TW201912745A - Adhesive sheet, display body and display body manufacturing method - Google Patents

Adhesive sheet, display body and display body manufacturing method Download PDF

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Publication number
TW201912745A
TW201912745A TW107113525A TW107113525A TW201912745A TW 201912745 A TW201912745 A TW 201912745A TW 107113525 A TW107113525 A TW 107113525A TW 107113525 A TW107113525 A TW 107113525A TW 201912745 A TW201912745 A TW 201912745A
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Taiwan
Prior art keywords
adhesive
adhesive layer
meth
active energy
display body
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TW107113525A
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Chinese (zh)
Inventor
小鯖翔
高橋洋一
渡邉旭平
荒井隆行
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日商琳得科股份有限公司
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Publication of TW201912745A publication Critical patent/TW201912745A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

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

Abstract

An object of the present invention is to provide an adhesive sheet, a display body, and a method of producing the display body, which are excellent in blister resistance and capable of suppressing yellowing of an adhesive layer. To solve the problem, there is provided an adhesive sheet 1 including an adhesive layer 11 for bonding a display body constitution member 21 to another display body constitution member 22. At least one of the display body constitution member 21 and the other display body constitution member 22 is an ultraviolet shielding member having a light transmittance of 5% or less at a wavelength of 340 nm and a light transmittance of 10% or more at a wavelength of 390 nm. The adhesive layer 11 is composed of an active energy ray-curable adhesive containing a photopolymerization initiator having an absorbance of 0.3 or more at a wavelength of 390 nm in an acetonitrile solution having a concentration of 0.1% by mass.

Description

黏著片、顯示體及顯示體的製造方法Adhesive sheet, display body and manufacturing method of display body

本發明是有關於一種適合使用在顯示體(顯示器)之黏著片、使用該黏著片而能夠得到之顯示體及顯示體的製造方法。The present invention relates to an adhesive sheet suitable for use in a display (display), a display and a method for manufacturing the display that can be obtained by using the adhesive.

近年來，汽車搭載有汽車導航系統增多。在汽車導航系統的顯示體(顯示器)在顯示體模組的表面側設置有保護面板。通常保護面板是透過黏著劑層而與顯示體模組等接著。In recent years, car navigation systems have increased in automobiles. A display body (display) of a car navigation system is provided with a protective panel on a surface side of the display body module. Usually, the protective panel is connected to the display body module and the like through an adhesive layer.

作為汽車導航系統用的保護面板，從安全性的觀點而言，主要不是使用玻璃板，多半是使用塑膠板。但是塑膠板與玻璃板不同，在高溫高濕(濕熱)條件下產生排氣、或透過水蒸氣。因此，有在塑膠板與黏著劑層之間產生氣泡、浮起、剝落等的起泡之情形。因而，上述的黏著劑層被要求耐起泡性。As a protective panel for a car navigation system, from a safety point of view, it is not mainly a glass plate but a plastic plate. However, plastic plates are different from glass plates in that they generate exhaust gas or permeate water vapor under high temperature and high humidity (humid heat) conditions. For this reason, bubbles, such as bubbles, floating, peeling, and the like may occur between the plastic plate and the adhesive layer. Therefore, the above-mentioned adhesive layer is required to have foam resistance.

作為觸控面板用的黏著片，專利文獻1揭示一種紫外線交聯性黏著片，由含有具有紫外線交聯性部位(二苯基酮構造)之含(甲基)丙烯酸酯的單體之(甲基)丙烯基共聚物而成；而且規定在紫外線交聯前後的儲存彈性模數的紫外線交聯性黏著片。此種紫外線交聯性黏著片是貼合在被黏著物之後，藉由進行紫外線照射使交聯反應進行而提高凝聚力。藉由如此地提高黏著劑的凝聚力，具有能夠賦予耐起泡性之可能性。As a pressure-sensitive adhesive sheet for a touch panel, Patent Document 1 discloses an ultraviolet-crosslinkable pressure-sensitive adhesive sheet containing (meth) acrylate-containing monomer (meth) acrylate containing a monomer having a UV-crosslinkable site (diphenyl ketone structure). A) acrylic copolymer; and a UV-crosslinkable pressure-sensitive adhesive sheet that specifies the storage modulus before and after UV-crosslinking. Such an ultraviolet-crosslinkable pressure-sensitive adhesive sheet is adhered to an adherend, and then a crosslinking reaction proceeds by ultraviolet irradiation to improve cohesion. By increasing the cohesive force of the adhesive in this way, there is a possibility that the foam resistance can be imparted.

被使用在汽車的車內之汽車導航系統的情況，因為多半被暴露在紫外線中，所以紫外線容易通過保護面板而到達黏著劑層。由通常的黏著劑所構成的黏著劑層之情況，多半因照射紫外線而產生黃變，此時，顯示器的外觀及視認性低落。In the case of a car navigation system used in a car, since it is mostly exposed to ultraviolet rays, ultraviolet rays easily pass through the protective panel and reach the adhesive layer. In the case of an adhesive layer composed of a general adhesive, yellowing is likely to occur due to ultraviolet radiation. At this time, the appearance and visibility of the display are lowered.

就被使用在光學關聯製品且以耐黃變性作為課題之黏著劑而言，專利文獻2提案揭示一種黏著劑。該黏著劑是由含有使多元醇(a)、聚異氰酸酯(b)及具有羥基的(甲基)丙烯酸化合物(c)反應而得到之胺甲酸酯(甲基)丙烯酸酯樹脂(A)；(甲基)丙烯酸單體(B)；及光聚合起始劑(C)；而且以質量比95/5~5/95的範圍進一步含有光安定劑(D)及抗氧化劑(E)之紫外線硬化型黏著劑用樹脂組成物所得到的黏著劑。 先前技術文獻 專利文獻As for an adhesive used in an optical-related product and having yellowing resistance as a subject, Patent Document 2 proposes an adhesive. The adhesive is a urethane (meth) acrylate resin (A) obtained by reacting a polyol (a), a polyisocyanate (b), and a (meth) acrylic compound (c) having a hydroxyl group; (Meth) acrylic monomer (B); and photopolymerization initiator (C); and ultraviolet rays containing a photo stabilizer (D) and an antioxidant (E) in a mass ratio of 95/5 to 5/95 An adhesive obtained from a resin composition for a curable adhesive. Prior Art Literature Patent Literature

[專利文獻1] 日本特開2011-184582號公報 [專利文獻2] 日本特開2014-015573號公報[Patent Document 1] Japanese Patent Application Publication No. 2011-184582 [Patent Document 2] Japanese Patent Application Publication No. 2014-015573

發明欲解決之課題Problems to be solved by the invention

為了抑制黏著劑層產生黃變，認為不是提高黏著劑本身的耐黃變性，而是以紫外線不到達黏著劑層之方式使保護面板具有紫外線(UV)阻隔性的功能。In order to suppress the yellowing of the adhesive layer, it is considered that instead of improving the yellowing resistance of the adhesive itself, the protective panel has a function of blocking ultraviolet (UV) rays so that ultraviolet rays do not reach the adhesive layer.

但是，將如專利文獻1的紫外線交聯性黏著片使用在UV阻隔性保護面板，對隔著該保護面板對黏著劑層照射紫外線時，紫外線被保護面板阻隔而未到達黏著劑層，致使紫外線硬化性黏著劑未充分地硬化。如此黏著劑未充分地硬化之黏著劑層容易產生起泡。However, when an ultraviolet-crosslinkable adhesive sheet such as Patent Document 1 is used in a UV-blocking protective panel, when the adhesive layer is irradiated with ultraviolet rays through the protective panel, the ultraviolet rays are blocked by the protective panel and do not reach the adhesive layer, causing ultraviolet rays. The hardening adhesive is not sufficiently hardened. Such an adhesive layer in which the adhesive is not sufficiently hardened is liable to cause foaming.

本發明是鑒於如上述的實際情況而進行，其目的是供一種能夠抑制黏著劑層產生黃變，同時具有優異的耐起泡性之黏著片、顯示體及顯示體的製造方法。 用以解決課題之手段The present invention has been made in view of the above-mentioned actual situation, and an object thereof is to provide a method for producing an adhesive sheet, a display body, and a display body which can suppress yellowing of the adhesive layer and have excellent foam resistance. Means to solve the problem

為了達成上述目的，本發明第1是提供一種黏著片，是具備用以將一顯示體構成構件、與另一顯示體構成構件貼合的黏著劑層之黏著片，其特徵在於：前述一顯示體構成構件及前述另一顯示體構成構件的至少一方是波長340nm的光線透射率為5%以下且波長390nm的光線透射率為10%以上之紫外線遮蔽性構件，前述黏著劑層是由含有在濃度0.1質量%的乙腈溶液之波長390nm的吸光度為0.3以上之光聚合起始劑的活性能量線硬化性黏著劑所構成是(發明1)。In order to achieve the above object, the first aspect of the present invention is to provide an adhesive sheet, which is an adhesive sheet provided with an adhesive layer for bonding one display component and another display component, and is characterized by: At least one of the body constituent member and the other display constituent member is an ultraviolet shielding member having a light transmittance of 340 nm or less and a light transmittance of 10% or more at a wavelength of 390 nm. The adhesive layer is composed of The acetonitrile solution having a concentration of 0.1% by mass has an active energy ray-curable adhesive with a photopolymerization initiator having a wavelength of 390 nm and an absorbance of 0.3 or more (Invention 1).

在上述發明(發明1)，黏著劑層是由含有上述光聚合起始劑之黏著劑所構成。藉此，即便透過紫外線遮蔽性構件而對該黏著劑層照射活性能量線，因為該黏著劑層是充分地硬化且成為具有需要的凝聚性之硬化後黏著劑層，所以該硬化後黏著劑層是成為具有優異的耐起泡性之物。又，因為容易使硬化後黏著劑層產生黃變之紫外線，是被紫外線遮蔽性構件遮蔽，所以能夠抑制硬化後黏著劑層產生黃變。In the above invention (Invention 1), the adhesive layer is composed of an adhesive containing the photopolymerization initiator. Thereby, even if an active energy ray is irradiated to the adhesive layer through the ultraviolet shielding member, the adhesive layer is hardened sufficiently and becomes a post-cured adhesive layer having required cohesiveness, so the post-cured adhesive layer It has excellent foam resistance. In addition, since it is easy to cause yellowing of the adhesive layer after curing, and it is shielded by the ultraviolet shielding member, yellowing of the adhesive layer after curing can be suppressed.

在上述發明(發明1)，較佳是其中前述黏著劑是從含有(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、活性能量線硬化性成分(C)、及前述光聚合起始劑(D)之黏著性組成物而得到，而且含有前述(甲基)丙烯酸酯聚合物(A)互相透過前述交聯劑(B)進行交聯而成之聯結構；及未反應的前述活性能量線硬化性成分(C)及前述光聚合起始劑(D)之活性能量線硬化性黏著劑(發明2)。In the above invention (Invention 1), it is preferable that the adhesive is prepared from a (meth) acrylate polymer (A), a crosslinking agent (B), an active energy ray-curable component (C), and the light. Obtained by polymerizing an adhesive composition of the initiator (D), and containing a cross-linked structure in which the (meth) acrylate polymer (A) is cross-linked through the cross-linking agent (B); and unreacted The active energy ray-curable adhesive (C) of the active energy ray-curable component (C) and the photopolymerization initiator (D) (Invention 2).

在上述發明(發明1、2)，其中前述(甲基)丙烯酸酯聚合物(A)含有5質量%以上且60質量%以下之在分子中具有羥基的單體作為構成該聚合物的單體為佳(發明3)。In the above invention (Inventions 1, 2), the (meth) acrylate polymer (A) contains a monomer having a hydroxyl group in a molecule of 5 to 60% by mass as a monomer constituting the polymer. Better (Invention 3).

在上述發明(發明1~3)，其中相對於前述(甲基)丙烯酸酯聚合物(A)100質量份，前述黏著性組成物中之前述交聯劑(B)的含量以0.01質量份以上且3質量份以下為佳(發明4)。In the above invention (Inventions 1 to 3), the content of the crosslinking agent (B) in the adhesive composition is 0.01 parts by mass or more based on 100 parts by mass of the (meth) acrylate polymer (A). It is preferably 3 parts by mass or less (Invention 4).

在上述發明(發明1~4)，其中前述活性能量線硬化性黏著劑的凝膠分率以30%以上且70%以下為佳(發明5)。In the above inventions (Inventions 1 to 4), the gel fraction of the active energy ray-curable adhesive is preferably 30% or more and 70% or less (Invention 5).

在上述發明(發明1~5)，其中前述紫外線遮蔽性構件以塑膠板為佳(發明6)。In the above invention (Inventions 1 to 5), the ultraviolet shielding member is preferably a plastic plate (Invention 6).

在上述發明(發明1~6)，其中較佳是具備2片剝離片；及以與前述2片剝離片的剝離面接觸之方式被前述剝離片夾持之前述黏著劑層(發明7)。In the above inventions (Inventions 1 to 6), it is preferable to include two release sheets; and the adhesive layer sandwiched between the release sheets so as to be in contact with the release surfaces of the two release sheets (Invention 7).

本發明第2是提供一種顯示體，是具備一顯示體構成構件、另一顯示體構成構件、及將前述一顯示體構成構件與前述另一顯示體構成構件互相貼合之硬化後黏著劑層之顯示體，其特徵在於：前述一顯示體構成構件及前述另一顯示體構成構件的至少一方是由波長340nm的光線透射率為5%以下且波長390nm的光線透射率為10%以上之紫外線遮蔽性構件所構成，前述硬化後黏著劑層是使前述黏著片(發明1~7)的前述黏著劑層進行活性能量線硬化而成之硬化後黏著劑層(發明8)。The second aspect of the present invention is to provide a display body including a display body constituting member, another display body constituting member, and a cured adhesive layer that adheres the one display body constituting member and the other display body constituting member to each other. The display body is characterized in that at least one of the foregoing display body constituent member and the other display body constituent member is ultraviolet light having a light transmittance of 340 nm or less and a light transmittance of 390 nm or more of 10% or more. The hardening adhesive layer is made of a shielding member, and is a hardened adhesive layer (invention 8) obtained by hardening the adhesive layer of the adhesive sheet (Inventions 1 to 7) by active energy ray.

在上述發明(發明8)，其中構成前述硬化後黏著劑層之黏著劑的凝膠分率以40%以上且95%以下為佳(發明9)。In the above invention (Invention 8), the gel fraction of the adhesive constituting the cured adhesive layer is preferably 40% or more and 95% or less (Invention 9).

本發明第3是提供一種顯示體的製造方法，其特徵在於：將至少一方為前述紫外線遮蔽性構件之一顯示體構成構件與另一顯示體構成構件透過前述黏著片(發明1~7)的黏著劑層貼合而製造積層體，而且對前述積層體的前述黏著劑層隔著前述紫外線遮蔽性構件照射活性能量線使前述黏著劑層硬化而成為硬化後黏著劑層(發明10)。 發明效果The third aspect of the present invention provides a method for manufacturing a display, characterized in that at least one of the display constituent members and the other display constituent members that are one of the ultraviolet shielding members is transmitted through the adhesive sheet (Inventions 1 to 7). The adhesive layer is laminated to produce a laminated body, and the adhesive layer of the laminated body is irradiated with active energy rays through the ultraviolet shielding member to harden the adhesive layer to become a cured adhesive layer (Invention 10). Invention effect

在本發明之黏著片及顯示體，是能夠抑制黏著劑層產生黃變，同時具有優異的耐起泡性。又，依照本發明之顯示體的製造方法，能夠製造能夠抑制黏著劑層產生黃變，同時具有優異的耐起泡性之顯示體。In the adhesive sheet and the display of the present invention, yellowing of the adhesive layer can be suppressed, and at the same time, it has excellent foam resistance. In addition, according to the method for producing a display body of the present invention, it is possible to produce a display body which can suppress yellowing of the adhesive layer and has excellent foam resistance.

以下，說明本發明的實施形態。 [黏著片] 本實施形態之黏著片，是具備有用以將一顯示體構成構件、與另一顯示體構成構件貼合之黏著劑層之黏著片。該等一顯示體構成構件及另一顯示體構成構件的至少一方是波長340nm的光線透射率為5%以下且波長390nm的光線透射率為10%以上之紫外線遮蔽性構件。針對顯示體及顯示體構成構件如後述。本實施形態之黏著片較佳是將剝離片層積在該黏著劑層的一面或兩面而成。Hereinafter, embodiments of the present invention will be described. [Adhesive Sheet] The adhesive sheet according to this embodiment is an adhesive sheet provided with an adhesive layer for bonding one display component and another display component. At least one of the one display component and the other display component is an ultraviolet shielding member having a light transmittance of 340 nm or less and a light transmittance of 390 nm or more. The display body and display body constituent members will be described later. The adhesive sheet of this embodiment is preferably formed by laminating a release sheet on one or both sides of the adhesive layer.

將作為本實施形態之黏著片的一個例子的具體構成顯示在第1圖。 如第1圖顯示，一實施形態之黏著片1，是由2片剝離片12a、12b及黏著劑層11所構成，其中該黏著劑層11是以與該等2片剝離片12a、12b的剝離面接觸之方式被該2片剝離片12a、12b挾持著。又，在本說明書所謂剝離片的剝離面，是指在剝離片之具有剝離性的面，包含經施行剝離處理的面及未施行剝離處理亦顯示剝離性之面的任一種。The specific structure of an example of the adhesive sheet of this embodiment is shown in FIG. As shown in FIG. 1, an adhesive sheet 1 according to an embodiment is composed of two peeling sheets 12 a and 12 b and an adhesive layer 11, wherein the adhesive layer 11 is formed with the two peeling sheets 12 a and 12 b. The peeling surface is held in contact with the two peeling sheets 12a and 12b. In addition, the release surface of a release sheet in this specification means the surface which has peelability in a release sheet, and includes the surface which performed the peeling process, and the surface which also showed peelability without the peeling process.

1.各構件 1-1.黏著劑層 上述黏著劑層11是由含有在濃度0.1質量%的乙腈溶液之波長390nm的吸光度為0.3以上之光聚合起始劑的活性能量線硬化性黏著劑所構成是。1. Each member 1-1. Adhesive layer The above-mentioned adhesive layer 11 is made of an active energy ray-curable adhesive containing a photopolymerization initiator having an absorbance of 0.3 or more at a wavelength of 390 nm in an acetonitrile solution at a concentration of 0.1% by mass. The composition is.

又，在本實施形態之活性能量線，較佳是在大於波長365nm的波長區域具有實質的強度之發光。作為該波長區域，是以380~450nm為佳，以390~410nm為較佳。又，將在365nm以下之最大發光強度(通常是在365nm附近具有最大尖峰強度)設為100%時，以在上述波長區域的至少一部分具有20%以上的強度為佳。In the active energy ray of this embodiment, it is preferable to emit light having a substantial intensity in a wavelength region greater than a wavelength of 365 nm. The wavelength range is preferably 380 to 450 nm, and more preferably 390 to 410 nm. When the maximum luminous intensity below 365 nm (generally, the maximum peak intensity near 365 nm) is set to 100%, it is preferable to have an intensity of at least 20% in at least a part of the above-mentioned wavelength region.

使用本實施形態之黏著片1時，藉由黏著片1的黏著劑層11將一顯示體構成構件與另一顯示體構成構件貼合之後，透過一顯示體構成構件或另一顯示體構成構件，且較佳是透過前述紫外線遮蔽性構件而對黏著劑層11照射活性能量線，使黏著劑層11硬化而成為硬化後黏著劑層(在後述第2圖中為硬化後黏著劑層11’)。When using the adhesive sheet 1 of this embodiment, one display component is bonded to another display component through the adhesive layer 11 of the adhesive sheet 1 and then passed through one display component or another display component. It is preferable that the adhesive layer 11 is irradiated with active energy rays through the ultraviolet shielding member to harden the adhesive layer 11 to become a cured adhesive layer (the cured adhesive layer 11 'in the second figure described later) ).

又，所謂在本實施形態之硬化後黏著劑層的「硬化後」，是指藉由活性能量線照射而黏著劑的凝膠分率上升為小於5百分點之狀態。The "post-curing" of the post-curing adhesive layer of the present embodiment refers to a state in which the gel fraction of the adhesive is increased to less than 5% by irradiation with active energy rays.

