-mentioned screen alone, calculate the mass of only the adhesive. The mass at this time is referred to as M1.

接著，將包裹在上述聚酯製篩網中的黏著劑，在室溫下(23℃)浸漬於醋酸乙酯中24小時。之後，取出黏著劑，在溫度23℃，相對溼度50%的環境下，使其風乾24小時，進一步在80℃的烤箱中使其乾燥12小時。乾燥後，其質量以精密天秤秤量，藉由扣除上述篩網單獨的質量，計算出僅黏著劑的質量。此時的質量作為M2。凝膠分率(%)以(M2/M1)×100表示。結果如表2所示。Next, the adhesive wrapped in the aforementioned polyester mesh was immersed in ethyl acetate at room temperature (23°C) for 24 hours. After that, the adhesive was taken out and air-dried for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, and further dried in an oven at 80°C for 12 hours. After drying, its mass is measured with a precision balance, and the mass of only the adhesive is calculated by subtracting the mass of the above-mentioned sieve alone. The mass at this time is referred to as M2. Gel fraction (%) is represented by (M2/M1)×100. The results are shown in Table 2.

[試驗例2] (水蒸氣穿透度的測定) 將實施例以及比較例所製作的黏著片的黏著劑層進行積層，成為厚度100μm。針對所得的厚度100μm的上述黏著劑層，以2片特多龍網目#380夾持，在40℃，90%RH的條件，以JIS K7129為準則，使用穿透率測定機(LYSSY公司製，製品名「L80-5000」)，測定水蒸氣穿透度(g/(m2 ．24h))。結果如表2所示。[Test Example 2] (Measurement of Water Vapor Transmittance) The adhesive layers of the adhesive sheets produced in the Examples and Comparative Examples were laminated to have a thickness of 100 μm. For the obtained above-mentioned adhesive layer with a thickness of 100 μm, it was sandwiched by two Tetoron mesh #380, and under the conditions of 40°C and 90% RH, in accordance with JIS K7129 as a guideline, a penetration rate measuring machine (manufactured by LYSSY, Inc., The product name is "L80-5000"), and the water vapor transmission rate (g/(m 2 ．24h)) is measured. The results are shown in Table 2.

[試驗例3] (儲存模數G’的測定) 將實施例以及比較例所製作的黏著片的黏著劑層積層複數層，成為厚度3mm的積層體。從所得的黏著劑層的積層體，打穿直徑8mm的圓柱體(高度3mm)，將此當作樣品。[Test Example 3] (Measurement of storage modulus G') The adhesives of the adhesive sheets produced in the examples and comparative examples were laminated in plural layers to form a laminate with a thickness of 3 mm. From the obtained laminate of adhesive layers, a cylinder having a diameter of 8 mm (height 3 mm) was punched, and this was used as a sample.

針對上述樣品，以JIS K7244-1為基準，使用黏彈性測定裝置(Anton paar社製，製品名稱「MCR302」)藉由扭轉剪力法(torsional shear)，在以下的條件測定儲存模數G’，取得在23℃時的儲存模數G’(23)以及在85℃時的儲存模數G’(85)(MPa)。結果如表2所示。 測定頻率：1Hz 測定溫度：-20℃〜150℃Regarding the above samples, in accordance with JIS K7244-1, a viscoelasticity measuring device (manufactured by Anton Paar, product name "MCR302") was used to measure the storage modulus G'by torsional shear under the following conditions , Get the storage modulus G'(23) at 23℃ and the storage modulus G'(85)(MPa) at 85℃. The results are shown in Table 2. Measurement frequency: 1Hz Measuring temperature: -20℃～150℃

[試驗例4] (霧度值的測定) 將實施例以及比較例所製作的黏著片的黏著劑層貼合於玻璃，將此當作測定用樣品。以玻璃進行背景測定後，針對上述測定用樣品，以JIS K7136：2000為基準，使用霧度計(日本電色工業公司製，製品名「NDH-5000」)，測定在23℃的霧度值(全光線霧度值；%)。結果如表2所示。[Test Example 4] (Measurement of Haze Value) The adhesive layer of the adhesive sheet produced in the Example and the comparative example was bonded to glass, and this was used as a sample for measurement. After background measurement with glass, the above-mentioned sample for measurement was measured with a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH-5000") based on JIS K7136:2000 for the above-mentioned sample for measurement, and the haze value at 23°C was measured (Full light haze value; %). The results are shown in Table 2.

