TWI792195B - Photocurable adhesive sheet, adhesive sheet, and image display device - Google Patents

Photocurable adhesive sheet, adhesive sheet, and image display device Download PDF

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TWI792195B
TWI792195B TW110106505A TW110106505A TWI792195B TW I792195 B TWI792195 B TW I792195B TW 110106505 A TW110106505 A TW 110106505A TW 110106505 A TW110106505 A TW 110106505A TW I792195 B TWI792195 B TW I792195B
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meth
acrylate
adhesive sheet
adhesive
sheet
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TW110106505A
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Chinese (zh)
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TW202126775A (en
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新美可保留
山本亮太
內田貴久
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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本發明提供一種可追隨貼合面之階差部而填充至各角落，即使長時間光照射亦不會降低接著可靠性，可容易地進行貼合作業之黏著片材。因此，本發明提出一種黏著片材，其特徵在於：其係由含有(甲基)丙烯酸系共聚物(A)、交聯劑(B)及光聚合起始劑(C)之樹脂組合物形成之光硬化前之黏著片材，並且具有光硬化性，且具備以下之(1)及(2)之特性。 (1)於0～40℃下可保持形狀，且顯示自黏著性。 (2)於70～100℃下黏度顯示為100～3000 Pa・s。The present invention provides an adhesive sheet that can follow the step of the bonding surface and fill to every corner, and can easily carry out the bonding operation without reducing the bonding reliability even if it is exposed to light for a long time. Therefore, the present invention proposes an adhesive sheet, which is characterized in that: it is formed from a resin composition containing a (meth)acrylic copolymer (A), a crosslinking agent (B) and a photopolymerization initiator (C) Adhesive sheet before light hardening, and has light hardening, and has the following characteristics of (1) and (2). (1) It can maintain its shape at 0-40°C and exhibit self-adhesiveness. (2) Viscosity at 70-100°C is 100-3000 Pa·s.

Description

光硬化型黏著片材、黏著片材及圖像顯示裝置Photocurable adhesive sheet, adhesive sheet, and image display device

本發明係關於一種光硬化前之光硬化型黏著片材及將其光硬化而成之黏著片材。詳細而言，係關於一種可較佳用作如電腦、移動終端(PDA)、遊戲機、電視(TV)、汽車導航、觸控面板、手寫板等之圖像顯示裝置及其構成構件之黏著片材。 The present invention relates to a photocurable adhesive sheet before photocuring and an adhesive sheet obtained by photocuring it. In detail, it relates to an image display device that can be preferably used as a computer, mobile terminal (PDA), game console, television (TV), car navigation, touch panel, tablet, etc. and the adhesion of its constituent components Sheet.

近年來，為提高圖像顯示裝置之視認性，將液晶顯示器(LCD)、電漿顯示器(PDP)或電致發光顯示器(ELD)等之圖像顯示面板與配置於其前方側(認性側)之保護面板或觸控面板構件之間之空隙以黏著片材或液狀之接著劑等填充，從而抑制入射光或來自顯示圖像之出射光於空氣層界面之反射。 In recent years, in order to improve the visibility of image display devices, image display panels such as liquid crystal displays (LCDs), plasma displays (PDPs) or electroluminescent displays (ELDs) are arranged on the front side (recognition side) ) between the protective panel or the touch panel components are filled with an adhesive sheet or a liquid adhesive to suppress the reflection of incident light or outgoing light from a display image at the interface of the air layer.

作為使用黏著劑填充此種圖像顯示裝置用構成構件間之空隙的方法，已知將含有紫外線硬化性樹脂之液狀之接著樹脂組合物填充至該空隙後，照射紫外線而使之硬化的方法(專利文獻1)。 As a method of filling the gaps between constituent members of such an image display device with an adhesive, there is known a method of filling the gaps with a liquid adhesive resin composition containing an ultraviolet curable resin and then irradiating it with ultraviolet rays to harden it. (Patent Document 1).

又，亦已知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，作為具備圖像顯示裝置構成構件積層於黏著片材之至少單側而成之構成的圖像顯示裝置構成用積層體之製造方法，揭示有藉由紫外線將一次交聯之黏著片材貼合於圖像顯示裝置構成構件後，介隔圖像顯示裝置構成構件對黏著片材照射紫外線使之二次硬化的方法。 Moreover, the method of filling the gap between the constituent members for image display devices using an adhesive sheet is also known. For example, in Patent Document 2, as a method for producing a laminate for image display device constituting a structure in which image display device constituent members are laminated on at least one side of an adhesive sheet, primary crosslinking by ultraviolet rays is disclosed. After the adhesive sheet is bonded to the components of the image display device, the adhesive sheet is irradiated with ultraviolet rays through the components of the image display device to make it secondary harden.

又，於專利文獻3中揭示有：使用有以重量平均分子量為2萬至10萬 之(甲基)丙烯酸胺基甲酸酯為主成分之於25℃下之損耗正切未達1之熱熔型接著組合物的片材。 Also, it is disclosed in Patent Document 3 that the use of a weight average molecular weight of 20,000 to 100,000 A sheet of a hot-melt adhesive composition whose loss tangent at 25°C is less than 1 with (meth)urethane acrylate as the main component.