在此，在黏著劑使用先前的光聚合起始劑、例如1-羥基環己基苯基酮時，透過紫外線遮蔽性構件而對黏著劑層照射活性能量線時，紫外線遮蔽性構件之波長340nm的光線透射率為5%以下。因此，用以使上述光聚合起始劑開裂之波長(340nm附近)的活性能量線被紫外線遮蔽性構件遮蔽，且光聚合起始劑的開裂受到阻礙。其結果，活性能量線硬化性成分未良好地進行硬化反應且黏著劑層的硬化不充分。如此進行時，耐起泡性低落且在顯示體構成構件與硬化後黏著劑層之界面，容易產生氣泡、浮起、剝落等的起泡。Here, when a conventional photopolymerization initiator such as 1-hydroxycyclohexylphenyl ketone is used as the adhesive, when an active energy ray is irradiated to the adhesive layer through the ultraviolet shielding member, the wavelength of the ultraviolet shielding member is 340 nm. The light transmittance is 5% or less. Therefore, an active energy ray having a wavelength (near 340 nm) for cracking the photopolymerization initiator is blocked by the ultraviolet shielding member, and the cracking of the photopolymerization initiator is hindered. As a result, the hardening reaction of the active energy ray-curable component did not proceed well, and the curing of the adhesive layer was insufficient. When this is done, the foam resistance is low, and bubbles such as bubbles, floating, and peeling are easily generated at the interface between the display component and the cured adhesive layer.

相對於此，在本實施形態之黏著片1之黏著劑層11，含有在濃度0.1質量%的乙腈溶液之波長390nm的吸光度為0.3以上之光聚合起始劑。此時，即便透過上述紫外線遮蔽性構件而對黏著劑層11照射活性能量線，因為紫外線遮蔽性構件之波長390nm的光線透射率為10%以上，所以用以使光聚合起始劑開裂之波長(390nm附近)的活性能量線不會被紫外線遮蔽性構件遮蔽且光聚合起始劑沒有問題地開裂。其結果，活性能量線硬化性的黏著劑之硬化反應為良好地進行且黏著劑層11充分地硬化，而且所得到的硬化後黏著劑層的凝聚力提升。藉此，即便將具備一顯示體構成構件(紫外線遮蔽性構件)、另一顯示體構成構件、及將該等貼合之硬化後黏著劑層之積層體，特別是一顯示體構成構件(紫外線遮蔽性構件)是在高溫高濕條件下產生排氣、或透過水蒸氣之塑膠板的積層體，在嚴格的高溫高濕條件下例如85℃、85%RH條件下放置1000小時後之情況，亦能夠抑制在顯示構成構件與硬化後黏劑層之界面產生氣泡、浮起、剝落等的起泡。In contrast, the adhesive layer 11 of the adhesive sheet 1 of this embodiment contains a photopolymerization initiator having an absorbance of 0.3 or more at a wavelength of 390 nm in an acetonitrile solution having a concentration of 0.1% by mass. At this time, even if the adhesive layer 11 is irradiated with active energy rays through the ultraviolet shielding member, the wavelength of the ultraviolet shielding member at a wavelength of 390 nm is 10% or more. Therefore, the wavelength used to crack the photopolymerization initiator. The active energy rays (near 390 nm) are not blocked by the ultraviolet shielding member, and the photopolymerization initiator does not crack with any problems. As a result, the hardening reaction of the active energy ray-curable adhesive proceeds well, the adhesive layer 11 is sufficiently cured, and the cohesive force of the obtained cured adhesive layer is improved. Thereby, even if it is a laminated body provided with one display body constituting member (ultraviolet shielding member), another display body constituting member, and the bonded adhesive layer after curing, especially a display body constituting member (ultraviolet rays) Shielding member) is a laminated body of a plastic sheet that generates exhaust gas or permeates water vapor under high temperature and high humidity conditions, and is left for 1000 hours under strict high temperature and high humidity conditions such as 85 ° C and 85% RH conditions. It is also possible to suppress the occurrence of bubbles, floating, peeling, etc. at the interface between the display constituent member and the cured adhesive layer.

又，在將上述紫外線遮蔽性構件及硬化後黏著劑層層積而成之積層體，能夠抑制波長340nm附近的紫外線透過紫外線遮蔽性構件。該波長城的紫外線容易使黏著劑(特別是交聯劑、活性能量線硬化性成分等的成分)產生黃變之紫外線，但是藉由紫外線遮蔽性構件抑制紫外線在波長340nm附近透過，該紫外線不容易從紫外線遮蔽性構件側至達硬化後黏著劑層。因而，能夠抑制硬化後黏著劑層產生黃變。Moreover, in the laminated body which laminated | stacked the said ultraviolet shielding member and the hardened adhesive layer, it is possible to suppress ultraviolet rays in the vicinity of a wavelength of 340 nm from transmitting an ultraviolet shielding member. The ultraviolet rays at this wavelength are likely to cause yellowing of the adhesive (especially components such as a cross-linking agent and an active energy ray-curable component). However, the ultraviolet shielding member inhibits ultraviolet rays from transmitting around the wavelength of 340 nm. It is easy to reach the cured adhesive layer from the ultraviolet shielding member side. Therefore, yellowing of the adhesive layer after hardening can be suppressed.

構成上述黏著劑層11之黏著劑，以丙烯酸系的活性能量線硬化性黏著劑為佳，特別是以從含有(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、活性能量線硬化性成分(C)、及在濃度0.1質量%的乙腈溶液之波長390nm的吸光度為0.3以上之光聚合起始劑(D)之黏著性組成物(以下有稱為「黏著性組成物P」之情形)得到為佳。而且，上述黏著劑以含有(甲基)丙烯酸酯聚合物(A)互相透過交聯劑(B)進行交聯而成之交聯結構、及未反應的活性能量線硬化性成分(C)及光聚合起始劑(D)之活性能量線硬化性黏著劑為佳。因為上述活性能量線硬化性黏著劑能夠藉由將黏著性組成物P進行交聯(熱交聯)而得到，且含有未反應的活性能量線硬化性成分(C)及光聚合起始劑(D)，具有活性能量線硬化性。活性能量線硬化性成分(C)是在黏著片1使用時(貼合被黏著物後)，對黏著劑層11照射活性能量線時進行聚合且硬化。又，在本說明書，所謂(甲基)丙烯酸，是意味著丙烯酸及甲基丙烯酸之雙方。其他類似用語亦同樣。又，「聚合物」是設為亦包含「共聚物」的概念。The adhesive constituting the above-mentioned adhesive layer 11 is preferably an acrylic active energy ray-curable adhesive. In particular, the adhesive includes a (meth) acrylate polymer (A), a crosslinking agent (B), and active energy. Adhesive composition of a linear hardening component (C) and a photopolymerization initiator (D) having an absorbance of 0.3 or more at a wavelength of 390 nm in an acetonitrile solution having a concentration of 0.1% by mass (hereinafter referred to as "adhesive composition P" ") Is better. In addition, the above-mentioned adhesive has a cross-linked structure obtained by crosslinking the (meth) acrylate polymer (A) with each other through the cross-linking agent (B), and an unreacted active energy ray-curable component (C) and The photopolymerization initiator (D) is preferably an active energy ray-curable adhesive. The above-mentioned active energy ray-curable adhesive can be obtained by crosslinking (thermal crosslinking) the adhesive composition P, and contains an unreacted active energy ray-curable component (C) and a photopolymerization initiator ( D). It has active energy ray hardenability. The active energy ray-curable component (C) is polymerized and hardened when the adhesive layer 11 is irradiated with the active energy ray when the adhesive sheet 1 is used (after the adherend is bonded). In this specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms. In addition, "polymer" is a concept including "copolymer".

將黏著性組成物P進行交聯(熱交聯)而成之上述活性能量線硬化性黏著劑，因為在藉由照射活性能量線而硬化前的階段為較柔軟，所以將黏著片1貼附在具有段差的顯示體構成構件時，黏著劑層11容易追隨段差而能夠抑制在段差附近產生間隙、浮起等。亦即，黏著劑層11初期的段差追隨性優良。又，將構成黏著劑層11之黏著劑進行熱交聯，因為具有某種程度的交聯密度且具有預定凝聚力，所以黏著劑層11被膜強度較高。因而，例如在將黏著片進行裁斷加工等的時候，能夠抑制黏著劑附著在刀刃、或是在保管時等能夠抑制黏著劑從黏著劑層11滲出。The above-mentioned active energy ray hardening adhesive obtained by cross-linking (heat-crosslinking) the adhesive composition P is softer in the stage before hardening by irradiating the active energy ray, so the adhesive sheet 1 is attached In the case of a display constituent member having a step difference, the adhesive layer 11 can easily follow the step difference, and can suppress generation of gaps, floating, and the like near the step difference. That is, the initial step followability of the adhesive layer 11 is excellent. In addition, the adhesive constituting the adhesive layer 11 is thermally cross-linked. The adhesive strength of the adhesive layer 11 is high because the adhesive has a certain degree of cross-link density and a predetermined cohesive force. Therefore, for example, when the adhesive sheet is subjected to a cutting process or the like, it is possible to prevent the adhesive from adhering to the blade, or to prevent the adhesive from oozing out of the adhesive layer 11 during storage.

黏著劑層11是由將黏著性組成物P交聯(熱交聯)而成之活性能量線硬化性黏著劑所構成時，透過上述紫外線遮蔽性構件而對黏著劑層11照射活性能量線時，用以使光聚合起始劑(D)開裂之波長(390nm附近)的活性能量線未被紫外線遮蔽性構件遮蔽，所以光聚合起始劑(D)沒有問題地開裂。其結果，活性能量線硬化性成分(C)的硬化反應為良好地進行且黏著劑層11充分地硬化，而且所得到的硬化後黏著劑層的凝聚力提升。藉此，硬化後黏著劑層是成為具有優異的耐起泡性之物。When the adhesive layer 11 is composed of an active energy ray-curable adhesive obtained by crosslinking (heat-crosslinking) the adhesive composition P, when the active energy ray is irradiated to the adhesive layer 11 through the ultraviolet shielding member described above Since the active energy ray at a wavelength (near 390 nm) for cracking the photopolymerization initiator (D) is not shielded by the ultraviolet shielding member, the photopolymerization initiator (D) cracks without problems. As a result, the curing reaction of the active energy ray-curable component (C) proceeds well and the adhesive layer 11 is sufficiently cured, and the cohesive force of the obtained cured adhesive layer is improved. Thereby, the adhesive layer after hardening becomes a thing which has the outstanding foam resistance.

(1)構成成分 (1-1)(甲基)丙烯酸酯聚合物(A) (甲基)丙烯酸酯聚合物(A)以含有在分子內具有反應性官能基之含反應性官能基的單體作為構成該聚合物的單體為佳。藉由(甲基)丙烯酸酯聚合物(A)含有含反應性官能基的單體作為構成該聚合物的單體單元，在加熱下透過源自該含反應性官能基的單體的反應性官能基而與交聯劑(B)進行反應。藉此，能夠形成交聯結構(三維網狀結構)且能夠得到具有所需要的凝聚力之黏著劑。(1) Component (1-1) (meth) acrylate polymer (A) (meth) acrylate polymer (A) contains a reactive functional group-containing monomer having a reactive functional group in the molecule. It is preferable that the polymer is a monomer constituting the polymer. The (meth) acrylate polymer (A) contains a reactive functional group-containing monomer as a monomer unit constituting the polymer, and the reactivity derived from the reactive functional group-containing monomer is transmitted under heating. The functional group reacts with the crosslinking agent (B). Thereby, a crosslinked structure (three-dimensional network structure) can be formed, and an adhesive having a required cohesive force can be obtained.

就(甲基)丙烯酸酯聚合物(A)所含有作為構成該聚合物的單體單元之含反應性官能基的單體而言，可適合舉出在分子內具有羥基之單體(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。該等含反應性官能基的單體可單獨使用1種，亦可併用2種以上。As the reactive functional group-containing monomer contained in the (meth) acrylate polymer (A) as a monomer unit constituting the polymer, a monomer having a hydroxyl group in the molecule (a hydroxyl group-containing monomer) can be suitably cited. Monomers having a carboxyl group in the molecule (carboxyl-containing monomer), monomers having an amine group in the molecule (amine-containing monomer), and the like. These reactive functional group-containing monomers may be used alone or in combination of two or more.

上述含反應性官能基的單體之中，以含羥基的單體及含羧基的單體為佳，從耐起泡性的觀點而言，以含羥基的單體為特佳。含羥基的單體多半是玻璃轉移溫度(Tg)較高之物，藉由將此種含羥基的單體作為構成單體(特別是採用較多的量)，所得到的(甲基)丙烯酸酯聚合物(A)亦成為玻璃轉移溫度(Tg)較高之物。藉此，所形成的黏著劑層11之儲存彈性模數變高且成為具有更優異的耐起泡性之物。Among the above-mentioned reactive functional group-containing monomers, a hydroxyl-containing monomer and a carboxyl-containing monomer are preferred, and a hydroxyl-containing monomer is particularly preferred from the viewpoint of foam resistance. Most of the hydroxyl-containing monomers are those having a high glass transition temperature (Tg). By using such a hydroxyl-containing monomer as a constituent monomer (especially in a relatively large amount), the (meth) acrylic acid obtained The ester polymer (A) also has a higher glass transition temperature (Tg). Thereby, the storage elastic modulus of the formed adhesive layer 11 becomes high, and it becomes a thing which has more excellent foam resistance.

作為含羥基單體，例如可舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等的(甲基)丙烯酸羥基烷酯等。尤其是從耐起泡性之觀點而言，以(甲基)丙烯酸2-羥基乙酯及(甲基)丙烯酸4-羥基丁酯為佳。該等可單獨使用，亦可組合2種以上而使用。Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-methyl (meth) acrylate Hydroxybutyl (meth) acrylate and the like, such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. In particular, from the viewpoint of foam resistance, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred. These may be used alone or in combination of two or more.

作為含羧基的單體，例如可舉出丙烯酸、甲基丙烯酸、巴豆酸、順丁烯二酸、伊康酸、檸康酸等的乙烯性不飽和羧酸。尤其是就在所得到的(甲基)丙烯酸酯聚合物(A)之羧基與交聯劑(B)的反應性及其他單體的共聚合性而言，以丙烯酸為佳。該等可單獨使用，亦可組合2種以上而使用。Examples of 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. In particular, acrylic acid is preferred in terms of the reactivity of the carboxyl group of the obtained (meth) acrylate polymer (A) with the crosslinking agent (B) and the copolymerizability of other monomers. These may be used alone or in combination of two or more.

(甲基)丙烯酸酯聚合物(A)含反應性官能基的單體作為構成該聚合物的單體單元，其下限值以含有5質量%以上為佳，以含有10質量%以上為較佳，以有20質量%以上為特佳，進而以含有30質量%以上為佳。特別是(甲基)丙烯酸酯聚合物(A)，以含有上述量之含羥基的單體作為構成該聚合物的單體單元為佳。藉此，黏著片1具有更優異的耐起泡性，同時與活性能量線硬化性成分(C)的相溶性亦變成良好且所得到的硬化後黏著劑層之透明性亦提升。The (meth) acrylate polymer (A) has a reactive functional group-containing monomer as a monomer unit constituting the polymer, and the lower limit value thereof is preferably 5% by mass or more, and more preferably 10% by mass or more. It is particularly preferable that the content is 20% by mass or more, and it is more preferable that the content is 30% by mass or more. In particular, the (meth) acrylate polymer (A) preferably contains the above-mentioned hydroxyl-containing monomer as a monomer unit constituting the polymer. Thereby, the adhesive sheet 1 has more excellent foam resistance, and at the same time, the compatibility with the active energy ray-curable component (C) becomes good, and the transparency of the obtained cured adhesive layer is also improved.

又，(甲基)丙烯酸酯聚合物(A)是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，其上限值以含有60質量%以下為佳，以含有50質量%以下為特佳，進而以含有40質量%以下為佳。藉此，能夠充分地確保含反應性官能基的單體以外的單體之含量且所得到的黏著劑的黏著性變成更優異。The (meth) acrylate polymer (A) contains a reactive functional group-containing monomer as a monomer unit constituting the polymer, and its upper limit is preferably 60% by mass or less, and 50% by mass. It is particularly preferable that the content is not more than%, and it is more preferable that the content is not more than 40% by mass. Thereby, the content of monomers other than the reactive functional group-containing monomer can be sufficiently ensured, and the adhesiveness of the obtained adhesive can be further improved.

(甲基)丙烯酸酯聚合物(A)不含有含羧基的單體作為構成該聚合物的單體單元亦佳。因為羧基為酸成分，藉由不含有含羧基的單體，即便在黏著劑的貼附對象存在因酸而產生不良之物、例如錫摻雜氧化銦(ITO)等的透明導電膜、金屬膜、金屬網狀物等之情況，亦能夠抑制因酸引起該等的不良(腐蝕、電阻值變化等)。It is also preferable that the (meth) acrylate polymer (A) does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. The carboxyl group is an acid component, and because it does not contain a carboxyl group-containing monomer, even if there is a defect caused by an acid, such as a transparent conductive film such as tin-doped indium oxide (ITO), or a metal film, on the target of the adhesive, In the case of metal meshes, etc., such defects (corrosion, resistance change, etc.) caused by acids can be suppressed.

在此，所謂「不含有含羧基的單體」是意味著實質上不含有含羧基的單體，除了完全不含有含羧基的單體以外，在不產生因羧基引起透明導電膜、金屬配線等腐蝕之程度亦容許含有含羧基的單體。具體而言，在(甲基)丙烯酸酯聚合物(A)中，容許含有0.1質量%以下之量的含羧基的單體作為單體單元，較佳為0.01質量%以下，更佳為0.001質量%以下。Here, the term "containing no carboxyl group-containing monomer" means that there is substantially no carboxyl group-containing monomer. Except that the carboxyl group-containing monomer is not contained at all, no transparent conductive film, metal wiring, etc. due to the carboxyl group are generated. The degree of corrosion also allows for carboxyl-containing monomers. Specifically, in the (meth) acrylate polymer (A), a carboxyl group-containing monomer is allowed as a monomer unit in an amount of 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001% by mass. %the following.

(甲基)丙烯酸酯聚合物(A)以含有(甲基)丙烯酸烷酯作為構成該聚合物之單體單元為佳。藉此，能夠顯現良好的黏著性。烷基可為直鏈狀或分枝鏈狀，亦可具有環狀結構。The (meth) acrylate polymer (A) preferably contains an alkyl (meth) acrylate as a monomer unit constituting the polymer. Thereby, good adhesiveness can be expressed. The alkyl group may be linear or branched, or may have a cyclic structure.

從黏著性的觀點而言，作為(甲基)丙烯酸烷酯，以烷基的碳數為1~20的(甲基)丙烯酸烷酯為佳。作為烷基的碳數為1~20的(甲基)丙烯酸烷酯，例如可舉出(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)丙烯酸肉豆蔻酯、(甲基)丙烯酸棕櫚酯、(甲基)丙烯酸硬脂酸酯等。該等可單獨使用，亦可組合2種以上而使用。From the viewpoint of adhesiveness, the alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group. Examples of the alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) ) N-butyl acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n- (meth) acrylate Decyl ester, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearate (meth) acrylate, and the like. These may be used alone or in combination of two or more.

上述之中，有效率地賦予黏著力之同時，從耐起泡性的觀點而言，以烷基的碳數為2~12(甲基)丙烯酸烷酯為較佳，以烷基的碳數為4~10的丙烯酸烷酯為特佳。具體而言，可適合舉出(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯及(甲基)丙烯酸異辛酯，可更適合舉出丙烯酸丁酯、丙烯酸2-乙基己酯及丙烯酸異辛酯。該等可單獨使用，亦可組合2種以上而使用。Among the above, from the viewpoint of foaming resistance, it is preferable that the number of carbon atoms of the alkyl group is 2 to 12 (alkyl) methacrylate, and the number of carbon atoms of the alkyl group is effective. An alkyl acrylate having 4 to 10 is particularly preferable. Specific examples include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate, and more preferable examples include butyl acrylate and 2-ethyl acrylate Hexyl ester and isooctyl acrylate. These may be used alone or in combination of two or more.

(甲基)丙烯酸酯聚合物(A)含有(甲基)丙烯酸烷酯作為構成該聚合物的單體單元，其下限值以含有20質量%以上為佳，以含有25質量%以上為較佳，以含有30質量%以上為特佳，進而以含有40質量%以上為佳。(甲基)丙烯酸烷酯的含量之下限值為上述時，(甲基)丙烯酸酯聚合物(A)能夠發揮適合的黏著性。又，(甲基)丙烯酸酯聚合物(A)含有(甲基)丙烯酸烷酯作為構成該聚合物的單體單元時，其上限值以含有99質量%以下為佳，以含有90質量%以下為較佳。以含有80質量%以下為特佳，進而以含有60質量%以下為佳。(甲基)丙烯酸烷酯的含量之上限值為上述時，能夠將含反應性官能基的單體等的其他單體成分導入適合量至(甲基)丙烯酸酯聚合物(A)中。The (meth) acrylate polymer (A) contains alkyl (meth) acrylate as a monomer unit constituting the polymer, and the lower limit value thereof is preferably 20% by mass or more, and 25% by mass or more. It is particularly preferable that the content is 30% by mass or more, and it is more preferable that the content is 40% by mass or more. When the lower limit of the content of the alkyl (meth) acrylate is as described above, the (meth) acrylate polymer (A) can exhibit suitable adhesion. When the (meth) acrylate polymer (A) contains an alkyl (meth) acrylate as a monomer unit constituting the polymer, the upper limit is preferably 99% by mass or less, and 90% by mass. The following is preferred. The content is particularly preferably 80% by mass or less, and further preferably 60% by mass or less. When the upper limit of the content of the alkyl (meth) acrylate is as described above, other monomer components such as a reactive functional group-containing monomer can be introduced into the (meth) acrylate polymer (A) in an appropriate amount.