此外，將上述測定用樣品置於-40℃的環境下240小時後，在23℃，50%RH的環境下靜置1小時。然後，與上述同樣地測定霧度值(在-40℃的霧度值；%)。結果如表2所示。In addition, after the above-mentioned sample for measurement was placed in an environment of -40°C for 240 hours, it was allowed to stand for 1 hour in an environment of 23°C and 50% RH. Then, the haze value (haze value at -40°C; %) was measured in the same manner as described above. The results are shown in Table 2.

[試驗例5] (全光線穿透率的測定) 將實施例以及比較例所製作的黏著片的黏著劑層貼合於玻璃，將此當作測定用樣品。以玻璃進行背景測定後，針對上述測定用樣品，以JIS K7361-1：1997為基準，使用霧度計(日本電色工業公司製，製品名「SH-7000」)，測定在23℃的全光線穿透率(%)。結果如表2所示。[Test Example 5] (Measurement of total light transmittance) The adhesive layer of the adhesive sheet produced in the Example and the comparative example was bonded to glass, and this was used as a sample for measurement. After background measurement with glass, the above-mentioned sample for measurement was measured at 23°C using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SH-7000") based on JIS K7361-1:1997. Light transmittance (%). The results are shown in Table 2.

此外，將上述測定用樣品放置在-40℃的環境下240小時後，靜置在23℃，50%RH的環境下1小時。然後，與上述同樣地測定全光線穿透率(在-40℃的全光線穿透率；%)。結果如表2所示。In addition, after the above-mentioned sample for measurement was left in an environment of -40°C for 240 hours, it was left to stand in an environment of 23°C and 50% RH for 1 hour. Then, the total light transmittance (total light transmittance at -40°C; %) was measured in the same manner as described above. The results are shown in Table 2.

[試驗例6] (L*a*b*的測定) 針對實施例以及比較例所製作的黏著片的黏著劑層，使用同時測光分光式色度計(日本電色工業公司製，製品名「SQ2000」)，測定依CIE1976L*a*b*表色系所制定的明度L*、色度a*以及色度b*。結果如表2所示。[Test Example 6] (Measurement of L*a*b*) For the adhesive layer of the adhesive sheets produced in the examples and comparative examples, a simultaneous photometric spectrophotometer (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SQ2000") was used to measure the color system according to CIE1976L*a*b* The established lightness L*, chromaticity a* and chromaticity b*. The results are shown in Table 2.

[試驗例7] (黏著力的測定) 從實施例以及比較例所製作的黏著片將輕剝離型剝離片剝離，將露出的黏著劑層貼合在具有易接著層的聚對苯二甲酸乙二酯(PET)膜(東洋紡公司製，製品名稱「PET A4300」，厚度：100μm)的易接著層，獲得重剝離型剝離片/黏著劑層/PET膜的積層體。所得的積層體裁斷成25mm寬，110mm長。[Test Example 7] (Measurement of Adhesion) The light-peelable release sheet was peeled off from the adhesive sheets produced in the examples and comparative examples, and the exposed adhesive layer was bonded to a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., Product name "PET A4300", thickness: 100μm) easy-to-adhesive layer to obtain a laminate of heavy-peelable release sheet/adhesive layer/PET film. The resulting laminate was cut to 25 mm wide and 110 mm long.

