TW202307167A - Photocurable Adhesive Sheet - Google Patents

Photocurable Adhesive Sheet Download PDF

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TW202307167A
TW202307167A TW111140872A TW111140872A TW202307167A TW 202307167 A TW202307167 A TW 202307167A TW 111140872 A TW111140872 A TW 111140872A TW 111140872 A TW111140872 A TW 111140872A TW 202307167 A TW202307167 A TW 202307167A
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adhesive sheet
meth
light
acrylate
wavelength
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TW111140872A
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Chinese (zh)
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TWI842162B (en
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野澤大希
福田晋也
石井嘉穗儿
稲永誠
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日商三菱化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a pressure-sensitive adhesive sheet for use in laminating a resin member, the pressure-sensitive adhesive sheet being photocurable and exhibiting both surface conformance properties and anti-blistering properties. Proposed is a photocurable pressure-sensitive adhesive sheet for use in laminating a resin member (X) which has a light transmittance of 10% or less at a wavelength of 365 nm and a light transmittance of 60% or greater at a wavelength of 405 nm, characterized by including a pressure-sensitive adhesive layer (Y) having all of the following properties (1) to (3): (1) a gel content in the range of 0-60%; (2) a light transmittance of 89% or less at a wavelength of 390 nm and a light transmittance of 80% or greater at a wavelength of 410 nm; and (3) photocuring properties such that curing occurs upon irradiation with light having a wavelength of 405 nm.

Description

光硬化性黏著片材Photocurable Adhesive Sheet

本發明係關於一種光硬化性黏著片材，其係用以貼合具有並不透過紫外線之紫外線截止性的樹脂構件之黏著片材，其具有藉由照射光而硬化之性能(稱為「光硬化性」)。The present invention relates to a light-curable adhesive sheet, which is an adhesive sheet for laminating a resin member having ultraviolet cutoff properties that do not transmit ultraviolet rays, and has the property of being hardened by irradiation of light (called "photosensitive adhesive sheet"). Hardening").

近年來，為了使圖像顯示裝置之視認性提高而進行如下操作：藉由接著劑填充液晶顯示器(LCD)、電漿顯示器(PDP)、電致發光顯示器(ELD)等圖像顯示面板與配置於其前面側(視認側)之保護面板或觸控面板構件之間的空隙，藉此抑制入射光或來自顯示圖像之出射光於空氣層界面反射。In recent years, in order to improve the visibility of image display devices, the following operations have been carried out: filling liquid crystal display (LCD), plasma display (PDP), electroluminescence display (ELD) and other image display panels and configurations with adhesives The gap between the protective panel or touch panel components on the front side (viewing side) is used to suppress the reflection of incident light or outgoing light from a display image at the interface of the air layer.

作為此種藉由黏著劑填充圖像顯示裝置用構成構件間之空隙的方法，已知有將包含紫外線硬化性樹脂之液狀接著樹脂組合物填充於該空隙中之後，照射紫外線而使其硬化之方法(專利文獻1)。As a method of filling the gaps between constituent members of an image display device with such an adhesive, it is known to fill the gaps with a liquid adhesive resin composition containing an ultraviolet curable resin, and then irradiate it with ultraviolet rays to cure it. method (Patent Document 1).

又，亦已知有使用黏著片材填充圖像顯示裝置用構成構件間之空隙的方法。例如於專利文獻2中揭示了如下之方法：將藉由紫外線而一次交聯之黏著片材貼合於圖像顯示裝置構成構件上之後，介隔圖像顯示裝置構成構件對黏著片材進行紫外線照射而使其二次硬化。Moreover, the method of filling the gap between the constituent members for image display devices using an adhesive sheet is also known. For example, Patent Document 2 discloses a method in which an adhesive sheet that is primarily crosslinked by ultraviolet rays is attached to an image display device constituent member, and then ultraviolet rays are applied to the adhesive sheet through the image display device constituent member. secondary hardening by irradiation.

於專利文獻3中，作為於介隔透明雙面接著性片材貼合在貼合面具有階差部之圖像顯示裝置構成構件時，可追隨該階差部而填充至每個角落，且可緩和接著性片材內所產生之應變，可並不損及處理性地維持高溫或高濕環境下之耐發泡性的新穎之透明雙面接著性片材，揭示了如下之B-階段狀態之透明雙面接著性片材，其含有一種以上(甲基)丙烯酸酯(共)聚合物、波長365 nm之莫耳吸光係數為10以上且波長405 nm之莫耳吸光係數為0.1以下之紫外線聚合起始劑(A)及波長405 nm之莫耳吸光係數為10以上之可見光聚合起始劑(B)，藉由拉伸法而求出之60℃之動態儲存模數(E')除以藉由剪切法而求出之60℃之動態儲存模數(G')的值(E'/G')為10以上。 [先前技術文獻] [專利文獻] In Patent Document 3, when bonding an image display device component having a step portion on the bonding surface through a transparent double-sided adhesive sheet, it can follow the step portion and fill to every corner, and A novel transparent double-sided adhesive sheet that can relax the strain generated in the adhesive sheet and maintain foaming resistance in high-temperature or high-humidity environments without impairing the handling property reveals the following B-stage A transparent double-sided adhesive sheet containing one or more (meth)acrylate (co)polymers, with a molar absorption coefficient of 10 or more at a wavelength of 365 nm and a molar absorption coefficient of 0.1 or less at a wavelength of 405 nm The dynamic storage modulus (E') at 60°C obtained by the stretching method for the ultraviolet polymerization initiator (A) and the visible light polymerization initiator (B) with a molar absorption coefficient of 10 or more at a wavelength of 405 nm The value (E'/G') divided by the dynamic storage modulus (G') at 60°C obtained by the shear method was 10 or more. [Prior Art Literature] [Patent Document]

[專利文獻1]國際公開2010/027041號公報 [專利文獻2]日本專利第4971529號公報 [專利文獻3]日本專利特開2014-152295號公報 [Patent Document 1] International Publication No. 2010/027041 [Patent Document 2] Japanese Patent No. 4971529 [Patent Document 3] Japanese Patent Laid-Open No. 2014-152295

[發明所欲解決之問題][Problem to be solved by the invention]

如上所述地使用光硬化性黏著片材而貼著兩個圖像顯示裝置構成構件之情形時，可介隔該黏著片材而對兩個圖像顯示裝置構成構件進行一次貼著，然後自一個圖像顯示裝置構成構件之外側照射紫外線，通過該圖像顯示裝置構成構件而使該黏著片材紫外線硬化，從而進行二次貼著。 藉由此種方法，可一面填埋被黏著面之凹凸一面進行次貼著，且可最終使其紫外線硬化而更進一步提高接著可靠性，因此可兼顧於所貼合之構件(亦稱為「貼合構件」)之被黏著面具有凹凸之情形時之「階差吸收性」與貼合後之「耐發泡可靠性」。 In the case of pasting two image display device constituent members using a photocurable adhesive sheet as described above, the two image display device constituent members can be pasted once through the adhesive sheet, and then automatically The outer side of one image display device constituent member is irradiated with ultraviolet rays, and the adhesive sheet is cured by ultraviolet rays through the image display device constituent member, thereby performing secondary bonding. By this method, it is possible to fill in the unevenness of the surface to be adhered and carry out secondary adhesion, and finally make it harden by ultraviolet rays to further improve the reliability of adhesion, so it can take into account the components to be bonded (also known as " "Absorptivity of step difference" when the surface to be adhered of the bonding member") has unevenness and "reliability against foaming" after bonding.

例如於車載用圖像顯示裝置等中，為了防止玻璃飛散而使用樹脂製之前面板，有時於其內部側配置導電構件或偏光板等樹脂構件。於此情形時，需要防止前面板或配置於其內部側的導電構件或偏光板等樹脂構件由於紫外線暴露而黃變等劣化，因此進行如下操作：於該等暴露於紫外線之側的樹脂構件中調配紫外線吸收劑而使其具有吸收紫外線之性能。 然而，於此情形時，無法如上所述地自圖像顯示裝置構成構件之外側照射紫外線，通過該圖像顯示裝置構成構件而使該黏著片材紫外線硬化。 因此，於貼合樹脂製前面板時，不得不使用充分硬化為具有耐發泡可靠性之程度、並不具有光硬化性之非光硬化性黏著片材。 然而，該非光硬化性黏著片材於階差吸收性之方面未必能令人滿意。 For example, in an in-vehicle image display device, etc., a front panel made of resin is used to prevent glass from flying, and a resin member such as a conductive member or a polarizing plate is arranged on the inner side thereof. In this case, it is necessary to prevent deterioration of the front panel or resin members such as conductive members or polarizers disposed on the inner side thereof due to ultraviolet exposure, such as yellowing, so the following operations are performed: Formulate UV absorber to make it have the performance of absorbing UV rays. However, in this case, it is impossible to irradiate the ultraviolet rays from the outside of the image display device constituent member as described above, and the adhesive sheet cannot be cured by ultraviolet rays through the image display device constituent member. Therefore, when laminating the front panel made of a resin, it is necessary to use a non-photocurable adhesive sheet that is not photocurable and is sufficiently cured to be reliable against foaming. However, this non-photocurable adhesive sheet is not necessarily satisfactory in terms of step absorption.

本發明提供可與具有並不透過紫外線之紫外線截止性的樹脂構件貼合，且可兼顧於貼合構件之被黏著面具有凹凸之情形時之階差吸收性與貼合後之耐發泡可靠性的新穎之黏著片材。 [解決問題之技術手段] The present invention provides a resin member that can be bonded to a resin member that does not transmit ultraviolet rays and has UV cut-off properties, and can take into account both the step absorption and the foaming resistance after bonding when the adhered surface of the bonded member has unevenness. A novel adhesive sheet. [Technical means to solve the problem]

本發明提出一種光硬化性黏著片材，其特徵在於其係用以貼合具有並不透過紫外線之紫外線截止性的樹脂構件、亦即波長365 nm下之光線透過率為10%以下、且波長405 nm下之光線透過率為60%以上之樹脂構件(X)的光硬化性黏著片材， 其包含具有以下(1)～(3)之所有特性之黏著層(Y)。 (1)凝膠分率(光照射前凝膠分率X1)處於0～60%之範圍內。 (2)波長390 nm下之光線透過率為89%以下、且波長410 nm下之光線透過率為80%以上。 (3)具有藉由照射波長405 nm之光而硬化之光硬化性。 The present invention proposes a light-curable adhesive sheet, which is characterized in that it is used to bond a resin member with ultraviolet cutoff that does not transmit ultraviolet rays, that is, the light transmittance at a wavelength of 365 nm is 10% or less, and the wavelength A photocurable adhesive sheet of a resin member (X) with a light transmittance of 60% or more at 405 nm, It includes an adhesive layer (Y) having all the characteristics of the following (1) to (3). (1) The gel fraction (gel fraction X1 before light irradiation) is in the range of 0 to 60%. (2) The light transmittance at a wavelength of 390 nm is 89% or less, and the light transmittance at a wavelength of 410 nm is 80% or more. (3) It has photocurability that is cured by irradiating light with a wavelength of 405 nm.

本發明又提出一種光硬化性黏著片材積層體，其包含上述光硬化性黏著片材與波長365 nm下之光線透過率為10%以下、且波長405 nm下之光線透過率為60%以上之樹脂構件(X)積層而成之構成。 [發明之效果] The present invention further proposes a photocurable adhesive sheet laminate comprising the aforementioned photocurable adhesive sheet and a light transmittance of 10% or less at a wavelength of 365 nm, and a light transmittance of at least 60% at a wavelength of 405 nm. The composition of the resin member (X) is laminated. [Effect of Invention]

本發明所提出之光硬化性黏著片材之光硬化前之凝膠分率為0～60%，因此可獲得填埋被黏著面之凹凸等階差的階差吸收性，另一方面，其波長390 nm下之光線透過率為89%以下、且具有藉由照射波長405 nm之光而硬化之光硬化性，因此即便所貼合之樹脂構件(X)之波長365 nm下之光線透過率為10%以下、且波長405 nm下之光線透過率為60%以上，亦可藉由照射包含波長405 nm之光而使其硬化，從而可提高凝聚力而獲得貼合後之耐發泡可靠性。 又，本發明所提出之光硬化性黏著片材之波長410 nm下之光線透過率為80%以上，因此可獲得如下之效果：可達成貼合要求透明性之光學構件所需之足夠低之黃度(YI)。 The photocurable adhesive sheet proposed by the present invention has a gel fraction of 0 to 60% before photohardening, so it can obtain a step absorption that fills up the unevenness of the surface to be adhered. On the other hand, its The light transmittance at a wavelength of 390 nm is 89% or less, and it has photocurability that can be cured by irradiating light with a wavelength of 405 nm, so even if the light transmittance at a wavelength of 365 nm of the bonded resin member (X) It is less than 10% and has a light transmittance of more than 60% at a wavelength of 405 nm. It can also be hardened by irradiating light with a wavelength of 405 nm, thereby improving cohesion and obtaining foaming resistance after bonding. . In addition, the light transmittance of the photocurable adhesive sheet proposed by the present invention at a wavelength of 410 nm is more than 80%, so the following effect can be obtained: a sufficiently low light transmittance required for laminating optical components requiring transparency can be achieved. Yellowness (YI).

本發明所提出之光硬化性黏著片材積層體可如上所述地獲得階差吸收性，另一方面，該光硬化性黏著片材之黏著層(Y)具有於自樹脂構件(X)之外側介隔該樹脂構件(X)照射波長405 nm之光時，凝膠分率之差提高10%以上之光硬化性，因此藉由自樹脂構件(X)之外側介隔該樹脂構件(X)照射波長405 nm之光，可使該黏著層(Y)硬化，且亦可提高凝聚力而獲得貼合後之耐發泡可靠性。The photocurable adhesive sheet laminate proposed by the present invention can obtain step absorption as described above. On the other hand, the adhesive layer (Y) of the photocurable adhesive sheet has When the resin member (X) is irradiated with light having a wavelength of 405 nm from the outside, the difference in gel fraction improves the photocurability by more than 10%. Therefore, by interposing the resin member (X) from the outside of the resin member (X), ) is irradiated with light with a wavelength of 405 nm, which can harden the adhesive layer (Y), and also improve the cohesive force to obtain the reliability of anti-foaming after bonding.

其次，對本發明之實施形態之一例加以說明。但本發明並不限定於該實施形態。Next, an example of an embodiment of the present invention will be described. However, the present invention is not limited to this embodiment.

＜＜本黏著片材＞＞ 本發明之實施形態之一例的黏著片材(稱為「本黏著片材」)係包含具有特定特性之黏著層(Y)的光硬化性黏著片材。 ＜＜This adhesive sheet＞＞ An adhesive sheet (referred to as "this adhesive sheet") which is an example of an embodiment of the present invention is a photocurable adhesive sheet including an adhesive layer (Y) having specific characteristics.

本黏著片材係具有藉由照射光而硬化之光硬化性的黏著片材。此時，本黏著片材可為硬化為殘存有光硬化之餘地的狀態(亦稱為「暫時硬化」)者，亦可為尚未硬化、且具有光硬化性之未硬化(稱為「未硬化」)者。 本黏著片材若為暫時硬化或未硬化者，則於將該本黏著片材貼合於被黏著體上之後，可對本黏著片材進行光硬化(亦稱為「正式硬化」)，其結果可提高凝聚力而提高接著性。 This adhesive sheet is a photocurable adhesive sheet that is hardened by irradiation with light. At this time, the adhesive sheet may be cured to a state where light curing remains (also referred to as "temporary curing"), or it may be uncured and photocurable (referred to as "non-cured"). ")By. If this adhesive sheet is temporarily hardened or not hardened, after this adhesive sheet is pasted on the adherend, this adhesive sheet can be light-hardened (also called "full hardening"), and the result Can improve cohesion and improve adhesion.

作為上述之暫時硬化或未硬化，且具有可使其正式硬化之性質、亦即藉由照射波長405 nm之光而硬化之光硬化性的本黏著片材之較佳形態，可列舉包含如下(1)～(3)所示之黏著層(Y)之黏著片材。Preferable forms of the above-mentioned adhesive sheet that are temporarily cured or not cured, and have properties that can be fully cured, that is, photocurable by irradiating light with a wavelength of 405 nm, include the following ( Adhesive sheet for the adhesive layer (Y) shown in 1) to (3).

(1)黏著層(Y)係暫時硬化至凝膠分率成為60%以下，藉由含有下述之可見光起始劑(c)而可進行該可見光起始劑(c)之正式硬化的黏著層。 (2)黏著層(Y)係藉由下述之可見光起始劑(c)中的奪氫型之可見光起始劑(c-2)而暫時硬化至凝膠分率成為60%以下，可進行該可見光起始劑(c-2)之正式硬化的黏著層。 (3)黏著層(Y)係於未硬化之狀態下保持片材形狀，藉由含有下述之可見光起始劑(c)而可進行該可見光起始劑(c)之正式硬化的黏著層。 (1) Adhesive layer (Y) is temporarily cured until the gel fraction becomes 60% or less, and by containing the following visible light initiator (c), it is possible to carry out the adhesion of the main curing of the visible light initiator (c) layer. (2) The adhesive layer (Y) is temporarily hardened by the hydrogen abstraction type visible light initiator (c-2) in the following visible light initiator (c) until the gel fraction becomes 60% or less. Adhesive layer where full-scale hardening of the visible light initiator (c-2) was performed. (3) The adhesive layer (Y) maintains the shape of the sheet in an uncured state, and is an adhesive layer that can be fully cured by the visible light initiator (c) by containing the following visible light initiator (c) .

作為上述(1)之黏著層(Y)之形成方法，例如可列舉如下方法：對包含可見光起始劑(c)、具有官能基(i)之(甲基)丙烯酸酯(共)聚合物(a)、具有與該官能基(i)反應之官能基(ii)之化合物、其他視需要之具有碳-碳雙鍵之光聚合性化合物(尤其是多官能單體)等交聯劑(b)、進一步視需要之矽烷偶合劑(d)的組合物(後述之本樹脂組合物之一例)進行加熱或固化，形成黏著層(Y)。 根據該方法，藉由使(甲基)丙烯酸酯(共)聚合物中之官能基(i)與該化合物中之官能基(ii)反應形成化學鍵而進行硬化(交聯)，形成黏著層(Y)。藉由如上所述地形成黏著層(Y)，可使可見光起始劑(c)具有活性地存在於黏著層(Y)中。 As a method for forming the adhesive layer (Y) of the above (1), for example, the following method can be cited: a (meth)acrylate (co)polymer (meth)acrylate (co)polymer ( a), a compound having a functional group (ii) reacting with the functional group (i), other optional photopolymerizable compounds having carbon-carbon double bonds (especially multifunctional monomers) and other crosslinking agents (b ), and further optionally, the composition of the silane coupling agent (d) (an example of the present resin composition described later) is heated or cured to form an adhesive layer (Y). According to this method, the hardening (crosslinking) is carried out by reacting the functional group (i) in the (meth)acrylate (co)polymer with the functional group (ii) in the compound to form a chemical bond, forming an adhesive layer ( Y). By forming the adhesive layer (Y) as described above, the visible light initiator (c) can be actively present in the adhesive layer (Y).

作為上述官能基(i)與官能基(ii)之組合，例如可列舉羧基與環氧基、羧基與氮丙啶基、羥基與異氰酸基、胺基與異氰酸基、羧基與異氰酸基等。其中，尤佳為羥基與異氰酸基、胺基與異氰酸基、或羧基與異氰酸基之組合。更詳細而言，上述(甲基)丙烯酸酯共聚物(a)具有羥基(使用下述之含有羥基之單體)、且上述化合物具有異氰酸基之情形係尤佳之例。Examples of combinations of the above-mentioned functional group (i) and functional group (ii) include carboxyl and epoxy, carboxyl and aziridinyl, hydroxyl and isocyanato, amine and isocyanato, carboxyl and isocyanate, and carboxyl and isocyanate. Cyanate, etc. Among them, a combination of a hydroxyl group and an isocyanate group, an amine group and an isocyanate group, or a carboxyl group and an isocyanate group is particularly preferable. More specifically, the above-mentioned (meth)acrylate copolymer (a) has a hydroxyl group (the following hydroxyl-containing monomer is used), and the case where the said compound has an isocyanate group is a particularly preferable example.

又，上述具有官能基(ii)之化合物亦可進而具有(甲基)丙烯醯基等自由基聚合性官能基。藉此可形成維持由於上述自由基聚合性官能基所帶來的(甲基)丙烯酸酯(共)聚合物、具體而言具有下述活性能量線交聯性結構部位之(甲基)丙烯酸酯共聚物之光硬化(交聯)性的黏著層(Y)。更詳細而言，上述(甲基)丙烯酸酯(共)聚合物(a)具有羥基(使用下述之含有羥基之單體)，且上述化合物具有(甲基)丙烯醯基之情形(異氰酸2-丙烯醯氧基乙酯、異氰酸2-甲基丙烯醯氧基乙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯等)係尤佳之例。 如上所述，藉由利用由於該自由基聚合性官能基之(甲基)丙烯酸酯(共)聚合物彼此之交聯反應，具有即便不使用交聯劑(b)亦可效率良好地容易地提高光硬化(交聯)後之凝聚力且可靠性優異等優點，因此更佳。 Moreover, the compound which has the said functional group (ii) may further have a radically polymerizable functional group, such as a (meth)acryl group. Thereby, a (meth)acrylate (co)polymer, specifically, a (meth)acrylate having the following active energy ray crosslinkable structural site can be formed maintaining the above-mentioned radical polymerizable functional group A photocurable (crosslinked) adhesive layer (Y) of a copolymer. More specifically, when the above-mentioned (meth)acrylate (co)polymer (a) has a hydroxyl group (the following hydroxyl-containing monomer is used), and the above-mentioned compound has a (meth)acryl group (isocyanate 2-Acryloxyethyl isocyanate, 2-methacryloxyethyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate, etc.) are particularly preferable examples. As described above, by utilizing the crosslinking reaction between the (meth)acrylate (co)polymers due to the radically polymerizable functional group, it is possible to efficiently and easily use the crosslinking agent (b) It is more preferable because of the advantages of improved cohesion after photohardening (crosslinking) and excellent reliability.

再者，關於上述以外之方面而較佳之丙烯酸酯(共)聚合物(a)、或上述交聯劑(b)、上述可見光起始劑(c)及矽烷偶合劑(d)之較佳形態等，如下所述。Furthermore, preferred forms of the acrylate (co)polymer (a), the above-mentioned crosslinking agent (b), the above-mentioned visible light initiator (c) and the silane coupling agent (d) that are preferable in aspects other than the above etc., as described below.

作為上述(2)之黏著層(Y)之形成方法，例如可列舉利用下述之奪氫型之可見光起始劑(c-2)作為可見光起始劑(c)之方法。奪氫型起始劑即便激發一次，該起始劑中之未反應者亦返回至基底狀態，因此可作為可見光起始劑而再次利用。如上所述，藉由利用奪氫型之可見光起始劑，即便於利用可見光照射之暫時硬化後，亦可維持該可見光起始劑之可見光硬化(交聯)性。 再者，關於上述以外之方面及可見光起始劑(c-2)之較佳形態等，如下所述。 As a method of forming the adhesive layer (Y) of the above (2), for example, a method of using the following hydrogen abstraction type visible light initiator (c-2) as the visible light initiator (c) is mentioned. Even if the hydrogen abstraction initiator is excited once, the unreacted part of the initiator will return to the base state, so it can be used again as a visible light initiator. As described above, by using a hydrogen abstraction type visible light initiator, even after temporary hardening by visible light irradiation, the visible light curable (crosslinking) property of the visible light initiator can be maintained. In addition, it is as follows about the aspect other than the above, and the preferable aspect of a visible light initiator (c-2).