進而於專利文獻4中揭示有：含有使含有具有交聯性官能基之(甲基)丙烯酸系單體及特定之大分子單體之單體共聚合而獲得之(甲基)丙烯酸系聚合物、及交聯劑之適合於觸控面板之貼合的黏著劑層。 Furthermore, Patent Document 4 discloses a (meth)acrylic polymer obtained by copolymerizing a monomer containing a (meth)acrylic monomer having a crosslinkable functional group and a specific macromonomer. , and a cross-linking agent suitable for bonding the adhesive layer of the touch panel.

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Document]

[專利文獻1]國際公開2010/027041號公報 [Patent Document 1] International Publication No. 2010/027041

[專利文獻2]國際公開2012/032995號公報 [Patent Document 2] International Publication No. 2012/032995

[專利文獻3]國際公開2010/038366號公報 [Patent Document 3] International Publication No. 2010/038366

[專利文獻4]日本專利特開2013-18227號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2013-18227

[專利文獻5]日本專利特開2012-184423號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2012-184423

於以行動電話或移動終端等為中心之圖像顯示裝置之領域中，除薄化、高精密化外，設計之多樣化亦不斷發展，伴隨於此而產生了新課題。例如，通常於表面保護面板之周緣部印刷有框狀之黑色隱蔽部。因此，對用以貼合具備此種印刷部之構成構件之黏著片材要求具有可追隨印刷階差而填充至各角落之印刷階差追隨性。 In the field of image display devices centered on mobile phones and mobile terminals, in addition to thinning and high precision, the diversification of design is also progressing, and new issues have arisen along with it. For example, a frame-shaped black concealed portion is usually printed on the periphery of the surface protection panel. Therefore, an adhesive sheet for bonding components having such a printed portion is required to have printing level followability that can follow the printing level and fill to every corner.

又，觸控面板等圖像顯示裝置正被廣範圍使用，伴隨於此，對用於圖像顯示裝置構成用積層體之黏著片材要求具有即使長時間暴露於照明或太陽光等光下亦不會降低性能之接著可靠性。 In addition, image display devices such as touch panels are widely used. Along with this, adhesive sheets used in laminates for image display devices are required to have properties that are durable even when exposed to light such as lighting or sunlight for a long time. Will not reduce the reliability of performance.

本發明之第1目的在於提供一種新穎之黏著片材，其係於光硬化前之 狀態下可追隨貼合面之階差部而填充至各角落，並且於光硬化後之狀態下即使長時間光照射亦不會降低接著可靠性者，從而可容易地進行貼合作業。 The first object of the present invention is to provide a novel adhesive sheet which is pre-cured by light In this state, it can follow the step of the bonding surface and fill to every corner, and even if it is exposed to light for a long time in the state after photohardening, the bonding reliability will not be reduced, so that the bonding operation can be easily performed.

本發明之第2目的在於提供一種新穎之黏著片材，其即使於貼合於貼合面內具有印刷部等不透光部與透光部之圖像顯示裝置用構成構件之情形時，亦可獲得對階差部等之追隨性或表面平坦性，於不透光部中亦不會產生應變或變形，並且可具有較高之凝集力而將被黏著物彼此牢固地貼合，進而，即使於高溫高濕下等嚴酷之環境下，亦可使露出之黏著面不發黏。 The second object of the present invention is to provide a novel adhesive sheet, which can be adhered to a constituent member for an image display device having an opaque portion such as a printed portion and a light-transmitting portion in the bonding surface. It can obtain the followability or surface flatness of the step part, etc., and there will be no strain or deformation in the opaque part, and it can have a high cohesive force to firmly bond the adherends to each other. Furthermore, Even in harsh environments such as high temperature and high humidity, the exposed adhesive surface can be kept from sticking.

本發明之第3目的在於提供一種黏著片材，其係可光交聯者，其於光交聯前亦具有黏著性，貼合時黏著材不會過於流動而使黏著劑樹脂組合物溢出或潰縮，進而光交聯後可獲得充分之硬度。 The third object of the present invention is to provide an adhesive sheet, which is photocrosslinkable and has adhesiveness before photocrosslinking, so that the adhesive will not flow too much and cause the adhesive resin composition to overflow or Crushing, and then photo-crosslinking can obtain sufficient hardness.

本發明為達成第1目的而提出上述之黏著片材，其特徵在於：其係由含有(甲基)丙烯酸系共聚物(A)、交聯劑(B)及光聚合起始劑(C)之樹脂組合物形成之光硬化前之黏著片材，並且具有光硬化性，且具備以下之(1)及(2)之特性。 In order to achieve the first object, the present invention proposes the above-mentioned adhesive sheet, which is characterized in that: it is composed of (meth)acrylic copolymer (A), crosslinking agent (B) and photopolymerization initiator (C) The adhesive sheet formed by the resin composition before photocuring is photocurable and has the following characteristics (1) and (2).

