TW202113005A - Adhesive sheet, repeatedly bend laminated member and repeatedly bend device in which peeling is unlikely to occur at an interface between an adhesive layer and an object to be attached at a bent portion, and light leakage and deterioration of visibility caused by bending are suppressed - Google Patents

Adhesive sheet, repeatedly bend laminated member and repeatedly bend device in which peeling is unlikely to occur at an interface between an adhesive layer and an object to be attached at a bent portion, and light leakage and deterioration of visibility caused by bending are suppressed Download PDF

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TW202113005A
TW202113005A TW109123699A TW109123699A TW202113005A TW 202113005 A TW202113005 A TW 202113005A TW 109123699 A TW109123699 A TW 109123699A TW 109123699 A TW109123699 A TW 109123699A TW 202113005 A TW202113005 A TW 202113005A
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adhesive
adhesive layer
meth
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acrylate
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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J7/30—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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

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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)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Liquid Crystal (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provides an adhesive sheet, a repeatedly bend laminated member and a repeatedly bend device, in which peeling is unlikely to occur at an interface between an adhesive layer and an object to be attached at a bent portion, and light leakage and deterioration of visibility caused by bending are suppressed. The adhesive sheet 1 has an adhesive layer 11 for bonding one flexible member and another flexible member constituting the repeatedly bend device. The storage elastic modulus G'(-20) of the adhesive that constitutes the adhesive layer 11 at -20 DEG C is 0.01 MPa or more and 0.2 MPa or less, and the absolute value of photo elastic modulus of the adhesive that constitutes the adhesive layer 11 at -23 DEG C and a measurement wavelength of 400 nm is 9.9×10<SP>-10</SP> m2 N or less.

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 present invention relates to an adhesive sheet for a device that is repeatedly bent, and a layered component that is repeatedly bent and a device that is repeatedly bent.

近年來，作為裝置之一的電子儀器的顯示體(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，除了僅1次曲面成形者之外，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 display body (display) of an electronic device, which is one of the devices, a bendable display has been proposed. As a flexible display, in addition to only one-time curved surface forming, a repetitive bending display for repetitive bending (bending) is proposed.

在如上述的反覆彎曲顯示器中，構成該彎曲性顯示器的一可彎曲的部件(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過去的黏著片時，會有所謂在彎曲部位的黏著劑層與被附著物間的界面發生剝離的問題產生。In the repetitively curved display as described above, a bendable member (flexible member) constituting the flexible display is bonded to other flexible members by the adhesive layer of the adhesive sheet. However, when the past adhesive sheet is used in a repeatedly curved display, there is a problem of so-called peeling at the interface between the adhesive layer and the adherend at the curved portion.

專利文獻1揭示一種黏著劑，以抑制在反覆彎曲時剝離的發生為目的。 [先前技術文獻] [專利文獻]Patent Document 1 discloses an adhesive whose purpose is to suppress the occurrence of peeling during repeated bending. [Prior Technical Literature] [Patent Literature]

專利文獻1：日本特開2016-108555號公報Patent Document 1: Japanese Patent Application Laid-Open No. 2016-108555

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

另一方面，在如上述的反覆彎曲顯示器中，在彎曲時、彎曲後，會有在彎曲部位的周圍發生漏光，可視性降低下等情況。專利文獻1中所記載的黏著劑，無法充分解決相關漏光、可視性降低的問題。On the other hand, in the repeatedly curved display as described above, light leakage may occur around the curved portion during or after the curved portion, and the visibility may decrease. The adhesive described in Patent Document 1 cannot sufficiently solve the problems related to light leakage and reduced visibility.

本發明為鑑於上述情況而完成者，其目的為提供一種黏著片、反覆彎曲積層部件以及反覆彎曲裝置，其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可視性降低受到抑制。 [解決問題的手段]The present invention was completed in view of the above circumstances, and its object is to provide an adhesive sheet, a recursive bending laminate member, and a recursive bending device, which is not prone to peeling off at the interface between the adhesive layer and the adherend at the bending portion, and is caused by bending. The resulting light leakage and reduced visibility are suppressed. [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：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，上述構成黏著劑層的黏著劑在-20℃的儲存模數G’(-20)為0.01MPa以上，0.2MPa以下，上述構成黏著劑層的黏著劑在23℃，測定波長400nm時的光彈性係數的絕對值為9.9×10-10 m2 /N以下(發明1)。In order to achieve the above-mentioned object, first, 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 the above-mentioned constitutes the adhesive The storage modulus G'(-20) of the adhesive of the layer at -20°C is 0.01MPa or more and 0.2MPa or less. The adhesive that constitutes the adhesive layer is at 23°C, and the absolute value of the photoelastic coefficient at a wavelength of 400nm is measured It is 9.9×10 -10 m 2 /N or less (Invention 1).

在上述發明(發明1)中，構成黏著劑層的黏著劑藉由具有上述物性，使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反覆彎曲時，或處於長期彎曲狀態的情形時，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(在彎曲後)漏光以及可視性降低受到抑制。In the above invention (Invention 1), when the adhesive constituting the adhesive layer has the above physical properties, when a laminate formed by bonding a flexible member and another flexible member through the adhesive layer is repeatedly bent, Or in the case of a long-term bending state, peeling at the interface between the adhesive layer and the adherend at the bent portion is unlikely to occur, and light leakage and visibility reduction due to bending (after bending) are suppressed.

在上述發明(發明1)中，上述構成黏著劑層的黏著劑在23℃，測定波長500nm時的光彈性係數的絕對值以9.9×10-10 m2 /N以下為佳(發明2)。In the above invention (Invention 1), it is preferable that the absolute value of the photoelastic coefficient of the adhesive constituting the adhesive layer at 23°C and a wavelength of 500 nm is 9.9×10 -10 m 2 /N or less (Invention 2).

在上述發明(發明1、2)中，上述構成黏著劑層的黏著劑在23℃，測定波長600nm時的光彈性係數的絕對值以9.9×10-10 m2 /N以下為佳(發明3)。In the above inventions (Inventions 1 and 2), the absolute value of the photoelastic coefficient of the above-mentioned adhesive constituting the adhesive layer at a wavelength of 600nm measured at 23°C is preferably 9.9×10 -10 m 2 /N or less (Invention 3 ).

在上述發明(發明1〜3)中，上述構成黏著劑層的黏著劑在85℃的儲存模數G’(85)以0.005MPa以上，0.2MPa以下為佳(發明4)。In the above inventions (Inventions 1 to 3), the storage modulus G'(85) at 85°C of the adhesive constituting the adhesive layer is preferably 0.005 MPa or more and 0.2 MPa or less (Invention 4).

在上述發明(發明1〜4)中，上述構成黏著劑層的黏著劑在25℃的儲存模數G’(25)以0.01MPa以上，0.2MPa以下為佳(發明5)。In the above inventions (Inventions 1 to 4), the storage modulus G'(25) at 25°C of the adhesive constituting the adhesive layer is preferably 0.01 MPa or more and 0.2 MPa or less (Invention 5).

在上述發明(發明1〜5)中，上述構成黏著劑層的黏著劑的凝膠分率以30%以上，95%以下為佳(發明6)。In the above inventions (Inventions 1 to 5), the gel fraction of the adhesive constituting the adhesive layer is preferably 30% or more, and 95% or less (Invention 6).

在上述發明(發明1〜6)中，上述構成黏著劑層的黏著劑以丙烯酸系黏著劑為佳(發明7)。In the above inventions (Inventions 1 to 6), the adhesive constituting the adhesive layer is preferably an acrylic adhesive (Invention 7).

在上述發明(發明1〜7)中，上述黏著片具備2片的剝離片，上述黏著劑層以與上述2片剝離片的剝離面接觸的方式，挾持於上述剝離片為佳(發明8)。In the above invention (Inventions 1 to 7), the adhesive sheet includes two release sheets, and the adhesive layer is preferably sandwiched by the release sheet so as to be in contact with the release surfaces of the two release sheets (Invention 8) .

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，上述黏著劑層為由上述黏著片(發明1〜8)的黏著劑層所形成(發明9)。Secondly, the present invention provides a repetitive bending laminated member, comprising: a flexible member and other flexible members constituting a repetitive bending device, and an adhesive for bonding the above-mentioned one flexible member and the above-mentioned other flexible member to each other The layer is an overly curved laminated member, and the above-mentioned adhesive layer is formed by the above-mentioned adhesive layer of the above-mentioned adhesive sheet (Inventions 1 to 8) (Invention 9).

第三，本發明提供一種反覆彎曲裝置，為具備上述反覆彎曲積層部件(發明9)(發明10) [發明的效果]Thirdly, the present invention provides a repetitive bending device including the above repetitive bending laminated member (Invention 9) (Invention 10) [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，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可視性降低受到抑制。In the adhesive sheet, the recursive bending laminate component, and the recursive bending device of the present invention, the interface between the adhesive layer and the adherend at the bent portion is not easily peeled off, and the light leakage caused by the bending and the decrease in visibility are suppressed.

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，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 with other flexible members, preferably consisting of a single side or double side of the adhesive layer The area layer is made by peeling off the sheet. The repetitive bending device and the flexible member are as follows.

上述構成黏著劑層的黏著劑在-20℃的儲存模數G’(-20)為0.01MPa以上，0.2MPa以下，上述構成黏著劑層的黏著劑在23℃，測定波長400nm時的光彈性係數的絕對值為9.9×10-10 m2 /N以下。且，在本說明書中的儲存模數以及光彈性係數的測定方法如下述試驗例中所示。The storage modulus G'(-20) of the adhesive that constitutes the adhesive layer at -20°C is 0.01 MPa or more and 0.2 MPa or less, and the photoelasticity of the adhesive that constitutes the adhesive layer is measured at 23°C at a wavelength of 400 nm The absolute value of the coefficient is 9.9×10 -10 m 2 /N or less. In addition, the storage modulus and photoelastic coefficient measurement methods in this specification are as shown in the following test examples.