作為上述(3)之黏著層(Y)之形成方法，例如可列舉利用下述之巨單體作為構成(甲基)丙烯酸酯共聚物(a)之單體成分的方法。更具體而言，可列舉利用具有巨單體作為枝成分之接枝共聚物的方法。藉由利用此種巨單體，可於室溫狀態下維持枝成分彼此吸引而物理***聯為組合物(後述之本樹脂組合物之一例)之狀態。 因此，可形成可於未硬化(交聯)之狀態下保持片材形狀，且包含可見光起始劑(c)之黏著層(Y)。 再者，關於上述以外之方面及具有巨單體作為枝成分之接枝共聚物的較佳形態等，如下所述。 As a formation method of the adhesive layer (Y) of said (3), the method of using the following macromonomer as a monomer component which comprises a (meth)acrylate copolymer (a), for example is mentioned. More specifically, a method using a graft copolymer having a macromonomer as a branch component is exemplified. By using such a macromonomer, it is possible to maintain a state in which the branch components attract each other and physically cross-link a composition (an example of the present resin composition described later) at room temperature. Therefore, an adhesive layer (Y) that can maintain the shape of the sheet in an uncured (crosslinked) state and that contains the visible light initiator (c) can be formed. In addition, aspects other than those mentioned above and a preferred embodiment of the graft copolymer having a macromonomer as a branch component are as follows.

本黏著片材較佳為用以貼合後述之樹脂構件(X)。This adhesive sheet is preferably used to bond the resin member (X) described later.

本黏著片材可為上述黏著層(Y)之單層構成，亦可為具有上述黏著層(Y)之兩層以上之多層構成。又，於多層之情形時，若至少最表層為上述黏著層(Y)即可，亦可為所有之黏著層均為上述黏著層(Y)。This adhesive sheet may be composed of a single layer of the above-mentioned adhesive layer (Y), or may be composed of a multi-layer structure having two or more layers of the above-mentioned adhesive layer (Y). Also, in the case of multiple layers, at least the outermost layer may be the above-mentioned adhesive layer (Y), or all the adhesive layers may be the above-mentioned adhesive layer (Y).

＜黏著層(Y)＞ 較佳為上述黏著層(Y)具有如下之(1)～(3)之所有特性。 (1)通常狀態亦即光照射前之狀態的凝膠分率(稱為「光照射前凝膠分率X1」)處於0～60%之範圍內。 (2)波長390 nm下之光線透過率為89%以下，且波長410 nm下之光線透過率為80%以上。 (3)具有藉由照射波長405 nm之光而硬化之光硬化性。 ＜Adhesive layer (Y)＞ It is preferable that the above-mentioned adhesive layer (Y) has all the characteristics of the following (1)-(3). (1) The gel fraction in the normal state, that is, the state before light irradiation (referred to as "gel fraction X1 before light irradiation") is in the range of 0 to 60%. (2) The light transmittance at a wavelength of 390 nm is below 89%, and the light transmittance at a wavelength of 410 nm is above 80%. (3) It has photocurability that is cured by irradiating light with a wavelength of 405 nm.

黏著層(Y)若具有藉由加熱而軟化乃至於流動之熱熔性，則於貼合構件之被黏著面存在凹凸等階差之情形時，可使黏著劑進一步更容易地填充至階差之每個角落，可進一步提高階差吸收性，因此較佳。 自該觀點考慮，較佳為將黏著層(Y)設為上述(3)之黏著層(Y)。 If the adhesive layer (Y) has hot-melt properties that can be softened and even flowed by heating, it will be easier to fill the adhesive to the level difference when there are unevenness and other steps on the surface to be adhered of the bonding member. Each corner can further improve the absorbency of the step difference, so it is better. From this viewpoint, it is preferable to use the adhesive layer (Y) as the adhesive layer (Y) of the above (3).

(凝膠分率) 較佳為黏著層(Y)之凝膠分率(光照射前凝膠分率X1)為0～60%之範圍內。 若黏著層(Y)之凝膠分率為60%以下，則自如下觀點考慮而較佳：存在足夠多的具有藉由光照射而硬化之餘地的未交聯成分(處於暫時硬化狀態或未硬化狀態)，正因為如此而柔軟，且可於正式硬化時，將「光照射後凝膠分率X2－光照射前凝膠分率X1」設為10%以上。 自該觀點考慮，黏著層(Y)之凝膠分率較佳為0～60%之範圍內，其中進而較佳為55%以下，其中更佳為50%以下。 (gel fraction) Preferably, the gel fraction (gel fraction X1 before light irradiation) of the adhesive layer (Y) is within the range of 0 to 60%. If the gel fraction of the adhesive layer (Y) is 60% or less, it is preferable from the viewpoint that there are enough uncrosslinked components (in a temporarily hardened state or not yet hardened) that have room for hardening by light irradiation. hardened state), it is soft because of this, and it is possible to set the "gel fraction X2 after light irradiation - gel fraction X1 before light irradiation" to be 10% or more at the time of actual hardening. From this point of view, the gel fraction of the adhesive layer (Y) is preferably in the range of 0 to 60%, more preferably 55% or less, and more preferably 50% or less.

為了將黏著層(Y)之凝膠分率(光照射前凝膠分率X1)調整為上述範圍，若於後述之本樹脂組合物之聚合時及黏著片材之加工時將殘存觸媒充分除去，或使用聚合抑制劑、抗氧化劑等，藉此於正式硬化前並不進行由於熱、光等而引起之並不希望之硬化(交聯)反應即可；又，於藉由光照射而實施暫時硬化之情形時，若使為了進行暫時硬化而照射之光的累計光量足夠小，且使未交聯成分變得足夠多即可。但並不限定於該方法。In order to adjust the gel fraction (gel fraction X1 before light irradiation) of the adhesive layer (Y) to the above-mentioned range, if the residual catalyst is sufficiently added during the polymerization of the present resin composition and the processing of the adhesive sheet to be described later, Remove, or use polymerization inhibitors, antioxidants, etc., so that the undesired hardening (crosslinking) reaction caused by heat, light, etc. does not proceed before the official hardening; When temporary curing is performed, the cumulative light intensity of the light irradiated for temporary curing is sufficiently small, and the uncrosslinked component may be sufficiently increased. However, it is not limited to this method.

進而，較佳為黏著層(Y)具有藉由照射波長405 nm之光而硬化之光硬化性，作為該光硬化性之程度，例如較佳為具有於自樹脂構件(X)之外側，介隔該樹脂構件(X)照射波長405 nm之光時，凝膠分率之差提高10%以上、其中較佳為15%以上、其中更佳為20%以上、其中進一步更佳為30%以上、其中尤佳為50%以上之光硬化性。 再者，所謂「照射波長405 nm之光」係表示照射如下光感度之光，亦即使用紫外線光量計而測定之具有以波長405 nm為感光峰，周邊擴展至320～470 nm之波長範圍的光感度。 Furthermore, it is preferable that the adhesive layer (Y) has photocurability that is cured by irradiation with light having a wavelength of 405 nm. As the degree of this photocurability, for example, it is preferable that it has from the outside of the resin member (X) through When the resin member (X) is irradiated with light having a wavelength of 405 nm, the difference in gel fraction increases by 10% or more, preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more , Among them, the photohardenability of more than 50% is preferred. Furthermore, the so-called "irradiation of light with a wavelength of 405 nm" refers to the irradiation of light with the following photosensitivity, which has a wavelength of 405 nm as the sensitivity peak and extends to a wavelength range of 320 to 470 nm as measured by an ultraviolet light meter. light sensitivity.

其中，較佳為黏著層(Y)具有如下之光硬化性：自上述樹脂構件(X)之外側，介隔例如樹脂構件(X)而照射波長405 nm下之累計光量為3000(mJ/cm 2)之光時，光照射前之凝膠分率(光照射前凝膠分率X1)與光照射後之凝膠分率(稱為「光照射後凝膠分率X2」)之差(光照射後凝膠分率X2－光照射前凝膠分率X1)成為10%以上。 因此，較佳為具有如下之光硬化性：例如於光照射前凝膠分率X1為40%之情形時，照射波長405 nm下之累計光量為3000(mJ/cm 2)之光以後之黏著層(Y)之凝膠分率(稱為「光照射後凝膠分率X2」)成為50%以上。 若光硬化前後之黏著層(Y)之凝膠分率差為10%以上，則即便於嚴酷之高溫高濕環境等下亦成為高凝聚力，且可提高耐發泡可靠性，因此較佳。 因此，較佳為上述光照射前後之黏著層(Y)之凝膠分率差為10%以上，其中進而較佳為15%以上、其中更佳為20%以上、其中進而更佳為30%以上、其中尤佳為50%以上。 為了將上述光照射前後之黏著層(Y)之凝膠分率差調整為上述範圍，可於波長405 nm中存在光起始劑之吸收。但並不限定於該方法。 Among them, it is preferable that the adhesive layer (Y) has the following photocurability: from the outside of the above-mentioned resin member (X), through the resin member (X) for example, the cumulative light intensity at the irradiation wavelength of 405 nm is 3000 (mJ/cm 2 ) In the case of light, the difference between the gel fraction before light irradiation (gel fraction before light irradiation X1) and the gel fraction after light irradiation (referred to as "gel fraction after light irradiation X2") ( The gel fraction X2 after light irradiation - the gel fraction X1 before light irradiation is 10% or more. Therefore, it is preferable to have photocurability as follows: for example, when the gel fraction X1 is 40% before light irradiation, adhesion after irradiation with light with a cumulative light intensity of 3000 (mJ/cm 2 ) at a wavelength of 405 nm The gel fraction (referred to as "gel fraction X2 after light irradiation") of the layer (Y) is 50% or more. If the difference in gel fraction of the adhesive layer (Y) before and after photocuring is 10% or more, it will have high cohesion even under severe high-temperature, high-humidity environments, and the reliability of foaming resistance can be improved, so it is preferable. Therefore, the difference in gel fraction of the adhesive layer (Y) before and after the above-mentioned light irradiation is preferably 10% or more, more preferably 15% or more, more preferably 20% or more, and even more preferably 30% More than, especially preferably more than 50%. In order to adjust the gel fraction difference of the adhesive layer (Y) before and after the above-mentioned light irradiation to the above-mentioned range, the absorption of the photoinitiator may exist at a wavelength of 405 nm. However, it is not limited to this method.

再者，所謂「波長405 nm下之累計光量」係每單位面積所受之照射能量之總量，其係指藉由高壓水銀燈等而照射之光中，使用紫外線累計光量計「UIT-250」(牛尾電機股份有限公司製造)及受光器「UVD-C405」(牛尾電機股份有限公司製造)而測定的光照射能量之總量，其係指與受光器之感光特性(具有以405 nm為感光峰，周邊擴展至320～470 nm之波長範圍的光感度)對應之波長區域之累計光量。更具體而言，其係指依照實施例中所記載之方法而求出之累計光量。Furthermore, the so-called "cumulative light quantity at a wavelength of 405 nm" refers to the total amount of irradiation energy received per unit area, which refers to the light irradiated by a high-pressure mercury lamp, etc., using an ultraviolet cumulative light meter "UIT-250" (manufactured by Ushio Electric Co., Ltd.) and the photoreceiver "UVD-C405" (manufactured by Ushio Electric Co., Ltd.), which refers to the photosensitive characteristics of the photoreceptor (with 405 nm as the photosensitive The cumulative light intensity of the wavelength region corresponding to the peak, and the periphery extends to the light sensitivity of the wavelength range of 320-470 nm. More specifically, it refers to the cumulative light quantity calculated according to the method described in the examples.

(光線透過率) 較佳為黏著層(Y)之波長390 nm下之光線透過率為89%以下，且波長410 nm下之光線透過率為80%以上。 關於調配有於波長400 nm前後之紫外～可見光區域具有吸收之光起始劑的黏著劑調配物，光起始劑之光吸收越大，源自該吸收之波長390 nm下之光線透過率越低，則感光性越良好而變得容易進行硬化。 另一方面，若波長410 nm下之光線透過率並不高至一定程度以上，則黏著層(Y)著色為黃色而變得難以用於光學構件中。 (light transmittance) Preferably, the light transmittance at a wavelength of 390 nm of the adhesive layer (Y) is 89% or less, and the light transmittance at a wavelength of 410 nm is more than 80%. Regarding the adhesive formulation prepared with a photoinitiator that absorbs in the ultraviolet to visible region around a wavelength of 400 nm, the greater the light absorption of the photoinitiator, the higher the light transmittance at a wavelength of 390 nm derived from the absorption. The lower the photosensitivity is, the better the curing will be. On the other hand, if the light transmittance at a wavelength of 410 nm is not higher than a certain level, the adhesive layer (Y) will be colored yellow and it will be difficult to use it in an optical member.

作為以上之標準，若波長390 nm下之光線透過率為89%以下，則黏著層(Y)可確保充分之可見光硬化性，因此較佳；若波長410 nm下之光線透過率為80%以上，則可達成貼合要求透明性之光學構件所需之足夠低之黃度(YI)，因此較佳。 因此，黏著層(Y)之波長390 nm之上述光線透過率較佳為89%以下，其中進而較佳為88%以下。 又，波長410 nm下之光線透過率較佳為80%以上，其中更佳為85%以上，其中進而較佳為90%以上。 為了如上所述地設定黏著層(Y)之光線透過率，若使用於可見光中具有吸收之起始劑中的具有如下吸光峰特性者即可：吸收峰之周邊充分到達390 nm，相對於此，於410 nm處吸收峰變小。但並不限定於該方法。 As the above standard, if the light transmittance at a wavelength of 390 nm is 89% or less, then the adhesive layer (Y) can ensure sufficient visible light hardening, so it is better; if the light transmittance at a wavelength of 410 nm is 80% or more , it can achieve a sufficiently low yellowness (YI) required for bonding optical components that require transparency, so it is better. Therefore, the above-mentioned light transmittance at a wavelength of 390 nm of the adhesive layer (Y) is preferably 89% or less, and more preferably 88% or less. Also, the light transmittance at a wavelength of 410 nm is preferably at least 80%, more preferably at least 85%, and even more preferably at least 90%. In order to set the light transmittance of the adhesive layer (Y) as described above, it is only necessary to use one having the following absorption peak characteristics among initiators having absorption in visible light: the periphery of the absorption peak sufficiently reaches 390 nm. The absorption peak becomes smaller at 410 nm. However, it is not limited to this method.

(儲存模數) 黏著層(Y)之儲存模數(G')較佳為於溫度25℃、頻率1 Hz下為0.9×10 5Pa以下。 藉由具有此種黏彈性特性，本黏著片材變得可獲得填埋被黏著面之凹凸等階差所需之特別優異之階差吸收性。 自該觀點考慮，黏著層(Y)之儲存模數(G')較佳為於溫度25℃、頻率1 Hz下為0.9×10 5Pa以下，其中進而較佳為0.8×10 5Pa以下。 (Storage modulus) The storage modulus (G') of the adhesive layer (Y) is preferably 0.9×10 5 Pa or less at a temperature of 25° C. and a frequency of 1 Hz. By having such viscoelastic properties, the present adhesive sheet can obtain particularly excellent level difference absorption required to fill up unevenness and the like of the surface to be adhered. From this point of view, the storage modulus (G') of the adhesive layer (Y) is preferably 0.9×10 5 Pa or less at a temperature of 25° C. and a frequency of 1 Hz, and more preferably 0.8× 10 5 Pa or less.

又，黏著層(Y)之照射波長405 nm下之累計光量為3000(mJ/cm 2)的光之後之儲存模數(G')較佳為於溫度120℃、頻率1 Hz下為0.7×10 4Pa以上。 若光硬化後之黏著層(Y)之儲存模數(G')成為上述範圍，則於如下方面而言較佳：於將其與樹脂構件(X)之積層體供至高溫試驗、高溫高濕試驗等時，可抑制由於來自樹脂構件(X)之釋氣成分而造成之黏著層(Y)發泡。 自該觀點考慮，光硬化後之黏著層(Y)之儲存模數(G')較佳為於溫度120℃、頻率1 Hz下為0.7×10 4Pa以上，其中更佳為1.0×10 4Pa以上，其中進而較佳為2.0×10 4Pa以上。 In addition, the storage modulus (G') of the adhesive layer (Y) after being irradiated with light with a cumulative light intensity of 3000 (mJ/cm 2 ) at a wavelength of 405 nm is preferably 0.7× at a temperature of 120°C and a frequency of 1 Hz. Above 10 4 Pa. If the storage modulus (G') of the adhesive layer (Y) after photocuring falls within the above-mentioned range, it is preferable in the following respects: when the laminated body of it and the resin member (X) is subjected to a high-temperature test, a high-temperature high-temperature During a wet test, etc., foaming of the adhesive layer (Y) due to outgassing components from the resin member (X) can be suppressed. From this point of view, the storage modulus (G') of the adhesive layer (Y) after photocuring is preferably at least 0.7×10 4 Pa at a temperature of 120°C and a frequency of 1 Hz, and more preferably 1.0×10 4 Pa or more, especially preferably 2.0×10 4 Pa or more.

此處，於具有觸控面板功能之圖像顯示裝置等中，作為配置於前面板/黏著層之背面側的觸控感測器，根據模組設計而分別使用玻璃感測器、膜感測器、偏光板玻璃(於內部併入有感測器之表嵌型或內嵌型)等，由於感測器構件之結構而於環境試驗中之缺陷之產生容易度不同。 本申請發明中之實驗研究之結果係於黏著層(Y)以樹脂構件(X)/黏著層(Y)/玻璃感測器之結構而貼合使用之情形時，黏著層(Y)之儲存模數(G')之較佳範圍如上述範圍所示，另一方面，於以樹脂構件(X)/黏著層(Y)/膜感測器之結構而貼合使用之情形時，膜感測器通常為100 μm以下之薄壁而硬度小，由於矽烷偶合劑之可靠性提高效果比由於玻璃材料之可靠性提高效果低，因此於濕熱環境試驗中，比玻璃感測器之情形更容易產生發泡，變得需要進而更高水準之儲存模數(G')。 Here, in an image display device having a touch panel function, as a touch sensor arranged on the back side of the front panel/adhesive layer, a glass sensor, a film sensor, etc. are used according to the module design. Sensors, polarizer glass (surface-mounted or built-in type with sensors incorporated inside), etc., have different easiness of occurrence of defects in environmental tests due to the structure of sensor components. The result of the experimental research in the invention of the present application is the storage of the adhesive layer (Y) when the adhesive layer (Y) is bonded with the structure of resin member (X)/adhesive layer (Y)/glass sensor. The preferred range of modulus (G') is shown in the above range. On the other hand, when the structure of resin member (X)/adhesive layer (Y)/film sensor is used together, the film sensor The sensor is usually thin-walled below 100 μm and has low hardness. Since the reliability improvement effect of the silane coupling agent is lower than that of the glass material, it is easier to test in a humid heat environment than a glass sensor. Foaming occurs, and a higher level of storage modulus (G') is required.

因此，作為該觀點、亦即以樹脂構件(X)/黏著層(Y)/膜感測器之結構而貼合使用黏著層(Y)之情形時的光硬化後之黏著層(Y)之儲存模數(G')、亦即照射波長405 nm下之累計光量為3000(mJ/cm 2)之光時的黏著層(Y)之儲存模數(G')之較佳之範圍為2.0×10 4Pa以上，其中更佳為5.0×10 4Pa以上，其中進而較佳為8.0×10 4Pa以上。 Therefore, from this point of view, that is, when the adhesive layer (Y) is bonded and used with the structure of the resin member (X)/adhesive layer (Y)/film sensor, the effect of the adhesive layer (Y) after photocuring The storage modulus (G'), that is, the storage modulus (G') of the adhesive layer (Y) when irradiated with light with a cumulative light intensity of 3000 (mJ/cm 2 ) at a wavelength of 405 nm, preferably ranges from 2.0× 10 4 Pa or more, more preferably 5.0×10 4 Pa or more, and even more preferably 8.0×10 4 Pa or more.

(黏著層(Y)之組成) 黏著層(Y)可由含有(甲基)丙烯酸酯(共)聚合物(a)及可見光起始劑(c)、視需要進而含有之交聯劑(b)、視需要進而含有之矽烷偶合劑(d)、視需要進而含有之其他材料的黏著劑組合物(稱為「本樹脂組合物」)而形成。 (Composition of Adhesive Layer (Y)) The adhesive layer (Y) can be composed of a (meth)acrylate (co)polymer (a), a visible light initiator (c), a crosslinking agent (b) if necessary, and a silane coupling agent if necessary. (d) Formation of an adhesive composition (referred to as "this resin composition") containing other materials as needed.

[(甲基)丙烯酸酯(共)聚合物(a)] 較佳為上述(甲基)丙烯酸酯(共)聚合物(a)可光硬化。 [(meth)acrylate (co)polymer (a)] It is preferable that the above-mentioned (meth)acrylate (co)polymer (a) is photohardenable.

再者，所謂「(甲基)丙烯酸基」係表示丙烯酸基及甲基丙烯酸基，所謂「(甲基)丙烯醯基」係表示丙烯醯基及甲基丙烯醯基，所謂「(甲基)丙烯酸酯」係分別包括丙烯酸酯及甲基丙烯酸酯之含義。所謂「(共)聚合物」係包括聚合物及共聚物之含義。又，所謂「片材」係概念性包含片材、膜、帶者。Furthermore, the so-called "(meth)acryl" means acryl and methacryl, the so-called "(meth)acryl" means acryl and methacryl, and the so-called "(meth)acryl" means acryl and methacryl. "Acrylic ester" includes the meanings of acrylate and methacrylate respectively. The term "(co)polymer" includes polymers and copolymers. In addition, the term "sheet" conceptually includes a sheet, a film, and a tape.

作為上述(甲基)丙烯酸酯(共)聚合物(a)，例如除了(甲基)丙烯酸烷基酯之均聚物以外，可列舉藉由聚合可與其共聚之單體成分而獲得之共聚物。Examples of the above-mentioned (meth)acrylate (co)polymer (a) include, for example, copolymers obtained by polymerizing a monomer component copolymerizable therewith, in addition to a homopolymer of an alkyl (meth)acrylate .

更具體而言，作為上述(甲基)丙烯酸酯(共)聚合物(a)，可列舉(甲基)丙烯酸烷基酯與可與其共聚之單體成分、例如包含選自如下單體之任一種以上單體之單體成分的共聚物：(a)含有羧基之單體(以下亦稱為「共聚性單體A」)、(b)含有羥基之單體(以下亦稱為「共聚性單體B」)、(c)含有胺基之單體(以下亦稱為「共聚性單體C」)、(d)含有環氧基之單體(以下亦稱為「共聚性單體D」)、(e)含有醯胺基之單體(以下亦稱為「共聚性單體E」)、(f)乙烯基單體(以下亦稱為「共聚性單體F」)、(g)側鏈之碳數為1～3之(甲基)丙烯酸酯單體(以下亦稱為「共聚性單體G」)及(h)巨單體(以下亦稱為「共聚性單體H」)。More specifically, examples of the above-mentioned (meth)acrylate (co)polymer (a) include alkyl (meth)acrylate and a monomer component copolymerizable therewith, for example, any monomer component selected from the following monomers: A copolymer of monomer components of more than one monomer: (a) a monomer containing a carboxyl group (hereinafter also referred to as "copolymerizable monomer A"), (b) a monomer containing a hydroxyl group (hereinafter also referred to as "copolymerizable monomer A") Monomer B"), (c) a monomer containing an amino group (hereinafter also referred to as "copolymerizable monomer C"), (d) a monomer containing an epoxy group (hereinafter also referred to as "copolymerizable monomer D") "), (e) monomers containing amide groups (hereinafter also referred to as "copolymerizable monomer E"), (f) vinyl monomers (hereinafter also referred to as "copolymerizable monomer F"), (g ) a (meth)acrylate monomer with a carbon number of 1 to 3 in the side chain (hereinafter also referred to as "copolymerizable monomer G") and (h) a macromonomer (hereinafter also referred to as "copolymerizable monomer G") ").