又，(甲基)丙烯酸酯聚合物(A)以具有脂環式結構之單體(含脂環式結構的單體)作為構成該聚合物的單體單元為佳。因為含脂環式結構的單體之體積較大，藉由使其存在於聚合物中，推定可擴大聚合物之間之間隔且能夠使所得到的黏著劑成為具有優異的柔軟性之物。藉此，黏著劑成為具有優異的段差追隨性之物。The (meth) acrylate polymer (A) is preferably a monomer having an alicyclic structure (alicyclic structure-containing monomer) as a monomer unit constituting the polymer. Since the volume of the alicyclic structure-containing monomer is large, it is estimated that the presence of the monomer in the polymer can enlarge the interval between the polymers and make the obtained adhesive a substance having excellent flexibility. Thereby, the adhesive becomes a thing which has the excellent step-following property.

脂環式結構的碳環，可為飽和結構之物，亦可為具有不飽和鍵之物。又，脂環式結構可為單環的脂環式結構，亦可為二環、三環等多環的脂環式結構。脂環式結構的碳數以5~20為佳，以6~15為特佳，進而以7~12為佳。The carbocyclic ring of the alicyclic structure may be a thing having a saturated structure or a thing having an unsaturated bond. The alicyclic structure may be a monocyclic alicyclic structure or a polycyclic alicyclic structure such as a bicyclic ring or a tricyclic ring. The carbon number of the alicyclic structure is preferably from 5 to 20, particularly from 6 to 15, and even more preferably from 7 to 12.

作為脂環式結構，例如能夠適合舉出含有環己基骨架、二環戊二烯骨架、金剛烷骨架、異莰基骨架、環烷骨架(環庚烷骨架、環辛烷骨架、環壬烷骨架、環癸烷骨架、環十一烷骨架、環十二烷骨架等)、環烯骨架(環庚烯骨架、環辛烯骨架等)、降莰烯(norbornene)骨架、降莰二烯(norbornadiene)骨架、多環式骨架(立方體烷(cubane)骨架、籃烷(Basketane)骨架、房烷(Housane)骨架等)、螺骨架等之物。尤其是從使耐起泡性成為更優異的觀點而言，以含有金剛烷骨架及異莰基骨架為佳。Examples of the alicyclic structure include a cyclohexyl skeleton, a dicyclopentadiene skeleton, an adamantane skeleton, an isofluorenyl skeleton, and a cycloalkane skeleton (cycloheptane skeleton, cyclooctane skeleton, and cyclononane skeleton). , Cyclodecane skeleton, cycloundecane skeleton, cyclododecane skeleton, etc.), cycloolefin skeleton (cycloheptene skeleton, cyclooctene skeleton, etc.), norbornene skeleton, norbornadiene ) Skeletons, polycyclic skeletons (cubane skeleton, basketane skeleton, Housane skeleton, etc.), spiral skeletons and the like. In particular, it is preferable to contain an adamantane skeleton and an isofluorenyl skeleton from the viewpoint of making the foaming resistance more excellent.

作為上述含脂環式結構的單體，以含有上述骨架之(甲基)丙烯酸酯單體為佳，具體而言，可舉出(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊烷、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯等，尤其是以(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸異莰酯為佳。該等可單獨使用1種，亦可組合2種以上而使用。As the alicyclic structure-containing monomer, a (meth) acrylate monomer containing the above-mentioned skeleton is preferable, and specifically, cyclohexyl (meth) acrylate and dicyclo (meth) acrylate Pentane, adamantane (meth) acrylate, isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, etc. Adamantane (meth) acrylate and isoamyl (meth) acrylate are preferred. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(甲基)丙烯酸酯聚合物(A)以含有3質量%以上之含脂環式結構的單體作為構成該聚合物的單體單元為佳，以含有6質量%以上更佳，以含有9質量%以上為特佳。又，從確保其他成分的調配量之觀點而言，(甲基)丙烯酸酯聚合物(A)以將含脂環式結構的單體的含量設為30質量%以下為佳，以設為20質量%以下為更佳，以設為15質量%以下為特佳。含脂環式結構的單體之比率在上述範圍內時，所得到的黏著劑的段差追隨性為更優異之同時，對塑膠的黏著力更優異。The (meth) acrylate polymer (A) preferably contains a monomer having an alicyclic structure of 3% by mass or more as a monomer unit constituting the polymer, more preferably contains 6% by mass or more, and contains 9% by mass or more. A mass% or higher is particularly preferred. From the viewpoint of ensuring the blending amount of other components, the content of the (meth) acrylate polymer (A) is preferably 30% by mass or less, and is preferably 20% by mass. It is more preferable that the content is at most 15% by mass, and it is particularly preferable that the content is at most 15% by mass. When the ratio of the alicyclic structure-containing monomer is within the above-mentioned range, the obtained adhesive has more excellent followability of the step, and at the same time, it has more excellent adhesion to plastic.

又，上述(甲基)丙烯酸酯聚合物(A)是含有含氮原子單體作為構成該聚合物的單體單元亦佳。藉由使聚合物中存在含氮原子單體作為結構單元，能夠對黏著劑賦予預定極性且成為對如玻璃般之具有某種程度的極性之被黏著物具有優異的親和性之物。作為上述含氮原子單體，從使(甲基)丙烯酸酯聚合物(A)具有適當的剛性之觀點而言，以具有含氮雜環之單體為佳。The (meth) acrylate polymer (A) preferably contains a nitrogen atom-containing monomer as a monomer unit constituting the polymer. By having a nitrogen atom-containing monomer as a structural unit in the polymer, it is possible to impart a predetermined polarity to the adhesive and to have excellent affinity for an adherend having a certain degree of polarity like glass. As the nitrogen atom-containing monomer, a monomer having a nitrogen-containing heterocyclic ring is preferred from the viewpoint of imparting appropriate rigidity to the (meth) acrylate polymer (A).

作為具有含氮的雜環之單體，例如可舉出N-(甲基)丙烯醯基嗎啉、N-乙烯基-2-吡咯啶酮、N-(甲基)丙烯醯基吡咯啶酮、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶、N-(甲基)丙烯醯基吖環丙烷、(甲基)丙烯酸吖環丙烷基乙酯、2-乙烯基吡啶、4-乙烯基吡啶、2-乙烯基吡、1-乙烯基咪唑、N-乙烯基咔唑、N-乙烯基鄰苯二甲醯亞胺等，尤其是以可發揮更優異的黏著力之N-(甲基)丙烯醯基嗎啉為佳，以N-丙烯醯基嗎啉為特佳。該等可單獨使用1種，亦可組合2種以上而使用。Examples of the monomer having a nitrogen-containing heterocyclic ring include N- (meth) acrylfluorenylmorpholine, N-vinyl-2-pyrrolidone, and N- (meth) acrylfluorinylpyrrolidone , N- (meth) acrylfluorenylpiperidine, N- (meth) acrylfluorenyl pyrrolidine, N- (meth) acrylfluorenyl acrylpropane, acrylpropanyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinylpyridine, 1-vinylimidazole, N-vinylcarbazole, N-vinylphthalimide, etc. N- (meth) acrylfluorenylmorpholine having better adhesion is preferable, and N-acrylfluorenylmorpholine is particularly preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(甲基)丙烯酸酯聚合物(A)含有含氮原子單體作為構成該聚合物的單體單元時，該含氮原子單體以含有0.5質量%以上為佳，以含有1質量%以上為特佳，進而以含有3質量%以上為佳。又，(甲基)丙烯酸酯聚合物(A)含有20質量%以下的該含氮原子單體作為構成該聚合物的單體單元為佳，以含有15質量%以下為特佳，進而以含有10質量%以下為佳。藉由含氮原子單體的含量在上述範圍內，所得到的黏著劑能夠充分地發揮對玻璃之優異的黏著力。When the (meth) acrylate polymer (A) contains a nitrogen atom-containing monomer as a monomer unit constituting the polymer, the nitrogen atom-containing monomer preferably contains 0.5% by mass or more, and more preferably contains 1% by mass or more. Particularly preferred is a content of 3% by mass or more. The (meth) acrylate polymer (A) preferably contains 20% by mass or less of the nitrogen atom-containing monomer as a monomer unit constituting the polymer, particularly preferably contains 15% by mass or less, and further contains It is preferably 10% by mass or less. When the content of the nitrogen atom-containing monomer is within the above range, the obtained adhesive can sufficiently exert excellent adhesion to glass.

(甲基)丙烯酸酯聚合物(A)以使用溶液聚合法得到的溶液聚合物為佳。藉由為溶液聚合物，因為容易得到高分子量的聚合物且所得到的黏著劑能夠期待提升凝聚力，所以能夠成為具有更優異的耐起泡性之物。The (meth) acrylate polymer (A) is preferably a solution polymer obtained by a solution polymerization method. By being a solution polymer, a polymer having a high molecular weight is easy to obtain, and the obtained adhesive can be expected to improve cohesion, so that it can be a substance having more excellent foam resistance.

(甲基)丙烯酸酯聚合物(A)的聚合態樣，可為無規共聚物，亦可為嵌段共聚物。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)的重量平均分子量之下限值，以20萬以上為佳，以30萬以上為特佳，進而以40萬以上為佳。(甲基)丙烯酸酯聚合物(A)的重量平均分子量之下限值為上述以上時，所得到的黏著劑之耐起泡性為更優異。The lower limit of the weight average molecular weight of the (meth) acrylate polymer (A) is preferably at least 200,000, particularly preferably at least 300,000, and more preferably at least 400,000. When the lower limit of the weight average molecular weight of the (meth) acrylate polymer (A) is the above or more, the foaming resistance of the obtained adhesive is more excellent.

又，(甲基)丙烯酸酯聚合物(A)的重量平均分子量之上限值，以200萬以下為佳，以150萬以下為特佳，進而以100萬以下為佳。(甲基)丙烯酸酯聚合物(A)的重量平均分子量之上限值為上述以下時，所得到的黏著劑之段差追隨性為更優異。又，在本說明書之重量平均分子量，是使用凝膠滲透層析(GPC)法所測得之標準聚苯乙烯換算之值。The upper limit of the weight average molecular weight of the (meth) acrylate polymer (A) is preferably 2 million or less, particularly preferably 1.5 million or less, and further preferably 1 million or less. When the upper limit of the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is the following or lower, the step followability of the obtained adhesive is more excellent. In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value measured using the gel permeation chromatography (GPC) method.

又，在黏著性組成物P，(甲基)丙烯酸酯聚合物(A)可單獨使用1種，亦可組合2種以上而使用。Moreover, 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 type.

在本實施形態之黏著性組成物P中之(甲基)丙烯酸酯聚合物(A)的含量之下限值，以50質量%以上為佳，以60質量%以上為特佳，進而以70質量%以上為佳。藉由(甲基)丙烯酸酯聚合物(A)的含量之下限值為上述，所得到的黏著劑之黏著力成為更良好。又，(甲基)丙烯酸酯聚合物(A)的含量之上限值，以99質量%以下為佳，以97質量%以下為特佳，進而以95質量%以下為佳。藉由(甲基)丙烯酸酯聚合物(A)的含量之上限值為上述，能夠確保交聯劑(B)、活性能量線硬化性成分(C)及光聚合起始劑(D)之其他成分的含量且成為耐起泡性更優異之物。The lower limit of the content of the (meth) acrylate polymer (A) in the adhesive composition P of this embodiment is preferably 50% by mass or more, particularly preferably 60% by mass or more, and more preferably 70% by mass. A mass% or more is preferred. When the lower limit of the content of the (meth) acrylate polymer (A) is as described above, the adhesive force of the obtained adhesive becomes better. The upper limit of the content of the (meth) acrylate polymer (A) is preferably 99% by mass or less, particularly preferably 97% by mass or less, and further preferably 95% by mass or less. When the upper limit of the content of the (meth) acrylate polymer (A) is as described above, it is possible to ensure the contents of the crosslinking agent (B), the active energy ray-curable component (C), and the photopolymerization initiator (D). The content of other components is more excellent in foam resistance.

(1-2)交聯劑(B) 交聯劑(B)能夠藉由黏著性組成物P的加熱而將(甲基)丙烯酸酯聚合物(A)交聯且能夠良好地形成三維網狀結構。藉此，所得到的黏著劑之凝聚力進一步提升且成為具有更優異的耐起泡性之物。(1-2) Cross-linking agent (B) The cross-linking agent (B) can cross-link the (meth) acrylate polymer (A) by heating the adhesive composition P and can form a three-dimensional network well. structure. Thereby, the cohesive force of the obtained adhesive is further improved, and it becomes a thing with more excellent foam resistance.

作為上述交聯劑(B)，是與(甲基)丙烯酸酯聚合物(A)所具有之反應性官能基進行反應之物即可，例如可舉出異氰酸酯系交聯劑、環氧系交聯劑、胺系交聯劑、三聚氰胺系交聯劑、吖環丙烷系交聯劑、肼系交聯劑、醛系交聯劑、㗁唑啉系交聯劑、金屬烷氧化物系交聯劑、金屬鉗合物系交聯劑、金屬鹽系交聯劑、銨鹽系交聯劑等。在此，(甲基)丙烯酸酯聚合物(A)含有含羥基的單體作為構成單體單元時，以使用與羥基具有優異的反應性之異氰酸酯系交聯劑作為交聯劑(B)為佳。又，(甲基)丙烯酸酯聚合物(A)含有含羧基的單體作為構成單體單元時，以使用與羧基具有優異的反應性之環氧系交聯劑作為交聯劑(B)為佳。又，交聯劑(B)能夠單獨使用1種、或組合2種以上而使用。The crosslinking agent (B) may be a substance that reacts with a reactive functional group of the (meth) acrylate polymer (A), and examples thereof include an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent. Crosslinking agent, amine-based crosslinker, melamine-based crosslinker, acridine-based crosslinker, hydrazine-based crosslinker, aldehyde-based crosslinker, oxazoline-based crosslinker, metal alkoxide-based crosslinker Agents, metal clamp compound-based crosslinking agents, metal salt-based crosslinking agents, ammonium salt-based crosslinking agents, and the like. When the (meth) acrylate polymer (A) contains a hydroxyl-containing monomer as a constituent monomer unit, an isocyanate-based crosslinking agent having excellent reactivity with a hydroxyl group is used as the crosslinking agent (B). good. When the (meth) acrylate polymer (A) contains a carboxyl group-containing monomer as a constituent monomer unit, an epoxy-based crosslinking agent having excellent reactivity with a carboxyl group is used as the crosslinking agent (B). good. Moreover, a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.

異氰酸酯系交聯劑是至少含有聚異氰酸酯化合物之物。作為聚異氰酸酯化合物，例如可舉出甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、苯二甲基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、及該等的縮二脲體、三聚異氰酸酯體、進而與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等含低分子活性氫的化合物的反應物之加成物等。尤其是從與羥基的反應性之觀點而言，以三羥甲基丙烷改性的芳香族聚異氰酸酯、特別是三羥甲基丙烷改性甲苯二異氰酸酯及三羥甲基丙烷改性苯二甲基二異氰酸酯為佳。The isocyanate-based crosslinking agent is a substance containing at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, and isophorone. Alicyclic polyisocyanates, such as diisocyanates, hydrogenated diphenylmethane diisocyanates, and the like, biuret bodies, trimeric isocyanate bodies, and further, ethylene glycol, propylene glycol, neopentyl glycol, and trimethylol Adducts of reactants of compounds containing low-molecular active hydrogen, such as propane and castor oil. In particular, from the viewpoint of reactivity with a hydroxyl group, an aromatic polyisocyanate modified with trimethylolpropane, in particular a trimethylolpropane-modified toluene diisocyanate, and a trimethylolpropane-modified xylylene Diisocyanate is preferred.

作為環氧系交聯劑，例如可舉出1,3-雙(N,N-二環氧丙基胺甲基)環己烷、N,N,N’,N’-四環氧丙基-間苯二甲二胺(m-xylylenediamine)、乙二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、三羥甲基丙烷二環氧丙基醚、二環氧丙基苯胺、二環氧丙胺等。尤其是從與羧基的反應性的觀點而言，以1,3-雙(N,N-二環氧丙基胺甲基)環己烷為佳。Examples of the epoxy-based crosslinking agent include 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and N, N, N ', N'-tetraepoxypropyl -M-xylylenediamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, di Glycidylaniline, diglycidylamine, etc. In particular, from the viewpoint of reactivity with a carboxyl group, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane is preferred.

相對於(甲基)丙烯酸酯聚合物(A)100質量份，在黏著性組成物P中之交聯劑(B)的含量以0.01質量份以上為佳，以0.05質量份以上為特佳，進而以0.1質量份以上為佳。又，該含量以3質量份以下為佳，以1質量份以下為較佳，以0.5質量份以下為特佳，進而以0.3質量份以下為佳。藉由交聯劑(B)的含量在上述範圍，交聯程度成為適當且所得到的黏著劑成為具有更優異的耐起泡性之物。又，交聯劑(B)之中，特別是異氰酸酯系交聯劑是容易產生黃變的成分，藉由交聯劑(B)的含量在上述範圍，能夠進一步抑制硬化後黏著劑層的產生黃變。藉由(甲基)丙烯酸酯聚合物(A)具有前述較佳組成，能夠將交聯劑(B)的含量抑制成為如上述較少的量。With respect to 100 parts by mass of the (meth) acrylate polymer (A), the content of the cross-linking agent (B) in the adhesive composition P is preferably 0.01 parts by mass or more, and particularly preferably 0.05 parts by mass or more. It is more preferably 0.1 parts by mass or more. The content is preferably 3 parts by mass or less, more preferably 1 part by mass or less, particularly preferably 0.5 part by mass or less, and further preferably 0.3 part by mass or less. When the content of the cross-linking agent (B) is within the above range, the degree of cross-linking becomes appropriate, and the obtained adhesive becomes a substance having more excellent foam resistance. Among the cross-linking agents (B), especially the isocyanate-based cross-linking agent is a component that is liable to cause yellowing. When the content of the cross-linking agent (B) is within the above range, the generation of the adhesive layer after curing can be further suppressed. Yellow. Since the (meth) acrylate polymer (A) has the aforementioned preferable composition, the content of the crosslinking agent (B) can be suppressed to a smaller amount as described above.

(1-3)活性能量線硬化性成分(C) 藉由黏著性組成物P含有活性能量線硬化性成分(C)，將黏著性組成物P交聯(熱交聯)而得到的黏著劑成為活性能量線硬化性黏著劑。該黏著劑藉由貼附被黏著物後之活性能量線照射而硬化，推定活性能量線硬化性成分(C)互相聚合且該聚合後的活性能量線硬化性成分(C)糾纏在(甲基)丙烯酸酯聚合物(A)的交聯結構(三維網狀結構)。因為具有此種高次構造之黏著劑，因為凝聚力較高且顯示較高的被膜強度，所以成為具有更優異的耐起泡性之物。(1-3) Active energy ray-curable component (C) An adhesive obtained by cross-linking (heat-crosslinking) the adhesive composition P with the active energy ray-curable component (C) contained in the adhesive composition P It becomes an active energy ray hardening adhesive. The adhesive is hardened by irradiation with active energy rays after being adhered, and it is estimated that the active energy ray-curable components (C) are polymerized with each other and the polymerized active energy ray-curable components (C) are entangled in (methyl) ) Crosslinked structure (three-dimensional network structure) of the acrylate polymer (A). Since the adhesive having such a high-order structure has high cohesive force and exhibits high film strength, it is a substance having more excellent foam resistance.

活性能量線硬化性成分(C)是藉由照射活性能量線而硬化，只要能夠得到上述效果就沒有特別限制，可為單體、寡聚物或聚合物的任一種，亦可為該等的混合物。尤其是能夠適合舉出與(甲基)丙烯酸酯聚合物(A)等具有優異的相溶性之多官能丙烯酸酯系單體。The active energy ray-curable component (C) is hardened by irradiating the active energy ray, and is not particularly limited as long as the above-mentioned effects can be obtained. The active energy ray-curable component (C) may be any of monomers, oligomers, and polymers. mixture. In particular, a polyfunctional acrylate-based monomer having excellent compatibility with a (meth) acrylate polymer (A) and the like can be cited.