(1)於0~40℃下可保持形狀，且顯示自黏著性。 (1) It can maintain its shape at 0~40℃ and shows self-adhesiveness.

(2)於70~100℃下黏度顯示為100~3000Pa‧s。 (2) The viscosity shows 100~3000Pa‧s at 70~100℃.

本發明為達成第1目的而提出之上述黏著片材於0~40℃之室溫狀態即常態下可保持片材形狀，且可顯示自黏著性，因此容易操作，並且可高效進行貼合作業，例如可容易地進行貼著時之定位等。又，若成為70~100℃，則黏度成為100~3000Pa‧s，顯示熱熔性，因此例如可追隨印刷階差等凹凸部而填充黏著劑。進而，光硬化後表現較高之凝集力，例如 即使長時間光照射後亦發揮優異之耐發泡性，即使長時間光照射亦不會降低接著可靠性。因此，本發明提出之光硬化型黏著片材可較佳地用作如電腦、移動終端(PDA)、遊戲機、電視(TV)、汽車導航、觸控面板、手寫板等之圖像顯示裝置之構成構件。 The above-mentioned adhesive sheet proposed by the present invention to achieve the first object can maintain the shape of the sheet at a room temperature of 0 to 40°C, that is, under normal conditions, and can exhibit self-adhesiveness, so it is easy to handle and can be bonded efficiently. , For example, positioning when sticking can be easily performed. In addition, when the temperature is 70-100°C, the viscosity becomes 100-3000 Pa‧s, showing heat-fusibility, so for example, it is possible to fill the adhesive with the irregularities such as printing steps. Furthermore, it exhibits higher cohesion after photohardening, such as It exhibits excellent foaming resistance even after long-term light exposure, and will not reduce bonding reliability even after long-term light exposure. Therefore, the photocurable adhesive sheet proposed by the present invention can be preferably used as an image display device such as a computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation, a touch panel, a tablet, etc. the constituent components.

本發明為達成第2目的而提出一種黏著片材，其特徵在於：其係含有(甲基)丙烯酸系共聚物(A)且經光硬化而成者，並且具有凝膠分率未達1%之片材部與凝膠分率為40%以上之片材部。 In order to achieve the second object, the present invention proposes an adhesive sheet, which is characterized in that it contains a (meth)acrylic copolymer (A) and is light-cured, and has a gel fraction of less than 1%. The sheet part and the sheet part with a gel fraction of 40% or more.

本發明為達成第2目的而提出之上述黏著片材藉由凝膠分率未達1%之片材部，可獲得對階差部等之追隨性或表面平坦性，可緩和片材內之應變或變形，另一方面藉由凝膠分率為40%以上之片材部，不僅可使黏著面不發黏，亦可具有較高之凝集力而將被黏著物彼此牢固地接著。 The above-mentioned adhesive sheet proposed by the present invention to achieve the second object can obtain followability or surface flatness to the step portion and the like by the sheet portion with a gel fraction of less than 1%, and can alleviate the stress in the sheet. Strain or deformation. On the other hand, the sheet with a gel fraction of 40% or more can not only make the adhesive surface not sticky, but also have a high cohesive force to firmly bond the adherends to each other.

因此，例如，即使於貼合於貼合面內具有印刷部等不透光部與透光部之圖像顯示裝置用構成構件之情形時，亦可作為黏著片材整體而獲得對印刷階差部之追隨性或表面平坦性，於不透光部中亦不會產生應變或變形，進而，可具有較高之凝集力而將被黏著物彼此牢固地貼合。又，藉由將露出之黏著面作為硬質部，即使於高溫高濕下等嚴酷之環境下，亦可使露出之黏著面不發黏。 Therefore, for example, even in the case of bonding to a constituent member for an image display device having an opaque portion such as a printed portion and a light-transmitting portion in the bonding surface, it is possible to obtain a print level difference as a whole of the adhesive sheet. The followability or surface flatness of the part does not cause strain or deformation in the opaque part, and furthermore, it can have a high cohesive force to firmly bond the adherends to each other. Also, by using the exposed adhesive surface as a hard portion, the exposed adhesive surface can be kept from sticking even under severe environments such as high temperature and high humidity.

本發明為達成第3目的而提出一種黏著片材，其特徵在於：其係包含含有(甲基)丙烯酸系共聚物(A)100質量份、交聯劑(B)0.5~20質量份及光聚合起始劑(C)0.1~5質量份之樹脂組合物者，並且光交聯前之拉伸彈性模數(X1)與光交聯後之拉伸彈性模數(X2)之比(X1/X2)成為3以上。 In order to achieve the third object, the present invention proposes an adhesive sheet, which is characterized in that it contains 100 parts by mass of (meth)acrylic copolymer (A), 0.5 to 20 parts by mass of crosslinking agent (B) and light A polymerization initiator (C) of 0.1 to 5 parts by mass of the resin composition, and the ratio of the tensile modulus of elasticity (X1) before photocrosslinking to the tensile modulus of elasticity (X2) after photocrosslinking (X1 /X2) becomes 3 or more.