作為上述(甲基)丙烯酸烷基酯，較佳為側鏈之碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯。 作為該側鏈之碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸異𦯉基酯、3,5,5-三甲基環己烷(甲基)丙烯酸酯、(甲基)丙烯酸二雙環戊基酯、(甲基)丙烯酸二環戊烯基酯、(甲基)丙烯酸二環戊烯氧基乙酯等。該等可使用一種或組合使用兩種以上。 上述中，作為碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯，尤佳為包含(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯及(甲基)丙烯酸異𦯉基酯之任一種以上。 The above-mentioned alkyl (meth)acrylate is preferably a linear or branched alkyl (meth)acrylate having 4 to 18 carbon atoms in the side chain. As the linear or branched alkyl (meth)acrylate having 4 to 18 carbon atoms in the side chain, for example, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate, Base) second butyl acrylate, third butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate ester, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, ( Nonyl methacrylate, isononyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth) Undecyl acrylate, Lauryl (meth)acrylate, Tridecyl (meth)acrylate, Myristyl (meth)acrylate, Cetyl (meth)acrylate, (Meth) Stearyl acrylate, Isostearyl (meth)acrylate, Isostearyl (meth)acrylate, 3,5,5-Trimethylcyclohexane (meth)acrylate, Di(meth)acrylate Dicyclopentyl ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and the like. These can be used alone or in combination of two or more. Among the above, as the linear or branched alkyl (meth)acrylate having 4 to 18 carbon atoms, it is particularly preferable to include butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( One or more of lauryl methacrylate and iso(meth)acrylate.

作為上述共聚性單體A，例如可列舉：(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基馬來酸、2-(甲基)丙烯醯氧基丙基馬來酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基丙基琥珀酸、丁烯酸、富馬酸、馬來酸、伊康酸。該等可為一種或組合兩種以上。Examples of the above-mentioned copolymerizable monomer A include: (meth)acrylic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxypropylhexahydrophthalic acid, Hydrogen phthalate, 2-(meth)acryloxyethyl phthalate, 2-(meth)acryloxypropyl phthalate, 2-(meth)acryloxy Ethylmaleic acid, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxyethylsuccinic acid, 2-(meth)acryloxypropylsuccinate acid, crotonic acid, fumaric acid, maleic acid, itaconic acid. These may be used alone or in combination of two or more.

作為上述共聚性單體B，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯等(甲基)丙烯酸羥基烷基酯類。該等可為一種或組合兩種以上。Examples of the copolymerizable monomer B include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl ester. These may be used alone or in combination of two or more.

作為上述共聚性單體C，例如可列舉：(甲基)丙烯酸胺基甲酯、(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸胺基異丙酯等(甲基)丙烯酸胺基烷基酯，(甲基)丙烯酸N-烷基胺基烷基酯，(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯等(甲基)丙烯酸N,N-二烷基胺基烷基酯。該等可為一種或組合兩種以上。As the above-mentioned copolymerizable monomer C, for example, aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, aminoiso (meth)acrylate, Aminoalkyl (meth)acrylate, N-alkylaminoalkyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylic acid N,N-dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminopropyl. These may be used alone or in combination of two or more.

作為上述共聚性單體D，例如可列舉(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸4-羥基丁酯縮水甘油醚。該等可為一種或組合兩種以上。Examples of the copolymerizable monomer D include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (methyl) ) 4-hydroxybutyl glycidyl acrylate. These may be used alone or in combination of two or more.

作為上述共聚性單體E，例如可列舉(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、雙丙酮(甲基)丙烯醯胺、馬來醯胺、馬來醯亞胺。該等可為一種或組合兩種以上。Examples of the copolymerizable monomer E include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol N-methyl(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide Amide, diacetone (meth)acrylamide, maleimide, maleimide. These may be used alone or in combination of two or more.

作為上述共聚性單體F，可列舉於分子內具有乙烯基之化合物。作為此種化合物，可例示烷基之碳數為1～12之(甲基)丙烯酸烷基酯類，以及於分子內具有羥基、醯胺基及烷氧基烷基等官能基之官能性單體類，以及聚伸烷基二醇二(甲基)丙烯酸酯類，以及乙酸乙烯酯、丙酸乙烯酯及月桂酸乙烯酯等乙烯酯單體，以及苯乙烯、氯苯乙烯、氯甲基苯乙烯、α-甲基苯乙烯及其他經取代之苯乙烯等芳香族乙烯基單體。該等可為一種或組合兩種以上。 再者，上述中，較佳為選擇(甲基)丙烯酸烷基酯與該(甲基)丙烯酸烷基酯以外之上述共聚性單體F。 As said copolymerizable monomer F, the compound which has a vinyl group in a molecule|numerator is mentioned. Examples of such compounds include alkyl (meth)acrylates having an alkyl group having 1 to 12 carbon atoms, and functional monomers having functional groups such as hydroxyl groups, amido groups, and alkoxyalkyl groups in the molecule. monomers, polyalkylene glycol di(meth)acrylates, and vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl laurate, as well as styrene, chlorostyrene, and chloromethyl Aromatic vinyl monomers such as styrene, α-methylstyrene and other substituted styrenes. These may be used alone or in combination of two or more. Furthermore, among the above, it is preferable to select the above-mentioned copolymerizable monomer F other than the alkyl (meth)acrylate and the said alkyl (meth)acrylate.

作為上述共聚性單體G，例如可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯等。該等可為一種或組合兩種以上。 再者，上述中，較佳為選擇(甲基)丙烯酸烷基酯與該(甲基)丙烯酸烷基酯以外之上述共聚性單體G。 As said copolymerizable monomer G, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, etc. are mentioned, for example. These may be used alone or in combination of two or more. Furthermore, among the above, it is preferable to select the above-mentioned copolymerizable monomer G other than the alkyl (meth)acrylate and the said alkyl (meth)acrylate.

作為上述共聚性單體H之巨單體係具有末端之官能基與高分子量骨架成分之高分子單體，較佳為於藉由聚合而成為(甲基)丙烯酸酯共聚物時，側鏈之碳數成為20以上之單體。As the macromonomer system of the above-mentioned copolymerizable monomer H, it is a polymer monomer having a terminal functional group and a high-molecular-weight skeleton component. A monomer with a carbon number of 20 or more.

藉由使用共聚性單體H，可導入巨單體作為接枝共聚物之枝成分，使(甲基)丙烯酸酯共聚物成為接枝共聚物。例如可製成(甲基)丙烯酸酯共聚物(a-1)，其包含具有巨單體作為枝成分之接枝共聚物。 因此，可藉由共聚性單體H與其以外之單體之選擇或調配比率而使接枝共聚物之主鏈與側鏈之特性變化。 By using the copolymerizable monomer H, a macromonomer can be introduced as a branch component of the graft copolymer, and the (meth)acrylate copolymer can be made into a graft copolymer. For example, a (meth)acrylate copolymer (a-1) comprising a graft copolymer having a macromonomer as a branch component can be produced. Therefore, the characteristics of the main chain and side chain of the graft copolymer can be changed by the selection or preparation ratio of the copolymerizable monomer H and other monomers.

較佳為上述巨單體之骨架成分包含丙烯酸酯聚合物或乙烯系聚合物。例如可列舉於上述側鏈之碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯、上述共聚性單體A、上述共聚性單體B、上述共聚性單體G等中所例示者，該等可單獨使用或組合使用兩種以上。It is preferable that the skeleton component of the macromonomer includes an acrylate polymer or a vinyl polymer. For example, linear or branched alkyl (meth)acrylates having 4 to 18 carbon atoms in the above-mentioned side chain, the above-mentioned copolymerizable monomer A, the above-mentioned copolymerizable monomer B, the above-mentioned copolymerizable monomer G, etc. As exemplified in , these can be used alone or in combination of two or more.

其中，較佳為(甲基)丙烯酸酯共聚物(a-1)之乾成分含有疏水性(甲基)丙烯酸酯與親水性(甲基)丙烯酸酯作為結構單元。Among them, it is preferable that the dry component of the (meth)acrylate copolymer (a-1) contains hydrophobic (meth)acrylate and hydrophilic (meth)acrylate as structural units.

作為上述之疏水性(甲基)丙烯酸酯，較佳為並不具有極性基之烷基酯(其中，丙烯酸甲酯除外)，例如可列舉(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸庚酯、丙烯酸2-乙基己酯、丙烯酸正辛酯、丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山萮酯、(甲基)丙烯酸異𦯉基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊烯氧基乙酯、甲基丙烯酸甲酯。 又，作為疏水性之乙烯基單體，例如可列舉乙酸乙烯酯、苯乙烯、第三丁基苯乙烯、α-甲基苯乙烯、乙烯基甲苯、烷基乙烯基單體等。 As the above-mentioned hydrophobic (meth)acrylate, alkyl esters having no polar groups are preferred (among them, methyl acrylate is excluded), for example, n-butyl (meth)acrylate, (meth)acrylic acid Isobutyl, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth)acrylate , Isononyl (meth)acrylate, tert-Butylcyclohexyl (meth)acrylate, Decyl (meth)acrylate, Isodecyl (meth)acrylate, Undecyl (meth)acrylate , lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, (meth) Isothiol acrylate, cyclohexyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, methyl methacrylate. Moreover, as a hydrophobic vinyl monomer, vinyl acetate, styrene, tert-butylstyrene, (alpha)-methylstyrene, vinyl toluene, an alkyl vinyl monomer, etc. are mentioned, for example.

另一方面，作為上述親水性(甲基)丙烯酸酯單體，較佳為甲基丙烯酸酯或具有極性基之酯，例如可列舉：丙烯酸甲酯、(甲基)丙烯酸、(甲基)丙烯酸四氫糠酯，或(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸甘油酯等含有羥基之(甲基)丙烯酸酯，或(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基馬來酸、2-(甲基)丙烯醯氧基丙基馬來酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基丙基琥珀酸、丁烯酸、富馬酸、馬來酸、伊康酸、馬來酸單甲酯、伊康酸單甲酯等含有羧基之單體，馬來酸酐、伊康酸酐等含有酸酐基之單體，(甲基)丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯等含有環氧基之單體，甲氧基聚乙二醇(甲基)丙烯酸酯等烷氧基聚伸烷基二醇(甲基)丙烯酸酯，N,N-二甲基丙烯醯胺、羥基乙基丙烯醯胺等等。On the other hand, as the above-mentioned hydrophilic (meth)acrylate monomer, methacrylate or an ester having a polar group is preferable, for example, methyl acrylate, (meth)acrylic acid, (meth)acrylic acid Tetrahydrofurfuryl ester, or hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glyceryl (meth)acrylate and other (meth)acrylates containing hydroxyl groups , or (meth)acrylic acid, 2-(meth)acryloxyethylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydrophthalic acid, base) acryloxyethyl phthalic acid, 2-(meth)acryloxypropyl phthalic acid, 2-(meth)acryloxyethyl maleic acid, 2-(methyl) base) acryloxypropylmaleic acid, 2-(meth)acryloxyethylsuccinic acid, 2-(meth)acryloxypropylsuccinic acid, crotonic acid, fumaric acid, Carboxyl group-containing monomers such as maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconate, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, glycidyl (meth)acrylate Monomers containing epoxy groups such as esters, α-glycidyl ethacrylate, 3,4-epoxybutyl (meth)acrylate, etc., alkoxy groups such as methoxypolyethylene glycol (meth)acrylate Polyalkylene glycol (meth)acrylate, N,N-dimethylacrylamide, hydroxyethylacrylamide, etc.

作為上述共聚性單體H之上述巨單體，較佳為具有自由基聚合性基、羥基、異氰酸基、環氧基、羧基、胺基、醯胺基或硫醇基等官能基者。 作為上述巨單體，較佳為具有可與其他單體共聚之自由基聚合性基者。自由基聚合性基可含有一個或兩個以上，其中尤佳為一個。 於上述巨單體具有官能基之情形時，官能基亦可含有一個或兩個以上，其中尤佳為一個。 又，可含有自由基聚合性基與官能基之任一者，亦可含有兩者。於含有自由基聚合性基與官能基之兩者之情形時，與包含其他單體之聚合物單元加成之官能基或與其他單體共聚之自由基聚合性基之任一者以外之官能基或者自由基聚合性基亦可為兩個以上。 The macromonomer as the above-mentioned copolymerizable monomer H preferably has a functional group such as a radical polymerizable group, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amine group, an amide group, or a thiol group. . As the above-mentioned macromonomer, one having a radically polymerizable group copolymerizable with other monomers is preferable. One or more radically polymerizable groups may be contained, and one is particularly preferred. When the above-mentioned macromonomer has a functional group, one or more functional groups may be included, and one is particularly preferred. Moreover, either one of a radical polymerizable group and a functional group may be contained, and both may be contained. In the case of containing both a radical polymerizable group and a functional group, a function other than either a functional group added to a polymer unit including other monomers or a radical polymerizable group copolymerized with other monomers Two or more radicals or radically polymerizable groups may be used.

作為上述巨單體之末端官能基，例如除列舉甲基丙烯醯基、丙烯醯基、乙烯基等自由基性聚合基以外，亦可列舉羥基、異氰酸基、環氧基、羧基、胺基、醯胺基、硫醇基等官能基。 其中，較佳為具有可與其他單體共聚之自由基聚合性基。自由基聚合性基可含有一個或兩個以上，其中尤佳為一個。於巨單體具有官能基之情形時，官能基亦可含有一個或兩個以上，其中尤佳為一個。 又，可含有自由基聚合性基與官能基之任一者，亦可含有兩者。於含有自由基聚合性基與官能基之兩者之情形時，與包含其他單體之聚合物單元加成之官能基或與其他單體共聚之自由基聚合性基之任一者以外之官能基或者自由基聚合性基亦可為兩個以上。 Examples of the terminal functional group of the above-mentioned macromonomer include, for example, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, and an amine group in addition to radical polymerization groups such as a methacryl group, an acryl group, and a vinyl group. group, amide group, thiol group and other functional groups. Among them, it is preferable to have a radical polymerizable group copolymerizable with other monomers. One or more radically polymerizable groups may be contained, and one is particularly preferred. When the macromonomer has a functional group, one or more functional groups may be included, and one is particularly preferred. Moreover, either one of a radical polymerizable group and a functional group may be contained, and both may be contained. In the case of containing both a radical polymerizable group and a functional group, a function other than either a functional group added to a polymer unit including other monomers or a radical polymerizable group copolymerized with other monomers Two or more radicals or radically polymerizable groups may be used.

上述巨單體之數量平均分子量較佳為500～2萬，其中更佳為800以上或8000以下，其中進而較佳為1000以上或7000以下。The number average molecular weight of the macromonomer is preferably from 500 to 20,000, more preferably from 800 to 8,000, and even more preferably from 1,000 to 7,000.

較佳為上述巨單體之玻璃轉移溫度(Tg)高於構成上述(甲基)丙烯酸酯(共)聚合物(a-1)之共聚物成分之玻璃轉移溫度。 具體而言，巨單體之玻璃轉移溫度(Tg)對本黏著片材之加熱熔融溫度(熱熔溫度)有影響，因此較佳為30℃～120℃，其中更佳為40℃以上或110℃以下，其中進而較佳為50℃以上或100℃以下。 It is preferable that the glass transition temperature (Tg) of the said macromer is higher than the glass transition temperature of the copolymer component which comprises the said (meth)acrylate (co)polymer (a-1). Specifically, the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melting temperature) of the adhesive sheet, so it is preferably 30°C to 120°C, and more preferably 40°C or higher or 110°C below, and more preferably above 50°C or below 100°C.

若巨單體為此種玻璃轉移溫度(Tg)，則可藉由調整分子量而保持優異之加工性或保管穩定性，且可調整為於50℃至80℃附近發生熱熔。 所謂巨單體之玻璃轉移溫度係表示該巨單體自身之玻璃轉移溫度，可藉由示差掃描熱量計(DSC)而測定。 If the macromonomer has such a glass transition temperature (Tg), excellent processability or storage stability can be maintained by adjusting the molecular weight, and it can be adjusted so that thermal melting occurs around 50°C to 80°C. The so-called glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, which can be measured by a differential scanning calorimeter (DSC).

又，為了可於室溫狀態下維持枝成分彼此吸引而物理***聯為黏著劑組合物之狀態，且可藉由加熱至適度之溫度使上述物理***聯解開而獲得流動性，較佳為調整巨單體之分子量或含量。In addition, in order to maintain the state where the branch components attract each other and physically cross-link into the adhesive composition at room temperature, and to obtain fluidity by dissolving the above-mentioned physical cross-links by heating to a moderate temperature, it is preferable to Adjust the molecular weight or content of the macromonomer.

自該觀點考慮，較佳為於(甲基)丙烯酸酯共聚物(a)中以5質量%～30質量%之比率含有巨單體，其中更佳為以6質量%以上或25質量%以下之比率含有巨單體，其中進而較佳為以8質量%以上或20質量%以下之比率含有巨單體。 又，巨單體之數量平均分子量較佳為500～10萬，其中更佳為未達8000，其中進而較佳為800以上或未達7500，其中進而更佳為1000以上或未達7000。 From this point of view, the macromonomer is preferably contained in the (meth)acrylate copolymer (a) at a ratio of 5% by mass to 30% by mass, more preferably at least 6% by mass and at most 25% by mass. The macromonomer is contained in a ratio of 8 mass % or more or 20 mass % or less, and it is more preferable to contain a macromonomer in a ratio of 20 mass % or less. Also, the number average molecular weight of the macromonomer is preferably from 500 to 100,000, more preferably less than 8,000, more preferably at least 800 or less than 7,500, and more preferably at least 1,000 or less than 7,000.

較佳為上述(甲基)丙烯酸酯(共)聚合物(a)具有活性能量線交聯性結構部位。 所謂上述活性能量線交聯性結構係可於例如後述之可見光起始劑(c)之存在下，與(甲基)丙烯酸酯共聚物(a)之一部分、或(甲基)丙烯酸酯共聚物(a)以外之硬化成分反應，形成交聯結構之結構部位。 It is preferable that the said (meth)acrylate (co)polymer (a) has an active energy ray crosslinkable structural site. The above-mentioned active energy ray crosslinkable structure can be mixed with a part of (meth)acrylate copolymer (a) or a (meth)acrylate copolymer in the presence of a visible light initiator (c) described later, for example. The structural site where the hardening components other than (a) react to form a cross-linked structure.

作為上述活性能量線交聯性結構部位，例如可列舉具有自由基聚合性官能基之結構，該自由基聚合性官能基係(甲基)丙烯醯基、乙烯基等具有不飽和雙鍵之官能基等具有碳-碳雙鍵之自由基聚合性官能基。 由於上述(甲基)丙烯酸酯(共)聚合物(a)之聚合物鏈具有不飽和雙鍵，因此即便於並不含有交聯劑之情形時，聚合物鏈亦可彼此直接聚合，可將儲存模數(G')提高至較高之水準。 再者，於進行活性能量線照射時，只要使用包含波長405 nm之光的任意光源即可，自硬化速度、照射裝置之獲得容易性、價格等考慮，可利用可見光LED光源、高壓水銀燈等。 Examples of the above-mentioned active energy ray crosslinkable structural site include structures having radically polymerizable functional groups such as (meth)acryl and vinyl groups having unsaturated double bonds. Radical polymerizable functional groups having carbon-carbon double bonds. Since the polymer chains of the above (meth)acrylate (co)polymer (a) have unsaturated double bonds, even when no crosslinking agent is contained, the polymer chains can be directly polymerized with each other, and the The storage modulus (G') has been raised to a higher level. Furthermore, when irradiating active energy rays, any light source including light with a wavelength of 405 nm can be used. Considering the curing speed, availability of irradiation equipment, and price, visible light LED light sources, high-pressure mercury lamps, etc. can be used.

為了導入包含具有不飽和雙鍵之官能基等具有碳-碳雙鍵之自由基聚合性官能基的結構，例如預先於上述(甲基)丙烯酸酯(共)聚合物(a)上共聚具有官能基之單體，然後使具有可與該官能基反應之官能基(例如(甲基)丙烯酸2-異氰酸基乙酯等)及不飽和雙鍵之單體等具有碳-碳雙鍵之化合物，於維持碳-碳雙鍵之硬化性之狀態下與其反應即可。In order to introduce a structure containing a radically polymerizable functional group having a carbon-carbon double bond such as a functional group having an unsaturated double bond, for example, a functional group is previously copolymerized on the above-mentioned (meth)acrylate (co)polymer (a). group monomers, and then make monomers with carbon-carbon double bonds with functional groups that can react with the functional group (such as (meth)acrylic acid 2-isocyanatoethyl ester, etc.) and unsaturated double bonds The compound may react with the carbon-carbon double bond while maintaining its hardening properties.

其中，(甲基)丙烯酸酯共聚物(a)較佳為包含具有活性能量線交聯性結構部位、且具有碳數10～24之直鏈烷基之(甲基)丙烯酸酯單體之單體成分的(甲基)丙烯酸酯(共)聚合物(a-2)。 作為此種(甲基)丙烯酸酯(共)聚合物(a-2)，例如可列舉：(甲基)丙烯酸癸酯(烷基之碳數為10)、(甲基)丙烯酸月桂酯(碳數為12)、(甲基)丙烯酸十三烷基酯(碳數為13)、(甲基)丙烯酸十六烷基酯(碳數為16)、(甲基)丙烯酸硬脂酯(碳數為18)、(甲基)丙烯酸山萮酯(碳數為22)等。該等可單獨使用，亦可併用兩種以上。 Among them, the (meth)acrylate copolymer (a) is preferably a single (meth)acrylate monomer containing a linear alkyl group having 10 to 24 carbon atoms and having an active energy ray crosslinking structural site. The (meth)acrylate (co)polymer (a-2) of a body component. Examples of such (meth)acrylate (co)polymers (a-2) include decyl (meth)acrylate (the number of carbon atoms in the alkyl group is 10), lauryl (meth)acrylate (carbon number 12), tridecyl (meth)acrylate (13 carbons), hexadecyl (meth)acrylate (16 carbons), stearyl (meth)acrylate (13 carbons) 18), behenyl (meth)acrylate (carbon number 22), etc. These may be used alone or in combination of two or more.

又，具有碳數為10～24之烷基的直鏈之(甲基)丙烯酸烷基酯單體(a)中，自低介電常數化及可降低丙烯酸系樹脂之玻璃轉移溫度之方面考慮，較佳為使用甲基丙烯酸烷基酯，尤佳為具有碳數為12～20之烷基者，最佳為甲基丙烯酸硬脂酯、甲基丙烯酸月桂酯、甲基丙烯酸十三烷基酯。In addition, in the linear alkyl (meth)acrylate monomer (a) having an alkyl group having 10 to 24 carbon atoms, it is possible to lower the dielectric constant and lower the glass transition temperature of the acrylic resin. , it is preferred to use alkyl methacrylate, especially those having an alkyl group with 12 to 20 carbons, most preferably stearyl methacrylate, lauryl methacrylate, tridecyl methacrylate ester.

具有碳數為10～24之直鏈烷基之(甲基)丙烯酸烷基酯單體(a)之含量為相對於(共)聚合成分全體而言為50～94重量%，較佳為60～83重量%，尤佳為70～80重量%。藉由設為上述範圍內，並無介電常數變高，樹脂之熱穩定性降低之虞。The content of the alkyl (meth)acrylate monomer (a) having a linear alkyl group having 10 to 24 carbon atoms is 50 to 94% by weight, preferably 60% by weight, based on the entire (co)polymerization component. ~83% by weight, especially preferably 70-80% by weight. By setting it as the said range, a dielectric constant becomes high and there is no possibility that the thermal stability of resin may fall.

[交聯劑(b)] 作為上述交聯劑(b)，較佳為至少具有雙鍵交聯之交聯劑。例如可列舉具有選自(甲基)丙烯醯基、環氧基、異氰酸基、羧基、羥基、碳二醯亞胺基、㗁唑啉基、氮丙啶基、乙烯基、胺基、亞胺基、醯胺基的至少一種交聯性官能基之交聯劑，可使用一種或組合使用兩種以上。 尤其是藉由組合使用兩種以上之交聯劑，與分別單獨使用之情形相比而言，即便於總計之調配量相同之情形時，亦可達成更高之儲存模數(G')。 因此，更佳為組合使用兩種以上之交聯劑(b)。 又，亦包含交聯劑(b)與(甲基)丙烯酸酯(共)聚合物(a)進行化學鍵結之態樣。 [Crosslinking agent (b)] As said crosslinking agent (b), the crosslinking agent which has at least double bond crosslinking is preferable. Examples include (meth)acryl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridinyl group, vinyl group, amine group, As the cross-linking agent of at least one cross-linkable functional group of imine group and amide group, one type or two or more types may be used in combination. In particular, when two or more crosslinking agents are used in combination, a higher storage modulus (G') can be achieved even when the total amount of the crosslinking agent is the same as compared to the case of using each alone. Therefore, it is more preferable to use two or more crosslinking agents (b) in combination. Moreover, the aspect in which a crosslinking agent (b) and a (meth)acrylate (co)polymer (a) are chemically bonded is also included.