作為多官能丙烯酸酯系單體，例如可舉出1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸酯二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、己內酯改性二環戊烯基二(甲基)丙烯酸酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、二(丙烯醯氧基乙基)三聚異氰酸酯、烯丙基化環己基二(甲基)丙烯酸酯、乙氧基化雙酚A二丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀等的2官能型；三羥甲基丙烷參(甲基)丙烯酸酯、二新戊四醇參(甲基)丙烯酸酯、丙酸改性二新戊四醇參(甲基)丙烯酸酯、新戊四醇參(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷參(甲基)丙烯酸酯、參(丙烯醯氧基乙基)三聚異氰酸酯、E-己內酯改性參-(2-(甲基)丙烯氧基乙基)三聚異氰酸酯等的3官能型；雙甘油四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯等的4官能型；丙酸改性二新戊四醇五(甲基)丙烯酸酯等的5官能型；二新戊四醇六(甲基)丙烯酸酯、己內酯改性二新戊四醇六(甲基)丙烯酸酯等的6官能型等。上述之中，從所得到的黏著劑的耐起泡性及高溫高濕條件下的段差追隨性之觀點而言，以二(丙烯醯氧基乙基)三聚異氰酸酯、參(丙烯醯氧基乙基)三聚異氰酸酯、ε-己內酯改性參-(2-(甲基)丙烯氧基乙基)三聚異氰酸酯等在分子內含有三聚異氰酸酯構造之多官能丙烯酸酯系單體為佳，以3官能以上且在分子內含有三聚異氰酸酯構造之多官能丙烯酸酯系單體為較佳，以ε-己內酯改性參-(2-(甲基)丙烯氧基乙基)三聚異氰酸酯為特佳。該等可單獨使用1種，亦可組合2種以上而使用。又，從與(甲基)丙烯酸酯聚合物(A)的相溶性之觀點而言，多官能丙烯酸酯系單體以分子量小於1000之物為佳。Examples of the polyfunctional acrylate-based monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (methyl) Base) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate, Dicyclopentyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphate di (meth) acrylate, and bis (acrylic acid) Ethyl) trimeric isocyanate, allyl cyclohexyl di (meth) acrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-propenyloxyethoxy) (Phenyl) phenyl] fluorene and other bifunctional types; trimethylolpropane ginseng (meth) acrylate, dipentaerythritol (meth) acrylate, propionic acid-modified dipentaerythritol (a Base) acrylate, neopentaerythritol (meth) acrylate, propylene oxide modified trimethylolpropane ginseng (meth) acrylate, ginseng (propenyloxyethyl) trimer isocyanate, E- Caprolactone-modified ginseng- (2- (meth) acryloxyethyl) tri Trifunctional type such as isocyanate; 4-functional type such as diglycerol tetra (meth) acrylate, neopentyltetraol tetra (meth) acrylate, etc .; propionic acid modified dinepentaerythritol penta (meth) acrylate 5-functional types such as dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like. Among the above, from the viewpoint of the foam resistance of the obtained adhesive and the followability of the step under high temperature and high humidity conditions, bis (acryloxyethyl) trimeric isocyanate, and ginsyl (propyleneoxyl) Multifunctional acrylate monomers containing a trimeric isocyanate structure in the molecule, such as ethyl) trimeric isocyanate, ε-caprolactone-modified ginseng- (2- (meth) acryloxyethyl) trimeric isocyanate, are Preferably, a polyfunctional acrylate monomer having a trifunctional or higher function and containing a trimeric isocyanate structure in the molecule is preferred, and ε-caprolactone is used to modify the ginseng- (2- (meth) acryloxyethyl) Trimeric isocyanates are particularly preferred. These may be used individually by 1 type, and may be used in combination of 2 or more type. From the viewpoint of compatibility with the (meth) acrylate polymer (A), a polyfunctional acrylate-based monomer is preferably one having a molecular weight of less than 1,000.

亦能夠使用活性能量線硬化型的丙烯酸酯系寡聚物作為活性能量線硬化性成分(C)。作為此種丙烯酸酯系寡聚物的例子，可舉出聚酯丙烯酸酯系、環氧丙烯酸酯系、胺甲酸酯丙烯酸酯系、聚醚丙烯酸酯系、聚丁二烯丙烯酸酯系、聚矽氧丙烯酸酯系等。An active energy ray-curable acrylate-based oligomer can also be used as the active energy ray-curable component (C). Examples of such an acrylate oligomer include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polybutadiene acrylate, and poly Silicone acrylates, etc.

上述丙烯酸酯系寡聚物的重量平均分子量以50,000以下為佳，以1,000~50,000為特佳，進而以3,000~40,000為佳。該等丙烯酸酯系寡聚物可單獨使用1種，亦可組合2種以上而使用。The weight average molecular weight of the acrylate-based oligomer is preferably 50,000 or less, particularly preferably 1,000 to 50,000, and further preferably 3,000 to 40,000. These acrylate oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

又，作為活性能量線硬化性成分(C)，亦能夠使用在側鏈導入有具有(甲基)丙烯醯基之基之加成物丙烯酸酯系聚合物。此種加成物丙烯酸酯系聚合物，能夠使用(甲基)丙烯酸酯、與在分子內具有交聯性官能基的單體之共聚物，而且藉由使具有與(甲基)丙烯醯基及交聯性官能基反應之基之化合物對該共聚物的交聯性官能基的一部分進行反應來得到。Further, as the active energy ray-curable component (C), an adduct acrylic polymer having a group having a (meth) acrylfluorenyl group introduced into a side chain can also be used. Such an adduct acrylate-based polymer can be a copolymer of a (meth) acrylate and a monomer having a crosslinkable functional group in the molecule, and by having a (meth) acrylic acid fluorene group A compound that reacts with a crosslinkable functional group is obtained by reacting a part of the crosslinkable functional group of the copolymer.

上述加成物丙烯酸酯系聚合物的重量平均分子量是以5萬~90萬左右為佳，以10萬~50萬左右為特佳。The weight average molecular weight of the adduct acrylate polymer is preferably about 50,000 to 900,000, and particularly preferably about 100,000 to 500,000.

活性能量線硬化性成分(C)，能夠選自前述多官能丙烯酸酯系單體、丙烯酸酯系寡聚物及加成物丙烯酸酯系聚合物之中之1種而使用，亦能夠將2種以上組合而使用，且亦能夠與該等以外的活性能量線硬化性成分組合而使用。The active energy ray-curable component (C) can be selected from one of the aforementioned multifunctional acrylate-based monomers, acrylate-based oligomers, and adduct acrylate-based polymers, and it is also possible to use two types These are used in combination, and can be used in combination with other active energy ray-curable components other than these.

在黏著性組成物P中之活,活性能量線硬化性成分(C)的含量，從使所得到的黏著劑之凝聚力提升且成為具有更優異的耐起泡性之物的觀點而言，相對於(甲基)丙烯酸酯聚合物(A)100質量份，下限值以1質量份以上為佳，以3質量份以上為較佳，以5質量份以上為特佳。另一方面，從防止活性能量線硬化性成分(C)與(甲基)丙烯酸酯聚合物(A)產生相分離之觀點而言，上述含量之上限值以50質量份以下為佳，以20質量份以下為較佳，而且考慮使初期的段差追隨性更良好之觀點，以10質量份以下為特佳。The activity in the adhesive composition P, the content of the active energy ray-curable component (C), from the viewpoint of improving the cohesion of the obtained adhesive and becoming a substance having more excellent foam resistance, In 100 parts by mass of the (meth) acrylate polymer (A), the lower limit is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. On the other hand, from the viewpoint of preventing phase separation between the active energy ray-curable component (C) and the (meth) acrylate polymer (A), the upper limit of the content is preferably 50 parts by mass or less, and 20 parts by mass or less is preferred, and from the viewpoint of making the initial stage followability better, 10 parts by mass or less is particularly preferred.

(1-4)光聚合起始劑(D) 在本實施形態之光聚合起始劑(D)，其在濃度0.1質量%的乙腈溶液之波長390nm的吸光度為0.3以上。藉由構成黏著劑層11之黏著劑含有此種光聚合起始劑(D)，即便透過紫外線遮蔽性構件而對黏著劑層11照射活性能量線時，光聚合起始劑(D)亦沒有問題地開裂，黏著劑層11(活性能量線硬化性成分(C))良好地硬化。藉此，所形成的硬化後黏著劑層是成為凝聚力較高之物且成為具有優異的耐起泡性之物。(1-4) Photopolymerization initiator (D) The photopolymerization initiator (D) according to this embodiment has an absorbance of 0.3 or more at a wavelength of 390 nm in an acetonitrile solution having a concentration of 0.1% by mass. Since the adhesive constituting the adhesive layer 11 contains such a photopolymerization initiator (D), even when an active energy ray is irradiated to the adhesive layer 11 through an ultraviolet shielding member, the photopolymerization initiator (D) is not present. It cracked in a problem, and the adhesive layer 11 (active energy ray-curable component (C)) hardened well. Thereby, the hardened adhesive layer formed becomes a thing with high cohesive force and a thing with excellent foam resistance.

從上述的觀點而言，光聚合起始劑(D)之波長390nm的吸光度以0.5以上為佳，以1.0以上為特佳。該吸光度的上限值沒有特別限定，通常以2.5以下為佳，以2.0以下為特佳。吸光度大於2.5，在黏著片形成時或保管時，由於日光燈等的環境光線，使因光聚合起始劑(D)引起活性能量線硬化性成分(C)進行硬化反應，致使在隨後使用時有段差追隨性低落之情形。在此，光聚合起始劑(D)的吸光度之測定方法，是如後述之試驗例所顯示。From the viewpoint described above, the absorbance of the photopolymerization initiator (D) at a wavelength of 390 nm is preferably 0.5 or more, and particularly preferably 1.0 or more. The upper limit of the absorbance is not particularly limited, but is usually preferably 2.5 or less, and particularly preferably 2.0 or less. The absorbance is greater than 2.5. When the adhesive sheet is formed or stored, due to ambient light such as a fluorescent lamp, the hardening reaction of the active energy ray-curable component (C) caused by the photopolymerization initiator (D) is caused. Low level of follow-up. Here, the method for measuring the absorbance of the photopolymerization initiator (D) is as shown in the test examples described later.

又，光聚合起始劑(D)在濃度0.1質量%的乙腈溶液之波長200~500nm的吸光度之吸收極大波長，以350nm以上為佳，以370nm以上為特佳，進而以380nm以上為佳。又，波長200~500nm的吸光度之吸收極大波長存在複數個時，至少一個吸收極大波長在上述範圍即可。藉此，在透過紫外線遮蔽性構件而對黏著劑層11照射活性能量線時，黏著劑層11(活性能量線硬化性成分(C))的硬化性進一步提升且凝聚力變高而成為具有優異的耐起泡性之物。另一方面，上述吸收極大波長的上限值沒有特別限制，從防止在環境光線中保管黏著劑層11時進行硬化反應之觀點而言，以450nm以下為佳，以410nm以下為特佳，進而以405nm以下為佳。The photopolymerization initiator (D) has an absorption maximum wavelength at an absorbance of 200 to 500 nm in an acetonitrile solution having a concentration of 0.1% by mass, preferably 350 nm or more, particularly 370 nm or more, and further preferably 380 nm or more. In addition, when there are a plurality of absorption maximum wavelengths of absorbance having a wavelength of 200 to 500 nm, at least one absorption maximum wavelength may be in the above range. Thereby, when the adhesive layer 11 is irradiated with an active energy ray through the ultraviolet shielding member, the hardenability of the adhesive layer 11 (active energy ray-curable component (C)) is further improved, and the cohesive force becomes high, thereby being excellent. Resistant to blistering. On the other hand, the upper limit of the absorption maximum wavelength is not particularly limited. From the viewpoint of preventing a curing reaction from occurring when the adhesive layer 11 is stored in ambient light, it is preferably 450 nm or less, and particularly preferably 410 nm or less. It is preferably below 405 nm.

作為此種光聚合起始劑(D)，例如可舉出2,4,6-三甲基苯甲醯基-聯苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等。該等可單獨使用，亦可組合2種以上而使用。Examples of such a photopolymerization initiator (D) include 2,4,6-trimethylbenzylidene-biphenyl-phosphine oxide, and bis (2,4,6-trimethylbenzyl) Fluorenyl) -phenylphosphine oxide and the like. These may be used alone or in combination of two or more.

在黏著性組成物P中之光聚合起始劑(D)的含量，相對於活性能量線硬化性成分(C)100質量份，下限值以2質量份以上為佳，以4質量份以上為特佳，進而以5質量份以上為佳。又，光聚合起始劑(D)的含量，上限值以15質量份以下為佳，以12質量份以下為特佳，進而以10質量份以下為佳。The content of the photopolymerization initiator (D) in the adhesive composition P is preferably 2 parts by mass or more and 4 parts by mass or more with respect to 100 parts by mass of the active energy ray-curable component (C). Particularly preferred is 5 parts by mass or more. The upper limit of the content of the photopolymerization initiator (D) is preferably 15 parts by mass or less, particularly preferably 12 parts by mass or less, and further preferably 10 parts by mass or less.

(1-5)矽烷偶合劑(E) 黏著性組成物P以進一步含有矽烷偶合劑(E)為佳。藉此，被黏著物即使為塑膠板、玻璃構件等，與該被黏著物之密著性均提升且成為具有更優異的耐起泡性之物。(1-5) Silane coupling agent (E) The adhesive composition P preferably further contains a silane coupling agent (E). Thereby, even if the adherend is a plastic plate, a glass member, or the like, the adherence to the adherend is improved and it becomes a substance having more excellent foam resistance.

作為矽烷偶合劑(E)，以在分子內具有至少1個烷氧基矽烷基之有機矽化合物，而且與(甲基)丙烯酸酯聚合物(A)的相溶性良好且具有光透射性之物為佳。As the silane coupling agent (E), an organic silicon compound having at least one alkoxysilyl group in the molecule and having good compatibility with the (meth) acrylate polymer (A) and having light transmission properties Better.

作為此種矽烷偶合劑(E)，例如可舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯酸氧基丙基三甲氧基矽烷等含有聚合性不飽和基之矽化合物；3-環氧丙氧基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等具有環氧結構之矽化合物；3-氫硫基丙基三甲氧基矽烷、3-氫硫基丙基三乙氧基矽烷、3-氫硫基丙基二甲氧基甲基矽烷等含有氫硫基之矽化合物；3-胺基丙基三甲氧基矽烷、N-(2-胺乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺乙基)-3-胺基丙基甲基二甲氧基矽烷等含有胺基之矽化合物；3-氯丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、或該等至少1種、與甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等的烷基含有矽化合物之縮合物等。該等可單獨使用1種亦可組合2種以上而使用。Examples of such a silane coupling agent (E) include a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane. ; 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and other silicon compounds with epoxy structure; 3-hydrothiopropyltrimethyl Hydroxythio-containing silicon compounds such as oxysilane, 3-hydrothiopropyltriethoxysilane, 3-hydrothiopropyldimethoxymethylsilane; 3-aminopropyltrimethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, etc. Silicon compounds; 3-chloropropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, or at least one of these, with methyltriethoxysilane, ethyltriethoxysilane, methyl Alkyl groups such as trimethoxysilane and ethyltrimethoxysilane include a condensate of a silicon compound and the like. These may be used individually by 1 type, and may use 2 or more types together.

相對於(甲基)丙烯酸酯聚合物(A)100質量份，在黏著性組成物P中之矽烷偶合劑(E)的含量以0.01質量份以上為佳，以0.05質量份以上為特佳，進而以0.1質量份以上為佳。又，該含量以1質量份以下為佳，以0.5質量份以下為特佳，進而以0.3質量份以下為佳。The content of the silane coupling agent (E) in the adhesive composition P is preferably 0.01 parts by mass or more, and particularly preferably 0.05 parts by mass or more, based on 100 parts by mass of the (meth) acrylate polymer (A). It is more preferably 0.1 parts by mass or more. The content is preferably 1 part by mass or less, particularly preferably 0.5 part by mass or less, and further preferably 0.3 part by mass or less.

(1-6)各種添加劑 在黏著性組成物P，是能夠按照需要而添加在丙烯酸系黏著劑通常被使用之各種添加劑，例如紫外線吸收劑、抗靜電劑、黏著賦予劑、抗氧化劑、光安定劑、軟化劑、填充劑、折射率調整劑、防鏽劑等。又，後述聚合溶劑和稀釋溶劑不包含在構成黏著性組成物P之添加劑。(1-6) Various additives in the adhesive composition P are various additives that can be added to the acrylic adhesive as required, such as ultraviolet absorbers, antistatic agents, adhesion-imparting agents, antioxidants, and light stabilizers. Agents, softeners, fillers, refractive index adjusters, rust inhibitors, etc. In addition, the polymerization solvent and the dilution solvent mentioned later are not included in the additive which comprises the adhesive composition P.

但是，黏著性組成物P是以不含有紫外線吸收劑為佳。紫外線吸收劑有從黏著劑(硬化後黏著劑層)滲出之可能性，且有將所得到的顯示體污染之情形。在本實施形態，因為一顯示體構成構件及另一顯示體構成構件之至少一方為紫外線遮蔽性構件，所以硬化後黏著劑層含有紫外線吸收劑之必要性較低。However, it is preferable that the adhesive composition P does not contain an ultraviolet absorber. The ultraviolet absorbent may leak from the adhesive (adhesive layer after curing), and the obtained display may be contaminated. In this embodiment, since at least one of the display structure constituent member and the other display structure constituent member is an ultraviolet shielding member, the necessity of containing the ultraviolet absorber in the adhesive layer after curing is low.

(2)黏著性組成物的製造 黏著性組成物P，是能夠藉由製造(甲基)丙烯酸酯聚合物(A)且將所得到的(甲基)丙烯酸酯聚合物(A)與交聯劑(B)、活性能量線硬化性成分(C)、及光聚合起始劑(D)混合，同時按照需要而添加矽烷偶合劑(E)及添加劑來製造。(2) Production of Adhesive Composition The adhesive composition P is capable of producing a (meth) acrylate polymer (A) and cross-linking the obtained (meth) acrylate polymer (A) with the The agent (B), the active energy ray-curable component (C), and the photopolymerization initiator (D) are mixed, and a silane coupling agent (E) and an additive are added as necessary to produce the product.

(甲基)丙烯酸酯聚合物(A)，能夠藉由將構成聚合物之單體的混合物使用通常的自由基聚合法進行聚合來製造。(甲基)丙烯酸酯聚合物(A)的聚合，以按照需要使用聚合起始劑且藉由溶液聚合法來進行為佳。作為聚合溶劑，例如可舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲苯、丙酮、己烷、甲基乙基酮等，亦可併用2種類以上。The (meth) acrylate polymer (A) can be produced by polymerizing a mixture of monomers constituting the polymer using 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 necessary. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and two or more kinds may be used in combination.

作為聚合起始劑，可舉出偶氮系化合物、有機過氧化物等，亦可併用2種類以上。作為偶氮系化合物，例如可舉出2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷1-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-甲基丙酸酯)、4,4’-偶氮雙(4-氰基戊酸)、2,2’-偶氮雙(2-羥甲基丙腈)、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]等。Examples of the polymerization initiator include azo compounds, organic peroxides, and the like, and two or more kinds may be used in combination. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 1,1'-azobis (cyclohexyl) Alkanes 1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxypentyl) Nitrile), dimethyl 2,2'-azobis (2-methylpropionate), 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，例如可舉出過氧化苯甲醯、過氧化苯甲酸第三丁酯、異丙苯過氧化氫、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、過氧化新癸酸第三丁酯、過氧化三甲基乙酸第三丁酯、過氧化(3,5,5-三甲基己醯)、過氧化二丙醯、過氧化二乙醯等。Examples of the organic peroxide include benzamidine peroxide, third butyl peroxide benzoate, cumene hydrogen peroxide, diisopropyl peroxide dicarbonate, di-n-propyl peroxide dicarbonate, Di (2-ethoxyethyl) peroxydicarbonate, tertiary butyl peroxydecanoate, tertiary butyl peroxytrimethylacetate, peroxy (3,5,5-trimethylhexanoate) Ii), dipropylammonium peroxide, diethylammonium peroxide, and the like.