本發明為達成第3目的而提出之上述黏著片材具有光交聯前後之拉伸彈性模數(X1)之差明顯較大之特徵，即使於光交聯前亦具有黏著性，貼合 時黏著材不會過於流動而使黏著劑樹脂組合物溢出或潰縮，進而光交聯後可獲得充分之硬度。 The above-mentioned adhesive sheet proposed by the present invention to achieve the third object has the characteristic that the difference in tensile elastic modulus (X1) before and after photocrosslinking is significantly large, and it has adhesiveness even before photocrosslinking When the adhesive material does not flow too much, the adhesive resin composition will overflow or collapse, and sufficient hardness can be obtained after photo-crosslinking.

2:黏著片材 2: Adhesive sheet

21:片材面 21: sheet surface

22:軟質部 22: soft part

23:硬質部 23: Hard part

24:端面 24: end face

25:脫模膜 25: Release film

圖1係表示本發明之黏著片材之一例之俯視立體圖。 Fig. 1 is a top perspective view showing an example of the adhesive sheet of the present invention.

圖2係表示本發明之黏著片材之另一例之俯視立體圖。 Fig. 2 is a top perspective view showing another example of the adhesive sheet of the present invention.

圖3(A)、(B)係表示本發明之黏著片材之另外一例之俯視立體圖。 3(A) and (B) are top perspective views showing another example of the adhesive sheet of the present invention.

圖4係具備圖3(B)所示之黏著片材之黏著片材積層體之一例之圖，(A)係其俯視立體圖，(B)係剖面圖。 Fig. 4 is a diagram of an example of an adhesive sheet laminate provided with the adhesive sheet shown in Fig. 3(B), (A) is a top perspective view thereof, and (B) is a cross-sectional view.

圖5係表示本發明之黏著片材之另外一例之俯視立體圖。 Fig. 5 is a top perspective view showing another example of the adhesive sheet of the present invention.

以下，對本發明之實施形態之一例進行詳細說明。但本案發明並不限定於下述實施形態。 Hereinafter, an example of an embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[本黏著片材1] [this adhesive sheet 1]

本發明之實施形態之一例之黏著片材(稱為「本黏著片材1」)之特徵在於：其係由含有(甲基)丙烯酸系共聚物(1-A)、交聯劑(1-B)及光聚合起始劑(1-C)之樹脂組合物(稱為「本黏著劑組合物1」)形成之光硬化前之黏著片材，並且具有光硬化性，且具備以下之(1)及(2)之特性。 The adhesive sheet (referred to as "this adhesive sheet 1"), which is an example of the embodiment of the present invention, is characterized in that it is made of a (meth)acrylic copolymer (1-A), a crosslinking agent (1- B) and the resin composition of the photopolymerization initiator (1-C) (referred to as "this adhesive composition 1") is an adhesive sheet before photocuring, and has photocurability, and has the following ( 1) and (2) characteristics.

(1)於0~40℃下可保持形狀，且顯示自黏著性。 (1) It can maintain its shape at 0~40℃ and shows self-adhesiveness.

(2)於70~100℃下黏度顯示為100~3000Pa‧s。 (2) The viscosity shows 100~3000Pa‧s at 70~100℃.

此處，所謂「光硬化前之黏著片材」，若為具有光硬化性之黏著片材即可，並非僅指完全未經過光硬化過程之黏著片材。即，例如若為經過光硬化步驟，可進而光硬化並且可起到本發明之效果的黏著片材，則包含於本發明中。 Here, the so-called "adhesive sheet before photocuring" may be a photocurable adhesive sheet, and does not only refer to an adhesive sheet that has not undergone photocuring at all. That is, for example, if it is an adhesive sheet that can be further photocured through a photocuring step and can exhibit the effect of the present invention, it is included in the present invention.

本黏著片材1於光硬化前之狀態下具備上述(1)及(2)之特性，因此於0~40℃之室溫狀態，換言之可於常態下保持片狀，並且具備自黏著性即於原本之狀態下發揮黏著力之性質。進而，表現出加熱時發生熔融或流動之熱熔性，光硬化後發揮優異之凝集力，例如長時間光照射後可顯示耐發泡性。 This adhesive sheet 1 has the characteristics of (1) and (2) above in the state before photohardening, so it can maintain the sheet shape at room temperature of 0~40°C, in other words, it has self-adhesiveness. In the original state to play the nature of adhesive force. Furthermore, it exhibits hot-melt properties that melt or flow when heated, exhibits excellent cohesive force after photohardening, and exhibits foaming resistance after long-term light irradiation, for example.

<室溫狀態下之特性> <Characteristics at room temperature>

本黏著片材1具有(1)於光硬化前之狀態下，於0~40℃之室溫狀態下可保持片材形狀，且顯示自黏著性的特徵。 The present adhesive sheet 1 has (1) the characteristics of maintaining the shape of the sheet at a room temperature of 0-40° C. and exhibiting self-adhesiveness in the state before photohardening.