其中，較佳為使用具有碳-碳雙鍵之光聚合性化合物、尤其是多官能(甲基)丙烯酸酯。此處，多官能係指具有兩個以上交聯性官能基者。再者，亦可視需要具有3個以上、4個以上之交聯性官能基。 再者，上述交聯性官能基亦可藉由能夠脫保護之保護基而進行保護。 Among them, it is preferable to use a photopolymerizable compound having a carbon-carbon double bond, especially a polyfunctional (meth)acrylate. Here, polyfunctional means what has two or more crosslinkable functional groups. In addition, it may have 3 or more, 4 or more crosslinkable functional groups as needed. Furthermore, the above-mentioned crosslinkable functional group may be protected by a deprotectable protecting group.

作為上述多官能(甲基)丙烯酸酯，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、甘油縮水甘油醚二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、三環癸烷二甲基丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、雙酚A聚乙氧基二(甲基)丙烯酸酯、雙酚A聚丙氧基二(甲基)丙烯酸酯、雙酚F聚乙氧基二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲基丙烷三氧基乙基(甲基)丙烯酸酯、ε-己內酯改性異氰尿酸三(2-羥基乙基)酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、丙氧基化季戊四醇三(甲基)丙烯酸酯、乙氧基化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、丙氧基化季戊四醇四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、異氰尿酸三(丙烯醯氧基乙基)酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、三季戊四醇五(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇酯之ε-己內酯加成物之二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷聚乙氧基三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯等紫外線硬化型之多官能(甲基)丙烯酸系單體，除此以外亦可列舉聚酯(甲基)丙烯酸酯、(甲基)丙烯酸環氧酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能(甲基)丙烯酸系低聚物。該等可使用一種或組合使用兩種以上。Examples of the polyfunctional (meth)acrylate include: 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate , glycerin glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethyl Acrylates, tricyclodecane dimethanol di(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol A polypropoxy di(meth)acrylate, bisphenol F poly Ethoxylated Di(meth)acrylate, Ethylene Glycol Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, Trimethylolpropane Trioxyethyl(meth)acrylate , ε-caprolactone modified tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, Ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(acryloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(methyl) ) acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, hydroxypivalate neopentyl glycol ester Di(meth)acrylate of ε-caprolactone adduct, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, di-trimethylolpropane Ultraviolet curable polyfunctional (meth)acrylic monomers such as methylolpropane tetra(meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate , (meth)acrylate urethane, polyether (meth)acrylate and other multifunctional (meth)acrylic oligomers. These can be used alone or in combination of two or more.

於上述多官能(甲基)丙烯酸酯中，自賦予高凝聚力之觀點考慮，較佳為成為所形成之交聯結構中之交聯點間距離較短且交聯密度較密之結構者，例如較佳為未經環氧烷改性之3官能以上之多官能(甲基)丙烯酸酯，較佳為選自由季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、三季戊四醇五(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯所組成之群中之多官能(甲基)丙烯酸酯(b-1)。 該多官能(甲基)丙烯酸酯(b-1)可使用一種或組合(為混合物)而使用兩種以上。 Among the above-mentioned polyfunctional (meth)acrylates, from the viewpoint of imparting high cohesive force, it is preferable to have a structure in which the distance between crosslinking points in the formed crosslinked structure is short and the crosslinking density is relatively dense, such as It is preferably a polyfunctional (meth)acrylate with three or more functions not modified by alkylene oxide, preferably selected from pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate (Meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, trimethylol Polyfunctional (meth)acrylate (b-1) in the group consisting of trimethylolpropane tri(meth)acrylate and di-trimethylolpropane tetra(meth)acrylate. This polyfunctional (meth)acrylate (b-1) can be used 1 type or in combination (it is a mixture) and 2 or more types can be used.

又，於使用上述多官能(甲基)丙烯酸酯(b-1)作為交聯劑之情形時，自相容性之觀點考慮，上述(甲基)丙烯酸酯(a)較佳為包含親水性單體作為極性成分之單體成分的共聚物。 由於該(甲基)丙烯酸酯(a)包含極性成分，因此其與上述多官能(甲基)丙烯酸酯(b-1)之相容性變良好，於混合時變得容易混雜，於未交聯之狀態下長時間保管時變得難以產生相分離，且無霧度值上升之虞。 Also, when using the above-mentioned polyfunctional (meth)acrylate (b-1) as a crosslinking agent, from the viewpoint of compatibility, the above-mentioned (meth)acrylate (a) preferably contains hydrophilic Monomers are copolymers of monomeric components as polar components. Since the (meth)acrylate (a) contains polar components, its compatibility with the above-mentioned polyfunctional (meth)acrylate (b-1) becomes good, and it becomes easy to mix when mixed. When stored in a combined state for a long period of time, it becomes difficult to cause phase separation, and there is no risk of an increase in the haze value.

具體而言，作為上述(甲基)丙烯酸酯(共)聚合物(a)，較佳為上述(甲基)丙烯酸烷基酯與作為可與其共聚之共聚性單體的如下單體成分之共聚物，上述單體成分係自上述共聚性單體A～G中適宜選擇親水性單體之單體成分，其中含有上述之親水性(甲基)丙烯酸酯、或至少含有選自共聚性單體G之(甲基)丙烯酸甲酯。 進而，上述(甲基)丙烯酸酯(共)聚合物(a)尤佳為至少含有(甲基)丙烯酸甲酯、且(選自共聚性單體A～G之)親水性單體之合計量占(甲基)丙烯酸酯(共)聚合物(a)全體中之10質量份以上的單體成分之共聚物。 Specifically, as the above-mentioned (meth)acrylate (co)polymer (a), copolymerization of the above-mentioned alkyl (meth)acrylate and the following monomer components as a copolymerizable monomer copolymerizable therewith is preferable: The above-mentioned monomer component is a monomer component of a hydrophilic monomer selected from the above-mentioned copolymerizable monomers A to G, which contains the above-mentioned hydrophilic (meth)acrylate, or at least contains G of methyl (meth)acrylate. Furthermore, the above-mentioned (meth)acrylate (co)polymer (a) preferably contains at least methyl (meth)acrylate, and the total amount of hydrophilic monomers (selected from copolymerizable monomers A to G) A copolymer of monomer components accounting for 10 parts by mass or more of the entire (meth)acrylate (co)polymer (a).

再者，上述(甲基)丙烯酸酯(共)聚合物(a-1)較佳為包含作為骨架成分(幹成分)的上述側鏈之碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯、與作為可與其共聚之共聚性單體的上述親水性單體的單體成分之共聚物。Furthermore, the above-mentioned (meth)acrylate (co)polymer (a-1) is preferably a straight chain or a branched chain (a base) a copolymer of an alkyl acrylate and a monomer component of the above-mentioned hydrophilic monomer as a copolymerizable monomer copolymerizable therewith.

交聯劑(b)之含量較佳為相對於上述(甲基)丙烯酸酯(共)聚合物(a) 100質量份而言為0.5～50質量份之比率，其中更佳為1質量份以上或40質量份以下之比率，其中進而更佳為5質量份以上或30質量份以下之比率。The content of the crosslinking agent (b) is preferably a ratio of 0.5 to 50 parts by mass relative to 100 parts by mass of the above-mentioned (meth)acrylate (co)polymer (a), more preferably at least 1 part by mass Or a ratio of 40 parts by mass or less, and more preferably a ratio of 5 parts by mass or more or 30 parts by mass or less.

[可見光起始劑(c)] 可見光起始劑(c)較佳為藉由照射可見光線、至少具有390 nm、405 nm及410 nm之波長的光線、例如380 nm～700 nm之波長區域之光線而產生自由基，成為(甲基)丙烯酸酯(共)聚合物(a)之反應起點的可見光起始劑。 其中，可見光起始劑(c)可為藉由僅照射可見光線而產生自由基者，又，亦可為藉由照射可見光區域以外之波長區域之光線亦可產生自由基者。 [Visible light initiator (c)] Visible light initiator (c) is preferably generated free radicals by irradiating visible light, light with wavelengths of at least 390 nm, 405 nm and 410 nm, such as light in the wavelength region of 380 nm to 700 nm, and becomes (a base) a visible light initiator for the reaction origin of the acrylate (co)polymer (a). Among them, the visible light initiator (c) may generate radicals only by irradiating visible light, or may generate radicals by irradiating light of a wavelength region other than the visible light region.

可見光起始劑(c)較佳為波長405 nm之吸光係數為10 mL/(g・/cm)以上，其中進而較佳為15 mL/(g・/cm)以上，其中進而更佳為25 mL/(g・/cm)以上。藉由使波長405 nm之吸光係數為10 mL/(g・/cm)以上，可充分地進行照射可見光線之硬化(交聯)。 另一方面，作為波長405 nm之吸光係數之上限，較佳為1×10 4mL/(g・/cm)以下，更佳為1×10 3mL/(g・/cm)以下。再者，亦可與波長405 nm之吸光係數未達10 mL/(g・/cm)之光起始劑併用。 The visible light initiator (c) preferably has an absorptivity at a wavelength of 405 nm of 10 mL/(g·/cm) or more, more preferably 15 mL/(g·/cm) or more, and more preferably 25 mL/(g·/cm) mL/(g・/cm) or more. By setting the absorption coefficient at a wavelength of 405 nm to 10 mL/(g・/cm) or more, curing (crosslinking) by irradiation with visible light can be sufficiently performed. On the other hand, the upper limit of the absorption coefficient at a wavelength of 405 nm is preferably not more than 1×10 4 mL/(g·/cm), more preferably not more than 1×10 3 mL/(g·/cm). Furthermore, it can also be used together with a photoinitiator whose absorption coefficient at a wavelength of 405 nm does not reach 10 mL/(g・/cm).

光起始劑根據自由基產生機制大致分類為兩種，大致分為：裂解型光起始劑，光起始劑自身的單鍵可裂解分解而產生自由基；及奪氫型光起始劑，光激發之起始劑與系統中之氫供與體可形成激發錯合物，從而使氫供與體之氫轉移。Photoinitiators are roughly classified into two types according to the mechanism of free radical generation, roughly divided into: cracking type photoinitiator, the single bond of the photoinitiator itself can be cleaved and decomposed to generate free radicals; and hydrogen abstraction type photoinitiator , the photo-excited initiator and the hydrogen donor in the system can form an excited complex, so that the hydrogen of the hydrogen donor can be transferred.

該等中之裂解型光起始劑於藉由光照射而產生自由基時分解而成為其他之化合物，一旦激發便變得並不具有作為反應起始劑之功能。因此，並不作為活性種而殘存於交聯反應結束後之黏著劑中，並不存在對黏著劑帶來並不期望之光劣化等的可能性，因此較佳。 又，關於光起始劑特有之著色，先前於黏著劑中添加照射可見光線而使其硬化之裂解型可見光起始劑(c-1)之情形時，存在著色之虞。因此，作為可見光起始劑(c)，較佳為適宜選擇反應分解物並無可見光線區域之吸收而消色者。 另一方面，奪氫型之光起始劑不僅即便進行複數次光照射亦可維持作為反應起始劑之功能，而且於藉由照射紫外線等活性能量線而進行自由基產生反應時，並不如裂解型光起始劑那樣生成分解物，因此難以於反應結束後成為揮發成分，於可減低對被黏著體之損傷之方面有用。 因此，尤佳為受可見光激發而開始聚合之奪氫型可見光聚合起始劑(c-2)。 Among them, the cleavage-type photoinitiator decomposes into other compounds when free radicals are generated by light irradiation, and does not have the function as a reaction initiator once excited. Therefore, it is preferable that it does not remain as an active species in the adhesive after the crosslinking reaction is completed, and there is no possibility of causing undesired photodegradation to the adhesive. Moreover, regarding the coloring peculiar to a photoinitiator, when the cleavage-type visible light initiator (c-1) which was irradiated with visible light and hardened was added to an adhesive conventionally, there was a possibility of coloration. Therefore, as the visible light initiator (c), it is preferable to select a reaction decomposition product that does not absorb in the visible light region and decolorizes. On the other hand, the photoinitiator of the hydrogen abstraction type can not only maintain the function as a reaction initiator even after multiple times of light irradiation, but also is not as good as the Cleavage-type photoinitiators generate decomposition products, so it is difficult to become a volatile component after the reaction is completed, and it is useful in reducing damage to the adherend. Therefore, a hydrogen abstraction-type visible light polymerization initiator (c-2) that initiates polymerization upon excitation by visible light is particularly preferred.

作為上述裂解型可見光起始劑(c-1)，例如可列舉：2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-(4-(2-羥基乙氧基)苯基)-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-[4-{4-(2-羥基-2-甲基-丙醯基)苄基}苯基]-2-甲基-丙烷-1-酮、低聚(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮)、苯基乙醛酸甲酯、2-苄基-2-二甲胺基-1-(4-𠰌啉基苯基)丁烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-𠰌啉基丙烷-1-酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基)-1-[4-(4-𠰌啉基)苯基]-1-丁酮、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、(2,4,6-三甲基苯甲醯基)乙氧基苯基氧化膦或該等之衍生物等。 其中，於反應後成為分解物而消色之方法而言，較佳為雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、(2,4,6-三甲基苯甲醯基)乙氧基苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)2,4,4-三甲基戊基氧化膦等醯基氧化膦系光起始劑。 Examples of the cleavage-type visible light initiator (c-1) include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-Hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane- 1-keto, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}phenyl]-2-methyl-propan-1-one, oligomeric (2-Hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)acetone), methyl phenylglyoxylate, 2-benzyl-2-dimethylamino-1 -(4-𠰌linylphenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linylpropane-1-one, 2-( Dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-𠰌linyl)phenyl]-1-butanone, bis(2,4,6- Trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxy phenylphosphine oxide or their derivatives. Among them, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)2, Acyl phosphine oxide-based photoinitiators such as 4,4-trimethylpentyl phosphine oxide.

作為上述奪氫型可見光起始劑(c-2)，例如可列舉雙(2-苯基-2-側氧基乙酸)氧基雙伸乙酯、苯基乙醛酸甲酯、羥基苯乙酸2-[2-側氧基-2-苯基乙醯氧基乙氧基]乙酯與羥基苯乙酸2-[2-羥基乙氧基]乙酯之混合物、9-氧硫𠮿

Figure 111140872-001
、2-氯-9-氧硫𠮿
Figure 111140872-001
、3-甲基-9-氧硫𠮿
Figure 111140872-001
、2,4-二甲基-9-氧硫𠮿
Figure 111140872-001
、蒽醌、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、樟腦醌或其衍生物等。 其中，較佳為選自由苯基乙醛酸甲酯、羥基苯乙酸2-[2-側氧基-2-苯基乙醯氧基乙氧基]乙酯與羥基苯乙酸2-[2-羥基乙氧基]乙酯之混合物所組成之群中之任一種或兩種。 Examples of the hydrogen abstraction-type visible light initiator (c-2) include bis(2-phenyl-2-oxoacetic acid)oxybisethylene, methyl phenylglyoxylate, and hydroxyphenylacetic acid. A mixture of 2-[2-oxo-2-phenylacetyloxyethoxy]ethyl ester and 2-[2-hydroxyethoxy]ethyl hydroxyphenylacetate, 9-oxothiol
Figure 111140872-001
, 2-Chloro-9-oxosulfur
Figure 111140872-001
, 3-methyl-9-oxosulfur
Figure 111140872-001
, 2,4-Dimethyl-9-oxosulfur 𠮿
Figure 111140872-001
, Anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, camphorquinone or its derivatives, etc. Among them, it is preferably selected from methyl phenylglyoxylate, 2-[2-oxo-2-phenylacetyloxyethoxy] ethyl hydroxyphenylacetic acid and 2-[2- Any one or two of the group consisting of mixtures of hydroxyethoxy] ethyl esters.

再者，可見光起始劑(c)並不限定於上述所列舉之物質。可使用上述所列舉之可見光起始劑(c)中之任一種或其衍生物，亦可組合使用兩種以上。 又，除了可見光起始劑(c)以外，亦可混合藉由照射紫外線等其他光線而僅僅產生自由基者。 Furthermore, the visible light initiator (c) is not limited to the substances listed above. Any one of the above-listed visible light initiators (c) or its derivatives may be used, or two or more of them may be used in combination. In addition to the visible light initiator (c), those that only generate radicals by irradiating other rays such as ultraviolet rays may be mixed.

可見光起始劑(c)之含量並無特別限制。較佳為以相對於黏著層(Y)中之(甲基)丙烯酸酯(共)聚合物(a) 100質量份而言為0.1～10質量份之之比率含有，其中更佳為以0.5質量份以上或5質量份以下之比率含有，其中進而更佳為以1質量份以上或3質量份以下之比率含有。 藉由將可見光起始劑(c)之含量設為上述範圍，可獲得對於可見光線之適度之反應感度。 The content of the visible light initiator (c) is not particularly limited. It is preferably contained in a ratio of 0.1 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylate (co)polymer (a) in the adhesive layer (Y), more preferably 0.5 parts by mass It is contained in a ratio of not less than 1 part by mass or not more than 5 parts by mass, and more preferably contained by a ratio of not less than 1 part by mass or not more than 3 parts by mass. Moderate reaction sensitivity with respect to visible light can be acquired by making content of a visible light initiator (c) into the said range.

[矽烷偶合劑(d)] 矽烷偶合劑(d)可提高接著性，其中尤其可提高對於玻璃材料之接著力。 作為矽烷偶合劑，例如可列舉具有如乙烯基、丙烯醯氧基、甲基丙烯醯氧基之不飽和基、胺基、環氧基等，以及如烷氧基之可水解之官能基的化合物。 作為矽烷偶合劑之具體例，可例示：N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等。 其中，於黏著層(Y)中，自接著性良好、黃變等變色少等觀點考慮，可較佳地使用γ-縮水甘油氧基丙基三甲氧基矽烷或γ-甲基丙烯醯氧基丙基三甲氧基矽烷。 上述矽烷偶合劑可單獨使用僅一種或組合使用兩種以上。 [Silane coupling agent (d)] The silane coupling agent (d) can improve the adhesion, especially the adhesion to glass materials. Examples of silane coupling agents include compounds having unsaturated groups such as vinyl, acryloxy, and methacryloxy groups, amine groups, epoxy groups, etc., and hydrolyzable functional groups such as alkoxy groups. . Specific examples of silane coupling agents include: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl Methyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc. Among them, γ-glycidoxypropyltrimethoxysilane or γ-methacryloxysilane can be preferably used in the adhesive layer (Y) from the viewpoint of good adhesion and less discoloration such as yellowing. Propyltrimethoxysilane. The above-mentioned silane coupling agents may be used alone or in combination of two or more.

上述矽烷偶合劑(d)之含量較佳為相對於黏著層(Y)100質量份而言為0.1～5質量份，其中進而較佳為0.2質量份以上或3.0質量份以下。 再者，亦可與矽烷偶合劑同樣地有效利用有機鈦酸酯化合物等偶合劑。 The content of the silane coupling agent (d) is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the adhesive layer (Y), and more preferably 0.2 parts by mass or more or 3.0 parts by mass or less. Furthermore, a coupling agent such as an organic titanate compound can also be effectively used in the same manner as a silane coupling agent.

[其他材料] 作為形成黏著層(Y)之本樹脂組合物中所含之上述以外之成分，例如可列舉：光穩定化劑、紫外線吸收劑、金屬減活劑、抗金屬腐蝕劑、抗老化劑、抗靜電劑、吸濕劑、發泡劑、消泡劑、無機粒子、黏度調整劑、黏著賦予樹脂、光增感劑、螢光劑等各種添加劑，反應觸媒(三級胺系化合物、四級銨系化合物、月桂酸錫化合物等)等。 又，另外，亦可適宜地含有於通常之黏著劑組合物中所調配之公知之成分。 又，各成分亦可併用兩種以上。 [other materials] Examples of components other than the above contained in the resin composition forming the adhesive layer (Y) include light stabilizers, ultraviolet absorbers, metal deactivators, metal corrosion inhibitors, antiaging agents, and antistatic agents. , hygroscopic agent, foaming agent, defoaming agent, inorganic particles, viscosity modifier, adhesion imparting resin, photosensitizer, fluorescent agent and other additives, reaction catalyst (tertiary amine compound, quaternary ammonium compounds, tin laurate compounds, etc.), etc. In addition, known components formulated in usual adhesive compositions may also be contained as appropriate. Moreover, each component can also use 2 or more types together.

於上述中，尤佳為形成黏著層(Y)之本樹脂組合物含有紫外線吸收劑。如上所述，黏著層(Y)具有藉由照射波長405 nm之光而硬化之光硬化性，因此即便含有紫外線吸收劑亦不阻礙該光硬化。因此，藉由含有紫外線吸收劑，可並不損害本黏著片材所具有之性質地兼具優異之紫外線截止性。Among the above, it is particularly preferable that the present resin composition forming the adhesive layer (Y) contains an ultraviolet absorber. As described above, since the adhesive layer (Y) has photocurability to be cured by irradiation with light having a wavelength of 405 nm, even if it contains an ultraviolet absorber, it does not inhibit the photocuring. Therefore, by containing the ultraviolet absorber, it is possible to simultaneously have excellent ultraviolet cutoff properties without impairing the properties of the adhesive sheet.

作為上述紫外線吸收劑，例如可列舉苯并***系紫外線吸收劑、二苯甲酮系紫外線吸收劑、三𠯤系紫外線吸收劑等。再者，上述紫外線吸收劑可單獨使用或組合使用兩種以上。 其中，自透明性、紫外線吸收性及相容性之觀點考慮，上述紫外線吸收劑尤佳為三𠯤系紫外線吸收劑。 As said ultraviolet absorber, a benzotriazole type ultraviolet absorber, a benzophenone type ultraviolet absorber, a trioxane type ultraviolet absorber, etc. are mentioned, for example. In addition, the said ultraviolet absorber can be used individually or in combination of 2 or more types. Among them, the above-mentioned ultraviolet absorber is particularly preferably a tri-series ultraviolet absorber from the viewpoint of transparency, ultraviolet absorbability, and compatibility.

[本樹脂組合物之較佳之組成態樣] 作為形成黏著層(Y)之較佳之本樹脂組合物之一例，可列舉含有(甲基)丙烯酸酯(共)聚合物(a)、上述交聯劑(b)、可見光起始劑(c)、及視需要之矽烷偶合劑的組成。 其中，較佳為使用波長405 nm之吸光係數為10 mL/(g・/cm)以上之可見光起始劑(c)作為可見光起始劑(c)；又，尤佳為使用上述裂解型可見光起始劑(c-1)及/或奪氫型可見光起始劑(c-2)作為可見光起始劑(c)。 [The preferred composition of the present resin composition] As an example of a preferable present resin composition for forming the adhesive layer (Y), a (meth)acrylate (co)polymer (a), the above-mentioned crosslinking agent (b), and a visible light initiator (c) can be cited. , and the composition of the silane coupling agent as required. Among them, it is preferable to use a visible light initiator (c) with an absorption coefficient of 10 mL/(g/cm) or more at a wavelength of 405 nm as the visible light initiator (c); and it is especially preferable to use the above-mentioned splitting visible light The initiator (c-1) and/or the hydrogen abstraction type visible light initiator (c-2) is used as the visible light initiator (c).

其中，較佳為(甲基)丙烯酸酯(共)聚合物(a)形成有基於選自羧基與環氧基、羧基與氮丙啶基、羥基與異氰酸基、胺基與異氰酸基、及羧基與異氰酸基中之任一官能基組合的化學鍵。 又，(甲基)丙烯酸酯(共)聚合物(a)較佳為包含上述側鏈之碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯與上述親水性(甲基)丙烯酸酯作為共聚成分之共聚物。 進而，交聯劑(b)較佳為上述多官能(甲基)丙烯酸酯(b-1)。 Among them, it is preferred that the (meth)acrylate (co)polymer (a) is formed based on a compound selected from carboxyl and epoxy, carboxyl and aziridinyl, hydroxyl and isocyanate, amine and isocyanate group, and a chemical bond in which any functional group in the carboxyl group and the isocyanate group is combined. In addition, the (meth)acrylate (co)polymer (a) is preferably a linear or branched chain (meth)acrylic acid alkyl ester having 4 to 18 carbon atoms in the above-mentioned side chain and the above-mentioned hydrophilic (meth)acrylic acid ester. base) acrylate as the copolymerization component of the copolymer. Furthermore, the crosslinking agent (b) is preferably the above-mentioned polyfunctional (meth)acrylate (b-1).