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

得到(甲基)丙烯酸酯聚合物(A)之後，能夠藉由在(甲基)丙烯酸酯聚合物(A)的溶液，添加交聯劑(B)、活性能量線硬化性成分(C)、光聚合起始劑(D)及按照需要矽烷偶合劑(E)、添加劑且充分地混合而得到經溶劑稀釋的黏著性組成物P(塗佈溶液)。又，在上述各成分的任一種是使用固體狀物時、或是未稀釋的狀態下與其他成分混合時產生析出之情況，亦可將該成分預先單獨溶解或稀釋於稀釋溶劑之後，與其他成分混合。After the (meth) acrylate polymer (A) is obtained, a solution of the (meth) acrylate polymer (A) can be added with a crosslinking agent (B), an active energy ray-curable component (C), The photopolymerization initiator (D) and the silane coupling agent (E) and additives as necessary are sufficiently mixed to obtain a solvent-diluted adhesive composition P (coating solution). In addition, when any one of the above components is used in a solid state or mixed with other components in an undiluted state, precipitation may occur. The component may be separately dissolved in advance or diluted in a diluent solvent, and then mixed with other components. Ingredients are mixed.

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

作為如此進行而調製的塗佈溶液之濃度‧黏度，是能夠塗佈的範圍即可，而沒有特別限制，能夠按照狀況而適當地選定。例如以黏著性組成物P的濃度成為10~60質量%的方式稀釋。又，得到塗佈溶液時，添加稀釋溶劑等不是必要條件，黏著性組成物P為能夠塗佈的黏度等之情況，亦可不添加稀釋溶劑。此時，黏著性組成物P是成為將(甲基)丙烯酸酯聚合物(A)的聚合溶劑直接作為稀釋溶劑之塗佈溶液。The concentration and viscosity of the coating solution prepared as described above are not particularly limited as long as they can be applied, and can be appropriately selected according to the situation. For example, it dilutes so that the density | concentration of the adhesive composition P may become 10-60 mass%. In addition, when a coating solution is obtained, it is not necessary to add a diluent or the like. In the case where the adhesive composition P is a viscosity that can be applied, the diluent or the like may not be added. At this time, the adhesive composition P is a coating solution in which a polymerization solvent of the (meth) acrylate polymer (A) is directly used as a dilution solvent.

(3)黏著劑層的形成 黏著劑層11是以由將黏著性組成物P進行熱交聯而成之黏著劑所構成為佳。亦即，黏著性組成物P的交聯是藉由加熱處理而進行。又，該加熱處理亦能夠兼作黏著性組成物P的塗佈後之乾燥處理。(3) Formation of Adhesive Layer The adhesive layer 11 is preferably composed of an adhesive obtained by thermally crosslinking the adhesive composition P. That is, the crosslinking of the adhesive composition P is performed by heat treatment. This heat treatment can also be used as a drying treatment after the application of the adhesive composition P.

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

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

(4)黏著劑層的厚度 黏著劑層11厚度(依據JIS K7130所測得的值)之下限值，以20μm以上為佳，以25μm以上為較佳，以30μm以上為特佳，進而以50μm以上為佳。又，黏著劑層11厚度之上限值以500μm以下為佳，以400μm以下為較佳，以300μm以下為特佳。黏著劑層11厚度在上述範圍時，成為具有更優異的耐起泡性之物。(4) Thickness of the adhesive layer The lower limit of the thickness of the adhesive layer 11 (value measured in accordance with JIS K7130) is preferably 20 μm or more, more preferably 25 μm or more, particularly preferably 30 μm or more, and more preferably It is preferably at least 50 μm. The upper limit of the thickness of the adhesive layer 11 is preferably 500 μm or less, more preferably 400 μm or less, and particularly preferably 300 μm or less. When the thickness of the adhesive layer 11 is in the said range, it will become a thing with more excellent foam resistance.

1-2.剝離片 剝離片12a、12b是保護黏著劑層11至黏著片1使用時為止之物，在使用黏著片1(黏著劑層11)時被剝離。在本實施形態之黏著片1，剝離片12a、12b的一方或雙方未必需要。1-2. Release Sheet The release sheets 12a and 12b protect the adhesive layer 11 until the use of the adhesive sheet 1, and are peeled off when the adhesive sheet 1 (adhesive layer 11) is used. In the adhesive sheet 1 of this embodiment, one or both of the release sheets 12a and 12b are not necessarily required.

作為剝離片12a、12b，例如能夠使用聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯、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、聚胺酯膜、乙烯乙酸乙烯酯膜、離子聚合物樹脂膜、乙烯‧(甲基)丙烯酸共聚物膜、乙烯‧(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚醯亞胺膜、氟樹脂膜等。又，亦可使用該等的交聯膜。而且，亦可為該等的積層膜。As the release sheet 12a, 12b, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride, a vinyl chloride copolymer film, or a polyparaphenylene can be used Ethylene formate film, Polyethylene naphthalate film, Polybutylene terephthalate film, Polyurethane film, Ethylene vinyl acetate film, Ion polymer resin film, Ethylene (meth) acrylic copolymer film , Ethylene ‧ (meth) acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. Moreover, such a crosslinked film can also be used. Moreover, such a laminated film may be used.

上述剝離片12a、12b的剝離面(特別是與黏著劑層11接觸之面)以經剝離處理為佳。作為在剝離處理所使用的剝離劑，例如可舉出醇酸系、聚矽氧系、氟系、不飽和聚酯系、聚烯烴系、蠟系的剝離劑。又，剝離片12a、12b之中，以將一方的剝離片設為剝離力較大的重剝離型剝離片且將另一方的剝離片設為剝離力較小的輕剝離型剝離片為佳。It is preferable that the peeling surfaces (particularly the surfaces which are in contact with the adhesive layer 11) of the peeling sheets 12a and 12b are subjected to a peeling treatment. Examples of the release agent used in the release treatment include alkyd-based, polysiloxane-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents. Among the release sheets 12a and 12b, it is preferable that one of the release sheets is a heavy release-type release sheet having a large release force and the other release sheet is a light-release type release sheet having a small release force.

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

2.黏著片的製造 作為黏著片1的一製造例，是將上述黏著性組成物P的塗佈溶液塗佈在一方的剝離片12a(或12b)之剝離面，進行加熱處理而將黏著性組成物P交聯(熱交聯)且形成塗佈層之後，將另一方的剝離片12b(或12a)的剝離面疊合在該塗佈層。熟化期間為必要時是藉由放置熟化期間，熟化期間不需要時上述塗佈層是直接成為黏著劑層11。藉此，能夠得到上述黏著片1。針對加熱處理及熟化的條件，如前述。2. Production of Adhesive Sheet As an example of the production of the adhesive sheet 1, the coating solution of the adhesive composition P is applied to the release surface of one of the release sheets 12a (or 12b), and heat treatment is performed to make the adhesiveness. After the composition P is crosslinked (thermally crosslinked) to form a coating layer, the release surface of the other release sheet 12b (or 12a) is laminated on the coating layer. When the aging period is necessary, the aging period is left to stand. When the aging period is not required, the coating layer directly becomes the adhesive layer 11. Thereby, the said adhesive sheet 1 can be obtained. The conditions for heat treatment and aging are as described above.

作為黏著片1其他製造例，是將上述黏著性組成物P的塗佈溶液塗佈在一方的剝離片12a之剝離面，進行加熱處理而將黏著性組成物P交聯(熱交聯)且形成塗佈層而得到附塗佈層的剝離片12a。而且，將上述黏著性組成物P的塗佈溶液塗佈在另一方的剝離片12b之剝離面，進行加熱處理而將黏著性組成物P交聯(熱交聯)且形成塗佈層而得到附塗佈層的剝離片12b。然後，將附塗佈層的剝離片12a與附塗佈層的剝離片12b以兩塗佈層互相接觸的方式貼合。熟化期間為必要時，是藉由放置熟化期間，熟化期間為不需要時上述層積的塗佈層是直接成為黏著劑層11。藉此，能夠得到上述黏著片1。依照該製造例，即便黏著劑層11為較厚時亦能夠穩定地製造。As another manufacturing example of the adhesive sheet 1, the above-mentioned coating solution of the adhesive composition P is applied to the release surface of one of the release sheets 12a, and heat treatment is performed to crosslink (thermally crosslink) the adhesive composition P and A coating layer was formed to obtain a release sheet 12a with a coating layer. Then, the coating solution of the adhesive composition P is applied to the release surface of the other release sheet 12b, and heat treatment is performed to crosslink (thermally crosslink) the adhesive composition P to form a coating layer. A release sheet 12b with a coating layer. Then, the peeling sheet 12a with a coating layer and the peeling sheet 12b with a coating layer are bonded together so that both coating layers may contact each other. When the curing period is necessary, the curing layer is left as it is, and when the curing period is unnecessary, the above-mentioned laminated coating layer directly becomes the adhesive layer 11. Thereby, the said adhesive sheet 1 can be obtained. According to this manufacturing example, even when the adhesive layer 11 is thick, it can be manufactured stably.

作為塗佈上述黏著性組成物P的塗佈溶液之方法，例如能夠利用棒塗佈法、刮刀塗佈法、輥塗佈法、刮板塗佈法、模塗佈法、凹版塗佈法等。As a method for applying the coating solution of the adhesive composition P, for example, a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used. .

3.黏著片物性 (1)凝膠分率 (1-1)活性能量線照射前的凝膠分率 構成黏著劑層11之黏著劑(活性能量線照射前)的凝膠分率之下限值，以設為30%以上為佳，以設為40%以上為較佳，以設為45%以上為特佳。活性能量線照射前的黏著劑的凝膠分率之下限值為上述時，黏著劑層11凝聚力提升且能夠有效地抑制在將黏著片1進行裁斷加工等時黏著劑附著在刀刃、或在保管時等黏著劑從黏著劑層11滲出。又，活性能量線照射前之黏著劑的凝膠分率之上限值，以設為70%以下為佳，以設為65%以下為特佳，進而以設為61%以下為佳。活性能量線照射前之黏著劑的凝膠分率之上限值為上述時，黏著劑不會變成太硬且成為具有優異的初期段差追隨性之物。該活性能量線硬化性黏著劑(活性能量線照射前)的凝膠分率的測定方法如後述之試驗例所顯示。3. Physical properties of the adhesive sheet (1) Gel fraction (1-1) Gel fraction before active energy ray irradiation Lower limit of gel fraction of the adhesive constituting the adhesive layer 11 (before active energy ray irradiation) The value is preferably 30% or more, more preferably 40% or more, and particularly preferably 45% or more. When the lower limit value of the gel fraction of the adhesive before the active energy ray irradiation is as described above, the cohesive force of the adhesive layer 11 is improved and it is possible to effectively prevent the adhesive from adhering to the blade when cutting the adhesive sheet 1 or the like, or At the time of storage, the adhesive oozes out of the adhesive layer 11. The upper limit of the gel fraction of the adhesive before the active energy ray irradiation is preferably 70% or less, particularly preferably 65% or less, and more preferably 61% or less. When the upper limit of the gel fraction of the adhesive before the active energy ray irradiation is as described above, the adhesive does not become too hard and has an excellent initial stage followability. The measurement method of the gel fraction of this active energy ray hardening adhesive (before active energy ray irradiation) is as shown in the test example mentioned later.

(1-2)活性能量線照射後的凝膠分率 構成對黏著劑層11照射活性能量線而成之硬化後黏著劑層之黏著劑的凝膠分率，其下限值是以40%以上為佳，以50%以上為較佳，以60%以上為特佳，進而以66%以上為佳。上述凝膠分率的下限值為上述時，構成硬化後黏著劑層之黏著劑的凝聚力為充分且能夠發揮更優異的耐起泡性。又，構成硬化後黏著劑層之黏著劑的凝膠分率，其上限值是以95%以下為佳，以90%以下為特佳，進而以80%以下為佳。上述凝膠分率的上限值為上述時，能夠確保硬化後黏著劑層的黏著力且能夠得到充分的耐久性。構成硬化後黏著劑層之黏著劑(活性能量線照射後)的凝膠分率的測定方法如後述之試驗例所顯示。(1-2) Gel fraction after active energy ray irradiation constitutes the gel fraction of the adhesive of the hardened adhesive layer formed by irradiating the adhesive layer 11 with active energy rays, and the lower limit is 40%. The above is preferably, 50% or more is preferable, 60% or more is particularly preferable, and 66% or more is more preferable. When the lower limit value of the gel fraction is as described above, the cohesive force of the adhesive constituting the adhesive layer after curing is sufficient and more excellent foam resistance can be exhibited. The upper limit of the gel fraction of the adhesive constituting the adhesive layer after curing is preferably 95% or less, particularly preferably 90% or less, and even more preferably 80% or less. When the upper limit value of the gel fraction is as described above, the adhesive force of the adhesive layer after curing can be secured and sufficient durability can be obtained. The measurement method of the gel fraction of the adhesive (after active energy ray irradiation) which comprises the adhesive layer after hardening is shown by the test example mentioned later.

(1-3)凝膠分率的變化量 伴隨著構成黏著劑層11之活性能量線硬化性黏著劑的因照射活性能量線引起凝膠分率的變化量(從構成硬化後黏著劑層之黏著劑的凝膠分率減去活性能量線硬化性黏著劑的凝膠分率後之值)，以5百分點以上為佳，以10百分點以上為特佳，進而以15百分點以上為佳。藉由凝膠分率如此地上升，所得到的硬化後黏著劑層具有更優異的耐起泡性。又，該凝膠分率的上升之上限，沒有特別限定，從防止硬化後黏著劑層變成太硬的觀點而言，凝膠分率的上升以40百分點以下為佳，以30百分點以下為較佳，以25百分點以下為特佳。(1-3) The amount of change in the gel fraction is accompanied by the amount of change in the gel fraction caused by irradiating the active energy ray of the active energy ray-hardening adhesive constituting the adhesive layer 11 (from The gel fraction of the adhesive minus the gel fraction of the active energy ray-curable adhesive) is preferably at least 5 percent, particularly preferably at least 10 percent, and more preferably at least 15 percent. When the gel fraction is increased in this way, the obtained cured adhesive layer has more excellent foam resistance. The upper limit of the increase in the gel fraction is not particularly limited. From the viewpoint of preventing the adhesive layer from becoming too hard after hardening, the increase in the gel fraction is preferably 40% or less, and 30% or less is preferable. Good, especially below 25%.

(2)黏著力 藉由對本實施形態之黏著片1的黏著劑層11照射活性能量線使其硬化而成為硬化後黏著劑層時，該黏著片1對鈉鈣玻璃的黏著力之下限值，以20N/25mm以上為佳，以25N/25mm以上為較佳，以30N/25mm以上為特佳，進而以35N/25mm以上為佳。黏著片1黏著力的下限值為上述時，成為具有更優異的耐起泡性之物。另一方面，上述黏著力的上限值沒有特別限定，通常以100N/25mm以下為佳，以90N/25mm以下為較佳，以80N/25mm以下為特佳。又，上述黏著力是指基本上使用依據JIS Z0237：2009之180度剝離法所測得的黏著力，具體的試驗方法如後述之試驗例所顯示。(2) Adhesive force When the adhesive layer 11 of the adhesive sheet 1 of this embodiment is irradiated with active energy rays to harden it to become a cured adhesive layer, the lower limit of the adhesive force of the adhesive sheet 1 to soda lime glass 20N / 25mm or more is preferable, 25N / 25mm or more is preferable, 30N / 25mm or more is particularly preferable, and 35N / 25mm or more is more preferable. When the lower limit value of the adhesive force of the adhesive sheet 1 is as mentioned above, it will become a thing which has more excellent foam resistance. On the other hand, the upper limit of the adhesive force is not particularly limited, but is usually preferably 100 N / 25 mm or less, more preferably 90 N / 25 mm or less, and particularly preferably 80 N / 25 mm or less. In addition, the said adhesive force means the adhesive force measured using the 180 degree peeling method based on JISZ0237: 2009 basically, and a specific test method is shown by the test example mentioned later.

[顯示體] 本實施形態之黏著片1是能夠使用在製造如第2圖所例示之顯示體2。如第2圖顯示，本實施形態之顯示體2是具備下列而構成：至少在被貼合側之面具有段差之第1顯示體構成構件21(一顯示體構成構件)；第2顯示體構成構件22(另一顯示體構成構件)；及位於該等之間且將第1顯示體構成構件21及第2顯示體構成構件22互相貼合之硬化後黏著劑層11’。在本實施形態之顯示體2，第1顯示體構成構件21是在硬化後黏著劑層11’側的面或黏著劑層11側的面具有段差，具體而言，具有印刷層3形成的段差，但是不被此限定。[Display body] The adhesive sheet 1 of this embodiment can be used for manufacturing a display body 2 as illustrated in FIG. 2. As shown in FIG. 2, the display body 2 of the present embodiment is configured to include a first display body structural member 21 (a display body structural member) having a step at least on a surface to be bonded, and a second display body structure. A member 22 (another display body constituent member); and a hardened adhesive layer 11 ′ located between the first and second display body constituent members 21 and the second display body constituent member 22 and bonded to each other. In the display body 2 of the present embodiment, the first display body constituting member 21 has a step on the surface of the adhesive layer 11 ′ side or the surface of the adhesive layer 11 side after curing, and specifically has a step formed by the printing layer 3. , But not limited to this.

在此，一方的顯示體構成構件(例如第1顯示體構成構件21)為紫外線遮蔽構件時，另一方的顯示體構成構件(例如第2顯示體構成構件22)，以因紫外線照射而性能劣化之構件、或無法從該另一方的顯示體構成構件側對黏著劑層11照射活性能量線的構造之構件為佳。即便將具有此種限制之構件使用在顯示體構成構件時，使用前述的實施形態之光學用黏著片1時，藉由從紫外線遮蔽性構件側照射活性能量線，黏著劑層11充分地硬化而成為硬化後黏著劑層11’且能夠得到具有優異的耐起泡性之顯示體2。Here, when one display body constituent member (for example, the first display body constituent member 21) is an ultraviolet shielding member, the other display body constituent member (for example, the second display body constituent member 22) is deteriorated in performance due to ultraviolet irradiation. A member having a structure, or a member having a structure in which the active energy ray cannot be irradiated to the adhesive layer 11 from the other display member constituting member side is preferable. Even when a member having such a limitation is used as a display constituent member, when the optical adhesive sheet 1 of the aforementioned embodiment is used, the adhesive layer 11 is sufficiently hardened by irradiating active energy rays from the ultraviolet shielding member side. It becomes the hardened adhesive layer 11 'and can obtain the display body 2 which has the outstanding foam resistance.

上述顯示體2所具有的硬化後黏著劑層11’，是將前述黏著片1的黏著劑層11藉由照射能量線而使其硬化而成。構成黏著劑層11之黏著劑是由黏著性組成物P交聯而成時，構成該硬化後黏著劑層11’之黏著劑，具有由(甲基)丙烯酸酯聚合物(A)及交聯劑(B)所構成之交聯結構之同時，亦可含有能量線硬化性成分(C)的硬化物(聚合物)且按照需要進一步含有光聚合起始劑(D)及添加劑。此時，推定聚合後的能量線硬化性成分(C)是糾纏在由(甲基)丙烯酸酯聚合物(A)及熱交聯劑(B)所構成之交聯結構且形成高次構造之物。The cured adhesive layer 11 'of the display body 2 is obtained by curing the adhesive layer 11 of the adhesive sheet 1 by irradiating energy rays. When the adhesive constituting the adhesive layer 11 is cross-linked from the adhesive composition P, the adhesive constituting the cured adhesive layer 11 'has a (meth) acrylate polymer (A) and a cross-linking agent. The crosslinking structure composed of the agent (B) may also contain a hardened product (polymer) of the energy ray-curable component (C), and may further contain a photopolymerization initiator (D) and additives as necessary. At this time, it is presumed that the energy ray-curable component (C) after polymerization is entangled in a crosslinked structure composed of a (meth) acrylate polymer (A) and a thermal crosslinking agent (B), and forms a higher-order structure. Thing.

又，在構成上述硬化後黏著劑層11’之黏著劑所含有的光聚合起始劑(D)，是在黏著性組成物P所含有的光聚合起始劑(D)即便照射能量線亦未開裂而殘留之物。因而，其含量不多，通常在黏著劑中為0.00001質量%以上且0.1質量%以下，較佳為0.0001質量%以上且0.01質量%以下。The photopolymerization initiator (D) contained in the adhesive constituting the hardened adhesive layer 11 ′ is the photopolymerization initiator (D) contained in the adhesive composition P even when it irradiates energy rays. What remains without cracking. Therefore, its content is not large, and it is usually 0.00001% by mass or more and 0.1% by mass or less in the adhesive, and preferably 0.0001% by mass or more and 0.01% by mass or less.

硬化後黏著劑層11’的霧度值以5%以下為佳，以3%以下為較佳，以1%以下為特佳，進而以0.5%以下為佳。硬化後黏著劑層11’的霧度值為5%以下時，透明性非常高且適合作為光學用途(顯示體用)。在本說明書之霧度值是設為依據JIS K7136：2000所測得的值。The haze value of the hardened adhesive layer 11 'is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less, and further preferably 0.5% or less. When the haze value of the cured adhesive layer 11 'is 5% or less, the transparency is very high and it is suitable as an optical application (for a display). The haze value in this specification is a value measured based on JIS K7136: 2000.