本實施形態中的構成黏著劑層的黏著劑藉由具有上述物性，使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反覆彎曲時，或處於長期彎曲狀態的情形時，在彎曲部位的黏著劑層與被附著物間的界面不以發生剝離，且，因彎曲引起(在彎曲後)的漏光以及可視性降低受到抑制。特別是當上述儲存模數G’(-20)為0.2MPa以下時，可抑制因反覆彎曲而發生的形變，亦即應力(在低溫時變得特別大)較小，因為在彎曲部位的黏著劑層與被附著物間的界面變得不易發生剝離。此外，特別是當上述光彈性係數為9.9×10-10 m2 /N以下時，伴隨彎曲的殘存應力引起的雙折射的發生可被壓抑，因彎曲引起的漏光以及可視性降低受到抑制。The adhesive constituting the adhesive layer in this embodiment has the above-mentioned physical properties, so that a laminate formed by bonding a flexible member and another flexible member through the adhesive layer is repeatedly bent, or is bent for a long time. In the case of the state, peeling does not occur at the interface between the adhesive layer and the adherend at the bent portion, and light leakage and visibility reduction due to bending (after bending) are suppressed. Especially when the above-mentioned storage modulus G'(-20) is 0.2MPa or less, the deformation due to repeated bending can be suppressed, that is, the stress (which becomes particularly large at low temperatures) is small, because the adhesion at the bending part The interface between the agent layer and the adherend becomes less likely to peel off. In addition, particularly when the photoelastic coefficient is 9.9×10 -10 m 2 /N or less, the occurrence of birefringence due to residual stress accompanying bending can be suppressed, and light leakage and visibility reduction due to bending can be suppressed.

由上述耐剝離性、耐漏光性以及可視性的觀點而言，特別是由耐剝離性的觀點而言，上述構成黏著劑層的黏著劑在-20℃時的儲存模數G’(-20)必須為0.2MPa以下，以0.15MPa以下為佳，特別是以0.10MPa以下為佳，進一步以0.08MPa以下為佳。此外，從凝聚力的觀點而言，上述構成黏著劑層的黏著劑在-20℃時的儲存模數G’(-20)必須為0.01MPa以上，以0.03MPa以上為佳，特別是以0.05MPa以上為佳，進一步以0.07MPa以上為佳。From the standpoint of peel resistance, light leakage resistance, and visibility, especially from the standpoint of peel resistance, the storage modulus G'(-20 ) Must be 0.2 MPa or less, preferably 0.15 MPa or less, particularly preferably 0.10 MPa or less, and further preferably 0.08 MPa or less. In addition, from the point of view of cohesion, the storage modulus G'(-20) of the adhesive constituting the adhesive layer at -20°C must be 0.01 MPa or more, preferably 0.03 MPa or more, especially 0.05 MPa The above is preferable, and more preferably 0.07 MPa or more.

上述構成黏著劑層的黏著劑在85℃時的儲存模數G’(85)，以0.2MPa以下為佳，以0.1MPa以下為更佳，特別是以0.05MPa以下為佳，進一步以0.03MPa以下為佳。藉此，隨著彎曲，由黏著劑層作用至被附著物的力減低，可獲得在高溫時耐剝離性佳的裝置。另一方面，在85℃時的儲存模數G’(85)以0.005MPa以上為佳，以0.010MPa以上為更佳，特別是以0.015MPa以上為佳。藉此，即使在高溫黏著劑層不會變得過於柔軟而維持凝聚力。The storage modulus G'(85) of the adhesive constituting the adhesive layer at 85°C is preferably 0.2 MPa or less, more preferably 0.1 MPa or less, particularly preferably 0.05 MPa or less, and further 0.03 MPa The following is better. As a result, the force acting on the adherend from the adhesive layer decreases with bending, and a device with good peel resistance at high temperatures can be obtained. On the other hand, the storage modulus G'(85) at 85°C is preferably 0.005 MPa or more, more preferably 0.010 MPa or more, and particularly preferably 0.015 MPa or more. Thereby, even at high temperature, the adhesive layer does not become too soft and maintains cohesion.

上述構成黏著劑層的黏著劑在25℃時的儲存模數G’(25)，以0.2MPa以下為佳，以0.1MPa以下為更佳，特別是以0.08MPa以下為佳，進一步以0.05MPa以下為佳。藉此，黏著性變得易於發揮。另一方面，在25℃時的儲存模數G’(25)，以0.01MPa以上為佳，0.02MPa以上為更佳，特別是以0.03MPa以上為佳。藉此，在標準環境溫度區域的耐剝離性佳之外，脫除加工等的加工性變得良好。The storage modulus G'(25) of the adhesive constituting the adhesive layer at 25°C is preferably 0.2 MPa or less, more preferably 0.1 MPa or less, especially 0.08 MPa or less, and further 0.05 MPa The following is better. With this, the adhesiveness becomes easy to play. On the other hand, the storage modulus G'(25) at 25°C is preferably 0.01 MPa or more, more preferably 0.02 MPa or more, and particularly preferably 0.03 MPa or more. Thereby, in addition to good peel resistance in the standard ambient temperature region, workability such as removal processing becomes good.

此外，從上述耐剝離性、耐漏光性以及可視性的觀點而言，特別是由耐漏光性以及可視性的觀點而言，上述構成黏著劑層的黏著劑在23℃，測定波長400nm時的光彈性係數的絕對值必須為9.9×10-10 m2 /N以下，以8.0×10-10 m2 /N以下為佳，以6.0×10-10 m2 /N以下為更佳，特別是以5.0×10-10 m2 /N以下為佳。上述光彈性係數的絕對值得下限値並無特別限制，可以是0m2 /N。但是，從易於獲得在-20℃時的儲存模數G’(-20)滿足上述値的黏著劑的觀點而言，上述光彈性係數的絕對值，以1.0×10-10 m2 /N以上為佳，以2.0×10-10 m2 /N以上為較佳，以3.0×10-10 m2 /N以上為更佳，特別是以4.0×10-10 m2 /N以上為佳。In addition, from the standpoints of peel resistance, light leakage resistance, and visibility, especially from the standpoints of light leakage resistance and visibility, the adhesive that constitutes the adhesive layer is measured at 23°C at a wavelength of 400 nm. The absolute value of the photoelastic coefficient must be 9.9×10 -10 m 2 /N or less, preferably 8.0×10 -10 m 2 /N or less, preferably 6.0×10 -10 m 2 /N or less, especially It is preferably 5.0×10 -10 m 2 /N or less. The lower limit value of the absolute value of the photoelastic coefficient is not particularly limited, and it may be 0 m 2 /N. However, from the viewpoint of easily obtaining an adhesive whose storage modulus G'(-20) at -20°C satisfies the above-mentioned value, the absolute value of the above-mentioned photoelastic coefficient is 1.0×10 -10 m 2 /N or more Preferably, 2.0×10 -10 m 2 /N or more is more preferable, 3.0×10 -10 m 2 /N or more is more preferable, and 4.0×10 -10 m 2 /N or more is especially preferable.

從耐漏光性以及可視性成為更佳者的觀點而言，上述構成黏著劑層的黏著劑在23℃，測定波長500nm時的光彈性係數的絕對值，以9.9×10-10 m2 /N以下為佳，以8.0×10-10 m2 /N以下為更佳，特別是以6.0×10-10 m2 /N以下為佳，進一步以5.0×10-10 m2 /N以下為佳。上述光彈性係數的絕對值的下限値並無特別限制，可以是0m2 /N。但是，從易於獲得在-20℃時的儲存模數G’(-20)滿足上述値的黏著劑的觀點而言，上述光彈性係數的絕對值，以1.0×10-10 m2 /N以上為佳，以2.0×10-10 m2 /N以上為更佳，特別是以3.0×10-10 m2 /N以上為佳，進一步以3.5×10-10 m2 /N以上為佳。From the viewpoint of better light leakage resistance and better visibility, the absolute value of the photoelastic coefficient of the above-mentioned adhesive constituting the adhesive layer is measured at 23°C at a wavelength of 500 nm, and the absolute value is 9.9×10 -10 m 2 /N The following is preferable, and 8.0×10 -10 m 2 /N or less is more preferable, especially 6.0×10 -10 m 2 /N or less, and more preferably 5.0×10 -10 m 2 /N or less. The lower limit value of the absolute value of the photoelastic coefficient is not particularly limited, and it may be 0 m 2 /N. However, from the viewpoint of easily obtaining an adhesive whose storage modulus G'(-20) at -20°C satisfies the above-mentioned value, the absolute value of the above-mentioned photoelastic coefficient is 1.0×10 -10 m 2 /N or more Preferably, it is more preferably 2.0×10 -10 m 2 /N or more, especially 3.0×10 -10 m 2 /N or more, and further preferably 3.5×10 -10 m 2 /N or more.

從耐漏光性以及可視性成為更佳者的觀點而言，上述構成黏著劑層的黏著劑在23℃，測定波長600nm時的光彈性係數的絕對值，以9.9×10-10 m2 /N以下為佳，以8.0×10-10 m2 /N以下為更佳，特別是以6.0×10-10 m2 /N以下為佳，進一步以4.0×10-10 m2 /N以下為佳。上述光彈性係數的絕對值得下限値並無特別限制，可以是0m2 /N。但是，從易於獲得在-20℃時的儲存模數G’(-20)滿足上述値的黏著劑的觀點而言，上述光彈性係數的絕對值，以0.8×10-10 m2 /N以上為佳，以1.5×10-10 m2 /N以上為更佳，特別是以2.0×10-10 m2 /N以上為佳，進一步以3.0×10-10 m2 /N以上為佳。From the viewpoint of better light leakage resistance and better visibility, the absolute value of the photoelastic coefficient of the above-mentioned adhesive constituting the adhesive layer is measured at a wavelength of 600 nm at 23°C, and the absolute value is 9.9×10 -10 m 2 /N The following is preferable, and 8.0×10 -10 m 2 /N or less is more preferable, especially 6.0×10 -10 m 2 /N or less is preferable, and 4.0×10 -10 m 2 /N or less is further preferable. The lower limit value of the absolute value of the photoelastic coefficient is not particularly limited, and it may be 0 m 2 /N. However, from the viewpoint of easily obtaining an adhesive whose storage modulus G'(-20) at -20°C satisfies the above-mentioned value, the absolute value of the above-mentioned photoelastic coefficient is 0.8×10 -10 m 2 /N or more Preferably, it is more preferably 1.5×10 -10 m 2 /N or more, especially 2.0×10 -10 m 2 /N or more, and more preferably 3.0×10 -10 m 2 /N or more.