如此若於室溫狀態，即常態下可保持片狀，則操作容易，並且貼合構件之生產性尤其優異。進而，若於常態下顯示自黏著性，則例如易於進行貼著時之定位，貼合作業非常便利。 In this way, if the sheet shape can be maintained at room temperature, that is, under normal conditions, handling is easy, and the productivity of laminated members is particularly excellent. Furthermore, if self-adhesiveness is exhibited under normal conditions, for example, positioning at the time of sticking is easy, and the sticking operation is very convenient.

為獲得此種特性，例如自下述黏著劑組合物(1-I)或(1-II)製造本黏著片材1即可。但並不限定於此。 In order to obtain such a characteristic, what is necessary is just to manufacture this adhesive sheet 1 from the following adhesive composition (1-I) or (1-II), for example. But it is not limited to this.

(23℃、40%RH下之180°剝離力) (180°peel force at 23°C, 40%RH)

本黏著片材1可具有以下之(6)之特徵。即(6)壓接於鈉鈣玻璃上，於23℃、40%RH下，以剝離角180°、剝離速度60mm/min，自上述鈉鈣玻璃剝離本黏著片材1時之對玻璃之180°剝離力可為3N/cm以上。藉由使23℃下之180°剝離力為3N/cm以上，具有常溫下之對被黏著體之適度之附著性，貼合作業性優異，故而較佳。 The present adhesive sheet 1 may have the following feature (6). That is (6) when it is crimped on the soda-lime glass, at 23°C and 40% RH, at a peeling angle of 180° and a peeling speed of 60mm/min, the adhesive sheet 1 is peeled off from the above-mentioned soda-lime glass. ° The peeling force may be 3 N/cm or more. By setting the 180° peeling force at 23°C to 3 N/cm or more, it has moderate adhesion to the adherend at room temperature and excellent bonding workability, so it is preferable.

就該觀點而言，本黏著片材1之23℃、40%RH下之180°剝離力較佳為3N/cm以上，其中較佳為20N/cm以下，其中尤佳為4N/cm以上或15N/cm以下。 From this point of view, the 180° peel force of the present adhesive sheet 1 at 23° C. and 40% RH is preferably 3 N/cm or more, preferably 20 N/cm or less, particularly preferably 4 N/cm or more or Below 15N/cm.

於本黏著片材1中，為調整23℃、40%RH下之180°剝離力，例如自 下述黏著劑組合物(1-I)或(1-II)製造本黏著片材1，進而調整交聯劑或光聚合起始劑之種類或組成比，或調整貼合時之加熱、加壓條件或貼合後之光照射條件即可。但並不限定於此種方法。 In this adhesive sheet 1, in order to adjust the 180° peel force at 23°C and 40%RH, for example, from The following adhesive composition (1-I) or (1-II) is used to manufacture this adhesive sheet 1, and then adjust the type or composition ratio of the crosslinking agent or photopolymerization initiator, or adjust the heating, adding Pressing conditions or light irradiation conditions after lamination are sufficient. However, it is not limited to this method.

<70~100℃加熱時之特性> <Characteristics when heated at 70~100°C>

本黏著片材1具有(2)於光硬化前，若加熱至70~100℃，則黏度成為100~3000Pa‧s，顯示流動性的特徵。 The present adhesive sheet 1 has (2) the viscosity becomes 100-3000 Pa‧s when heated to 70-100° C. before photocuring, showing fluidity.

若本黏著片材1具備此種熱熔性，則藉由進行加熱而使之軟化或流動化，可追隨印刷階差等凹凸部而填充黏著劑，因此可於不產生發泡等之狀態下填充。 If the present adhesive sheet 1 has such hot-melt properties, it can be softened or fluidized by heating, and the adhesive can be filled with the uneven parts such as printing steps. filling.

為獲得此種特性，例如自下述黏著劑組合物(1-I)或(1-II)製造本黏著片材1即可。但並不限定於此。 In order to obtain such a characteristic, what is necessary is just to manufacture this adhesive sheet 1 from the following adhesive composition (1-I) or (1-II), for example. But it is not limited to this.

若本黏著片材1加熱至70~100℃，則黏度成為100~3000Pa‧s，其中較佳為150Pa‧s以上或2700Pa‧s以下，其中更佳為200Pa‧s以上或2500Pa‧s以下。 When the adhesive sheet 1 is heated to 70-100° C., the viscosity becomes 100-3000 Pa‧s, preferably 150 Pa‧s or 2700 Pa‧s, more preferably 200 Pa‧s or 2500 Pa‧s.

(80℃、10%RH下之180°剝離力) (180°peel force at 80°C, 10%RH)

本黏著片材1可具有以下之(7)之特徵。即(7)壓接於鈉鈣玻璃上，於80℃、10%RH下，以剝離角180°、剝離速度60mm/min，自上述鈉鈣玻璃剝離本黏著片材1時之剝離模式為凝集破壞，對玻璃之180°剝離力可為1N/cm以下。 The present adhesive sheet 1 may have the following feature (7). That is, (7) When it is crimped on soda-lime glass, at 80°C and 10% RH, the peeling mode when peeling this adhesive sheet 1 from the above-mentioned soda-lime glass is agglomeration at a peeling angle of 180° and a peeling speed of 60mm/min Destruction, the 180°peeling force to glass can be less than 1N/cm.