在23℃，50%RH的環境下，從上述積層體將重剝離型剝離片剝離，將露出的黏著劑層貼附在鈉鈣玻璃板(日本板硝子公司製，製品名「鈉鈣玻璃」，厚度：1.1mm)，於栗原製作所公司製的高壓釜，在0.5MPa，50℃，加壓20分鐘。之後，在23℃，50%RH的條件下，放置24小時之後，使用拉伸測試機(ORIENTEC CORPORATION製TENSILON)，在剝離速度300mm/min，剝離角度180度的條件，測定將PET膜與黏著劑層的積層體從被附著物進行剝離時的黏著力(N/25mm)。此處記載以外的條件以JIS Z0237：2009為基準，進行測定。結果如表2所示。In an environment of 23°C and 50% RH, the heavy-peelable release sheet is peeled from the laminate, and the exposed adhesive layer is attached to a soda lime glass plate (manufactured by Nippon Sheet Glass Co., Ltd., product name "soda lime glass", Thickness: 1.1 mm), pressurized in an autoclave manufactured by Kurihara Manufacturing Co., Ltd. at 0.5 MPa, 50°C, for 20 minutes. After that, after leaving for 24 hours under the conditions of 23°C and 50%RH, using a tensile tester (TENSILON manufactured by ORIENTEC CORPORATION), at a peeling speed of 300 mm/min and a peeling angle of 180 degrees, the PET film and the adhesion were measured. Adhesion (N/25mm) when the layered body of the agent layer is peeled from the adherend. Conditions other than those described here are measured based on JIS Z0237:2009. The results are shown in Table 2.

[試驗例8] (靜態耐久性的評價) 在23℃，50%RH的環境下，從實施例以及比較例所製作的黏著片將輕剝離型剝離片進行剝離，將露出的黏著劑層貼合在聚醯亞胺(PI)膜(DUPONT-TORAY CO., LTD.製，製品名「KAPTON 100PI」，厚度：25μm，楊氏係數：3.4GPa)一側的面上。接著，將重剝離型剝離片剝離，露出的黏著劑層貼合於同PI膜上。然後，於栗原製作所公司製的高壓釜，在0.5MPa，50℃，加壓20分鐘後，在23℃，50%RH的條件下，放置24小時。將如此所獲得的由PI膜/黏著劑層/PI膜所形成積層體，裁斷成50mm寬，200mm長，將此當作樣品。[Test Example 8] (Evaluation of Static Durability) In an environment of 23°C and 50% RH, the lightly peelable release sheet was peeled from the adhesive sheets produced in the examples and comparative examples, and the exposed adhesive layer was attached to a polyimide (PI) film (DUPONT -Manufactured by TORAY CO., LTD., product name "KAPTON 100PI", thickness: 25μm, Young's coefficient: 3.4GPa) on one side. Next, the heavy-peelable release sheet was peeled off, and the exposed adhesive layer was attached to the same PI film. Then, the autoclave manufactured by Kurihara Manufacturing Co., Ltd. was pressurized at 0.5 MPa, 50° C., and pressurized for 20 minutes, and then left under the conditions of 23° C. and 50% RH for 24 hours. The thus-obtained laminate formed of PI film/adhesive layer/PI film was cut to a width of 50 mm and a length of 200 mm, and this was used as a sample.

所得的樣品，在85℃的環境下，如圖4所示，在由站立設置的2片玻璃板而成的維持板(相互間距離：3mm)之間，在被彎曲狀態維持24小時。進行此靜態彎曲試驗後，在試驗片的彎曲部位上的黏著劑層與被附著物間的界面是否有剝離，以目視確認。且，各例針對10個樣品進行評價。結果如表3所示。 ◎：10樣品全部無剝離 ○：9〜5樣品中無剝離 △：4〜2樣品中無剝離 ×：9樣品以上有剝離The obtained sample was maintained in a bent state for 24 hours between two holding plates (distance between each other: 3 mm) made of two glass plates set up standing under an environment of 85°C, as shown in Fig. 4. After performing this static bending test, visually confirm whether there is peeling at the interface between the adhesive layer and the adherend on the bent portion of the test piece. In addition, each case was evaluated for 10 samples. The results are shown in Table 3. ◎: All 10 samples have no peeling ○: No peeling in 9~5 samples △: No peeling in 4~2 samples ×: 9 samples or more have peeling