上述構成黏著劑層的黏著劑在23℃，測定波長400nm時的光彈性係數的絕對值，同樣的在測定波長500nm時的光彈性係數的絕對值，以及同樣的在測定波長600nm時的光彈性係數的絕對值的最大値與最小値的差，以8×10-10 m2 /N以下為佳，以4×10-10 m2 /N以下為更佳，以2.0×10-10 m2 /N以下為特別佳，以1.5×10-10 m2 /N以下為進一步更佳。藉此，因所使用的發光體的種類的相異，使耐漏光性以及可視性受到影響能被抑制。The absolute value of the photoelastic coefficient at a wavelength of 400nm of the adhesive constituting the adhesive layer above is measured at 23°C, the same absolute value of the photoelastic coefficient at a wavelength of 500nm is measured, and the same photoelasticity at a wavelength of 600nm is measured The difference between the maximum value and the minimum value of the absolute value of the coefficient is preferably 8×10 -10 m 2 /N or less, more preferably 4×10 -10 m 2 /N or less, and 2.0×10 -10 m 2 /N or less is particularly preferable, and 1.5×10 -10 m 2 /N or less is even more preferable. Thereby, the influence of light leakage resistance and visibility can be suppressed due to differences in the types of luminous bodies used.

上述構成黏著劑層的黏著劑的凝膠分率，以30%以上為佳，以40%以上為更佳，特別是以50%以上為佳，進一步以60%以上為佳。藉此，黏著劑發揮能夠承受反覆彎曲的適當凝聚力。其結果為上述耐剝離性變得更佳。另一方面，在本實施形態中的黏著劑的凝膠分率，以95%以下為佳，以90%以下為更佳，特別是以80%以下為佳，進一步以75%以下為佳，以70%以下為最佳。藉此，推測因反覆彎曲引起的黏著劑中的交聯構造的破壞受到抑制，而成為可視性更佳者。且，在本說明書中的凝膠分率的測定方法如下述試驗例所示。The gel fraction of the adhesive constituting the adhesive layer is preferably 30% or more, more preferably 40% or more, especially 50% or more, and more preferably 60% or more. In this way, the adhesive exerts an appropriate cohesive force capable of withstanding repeated bending. As a result, the above-mentioned peeling resistance becomes better. On the other hand, the gel fraction of the adhesive in this embodiment is preferably 95% or less, more preferably 90% or less, especially 80% or less, and further preferably 75% or less. The best is less than 70%. Therefore, it is estimated that the destruction of the cross-linked structure in the adhesive due to repeated bending is suppressed, and the visibility is better. In addition, the method of measuring the gel fraction in this specification is as shown in the following test example.

作為本實施形態相關的黏著片的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片的剝離片12a、12b，以與此2片的剝離片12a、12b的剝離面接觸的方式，挾持於該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在剝離片中具有剝離性的面，包含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 as an example of the adhesive sheet related to this embodiment is shown in FIG. As shown in FIG. 1, the adhesive sheet 1 according to one embodiment is composed of two release sheets 12a, 12b, which are sandwiched between the two release sheets 12a, 12b so as to contact 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 refers to the surface which has peelability in a peeling sheet, and includes any one of the surface to which the peeling process was performed 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(特別是在-20℃時的儲存模數G’(-20)以及在23℃，測定波長400nm時的光彈性係數)即可並無特別限制，可以是例如，丙烯酸系黏著劑、聚酯系黏著劑、聚氨酯系黏著劑、橡膠系黏著劑、矽酮系黏著劑等的任一者。此外，該黏著劑可以是乳劑型、溶劑型或無溶劑型任一者，可以是交聯式或非交聯式任一者。此等當中，以容易滿足上述物性，黏著物性、光學特性等皆優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 can be combined as long as it satisfies the above physical properties (especially the storage modulus G'(-20) at -20°C and the photoelastic coefficient at 23°C, measured at a wavelength of 400nm). It is not particularly limited, and it may be, for example, any of acrylic adhesives, polyester adhesives, polyurethane adhesives, rubber adhesives, silicone adhesives, and the like. 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.

在本實施形態中的黏著劑，具體而言，以將含有(甲基)丙烯酸酯聚合物(A)與交聯劑(B)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，就能滿足上述物性，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。其他類似用語亦同。此外，「聚合物」為也包括「共聚物」的概念者。The adhesive in this embodiment is specifically an adhesive composition containing a (meth)acrylate polymer (A) and a crosslinking agent (B) (hereinafter, sometimes referred to as "adhesive combination (P)”) is an adhesive that is cross-linked. As long as it is a relevant adhesive, it can satisfy the above-mentioned physical properties, and in addition, it is easy to obtain a good adhesive force. In addition, in this specification, (meth)acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms. In addition, the term "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，以包含用以顯示良好的黏著性的(甲基)丙烯酸烷基酯，以及具有成為交聯處的反應性官能基的單體(含反應性官能基的單體)者為佳。在此，一般的(甲基)丙烯酸烷基酯顯示負的雙折射性，雖然所得的聚合物成為具有雙折射性者，但是，藉由將顯示正的雙折射性的單體導入聚合物中，藉由正負的抵銷可解除雙折射性。藉此，可抑制所得的黏著劑的光彈性係數的絕對值變小，變得易於滿足上述光彈性係數。此外，(甲基)丙烯酸烷基酯使所得的聚合物的儲存模數有下降的傾向，另一方面，顯示正的雙折射性的單體(特別是下述含芳香環的單體)使所得的聚合物的儲存模數有上升的傾向，藉由將兩者導入聚合物中，變得易於滿足上述儲存模數G’有關的物性。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，顯示正的雙折射性的單體，以及含反應性官能基的單體為更佳。(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 exhibiting good adhesiveness, and has reactivity to become a crosslinking site Functional group monomers (reactive functional group-containing monomers) are preferred. Here, general alkyl (meth)acrylates exhibit negative birefringence. Although the resulting polymer has birefringence, it is possible to introduce monomers exhibiting positive birefringence into the polymer. , The birefringence can be eliminated by positive and negative offset. Thereby, it can suppress that the absolute value of the photoelastic coefficient of the obtained adhesive agent becomes small, and it becomes easy to satisfy|fill the said photoelastic coefficient. In addition, alkyl (meth)acrylates tend to lower the storage modulus of the resulting polymer. On the other hand, monomers showing positive birefringence (especially the following aromatic ring-containing monomers) make The storage modulus of the obtained polymer tends to increase, and by introducing both into the polymer, it becomes easier to satisfy the physical properties related to the storage modulus G′ described above. Therefore, the (meth)acrylate polymer (A), as a monomer unit constituting the polymer, contains an alkyl (meth)acrylate, a monomer showing positive birefringence, and a reactive functional group. The monomer is better.

作為(甲基)丙烯酸烷基酯，以包含烷基的碳數為1〜20的(甲基)丙烯酸烷基酯為佳。烷基以直鏈狀或分支鏈狀為佳。As the alkyl (meth)acrylate, an alkyl (meth)acrylate containing an alkyl group and having 1 to 20 carbon atoms is 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，可列舉，例如，(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸十四酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十八酯等。當中，由上述儲存模數G’以及光彈性係數的觀點而言，以烷基的碳數為1〜8的(甲基)丙烯酸酯為佳，以烷基的碳數為4〜8的(甲基)丙烯酸酯為特別佳。具體而言，以(甲基)丙烯酸正丁酯以及(甲基)丙烯酸2-乙基己酯為佳，特別是以丙烯酸正丁酯以及丙烯酸2-乙基己酯為佳。且，此等可單獨使用，亦可組合2種以上使用。Examples of alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ( N-butyl meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth) N-decyl acrylate, n-dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, etc. Among them, from the viewpoints of the storage modulus G'and the photoelastic coefficient, the (meth)acrylate having the carbon number of the alkyl group is preferably 1 to 8, and the (meth)acrylate having the carbon number of the alkyl group is 4 to 8 ( Meth)acrylates are particularly preferred. Specifically, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. Moreover, these can be used individually or in combination of 2 or more types.

(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50質量%以上的烷基的碳數為1〜20的(甲基)丙烯酸烷基酯為佳，以含有70質量%以上為更佳，特別是以含有80質量%以上為佳，進一步以含有90質量%以上為佳。此外，以含有該(甲基)丙烯酸烷基酯99質量%以下為佳，以含有98質量%以下為更佳，特別是以含有97質量%以下為佳，進一步以含有96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’以及光彈性係數。The (meth)acrylate polymer (A) is preferably an alkyl (meth)acrylate having 1 to 20 carbon atoms containing 50% by mass or more of alkyl groups as the monomer unit constituting the polymer, and The content is more preferably 70% by mass or more, particularly preferably 80% by mass or more, and more preferably 90% by mass or more. In addition, the alkyl (meth)acrylate is preferably contained at 99% by mass or less, more preferably at 98% by mass or less, particularly preferably at 97% by mass or less, and further preferably at 96% 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 Storage modulus G'and photoelastic coefficient.

作為顯示正的雙折射性的單體，可列舉，具有環狀構造的單體，特別是具有芳香環的單體(含芳香環的單體)為佳。作為芳香環，可列舉，苯環、萘環、蒽環、聯苯環、茀環等，當中，從正的雙折射性的觀點而言，以苯環為佳。Examples of monomers exhibiting positive birefringence include monomers having a cyclic structure, particularly monomers having aromatic rings (monomers containing aromatic rings). Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, a sulphur ring, etc. Among them, a benzene ring is preferred from the viewpoint of positive birefringence.