若80℃下之180°剝離力為1N/cm以下，則可獲得對被黏著體之較高之潤濕性，故而較佳。 If the 180° peeling force at 80°C is 1 N/cm or less, high wettability to the adherend can be obtained, which is preferable.

就該觀點而言，本黏著片材1之80℃、10%RH下之180°剝離力較佳為1N/cm以下，其中更佳為0.8N/cm以下，其中尤佳為0.5N/cm以下。 From this point of view, the 180° peeling force of the present adhesive sheet 1 at 80°C and 10% RH is preferably 1 N/cm or less, more preferably 0.8 N/cm or less, particularly preferably 0.5 N/cm the following.

於本黏著片材1中，為調整80℃、10%RH下之180°剝離力，例如自下述黏著劑組合物(1-I)或(1-II)製造本黏著片材1，進而調整交聯劑或光聚合起始劑之種類或組成比，或調整貼合時之加熱、加壓條件或貼合後之光照射條件即可。但並不限定於此種方法。 In this adhesive sheet 1, in order to adjust the 180° peel force at 80°C and 10% RH, this adhesive sheet 1 is manufactured from the following adhesive composition (1-I) or (1-II), for example, and then Just adjust the type or composition ratio of the crosslinking agent or photopolymerization initiator, or adjust the heating and pressurizing conditions during bonding or the light irradiation conditions after bonding. However, it is not limited to this method.

<光硬化後之特性> <Characteristics after photocuring>

本黏著片材1可光硬化，具有(3)光硬化後，70~100℃下之黏度成為3000~50000Pa‧s的特徵。 This adhesive sheet 1 can be photocured, and has (3) the characteristic that after photocuring, the viscosity at 70~100°C becomes 3000~50000 Pa‧s.

就獲得較高之凝集力之觀點而言，本黏著片材1於光硬化後，於70~100℃下之黏度較佳為成為3000~50000Pa‧s，其中更佳為成為3500Pa‧s以上或48000Pa‧s以下，其中進而較佳為成為4000Pa‧s以上或45000Pa‧s以下。 From the viewpoint of obtaining higher cohesion, the viscosity of the adhesive sheet 1 at 70-100°C after light curing is preferably 3000-50000 Pa‧s, more preferably 3500 Pa‧s or more 48000Pa‧s or less, and more preferably 4000Pa‧s or more or 45000Pa‧s or less.

(光硬化後之23℃、40%RH下之180°剝離力) (180°peel force at 23°C, 40%RH after light curing)

本黏著片材1於光硬化後可具有以下之(4)之特徵。即(4)壓接於鈉鈣玻璃上，作為光照射而硬化之光硬化後之黏著片材，於23℃、40%RH下，以剝離角180°、剝離速度60mm/min，自上述鈉鈣玻璃剝離黏著片材時之對玻璃之180°剝離力可為3N/cm以上。 The adhesive sheet 1 can have the following feature (4) after photocuring. That is, (4) pressure-bonded on soda-lime glass, as a light-cured adhesive sheet hardened by light irradiation, at 23°C and 40%RH, at a peeling angle of 180° and a peeling speed of 60mm/min, from the above-mentioned sodium When the lime glass peels off the adhesive sheet, the 180° peeling force against the glass can be more than 3N/cm.

若光硬化後之23℃下之180°剝離力為3N/cm以上，則可將被黏著體彼此牢固地接著，故而較佳。 If the 180° peel force at 23° C. after photocuring is 3 N/cm or more, adherends can be firmly bonded together, which is preferable.

就該觀點而言，本黏著片材1之光硬化後之23℃下之180°剝離力較佳為3N/cm以上，其中更佳為4N/cm以上，其中尤佳為5N/cm以上或30N/cm以下。 From this point of view, the 180° peeling force at 23° C. after photocuring of the present adhesive sheet 1 is preferably 3 N/cm or more, more preferably 4 N/cm or more, particularly preferably 5 N/cm or more, or Below 30N/cm.

(光硬化後之80℃、10%RH下之180°剝離力) (180°peel force at 80°C, 10%RH after light curing)

本黏著片材1於光硬化後可具有以下之(5)之特徵。即(5)壓接於鈉鈣 玻璃上，作為光照射而硬化之光硬化後之黏著片材，於80℃、10%RH下，以剝離角180°、剝離速度60mm/min，自上述鈉鈣玻璃剝離黏著片材時之對玻璃之180°剝離力可為3N/cm以上。 The adhesive sheet 1 can have the following feature (5) after photocuring. That is (5) crimping on sodium calcium On the glass, as the photohardened adhesive sheet hardened by light irradiation, at 80°C and 10% RH, at a peeling angle of 180° and a peeling speed of 60mm/min, the adhesive sheet is peeled from the above-mentioned soda-lime glass. The 180° peeling force of the glass can be above 3N/cm.