[試驗例9] (動態耐久性的評價) 將與試驗例8同樣所獲得的由PI膜/黏著劑層/PI膜所形成的積層體，裁斷成150mm×50mm，將此當作試驗片。所得的試驗片的兩端部，如圖5所示，固定在面狀態無負荷U字伸縮測試機(Yuasa System Co., Ltd.製，製品名「DLDMLH-FS」)的2個維持板上。然後，在85℃，50%RH的環境下，以彎曲徑3mmϕ，衝程80mm，彎曲速度30rpm，使試驗片彎曲3萬次。[Test Example 9] (Evaluation of Dynamic Durability) The laminated body formed of PI film/adhesive layer/PI film obtained in the same manner as in Test Example 8 was cut into a size of 150 mm×50 mm, and this was used as a test piece. The two ends of the obtained test piece, as shown in Fig. 5, were fixed on the two maintenance plates of a surface state no-load U-shaped stretch tester (manufactured by Yuasa System Co., Ltd., product name "DLDMLH-FS") . Then, under an environment of 85°C and 50%RH, the test piece was bent 30,000 times with a bending diameter of 3mmϕ, a stroke of 80mm, and a bending speed of 30rpm.

進行上述動態彎曲試驗後，在試驗片的彎曲部位的黏著劑層與被附著物的界面是否有剝離，以目視確認。且，各例針對10個樣品進行評價。結果如表3所示。 ◎：10樣品全部無剝離 ○：9〜5樣品中無剝離 △：4〜2樣品中無剝離 ×：9樣品以上有剝離After performing the above-mentioned dynamic bending test, visually confirm whether there is peeling at the interface between the adhesive layer and the adherend at the bent portion of the test piece. In addition, each case was evaluated for 10 samples. The results are shown in Table 3. ◎: All 10 samples have no peeling ○: No peeling in 9~5 samples △: No peeling in 4~2 samples ×: 9 samples or more have peeling

[試驗例10] (耐濕熱白化性的評價) 將實施例以及比較例所製作的黏著片的黏著劑層，以厚度1.1mm的無鹼玻璃板(水蒸氣穿透度0.0006g/(m2 ．24h))與厚度0.7mm的塑膠板(MITSUBISHI RAYON CO.,LTD.製，製品名「Acrylite MR-200」，水蒸氣穿透度44g/(m2 ．24h．100μm))夾持，將此當作樣品。所得的樣品在50℃，0.5MPa的條件下，20分鐘高壓釜處理後，在常壓，23℃，50%RH，放置24小時。[Test Example 10] (Evaluation of Resistance to Moisture and Heat Whitening) The adhesive layer of the adhesive sheet produced in the Examples and Comparative Examples was made of an alkali-free glass plate with a thickness of 1.1 mm (water vapor permeability 0.0006 g/(m 2) ．24h)) and a 0.7mm thick plastic plate (manufactured by MITSUBISHI RAYON CO., LTD., product name "Acrylite MR-200", water vapor permeability 44g/(m 2 ．24h．100μm))), and This serves as a sample. The obtained sample was treated in an autoclave at 50°C and 0.5MPa for 20 minutes, and then placed under normal pressure, 23°C and 50%RH for 24 hours.

針對上述樣品，以JIS K7136：2000為基準，使用霧度計(日本電色工業社製，製品名「NDH-5000」)，測定霧度值(耐久試驗前的霧度值；%)。For the above-mentioned sample, a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH-5000") was used to measure the haze value (haze value before endurance test; %) based on JIS K7136: 2000.

接著，將上述樣品在85℃，85%RH的濕熱條件下，保管1000小時(耐久試驗)，之後，在23℃，50%RH的常溫常濕，放置24小時。針對該樣品，與上述同樣地測定霧度值(耐久試驗後的霧度值；%)。Next, the above-mentioned sample was stored for 1000 hours under damp heat conditions of 85° C. and 85% RH (endurance test), and thereafter, it was left for 24 hours at 23° C. and 50% RH at normal temperature and humidity. For this sample, the haze value (haze value after the endurance test; %) was measured in the same manner as described above.