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)丙烯酸芐基酯、(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。當中，從正的雙折射性的觀點而言，以(甲基)丙烯酸2-苯氧乙酯或苯氧基聚乙二醇(甲基)丙烯酸酯為佳，特別是以(甲基)丙烯酸2-苯氧乙酯為佳，進一步以丙烯酸2-苯氧乙酯為佳。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 (meth)acrylate, phenoxybutyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene Diol (meth)acrylate, biphenyl di(meth)acrylate, pentafluorobenzyl (meth)acrylate, etc. Among them, from the viewpoint of positive birefringence, 2-phenoxyethyl (meth)acrylate or phenoxy polyethylene glycol (meth)acrylate is preferred, especially (meth)acrylic acid 2-phenoxyethyl is preferred, and 2-phenoxyethyl acrylate is further preferred. 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0.1質量%以上的含芳香環的單體為佳，以含有0.5質量%以上為更佳，特別是以含有1質量%以上為佳，進一步以含有2質量%以上為佳。此外，以含有30質量%以下的含芳香環的單體為佳，以含有20質量%以下為更佳，特別是以含有15質量%以下為佳，進一步以含有9質量%以下為佳。藉由含芳香環的單體的含量於上述範圍中，抵銷(甲基)丙烯酸烷基酯所具有的負的雙折射性，可更解除雙折射性，變得更容易滿足上述光彈性係數。此外，亦良好地維持黏著性。The (meth)acrylate copolymer (A), as the monomer unit constituting the polymer, preferably contains 0.1% by mass or more of aromatic ring-containing monomers, and more preferably contains 0.5% by mass or more, especially The content is preferably 1% by mass or more, and more preferably 2% by mass or more. In addition, the aromatic ring-containing monomer is preferably 30% by mass or less, more preferably 20% by mass or less, particularly 15% by mass or less, and more preferably 9% by mass or less. When the content of the aromatic ring-containing monomer is in the above range, the negative birefringence of the alkyl (meth)acrylate can be cancelled, the birefringence can be more relieved, and the photoelastic coefficient can be more easily satisfied. . In addition, adhesion is maintained well.

(甲基)丙烯酸酯聚合物(A)，由於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(B)進行反應，藉此形成交聯構造(三維網目構造)，可獲得具有期望的凝聚力的黏著劑。該黏著劑成為易於滿足上述儲存模數G’有關的物性以及光彈性係數(以及凝膠分率)者。Since the (meth)acrylate polymer (A) contains a reactive functional group-containing monomer as a monomer unit constituting the polymer, the reactive functional group derived from the reactive functional group-containing monomer can pass through the reactive functional group derived from the reactive functional group-containing monomer, and The following crosslinking agent (B) reacts to form a crosslinked structure (three-dimensional mesh structure), and an adhesive having a desired cohesive force can be obtained. The adhesive can easily satisfy the above-mentioned physical properties and photoelastic coefficient (and gel fraction) related to the storage modulus G'.

(甲基)丙烯酸酯聚合物(A)，作為當作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)，在分子內具有胺基的單體(含胺基的單體)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 includes a monomer having a hydroxyl group in the molecule (containing Hydroxyl monomers), monomers having carboxyl groups in the molecule (carboxyl group-containing monomers), monomers having amine groups in the molecule (amine group-containing monomers), and the like. These reactive functional group-containing monomers may be used alone or in combination of two or more kinds.

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。含羥基的單體容易滿足上述儲存模數G有關的物性。亦即，只要是含羥基的單體，特別是，低溫的儲存模數G’會變小，所得的黏著劑的儲存模數G’的微調變得容易。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 physical properties related to the storage modulus G described above. That is, as long as it is a hydroxyl-containing monomer, especially, the storage modulus G'at low temperature becomes smaller, and the fine adjustment of the storage modulus G'of the resulting adhesive becomes easy.

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，從容易滿足上述儲存模數G’有關的物性的觀點而言，以具有碳數為1〜4的羥烷基的(甲基)丙烯酸羥烷基酯為佳。具體而言，較佳可列舉，例如，(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸4-羥丁酯等，特別是可列舉丙烯酸2-羥乙酯或丙烯酸4-羥丁酯為佳。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 physical properties related to the storage modulus G', a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group having a carbon number of 1 to 4 is preferred. Specifically, preferred examples include, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc., particularly 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate. Esters are 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 the carboxyl group-containing monomer 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.

且，丙烯酸2-羥乙酯、丙烯酸4-羥丁酯以及丙烯酸顯示正的雙折射性。因此，連同上述顯示正的雙折射性的單體(含芳香環的單體)，可賦予抵銷(甲基)丙烯酸烷基酯所具有的負的雙折射性。In addition, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and acrylic acid exhibit positive birefringence. Therefore, together with the above-mentioned monomers (aromatic ring-containing monomers) exhibiting positive birefringence, it is possible to impart negative birefringence that offsets the negative birefringence possessed by the alkyl (meth)acrylate.

(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0.1質量%以上的含反應性官能基的單體為佳，特別是以含有0.4質量%以上為佳，進一步以含有0.8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18質量%以下的含反應性官能基的單體為佳，特別是以含有9質量%以下為佳，進一步以含有3質量%以下為佳。當(甲基)丙烯酸酯聚合物(A)中作為單體單元在上述基中含有含反應性官能基的單體時，藉由與交聯劑(B)的交聯反應，所得的黏著劑的凝聚力成為適當者，變成容易滿足上述儲存模數G’有關的物性(以及凝膠分率)，特別是容易滿足在-20℃時的儲存模數G’(-20)。The (meth)acrylate polymer (A), as the monomer unit constituting the polymer, preferably contains 0.1% by mass or more of reactive functional group-containing monomers, especially 0.4% by mass or more It is more preferable to contain 0.8% by mass or more. In addition, the (meth)acrylate polymer (A), as a monomer unit constituting the polymer, preferably contains a reactive functional group-containing monomer of 18% by mass or less, especially 9% by mass or less Preferably, the content is more preferably 3% by mass or less. When the monomer unit in the (meth)acrylate polymer (A) contains a reactive functional group-containing monomer in the above-mentioned group, the resulting adhesive is obtained by cross-linking reaction with the cross-linking agent (B) When the cohesive force becomes appropriate, it becomes easy to satisfy the physical properties (and gel fraction) related to the storage modulus G', especially the storage modulus G'(-20) at -20°C.

(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。因為羧基微酸成分，藉由不含有含羧基的單體，對於黏著劑的貼附對象，即使是因酸而產生缺陷者，例如，錫摻雜的氧化銦(ITO)等的透明導電膜、金屬膜、金屬網目等存在時，可抑制酸所引起的此等的缺陷(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. Because the carboxyl acid component does not contain carboxyl group-containing monomers, it is suitable for adhesives to be attached to objects that have defects due to acid, such as transparent conductive films such as tin-doped indium oxide (ITO), When metal film, metal mesh, etc. are present, such defects (corrosion, resistance value change, etc.) caused by acid can be suppressed.

在此，所謂「不含有含羧基的單體」，是指實質上不含有含羧基的單體的意思，除了含羧基的單體全部不含有之外，容許以不發生含有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，(甲基)丙烯酸酯聚合物(A)中，作為單體單元，容許含有含羧基的單體的量為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。Here, "does not contain carboxyl group-containing monomers" means that it does not substantially contain carboxyl group-containing monomers. Except that all carboxyl group-containing monomers are not contained, transparent conduction caused by carboxyl group-containing is allowed. The degree of corrosion of the film, metal wiring, etc. contains a carboxyl group-containing monomer. Specifically, in the (meth)acrylate polymer (A), as a monomer unit, the allowable amount of a carboxyl group-containing monomer is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001 Less than mass%.

(甲基)丙烯酸酯聚合物(A)，依照期望，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，為了不阻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。作為相關的單體，可列舉，例如，N-丙烯醯嗎啉、N-乙烯基-2-吡咯烷酮等的無反應活性的含氮原子的單體、(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 desired. 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. Examples of related monomers include non-reactive nitrogen-containing monomers such as N-acrylomorpholine and N-vinyl-2-pyrrolidone, methoxyethyl (meth)acrylate, Alkoxyalkyl (meth)acrylates such as ethoxyethyl (meth)acrylate, vinyl acetate, styrene, etc. These can be used alone or in combination of two or more kinds.

(甲基)丙烯酸酯聚合物(A)的聚合態樣可以使隨機共聚物，也可以使嵌段共聚物。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60萬以上為佳，以80萬以上為更佳，特別是以100萬以上為佳，進一步以120萬以上為佳。此外，(甲基)丙烯酸酯聚合物(A)的重量平均分子量，以250萬以下為佳，以200萬以下為更佳，特別是以170萬以下為佳，進一步以140萬以下為佳。(甲基)丙烯酸酯聚合物(A)的重量平均分子量在上述的範圍內時，上述儲存模數G’有關的物性(以及凝膠分率)，變得容易滿足特別是在25℃時的儲存模數G’(25)以及在85℃時的儲存模數G’(85)。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)法所測定的標準聚苯乙烯換算的値。The weight average molecular weight of the (meth)acrylate polymer (A) is preferably 600,000 or more, more preferably 800,000 or more, particularly preferably 1 million or more, and further preferably 1.2 million or more. In addition, the weight average molecular weight of the (meth)acrylate polymer (A) is preferably 2.5 million or less, more preferably 2 million or less, particularly preferably 1.7 million or less, and further preferably 1.4 million or less. When the weight average molecular weight of the (meth)acrylate polymer (A) is within the above-mentioned range, the physical properties (and gel fraction) related to the storage modulus G'mentioned above become easily satisfied, especially at 25°C. The storage modulus G'(25) and the storage modulus G'(85) at 85°C. In addition, the weight average molecular weight in this specification is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.

在黏著性組合物P中，(甲基)丙烯酸酯聚合物(A)可單獨1種使用，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)交聯劑(B) 交聯劑(B)作為含有該交聯劑(B)的黏著性組合物P的加熱等的觸發，(甲基)丙烯酸酯聚合物(A)進行交聯，形成三維網目構造。藉此，所得的黏著劑的凝聚力提升，變得容易滿足上述儲存模數G’有關的物性以及凝膠分率。(1-2) Crosslinking agent (B) The crosslinking agent (B) acts as a trigger such as heating of the adhesive composition P containing the crosslinking agent (B), and the (meth)acrylate polymer (A) is crosslinked to form a three-dimensional network structure. Thereby, the cohesive force of the obtained adhesive is improved, and it becomes easier to satisfy the physical properties and gel fraction related to the storage modulus G'described above.