若光硬化後之80℃下之180°剝離力為3N/cm以上，則高溫環境下之耐發泡性優異，故而較佳。 If the 180° peeling force at 80° C. after photocuring is 3 N/cm or more, the foaming resistance in a high-temperature environment is excellent, so it is preferable.

就該觀點而言，本黏著片材1之光硬化後之80℃下之180°剝離力較佳為3N/cm以上，其中更佳為4N/cm以上，其中尤佳為5N/cm以上或20N/cm以下。 From this point of view, the 180° peel force at 80° C. after photocuring of the present adhesive sheet 1 is preferably 3 N/cm or more, more preferably 4 N/cm or more, particularly preferably 5 N/cm or more, or Below 20N/cm.

於本黏著片材1中，為調整光硬化後之23℃或80℃下之180°剝離力，例如自下述黏著劑組合物(1-I)或(1-II)製造本黏著片材1，進而調整交聯劑或光聚合起始劑之種類或組成比，或調整貼合時之加熱、加壓條件或貼合後之光照射條件即可。但並不限定於此種方法。 In this adhesive sheet 1, in order to adjust the 180° peel force at 23°C or 80°C after photocuring, this adhesive sheet is produced from the following adhesive composition (1-I) or (1-II), for example 1. Further adjust the type or composition ratio of the crosslinking agent or photopolymerization initiator, or adjust the heating and pressure conditions during lamination or the light irradiation conditions after lamination. However, it is not limited to this method.

<釋氣產生量> <Outgas generation amount>

光硬化後之本黏著片材1之藉由JIS K7350-2(ISO4892-2)規定之氙弧燈式耐光性試驗機進行24小時光照射後之釋氣產生量，以十六烷換算較佳為40000ppm以上。 The amount of outgassing of the adhesive sheet 1 after light hardening after 24 hours of light irradiation by the xenon arc lamp light resistance tester specified in JIS K7350-2 (ISO4892-2), preferably in hexadecane conversion It is above 40000ppm.

若釋氣產生量以十六烷換算為40000ppm以上，則黏著片材之黏性或對被黏著體之潤濕性提高，故而較佳。 When the amount of outgassing is 40,000 ppm or more in terms of cetane, it is preferable because the viscosity of the adhesive sheet or the wettability to the adherend will increase.

因此，就該觀點而言，本黏著片材1中上述釋氣產生量以十六烷換算較佳為40000ppm以上，其中更佳為45000ppm以上，其中尤佳為50000ppm以上。 Therefore, from this point of view, the amount of outgassing in the present adhesive sheet 1 is preferably 40,000 ppm or more in terms of cetane, more preferably 45,000 ppm or more, and especially preferably 50,000 ppm or more.

再者，為使本黏著片材1中上述釋氣產生量為上述範圍，例如自下述黏著劑組合物(1-I)或(1-II)製造本黏著片材1即可。但並不限定於此。 In addition, in order to make the said outgassing amount in this adhesive sheet 1 into the said range, what is necessary is just to manufacture this adhesive sheet 1 from the following adhesive composition (1-I) or (1-II), for example. But it is not limited to this.

<耐發泡可靠性> <Reliability against foaming>

較佳為光硬化後之本黏著片材1於以下之耐發泡性試驗中，顯示氣泡之直徑為5mm以下之耐發泡性。 It is preferable that this adhesive sheet 1 after photocuring exhibits foaming resistance in which the diameter of the bubbles is 5 mm or less in the following foaming resistance test.

耐發泡性試驗：於對角線之長度為5英吋以上且厚度為1mm以下之2片玻璃板間夾持黏著片材製作積層體，依據JIS K7350-2(ISO4892-2)，藉由氙弧燈式耐光性試驗機進行24小時光照射後，測定黏著片材內產生之氣泡之直徑。 Foaming resistance test: The adhesive sheet is sandwiched between two glass plates with a diagonal length of 5 inches or more and a thickness of 1mm or less to make a laminate, according to JIS K7350-2 (ISO4892-2), by Xenon-arc light resistance testing machine measures the diameter of bubbles generated in the adhesive sheet after 24 hours of light irradiation.

本黏著片材1於光硬化後具有70~100℃下之黏度成為3000~50000Pa‧s之特徵，故而光硬化後可顯示此種耐發泡性。因此可發揮即使長時間光照射亦不會降低可靠性的性質，故而可獲得例如於各種圖像顯示裝置中使用時即使長時間暴露於照明或太陽光等光下亦不會降低性能之接著可靠性。 This adhesive sheet 1 has the characteristic that the viscosity at 70~100°C becomes 3000~50000 Pa‧s after photocuring, so it can show such foaming resistance after photocuring. Therefore, it can exhibit the property that the reliability will not be lowered even if it is exposed to light for a long time, so it can be used in various image display devices, even if it is exposed to light such as lighting or sunlight for a long time, it can be obtained. sex.

為獲得此種特性，例如自下述黏著劑組合物(1-I)或(1-II)製造本黏著片材1即可。但並不限定於此。 In order to obtain such a characteristic, what is necessary is just to manufacture this adhesive sheet 1 from the following adhesive composition (1-I) or (1-II), for example. But it is not limited to this.