根據所測定的在耐久試驗前後的霧度值的差，依以下的基準，評價耐濕熱白化性。 ◎：霧度值的差值未達1.5。 ○：霧度值的差值為1.5以上，未達8.0。 ×：霧度值的差值為8.0以上。Based on the measured difference in haze value before and after the endurance test, the humidity and heat whitening resistance was evaluated based on the following criteria. ◎: The difference in haze value is less than 1.5. ○: The difference in the haze value is 1.5 or more and less than 8.0. ×: The difference in haze value is 8.0 or more.

[表1]   (甲基)丙烯酸酯聚合物(Ａ) 聚輪烷 化合物(Ｂ) 交聯劑 (Ｃ) 矽烷 偶合劑 黏著劑層 的厚度 組成 Tg Mw BA MA PhEA DMAEA HEA ℃ 萬 質量份 質量份 質量份 μｍ 實施例1 70 10 15 1 4 -35 150 5.0 1.5 0.17 25 實施例2 70 10 15 1 4 -35 150 7.5 1.5 0.17 25 實施例3 70 10 15 1 4 -35 150 10 1.5 0.17 25 實施例4 70 10 15 1 4 -35 150 15 2.0 0.17 25 實施例5 70 10 15 1 4 -35 150 15 2.0 0.17 50 實施例6 70 10 15 1 4 -35 200 10 2.0 0.17 25 比較例1 70 10 15 1 4 -35 150 － 0.5 0.17 25 比較例2 70 10 15 1 4 -35 150 50 2.5 0.17 25 [Table 1] (Meth)acrylate polymer (A) Polyrotaxane compound (B) Crosslinking agent (C) Silane coupling agent Adhesive layer thickness composition Tg Mw BA MA PhEA DMAEA HEA °C ten thousand Mass parts Mass parts Mass parts μm Example 1 70 10 15 1 4 -35 150 5.0 1.5 0.17 25 Example 2 70 10 15 1 4 -35 150 7.5 1.5 0.17 25 Example 3 70 10 15 1 4 -35 150 10 1.5 0.17 25 Example 4 70 10 15 1 4 -35 150 15 2.0 0.17 25 Example 5 70 10 15 1 4 -35 150 15 2.0 0.17 50 Example 6 70 10 15 1 4 -35 200 10 2.0 0.17 25 Comparative example 1 70 10 15 1 4 -35 150 - 0.5 0.17 25 Comparative example 2 70 10 15 1 4 -35 150 50 2.5 0.17 25

[表2] 凝膠分率 儲存模數 (MPa) 水蒸氣穿透度 霧度值(％) 全光線穿透率 (％) 表色系 黏著力 ％ G’(23) G’(85) g/(m2 ．24h) 23℃ -40℃ 23℃ -40℃ L* a* b* N/25mm 實施例1 45 0.08 0.05 180 0.6 0.6 ≧99 ≧99 96.8 -0.3 0.2 5.5 實施例2 45 0.08 0.05 195 0.7 0.7 ≧99 ≧99 96.8 -0.2 0.2 7.1 實施例3 40 0.07 0.05 198 0.6 0.7 ≧99 ≧99 96.7 -0.3 0.2 4.8 實施例4 45 0.08 0.05 205 0.7 0.7 ≧99 ≧99 96.8 -0.3 0.1 3.8 實施例5 45 0.08 0.05 205 0.6 0.8 ≧99 ≧99 96.8 -0.3 0.1 6.2 實施例6 54 0.10 0.07 201 0.7 0.9 ≧99 ≧99 96.7 -0.3 0.2 3.2 比較例1 62 0.09 0.05 140 0.5 0.5 ≧99 ≧99 96.7 -0.3 0.2 6.8 比較例2 12 0.06 0.01 182 5.5 8.8 ≧99 ≧99 96.8 0.0 0.6 1.2 [Table 2] Gel fraction Storage modulus (MPa) Water vapor penetration Haze value (%) Total light transmittance (%) Color system Adhesion % G'(23) G'(85) g/(m 2 ．24h) 23℃ -40°C 23℃ -40°C L* a* b* N/25mm Example 1 45 0.08 0.05 180 0.6 0.6 ≧99 ≧99 96.8 -0.3 0.2 5.5 Example 2 45 0.08 0.05 195 0.7 0.7 ≧99 ≧99 96.8 -0.2 0.2 7.1 Example 3 40 0.07 0.05 198 0.6 0.7 ≧99 ≧99 96.7 -0.3 0.2 4.8 Example 4 45 0.08 0.05 205 0.7 0.7 ≧99 ≧99 96.8 -0.3 0.1 3.8 Example 5 45 0.08 0.05 205 0.6 0.8 ≧99 ≧99 96.8 -0.3 0.1 6.2 Example 6 54 0.10 0.07 201 0.7 0.9 ≧99 ≧99 96.7 -0.3 0.2 3.2 Comparative example 1 62 0.09 0.05 140 0.5 0.5 ≧99 ≧99 96.7 -0.3 0.2 6.8 Comparative example 2 12 0.06 0.01 182 5.5 8.8 ≧99 ≧99 96.8 0.0 0.6 1.2