作為上述交聯劑(B)，只要與(甲基)丙烯酸酯聚合物(A)所具有的反應性基進行反應者即可，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、吖丙啶系交聯劑、肼系交聯劑、醛系交聯劑、㗁唑啉系交聯劑、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。上述當中，以使用與含反應性官能基的單體的反應性佳的異氰酸酯系交聯劑為佳。且，交聯劑(B)可單獨1種，或組合2種以上使用。As the above-mentioned crosslinking agent (B), what is necessary is to react with the reactive group possessed by the (meth)acrylate polymer (A), and examples include isocyanate-based crosslinking agents and epoxy-based crosslinking agents. Agents, amine-based cross-linking agents, melamine-based cross-linking agents, aziridine-based cross-linking agents, hydrazine-based cross-linking agents, aldehyde-based cross-linking agents, azoline-based cross-linking agents, metal alkoxide-based cross-linking agents, Metal chelating cross-linking agents, metal salt-based cross-linking agents, ammonium salt-based cross-linking agents, etc. Among the above, it is preferable to use an isocyanate-based crosslinking agent having high reactivity with a monomer containing a reactive functional group. Moreover, the crosslinking agent (B) 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、二甲苯二異氰酸酯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；以及其雙縮脲物、異氰脲酸酯物，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物的加成物等。當中，從與羥基的反應性的觀點而言，三羥甲基丙烷改質的芳香族聚異氰酸酯，特別是三羥甲基丙烷改質的甲苯二異氰酸酯或三羥甲基丙烷改質的二甲苯二異氰酸酯為佳。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 xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate; Alicyclic polyisocyanates such as isocyanate, hydrogenated diphenylmethane diisocyanate, etc.; and its biuret products, isocyanurate products, and also used as ethylene glycol, propylene glycol, neopentyl glycol, trimethylol Addition products of reactants containing low molecular active hydrogen compounds such as propyl propane and castor oil. Among them, from the viewpoint of reactivity with hydroxyl groups, trimethylolpropane-modified aromatic polyisocyanates, especially trimethylolpropane-modified toluene diisocyanate or trimethylolpropane-modified xylene Diisocyanate is preferred.

黏著性組合物P中的交聯劑(B)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0.06質量份以上為佳，進一步以0.12質量份以上為佳。此外，該含量以5質量份以下為佳，以2質量份以下為更佳，特別是以1質量份以下為佳，進一步以0.4質量份以下為佳。當交聯劑(B)的含量在上述範圍內時，變得容易滿足上述儲存模數G’有關的物性以及凝膠分率。The content of the crosslinking agent (B) in the adhesive composition P is preferably 0.01 parts by mass or more, especially 0.06 parts by mass or more, relative to 100 parts by mass of the (meth)acrylate polymer (A) , And more preferably 0.12 parts by mass or more. In addition, the content is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, particularly preferably 1 part by mass or less, and further preferably 0.4 parts by mass or less. When the content of the crosslinking agent (B) is within the above-mentioned range, it becomes easy to satisfy the above-mentioned physical properties related to the storage modulus G'and the gel fraction.

(1-3)各種添加劑 黏著性組合物P中，依照期望，可添加丙烯酸系黏著劑中經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、光安定劑、軟化劑、填充劑、折射率調整劑等。且，下述的聚合溶媒、稀釋溶媒不包含在構成黏著性組合物P的添加劑中。(1-3) Various additives In the adhesive composition P, various additives commonly used in acrylic adhesives can be added as desired, such as silane coupling agents, ultraviolet absorbers, antistatic agents, tackifiers, antioxidants, light stabilizers, and softeners. , Fillers, refractive index modifiers, etc. In addition, the following polymerization solvents and dilution solvents are not included in the additives constituting the adhesive composition P.

黏著性組合物P以含有上述的矽烷偶合劑為佳。藉此，在所得的黏著劑層中，與作為被附著物的彎曲性部件的密著性提升，成為黏著力更佳者。The adhesive composition P preferably contains the above-mentioned silane coupling agent. Thereby, in the obtained adhesive agent layer, the adhesiveness with the flexible member which is an adherend improves, and it becomes a thing with better adhesive force.

作為矽烷偶合劑，為在分子內中具有至少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)的相溶性佳，具有光穿透性者為佳。As a silane coupling agent, it is an organosilicon compound having at least one alkoxysilyl group in the molecule, and has good compatibility with the (meth)acrylate polymer (A), preferably having light penetration .

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-縮水甘油氧丙基三甲氧矽烷、3-縮水甘油氧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物等。其可單獨1種使用，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, and 3-glycidol Silicon compounds with epoxy structure such as oxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3 -Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane and other mercapto group-containing silicon compounds, 3-aminopropyltrimethoxysilane, N-( Amino-containing silicon compounds such as 2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-chloropropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, or at least one of them and methyl triethoxysilane, ethyl triethoxysilane, methyl trimethoxysilane, ethyl trimethoxysilane Condensates of alkyl-containing silicon compounds such as silane. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

在黏著性組合物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在上述範圍，所得的黏著劑層與作為被附著物的彎曲性部件的密著性提升，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). It is preferably 0.1 part by mass or more. 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 in the above-mentioned range, the adhesion between the obtained 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可透過製造(甲基)丙烯酸酯聚合物(A)，將所得的(甲基)丙烯酸酯聚合物(A)與交聯劑(B)混合，同時添加依照期望的添加劑而製造。(2) Production of adhesive composition P The adhesive composition P can be prepared by manufacturing the (meth)acrylate polymer (A), mixing the obtained (meth)acrylate polymer (A) with the crosslinking agent (B), and adding the desired additives at the same time. manufacture.

(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，以使用依需要的聚合起始劑，藉由溶液聚合法進行為佳。藉由透過溶液聚合法將(甲基)丙烯酸酯聚合物(A)進行聚合，所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，可降低低分子量產物的生成。因此，即使凝膠分率比較小且交聯的程度緩和時，隨著反覆彎曲而來的黏著劑的偏離不易發生，可獲得耐剝離性佳的黏著劑。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) is preferably 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 of the obtained polymer and the adjustment of the molecular weight distribution become easy, and 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 relaxed, the deviation of the adhesive due to repeated bending is unlikely to occur, and an adhesive with excellent peel resistance can be obtained.

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-碳化腈)、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(cyclo Hexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxy Valeronitrile), dimethyl 2,2'-azobis(2-propionic acid methyl ester), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2 -Hydroxymethylpropionitrile), 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(t-butyl peroxypivalate)、(3,5,5-三甲基己醯基)過氧化物、二丙醯過氧化物、二乙醯過氧化物等。Examples of organic peroxides include, for example, benzyl peroxide, tertiary butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, Di(2-ethoxyethyl) peroxydicarbonate, tertiary butyl peroxyneodecanoate, tertiary butyl peroxyisobutyrate (t-butyl peroxypivalate), (3,5,5-tri (Methylhexyl) peroxide, 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)後，藉由在(甲基)丙烯酸酯聚合物(A)的溶液中，添加交聯劑(B)，以及依照需要的添加劑及稀釋溶劑，充分地混合，可獲得以溶劑進行稀釋的黏著性組合物P(塗佈溶液)。After the (meth)acrylate polymer (A) is obtained, the crosslinking agent (B) is added to the solution of the (meth)acrylate polymer (A), as well as additives and diluting solvents as required, to ensure sufficient It is mixed with each other to obtain an adhesive composition P (coating solution) diluted with a solvent.

且，在上述各成分的任一者中，使用固體狀者，或是，以未經稀釋狀態與其他成分混合產生析出時，可預先將此成分單獨溶解或稀釋於稀釋溶媒中，再與其他成分混合。In addition, when any of the above-mentioned components is solid, or when it is mixed with other components in an undiluted state to cause precipitation, this component can be dissolved or diluted in a diluting solvent in advance, and then mixed with other components. The ingredients are mixed.

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；氯化甲烷、氯化乙烷等的鹵化烴；甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等的醇；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 aforementioned dilution solvent, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chlorinated methane and chlorinated ethane; methanol, ethanol Alcohols such as, propanol, butanol, 1-methoxy-2-propanol; ketones such as acetone, butanone, 2-pentanone, isophorone, cyclohexanone, etc.; ethyl acetate, butyl acetate Ethyl esters; Ethyl Cyrosu series 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使，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(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 %. Moreover, when obtaining a coating solution, the addition of a dilution solvent etc. is not an essential condition, and as long as it is the viscosity etc. which can apply|coat the adhesive composition P, you may not add a dilution solvent. At this time, the adhesive composition P becomes a coating solution which becomes the polymerization solvent of the (meth)acrylate polymer (A) as it is as a diluent 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的交聯一般可藉由加熱處理而進行。且，此加熱處理可藉由從塗佈在期望的對象物上的黏著性組合物P的塗膜使稀釋溶劑揮發時的乾燥處理擔任。(3) Manufacture 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 generally be performed by heat treatment. In addition, this heat treatment can be performed by a drying treatment when the diluent solvent is volatilized 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分為佳，特別是以50秒〜2分為佳。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，當熟成期間為不必要時，在加熱處理結束後，使黏著劑形成。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 unnecessary, the adhesive is formed after the heat treatment is completed.

藉由上述的加熱處理(及熟成)，可透過交聯劑(B)使(甲基)丙烯酸酯聚合物(A)充分交聯而形成交聯構造，獲得黏著劑。Through the above-mentioned heat treatment (and aging), the (meth)acrylate polymer (A) can be sufficiently cross-linked by the cross-linking agent (B) to form a cross-linked structure, and an adhesive can be obtained.

(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為準則所測定的値)，作為下限値以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的厚度的下限値為上述時，易於發揮期望的黏著力，成為耐剝離性更佳者。(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 in accordance with JIS K7130) is preferably 1 μm or more as the lower limit value, 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 value of the thickness of the adhesive layer 11 is the above, the desired adhesive force is easily exhibited, and the peeling resistance is better.

此外，黏著劑層11的厚度，作為上限値以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的厚度的上限値為上述時，抑制因反覆彎曲發生在黏著劑層的應力過大，可成為耐剝離性更佳者。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, and particularly preferably 90 μm or less. From the viewpoint of obtaining a thinner repeating bending device, it is further 40 μm. The following is better. When the upper limit value of the thickness of the adhesive layer 11 is the above, it is possible to suppress excessive stress that occurs in the adhesive layer due to repeated bending, and it is possible to achieve better peel resistance. 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、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 Films, ethylene-(meth)acrylate copolymer films, polystyrene films, polycarbonate films, polyimide films, fluororesin films, etc. In addition, its crosslinked film can also be used. Furthermore, the laminated film may be used.