在本實施形態之顯示體2，第1顯示體構成構件21及第2顯示體構成構件22至少一方是具有紫外線遮蔽性之紫外線遮蔽性構件。該紫外線遮蔽性構件如前述，在波長340nm的光線透射率為5%以下，波長390nm的光線透射率為10%以上。又，在本說明書之光線透射率的測定方法如後述之試驗例所顯示。In the display body 2 of this embodiment, at least one of the first display body constituent member 21 and the second display body constituent member 22 is an ultraviolet shielding member having ultraviolet shielding properties. As described above, the ultraviolet shielding member has a light transmittance of 5% or less at a wavelength of 340 nm and a light transmittance of 10% or more at a wavelength of 390 nm. In addition, the measurement method of the light transmittance in this specification is as shown in the test example mentioned later.

紫外線遮蔽性構件之波長390nm的光線透射率為10%以上時，透過該紫外線遮蔽性構件而對黏著劑層11照射活性能量線時，光聚合起始劑沒有問題地開裂。其結果，活性能量線硬化性黏著劑的硬化反應為良好地進行，黏著劑層11充分地硬化且能夠形成具有優異的耐起泡性之硬化後黏著劑層11’。從此種的觀點而言，紫外線遮蔽性構件之波長390nm的光線透射率之下限值為10%以上，以30%以上為佳，以50%以上為特佳，進而以60%以上為佳。紫外線遮蔽性構件之波長390nm的光線透射率的上限值沒有特別限定，通常為98%以下為佳，以85%以下為特佳。When the ultraviolet-shielding member has a light transmittance at a wavelength of 390 nm of 10% or more, when the adhesive layer 11 is irradiated with active energy rays through the ultraviolet-shielding member, the photopolymerization initiator is cracked without problems. As a result, the hardening reaction of the active energy ray-curable adhesive progresses well, and the adhesive layer 11 is sufficiently cured to form a cured adhesive layer 11 'having excellent foam resistance. From such a viewpoint, the lower limit of the light transmittance of the ultraviolet-shielding member at a wavelength of 390 nm is 10% or more, preferably 30% or more, particularly preferably 50% or more, and even more preferably 60% or more. The upper limit of the light transmittance of the ultraviolet shielding member at a wavelength of 390 nm is not particularly limited, but it is usually preferably 98% or less, and particularly preferably 85% or less.

另一方面，紫外線遮蔽性構件之波長340nm的光線透射率為5%以下時，使硬化後黏著劑層11’容易產生黃變的活性能量線被紫外線遮蔽性構件遮斷且不容易到達硬化後黏著劑層11’。藉此，能夠抑制硬化後黏著劑層11’產生黃變。從此種的觀點而言、紫外線遮蔽性構件之波長340mm的光線透射率之上限值為5%以下，3%以下為佳，以1%以下為特佳。紫外線遮蔽性構件之波長340nm的光線透射率的下限值沒有特別限定，通常以0.01%以上為佳，以0.1%以上為特佳。On the other hand, when the light transmittance of the ultraviolet-shielding member at a wavelength of 340 nm is 5% or less, the active energy rays that cause yellowing of the adhesive layer 11 'after curing are blocked by the ultraviolet-shielding member and do not easily reach after curing. Adhesive layer 11 '. Thereby, yellowing of the adhesive layer 11 'after curing can be suppressed. From such a viewpoint, the upper limit of the light transmittance of the ultraviolet shielding member at a wavelength of 340 mm is 5% or less, preferably 3% or less, and particularly preferably 1% or less. The lower limit of the light transmittance of the ultraviolet shielding member at a wavelength of 340 nm is not particularly limited, but it is usually preferably 0.01% or more, and particularly preferably 0.1% or more.

在此，硬化後黏著劑層11’產生黃變的程度，能夠藉由依據CIE1976L*a*b*表色系規定之透射色相b*變化量進行判斷。具體而言，對具備紫外線遮蔽性構件之一顯示體構成構件、另一顯示體構成構件、將該等貼合的硬化後黏著劑層之積層體，在43℃、50%RH的環境下進行從紫外線遮蔽性構件側照射照度350mW/cm2 活性能量線1000小時之耐光試驗，而且從該耐光試驗後的b*1 減去耐光試驗前的b*0 後之值Δb*，以0.3以下為佳，以0.2以下為特佳，進而以0.1以下為佳。藉由Δb*為上述，能夠抑制硬化後黏著劑層11’產生黃變。Here, the degree of yellowing of the adhesive layer 11 'after hardening can be judged by the amount of change in the transmission hue b * according to the CIE1976L * a * b * color system. Specifically, a laminated body including one display body constituting member, the other display body constituting member, and the cured adhesive layer bonded to each other is provided at a temperature of 43 ° C and 50% RH. ultraviolet shielding member side illuminance 350mW / cm 2 of the active energy ray 1000 hours light resistance test, and from after the light resistance test b * b 1 is subtracted before the light resistance test * [Delta] b * value of 0, to 0.3 or less as It is particularly preferably 0.2 or less, and further preferably 0.1 or less. With Δb * as described above, yellowing of the adhesive layer 11 'after curing can be suppressed.

硬化後黏著劑層11’的b*，以耐光試驗前後，任一者均以-1.0~1.0為佳，以-0.7~0.7為特佳，進而以-0.5~0.5為佳。藉由硬化後黏著劑層11’的b*在上述範圍，能夠抑制硬化後黏著劑層11’產生黃色且顯示器的外觀及視認性變為良好。又，b*的測定方法如後述之試驗例所顯示。The b * of the adhesive layer 11 'after curing is preferably -1.0 to 1.0, particularly -0.7 to 0.7, and more preferably -0.5 to 0.5, before and after the light resistance test. When b * of the hardened adhesive layer 11 'is in the above range, yellowing of the hardened adhesive layer 11' can be suppressed and the appearance and visibility of the display can be improved. The method for measuring b * is shown in the test examples described later.

上述紫外線遮蔽性構件以由塑膠板所構成為佳，以由含有紫外線吸收劑的塑膠板所構成為佳。在此，塑膠板是通常被放置在高溫條件下、例如85℃的條件下時，內部的低沸點成分氣化且有在塑膠板與硬化後黏著劑層11’之界面產生氣泡、浮起、剝落等的起泡之可能性。但是，本實施形態之顯示體2即便具備此種塑膠板，藉由硬化後黏著劑層11’是來自本實施形態之黏著片1，能夠良好地抑制產生起泡。The ultraviolet shielding member is preferably composed of a plastic plate, and is preferably composed of a plastic plate containing an ultraviolet absorbent. Here, when the plastic plate is usually placed under high temperature conditions, such as 85 ° C, the internal low-boiling point components vaporize and bubbles, floating, Possibility of blistering, etc. However, even if the display body 2 of this embodiment is provided with such a plastic plate, the adhesive layer 11 'after curing is the adhesive sheet 1 from this embodiment, and it is possible to suppress the occurrence of foaming.

作為塑膠板，沒有特別限定，例如可舉出聚碳酸酯樹脂(PC)板、聚甲基丙烯酸甲酯樹脂(PMMA)板等的丙烯酸樹脂板；及將聚甲基丙烯酸甲酯樹脂層等的丙烯酸樹脂層層積在聚碳酸酯樹脂板而成之塑膠板等。又，上述聚碳酸酯樹脂板亦可含有聚碳酸酯樹脂以外的樹脂作為構成材料，又，上述丙烯酸樹脂板亦可含有丙烯酸樹脂以外的樹脂作為構成材料。The plastic plate is not particularly limited, and examples thereof include an acrylic resin plate such as a polycarbonate resin (PC) plate, a polymethyl methacrylate resin (PMMA) plate, and a polymethyl methacrylate resin layer. A plastic plate made of a layer of acrylic resin laminated on a polycarbonate resin plate. The polycarbonate resin sheet may contain a resin other than a polycarbonate resin as a constituent material, and the acrylic resin sheet may contain a resin other than an acrylic resin as a constituent material.

塑膠板的厚度沒有特別限定，通常為0.2~5mm，較佳為0.4~3mm，特佳為0.6~2.5mm，更佳為1~2.1mm。The thickness of the plastic plate is not particularly limited, but is usually 0.2 to 5 mm, preferably 0.4 to 3 mm, particularly preferably 0.6 to 2.5 mm, and more preferably 1 to 2.1 mm.

第1顯示體構成構件21以由上述紫外線遮蔽性構件所構成之保護面板(覆蓋材)為佳。在紫外線遮蔽性構件的一面或兩面，亦可設置各種的功能層(透明導電膜、金屬層、氧化矽層、硬塗層、防眩層等)，亦可層積有光學構件。又，透明導電膜及金屬層亦可經圖案化。The first display body constituent member 21 is preferably a protective panel (covering material) composed of the above-mentioned ultraviolet shielding member. Various functional layers (transparent conductive film, metal layer, silicon oxide layer, hard coat layer, anti-glare layer, etc.) may be provided on one or both sides of the ultraviolet shielding member, and an optical member may be laminated. The transparent conductive film and the metal layer may be patterned.

第2顯示體構成構件22亦可為玻璃板，亦可為預定貼附在第1顯示體構成構件21之光學構件、顯示體模組(例如液晶(LCD)模組、發光二極體(LED)模組、有機電激發光(有機EL)模組等)、作為顯示體模組的一部分之光學構件、或包含顯示體模組之積層體。又，該等光學構件、顯示體模組、積層體等亦可為具備玻璃板之物。The second display body constituent member 22 may be a glass plate, or may be an optical member, a display module (such as a liquid crystal (LCD) module, or a light emitting diode (LED) ) Module, organic electroluminescence (organic EL) module, etc.), an optical component as a part of a display body module, or a multilayer body including a display body module. In addition, the optical member, the display module, the laminated body, and the like may be a thing provided with a glass plate.

作為上述玻璃板，沒有特別限定，例如可舉出化學強化玻璃、無鹼玻璃、石英玻璃、鈉鈣玻璃、含鋇‧鍶玻璃、鋁矽酸玻璃、鉛玻璃、硼矽酸玻璃、鋇硼矽酸玻璃等。玻璃板的厚度，沒有特別限定，通常為0.1~10mm，較佳為0.2~5mm，更佳為0.8~2mm。The glass plate is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, barium and strontium glass, aluminosilicate glass, lead glass, borosilicate glass, and barium borosilicate Acid glass and so on. The thickness of the glass plate is not particularly limited, but is usually 0.1 to 10 mm, preferably 0.2 to 5 mm, and more preferably 0.8 to 2 mm.

在構成第2顯示體構成構件22之玻璃板的一面或兩面，亦可設置各種的功能層(透明導電膜、金屬層、氧化矽層、硬塗層、防眩層等)，亦可層積有光學構件。又，透明導電膜及金屬層亦可經圖案化。Various functional layers (transparent conductive film, metal layer, silicon oxide layer, hard coating layer, anti-glare layer, etc.) may be provided on one or both sides of the glass plate constituting the second display member 22, or may be laminated. There are optical components. The transparent conductive film and the metal layer may be patterned.

作為上述光學構件，例如可舉出防飛散膜、偏光板(偏光膜)、偏光鏡、相位差板(相位差膜)、視野角補償膜、亮度提升膜、對比提升膜、液晶聚合物膜、擴散膜、半透射反射膜、透明導電性膜等。作為防飛散膜，可例示將硬塗層形成在基材膜的一面而成之硬塗膜等。上述光學構件亦可含有紫外線吸收劑。Examples of the optical member include an anti-scattering film, a polarizing plate (polarizing film), a polarizer, a retardation plate (a retardation film), a viewing angle compensation film, a brightness enhancement film, a contrast enhancement film, a liquid crystal polymer film, Diffusion film, transflective film, transparent conductive film, etc. Examples of the anti-scattering film include a hard coat film in which a hard coat layer is formed on one surface of a base film. The optical member may contain an ultraviolet absorber.

又，第2顯示體構成構件22以因照射紫外線而性能劣化之構件、或無法從該第2顯示體構成構件22側對活性能量線硬化性黏著劑層11照射活性能量線之構件為佳。具體而言，第2顯示體構成構件22以顯示體模組或包含顯示體模組之積層體為佳。In addition, the second display body constituent member 22 is preferably a member that has deteriorated performance due to ultraviolet radiation or a member that cannot irradiate the active energy ray-curable adhesive layer 11 from the second display body constituent member 22 side with active energy rays. Specifically, the second display body constituent member 22 is preferably a display body module or a laminated body including the display body module.

第1顯示體構成構件21為保護面板時，印刷層3是通常在第1顯示體構成構件21之硬化後黏著劑層11’側形成框狀。When the first display body constituent member 21 is a protective panel, the printed layer 3 is generally formed in a frame shape on the hardened adhesive layer 11 'side of the first display body constituent member 21.

構成印刷層3之材料沒有特別限定，能夠使用印刷用的習知材料。印刷層3的厚度亦即段差的高度為通常3~50μm左右。該硬化後黏著劑層11’時，即便對此種印刷層3亦能夠顯示充分的追隨性且能夠成為在與印刷層3之界面不產生氣泡等之物。The material constituting the printed layer 3 is not particularly limited, and a known material for printing can be used. The thickness of the printed layer 3, that is, the height of the step is usually about 3 to 50 μm. In the post-curing adhesive layer 11 ', it is possible to exhibit sufficient followability even for such a printed layer 3, and it is possible to prevent the occurrence of bubbles or the like at the interface with the printed layer 3.

作為顯示體2，例如可舉出液晶(LCD)顯示器、發光二極體(LED)顯示器、有機電激發光(有機EL)顯示器、電子紙等，亦可為觸控面板。又，作為顯示體2，亦可為構成該等的一部分之構件。Examples of the display body 2 include a liquid crystal (LCD) display, a light emitting diode (LED) display, an organic electroluminescent (organic EL) display, an electronic paper, and the like, and may also be a touch panel. The display body 2 may be a component constituting a part of these.

為了製造上述顯示體2，作為一個例子，是將黏著片1一方的剝離片12a剝離，將黏著片1露出的黏著劑層11貼合在第1顯示體構成構件21之存在印刷層3之側的面。此時，因為黏著劑層11是具有優異的初期段差追隨性，所以能夠抑制印刷層3引起的在段差附近產生間隙和浮起。In order to manufacture the above-mentioned display body 2, as an example, the release sheet 12a on one side of the adhesive sheet 1 is peeled off, and the adhesive layer 11 exposed by the adhesive sheet 1 is adhered to the side where the printed layer 3 exists on the first display body constituent member 21 Noodles. At this time, since the adhesive layer 11 has excellent initial step-following followability, it is possible to suppress generation of gaps and floating near the step due to the printed layer 3.

其次，將另一方的剝離片12b從黏著片1的黏著劑層11剝離，將黏著片1露出的黏著劑層11與第2顯示體構成構件22貼合而得到積層體。又，作為其他例子，亦可變更第1顯示體構成構件21及第2顯示體構成構件22之貼合順序。Next, the other peeling sheet 12b is peeled from the adhesive layer 11 of the adhesive sheet 1, and the adhesive layer 11 exposed by the adhesive sheet 1 and the 2nd display body structure member 22 are bonded together, and a laminated body is obtained. In addition, as another example, the bonding order of the first display body constituent member 21 and the second display body constituent member 22 may be changed.

得到上述積層體之後，對該積層體中的黏著劑層11，隔著紫外線遮蔽性構件之顯示體構成構件、較佳是第1顯示體構成構件21而進行照射活性能量線。如前述，因為用以使黏著劑層11硬化之波長的活性能量線是透射該紫外線遮蔽性構件，所以藉由照射該活性能量線，黏著劑層11充分地硬化而成為硬化後黏著劑層11’。藉此，能夠得到具有優異的耐起泡性之顯示體2。After the laminated body is obtained, the adhesive layer 11 in the laminated body is irradiated with active energy rays through a display body constituting member, preferably a first display body constituting member 21 through an ultraviolet shielding member. As described above, since the active energy ray of the wavelength used to harden the adhesive layer 11 is transmitted through the ultraviolet shielding member, by irradiating the active energy ray, the adhesive layer 11 is sufficiently hardened to become the hardened adhesive layer 11. '. Thereby, a display body 2 having excellent foam resistance can be obtained.

如前述，在本實施形態所使用的活性能量線在大於波長365nm之波長區域具有實質上強度的發光之物。作為此種活性能量線的照射光源，例如可適合舉出高壓水銀燈、鹵化金屬燈、氙燈等。該活性能量線的照射量，以照射度為50~1000mW/cm2 左右為佳。又，光量以50~10000mJ/cm2 為佳，以80~5000mJ/cm2 為較佳，以200~2000mJ/cm2 為特佳。As described above, the active energy ray used in this embodiment has a light emitting substance having a substantial intensity in a wavelength region greater than a wavelength of 365 nm. As an irradiation light source of such an active energy ray, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, etc. are mentioned suitably, for example. The irradiation dose of the active energy ray is preferably about 50 to 1000 mW / cm 2 . The light amount is preferably 50 to 10,000 mJ / cm 2 , more preferably 80 to 5000 mJ / cm 2, and particularly preferably 200 to 2000 mJ / cm 2 .

在上述顯示體2，容易使黏著劑產生黃變之波長區域的活性能量線被紫外線遮蔽性構件之顯示體構成構件(第1顯示體構成構件21)遮蔽而不容易到達硬化後黏著劑層11’。藉此，能夠抑制硬化後黏著劑層11’產生黃變。In the above-mentioned display body 2, the active energy rays in the wavelength region where the adhesive easily yellows are blocked by the display body constituting member (the first display body constituting member 21) of the ultraviolet shielding member and cannot easily reach the hardened adhesive layer 11 '. Thereby, yellowing of the adhesive layer 11 'after curing can be suppressed.

又，本發明亦提供構成上述顯示體(顯示體2)的一部分之構成體。該構成體具備下列構成：一顯示體構成構件、另一顯示體構成構件、及將一顯示體構成構件與另一顯示體構成構件互相貼合之硬化後黏著劑層。上述一顯示體構成構件是具有紫外線遮蔽性之紫外線遮蔽性構件。上述另一顯示體構成構件亦可為具有紫外線透過性之紫外線透過性構件。The present invention also provides a constituent body constituting a part of the display body (display body 2). This structure has the following structures: one display body constituent member, another display body constituent member, and a cured adhesive layer that adheres one display body constituent member and another display body constituent member to each other. The above-mentioned display constituent member is an ultraviolet shielding member having ultraviolet shielding properties. The other display body constituent member may be an ultraviolet-transmitting member having ultraviolet-transmittance.

上述硬化後黏著劑層是使活性能量線硬化性黏著劑層硬化而成。該活性能量線硬化性黏著劑層以上述實施形態之黏著片1的黏著劑層11為佳，以對該黏著劑層11透過紫外線遮蔽性構件之顯示體構成構件而照射活性能量線，而使黏著劑層11成為完全硬化狀態的硬化後黏著劑層為佳。The above-mentioned cured adhesive layer is formed by curing an active energy ray-curable adhesive layer. The active energy ray-curable adhesive layer is preferably the adhesive layer 11 of the adhesive sheet 1 of the embodiment described above. The active energy ray is irradiated with active energy rays through the adhesive layer 11 through the display member constituting member of the ultraviolet shielding member. It is preferable that the adhesive layer 11 is a cured adhesive layer in a fully cured state.

作為上述一顯示體構成構件，例如可適合舉出具備含有紫外線吸收劑的塑膠板之保護面板。又，作為上述另一顯示體構成構件，例如可舉出玻璃板、前述各種光學構件等。As one of the above-mentioned display structural members, for example, a protective panel including a plastic plate containing an ultraviolet absorber can be suitably cited. Examples of the other display body constituent member include a glass plate and the aforementioned various optical members.

以上說明的實施形態，是為了容易理解本發明而記載，不是為了限定本發明而記載。因而，在上述實施形態所揭示的各要素，其宗旨亦包含屬於本發明的技術範圍之全部的設計變更和均等物。The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment also includes all design changes and equivalents belonging to the technical scope of the present invention.