[表3] 靜態耐久性 動態耐久性 耐濕熱白化性 實施例1 ◎ ◎ ○ 實施例2 ◎ ◎ ◎ 實施例3 ◎ ◎ ◎ 實施例4 ○ ◎ ◎ 實施例5 ○ ◎ ◎ 實施例6 △ △ ○ 比較例1 △ △ × 比較例2 × × ○ [table 3] Static durability Dynamic durability Resistance to damp and heat whitening Example 1 ◎ ◎ ○ Example 2 ◎ ◎ ◎ Example 3 ◎ ◎ ◎ Example 4 ○ ◎ ◎ Example 5 ○ ◎ ◎ Example 6 △ △ ○ Comparative example 1 △ △ X Comparative example 2 X X ○

由表3可清楚得知，實施例的黏著片的黏著劑層，在貼合2個彎曲性部件處於長時間彎曲狀態時，以及使其反覆彎曲時，在黏著劑層與彎曲性部件的界面未發生剝離，為耐久性良好者。此外，實施例的黏著片的黏著劑層，為耐濕熱白化性亦良好者。 [產業可利用性]It can be clearly seen from Table 3 that the adhesive layer of the adhesive sheet of the embodiment is at the interface between the adhesive layer and the flexible member when the two flexible members are bonded for a long time and when they are bent repeatedly. No peeling occurred, and it was the one with good durability. In addition, the adhesive layer of the adhesive sheet of the example is one having good resistance to damp and heat whitening. [Industry Availability]

本發明為適合將構成反覆彎曲裝置之一彎曲性部件與其他彎曲性部件貼合者。The present invention is suitable for bonding a flexible member that constitutes a repetitive bending device to another flexible member.

1:黏著片 11:黏著劑層 12a,12b:剝離片 2:反覆彎曲積層部件 21:第1彎曲性部件 22:第2彎曲性部件 3:反覆彎曲裝置 31:覆蓋膜 32:第1黏著劑層 33:偏光膜 34:第2黏著劑層 35:觸控感測膜 36:第3黏著劑層 37:有機EL元件 38:第4黏著劑層 39:TFT基板 S:試驗片 P:維持板1: Adhesive sheet 11: Adhesive layer 12a, 12b: peeling sheet 2: Repeated bending of laminated parts 21: The first flexible part 22: The second flexible part 3: Repeated bending device 31: Cover film 32: The first adhesive layer 33: Polarizing film 34: The second adhesive layer 35: Touch sensor film 36: The third adhesive layer 37: Organic EL element 38: The fourth adhesive layer 39: TFT substrate S: Test piece P: Maintain the board

[圖1] 為本發明一實施形態相關的黏著片的剖面圖。 [圖2] 為本發明一實施形態相關的反覆彎曲積層部件的剖面圖。 [圖3] 為本發明一實施形態相關的反覆彎曲裝置的剖面圖。 [圖4] 為說明靜態彎曲試驗的解說圖(側視圖)。 [圖5] 為說明動態彎曲試驗的解說圖(側視圖)。[Fig. 1] is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention. [Fig. 2] is a cross-sectional view of a repetitively bent laminated member according to an embodiment of the present invention. [Fig. 3] is a cross-sectional view of a repetitive bending device according to an embodiment of the present invention. [Figure 4] An explanatory diagram (side view) for explaining the static bending test. [Figure 5] An explanatory diagram (side view) for explaining the dynamic bending test.