在上述剝離片12a、12b的剝離面(特別是與黏著劑層11接觸的面)，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。It is preferable to perform a peeling process on the peeling surface of the said peeling sheet 12a, 12b (especially the surface contacting the adhesive layer 11). 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的對鈉鈣玻璃的黏著力，作為下限値，以1N/25mm以上為佳，以3N/25mm以上為更佳，特別是以5N/25mm以上為佳，進一步以8N/25mm以上為佳。黏著片1的對鈉鈣玻璃的黏著力的下限値為上述時，成為耐剝離性更佳者。另一方面，關於上述黏著力的上限値，雖然無特別限制，但有時重工性(rework)為必要。從此種觀點而言，上述黏著力，以30N/25mm以下為佳，以25N/25mm以下為更佳，以20N/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 the present embodiment to the soda lime glass is preferably 1N/25mm or more, more preferably 3N/25mm or more, especially 5N/25mm or more, and further Above 8N/25mm is better. When the lower limit value of the adhesive force of the adhesive sheet 1 to the soda lime glass is the above, the peel resistance is better. On the other hand, regarding the upper limit of the adhesive force, although there is no particular limitation, rework may be necessary. From this point of view, the above-mentioned adhesive force is preferably 30N/25mm or less, more preferably 25N/25mm or less, and particularly preferably 20N/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.

本實施形態相關的黏著片1的對聚醯亞胺的黏著力，作為下限値，以1N/25mm以上為佳，以3N/25mm以上為更佳，特別是以5N/25mm以上為佳，進一步以10N/25mm以上為佳。黏著片1的對聚醯亞胺的黏著力的下限値為上述時，即使是聚醯亞胺膜等作為被附著物時，仍成為耐剝離性更佳者。另一方面，關於上述黏著力的上限値，雖然無特別限制，但有時重工性為必要。從此種觀點而言，上述黏著力，以30N/25mm以下為佳，以25N/25mm以下為更佳，以20N/25mm以下為特別佳。The lower limit of the adhesive force of the adhesive sheet 1 related to the present embodiment to polyimide is preferably 1N/25mm or more, more preferably 3N/25mm or more, especially 5N/25mm or more, and further 10N/25mm or more is preferred. When the lower limit value of the adhesive force of the adhesive sheet 1 to the polyimide is the above, even when a polyimide film or the like is used as an adherend, the peeling resistance is better. On the other hand, regarding the upper limit of the adhesive force, although there is no particular limitation, heavy workability may be necessary. From this point of view, the above-mentioned adhesive force is preferably 30N/25mm or less, more preferably 25N/25mm or less, and particularly preferably 20N/25mm or less.

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。藉此，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. Thereby, 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予以貼合。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。藉此，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 is 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 release sheet 12a with a coating layer and the release 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. Thereby, 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 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的彎曲(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 (repetitive bending display) that can be repeatedly bent (including bending), 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、金屬網目膜、可撓玻璃、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(薄膜狀電子紙)、TET(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 Measuring (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-shaped electronic paper), TET (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著性低，但只要根據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，仍可獲得優良的耐剝離性。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 peel resistance 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，以分別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，變得容易使其反覆彎曲。The Young's coefficients of the first flexible member 21 and the second flexible member 22 are preferably 0.1-10 GPa, respectively, preferably 0.5-7 GPa, and further preferably 1.0-5 GPa. When the Young's coefficients of the first flexible member 21 and the second flexible member 22 are in the relevant range, it becomes easy to repeatedly bend each flexible member.

第1彎曲性部件21以及第2彎曲性部件22的厚度，以分別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，針對各彎曲性部件，變得容易使其反覆彎曲。The thickness of the first flexible member 21 and the second flexible member 22 is preferably 10 to 3000 μm, particularly 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 easy 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的一側的剝離片12a，將黏著片1的露出的黏著劑層11貼合於第1彎曲性部件21的一側的面。When manufacturing the above-mentioned repetitively curved laminated member 2, as an example, the peeling sheet 12 a on one side of the adhesive sheet 1 is peeled off, and the exposed adhesive layer 11 of the adhesive sheet 1 is bonded to the side surface of the first flexible member 21.

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的露出的黏著劑層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 12 b is peeled from the adhesive layer 11 of the adhesive sheet 1, and the exposed adhesive layer 11 of the adhesive sheet 1 is bonded to the second flexible member 22 to obtain the repetitive 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與其他反覆彎曲積層部件2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, and may be composed of only the repetitive bending laminate member 2, or it may be provided with one or more repetitive bending laminate members 2 and other repetitive bending laminate members. 2 constituted. 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可視性降低受到抑制。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 visibility reduction 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.

如圖3所示，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。As shown in FIG. 3, the repetitive bending device 3 related to this embodiment, from the top, is laminated with a cover film 31, a first adhesive layer 32, a polarizing film 33, a second adhesive layer 34, and a touch sensor film. 35. The third adhesive layer 36, the organic EL element 37, the fourth adhesive layer 38, and the TFT substrate 39 are constituted. The above-mentioned cover film 31, polarizing film 33, touch sensing film 35, organic EL element 37, and TFT substrate 39 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黏著劑層1。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 1 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 above-mentioned adhesive sheet 1 and the adhesive layer 11, and all the adhesives Preferably, the layers 32, 34, 36, and 38 are the adhesive layer 11 of the adhesive sheet 1.

在此，例如，TFT基板39為包括聚醯亞胺膜時，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以也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 embodiment is intended to include all design changes and equivalents that also include 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，亦可積層期望的彎曲性部件取代剝離片12a及/或剝離片12b。 [實施例]For example, either or both of the peeling sheets 12a and 12b in the adhesive sheet 1 may be omitted, and a desired flexible member may be laminated instead of the peeling sheet 12a and/or the peeling 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 further specifically described 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46質量份、丙烯酸2-乙基己酯50質量份、丙烯酸4-羥丁酯1質量份以及丙烯酸2-苯氧乙酯3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)的分子量依下述方法進行測定，重量平均分子量(Mw)為120萬。[Example 1] 1. Preparation of (meth)acrylate polymer (A) 46 parts by mass of n-butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of 4-hydroxybutyl acrylate, and 3 parts by mass of 2-phenoxyethyl acrylate were copolymerized by solution polymerization , To prepare (meth)acrylate polymer (A). The molecular weight of this (meth)acrylate polymer (A) was measured by the following method, and the weight average molecular weight (Mw) was 1.2 million.

2.黏著性組合物的調製 將於上述步驟1所得的(甲基)丙烯酸酯聚合物(A)100質量份(固形份換算値；以下相同)，作為交聯劑(B)的三羥甲基丙烷改質的二甲苯二異氰酸酯(XDI：綜研化學公司製，製品名稱「TD-75」)0.14質量份，作為矽烷偶合劑的3-縮水甘油氧丙基三甲氧矽烷0.20質量份混合，充分攪拌，藉由以丁酮進行稀釋，獲得黏著性組合物的塗佈溶液。2. Preparation of adhesive composition 100 parts by mass of the (meth)acrylate polymer (A) obtained in step 1 above (solid content conversion value; the same below) is used as a crosslinking agent (B) of trimethylolpropane modified xylene 0.14 parts by mass of isocyanate (XDI: manufactured by Soken Chemical Co., Ltd., product name "TD-75"), 0.20 parts by mass of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent, mixed, fully stirred, and carried out with methyl ethyl ketone Dilute 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，在聚對苯二甲酸乙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，製品名稱「SP-PET752150」)的剝離處理面上，以刀式塗佈機進行塗佈。然後，對於塗佈層，在90℃加熱處理1分鐘，形成塗佈層。3. Manufacture of Adhesive Sheet A heavy release type release sheet (manufactured by Lintec Corporation, product name "SP-") in which the obtained coating solution of the adhesive composition is peeled off with a silicone-based release agent on one side of a polyethylene terephthalate film. PET752150") is coated on the peeling surface 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，製品名稱「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的條件下進行熟成7日，製作具有厚度25μm的黏著劑層的黏著片，亦即，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，黏著劑層的厚度為以JIS K7130為基準，使用定壓厚度測定器(TECLOCK公司製，製品名稱「PG-02」)所測定的値。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 cured at 23°C and 50%RH for 7 days to produce a thickness of 25μm The adhesive sheet of the adhesive layer, that is, an adhesive sheet formed by a heavy peeling type release sheet/adhesive layer (thickness: 25 μm)/light peeling type peeling 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(固形份換算値)時的黏著性組合物的各調配(固形份換算値)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 2EHA：丙烯酸2-乙基己酯 4HBA：丙烯酸4-羥丁酯 PHEA：丙烯酸2-苯氧乙酯 MA：丙烯酸甲酯 MEA：丙烯酸2-甲氧基乙酯 AA：丙烯酸 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 2EHA: 2-ethylhexyl acrylate 4HBA: 4-hydroxybutyl acrylate PHEA: 2-phenoxyethyl acrylate MA: methyl acrylate MEA: 2-methoxyethyl acrylate AA: Acrylic HEA: 2-hydroxyethyl acrylate.

[實施例2、比較例1~3] 除了構成(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)，以及交聯劑(B)的調配量如表1所示般進行變更以外，其餘與實施例1同樣地製造黏著片。[Example 2, Comparative Examples 1 to 3] 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 formulation of the crosslinking agent (B) Except that the amount was changed as shown in Table 1, the pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.

[試驗例1] (凝膠分率的測定) 將實施例以及比較例所製作的黏著片裁斷成80mm×80mm的尺寸，其黏著劑層包裹在聚酯製篩網(品名：Tetron mesh#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] (Determination 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: Tetron mesh#200), and its mass was measured by a precision balance. The mass of the above sieve alone is calculated as the mass of only the adhesive. The mass at this time is referred to as M1.

接著，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, 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. The gel fraction (%) is expressed as (M2/M1)×100. The results are shown in Table 2.

[試驗例2] (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)，將此當作試樣。[Test example 2] (Measurement of storage modulus G') The adhesives of the adhesive sheets produced in the examples and comparative examples were laminated in plural 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.