作為形成黏著層(Y)之較佳之本樹脂組合物之一例，可列舉含有上述(甲基)丙烯酸酯共聚物(a-1)、上述交聯劑(b)、可見光起始劑(c)、及視需要之矽烷偶合劑的組成，上述(甲基)丙烯酸酯共聚物(a-1)包含具有巨單體作為枝成分之接枝共聚物。 其中，較佳為使用波長405 nm之吸光係數為10 mL/(g・/cm)以上之可見光起始劑(c)作為可見光起始劑(c)；又，尤佳為使用上述裂解型可見光起始劑(c-1)及/或奪氫型可見光起始劑(c-2)作為可見光起始劑(c)。 As an example of a preferable resin composition for forming the adhesive layer (Y), there may be mentioned one containing the above-mentioned (meth)acrylate copolymer (a-1), the above-mentioned crosslinking agent (b), and the visible light initiator (c). , and optionally a composition of a silane coupling agent, the (meth)acrylate copolymer (a-1) includes a graft copolymer having a macromonomer as a branch component. Among them, it is preferable to use a visible light initiator (c) with an absorption coefficient of 10 mL/(g/cm) or more at a wavelength of 405 nm as the visible light initiator (c); and it is especially preferable to use the above-mentioned splitting visible light The initiator (c-1) and/or the hydrogen abstraction type visible light initiator (c-2) is used as the visible light initiator (c).

其中，上述(甲基)丙烯酸酯(共)聚合物(a-1)較佳為包含作為骨架成分(幹成分)的上述側鏈之碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯、與上述親水性(甲基)丙烯酸酯作為共聚成分的共聚物。 又，交聯劑(b)較佳為上述多官能(甲基)丙烯酸酯(b-1)。 Among them, the above-mentioned (meth)acrylate (co)polymer (a-1) is preferably a linear or branched chain (methyl) having 4 to 18 carbon atoms in the side chain as a skeleton component (dry component). ) a copolymer of alkyl acrylate and the aforementioned hydrophilic (meth)acrylate as a copolymerization component. Moreover, it is preferable that a crosslinking agent (b) is said polyfunctional (meth)acrylate (b-1).

作為形成黏著層(Y)之較佳之本樹脂組合物之進而其他之一例，可列舉含有上述(甲基)丙烯酸酯共聚物(a-1)、上述交聯劑(b)、上述可見光起始劑(c)、及視需要之矽烷偶合劑的組成，上述(甲基)丙烯酸酯共聚物(a-1)包含具有巨單體作為枝成分、且具有活性能量線交聯性結構部位之接枝共聚物。 其中，較佳為使用波長405 nm之吸光係數為10 mL/(g・/cm)以上之可見光起始劑(c)作為可見光起始劑(c)；又，尤佳為使用上述裂解型可見光起始劑(c-1)及/或奪氫型可見光起始劑(c-2)作為可見光起始劑(c)。 Still another example of this resin composition suitable for forming the adhesive layer (Y) includes the above-mentioned (meth)acrylate copolymer (a-1), the above-mentioned crosslinking agent (b), the above-mentioned visible light initiator agent (c), and optionally a silane coupling agent, the (meth)acrylate copolymer (a-1) includes a macromonomer as a branch component and a linker having an active energy ray crosslinkable structural site. branch copolymers. Among them, it is preferable to use a visible light initiator (c) with an absorption coefficient of 10 mL/(g/cm) or more at a wavelength of 405 nm as the visible light initiator (c); and it is especially preferable to use the above-mentioned splitting visible light The initiator (c-1) and/or the hydrogen abstraction type visible light initiator (c-2) is used as the visible light initiator (c).

其中，上述(甲基)丙烯酸酯(共)聚合物(a-1)較佳為包含作為骨架成分(幹成分)的上述側鏈之碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯、與上述親水性(甲基)丙烯酸酯作為共聚成分的共聚物。 又，交聯劑(b)較佳為上述多官能(甲基)丙烯酸酯(b-1)。 Among them, the above-mentioned (meth)acrylate (co)polymer (a-1) is preferably a linear or branched chain (methyl) having 4 to 18 carbon atoms in the side chain as a skeleton component (dry component). ) a copolymer of alkyl acrylate and the aforementioned hydrophilic (meth)acrylate as a copolymerization component. Moreover, it is preferable that a crosslinking agent (b) is said polyfunctional (meth)acrylate (b-1).

若使用如上所述之組成之本樹脂組合物而形成黏著層(Y)，則以(甲基)丙烯酸酯共聚物(a)或(a-1)為基底樹脂之黏著層(Y)可於室溫狀態下保持片材狀且顯示自黏性，可使黏著劑填充至貼合構件之被黏著面之階差之每個角落。而且，由於可見光起始劑(c)而可藉由可見光照射進行光硬化，可藉由光硬化而提高凝聚力且提高耐發泡可靠性。 進而，藉由調配矽烷偶合劑，可進而提高接著性、尤其是對玻璃材料之接著性。 又，以(甲基)丙烯酸酯共聚物(a-1)為基底樹脂之黏著層(Y)，除了上述以外亦具有若加熱則熔融或流動之熱熔性，因此可具有更高之階差吸收性。 If the adhesive layer (Y) is formed using the resin composition of the above composition, the adhesive layer (Y) using (meth)acrylate copolymer (a) or (a-1) as the base resin can be used in It maintains a sheet shape at room temperature and exhibits self-adhesiveness, allowing the adhesive to be filled to every corner of the step of the adhered surface of the bonding member. Moreover, photocuring can be performed by visible light irradiation due to the visible light initiator (c), and the cohesive force and foaming resistance reliability can be improved by photocuring. Furthermore, by formulating a silane coupling agent, the adhesiveness, especially the adhesiveness to glass materials can be further improved. In addition, the adhesive layer (Y) using the (meth)acrylate copolymer (a-1) as the base resin also has thermal fusibility that melts or flows when heated, so that it can have a higher level difference absorbent.

作為形成黏著層(Y)之較佳之本樹脂組合物之進而其他一例，可列舉含有如下單體成分之(甲基)丙烯酸酯(共)聚合物(a-2)、上述交聯劑(b)、上述可見光起始劑(c)、視需要之矽烷偶合劑的組成，上述單體成分包含具有活性能量線交聯性結構部位、且具有碳數10～24之直鏈烷基之(甲基)丙烯酸酯單體。其中，較佳為使用波長405 nm之吸光係數為10 mL/(g・/cm)以上之可見光起始劑(c)作為可見光起始劑(c)；又，尤佳為使用上述裂解型可見光起始劑(c-1)及/或奪氫型可見光起始劑(c-2)作為可見光起始劑(c)。Still another example of a preferable present resin composition for forming the adhesive layer (Y) includes a (meth)acrylate (co)polymer (a-2) containing the following monomer components, the above-mentioned crosslinking agent (b ), the above-mentioned visible light initiator (c), and the optional silane coupling agent, the above-mentioned monomer components include (a base) acrylate monomer. Among them, it is preferable to use a visible light initiator (c) with an absorption coefficient of 10 mL/(g/cm) or more at a wavelength of 405 nm as the visible light initiator (c); and it is especially preferable to use the above-mentioned splitting visible light The initiator (c-1) and/or the hydrogen abstraction type visible light initiator (c-2) is used as the visible light initiator (c).

若使用如上所述之組成的本樹脂組合物，則可形成暫時硬化為尚存在光硬化之餘地之狀態或未硬化之黏著層(Y)，其後可藉由一次或兩次以上之可見光照射而使其光硬化。因此，例如於將本黏著片材貼合於被黏著體上之後，可藉由可見光照射使本黏著片材光硬化(「正式硬化」)，可藉由該正式硬化提高凝聚力而提高耐發泡可靠性。 尤其是對於常溫下之流動性高且於保管性方面存在難點之(甲基)丙烯酸酯(共)聚合物，即便於經過藉由暫時硬化而提高保管性之步驟之情形時，亦可藉由貼合後之可見光硬化之後續步驟而進行硬化。 藉由進而調配矽烷偶合劑，可進而提高接著性、尤其是對玻璃材料之接著性。 If the resin composition with the composition as described above is used, the adhesive layer (Y) can be temporarily hardened to a state where there is still room for light hardening or uncured, and can be irradiated with visible light once or twice. to make it photohardenable. Therefore, for example, after attaching this adhesive sheet to an adherend, this adhesive sheet can be light-cured by visible light irradiation (“main curing”), and the cohesive force can be improved by this formal curing to improve foaming resistance. reliability. In particular, the (meth)acrylate (co)polymer, which has high fluidity at room temperature and is difficult to store, can be cured by Hardening is carried out in the subsequent step of visible light hardening after lamination. By further formulating a silane coupling agent, the adhesiveness, especially the adhesiveness to glass materials can be further improved.

(積層構成) 如上所述，將黏著層(Y)設為積層構成之情形時，自耐發泡性之觀點考慮，較佳為使用本樹脂組合物之黏著層(Y)為最外層之表背層。 此時，作為表背層之黏著層(Y)之厚度較佳為15 μm以上，更佳為20 μm以上。黏著層(Y)之厚度若為15 μm以上，則於如下方面而言較佳：於可靠性試驗中，壓退自被黏著體構件產生之釋氣壓力，產生發泡等異常之虞較少。 (layered composition) As described above, when the adhesive layer (Y) is formed as a laminated layer, it is preferable to use the adhesive layer (Y) of the present resin composition as the outermost surface and back layers from the viewpoint of foam resistance. At this time, the thickness of the adhesive layer (Y) as the front and back layers is preferably at least 15 μm, more preferably at least 20 μm. If the thickness of the adhesive layer (Y) is 15 μm or more, it is preferable in terms of reducing the risk of abnormalities such as foaming due to the degassing pressure generated from the adherend member in the reliability test .

又，自兼具保管穩定性之觀點考慮，存在如下之情形：進而具有黏度比該黏著層(Y)高之其他層者較佳。 亦即，使用具有巨單體之接枝共聚物而形成之黏著層(Y)於光硬化前為未交聯狀態，若使用多官能(甲基)丙烯酸酯單體，則由於該多官能(甲基)丙烯酸酯單體成分之作用而存在光硬化前之黏著層(Y)成為黏度比較低之層之情形。 因此，於此種情形時，較佳為將黏度比該黏著層(Y)高之其他層(Z)積層於該黏著層(Y)。 例如，若為包含黏著層(Y)/層(Z)/黏著層(Y)之3層的多層構成，則可兼具優異之保管穩定性。 自此種保管穩定性之觀點考慮，上述其他層(Z)之黏度較佳為於溫度為70℃～100℃之範圍內為1～10 kPa・s，更佳為1.5～5 kPa・s。 再者，該黏度係依照實施例中所記載之方法而測定之值。 Moreover, it may be preferable to have another layer with a higher viscosity than this adhesive layer (Y) from the viewpoint of both storage stability. That is, the adhesive layer (Y) formed by using a graft copolymer with a macromonomer is in an uncrosslinked state before photohardening. If a multifunctional (meth)acrylate monomer is used, the multifunctional ( The adhesive layer (Y) before photohardening may become a layer with a relatively low viscosity due to the effect of the meth)acrylate monomer component. Therefore, in such a case, it is preferable to laminate another layer (Z) having a higher viscosity than the adhesive layer (Y) on the adhesive layer (Y). For example, if it is a three-layer structure including an adhesive layer (Y)/layer (Z)/adhesive layer (Y), excellent storage stability can be achieved at the same time. From the viewpoint of such storage stability, the viscosity of the other layer (Z) is preferably 1 to 10 kPa·s, more preferably 1.5 to 5 kPa·s at a temperature of 70°C to 100°C. In addition, this viscosity is the value measured according to the method described in the Example.

又，於本黏著片材為如上所述之多層構成之情形時，自進而兼具耐衝擊吸收性之觀點考慮，本黏著片材之405 nm光照射後之玻璃轉移溫度(Tg)較佳為未達20℃，更佳為未達10℃。 藉由使本黏著片材具有此種比較低之Tg，可使低溫黏著特性(低溫剝離強度等)提高，且具有耐衝擊吸收性。 因此，自耐衝擊吸收性之觀點考慮，與上述黏著層(Y)積層之其他層之405 nm光照射後之Tg尤佳為未達15℃，其中更佳為未達10℃，尤其是未達5℃。 再者，該Tg係於動態黏彈性之Tanδ之峰溫度下測定之值，詳細而言為依照實施例中所記載之方法而測定之值。 Also, when the adhesive sheet is composed of multiple layers as described above, the glass transition temperature (Tg) of the adhesive sheet after irradiation with 405 nm light is preferably It is less than 20°C, more preferably less than 10°C. By making the present adhesive sheet have such a relatively low Tg, low-temperature adhesive properties (low-temperature peel strength, etc.) can be improved, and shock-absorbing properties can be provided. Therefore, from the viewpoint of impact resistance absorption, the Tg of other layers laminated with the above-mentioned adhesive layer (Y) after irradiation with 405 nm light is preferably less than 15°C, more preferably less than 10°C, especially not more than 10°C. up to 5°C. In addition, this Tg is the value measured at the peak temperature of Tanδ of dynamic viscoelasticity, and it is the value measured according to the method described in an Example specifically.

＜附脫模膜之黏著片材＞ 本黏著片材亦可設為附脫模膜之黏著片材。 例如亦可於脫模膜上形成單層或多層之片材狀黏著層而製成附脫模膜之黏著片材。 ＜Adhesive sheet with release film＞ The adhesive sheet can also be used as an adhesive sheet with a release film attached. For example, a single-layer or multi-layer sheet-like adhesive layer can be formed on a release film to produce an adhesive sheet with a release film.

作為該脫模膜之材質，可適宜使用公知之脫模膜。 作為脫模膜之材質，例如可適宜選擇於聚酯膜、聚烯烴膜、聚碳酸酯膜、聚苯乙烯膜、丙烯酸系樹脂膜、三乙醯纖維素膜、氟樹脂膜等膜上塗佈聚矽氧樹脂而進行了脫模處理者、或脫模紙等而使用。 As a material of this release film, a well-known release film can be used suitably. As the material of the release film, for example, polyester film, polyolefin film, polycarbonate film, polystyrene film, acrylic resin film, triacetyl cellulose film, fluororesin film, etc. Silicone resin has been used for release treatment, or release paper, etc.

於本黏著片材之兩側積層脫模膜之情形時，一脫模膜可為與另一脫模膜相同之積層構成或材料者，亦可為不同之積層構成或材料。 又，可為相同厚度，亦可為不同厚度。 又，可將剝離力不同之脫模膜或厚度不同之脫模膜積層於本黏著片材之兩側。 In the case of laminating release films on both sides of this adhesive sheet, one release film may have the same lamination composition or material as the other release film, or may be a different lamination composition or material. Also, the same thickness may be used, or different thicknesses may be used. Also, release films with different peeling forces or release films with different thicknesses can be laminated on both sides of this adhesive sheet.

上述脫模膜較佳為波長410 nm以下之光的光線透過率為40%以下。 藉由於本黏著片材之至少一個面上積層波長410 nm以下之光的光線透過率為40%以下的脫模膜，可有效地防止由於照射可見光而進行光聚合。 自該觀點考慮，積層於本黏著片材之一個面或兩個面之脫模膜較佳為波長410 nm以下之光的光線透過率為40%以下，其中進而較佳為30%以下，其中更佳為20%以下。 The release film preferably has a light transmittance of 40% or less for light having a wavelength of 410 nm or less. By laminating a release film having a light transmittance of 40% or less for light having a wavelength of 410 nm or less on at least one surface of the adhesive sheet, photopolymerization due to irradiation of visible light can be effectively prevented. From this point of view, the release film laminated on one or both sides of this adhesive sheet preferably has a light transmittance of 40% or less for light having a wavelength of 410 nm or less, and more preferably 30% or less, wherein More preferably, it is less than 20%.

此處，作為波長410 nm以下之光的光線透過率為40%以下之脫模膜、亦即具有遮斷一部分可見光及紫外光之透過之作用的膜，例如可列舉包含紫外線吸收層之積層膜，上述紫外線吸收層係於聚酯系、聚丙烯系、聚乙烯系的流延膜或延伸膜之一個面塗佈具有再剝離性之微黏著樹脂，於另一個面塗佈包含紫外線吸收劑之塗料而成者。 又，可列舉於聚丙烯系、聚乙烯系的流延膜或延伸膜之一個面，塗佈調配有紫外線吸收劑且具有再剝離性之微黏著樹脂而成者。 又，可列舉於包含調配有紫外線吸收劑之聚酯系、聚丙烯系、聚乙烯系樹脂的流延膜或延伸膜，塗佈具有再剝離性之微黏著樹脂而成者。 又，可列舉於多層流延膜或延伸膜之一個面塗佈具有再剝離性之微黏著樹脂而成者，該多層流延膜或延伸膜係於包含調配有紫外線吸收劑之聚酯系、聚丙烯系、聚乙烯系樹脂之層的單面或雙面，成形包含不含紫外線吸收劑之樹脂的層而成者。 又，可列舉於包含聚酯系、聚丙烯系、聚乙烯系樹脂之流延膜或延伸膜的一個面塗佈包含紫外線吸收劑之塗料而設置紫外線吸收層，進而於該紫外線吸收層上塗佈具有再剝離性之微黏著樹脂而成者。 又，可列舉於包含聚酯系、聚丙烯系、聚乙烯系樹脂之流延膜或延伸膜之一個面塗佈包含紫外線吸收劑之塗料而設置紫外線吸收層，於另一個面塗佈具有再剝離性之微黏著樹脂而成者。 又，進而可列舉介隔包含紫外線吸收劑之接著層或黏著層，將於一個面塗佈有具有再剝離性之微黏著樹脂的包含聚酯系、聚丙烯系、聚乙烯系樹脂之樹脂膜之另一個面、與另行準備之樹脂膜積層而成者等。 上述膜亦可具有抗靜電層或硬塗層、增黏層等視需要之其他層。 Here, as a release film having a light transmittance of 40% or less for light with a wavelength of 410 nm or less, that is, a film that blocks the transmission of a part of visible light and ultraviolet light, for example, a laminated film including an ultraviolet absorbing layer The above-mentioned ultraviolet absorbing layer is coated on one side of polyester-based, polypropylene-based, polyethylene-based cast film or stretched film with a slightly adhesive resin with releasable properties, and coated on the other side with a UV-absorbing agent. Painted by. In addition, one surface of a polypropylene-based or polyethylene-based cast film or stretched film is coated with a slightly adhesive resin having a releasable UV absorber. In addition, it can be exemplified by coating a slightly adhesive resin having releasability on a cast film or stretched film made of a polyester-based, polypropylene-based, or polyethylene-based resin blended with an ultraviolet absorber. In addition, one surface of a multilayer cast film or stretched film coated with a slightly adhesive resin having releasability can be mentioned. The multilayer cast film or stretched film is made of a polyester-based, One or both sides of a polypropylene-based or polyethylene-based resin layer are molded into a layer containing a resin that does not contain an ultraviolet absorber. In addition, it is possible to apply a coating containing an ultraviolet absorber to one surface of a cast film or a stretched film comprising a polyester-based, polypropylene-based, or polyethylene-based resin to form an ultraviolet-absorbing layer, and further coat the ultraviolet-absorbing layer. The cloth is made of releasable slightly adhesive resin. In addition, it is possible to apply a coating containing an ultraviolet absorber to one side of a cast film or stretched film comprising a polyester-based, polypropylene-based, or polyethylene-based resin to form an ultraviolet-absorbing layer, and to coat the other side with a further coating. It is made of peelable and slightly adhesive resin. In addition, resin films containing polyester, polypropylene, and polyethylene resins coated with a releasable slightly adhesive resin via an adhesive layer or an adhesive layer containing an ultraviolet absorber may be further mentioned. The other side, laminated with a separately prepared resin film, etc. The above-mentioned film may also have an antistatic layer, a hard coat layer, an adhesion-promoting layer, and other optional layers.

脫模膜之厚度並無特別限制。其中，自例如加工性及處理性之觀點考慮，較佳為25 μm～500 μm，其中更佳為38 μm以上或250 μm以下，其中進而較佳為50 μm以上或200 μm以下。The thickness of the release film is not particularly limited. Among them, from the viewpoint of workability and handleability, the thickness is preferably 25 μm to 500 μm, more preferably 38 μm or more and 250 μm or less, and still more preferably 50 μm or more and 200 μm or less.

再者，本黏著片材亦可採用如下之方法：如上所述地並未使用被黏著體或脫模膜，例如直接對本樹脂組合物進行擠出成形之方法，或藉由將其注入至模具中而成形之方法。 進而，亦可將本樹脂組合物直接填充於作為被黏著體的圖像顯示裝置用構成構件間，藉此使其成為本黏著片材之態樣。 Furthermore, this adhesive sheet can also adopt the following method: as mentioned above, without using an adherend or a release film, such as a method of directly extruding this resin composition, or by injecting it into a mold The method of forming in the middle. Furthermore, this resin composition can also be made into the aspect of this adhesive sheet by directly filling between the structural members for image display apparatuses which are an adherend.

＜本黏著片材之製造方法＞ 關於製造本黏著片材之方法之一例而加以說明。 首先，將(甲基)丙烯酸酯(共)聚合物(a)及可見光起始劑(c)、視需要進而將交聯劑(b)、視需要進而將矽烷偶合劑(d)、視需要進而將其他材料分別以特定量加以混合，製備本樹脂組合物即可。 作為該等之混合方法，並無特別限制，各成分之混合順序亦無特別限定。又，於製造組合物時亦可加入熱處理步驟，於此情形時，理想的是預先將本樹脂組合物之各成分加以混合後進行熱處理。 又，亦可使用將各種混合成分濃縮，進行母料化而成者。 ＜Manufacturing method of this adhesive sheet＞ An example of the method of manufacturing this adhesive sheet is demonstrated. First, the (meth)acrylate (co)polymer (a) and the visible light initiator (c), if necessary, then the crosslinking agent (b), if necessary, then the silane coupling agent (d), if necessary Furthermore, what is necessary is just to prepare this resin composition by mixing other materials in a specific amount, respectively. The mixing method is not particularly limited, and the order of mixing the components is also not particularly limited. In addition, a heat treatment step may be added during the production of the composition. In this case, it is desirable to heat-treat after mixing the components of the present resin composition in advance. Moreover, what concentrated and masterbatched various mixing components can also be used.

混合時之裝置亦無特別限制，例如可使用萬能混練機、行星式攪拌機、班布里混合機、捏合機、框式混合機、加壓捏合機、三輥研磨機、二輥研磨機。亦可視需要使用溶劑而加以混合。 又，本樹脂組合物可製成不含溶劑之無溶劑系而使用。藉由製成無溶劑系而使用，可具有如下優點：並不殘存溶劑，耐熱性及耐光性提高。 自該觀點考慮，亦較佳為本樹脂組合物係包含(甲基)丙烯酸酯(共)聚合物(a)、交聯劑(b)及可見光起始劑(c)之形態。 The mixing device is not particularly limited. For example, a universal kneader, a planetary mixer, a Banbury mixer, a kneader, a rack mixer, a pressure kneader, a three-roll mill, and a two-roll mill can be used. They can also be mixed using a solvent as needed. Moreover, this resin composition can be used as a solvent-free system which does not contain a solvent. By using it as a solvent-free system, there is an advantage that heat resistance and light resistance are improved without leaving a solvent. From this viewpoint, it is also preferable that this resin composition is a form containing a (meth)acrylate (co)polymer (a), a crosslinking agent (b), and a visible light initiator (c).