例如，在黏著片1之剝離片12a、12b的任一方均能夠省略。又，第1顯示體構成構件21亦可具有印刷層3以外的段差，亦可不具有段差。而且，不僅是第1顯示體構成構件21，第2顯示體構成構件22亦可在硬化後黏著劑層11’側具有段差。 [實施例]For example, any one of the release sheets 12 a and 12 b of the adhesive sheet 1 can be omitted. In addition, the first display body constituent member 21 may or may not have a step other than the printing layer 3. Furthermore, not only the first display body constituent member 21 but also the second display body constituent member 22 may have a step on the side of the adhesive layer 11 'after curing. [Example]

以下，藉由實施例等而更具體地說明本發明，但是本發明範圍不被該等實施例等限定。Hereinafter, the present invention will be described more specifically with examples and the like, but the scope of the present invention is not limited by 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2-乙基己酯60質量份、N-丙烯醯基嗎啉5質量份、丙烯酸異莰酯15質量份、及丙烯酸2-羥基乙酯20質量份藉由溶液聚合法使其共聚合，而調製(甲基)丙烯酸酯聚合物(A)。使用後述方法測定該(甲基)丙烯酸酯聚合物(A)的分子量時，重量平均分子量(Mw)為50萬。[Example 1] 1. Preparation of (meth) acrylate polymer (A): 60 parts by mass of 2-ethylhexyl acrylate, 5 parts by mass of N-acrylfluorenylmorpholine, and 15 parts by mass of isofluorenyl acrylate And 20 parts by mass of 2-hydroxyethyl acrylate were copolymerized by a solution polymerization method to prepare a (meth) acrylate polymer (A). When the molecular weight of this (meth) acrylate polymer (A) was measured by the method mentioned later, the weight average molecular weight (Mw) was 500,000.

2.黏著性組成物的調製 將在上述步驟1所得到的(甲基)丙烯酸酯聚合物(A)100質量份(固體成分換算值；以下相同)、作為交聯劑(B)之三羥甲基丙烷改性甲苯二異氰酸酯(TOYOCHEM公司製、製品名「BHS8515」)0.2質量份、作為活性能量線硬化性成分(C)之ε-己內酯改性參-(2-丙烯醯氧基乙基)三聚異氰酸酯(新中村化學公司製、製品名「A-9300-1CL」)7質量份、作為光聚合起始劑(D)之雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(D1)0.7質量份、作為矽烷偶合劑之3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業公司製、製品名「KBM-403」)0.28質量份進行混合且充分地攪拌，而且藉由使用甲基乙基酮進行稀釋來得到黏著性組成物的塗佈溶液。2. Preparation of Adhesive Composition 100 parts by mass of the (meth) acrylate polymer (A) obtained in the above step 1 (solid content conversion value; the same applies hereinafter), as the trihydroxy group of the crosslinking agent (B) 0.2 parts by mass of methyl propane-modified toluene diisocyanate (manufactured by TOYOCHEM, product name "BHS8515"), ε-caprolactone-modified ginseng- (2-propenyloxy) as active energy ray-curable component (C) (Ethyl) Trimeric isocyanate (manufactured by Shin Nakamura Chemical Co., Ltd., product name "A-9300-1CL"), 7 parts by mass, bis (2,4,6-trimethylbenzoic acid) as a photopolymerization initiator (D) 0.7 parts by mass of phenylphosphine oxide (D1), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403") as a silane coupling agent 0.28 mass Parts were mixed and sufficiently stirred, and a coating solution of an adhesive composition was obtained by diluting with methyl ethyl ketone.

在此，將(甲基)丙烯酸酯聚合物(A)設為100質量份(固體成分換算值)時之黏著性組成物的各調配(固體成分換算值)顯示在表1。又，表1所記載的略號等之詳細如以下。 [(甲基)丙烯酸酯聚合物(A)] 2EHA：丙烯酸2-乙基己酯 BA：丙烯酸正丁酯 ACMO：N-丙烯醯基嗎啉 IBXA：丙烯酸異莰酯 HEA：丙烯酸2-羥基乙酯 4HBA：丙烯酸4-羥基丁酯 AA：丙烯酸 [交聯劑(B)] TDI：三羥甲基丙烷改性甲苯二異氰酸酯(TOYOCHEM公司製、製品名「BHS8515」) 環氧系：1,3-雙(N,N-二環氧丙基胺甲基)環己烷(三菱氣體化學公司製、製品名「TC-5」) [光聚合起始劑(D)] D1：雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦 D2：2,4,6-三甲基苯甲醯基-二苯基-氧化膦 D3：1-羥基環己基苯基酮Table 1 shows each formulation (solid content conversion value) of the adhesive composition when the (meth) acrylate polymer (A) is 100 parts by mass (solid content conversion value). The abbreviations and the like described in Table 1 are as follows. [(Meth) acrylate polymer (A)] 2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate ACMO: N-acrylfluorenylmorpholine IBXA: isoammonium acrylate HEA: 2-hydroxyethyl acrylate Ester 4HBA: 4-hydroxybutyl acrylate AA: acrylic acid [crosslinking agent (B)] TDI: trimethylolpropane modified toluene diisocyanate (manufactured by TOYOCHEM, product name "BHS8515") Epoxy: 1,3 -Bis (N, N-glycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "TC-5") [Photopolymerization initiator (D)] D1: Bis (2, 4,6-trimethylbenzylidene) -phenylphosphine oxide D2: 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide D3: 1-hydroxycyclohexylphenyl ketone

3.黏著片的製造 將在上述步驟2所得到的黏著性組成物之塗佈溶液，使用刮刀塗佈器塗佈在經使用聚矽氧系剝離劑對聚對苯二甲酸乙二酯膜的一面進行剝離處理之重剝離型剝離片(LINTEC公司製、製品名「SP-PET752150」)的剝離處理面之後，在90℃進行加熱處理1分鐘而形成塗佈層(厚度：50μm)。將在所得到之附塗佈層的重剝離型剝離片之塗佈層側的面、與經使用聚矽氧系剝離劑對聚對苯二甲酸乙二酯膜的一面進行剝離處理之輕剝離型剝離片(LINTEC公司製、製品名「SP-PET381130」)的剝離處理面進行貼合，藉由在23℃、50%RH的條件下熟化7天，來製造由重剝離型剝離片/活性能量線硬化性黏著劑層(厚度：50μm)/輕剝離型剝離片的構成所構成之黏著片。3. Production of adhesive sheet The coating solution of the adhesive composition obtained in the above step 2 was applied to a polyethylene terephthalate film using a silicone-based release agent using a doctor blade applicator. After peeling the peeled surface of a heavy peeling type release sheet (manufactured by LINTEC Corporation, product name "SP-PET752150") on one side, a heat treatment was performed at 90 ° C for 1 minute to form a coating layer (thickness: 50 µm). The surface of the coating layer side of the obtained heavy release type release sheet with a coating layer was lightly peeled off from one side of the polyethylene terephthalate film by using a silicone release agent. Type peeling sheet (manufactured by LINTEC, product name "SP-PET381130") is bonded to the peeling treatment surface, and is cured for 7 days at 23 ° C and 50% RH to produce a heavy peeling type release sheet / active Adhesive sheet composed of energy ray-curable adhesive layer (thickness: 50 μm) / light release type release sheet.

又，上述黏著劑層的厚度，是依據JIS K7130且使用定壓厚度測定器(Teclock公司製、製品名「PG-02」)而測得的值。The thickness of the adhesive layer is a value measured in accordance with JIS K7130 using a constant pressure thickness measuring device (manufactured by Teclock Corporation, product name "PG-02").

4.附覆蓋材的黏著片之製造 將輕剝離型剝離片從上述步驟3所得到的黏著片剝離，將露出的活性能量線硬化性黏著劑層，貼合在作為覆蓋材之將聚甲基丙烯酸甲酯樹脂層等的丙烯酸樹脂層層積在聚碳酸酯樹脂板而成之塑膠板A(厚度：0.7mm、含有紫外線吸收劑)的聚碳酸酯樹脂板側的面，而得到附覆蓋材的黏著片。同樣地，而且上述覆蓋材是相當於紫外線遮蔽性構件。4. Manufacture of adhesive sheet with cover material Peel off the light-peelable release sheet from the adhesive sheet obtained in step 3 above, and attach the exposed active energy ray-curable adhesive layer to the polymethyl group as the cover material. An acrylic resin layer such as a methyl acrylate resin layer is laminated on a polycarbonate resin plate A (thickness: 0.7 mm, containing ultraviolet absorber) side surface of the polycarbonate resin plate to obtain a covering material Adhesive sheet. Similarly, the covering material is equivalent to an ultraviolet shielding member.

[實施例2] 除了將光聚合起始劑(D)變更成為2,4,6-三甲基苯甲醯基-二苯基-氧化膦(D2)以外，與實施例1同樣地進行而調製成為黏著性組成物的塗佈溶液，將該黏著性組成物的塗佈溶液使用刮刀塗佈器塗佈在使用聚矽氧系剝離劑將聚對苯二甲酸乙二酯膜的一面進行剝離處理而成之重剝離型剝離片(LINTEC公司製、製品名「SP-PET752150」)的剝離處理面之後，藉由在90℃加熱處理1分鐘而形成塗佈層(厚度：50μm)，來製造附塗佈層的重剝離型剝離片。[Example 2] The same procedure as in Example 1 was performed except that the photopolymerization initiator (D) was changed to 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (D2). A coating solution of an adhesive composition was prepared, and the coating solution of the adhesive composition was applied using a doctor blade applicator to peel off one side of a polyethylene terephthalate film using a silicone-based release agent. After processing the peeled surface of the heavy peelable release sheet (manufactured by LINTEC, product name "SP-PET752150"), a heat treatment was performed at 90 ° C for 1 minute to form a coating layer (thickness: 50 μm) to manufacture Heavy release type release sheet with coating layer.

另一方面，除了將光聚合起始劑(D)變更成為2,4,6-三甲基苯甲醯基-二苯基-氧化膦(D2)以外，與實施例1同樣地而調製成為黏著性組成物的塗佈溶液，將該黏著性組成物的塗佈溶液使用刮刀塗佈器塗佈在使用聚矽氧系剝離劑將聚對苯二甲酸乙二酯膜的一面進行剝離處理而成之輕剝離型剝離片(LINTEC公司製、製品名「SP-PET381130」)的剝離處理面之後，藉由在90℃加熱處理1分鐘而形成塗佈層(厚度：50μm)，來製造3片附塗佈層的輕剝離型剝離片。On the other hand, except that the photopolymerization initiator (D) was changed to 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (D2), it was prepared in the same manner as in Example 1. A coating solution of an adhesive composition, and the coating solution of the adhesive composition was applied using a doctor blade applicator to a surface of a polyethylene terephthalate film using a silicone-based release agent to release the film. After the release-treated surface of the finished light release type release sheet (manufactured by LINTEC, product name "SP-PET381130"), a heat treatment was performed at 90 ° C for 1 minute to form a coating layer (thickness: 50 μm) to produce 3 pieces Light release type release sheet with coating layer.

將在如上述所得到之附塗佈層的重剝離型剝離片之塗佈層側的面、與在如上述所得到之附塗佈層的輕剝離型剝離片之中的1片之塗佈面側的面進行貼附，來得到厚度合計100μm之塗佈層被重剝離型剝離片與輕剝離型剝離片夾住而成之第1積層體。One of the surface of the coating layer side of the heavy release type release sheet with a coating layer obtained as described above and one of the light release type release sheet with a coating layer obtained as described above are applied. The surface on the surface side was adhered to obtain a first laminated body in which a coating layer having a total thickness of 100 μm was sandwiched between a heavy release type release sheet and a light release type release sheet.

接著，對從上述第1積層體剝離輕剝離型剝離片而露出的塗佈層的露出面，將上述得到的附塗佈層的輕剝離型剝離片之中的1片之塗佈面側的面進行貼附，來得到厚度合計150μm之塗佈層被重剝離型剝離片與輕剝離型剝離片夾住而成之第2積層體。Next, on the exposed surface of the coating layer exposed by peeling the light-peelable release sheet from the first laminate, the coated surface side of one of the light-peelable release sheets with a coating layer obtained as described above is The second laminated body was obtained by attaching the surface to a coating layer having a total thickness of 150 μm between the heavy release type release sheet and the light release type release sheet.

接著，對從上述第2積層體剝離輕剝離型剝離片而露出的塗佈層的露出面，將上述得到的附塗佈層的輕剝離型剝離片之中的1片之塗佈面側的面進行貼附，來得到厚度合計200μm之塗佈層被重剝離型剝離片與輕剝離型剝離片夾住而成之第3積層體。Next, on the exposed surface of the coating layer exposed by peeling the light-peelable release sheet from the second laminate, the coated surface side of one of the light-peelable release sheets with a coating layer obtained as described above is A third laminated body was obtained in which the coating layer with a total thickness of 200 μm was sandwiched between the heavy release type release sheet and the light release type release sheet.

將上述第3積層體，藉由在23℃、50%RH的條件下熟化7天，來製造由重剝離型剝離片/活性能量線硬化性黏著劑層(厚度：200μm)/輕剝離型剝離片的構成所構成之黏著片。The third laminated body was cured at 23 ° C. and 50% RH for 7 days to produce a heavy release type release sheet / active energy ray-curable adhesive layer (thickness: 200 μm) / light release type peeling. The composition of the sheet constitutes an adhesive sheet.

將輕剝離型剝離片從上述所得到的黏著片剝離，將露出的活性能量線硬化性黏著劑層，貼合在作為覆蓋材之將聚甲基丙烯酸甲酯樹脂層等的丙烯酸樹脂層層積在聚碳酸酯樹脂板而成之塑膠板A(厚度：0.7mm、含有紫外線吸收劑)的聚碳酸酯樹脂板側的面，而得到附覆蓋材的黏著片。又，上述覆蓋材是相當紫外線遮蔽性構件。The lightly peelable release sheet was peeled from the adhesive sheet obtained above, and the exposed active energy ray-curable adhesive layer was laminated to an acrylic resin layer such as a polymethyl methacrylate resin layer as a covering material. An adhesive sheet with a covering material was obtained on the side of the polycarbonate resin plate of the plastic plate A (thickness: 0.7 mm, containing an ultraviolet absorber) made of a polycarbonate resin plate. The covering material is a relatively ultraviolet shielding member.

[實施例3~9] 除了將構成(甲基)丙烯酸酯聚合物(A)之各單體的種類及比例、交聯劑(B)的種類及調配量、以及光聚合起始劑(D)的種類及調配量如表1顯示變更以外，與實施例1同樣地進行而製造黏著片及附覆蓋材的黏著片。[Examples 3 to 9] In addition to the types and proportions of the monomers constituting the (meth) acrylate polymer (A), the types and blending amounts of the crosslinking agent (B), and the photopolymerization initiator (D The types and blending amounts of) were changed in the same manner as in Example 1 except for the changes shown in Table 1. The adhesive sheet and the adhesive sheet with a covering material were produced.

[實施例10] 除了將覆蓋材，變更成為將聚甲基丙烯酸甲酯樹脂層層積在聚碳酸酯樹脂板而成之塑膠板B(厚度：2mm、含有紫外線吸收劑)以外，與實施例1同樣地進行而製造黏著片及附覆蓋材的黏著片。[Example 10] Except that the covering material was changed to a plastic plate B (thickness: 2 mm, containing an ultraviolet absorber) formed by laminating a polymethyl methacrylate resin layer on a polycarbonate resin plate, it was the same as the example 1 Proceed in the same manner to produce an adhesive sheet and an adhesive sheet with a covering material.

[實施例11] 除了將覆蓋材，變更成為將聚甲基丙烯酸甲酯樹脂層層積在聚碳酸酯樹脂板而成之塑膠板B(厚度：2mm、含有紫外線吸收劑)以外，與實施例2同樣地進行而製造黏著片及附覆蓋材的黏著片。[Example 11] Except that the covering material was changed to a plastic plate B (thickness: 2 mm, containing an ultraviolet absorber) in which a polymethyl methacrylate resin layer was laminated on a polycarbonate resin plate, it was the same as the example 2 Proceed in the same manner to produce an adhesive sheet and an adhesive sheet with a covering material.

[實施例12~16] 除了將覆蓋材，變更成為將聚甲基丙烯酸甲酯樹脂層層積在聚碳酸酯樹脂板而成之塑膠板B(厚度：2mm、含有紫外線吸收劑)且將構成(甲基)丙烯酸酯聚合物(A)之各單體的種類及比例、交聯劑(B)的種類及調配量、以及光聚合起始劑(D)的種類及調配量依照表1顯示變更以外，與實施例1同樣地進行而製造黏著片及附覆蓋材的黏著片。[Examples 12 to 16] Except that the covering material was changed to a plastic plate B (thickness: 2 mm, containing an ultraviolet absorber) in which a polymethyl methacrylate resin layer was laminated on a polycarbonate resin plate, the constitution was changed. The type and proportion of each monomer of the (meth) acrylate polymer (A), the type and blending amount of the crosslinking agent (B), and the type and blending amount of the photopolymerization initiator (D) are shown in Table 1. Except for the change, it carried out similarly to Example 1, and produced the adhesive sheet and the adhesive sheet with a cover material.

[比較例1] 除了將光聚合起始劑(D)變更成為1-羥基環己基苯基酮(D3)以外，與實施例2同樣地進行而製造黏著片。[Comparative Example 1] An adhesive sheet was produced in the same manner as in Example 2 except that the photopolymerization initiator (D) was changed to 1-hydroxycyclohexylphenyl ketone (D3).

將輕剝離型剝離片從所得到的黏著片剝離，將露出的活性能量線硬化性黏著劑層，貼合在作為覆蓋材之鈉鈣玻璃板(川村久藏商店公司製、製品名「鈉鈣玻璃」、厚度：1.1mm、不含有紫外線吸收劑)而得到附覆蓋材的黏著片。又，上述覆蓋材不相當於紫外線遮蔽性構件。The light release type peeling sheet was peeled from the obtained adhesive sheet, and the exposed active energy ray-curable adhesive layer was bonded to a soda-lime glass plate (manufactured by Kawamura Kuzura Store Co., Ltd. under the product name "Sodium-Calcium "Glass", thickness: 1.1 mm, does not contain ultraviolet absorber) to obtain an adhesive sheet with a covering material. The covering material does not correspond to an ultraviolet shielding member.

[比較例2~5] 除了將構成(甲基)丙烯酸酯聚合物(A)之各單體的種類及比例、交聯劑(B)的種類及調配量、以及光聚合起始劑(D)的種類及調配量如表1顯示變更以外，與實施例1同樣地進行而製造黏著片及附覆蓋材的黏著片。[Comparative Examples 2 to 5] In addition to the types and ratios of the respective monomers constituting the (meth) acrylate polymer (A), the types and blending amounts of the cross-linking agent (B), and the photopolymerization initiator (D The types and blending amounts of) were changed in the same manner as in Example 1 except for the changes shown in Table 1. The adhesive sheet and the adhesive sheet with a covering material were produced.

[比較例6~9] 除了將構成(甲基)丙烯酸酯聚合物(A)之各單體的種類及比例、交聯劑(B)的種類及調配量、光聚合起始劑(D)的種類及調配量、以及覆蓋材的種類如表1顯示變更以外，與實施例1同樣地進行而製造黏著片及附覆蓋材的黏著片。[Comparative Examples 6 to 9] Except the type and ratio of each monomer constituting the (meth) acrylate polymer (A), the type and blending amount of the crosslinking agent (B), and the photopolymerization initiator (D) The types and blending amounts, and the types of the covering materials were changed in the same manner as in Example 1 except for the changes shown in Table 1. Thus, an adhesive sheet and an adhesive sheet with a covering material were produced.

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

[試驗例1](光線透射率的測定) 將實施例及比較例所使用的覆蓋材之光線透射率(%)，使用霧度計量器(日本電色工業公司製、製品名「NDH5000」)且依據JIS K7361-1：1997而測定。將波長340nm的光線透射率及波長390nm之光線透射率的測定結果顯示在表1。[Test Example 1] (Measurement of light transmittance) The light transmittance (%) of the covering materials used in the examples and comparative examples was measured using a haze meter (manufactured by Nippon Denshoku Industries, Inc., product name "NDH5000") It is measured in accordance with JIS K7361-1: 1997. Table 1 shows the measurement results of the light transmittance at a wavelength of 340 nm and the light transmittance at a wavelength of 390 nm.

[試驗例2](吸光度的測定) 調製在實施例及比較例所使用之光聚合起始劑之濃度0.1質量%的乙腈溶液，使用紫外可見近赤外(UV-Vis-NIR)分光光度計(島津製作所公司製、製品名「UV-3600」)測定在該溶液之波長200~500nm範圍的吸光度。基於其結果而導出波長390nm的吸光度、及在波長200~500nm的吸光度之吸收極大波長(nm)。將結果顯示在表1。[Test Example 2] (Measurement of absorbance) An acetonitrile solution having a concentration of 0.1% by mass of the photopolymerization initiator used in the examples and comparative examples was prepared, and a UV-Vis-NIR spectrophotometer was used. (Shimadzu Corporation, product name "UV-3600") The absorbance of this solution in the wavelength range of 200 to 500 nm was measured. Based on the results, the absorption maximum wavelength (nm) of the absorbance at a wavelength of 390 nm and the absorbance at a wavelength of 200 to 500 nm were derived. The results are shown in Table 1.