針對上述試樣，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-20℃時的儲存模數G’(-20)，在25℃時的儲存模數G’(25)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, the storage modulus G was measured under the following conditions by the torsional shear method using a viscoelasticity measuring device (manufactured by Anton Paar, product name "MCR302") based on JIS K7244-1 ', get the storage modulus G'(-20) at -20°C, the storage modulus G'(25) at 25°C, and the storage modulus G'(85)(MPa) at 85°C. The results are shown in Table 2. Measurement frequency: 1Hz Measuring temperature: -20℃～150℃

[試驗例3] (光彈性係數的測定) 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0.2mm的積層體。所得的黏著劑層的積層體裁斷成2cm×4.5cm，安置在光彈性係數測定裝置(JASCO公司製，製品名稱「M-220」)。然後，下述條件下，一邊階段性的加大拉力負載，一邊測定在各拉力負載時的相位差。基於該測定結果，取出在400nm、500nm、600nm時的相位差的値，進行製圖，由其斜度計算出在各波長時的光彈性係數(m2 /N)。結果如表2所示。 ・光源燈：Xe ・測定波長：300nm〜800nm ・狹縫寬度：1nm[Test Example 3] (Measurement of Photoelasticity Coefficient) A plurality of layers of adhesives of the adhesive sheets produced in the examples and comparative examples were laminated to form a laminate with a thickness of 0.2 mm. The obtained laminate of the adhesive layer was cut into a size of 2 cm×4.5 cm, and set in a photoelastic coefficient measuring device (manufactured by JASCO, product name "M-220"). Then, under the following conditions, while gradually increasing the tensile load, the phase difference at each tensile load was measured. Based on the measurement results, the values of the retardation at 400 nm, 500 nm, and 600 nm were taken out, graphed, and the photoelastic coefficient (m 2 /N) at each wavelength was calculated from the slope. The results are shown in Table 2.・Light source lamp: Xe ・Measurement wavelength: 300nm~800nm ・Slit width: 1nm

[試驗例4](黏著力的測定) 從實施例以及比較例所得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 4] (Measurement of Adhesion) The light-peelable release sheet was peeled off from the adhesive sheets obtained in the examples and comparative examples, and the exposed adhesive layer was bonded to a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd.) with an easy-to-adhesive layer 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 into a width of 25 mm and a length of 110 mm.

另一方面，作為被附著物，準備以下2種。 (1)鈉鈣玻璃板(日本板硝子公司製，製品名稱「鈉鈣玻璃」，厚度：1.1mm) (2)在鈉鈣玻璃板(日本板硝子公司製，製品名稱「鈉鈣玻璃」，厚度：1.1mm)的一側的面上，貼附在附黏著劑層的聚醯亞胺膜(DUPONT-TORAY CO., LTD.製，製品名稱「KAPTON 100PI」，聚醯亞胺膜的厚度：25μm，黏著劑層的厚度：5μm)的積層體(聚醯亞胺膜側為被附著面)。On the other hand, as the adherend, the following two types were prepared. (1) Soda-lime glass plate (manufactured by Nippon Sheet Glass Co., Ltd., product name "soda-lime glass", thickness: 1.1mm) (2) On one side of the soda-lime glass plate (manufactured by Nippon Sheet Glass Co., Ltd., product name "soda-lime glass", thickness: 1.1mm), a polyimide film with adhesive layer (DUPONT- TORAY CO., LTD., product name "KAPTON 100PI", polyimide film thickness: 25μm, adhesive layer thickness: 5μm) laminate (polyimide film side is the adhered surface).

在23℃，50%RH的環境下，從上述積層體將重剝離型剝離片剝離，將漏出的黏著劑層貼附在上述各被附著物上，以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 was peeled off from the laminate, and the leaked adhesive layer was attached to each of the adherends, using an autoclave manufactured by Kurihara Seisakusho Co., at 0.5 MPa, 50°C, pressurized 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5](耐剝離性的評價) 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，製品名稱「KAPTON 100PI」，厚度：25μm，楊氏係數：3.4GPa)的一側的面上。接著，剝離重剝離型剝離片，露出的黏著劑層貼合在同PI膜。然後，以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。由如此所獲得的PI膜/黏著劑層/PI膜所形成的積層體裁斷成50mm寬，200mm長，將此當作試樣。[Test Example 5] (Evaluation of Peeling Resistance) In an environment of 23° C. and 50% RH, 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 polyimide (PI) film (DUPONT- Manufactured by TORAY CO., LTD., product name "KAPTON 100PI", thickness: 25μm, Young's coefficient: 3.4GPa). Next, the heavy-peelable release sheet was peeled, and the exposed adhesive layer was bonded to the 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 placed under the conditions of 23° C. and 50% RH for 24 hours. The laminate formed from the PI film/adhesive layer/PI film thus obtained was cut into a width of 50 mm and a length of 200 mm, and this was used as a sample.

所得的試樣在-20℃的環境下，如圖4所示般，在由站立的2片玻璃板所形成的維持板(相互間距離：4mm)之間，在使其彎曲的狀態維持24小時。進行此靜態彎曲試驗之後，在試驗片的彎曲部位的黏著劑層與被附著物間的界面是否有剝離，藉由目測確認。結果如表2所示。 〇：無剝離 △：有部分的剝離(氣泡發生) ×：有剝離The obtained sample was maintained in a bent state between two standing glass plates (distance between each other: 4mm) as shown in Fig. 4 in an environment of -20°C. hour. After performing this static bending test, whether there is peeling at the interface between the adhesive layer and the adherend at the bent portion of the test piece is visually confirmed. The results are shown in Table 2. 〇: No peeling △: Partial peeling (bubble generation) ×: There is peeling

[試驗例6](耐漏光性) 準備複數片以三醋酸纖維素(TAC)膜(厚度25μm)，聚乙烯醇(PVA)膜偏光片(厚度12μm)，以及環烯烴高分子(COP)膜(厚度23μm)此順序積層而成的COP偏光板(厚度60μm)。[Test Example 6] (Light Leak Resistance) Prepare a plurality of sheets laminated in this order of triacetyl cellulose (TAC) film (thickness 25μm), polyvinyl alcohol (PVA) film polarizer (thickness 12μm), and cycloolefin polymer (COP) film (thickness 23μm). COP polarizing plate (thickness 60μm).

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附在一COP偏光板的TAC膜側。接著，剝離重剝離型剝離片，將露出的黏著劑層，在另一COP偏光板的COP膜側上，以成為正交尼寇(crossed Nicol)狀態的方式貼合。然後，以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。將由如此所獲得的COP偏光板/黏著劑層/COP偏光板所形成的積層體，裁斷成50mm寬，200mm長，將此當作試樣。The light-peelable release sheet was peeled from the adhesive sheets produced in the Examples and Comparative Examples, and the exposed adhesive layer was attached to the TAC film side of a COP polarizer. Next, the heavy peeling type peeling sheet is peeled, and the exposed adhesive layer is bonded to the COP film side of the other COP polarizing plate in a crossed Nicol state. Then, the autoclave manufactured by Kurihara Manufacturing Co., Ltd. was pressurized at 0.5 MPa, 50° C., and pressurized for 20 minutes, and then placed under the conditions of 23° C. and 50% RH for 24 hours. The laminated body formed of the COP polarizing plate/adhesive layer/COP polarizing plate thus obtained was cut into a width of 50 mm and a length of 200 mm, and this was used as a sample.

將所得的試樣使用耐久測試機(Yuasa System Co., Ltd.製，製品名稱「面狀體無負載U字伸縮測試機 形式：CL09-typeD01-FSC90」)，在以下的條件使其反覆彎曲。之後，在23℃，50%RH的環境下解放彎曲狀態，放置24小時。然後，在暗房藉由螢光燈的穿透光，以目視確認漏光，根據以下的基準，評價耐漏光性。結果如表2所示。且，關於比較例2的黏著片，由於耐剝離性的評價不良，故未進行本評價。Use a durability tester (manufactured by Yuasa System Co., Ltd., product name "hedral unloaded U-shaped stretch tester type: CL09-typeD01-FSC90"), and bend repeatedly under the following conditions . After that, the bent state was released under an environment of 23°C and 50% RH, and left for 24 hours. Then, the light leakage was visually confirmed by the transmitted light of the fluorescent lamp in the dark room, and the light leakage resistance was evaluated based on the following criteria. The results are shown in Table 2. In addition, the pressure-sensitive adhesive sheet of Comparative Example 2 was not evaluated due to poor evaluation of peel resistance.

＜試驗條件＞ 彎曲方向：以一側的COP偏光板的TAC膜為外側，另一COP偏光板的COP膜為內側的方式彎曲 最小彎曲徑：3mmψ 彎曲次數：100,000次 試驗溫度：23℃ ＜耐漏光性的評價基準＞ ◎…在彎曲部位確認無漏光。 〇…在彎曲部位稍微產生漏光，但實用上無問題的程度。 ×…在彎曲部位確認有明確的漏光。<Test conditions> Bending direction: bend with the TAC film of the COP polarizer on one side as the outside and the COP film on the other COP polarizer as the inside Minimum bending diameter: 3mmψ Bending times: 100,000 times Test temperature: 23℃ <Evaluation criteria for light leakage resistance> ◎...Confirm that there is no light leakage at the curved part. ○...Slight leakage of light occurs at the curved part, but there is no problem in practical use. ×...A clear light leakage was confirmed at the curved part.

[試驗例7](可視性的評價) 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，露出的黏著劑層貼附在與試驗例6相同的COP偏光板的TAC膜側。接著，剝離重剝離型剝離片，將露出的黏著劑層貼合在相位差膜(λ/4，厚度25μm)，獲得積層體。另一方面，從實施例以及比較例所製作的另一黏著片將輕剝離型剝離片剝離，將露出的黏著劑層貼附在由在PET膜(厚度50μm)上蒸鍍鋁層(厚度1μm)所形成的鋁薄膜反射板的鋁層。接著，剝離重剝離型剝離片，將露出的黏著劑層貼合在上述積層體的相位差膜。然後，以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。將由如此所獲得的COP偏光板/黏著劑層/相位差膜/黏著劑層/鋁薄膜反射板所形成的積層體，裁斷成50mm寬，200mm長，將此當作試樣。[Test Example 7] (Evaluation of Visibility) 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 attached to the TAC film side of the same COP polarizing plate as in Test Example 6. Next, the heavy peeling type release sheet was peeled, and the exposed adhesive layer was bonded to a retardation film (λ/4, thickness 25 μm) to obtain a laminate. On the other hand, the light-peelable release sheet was peeled off from another adhesive sheet produced in the Examples and Comparative Examples, and the exposed adhesive layer was attached to a PET film (thickness 50μm) deposited with an aluminum layer (thickness 1μm). ) The aluminum layer of the formed aluminum thin film reflector. Next, the heavy-peelable release sheet was peeled, and the exposed adhesive layer was bonded to the retardation film of the laminate. Then, the autoclave manufactured by Kurihara Manufacturing Co., Ltd. was pressurized at 0.5 MPa, 50° C., and pressurized for 20 minutes, and then placed under the conditions of 23° C. and 50% RH for 24 hours. The laminate formed of the COP polarizer/adhesive layer/retardation film/adhesive layer/aluminum thin film reflector thus obtained was cut into a 50mm wide and 200mm long, and this was used as a sample.