本黏著片材可藉由將以上述方式製備之本樹脂組合物塗佈(塗敷)於基材片材或脫模片材上而製造。 又，例如積層構成之本黏著片材可藉由如下方法而製作：重複進行如下步驟之方法，即，將上述本樹脂組合物塗佈(塗敷)於基材片材或脫模片材上，形成第一層，於所形成之第一層上塗佈(塗敷)該本樹脂組合物，形成第二層之步驟；與上述同樣地形成第一層與第二層，其後將各個塗佈(塗敷)面彼此貼合之方法；或藉由多層塗佈或共擠出成型將該本樹脂組合物同時形成為第一層與第二層之方法。 The present adhesive sheet can be produced by coating (coating) the present resin composition prepared in the above manner on a base material sheet or a release sheet. Also, for example, this adhesive sheet composed of laminated layers can be produced by a method of repeating the steps of applying (coating) the above-mentioned present resin composition on a base sheet or a release sheet. , forming the first layer, coating (coating) the resin composition on the formed first layer to form the second layer; forming the first layer and the second layer in the same way as above, and then applying each A method of bonding coated (coated) surfaces together; or a method of simultaneously forming the present resin composition into a first layer and a second layer by multi-layer coating or co-extrusion molding.

上述塗佈(塗敷)方法只要若為一般之塗敷方法，則可並無特別限定地採用。例如，可列舉輥塗、模嘴塗佈、凹版塗佈、缺角輪塗佈、網版印刷等方法。The above-mentioned coating (coating) method can be adopted without particular limitation as long as it is a general coating method. For example, methods such as roll coating, die coating, gravure coating, chipped wheel coating, and screen printing may be mentioned.

繼而，可視需要對包含上述本樹脂組合物之黏著層照射光，使黏著層(Y)暫時硬化而殘存進行光硬化之餘地，將黏著層(Y)之凝膠分率設為0～60%。然而，亦可不必照射光而使黏著層(Y)暫時硬化，例如可藉由熱或固化而使黏著層(Y)暫時硬化，又，亦可為未硬化之狀態。Next, if necessary, light may be irradiated to the adhesive layer containing the above resin composition to temporarily harden the adhesive layer (Y) and leave room for photocuring, and the gel fraction of the adhesive layer (Y) shall be 0 to 60%. . However, the adhesive layer (Y) may be temporarily cured without irradiating light. For example, the adhesive layer (Y) may be temporarily cured by heat or curing, and may be in an uncured state.

＜本黏著片材之用途＞ 本黏著片材可如上所述般適宜用於貼合樹脂構件(X)。因此，可提供為包含具有特定特性之樹脂構件(X)與本黏著片材積層而成之構成的黏著片材積層體(稱為「本黏著片材積層體」)。 ＜Application of this adhesive sheet＞ This adhesive sheet can be used suitably for bonding a resin member (X) as mentioned above. Therefore, an adhesive sheet laminate (referred to as "the present adhesive sheet laminate") in which the resin member (X) having specific characteristics and the present adhesive sheet are laminated can be provided.

本黏著片材積層體例如可藉由如下步驟製作：使用含有(甲基)丙烯酸酯(共)聚合物及可見光起始劑之樹脂組合物而製作本黏著片材，將該本黏著片材積層於上述樹脂構件(X)。但本黏著片材積層體之製造方法並不限定於該方法。This adhesive sheet laminate can be produced, for example, by the steps of: using a resin composition containing a (meth)acrylate (co)polymer and a visible light initiator to produce this adhesive sheet, and laminating this adhesive sheet In the above-mentioned resin member (X). However, the method for producing the adhesive sheet laminate is not limited to this method.

(樹脂構件(X)) 樹脂構件(X)較佳為365 nm下之光線透過率為10%以下、且405 nm下之光線透過率為60%以上者。 (Resin member (X)) The resin member (X) preferably has a light transmittance of 10% or less at 365 nm and a light transmittance of 60% or more at 405 nm.

若樹脂構件(X)之365 nm下之光線透過率為10%以下、且405 nm下之光線透過率為60%以上，則可充分遮斷(截止)紫外線之透過，抑制樹脂構件(X)自身及位於其背面側(視認側面之相反面)之光學構件(例如偏光膜或相位差膜等光學膜)之光劣化，且可將黃度(YI)減低至光學構件所要求之水準。 作為此種樹脂構件(X)，可列舉以樹脂材料為主成分，使用紫外線吸收劑而調整為具有上述光線透過率者。 If the light transmittance at 365 nm of the resin member (X) is 10% or less, and the light transmittance at 405 nm is more than 60%, then the transmission of ultraviolet rays can be fully blocked (cut off), and the resin member (X) can be suppressed. The optical degradation of itself and the optical components (such as polarizing film or retardation film) located on the back side (the opposite side of the viewing side) can reduce the yellowness (YI) to the level required by the optical components. As such a resin member (X), what has a resin material as a main component, and adjusted so that it may have the said light transmittance using an ultraviolet absorber is mentioned.

作為上述樹脂材料，例如可列舉含有聚碳酸酯系樹脂或丙烯酸系樹脂作為主成分樹脂之材料。 此時，所謂「主成分樹脂」係指構成樹脂構件(X)之樹脂中的含有質量最多之樹脂。 As said resin material, the material containing a polycarbonate resin or an acrylic resin as a main component resin is mentioned, for example. In this case, the "main component resin" refers to the resin with the largest mass content among the resins constituting the resin member (X).

又，關於本黏著片材，例如可將上述樹脂構件(X)與圖像顯示面板(P)經由本黏著片材而貼合，形成光硬化性黏著片材積層體，自該樹脂構件(X)側通過樹脂構件(X)對本黏著片材照射405 nm下之累計光量成為3000(mJ/cm 2)之光，藉此使黏著層(Y)光硬化，使其凝聚以使光硬化前後之凝膠分率差成為10%以上，從而製造圖像顯示面板積層體。 In addition, regarding this adhesive sheet, for example, the above-mentioned resin member (X) and the image display panel (P) can be bonded via this adhesive sheet to form a photocurable adhesive sheet laminate, and the resin member (X) ) side through the resin member (X) to irradiate the adhesive sheet with light with a cumulative light intensity of 3000 (mJ/cm 2 ) at 405 nm, thereby photocuring the adhesive layer (Y) and coagulating it to make the difference between before and after photocuring The difference in gel fraction is 10% or more, and an image display panel laminate is produced.

本黏著片材積層體例如可與圖像顯示面板(P)貼合而製造圖像顯示面板積層體。 具體而言，包含本黏著片材積層體與圖像顯示面板(P)貼合而成之構成的圖像顯示面板積層體例如可於將樹脂構件(X)與圖像顯示面板(P)經由本黏著片材積層後，自該樹脂構件(X)之外側介隔該樹脂構件(X)照射波長405 nm之光，使本黏著片材之黏著層(Y)正式硬化而將上述樹脂構件(X)與圖像顯示面板(P)貼合，藉此製造圖像顯示面板積層體。 再者，將樹脂構件(X)與圖像顯示面板(P)經由本黏著片材而積層之方法並無特別限制，可於使樹脂構件(X)或圖像顯示面板(P)之任一者與本黏著片材積層後，使另一者與本黏著片材積層，又，亦可使樹脂構件(X)及圖像顯示面板(P)同時與本黏著片材積層。 For example, this adhesive sheet laminate can be bonded to an image display panel (P) to manufacture an image display panel laminate. Specifically, the image display panel laminate including the structure in which the adhesive sheet laminate and the image display panel (P) are bonded together, for example, can be obtained by laminating the resin member (X) and the image display panel (P) through After the adhesive sheet is laminated, light with a wavelength of 405 nm is irradiated from the outside of the resin member (X) through the resin member (X), so that the adhesive layer (Y) of the adhesive sheet is officially hardened, and the above resin member ( X) Bonding with the image display panel (P) produces an image display panel laminate. Furthermore, the method of laminating the resin member (X) and the image display panel (P) through this adhesive sheet is not particularly limited, and any one of the resin member (X) or the image display panel (P) can be used. After one is laminated with this adhesive sheet, the other is laminated with this adhesive sheet, and the resin member (X) and the image display panel (P) can also be laminated with this adhesive sheet at the same time.

(圖像顯示面板(P)) 作為上述圖像顯示面板(P)，例如為包含偏光膜、以及相位差膜等其他光學膜、液晶材料及背光系統(通常情況下，本組合物或黏著物品之相對於圖像顯示面板之被黏著面成為光學膜)者，根據液晶材料之控制方式而存在有STN方式或VA方式或IPS方式等，可為任意之方式。 又，圖像顯示面板可為將觸控面板功能內藏於TFT-LCD內之內嵌型，亦可為將觸控面板功能內藏於設有偏光板與彩色濾光片之玻璃基板間的表嵌型。 (Image display panel (P)) The image display panel (P) includes, for example, other optical films such as polarizing films and retardation films, liquid crystal materials, and backlight systems (usually, the composition or adhesive article is used for the substrate of the image display panel) If the adhesive surface is an optical film), there are STN method, VA method, or IPS method depending on the control method of the liquid crystal material, and any method may be used. In addition, the image display panel may be an in-cell type with the touch panel function embedded in the TFT-LCD, or may be a type in which the touch panel function is embedded between glass substrates provided with polarizers and color filters. Embedded type.

至於本黏著片材，自耐發泡可靠性之觀點考慮，尤佳為如上所述地貼著有目標物之狀態的黏著層(Y)、亦即光(本)硬化後之該黏著層(Y)具有本樹脂組合物之交聯結構。 尤其是該黏著層(Y)尤佳為如上所述地使用具有活性能量線硬化性部位之(甲基)丙烯酸酯共聚物，或具備具有官能基(i)之(甲基)丙烯酸酯(共)聚合物(a)、與具有與該官能基(i)反應之官能基(ii)之化合物的化學鍵，或使用未經環氧烷改性之3官能以上之多官能(甲基)丙烯酸酯而形成，具有由於該等所引起之交聯結構。 As for this adhesive sheet, from the standpoint of foaming resistance reliability, it is particularly preferable to be the adhesive layer (Y) in the state where the target object is stuck as described above, that is, the adhesive layer (Y) after light (this) curing. Y) has the cross-linked structure of the resin composition. In particular, the adhesive layer (Y) is preferably a (meth)acrylate copolymer having an active energy ray hardening site as described above, or a (meth)acrylate (copolymer) having a functional group (i). ) Polymer (a), a chemical bond with a compound having a functional group (ii) that reacts with the functional group (i), or using a trifunctional or higher polyfunctional (meth)acrylate that has not been modified by alkylene oxide And formed, has the cross-linked structure caused by these.

＜＜語句之說明等＞＞ 於本發明中，稱為「膜」之情形時亦包含「片材」，稱為「片材」之情形亦包含「膜」。 又，如圖像顯示面板、保護面板等那樣表現為「面板」之情形包含板體、片材及膜。 ＜＜Explanation of sentences, etc.＞＞ In the present invention, "sheet" is also included when called "film", and "film" is also included when called "sheet". Moreover, when expressing a "panel" like an image display panel, a protective panel, etc., a plate, a sheet, and a film are included.

於本發明中，於記載為「X～Y」(X、Y為任意之數字)之情形時，若無特別說明則包含「X以上Y以下」之含義及「較佳為大於X」或「較佳為小於Y」之含義。 又，於記載為「X以上」(X為任意之數字)之情形時，若無特別說明則包含「較佳為大於X」之含義，於記載為「Y以下」(Y為任意之數字)之情形時，若無特別說明則包含「較佳為小於Y」之含義。 [實施例] In the present invention, when it is described as "X~Y" (X, Y are arbitrary numbers), unless otherwise specified, it includes the meaning of "more than X but less than Y" and "preferably greater than X" or " It is preferably less than Y". Also, when it is described as "more than X" (X is an arbitrary number), unless otherwise specified, it includes the meaning of "preferably greater than X", and when it is described as "below Y" (Y is an arbitrary number) In the case of , it includes the meaning of "preferably smaller than Y" unless otherwise specified. [Example]

以下，藉由實施例進而加以詳細說明。但本發明並不限定於以下所說明之實施例。Hereinafter, it will be further described in detail with examples. However, the present invention is not limited to the examples described below.

＜實施例、比較例＞ 關於實施例、比較例中所使用之材料而加以說明。 <Example, Comparative Example> The materials used in Examples and Comparative Examples will be described.

[實施例1] (光硬化性黏著片材Y) 作為(甲基)丙烯酸酯(共)聚合物，準備使包含甲基丙烯酸異𦯉酯：甲基丙烯酸甲酯＝1：1的末端官能基為甲基丙烯醯基之巨單體(數量平均分子量為3000) 13.5質量份、丙烯酸月桂酯43.7質量份、丙烯酸2-乙基己酯40質量份、及丙烯醯胺2.8質量份進行無規共聚而成之丙烯酸系接枝共聚物(質量平均分子量：16萬)。 相對於該丙烯酸系接枝共聚物1 kg而添加作為交聯劑之丙氧基化季戊四醇三丙烯酸酯(新中村化學公司製造、NK ESTER ATM-4PL) 90 g、作為可見光起始劑的包含裂解型可見光起始劑之混合物，亦即2,4,6-三甲基苯甲醯基二苯基氧化膦、低聚(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮)、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮之混合物(Lamberti公司製造之Esacure KTO46) 15 g，均勻混合而獲得光硬化性組合物。 其次，於表面進行了剝離處理之聚對苯二甲酸乙二酯膜(三菱樹脂公司製造、DIAFOIL MRV、厚度100 μm)上，以厚度成為150 μm之方式將上述光硬化性組合物成形為片材狀，然後被覆對表面進行了剝離處理之聚對苯二甲酸乙二酯膜(三菱樹脂公司製造、DIAFOIL MRQ、厚度為75 μm)，製作附脫模膜之光硬化性黏著片材Y1。 再者，光硬化性黏著片材Y1係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 1] (Photocurable adhesive sheet Y) As a (meth)acrylate (co)polymer, prepare a macromonomer (number average molecular weight 3000) 13.5 parts by mass, 43.7 parts by mass of lauryl acrylate, 40 parts by mass of 2-ethylhexyl acrylate, and 2.8 parts by mass of acrylamide for random copolymerization of acrylic graft copolymers (mass average molecular weight: 160,000). 90 g of propoxylated pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER ATM-4PL) as a crosslinking agent was added to 1 kg of the acrylic graft copolymer, and cleavage-containing lysate as a visible light initiator was added. A mixture of visible light initiators, namely 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo(2-hydroxy-2-methyl-1-(4-(1-methyl (vinyl) phenyl) acetone), 2,4,6-trimethylbenzophenone, a mixture of 4-methylbenzophenone (Esacure KTO46 manufactured by Lamberti Company) 15 g, uniformly mixed to obtain light hardening composition. Next, on a polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., DIAFOIL MRV, thickness 100 μm) on which the surface was peeled, the above-mentioned photocurable composition was molded into a sheet so as to have a thickness of 150 μm. It was in the shape of a material, and then covered with a polyethylene terephthalate film (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRQ, thickness: 75 μm) with a peeling treatment on the surface to prepare a photocurable adhesive sheet Y1 with a release film. In addition, photocurable adhesive sheet Y1 is a photocurable adhesive sheet which hardens by irradiation of light.

(樹脂構件X) 作為樹脂構件(X)，使用含有紫外線吸收劑之聚碳酸酯系樹脂板(三菱瓦斯化學公司製造、Iupilon片材MR58)之厚度為1.0 mm (於貼合結構P中使用)及1.5 mm (於貼合結構Q及貼合結構R中使用)者。 任意厚度者均係365 nm下之光線透過率為0%、405 nm下之光線透過率為83%。 (resin member X) As the resin member (X), a polycarbonate-based resin plate (manufactured by Mitsubishi Gas Chemical Co., Ltd., Iupilon sheet MR58) containing an ultraviolet absorber with a thickness of 1.0 mm (used in the laminated structure P) and 1.5 mm (used in the Those used in the bonding structure Q and bonding structure R). For any thickness, the light transmittance at 365 nm is 0%, and the light transmittance at 405 nm is 83%.

(光硬化性黏著片材積層體) 將附脫模膜之光硬化性黏著片材Y1之一個面之剝離膜剝下，用輥貼合於上述聚碳酸酯板(樹脂構件X)之一個面，獲得樹脂構件(X)/光硬化性黏著片材Y1之光硬化性黏著片材積層體(亦稱為「X/Y1積層體」)。 (Photocurable adhesive sheet laminate) Peel off the release film on one side of the photocurable adhesive sheet Y1 with a release film, and stick it to one side of the polycarbonate plate (resin member X) with a roller to obtain the resin member (X)/photocurable Photocurable adhesive sheet laminate (also called "X/Y1 laminate") of permanent adhesive sheet Y1.

[實施例2] 將光硬化性黏著片材Y之交聯劑之種類變更為季戊四醇三丙烯酸酯(新中村化學公司製造、NK ESTER ATMM3)，將調配份數變更為相對於丙烯酸系接枝共聚物1 kg而言為70 g，除此以外與實施例1同樣地進行而獲得光硬化性黏著片材Y2及X/Y2積層體。 再者，光硬化性黏著片材Y2係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 2] The type of the crosslinking agent of the photocurable adhesive sheet Y was changed to pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER ATMM3), and the number of parts prepared was changed to 1 kg of the acrylic graft copolymer Except having been 70 g, it carried out similarly to Example 1, and obtained photocurable adhesive sheet Y2 and X/Y2 laminated body. In addition, photocurable adhesive sheet Y2 is a photocurable adhesive sheet which hardens by irradiation of light.

[實施例3] 將光硬化性黏著片材Y之(甲基)丙烯酸系共聚物之組成變更為相對於包含甲基丙烯酸異𦯉酯：甲基丙烯酸甲酯＝1：1的末端官能基為甲基丙烯醯基之巨單體(數量平均分子量為3000) 12.7質量份、丙烯酸月桂酯41.1質量份、丙烯酸2-乙基己酯37.6質量份、丙烯醯胺2.6質量份及丙烯酸4-羥基丁酯6質量份進行無規共聚而成之含有羥基之丙烯酸系接枝共聚物(質量平均分子量：16萬) 100質量份，加成反應甲基丙烯酸2-異氰酸基乙酯6.5質量份而獲得之具有碳-碳雙鍵之活性能量線交聯性結構部位的(甲基)丙烯酸系共聚物，除此以外與實施例1同樣地進行而獲得光硬化性黏著片材Y3及X/Y3積層體。再者，光硬化性黏著片材Y3係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 3] The composition of the (meth)acrylic copolymer of the photocurable adhesive sheet Y was changed to a methacryl group with respect to the terminal functional group containing isomethacrylate:methyl methacrylate = 1:1 12.7 parts by mass of macromonomer (number average molecular weight is 3000), 41.1 parts by mass of lauryl acrylate, 37.6 parts by mass of 2-ethylhexyl acrylate, 2.6 parts by mass of acrylamide and 6 parts by mass of 4-hydroxybutyl acrylate 100 parts by mass of acrylic graft copolymer containing hydroxyl groups (mass average molecular weight: 160,000) obtained by random copolymerization, and obtained by addition reaction of 6.5 parts by mass of 2-isocyanatoethyl methacrylate Except for the (meth)acrylic copolymer of the active energy ray crosslinkable structure part of a carbon double bond, it carried out similarly to Example 1, and obtained the photocurable adhesive sheet Y3 and X/Y3 laminated body. In addition, photocurable adhesive sheet Y3 is a photocurable adhesive sheet which hardens by irradiation of light.

[實施例4] 使用如下者作為光硬化性黏著片材，亦即使用作為可見光起始劑之奪氫型可見光起始劑苯基乙醛酸甲酯(BASF公司製造、Irgacure MBF)，預先以405 nm下之累計光量成為100(mJ/cm 2)之方式照射光而進行了一次硬化(交聯)者，除此以外與實施例1同樣地進行而獲得光硬化性黏著片材Y4及X/Y4積層體。 再者，光硬化性黏著片材Y4係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 4] Use the following as a photocurable adhesive sheet, that is, use a hydrogen abstraction-type visible light initiator methyl phenylglyoxylate (manufactured by BASF, Irgacure MBF) as a visible light initiator, and pre-set with Photocurable adhesive sheets Y4 and X were obtained in the same manner as in Example 1 except that the cumulative light intensity at 405 nm became 100 (mJ/cm 2 ) and primary curing (crosslinking) was performed. /Y4 laminated body. In addition, photocurable adhesive sheet Y4 is a photocurable adhesive sheet which hardens by irradiation of light.

[實施例5] 作為(甲基)丙烯酸酯(共)聚合物，使用包含甲基丙烯酸異𦯉酯：甲基丙烯酸甲酯＝1：1的末端官能基為甲基丙烯醯基之巨單體(數量平均分子量為3000) 13.5質量份、丙烯酸2-乙基己酯73.7質量份、丙烯醯胺2.8質量份及甲基丙烯酸酯10質量份進行無規共聚而成之丙烯酸系接枝共聚物(質量平均分子量：26萬)，且將交聯劑之種類變更為季戊四醇三丙烯酸酯(新中村化學公司製造、NK ESTER ATMM3L)，將調配份數變更為相對於丙烯酸系接枝共聚物1 kg而言為70 g，除此以外與實施例1同樣地進行而獲得光硬化性黏著片材Y5及X/Y5積層體。 再者，光硬化性黏著片材Y5係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 5] As the (meth)acrylate (co)polymer, a macromonomer (number average molecular weight of 3000) 13.5 parts by mass, 73.7 parts by mass of 2-ethylhexyl acrylate, 2.8 parts by mass of acrylamide and 10 parts by mass of methacrylate, which are randomly copolymerized into an acrylic graft copolymer (mass average molecular weight: 26 10,000), and the type of crosslinking agent was changed to pentaerythritol triacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., NK ESTER ATMM3L), and the number of parts prepared was changed to 70 g relative to 1 kg of acrylic graft copolymer, Except for this, it carried out similarly to Example 1, and obtained the photocurable adhesive sheet Y5 and X/Y5 laminated body. In addition, photocurable adhesive sheet Y5 is a photocurable adhesive sheet which hardens by irradiation of light.

[實施例6] 將交聯劑之調配量變更為相對於丙烯酸系接枝共聚物1 kg而言為120 g，除此以外與實施例5同樣地進行而獲得光硬化性黏著片材Y6及X/Y6積層體。 再者，光硬化性黏著片材Y6係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 6] Except changing the compounding amount of the crosslinking agent to 120 g with respect to 1 kg of the acrylic graft copolymer, it carried out similarly to Example 5, and obtained the photocurable adhesive sheet Y6 and X/Y6 laminated body . In addition, photocurable adhesive sheet Y6 is a photocurable adhesive sheet which hardens by irradiation of light.

[實施例7] 將交聯劑之種類設為相對於丙烯酸系接枝共聚物1 kg，併用使用季戊四醇三丙烯酸酯(新中村化學公司製造、NK ESTER ATMM3L)與二季戊四醇四丙烯酸酯(新中村化學公司製造、NK ESTER A9570W)各90 g、30 g，除此以外與實施例5同樣地進行而獲得光硬化性黏著片材Y7及X/Y7積層體。 再者，光硬化性黏著片材Y7係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 7] The type of crosslinking agent was set to 1 kg of the acrylic graft copolymer, and pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER ATMM3L) and dipentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A9570W) except each 90 g and 30 g, and carried out similarly to Example 5, and obtained photocurable adhesive sheet Y7 and X/Y7 laminated body. In addition, photocurable adhesive sheet Y7 is a photocurable adhesive sheet which hardens by irradiation of light.

[實施例8] 將交聯劑之種類設為相對於丙烯酸系接枝共聚物1 kg，併用使用季戊四醇三丙烯酸酯(新中村化學公司製造、NK ESTER ATMM3L)與二季戊四醇四丙烯酸酯(新中村化學公司製造、NK ESTER A9570W)各120 g、40 g，除此以外與實施例5同樣地進行而獲得光硬化性黏著片材Y8及X/Y8積層體。 再者，光硬化性黏著片材Y8係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 8] The type of crosslinking agent was set to 1 kg of the acrylic graft copolymer, and pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER ATMM3L) and dipentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A9570W) except each 120 g, 40 g, it carried out similarly to Example 5, and obtained photocurable adhesive sheet Y8 and X/Y8 laminated body. In addition, photocurable adhesive sheet Y8 is a photocurable adhesive sheet which hardens by irradiation of light.