[試驗例3](凝膠分率的測定) 將實施例及比較例所得到的黏著片裁斷成為80mm×80mm的大小，藉由在聚酯製網狀物(網眼尺寸200)將該活性能量線硬化性黏著劑層包住，且使用精密天秤稱量其質量，而且減去上述網狀物單獨的質量來算出只有黏著劑的質量。將此時的質量設為M1。[Test Example 3] (Measurement of gel fraction) The adhesive sheets obtained in the examples and comparative examples were cut into a size of 80 mm × 80 mm, and the activity was measured in a polyester mesh (mesh size 200). The energy ray hardening adhesive layer is covered, and its mass is weighed using a precision balance, and the mass of only the adhesive is calculated by subtracting the above-mentioned individual mass of the mesh. Let the mass at this time be M1.

其次，將被上述聚酯製網狀物包住之黏著劑，使其在室溫下(23℃)浸漬在乙酸乙酯24小時。隨後將黏著劑取出且在溫度23℃、相對濕度50%的環境下使其風乾24小時，而且在80℃的烘箱中使其乾燥12小時。乾燥後，使用精密天秤稱量其質量，藉由減去上述網狀物單獨的質量來算出只有黏著劑的質量。將此時的質量設為M2。凝膠分率(%)以(M2/M1)×100表示。藉此，導出黏著劑(活性能量線硬化性黏著劑)的凝膠分率(活性能量線照射前)。將結果顯示在表2。Next, the adhesive covered with the polyester mesh was immersed in ethyl acetate at room temperature (23 ° C) for 24 hours. Subsequently, the adhesive was taken out and air-dried in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then dried in an oven at 80 ° C. for 12 hours. After drying, the mass is weighed using a precision balance, and the mass of only the adhesive is calculated by subtracting the above-mentioned individual mass of the mesh. Let the mass at this time be M2. The gel fraction (%) is represented by (M2 / M1) × 100. Thereby, the gel fraction of the adhesive (active energy ray-curable adhesive) (before active energy ray irradiation) was derived. The results are shown in Table 2.

另一方面，對實施例及比較例所得到之附覆蓋材的黏著片，隔著覆蓋材且在下述的條件下照射活性能量線使活性能量線硬化性黏著劑層硬化而成為硬化後黏著劑層。針對該硬化後黏著劑層的黏著劑(硬化後黏著劑)，與上述同樣地進行而導出凝膠分率(活性能量線照射後)。又，算出從活性能量線照射後的凝膠分率減去活性能量線照射前的凝膠分率之值(變化量；百分點)。將結果顯示在表2。On the other hand, the adhesive sheet with a covering material obtained in Examples and Comparative Examples was irradiated with active energy rays through the covering material under the following conditions to harden the active energy ray-curable adhesive layer to become a cured adhesive. Floor. The gel fraction (after active energy ray irradiation) of the adhesive (post-curing adhesive) of this adhesive layer after hardening was performed similarly to the above. In addition, the value of the gel fraction before the active energy ray irradiation (the amount of change; percentage) was calculated from the gel fraction after the active energy ray irradiation. The results are shown in Table 2.

＜活性能量線照射條件＞ ‧高壓水銀燈使用 ‧照度200mW/cm2 、光量1000mJ/cm2 ‧照度‧光量計是使用EYEGRAPHICS公司製「UVPF-A1」＜ Active energy ray irradiation conditions ＞ ‧Use of high-pressure mercury lamp ‧Illumination 200mW / cm 2 , 1000mJ / cm 2 light ‧Illuminance ‧UVmeter-A1 manufactured by EYEGRAPHICS

[試驗例4](霧度值的測定) 對實施例及比較例所得到之附覆蓋材的黏著片，越過覆蓋材、在與試驗例2相同活性能量線照射條件下照射活性能量線，使黏著劑層硬化而成為硬化後黏著劑層。針對該硬化後黏著劑層，依據JIS K7136：2000，使用霧度計量器(日本電色工業公司製、製品名「ND H-2000」)而測定霧度值(%)。將結果顯示在表2。[Test Example 4] (Measurement of Haze Value) The adhesive sheet with a covering material obtained in Examples and Comparative Examples was irradiated with an active energy ray under the same conditions as in Experimental Example 2 under the conditions of the active energy ray irradiation across the covering material. The adhesive layer is hardened to become a hardened adhesive layer. With respect to this cured adhesive layer, a haze value (%) was measured using a haze meter (manufactured by Nippon Denshoku Industries, Ltd., product name "ND H-2000") in accordance with JIS K7136: 2000. The results are shown in Table 2.

[試驗例5](黏著力的測定) 將輕剝離型剝離片從實施例及比較例所得到的黏著片剝離，將露出的黏著劑層貼合在具有易接著層之聚對苯二甲酸乙二酯(PET)膜(東洋紡公司製、製品名「PET A4300」、厚度：100μm)的易接著層，來得到重剝離型剝離片/活性能量線硬化性黏著劑層/PET膜的積層體。將所得到的積層體裁斷成為25mm寬、100mm長。[Test Example 5] (Measurement of Adhesive Strength) The lightly peelable release sheet was peeled from the adhesive sheets obtained in Examples and Comparative Examples, and the exposed adhesive layer was bonded to polyethylene terephthalate having an easy-adhesive layer. A die-bond (PET) film (manufactured by Toyobo Co., Ltd., product name "PET A4300", thickness: 100 µm) was used as an easy-adhesive layer to obtain a laminated body of a heavy release type release sheet / active energy ray-curable adhesive layer / PET film. The obtained laminated body was cut into a width of 25 mm and a length of 100 mm.

在23℃、50%RH的環境下，將重剝離型剝離片從上述積層體剝離，將露出的黏著劑層貼合在鈉鈣玻璃(日本板硝子公司製)且使用栗原製作所公司製高壓釜在0.5MPa、50℃加壓20分鐘。隨後，使PET膜面朝向上側，將作為覆蓋材之將聚甲基丙烯酸甲酯樹脂層等的丙烯酸樹脂層層積在聚碳酸酯樹脂板而成之塑膠板A(厚度：0.7mm、含有紫外線吸收劑)載置在PET膜上。然後，隔著該覆蓋材及PET膜，對活性能量線硬化性黏著劑層在與試驗例2相同活性能量線照射條件下照射活性能量線，使黏著劑層而成為硬化後黏著劑層。在23℃、50%RH的條件下放置24小時之後，將覆蓋材除去且針對具有該硬化後黏著劑層之試樣，使用拉伸試驗機(ORIENTEC公司製、TENSILON)在剝離速度300mm/min、剝離角度180度的條件下，進行測定黏著力(N/25mm)。除了在此所記載以外之條件，是依據JIS Z0237：2009進行測定。將結果顯示在表2。In a 23 ° C, 50% RH environment, the heavy release type peeling sheet was peeled from the laminated body, and the exposed adhesive layer was bonded to a soda lime glass (manufactured by Nippon Glass Glass Co., Ltd.) using an autoclave manufactured by Kurihara Manufacturing 0.5 MPa and 50 ° C for 20 minutes. Subsequently, the PET film surface was oriented upward, and a plastic plate A (thickness: 0.7 mm, containing Ultraviolet absorbent) is placed on a PET film. Then, the active energy ray-curable adhesive layer was irradiated with the active energy ray under the same conditions of active energy ray irradiation as in Test Example 2 through the covering material and the PET film to make the adhesive layer into a cured adhesive layer. After leaving it for 24 hours at 23 ° C and 50% RH, the cover was removed and a sample having the cured adhesive layer was subjected to a tensile tester (manufactured by ORIENTEC, TENSILON) at a peeling speed of 300 mm / min. The adhesive force (N / 25mm) was measured under the conditions of a peeling angle of 180 degrees. Conditions other than those described herein are measured in accordance with JIS Z0237: 2009. The results are shown in Table 2.

[試驗例6](透射色相b*的測定) 將重剝離型剝離片從實施例及比較例所得到之附覆蓋材的黏著片剝離，將露出的活性能量線硬化性黏著劑層貼合在鈉鈣玻璃(日本板硝子公司製、厚度1.1mm)。然後，在50℃、0.5MPa的條件下進行高壓釜處理20分鐘且在常壓、23℃、50%RH放置24小時。[Test Example 6] (Measurement of transmission hue b *) The re-peelable release sheet was peeled from the adhesive sheet with a covering material obtained in Examples and Comparative Examples, and the exposed active energy ray-curable adhesive layer was bonded to Soda-lime glass (manufactured by Nippon Itachi Glass Co., Ltd., 1.1 mm thick). Then, the autoclave process was performed under the conditions of 50 ° C. and 0.5 MPa for 20 minutes, and left at normal pressure, 23 ° C., and 50% RH for 24 hours.

其次，對活性能量線硬化性黏著劑層，隔著覆蓋材、在與試驗例2相同的活性能量線照射條件下，照射活性能量線，使黏著劑層硬化而成為硬化後黏著劑層。針對該硬化後黏著劑層，使用同時測光分光式色度計(日本電色工業公司製、製品名「SQ2000」)，測定依據CIE1976L*a*b*表色系規定之透射色相b*0 (初期)。將結果顯示在表2。Next, the active energy ray-curable adhesive layer was irradiated with an active energy ray under the same active energy ray irradiation conditions as in Test Example 2 through a covering material, and the adhesive layer was hardened to become a cured adhesive layer. For the hardened adhesive layer, a simultaneous photometric spectrophotometer (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SQ2000") was used to measure the transmission hue b * 0 (according to the CIE1976L * a * b * table color system) Early). The results are shown in Table 2.

其次，將活性能量線硬化性黏著劑層已成為硬化後黏著劑層之附覆蓋材的黏著片，投入耐光性試驗機(SUGA試驗機公司製、製品名「紫外線褪色測試儀(fade-meter)U48、光源：碳弧燈)，從覆蓋材側照射活性能量線(照度：350mW/cm2 )1000小時(耐光試驗)。隨後，針對硬化後黏著劑層，與上述同樣地進行而測定透射色相b*1 (耐光試驗後)。而且，算出從耐光試驗後的b*1 減去初期的b*0 後之值Δb*(變化量)。將結果顯示在表2。Next, the active energy ray-curable adhesive layer has become an adhesive sheet with a covering material after the cured adhesive layer is put into a light resistance tester (manufactured by SUGA Tester Co., Ltd., product name "Fade-meter" U48, light source: carbon arc lamp), irradiate the active energy ray (illumination: 350mW / cm 2 ) from the covering material side for 1000 hours (light resistance test). Then, the hardened adhesive layer was tested in the same manner as above to measure the transmission hue. b * 1 (after the light resistance test). A value Δb * (amount of change) after subtracting the initial b * 0 from b * 1 after the light resistance test was calculated. The results are shown in Table 2.

[試驗例7](耐起泡性的評價) 將重剝離型剝離片從實施例及比較例所得到之附覆蓋材的黏著片剝離，將露出的活性能量線硬化性黏著劑層貼附在鈉鈣玻璃(日本板硝子公司製、厚度1.1mm)。然後，在50℃、0.5MPa的條件下進行高壓釜處理20分鐘且在常壓、23℃、50%RH放置24小時。[Test Example 7] (Evaluation of Foaming Resistance) The heavy release type peeling sheet was peeled from the adhesive sheet with a covering material obtained in Examples and Comparative Examples, and the exposed active energy ray-curable adhesive layer was attached to Soda-lime glass (manufactured by Nippon Itachi Glass Co., Ltd., 1.1 mm thick). Then, the autoclave process was performed under the conditions of 50 ° C. and 0.5 MPa for 20 minutes, and left at normal pressure, 23 ° C., and 50% RH for 24 hours.

其次，對活性能量線硬化性黏著劑層，隔著覆蓋材，在與試驗例2相同的活性能量線照射條件下照射活性能量線，且使黏著劑層硬化而成為硬化後黏著劑層。接著，將所得到的積層體在85℃、85%RH的高溫高濕條件下保管1000小時。隨後，藉由目視確認硬化後黏著劑層與被黏著物的界面之狀態，依照以下的基準而進行評價耐起泡性。將結果顯示在表2。 ◎…無氣泡和浮起‧剝落。 ○…產生2個或1個直徑小於1mm的氣泡，但是無浮起‧剝落。 △…產生3個以上且9個以下直徑小於1mm的氣泡，但是無浮起‧剝落 ×…產生氣泡、浮起‧剝落。Next, the active energy ray-curable adhesive layer was irradiated with an active energy ray under the same active energy ray irradiation conditions as in Test Example 2 through a covering material, and the adhesive layer was hardened to become a hardened adhesive layer. Next, the obtained laminated body was stored under high temperature and high humidity conditions of 85 ° C. and 85% RH for 1,000 hours. Subsequently, the state of the interface between the adhesive layer and the adherend after curing was visually confirmed, and the foam resistance was evaluated in accordance with the following criteria. The results are shown in Table 2. ◎ ... No bubbles and floating ‧ peeling. ○ ... Two or one bubbles with a diameter of less than 1 mm were generated, but no floating and peeling occurred. △ ... Three or more and nine or less bubbles with a diameter of less than 1 mm were generated, but there was no floating and peeling × ... Bubbles and floating and peeling were generated.

[表1] [Table 1]

[表2] [Table 2]

從表2能夠得知，使用實施例所得到的黏著片而形成之硬化後黏著劑層不容易產生黃變，而且亦具有優異的耐起泡性。 產業上之可利用性From Table 2, it can be seen that the hardened adhesive layer formed using the adhesive sheet obtained in the example is not likely to cause yellowing, and also has excellent foam resistance. Industrial availability

本發明的黏著片，是能夠適合使用在例如汽車導航系統的顯示體之由含有紫外線吸收劑的塑膠板所構成之保護面板、與顯示體構成構件之貼合。The adhesive sheet of the present invention can be suitably used in, for example, a display panel of a car navigation system, a protective panel made of a plastic plate containing an ultraviolet absorber, and a display panel constituent member.

1‧‧‧黏著片1‧‧‧ adhesive sheet

11‧‧‧黏著劑層11‧‧‧ Adhesive layer

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

2‧‧‧顯示體2‧‧‧ Display

11’‧‧‧硬化後黏著劑層11’‧‧‧ Adhesive layer after hardening

21‧‧‧第1顯示體構成構件(紫外線遮蔽性構件)21‧‧‧The first display body constituting member (ultraviolet shielding member)

22‧‧‧第2顯示體構成構件22‧‧‧Second display component

3‧‧‧印刷層3‧‧‧print layer

第1圖是本發明一實施形態之黏著片的剖面圖。 第2圖是本發明一實施形態之顯示體的剖面圖。FIG. 1 is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention. Fig. 2 is a sectional view of a display body according to an embodiment of the present invention.

Claims (10)

一種黏著片，係具備用以將一顯示體構成構件、與另一顯示體構成構件貼合的黏著劑層之黏著片，其特徵在於： 前述一顯示體構成構件及前述另一顯示體構成構件的至少一方係波長340nm的光線透射率為5%以下且波長390nm的光線透射率為10%以上之紫外線遮蔽性構件， 前述黏著劑層係由含有在濃度0.1質量%的乙腈溶液之波長390nm的吸光度為0.3以上之光聚合起始劑之活性能量線硬化性黏著劑所構成。An adhesive sheet is an adhesive sheet provided with an adhesive layer for bonding one display component and another display component, and is characterized in that: the foregoing display component and the other display component At least one of the light-shielding members is an ultraviolet shielding member having a light transmittance of 340 nm or less and a light transmittance of 390 nm or more of 10% or more. The adhesive layer is composed of an acetonitrile solution having a concentration of 0.1% by mass and a wavelength of 390 nm. An active energy ray-curable adhesive of a photopolymerization initiator having an absorbance of 0.3 or more. 如申請專利範圍第1項所述之黏著片，其中前述黏著劑係從含有(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、活性能量線硬化性成分(C)、及前述光聚合起始劑(D)之黏著性組成物而得到，而且含有前述(甲基)丙烯酸酯聚合物(A)相互之間透過前述交聯劑(B)進行交聯而成之交聯結構；及未反應的前述活性能量線硬化性成分(C)及前述光聚合起始劑(D)之活性能量線硬化性黏著劑。The pressure-sensitive adhesive sheet according to item 1 of the patent application range, wherein the pressure-sensitive adhesive is selected from the group consisting of a (meth) acrylate polymer (A), a cross-linking agent (B), an active energy ray-curable component (C), and Crosslinking obtained by the adhesive composition of the photopolymerization initiator (D) and containing the (meth) acrylate polymer (A) through the crosslinker (B) Structure; and the unreacted active energy ray-curable adhesive of the active energy ray-curable component (C) and the photopolymerization initiator (D). 如申請專利範圍第1項所述之黏著片，其中前述(甲基)丙烯酸酯聚合物(A)係含有5質量%以上且60質量%以下之在分子中具有羥基的單體作為構成該聚合物的單體。The pressure-sensitive adhesive sheet according to item 1 of the scope of patent application, wherein the (meth) acrylate polymer (A) contains a monomer having a hydroxyl group in a molecule of 5% by mass or more and 60% by mass or less as a constituent of the polymerization.物 的 monomonomer. 如申請專利範圍第1項所述之黏著片，其中相對於前述(甲基)丙烯酸酯聚合物(A)100質量份，前述黏著性組成物中之前述交聯劑(B)的含量為0.01質量份以上且3質量份以下。The pressure-sensitive adhesive sheet according to item 1 of the scope of patent application, wherein the content of the cross-linking agent (B) in the adhesive composition is 0.01 with respect to 100 parts by mass of the (meth) acrylate polymer (A). At least 3 parts by mass. 如申請專利範圍第1項所述之黏著片，其中前述活性能量線硬化性黏著劑的凝膠分率為30%以上且70%以下。The adhesive sheet according to item 1 of the scope of patent application, wherein the gel fraction of the active energy ray-curable adhesive is 30% or more and 70% or less. 如申請專利範圍第1項所述之黏著片，其中前述紫外線遮蔽性構件為塑膠板。The adhesive sheet according to item 1 of the scope of patent application, wherein the ultraviolet shielding member is a plastic plate. 如申請專利範圍第1項所述之黏著片，其中具備2片剝離片；及以與前述2片剝離片的剝離面接觸之方式被前述剝離片夾持之前述黏著劑層。The pressure-sensitive adhesive sheet according to item 1 of the patent application scope includes two release sheets; and the pressure-sensitive adhesive layer sandwiched between the two release sheets so as to be in contact with the release surfaces of the two release sheets. 一種顯示體，係具備一顯示體構成構件、另一顯示體構成構件、及將前述一顯示體構成構件與前述另一顯示體構成構件互相貼合之硬化後黏著劑層之顯示體，其特徵在於： 前述一顯示體構成構件及前述另一顯示體構成構件的至少一方係由波長340nm的光線透射率為5%以下且波長390nm的光線透射率為10%以上之紫外線遮蔽性構件所構成， 前述硬化後黏著劑層係使如申請專利範圍第1至7項中任一項所述之黏著片的前述黏著劑層進行活性能量線硬化而成之硬化後黏著劑層。A display body is a display body comprising a display body constituent member, another display body constituent member, and a cured adhesive layer that adheres the aforementioned one display body constituent member and the other display body constituent member to each other. The at least one of the one display component and the other display component is an ultraviolet shielding member having a light transmittance of 340 nm or less and a light transmittance of 390 nm or more of 10%. The above-mentioned hardened adhesive layer is a hardened adhesive layer formed by hardening the above-mentioned adhesive layer of the adhesive sheet according to any one of claims 1 to 7 of the patent application by active energy ray hardening. 如申請專利範圍第8項所述之顯示體，其中構成前述硬化後黏著劑層之黏著劑的凝膠分率為40%以上且95%以下。The display according to item 8 of the scope of application for a patent, wherein the gel fraction of the adhesive constituting the hardened adhesive layer is 40% or more and 95% or less. 一種顯示體的製造方法，其特徵在於： 將至少一方為前述紫外線遮蔽性構件之一顯示體構成構件與另一顯示體構成構件透過如申請專利範圍第1至7項中任一項所述之黏著片的黏著劑層貼合而製造積層體，而且 對前述積層體的前述黏著劑層隔著前述紫外線遮蔽性構件照射活性能量線，使前述黏著劑層硬化而成為硬化後黏著劑層。A method for manufacturing a display body, characterized in that at least one of the display body structural members and the other display body structural member that is one of the ultraviolet shielding members is transmitted as described in any one of claims 1 to 7 of the scope of patent application. The adhesive layer of the adhesive sheet is laminated to produce a laminated body, and the adhesive layer of the laminated body is irradiated with active energy rays through the ultraviolet shielding member, so that the adhesive layer is hardened to become a cured adhesive layer.
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