使用耐久測試機(Yuasa System Co., Ltd.製，製品名稱「面狀體無負載U字伸縮測試機 形式：CL09-typeD01-FSC90」)，將上述試樣在以下的條件使其靜態彎曲24小時。之後，解放彎曲狀態，在螢光燈下藉由目視確認反射光的情況，根據以下基準，評價可視性。結果如表2所示。Using a durability tester (manufactured by Yuasa System Co., Ltd., product name "flat body no-load U-shaped expansion tester type: CL09-typeD01-FSC90"), the above sample was statically bent under the following conditions 24 hour. After that, the bending state was released, the reflected light was visually confirmed under a fluorescent lamp, and the visibility was evaluated based on the following criteria. The results are shown in Table 2.

＜試驗條件＞ 彎曲方向：以COP偏光板為外側，鋁薄膜反射板為內側的方式彎曲 最小彎曲徑：3mmФ 試驗溫度：23℃ ＜可視性的評價基準＞ 〇…在彎曲部位無反射光，不認為可視性降低。 ×…在彎曲部位可見到來自反射光的波紋，認為可視性降低。<Test conditions> Bending direction: bend with the COP polarizing plate as the outer side and the aluminum film reflector as the inner side Minimum bending diameter: 3mmФ Test temperature: 23℃ ＜Evaluation criteria of visibility＞ ○...There is no reflected light at the curved part, and visibility is not considered to be reduced. ×...Waviness from reflected light is seen at the curved portion, and visibility is considered to be reduced.

[表1] (甲基)丙烯酸酯聚合物(A) 交聯劑(B) 矽烷偶合劑 組　成 Mw 質量份 質量份 實施例1 BA/2EHA/4HBA/PHEA=46/50/1/3 120萬 0.14 0.2 實施例2 BA/2EHA/4HBA/PHEA=41/50/1/8 比較例1 BA/2EHA/4HBA=49/50/1 比較例2 BA/MA/MEA/PHEA/AA/HEA=69.8/20/1/8/0.2/1 150萬 0.13 比較例3 BA/2EHA/4HBA/PHEA=33/50/1/16 120萬 0.14 [Table 1] (Meth)acrylate polymer (A) Crosslinking agent (B) Silane coupling agent composition Mw Mass parts Mass parts Example 1 BA/2EHA/4HBA/PHEA=46/50/1/3 1.2 million 0.14 0.2 Example 2 BA/2EHA/4HBA/PHEA=41/50/1/8 Comparative example 1 BA/2EHA/4HBA=49/50/1 Comparative example 2 BA/MA/MEA/PHEA/AA/HEA=69.8/20/1/8/0.2/1 1.5 million 0.13 Comparative example 3 BA/2EHA/4HBA/PHEA=33/50/1/16 1.2 million 0.14

[表2] 凝膠 分率(％) 儲存模數G’(MPa) 光彈性係數 （×10-10 m2 /N） 黏著力 (N/25mm) 耐剝離性 [-20℃] 耐漏光性 可視性 G’(-20) G’(25) G’(85) 400nm 500nm 600nm 鈉鈣玻璃 PI膜 實施例1 67 0.083 0.046 0.024 4.3 4.2 3.8 10.5 15.2 ○ ◎ ○ 實施例2 65 0.074 0.033 0.020 4.6 3.7 3.5 10.4 15.7 ○ ◎ ○ 比較例1 73 0.113 0.039 0.027 13.6 12.0 11.2 10.3 10.1 ○ × × 比較例2 85 6.73 0.119 0.075 2.2 2.1 2.0 10.5 12.0 × － × 比較例3 62 0.115 0.045 0.015 -89.0 -89.4 -120 13.4 16.3 ○ × × [Table 2] Gel fraction (%) Storage modulus G'(MPa) Photoelastic coefficient (×10 -10 m 2 /N) Adhesion (N/25mm) Peeling resistance [-20℃] Light leakage resistance Visibility G'(-20) G'(25) G'(85) 400nm 500nm 600nm Soda lime glass PI film Example 1 67 0.083 0.046 0.024 4.3 4.2 3.8 10.5 15.2 ○ ◎ ○ Example 2 65 0.074 0.033 0.020 4.6 3.7 3.5 10.4 15.7 ○ ◎ ○ Comparative example 1 73 0.113 0.039 0.027 13.6 12.0 11.2 10.3 10.1 ○ X X Comparative example 2 85 6.73 0.119 0.075 2.2 2.1 2.0 10.5 12.0 X - X Comparative example 3 62 0.115 0.045 0.015 -89.0 -89.4 -120 13.4 16.3 ○ X X

由表2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(聚醯亞胺膜/聚醯亞胺膜)並置於彎曲狀態時，在黏著劑層與彎曲性部件的界面未發生剝離，成為耐剝離性佳者。此效果在-20℃的低溫環境下充分發揮。此外，實施例的黏著片的黏著劑層為在彎曲後的耐漏光性以及可視性優良者。 [產業可利用性]It can be clearly seen from Table 2 that when the adhesive layer of the adhesive sheet of the embodiment is attached to two flexible members (polyimide film/polyimide film) and placed in a curved state, the adhesive layer and the curved There was no peeling at the interface of the sexual part, and it was the one with good peeling resistance. This effect is fully exerted in a low temperature environment of -20°C. In addition, the adhesive layer of the adhesive sheet of the embodiment has excellent light leakage resistance and visibility after bending. [Industry Availability]

本發明適合將構成反覆彎曲裝置的一彎曲性部件(特別是聚醯亞胺膜或包含聚醯亞胺膜的積層體)與其他彎曲性部件進行貼合。The present invention is suitable for bonding a flexible member (especially a polyimide film or a laminate containing a polyimide film) constituting a repetitive bending device with other flexible members.

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(側面圖)。[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. [Fig. 4] An explanatory diagram (side view) for explaining the static 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 (10)

一種黏著片，為具有：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， 構成上述黏著劑層的黏著劑在-20℃的儲存模數G’(-20)為0.01MPa以上，0.2MPa以下， 構成上述黏著劑層的黏著劑在23℃，測定波長400nm時的光彈性係數的絕對值為9.9×10-10 m2 /N以下。An adhesive sheet is an adhesive sheet having an adhesive layer for bonding a flexible member of a device that constitutes a repetitive bending device with other flexible members, and a storage mold of the adhesive constituting the above-mentioned adhesive layer at -20°C The number G'(-20) is 0.01MPa or more and 0.2MPa or less. The absolute value of the photoelastic coefficient of the adhesive constituting the above-mentioned adhesive layer at 23°C and measured at a wavelength of 400nm is 9.9×10 -10 m 2 /N or less . 如請求項1所述之黏著片，其中，構成上述黏著劑層的黏著劑在23℃，測定波長500nm時的光彈性係數的絕對值為9.9×10-10 m2 /N以下。The pressure-sensitive adhesive sheet according to claim 1, wherein the absolute value of the photoelastic coefficient of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer at a measured wavelength of 500 nm at 23°C is 9.9×10 -10 m 2 /N or less. 如請求項1所述之黏著片，其中，構成上述黏著劑層的黏著劑在23℃，測定波長600nm時的光彈性係數的絕對值為9.9×10-10 m2 /N以下。The pressure-sensitive adhesive sheet according to claim 1, wherein the absolute value of the photoelastic coefficient of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer at a wavelength of 600 nm measured at 23°C is 9.9×10 -10 m 2 /N or less. 如請求項1所述之黏著片，其中，構成上述黏著劑層的黏著劑在85℃時的儲存模數G’(85)為0.005MPa以上，0.2MPa以下。The adhesive sheet according to claim 1, wherein the storage modulus G'(85) at 85°C of the adhesive constituting the adhesive layer is 0.005 MPa or more and 0.2 MPa or less. 如請求項1所述之黏著片，其中，構成上述黏著劑層的黏著劑在25℃時的儲存模數G’(25)為0.01MPa以上，0.2MPa以下。The adhesive sheet according to claim 1, wherein the storage modulus G'(25) at 25°C of the adhesive constituting the adhesive layer is 0.01 MPa or more and 0.2 MPa or less. 如請求項1所述之黏著片，其中，構成上述黏著劑層的黏著劑的凝膠分率為30%以上，95%以下。The adhesive sheet according to claim 1, wherein the gel fraction of the adhesive constituting the adhesive layer is 30% or more and 95% or less. 如請求項1所述之黏著片，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 according to claim 1, wherein the adhesive constituting the adhesive layer is an acrylic adhesive. 如請求項1所述之黏著片，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，挾持於上述剝離片。The adhesive sheet according to claim 1, wherein the adhesive sheet includes two release sheets, The said adhesive layer is pinched by the said peeling sheet so that it may contact with the peeling surface of the said 2 sheet|seat peeling sheet. 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， 其中，上述黏著劑層為由如請求項1〜8中任一項所述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 Adhesive layer for bonding the above-mentioned one flexible member and the above-mentioned other flexible member to each other, Wherein, the adhesive layer is composed of the adhesive layer of the adhesive sheet according to any one of claims 1 to 8. 一種反覆彎曲裝置，具備：如請求項9所述之反覆彎曲積層部件。A repetitive bending device comprising: the repetitive bending laminated member according to claim 9.
TW109123699A 2019-09-18 2020-07-14 Adhesive sheet, repeatedly bend laminated member and repeatedly bend device in which peeling is unlikely to occur at an interface between an adhesive layer and an object to be attached at a bent portion, and light leakage and deterioration of visibility caused by bending are suppressed TW202113005A (en)

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