[實施例9] 相對於作為(甲基)丙烯酸系共聚物的包含甲基丙烯酸異𦯉酯：甲基丙烯酸甲酯＝1：1的末端官能基為甲基丙烯醯基之巨單體(數量平均分子量3,000) 13.5質量份、丙烯酸2-乙基己酯73.7質量份、丙烯醯胺2.8質量份及甲基丙烯酸酯10質量份進行無規共聚而成之丙烯酸系接枝共聚物(質量平均分子量：26萬) 1 kg，以分別為75 g、25 g之量併用季戊四醇三丙烯酸酯(新中村化學公司製造、NK ESTER ATMM3L)與二季戊四醇四丙烯酸酯(新中村化學公司製造、NK ESTER A9570W)作為交聯劑，添加作為可見光起始劑的包含裂解型可見光起始劑之混合物，亦即2,4,6-三甲基苯甲醯基二苯基氧化膦、低聚(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮)、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮之混合物(Lamberti公司製造之Esacure KTO46) 15 g，均勻混合作為矽烷偶合劑之3-縮水甘油氧基丙基三甲氧基矽烷2 g(信越矽利光股份有限公司製造之KBM403)，獲得光硬化性組合物。 其次，於表面進行了剝離處理之聚對苯二甲酸乙二酯膜(三菱化學公司製造、DIAFOIL MRV、厚度為100 μm)上，以厚度成為25 μm之方式將上述光硬化性組合物成形為片材狀，然後被覆對表面進行了剝離處理之聚對苯二甲酸乙二酯膜(三菱化學公司製造、DIAFOIL MRQ、厚度為75 μm)，製作附脫模膜之表背層用黏著片材Y9a。 [Example 9] For (meth)acrylic copolymers containing isomethacrylate:methyl methacrylate = 1:1 macromonomer whose terminal functional group is methacryl group (number average molecular weight 3,000) 13.5 Acrylic graft copolymer (mass average molecular weight: 260,000) 1 kg, with pentaerythritol triacrylate (manufactured by Shin Nakamura Chemical Co., NK ESTER ATMM3L) and dipentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., NK ESTER A9570W) in amounts of 75 g and 25 g respectively as crosslinking agents, As a visible light initiator, a mixture containing a cleavage-type visible light initiator, namely, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo(2-hydroxy-2-methyl- A mixture of 1-(4-(1-methylvinyl)phenyl)acetone), 2,4,6-trimethylbenzophenone, and 4-methylbenzophenone (Esacure KTO46 manufactured by Lamberti ) 15 g, and 2 g of 3-glycidoxypropyltrimethoxysilane (KBM403 manufactured by Shin-Etsu Silicone Co., Ltd.) as a silane coupling agent were uniformly mixed to obtain a photocurable composition. Next, on a polyethylene terephthalate film (Mitsubishi Chemical Corporation, DIAFOIL MRV, thickness 100 μm) on which the surface was peeled, the photocurable composition was molded so as to have a thickness of 25 μm. In sheet form, it is coated with a polyethylene terephthalate film (manufactured by Mitsubishi Chemical Corporation, DIAFOIL MRQ, thickness: 75 μm) with a peeling treatment on the surface to make an adhesive sheet for the front and back layers with a release film Y9a.

相對於作為(甲基)丙烯酸系共聚物的與表背層用黏著片材Y9a中所使用者相同之丙烯酸系接枝共聚物1 kg，添加作為交聯劑之季戊四醇三丙烯酸酯(新中村化學公司製造、NK ESTER ATMM3L) 30 g、作為可見光起始劑的包含裂解型可見光起始劑之混合物，亦即2,4,6-三甲基苯甲醯基二苯基氧化膦、低聚(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮)、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮之混合物(Lamberti公司製造之Esacure KTO46) 15 g，均勻混合而獲得光硬化性組合物。 其次，於表面進行了剝離處理之聚對苯二甲酸乙二酯膜(三菱化學公司製造、DIAFOIL MRV、厚度為100 μm)上，以厚度成為100 μm之方式將上述光硬化性組合物成形為片材狀，然後被覆對表面進行了剝離處理之聚對苯二甲酸乙二酯膜(三菱化學公司製造、DIAFOIL MRQ、厚度為75 μm)，製作附脫模膜之中間層用黏著片材Y9b。 Pentaerythritol triacrylate (Shin Nakamura Chemical Co., Ltd. Manufactured by the company, NK ESTER ATMM3L) 30 g, a mixture containing a cleavage-type visible light initiator as a visible light initiator, that is, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo( 2-Hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)acetone), 2,4,6-trimethylbenzophenone, 4-methylbenzophenone 15 g of the mixture (Esacure KTO46 manufactured by Lamberti Co., Ltd.), and uniformly mixed to obtain a photocurable composition. Next, on a polyethylene terephthalate film (manufactured by Mitsubishi Chemical Corporation, DIAFOIL MRV, thickness 100 μm) on which the surface was peeled, the photocurable composition was molded so that the thickness became 100 μm. In sheet form, it was covered with a polyethylene terephthalate film (manufactured by Mitsubishi Chemical Corporation, DIAFOIL MRQ, thickness: 75 μm) with a peeling treatment on the surface, and an adhesive sheet Y9b for an intermediate layer with a release film was produced. .

將中間層用黏著片材Y9b之兩側之PET膜順次剝離除去，且將2枚表背層用黏著片材Y9a之黏著面順次貼合於中間層用黏著片材Y9b之兩個表面，獲得光硬化性黏著片材Y9，該光硬化性黏著片材Y9係包含(表背層用黏著片材Y9a)/(中間層用黏著片材Y9b)/(表背層用黏著片材Y9a)之2種3層積層體(總厚度為150 μm)，且與實施例1同樣地進行而獲得X/Y9積層體。The PET films on both sides of the adhesive sheet Y9b for the middle layer were peeled off sequentially, and the adhesive surfaces of the two adhesive sheets Y9a for the front and back layers were sequentially pasted on the two surfaces of the adhesive sheet Y9b for the middle layer to obtain Photocurable adhesive sheet Y9, the photocurable adhesive sheet Y9 is composed of (adhesive sheet Y9a for front and back layers)/(adhesive sheet Y9b for middle layer)/(adhesive sheet Y9a for front and back layers) Two types of three-layer laminates (total thickness: 150 μm) were carried out in the same manner as in Example 1 to obtain an X/Y9 laminate.

[實施例10] 將上述中間層用黏著片材Y9b中所使用之(甲基)丙烯酸系共聚物變更為包含甲基丙烯酸異𦯉酯：甲基丙烯酸甲酯＝1：1之末端官能基為甲基丙烯醯基之巨單體(數量平均分子量為3,000) 13.5質量份、丙烯酸月桂酯43.7質量份、丙烯酸2-乙基己酯40質量份、及丙烯醯胺2.8質量份進行無規共聚而成之丙烯酸系接枝共聚物(質量平均分子量：16萬)而形成中間層用黏著片材Y10b，除此以外與實施例9同樣地進行而獲得光硬化性黏著片材Y10及X/Y10積層體，該光硬化性黏著片材Y10係包含(表背層用黏著片材Y9a)/(中間層用黏著片材Y10b)/(表背層用黏著片材Y9a)之2種3層積層體(總厚度為150 μm)。 再者，光硬化性黏著片材Y10係具有藉由照射光而硬化之光硬化性的黏著片材。 [Example 10] The (meth)acrylic copolymer used in the above-mentioned adhesive sheet Y9b for the intermediate layer was changed to include isomethacrylate: methyl methacrylate = 1:1, and the terminal functional group was methacryl group An acrylic-based bonded polymer obtained by random copolymerization of 13.5 parts by mass of macromonomer (number average molecular weight: 3,000), 43.7 parts by mass of lauryl acrylate, 40 parts by mass of 2-ethylhexyl acrylate, and 2.8 parts by mass of acrylamide. branch copolymer (mass average molecular weight: 160,000) to form the adhesive sheet Y10b for the intermediate layer, and to obtain the photocurable adhesive sheet Y10 and X/Y10 laminate in the same manner as in Example 9, the photocurable The permanent adhesive sheet Y10 is a 3-layer laminate consisting of (adhesive sheet Y9a for the front and back layers)/(adhesive sheet Y10b for the middle layer)/(adhesive sheet Y9a for the front and back layers) (the total thickness is 150 μm). In addition, photocurable adhesive sheet Y10 is a photocurable adhesive sheet which hardens by irradiation of light.

[比較例1] 作為光硬化性黏著片材，使用作為光起始劑之奪氫型起始劑，亦即2,4,6-三甲基二苯甲酮與4-甲基二苯甲酮之混合物(Lamberti公司製造、Esacure TZT)，除此以外與實施例1同樣地進行而獲得光硬化性黏著片材Y11及X/Y11積層體。 [Comparative example 1] As a light-curable adhesive sheet, a hydrogen-abstracting initiator as a photoinitiator, that is, a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (Lamberti Company make, Esacure TZT), except that it carried out similarly to Example 1, and obtained the photocurable adhesive sheet Y11 and X/Y11 laminated body.

[比較例2] 作為光硬化性黏著片材，使用作為光起始劑之奪氫型起始劑，亦即1-[4-(4-苯甲醯基苯基硫基)苯基]-2-甲基-2-(4-甲基苯基磺醯基)丙烷-1-酮(Lamberti公司製造、Esacure1001M)，除此以外與實施例1同樣地進行而獲得光硬化性黏著片材Y12及X/Y12積層體。 [Comparative example 2] As a light-curable adhesive sheet, a hydrogen-abstracting initiator as a photoinitiator, that is, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl- 2-(4-methylphenylsulfonyl)propan-1-one (manufactured by Lamberti, Esacure 1001M), except that it was carried out in the same manner as in Example 1 to obtain a photocurable adhesive sheet Y12 and X/Y12 laminated body.

[比較例3] 作為光硬化性黏著片材，使用並不具有光硬化性的市售之非硬化性光學用透明黏著片材，除此以外與實施例1同樣地進行而獲得光硬化性黏著片材Y13及X/Y13積層體。 [Comparative example 3] As the photocurable adhesive sheet, a commercially available non-curable optical transparent adhesive sheet that does not have photocurability was used, and the photocurable adhesive sheets Y13 and X were obtained in the same manner as in Example 1. /Y13 laminated body.

[比較例4] 作為樹脂構件X，使用不含紫外線吸收劑之聚碳酸酯系樹脂板(厚度為1.0 mm、365 nm下之光線透過率為45%、405 nm下之光線透過率為91%)，除此以外與實施例1同樣地進行而獲得光硬化性黏著片材Y14及X/Y14積層體。 [Comparative example 4] As the resin member X, a polycarbonate-based resin plate (thickness 1.0 mm, light transmittance at 365 nm of 45%, and light transmittance at 405 nm of 91%) was used without an ultraviolet absorber. It carried out similarly to Example 1, and obtained the photocurable adhesive sheet Y14 and X/Y14 laminated body.

＜評價＞ 關於本說明書中所表示之評價方法而加以說明。 ＜Evaluation＞ The evaluation method shown in this specification is demonstrated.

(1)動態儲存模數(G') 關於實施例及比較例中所獲得之150 μm之光硬化性黏著片材Y1～Y14(無脫模膜)之各個，8枚重疊而使其成為1200 μm，使用動態黏彈性測定裝置流變計(英弘精機股份有限公司製造之「MARS」)，於黏著治具為Φ25mm平行板、應變為0.5%、頻率為1 Hz、升溫速度為3℃/min之條件下進行測定。 (1) Dynamic storage modulus (G') For each of the 150 μm photocurable adhesive sheets Y1 to Y14 (without release film) obtained in Examples and Comparative Examples, 8 sheets were stacked so as to have a thickness of 1200 μm, and a dynamic viscoelasticity measuring device rheometer was used. ("MARS" manufactured by Yinghong Seiki Co., Ltd.), under the conditions that the adhesive fixture is a Φ25mm parallel plate, the strain is 0.5%, the frequency is 1 Hz, and the heating rate is 3°C/min.

(2)分光透過率 關於樹脂構件(X)，使用分光光度計(島津製作所製造之UV2000)，測定波長300 nm～800 nm之分光透過率(%T)。將該分光透過率作為光線透過率。 (2) Spectral transmittance Regarding the resin member (X), the spectral transmittance (%T) at a wavelength of 300 nm to 800 nm was measured using a spectrophotometer (UV2000 manufactured by Shimadzu Corporation). Let this spectral transmittance be the light transmittance.

(3)凝膠分率 關於實施例及比較例中所獲得之光硬化性黏著片材Y1～Y14(無脫模膜)之各個，藉由預先測定了質量(X)之SUS網(♯200)而包為袋狀，摺疊袋口將其封閉，測定該包之質量(Y)，然後將其浸漬於100 ml之乙酸乙酯中，於23℃、暗處保管24小時後，取出包而於70℃加熱4.5小時，使附著之乙酸乙酯蒸發，測定乾燥之包之質量(Z)，將所求出之質量代入至下述式中而求出凝膠分率X1。 凝膠分率(%)＝[(Z-X)/(Y-X)]×100 (3) Gel fraction Each of the photocurable adhesive sheets Y1 to Y14 (without release film) obtained in Examples and Comparative Examples was wrapped in a bag with a SUS net (♯200) whose mass (X) was measured in advance, Fold the mouth of the bag to seal it, measure the mass (Y) of the bag, then immerse it in 100 ml of ethyl acetate, store it in the dark at 23°C for 24 hours, take out the bag and heat it at 70°C for 4.5 hours, The attached ethyl acetate was evaporated, the mass (Z) of the dried bag was measured, and the obtained mass was substituted into the following formula to obtain the gel fraction X1. Gel fraction (%)=[(Z-X)/(Y-X)]×100

又，關於實施例及比較例中所獲得之X/Y1～Y14積層體之各個，自樹脂構件(X)側，使用高壓水銀燈以405 nm下之累計光量成為3000(mJ/cm 2)之方式照射光，然後自光硬化性黏著片材之樹脂構件(X)側表面之黏著層部位採取樣品，藉由與上述同樣之方法求出凝膠分率X2。並且算出X2-X1。 Also, for each of the X/Y1 to Y14 laminates obtained in Examples and Comparative Examples, from the resin member (X) side, the integrated light intensity at 405 nm was 3000 (mJ/cm 2 ) using a high-pressure mercury lamp. After irradiating light, samples were taken from the adhesive layer portion of the surface of the photocurable adhesive sheet on the resin member (X) side, and the gel fraction X2 was determined by the same method as above. And calculate X2-X1.

(4)階差吸收性 對58 mm×110 mm×厚度0.8 mm之玻璃之周緣部(長邊側3 mm、短邊側15 mm)實施厚度為22～24 μm之印刷，準備中央之凹部為52 mm×80 mm之附印刷階差之玻璃板。 關於實施例及比較例中所獲得之附脫模膜之光硬化性黏著片材Y1～Y14之各個，剝去一脫模膜，以輥貼合於鈉鈣玻璃(54 mm×82 mm×厚度0.5 mm)之整個面上之後，剝去殘存之另一脫模膜，以黏著片材覆蓋於上述附印刷階差之玻璃板之邊框狀印刷階差之方式使用真空加壓進行真空壓接(溫度為25℃、加壓壓力為0.13 MPa)，製成評價樣品。 於60℃、0.2 MPa、20 min之條件下對評價樣品進行高壓釜處理後，藉由下述評價基準判定合格與否。 ○(良)：於階差周邊部完全未看到微小氣泡 ×(差)：於階差周邊部看到微小氣泡 (4) Step absorption Printing with a thickness of 22-24 μm on the peripheral part of the glass of 58 mm × 110 mm × thickness 0.8 mm (3 mm on the long side and 15 mm on the short side), and prepare a central concave part of 52 mm × 80 mm Printed step glass plate. With regard to each of the photocurable adhesive sheets Y1 to Y14 with release films obtained in Examples and Comparative Examples, one release film was peeled off, and a roll was attached to soda-lime glass (54 mm×82 mm×thickness 0.5 mm) on the entire surface, peel off the other remaining release film, and use vacuum pressure to vacuum-bond the frame-shaped printed step of the above-mentioned glass plate with printed step with an adhesive sheet ( The temperature was 25° C. and the applied pressure was 0.13 MPa), and an evaluation sample was produced. After autoclaving the evaluation samples under the conditions of 60°C, 0.2 MPa, and 20 min, the following evaluation criteria are used to judge whether the product is qualified or not. ○ (good): Micro bubbles are not seen at all around the level difference × (poor): tiny bubbles are seen around the level difference

(5)黃度(YI) 關於實施例及比較例中所獲得之X/Y1～Y14積層體之各個，自樹脂構件(X)側，使用高壓水銀燈以405 nm下之累計光量成為3000(mJ/cm 2)之方式照射光。 所謂405 nm下之累計光量係使用紫外線累計光量計「UIT-250」(牛尾電機股份有限公司製造)及受光器「UVD-C405」(牛尾電機股份有限公司製造)，於樹脂構件(X)之藉由高壓水銀燈進行照射之側之面的相反面設置光量計而測定的，透過樹脂構件(X)而照射至光硬化性黏著片材(Y1～Y14)上的累計光量。 其後，使用分光測色計(須賀試驗機(股))「SC-T」，基於JIS K7103測定X/Y1～Y14積層體之黃度(YI)，藉由下述評價基準判定合格與否。 ○(良)：YI未達2 ×(差)：YI為2以上 (5) Yellowness (YI) For each of the X/Y1 to Y14 laminates obtained in Examples and Comparative Examples, the cumulative light intensity at 405 nm was 3000 (mJ) from the resin member (X) side using a high-pressure mercury lamp. /cm 2 ) to irradiate light. The so-called cumulative light intensity at 405 nm is measured on the resin member (X) using an ultraviolet integrated light meter "UIT-250" (manufactured by Ushio Electric Co., Ltd.) and a photoreceptor "UVD-C405" (manufactured by Ushio Electric Co., Ltd.). The integrated light quantity irradiated onto the photocurable adhesive sheets (Y1-Y14) through the resin member (X) was measured by installing a light meter on the opposite side of the side irradiated by the high-pressure mercury lamp. Thereafter, the yellowness (YI) of X/Y1-Y14 laminates was measured based on JIS K7103 using a spectrophotometer (Suga Testing Instrument Co., Ltd.) "SC-T", and the pass or fail was judged by the following evaluation criteria . ○ (good): YI is less than 2 × (poor): YI is 2 or more

(6)耐UV可靠性(ΔYI) 關於實施例及比較例中所獲得之X/Y1～Y14積層體，自樹脂構件(X)側，使用高壓水銀燈以405 nm下之累計光量成為3000(mJ/cm 2)之方式照射光。 所謂405 nm下之累計光量係使用紫外線累計光量計「UIT-250」(牛尾電機股份有限公司製造)及受光器「UVD-C405」(牛尾電機股份有限公司製造)，於樹脂構件(X)之藉由高壓水銀燈進行照射之側之面的相反面設置光量計而測定的，透過樹脂構件(X)而照射至光硬化性黏著片材(Y1～Y14)上的累計光量。 其後，使用UVB螢光燈(G15T8E、三共電氣股份有限公司製造、放射照度為70 μW/cm 2)而實施距離為20 cm、72 hr之照射試驗。 根據照射前後之X/Y1～Y14積層體之黃度(YI)之變化量ΔYI，藉由下述評價基準判定合格與否。 ○(良)：ΔYI未達0.2 ×(差)：ΔYI為0.2以上 (6) UV resistance reliability (ΔYI) Regarding the X/Y1 to Y14 laminates obtained in Examples and Comparative Examples, the cumulative light intensity at 405 nm from the resin member (X) side was 3000 (mJ) using a high-pressure mercury lamp. /cm 2 ) to irradiate light. The so-called cumulative light intensity at 405 nm is measured on the resin member (X) using an ultraviolet integrated light meter "UIT-250" (manufactured by Ushio Electric Co., Ltd.) and a photoreceptor "UVD-C405" (manufactured by Ushio Electric Co., Ltd.). The integrated light quantity irradiated onto the photocurable adhesive sheets (Y1-Y14) through the resin member (X) was measured by installing a light meter on the opposite side of the side irradiated by the high-pressure mercury lamp. Thereafter, an irradiation test was implemented at a distance of 20 cm for 72 hr using a UVB fluorescent lamp (G15T8E, manufactured by Sankyo Electric Co., Ltd., irradiance: 70 μW/cm 2 ). According to the change ΔYI of the yellowness (YI) of the X/Y1-Y14 laminate before and after irradiation, the pass or fail is judged by the following evaluation criteria. ○ (good): ΔYI is less than 0.2 × (poor): ΔYI is 0.2 or more

(7)耐發泡可靠性 關於實施例及比較例中所獲得之X/Y積層體之各個，剝去殘存於Y面側之另一脫模膜，藉由手壓輥於其露出面貼著如下3種構件，分別評價貼合時之耐發泡可靠性。 又，將X/Y積層體切為各個構件之尺寸而使用。 具體的貼合結構係X/Y積層體/構件P(貼合結構P)、X/Y積層體/構件Q(貼合結構Q)及X/Y積層體/構件R(貼合結構R)此3種。 構件P：鈉鈣玻璃 54 mm×82 mm×厚度0.55 mm 構件Q：鈉鈣玻璃 100 mm×180 mm×厚度0.55 mm 構件R：PET膜 100 mm×180 mm×厚度100 μm (7) Reliability against foaming For each of the X/Y laminates obtained in the examples and comparative examples, the other release film remaining on the Y side was peeled off, and the following three members were attached to the exposed surface by a hand roller, and evaluated respectively Reliability against foaming during bonding. Also, the X/Y laminate was cut into the size of each member and used. The specific bonding structure system is X/Y laminate/component P (bonding structure P), X/Y laminate/component Q (bonding structure Q) and X/Y laminate/component R (bonding structure R) These 3 types. Component P: soda-lime glass 54 mm×82 mm×thickness 0.55 mm Component Q: soda-lime glass 100 mm×180 mm×thickness 0.55 mm Component R: PET film 100 mm×180 mm×thickness 100 μm

又，對於構件P(貼合結構P)，於溫度為60℃、氣壓為0.2 MPa、30分鐘之條件下實施高壓釜處理而進行最終貼著，對於構件Q及R(貼合結構Q及R)，於溫度為80℃、氣壓為0.2 MPa、30分鐘之條件下實施高壓釜處理而進行最終貼著。In addition, for the member P (bonding structure P), the temperature is 60 ℃, the air pressure is 0.2 MPa, 30 minutes under the conditions of autoclave treatment, and the final bonding is carried out. For the members Q and R (bonding structure Q and R ), under the conditions of a temperature of 80°C, an air pressure of 0.2 MPa, and a pressure of 0.2 MPa for 30 minutes, autoclave treatment was carried out for final sticking.

於上述最終貼著後，自樹脂構件(X)側，使用高壓水銀燈以405 nm下之累計光量成為3000(mJ/cm 2)之方式照射光，製作耐發泡可靠性評價樣品。 將上述評價樣品於85℃、85%R.H.之環境下暴露24 hr，將未發現發泡或剝離等外觀不良者判定為「○(良)」，將發現發泡或剝離者判定為「×(差)」。 又，將於貼合結構P或Q(單面玻璃構件)與貼合結構R(雙面樹脂構件)中未發現發泡或剝離等外觀不良者綜合判定為「◎(優)」，將於貼合結構P、Q及R之任意者中未發現發泡或剝離等外觀不良者綜合判定為「〇(良)」，將於貼合結構P、Q及R之全部中發現發泡或剝離者綜合判定為「×(差)」。 After the above-mentioned final bonding, light was irradiated from the resin member (X) side using a high-pressure mercury lamp so that the cumulative light intensity at 405 nm became 3000 (mJ/cm 2 ), and a foaming resistance reliability evaluation sample was produced. The above-mentioned evaluation samples were exposed to an environment of 85°C and 85%RH for 24 hours, and those with no appearance defects such as foaming or peeling were judged as "○ (good)", and those with foaming or peeling were judged as "×( Difference)". In addition, if no defects in appearance such as foaming or peeling are found in the bonded structure P or Q (one-sided glass member) and the bonded structure R (double-sided resin member), the overall judgment is "◎ (excellent)", and the In any of the bonded structures P, Q, and R, if no defects in appearance such as foaming or peeling are found, the overall judgment is "0 (good)", and foaming or peeling is found in all of the bonded structures P, Q, and R The comprehensive judgment was "× (poor)".