1:黏著片 1: Adhesive sheet

11:黏著劑層 11: Adhesive layer

12a,12b:剝離片 12a, 12b: peeling sheet

Claims (9)

一種黏著片，為具有用以將構成反覆彎曲的裝置之一的彎曲性部件與其他彎曲性部件貼合的黏著劑層的黏著片， 針對上述黏著劑層為厚度100μm者，以2片特多龍(Tetoron)網目#380夾持，在40℃，90%RH的條件，根據JIS K7129所測定的水蒸氣穿透度為150g/(m2 ．24h)以上， 構成上述黏著劑層的黏著劑在85℃的儲存模數G’(85)為0.02MPa以上，0.2MPa以下。An adhesive sheet is an adhesive sheet having an adhesive layer for bonding a flexible member that constitutes one of the devices for repetitive bending with other flexible members. For the above-mentioned adhesive layer with a thickness of 100 μm, there are 2 sheets. Tetoron mesh #380 is clamped at 40°C and 90%RH, and the water vapor permeability measured in accordance with JIS K7129 is 150g/(m 2 .24h) or more. The adhesive constituting the above-mentioned adhesive layer The storage modulus G'(85) at 85°C is above 0.02MPa and below 0.2MPa. 如請求項1之黏著片，其中，構成上述黏著劑層的黏著劑的凝膠分率為10%以上，90%以下。The adhesive sheet of claim 1, wherein the gel fraction of the adhesive constituting the adhesive layer is 10% or more and 90% or less. 如請求項1之黏著片，其中，上述黏著劑層在23℃的霧度值為10%以下。Such as the adhesive sheet of claim 1, wherein the haze value of the adhesive layer at 23° C. is 10% or less. 如請求項1之黏著片，其中，構成上述黏著劑層的黏著劑在23℃的儲存模數G’(23)為0.02MPa以上，0.3MPa以下。The adhesive sheet of claim 1, wherein the storage modulus G'(23) of the adhesive constituting the adhesive layer at 23°C is 0.02 MPa or more and 0.3 MPa or less. 如請求項1之黏著片，其中，構成上述黏著劑層的黏著劑含有聚輪烷(polyrotaxane)化合物。The adhesive sheet of claim 1, wherein the adhesive constituting the adhesive layer contains a polyrotaxane compound. 如請求項1之黏著片，其中，構成上述黏著劑層的黏著劑為丙烯酸系黏著劑。The adhesive sheet of claim 1, wherein the adhesive constituting the adhesive layer is an acrylic adhesive. 如請求項1之黏著片，其中，上述黏著片具備2片剝離片， 上述黏著劑層以與上述2片剝離片的剝離面接觸的方式，夾持於上述剝離片之間。Such as the adhesive sheet of claim 1, wherein the adhesive sheet includes two release sheets, The adhesive layer is sandwiched between the peeling sheets so as to be in contact with the peeling surfaces of the two peeling sheets. 一種反覆彎曲積層部件，為具備： 構成反覆彎曲的裝置的一彎曲性部件及其他彎曲性部件，以及 將上述一彎曲性部件與上述其他彎曲性部件彼此貼合的黏著劑層的反覆彎曲積層部件， 上述黏著劑層為由請求項1〜7中任一項之黏著片的黏著劑層所構成。A repetitive bending laminated component, which has: A flexible part and other flexible parts that constitute the device for repeated bending, and A repetitively curved laminated member of an adhesive layer in which the above-mentioned flexible member and the above-mentioned other flexible member are bonded to each other, The above-mentioned adhesive layer is composed of the adhesive layer of the adhesive sheet of any one of claims 1-7. 一種反覆彎曲裝置，具備：請求項8之反覆彎曲積層部件。A repetitive bending device comprising: the repetitive bending laminated member of claim 8.
TW109143017A 2020-01-27 2020-12-07 Adhesive sheet, repeatedly bending laminated component and repeatedly bending device to provide an adhesive sheet having excellent durability against bending TW202130759A (en)

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