(8)長期保管後之霧度(與交聯劑之相容性之指標) 關於實施例及比較例中所獲得之光硬化性黏著片材Y之各個，於製作片材後經過2個月以上後，以藉由2枚鈉鈣玻璃(厚度為0.55 mm)夾住黏著片材Y的剝去脫模膜而露出之雙面之黏著面的方式進行貼合，使用高壓水銀燈以405 nm下之累計光量成為3000(mJ/cm 2)之方式照射光後，測定霧度值。 霧度值之測定係使用霧度計(日本電色工業公司製造、NDH5000)，依據JIS K7136而進行。 將霧度值未達0.5者判定為「○(良)」，將霧度值為0.5以上、未達1.0者判定為「△(尚可)」，將霧度值為1.0以上者判定為「×(差)」。 (8) Haze after long-term storage (indicator of compatibility with cross-linking agent) Regarding each of the photocurable adhesive sheets Y obtained in Examples and Comparative Examples, two months had elapsed after production of the sheets After the above, the two sides of the adhesive sheet Y, which are exposed by peeling off the release film, are sandwiched between two pieces of soda-lime glass (thickness 0.55 mm). Use a high-pressure mercury lamp at 405 nm After the light was irradiated so that the cumulative light quantity became 3000 (mJ/cm 2 ), the haze value was measured. The measurement of the haze value was carried out in accordance with JIS K7136 using a haze meter (manufactured by Nippon Denshoku Industries, Ltd., NDH5000). A haze value of less than 0.5 was judged as "○ (good)", a haze value of 0.5 or more and less than 1.0 was judged as "△ (fair)", and a haze value of 1.0 or more was judged " × (bad)".

(9)光硬化後之Tg 關於實施例及比較例中所獲得之150 μm之光硬化性黏著片材Y1～Y14(無脫模膜)之各個，預先以405 nm下之累計光量成為3000(mJ/cm 2)之方式照射光之後，將光硬化性黏著片材Y1～Y14分別8枚重疊而使其成為1200 μm，使用動態黏彈性測定裝置流變計(英弘精機股份有限公司製造之「MARS」)，於黏著治具為Φ25 mm平行板、應變為0.5%、頻率為1 Hz、升溫速度為3℃/min之條件進行測定，測定所獲得之Tanδ之值成為峰值之溫度作為Tg。 (9) Tg after photocuring For each of the 150 μm photocurable adhesive sheets Y1 to Y14 (without release film) obtained in Examples and Comparative Examples, the cumulative light intensity at 405 nm was set to 3000 ( mJ/cm 2 ) after irradiating light, eight photocurable adhesive sheets Y1 to Y14 were stacked to make it 1200 μm, and a dynamic viscoelasticity measuring device rheometer (manufactured by Yinghong Seiki Co., Ltd. MARS"), the measurement was carried out under the conditions that the adhesive fixture was a Φ25 mm parallel plate, the strain was 0.5%, the frequency was 1 Hz, and the heating rate was 3°C/min, and the temperature at which the obtained Tanδ value became the peak value was measured as Tg.

(10)黏度 關於實施例及比較例中所獲得之150 μm之光硬化性黏著片材Y1～Y14(無脫模膜)之各個，將其8枚重疊而使其成為1200 μm，使用動態黏彈性測定裝置流變計(英弘精機股份有限公司製造之「MARS」)，於黏著治具為Φ25mm平行板、應變為0.5%、頻率為1 Hz、升溫速度為3℃/min之條件下，測定70℃、100℃之各個的光硬化前之黏著片材之複黏度。 (10) Viscosity For each of the 150 μm photocurable adhesive sheets Y1 to Y14 (without release film) obtained in Examples and Comparative Examples, 8 sheets were stacked so as to have a thickness of 1200 μm, and flowed using a dynamic viscoelasticity measuring device. Variable gauge ("MARS" manufactured by Yinghong Seiki Co., Ltd.), under the conditions that the adhesion fixture is a Φ25mm parallel plate, the strain is 0.5%, the frequency is 1 Hz, and the heating rate is 3°C/min. Measure 70°C, 100°C The complex viscosity of the adhesive sheet before photohardening at each temperature of ℃.

(11)保管性 將剪裁為50 mm×50 mm見方之光硬化性黏著片材Y1～Y14夾於2枚100 mm×100 mm見方之厚度為100 μm之PET膜之間而製作積層體，於23℃、50%之環境下放置300小時後，目視觀察黏著劑是否自積層體溢出。 目視觀察所製作之積層體，將黏著劑整體溢出者判定為「×(差)」，將黏著劑僅自角部溢出者判定為「△(尚可)」，將黏著劑並不溢出者判定為「○(良)」。 (11) Custody The light-curable adhesive sheets Y1~Y14 cut into 50 mm×50 mm squares were sandwiched between two 100 mm×100 mm square PET films with a thickness of 100 μm to make a laminate, at 23°C, 50% After 300 hours in the environment, visually observe whether the adhesive overflows from the laminate. Visually observe the produced laminate, and judge "× (poor)" if the adhesive overflows as a whole, judge "△ (fair)" if the adhesive overflows only from the corner, and judge "△ (fair)" if the adhesive does not overflow It is "○ (good)".

[表1]       實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 比較例1 比較例2 比較例3 比較例4 樹脂構件X 光線透過率(%)  365 nm 0 0 0 0 0 0 0 0 0 0 0 0 0 45 光線透過率(%)  405 nm 83 83 83 83 83 83 83 83 83 83 83 83 83 91 光硬化性黏著片材Y之黏著劑層 光線透過率(%)  390 nm 77 77 77 86 76 76 76 76 76 76 91 91 90 77 光線透過率(%)  410 nm 90 90 90 92 88 88 88 88 88 88 92 92 91 90 凝膠分率X1(%) 0 0 0 45 0 0 0 0 0 0 0 0 88 0 動態儲存模數(G')(25℃)(Pa) 3.8×10 4 4.1×10 4 7.9×10 4 6.5×10 4 6.0×10 4 5.4×10 4 5.4×10 4 5.1×10 4 8.2×10 4 5.4×10 4 3.8×10 4 3.8×10 4 9.0×10 4 3.8×10 4 黏度(Pa.s)(70℃) 1050 1120 1139 1630 1405 1178 1290 1080 1930 1570 1018 1091 13700 1018 黏度(Pa.s)(100℃) 154 169 168 398 334 273 291 266 436 379 149 170 14100 149 保管性 △ △ △ 〇 △ △ △ △ 〇 〇 △ △ 〇 △ X/Y積層體 階差吸收性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 × 〇 405 nm光照射後之Tg(℃) 0 5 9 -1 21 37 40 43 4 21 -5 -5 0 -5 405 nm光照射後之凝膠分率X2(%) 78 82 88 74 78 80 82 86 69 74 0 0 90 81 X2-X1(%) 78 82 88 29 78 80 82 86 69 74 0 0 2 81 405 nm光照射後之動態儲存模數(G')(120℃)(Pa) 0.8×10 4 3.3×10 4 9.3×10 4 0.8×10 4 4.0×10 4 1.7×10 5 2.2×10 5 2.7×10 5 2.4×10 4 3.4×10 4 5.7×10 1 5.7×10 1 5.4×10 4 0.8×10 4 耐發泡可靠性 〇 〇 ◎ 〇 〇 〇 ◎ 〇 ◎ ◎ × × ◎ 〇 貼合結構P：X/Y/玻璃 尺寸：54×82 mm 〇 〇 〇 〇 - - - - - - × × 〇 〇 貼合結構Q：X/Y/玻璃 尺寸：100×180 mm 〇 〇 〇 〇 〇 〇 〇 × 〇 〇 × × 〇 〇 貼合結構R：X/Y/PET 尺寸：100×180 mm × × 〇 × × × 〇 〇 〇 〇 × × 〇 × 黃度(YI) 〇 1.85 〇 1.85 〇 1.85 〇 1.85 〇 1.85 〇 1.85 〇 1.85 〇 1.85 〇 1.85 〇 1.85 〇 1.82 〇 1.82 〇 1.90 〇 1.76 耐UV可靠性(ΔYI) 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 〇 0.2 × 1.65 長期保管後之霧度 〇 0.3 △ 0.6 〇 0.3 〇 0.3 〇 0.3 〇 0.3 〇 0.3 〇 0.3 〇 0.3 〇 0.3 〇 0.3 〇 0.3 〇 0.3 〇 0.3 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Resin ComponentsX Light transmittance (%) 365 nm 0 0 0 0 0 0 0 0 0 0 0 0 0 45 Light transmittance (%) 405 nm 83 83 83 83 83 83 83 83 83 83 83 83 83 91 Adhesive layer of photocurable adhesive sheet Y Light transmittance (%) 390 nm 77 77 77 86 76 76 76 76 76 76 91 91 90 77 Light transmittance (%) 410 nm 90 90 90 92 88 88 88 88 88 88 92 92 91 90 Gel fraction X1(%) 0 0 0 45 0 0 0 0 0 0 0 0 88 0 Dynamic storage modulus(G')(25℃)(Pa) 3.8×10 4 4.1×10 4 7.9×10 4 6.5×10 4 6.0×10 4 5.4×10 4 5.4×10 4 5.1×10 4 8.2×10 4 5.4×10 4 3.8×10 4 3.8×10 4 9.0×10 4 3.8×10 4 Viscosity(Pa.s)(70℃) 1050 1120 1139 1630 1405 1178 1290 1080 1930 1570 1018 1091 13700 1018 Viscosity(Pa.s)(100℃) 154 169 168 398 334 273 291 266 436 379 149 170 14100 149 Custody △ △ △ 〇 △ △ △ △ 〇 〇 △ △ 〇 △ X/Y laminate Step absorbency 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 x 〇 Tg(°C) after 405 nm light irradiation 0 5 9 -1 twenty one 37 40 43 4 twenty one -5 -5 0 -5 Gel fraction X2(%) after 405 nm light irradiation 78 82 88 74 78 80 82 86 69 74 0 0 90 81 X2-X1(%) 78 82 88 29 78 80 82 86 69 74 0 0 2 81 Dynamic storage modulus after 405 nm light irradiation (G')(120℃)(Pa) 0.8×10 4 3.3×10 4 9.3×10 4 0.8×10 4 4.0×10 4 1.7×10 5 2.2×10 5 2.7×10 5 2.4×10 4 3.4×10 4 5.7×10 1 5.7×10 1 5.4×10 4 0.8×10 4 Reliability against foaming 〇 〇 ◎ 〇 〇 〇 ◎ 〇 ◎ ◎ x x ◎ 〇 Fitting structure P: X/Y/glass size: 54×82 mm 〇 〇 〇 〇 - - - - - - x x 〇 〇 Fitting structure Q: X/Y/glass size: 100×180 mm 〇 〇 〇 〇 〇 〇 〇 x 〇 〇 x x 〇 〇 Fitting structure R: X/Y/PET Size: 100×180 mm x x 〇 x x x 〇 〇 〇 〇 x x 〇 x Yellowness (YI) 〇1.85 〇1.85 〇1.85 〇1.85 〇1.85 〇1.85 〇1.85 〇1.85 〇1.85 〇1.85 〇1.82 〇1.82 〇1.90 〇1.76 UV Reliability (ΔYI) 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 〇0.2 × 1.65 Haze after long-term storage 〇0.3 △ 0.6 〇0.3 〇0.3 〇0.3 〇0.3 〇0.3 〇0.3 〇0.3 〇0.3 〇0.3 〇0.3 〇0.3 〇0.3

＜考察＞ 實施例1～10之樹脂構件(X)/光硬化性黏著片材(Y1～Y10)之光硬化性黏著片材積層體(X/Y1～Y10積層體)於自樹脂構件(X)側以波長405 nm下之累計光量成為3000(mJ/cm 2)之方式而照射光時，光硬化性黏著片材Y1～Y10可充分硬化至凝膠分率差提高10%以上，動態儲存模數(G')於120℃、1 Hz下保持0.7×10 4Pa以上之高溫凝聚力，因此獲得良好之耐發泡可靠性。尤其是觸控感測器於假定玻璃感測器之情形的試驗中獲得良好之耐發泡可靠性。 其中，實施例3、7、9、10之動態儲存模數(G')於120℃、1 Hz下保持2.0×10 4Pa以上之高溫凝聚力，因此觸控感測器於假定膜感測器之情形的試驗中亦獲得良好之耐發泡可靠性。 <Review> The photocurable adhesive sheet laminate (X/Y1~Y10 laminate) of the resin member (X)/photocurable adhesive sheet (Y1~Y10) in Examples 1 to 10 was separated from the resin member (X ) side is irradiated with light so that the cumulative light intensity at a wavelength of 405 nm becomes 3000 (mJ/cm 2 ), the photocurable adhesive sheets Y1~Y10 can be fully cured until the gel fraction difference increases by more than 10%, and dynamic storage The modulus (G') maintains a high-temperature cohesion force above 0.7×10 4 Pa at 120°C and 1 Hz, thus obtaining good reliability against foaming. Especially the touch sensor obtained good reliability against foaming in tests assuming the case of a glass sensor. Among them, the dynamic storage modulus (G') of Examples 3, 7, 9, and 10 maintains a high-temperature cohesion of more than 2.0×10 4 Pa at 120°C and 1 Hz, so the touch sensor is used as a hypothetical film sensor Good foaming resistance reliability was also obtained in the test of the case.

又，實施例8雖然觸控感測器於假定膜感測器之情形的試驗中獲得良好之耐發泡可靠性，但觸控感測器於假定玻璃感測器之情形的試驗中產生玻璃之剝落。認為其原因在於：動態儲存模數(G')於120℃、1 Hz下變得過高，黏性、接著性能降低。 再者，實施例2由於構成(甲基)丙烯酸酯(共)聚合物(a)之親水性單體之含量為10質量份以下，因此於長期保管中進行相分離，因此長期保管後之霧度為「△(尚可)」。 實施例1～10均階差吸收性良好，對於具有印刷階差之罩蓋構件，亦根據觸控感測器之種類而可耐實用。 Also, in Example 8, although the touch sensor obtained good reliability against foaming in the test assuming a film sensor, the touch sensor produced glass in the test assuming a glass sensor. peeling off. The reason for this is considered to be that the dynamic storage modulus (G') becomes too high at 120° C. and 1 Hz, and the viscosity and adhesion properties decrease. Furthermore, in Example 2, since the content of the hydrophilic monomer constituting the (meth)acrylate (co)polymer (a) is 10 parts by mass or less, phase separation occurs during long-term storage, so the fog after long-term storage The degree is "△ (acceptable)". Examples 1 to 10 have good average level difference absorption, and are practical for cover members with printed steps, depending on the type of touch sensor.

又，實施例4、9、10之黏度(70℃)高達1.5 kPa・s以上，因此即使於長期保管後亦未發現糊溢出，保管性優異。In addition, the viscosity (70° C.) of Examples 4, 9, and 10 was as high as 1.5 kPa·s or more, so even after long-term storage, the paste did not overflow, and the storage properties were excellent.

比較例1及2之光硬化性黏著片材Y11及Y12之波長390 nm下之光線透過率(%)高達90%以上，自樹脂構件(X)側以波長405 nm下之累計光量成為3000(mJ/cm 2)之方式照射光時，由於光起始劑吸收光而進行激發及硬化(交聯)反應並不充分，因此無法使黏著層(Y)充分硬化，於耐發泡可靠性試驗時產生氣泡。 The light transmittance (%) at a wavelength of 390 nm of the photocurable adhesive sheets Y11 and Y12 of Comparative Examples 1 and 2 was as high as 90% or more, and the cumulative light intensity at a wavelength of 405 nm from the resin member (X) side was 3000 ( mJ/cm 2 ) when irradiated with light, the excitation and curing (crosslinking) reaction is not sufficient due to the absorption of light by the photoinitiator, so the adhesive layer (Y) cannot be fully cured. In the foaming resistance reliability test Bubbles are generated.

比較例3之光硬化性黏著片材Y13之凝膠分率為88%，動態儲存模數(G')(25℃)高達1.1×10 5Pa，因此階差吸收性差，產生氣泡。 比較例4之樹脂構件(X)不含紫外線吸收劑，波長365 nm下之光線透過率高達45%，因此進行耐UV可靠性試驗中之黃變。 The photocurable adhesive sheet Y13 of Comparative Example 3 has a gel fraction of 88% and a dynamic storage modulus (G') (25°C) as high as 1.1×10 5 Pa, so the step absorption is poor and air bubbles are generated. The resin member (X) of Comparative Example 4 does not contain ultraviolet absorbers, and the light transmittance at a wavelength of 365 nm is as high as 45%, so it is subject to yellowing in the UV reliability test.

Claims (17)

一種光硬化性黏著片材，其特徵在於包含具有以下(1)～(3)之所有特性之黏著層(Y)： (1)凝膠分率(稱為「光照射前凝膠分率X1」)處於0～60%之範圍內； (2)波長390 nm下之光線透過率為89%以下，且波長410 nm下之光線透過率為80%以上； (3)於溫度25℃、頻率1 Hz下，儲存模數(G')為0.9×10 5Pa以下； (4)具有藉由照射波長405 nm之光而硬化之光硬化性，照射波長405 nm下之累計光量為3000(mJ/cm 2)之光後之儲存模數(G')於溫度120℃、頻率1 Hz下為0.7×10 4Pa以上。 A photocurable adhesive sheet characterized by comprising an adhesive layer (Y) having all the following characteristics (1) to (3): (1) Gel fraction (referred to as "gel fraction before light irradiation X1 ”) in the range of 0 to 60%; (2) The light transmittance at a wavelength of 390 nm is below 89%, and the light transmittance at a wavelength of 410 nm is above 80%; (3) At a temperature of 25°C and a frequency of At 1 Hz, the storage modulus (G') is 0.9×10 5 Pa or less; (4) It has photocurability by irradiating light with a wavelength of 405 nm, and the cumulative light amount at 405 nm is 3000 (mJ) /cm 2 ) storage modulus (G') at a temperature of 120°C and a frequency of 1 Hz is above 0.7×10 4 Pa. 如請求項1之光硬化性黏著片材，其中上述(4)中之光硬化性係於照射波長405 nm之光時，凝膠分率之差提高10%以上之光硬化性。For example, the photocurable adhesive sheet according to claim 1, wherein the photocurability in (4) above refers to the photocurability in which the difference in gel fraction increases by more than 10% when irradiated with light having a wavelength of 405 nm. 如請求項1之光硬化性黏著片材，其中上述(4)之光硬化性，係對具有上述光硬化性黏著片材、與波長365 nm下之光線透過率為10%以下且波長405 nm下之光線透過率為60%以上之樹脂構件(X)積層而成之構成的積層體，自樹脂構件(X)側照射波長405 nm之光時，凝膠分率之差提高30%以上之光硬化性。Such as the photocurable adhesive sheet of claim 1, wherein the photocurable property of the above (4) refers to the photocurable adhesive sheet having the above photocurable adhesive sheet, and the light transmittance at a wavelength of 365 nm is 10% or less and the wavelength is 405 nm When the laminated body formed by laminating resin members (X) with a light transmittance of 60% or more is irradiated from the side of the resin member (X) with a wavelength of 405 nm, the difference in gel fraction increases by 30% or more Light hardening. 如請求項1之光硬化性黏著片材，其具有如下之光硬化性：於照射波長405 nm下之累計光量為3000(mJ/cm 2)之光時，光照射前之凝膠分率(光照射前凝膠分率X1)與光照射後之凝膠分率(稱為「光照射後凝膠分率X2」)之差(光照射後凝膠分率X2－光照射前凝膠分率X1)成為10%以上。 For example, the light-curable adhesive sheet of claim 1 has the following light-curability: when the cumulative light intensity at a wavelength of 405 nm is 3000 (mJ/cm 2 ), the gel fraction before light irradiation ( The difference between the gel fraction before light irradiation X1) and the gel fraction after light irradiation (referred to as "gel fraction after light irradiation X2") (gel fraction after light irradiation X2 - gel fraction before light irradiation The ratio X1) becomes 10% or more. 如請求項1之光硬化性黏著片材，其具如下之光硬化性：對具有上述光硬化性黏著片材、與波長365 nm下之光線透過率為10%以下且波長405 nm下之光線透過率為60%以上之樹脂構件(X)積層而成之構成的積層體，自上述樹脂構件(X)側照射波長405 nm下之累計光量為3000(mJ/cm 2)之光時，光照射前之凝膠分率(光照射前凝膠分率X1)與光照射後之凝膠分率(稱為「光照射後凝膠分率X2」)之差(光照射後凝膠分率X2－光照射前凝膠分率X1)成為30%以上。 Such as the photocurable adhesive sheet of claim 1, which has the following photocurability: for light with a light transmittance of 10% or less at a wavelength of 365 nm and light at a wavelength of 405 nm When a laminate composed of laminated resin members (X) with a transmittance of 60% or more is irradiated from the resin member (X) side with a cumulative light intensity of 3000 (mJ/cm 2 ) at a wavelength of 405 nm, the light The difference between the gel fraction before irradiation (gel fraction before light irradiation X1) and the gel fraction after light irradiation (referred to as "gel fraction after light irradiation X2") (gel fraction after light irradiation X2—The gel fraction X1) before light irradiation becomes 30% or more. 如請求項1之光硬化性黏著片材，其中上述光硬化性黏著片材之凝膠分率為0～50%以下。The photocurable adhesive sheet according to claim 1, wherein the gel fraction of the photocurable adhesive sheet is 0% to 50% or less. 如請求項1之光硬化性黏著片材，其中上述光硬化性黏著片材藉由光照射而暫時硬化。The photocurable adhesive sheet according to claim 1, wherein the above photocurable adhesive sheet is temporarily cured by light irradiation. 如請求項1之光硬化性黏著片材，其中上述黏著層(Y)係由含有(甲基)丙烯酸酯(共)聚合物及可見光起始劑的黏著劑組合物所形成。The light-curable adhesive sheet according to claim 1, wherein the above-mentioned adhesive layer (Y) is formed of an adhesive composition containing a (meth)acrylate (co)polymer and a visible light initiator. 如請求項8之光硬化性黏著片材，其中上述黏著層(Y)含有矽烷偶合劑。The light-curable adhesive sheet according to claim 8, wherein the above-mentioned adhesive layer (Y) contains a silane coupling agent. 如請求項8之光硬化性黏著片材，其中上述黏著劑組合物含有交聯劑。The photocurable adhesive sheet according to claim 8, wherein the adhesive composition contains a crosslinking agent. 如請求項10之光硬化性黏著片材，其中上述交聯劑與上述(甲基)丙烯酸酯(共)聚合物化學鍵結。The photocurable adhesive sheet according to claim 10, wherein the above-mentioned crosslinking agent is chemically bonded to the above-mentioned (meth)acrylate (co)polymer. 如請求項10之光硬化性黏著片材，其中上述交聯劑係多官能(甲基)丙烯酸酯。The light-curable adhesive sheet according to claim 10, wherein the above-mentioned crosslinking agent is a multifunctional (meth)acrylate. 如請求項8之光硬化性黏著片材，其中上述(甲基)丙烯酸酯(共)聚合物具有活性能量線交聯性結構部位。The photocurable adhesive sheet according to claim 8, wherein the (meth)acrylate (co)polymer has an active energy ray crosslinkable structural site. 如請求項8之光硬化性黏著片材，其中上述可見光起始劑於波長405 nm之吸光係數為10 mL/(g・/cm)以上。The photocurable adhesive sheet as claimed in item 8, wherein the visible light initiator has an absorption coefficient of 10 mL/(g·/cm) or more at a wavelength of 405 nm. 如請求項8之光硬化性黏著片材，其中上述可見光起始劑為奪氫型可見光起始劑。The photocurable adhesive sheet according to claim 8, wherein the visible light initiator is a hydrogen abstraction type visible light initiator. 如請求項1之光硬化性黏著片材，其中上述光硬化性黏著片材之凝膠分率為0～50%以下。The photocurable adhesive sheet according to claim 1, wherein the gel fraction of the photocurable adhesive sheet is 0% to 50% or less. 如請求項1之光硬化性黏著片材，其中上述光硬化性黏著片材藉由光照射而暫時硬化。The photocurable adhesive sheet according to claim 1, wherein the above photocurable adhesive sheet is temporarily cured by light irradiation.
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