<本黏著劑組合物1> <This adhesive composition 1>

作為本黏著片材1之製作中所使用之本黏著劑組合物1之較佳一例，可列舉：含有包含具備巨單體作為分枝成分之接枝共聚物之丙烯酸系共聚物(1-A1)、交聯劑(1-B1)及光聚合起始劑(1-C1)的黏著劑組合物(1-I)。 As a preferable example of the adhesive composition 1 used in the production of the adhesive sheet 1, an acrylic copolymer (1-A1) containing a graft copolymer having a macromonomer as a branch component can be cited. ), an adhesive composition (1-I) of a crosslinking agent (1-B1) and a photopolymerization initiator (1-C1).

又，作為本黏著劑組合物1之另一例，可列舉：含有使玻璃轉移溫度(Tg)未達0℃之單體a1、玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體a2及玻璃轉移溫度(Tg)為80℃以上之單體a3，以a1：a2：a3=10~40：90~35：0~25之莫耳比率進行共聚合而成且重量平均分子量為50000~400000之(甲基)丙烯酸系共聚物(1-A2)；交聯劑(1-B2)及光聚合起始劑(1- C2)的黏著劑組合物(1-II)。 In addition, as another example of the present adhesive composition 1, monomer a1 containing a glass transition temperature (Tg) of less than 0°C and a monomer having a glass transition temperature (Tg) of 0°C or higher and less than 80°C can be cited. Monomer a2 and monomer a3 with a glass transition temperature (Tg) above 80°C are copolymerized at a molar ratio of a1:a2:a3=10~40:90~35:0~25, and the weight average molecular weight is 50000~400000 (meth)acrylic copolymer (1-A2); crosslinking agent (1-B2) and photopolymerization initiator (1- C2) The adhesive composition (1-II).

其中，用以形成本黏著片材1之黏著劑組合物並不限定於黏著劑組合物(1-I)或(1-II)。 Wherein, the adhesive composition used to form the adhesive sheet 1 is not limited to the adhesive composition (1-I) or (1-II).

再者，數量平均分子量及重量平均分子量係使用凝膠滲透層析儀(GPC)，採用使用聚苯乙烯作為標準物質之換算值。 In addition, the number average molecular weight and weight average molecular weight are conversion values using polystyrene as a standard substance using gel permeation chromatography (GPC).

若自藉由公知之方法調製之黏著劑組合物(1-I)或(1-II)製作本黏著片材1，則可於室溫狀態下保持片狀並且顯示自黏著性，具有當於未交聯狀態下加熱時發生熔融或流動之熱熔性，進而可光硬化，光硬化後發揮優異之凝集力。 If this adhesive sheet 1 is produced from the adhesive composition (1-I) or (1-II) prepared by a known method, it can maintain a sheet shape at room temperature and exhibit self-adhesiveness, and has a property equivalent to In the uncrosslinked state, it melts or flows when heated, and can be photohardened. After photohardening, it exhibits excellent cohesive force.

<黏著劑組合物(1-I)> <Adhesive composition (1-I)>

作為黏著劑組合物(1-I)，可列舉：含有包含具備巨單體作為分枝成分之接枝共聚物之丙烯酸系共聚物(1-A1)、交聯劑(1-B1)及光聚合起始劑(1-C1)的黏著劑組合物。 Examples of the adhesive composition (1-I) include: an acrylic copolymer (1-A1) containing a graft copolymer having a macromonomer as a branch component, a crosslinking agent (1-B1), and a photopolymer. Adhesive composition of a polymerization initiator (1-C1).

(丙烯酸系共聚物(1-A1)) (Acrylic Copolymer (1-A1))

作為基礎聚合物之丙烯酸系共聚物(1-A1)若為具備巨單體作為分枝成分之接枝共聚物即可。 The acrylic copolymer (1-A1) as the base polymer may be a graft copolymer having a macromonomer as a branch component.

(主幹成分) (main ingredient)

上述丙烯酸系共聚物(1-A1)之主幹成分較佳為包含含有源自(甲基)丙烯酸酯之重複單元之共聚物成分。 It is preferable that the backbone component of the said acrylic-type copolymer (1-A1) contains the copolymer component containing the repeating unit derived from (meth)acrylate.

構成上述丙烯酸系共聚物(1-A1)之主幹成分之共聚物之玻璃轉移溫度較佳為-70~0℃。 The glass transition temperature of the copolymer constituting the main component of the acrylic copolymer (1-A1) is preferably -70 to 0°C.

此時，所謂構成主幹成分之共聚物成分之玻璃轉移溫度，係指僅將組成丙烯酸系共聚物(1-A1)之主幹成分之單體成分共聚合而獲得之聚合物 之玻璃轉移溫度。具體而言，係指由自該共聚物各成分之均聚物獲得之聚合物之玻璃轉移溫度與構成比率，藉由Fox之計算式而算出之值。 In this case, the glass transition temperature of the copolymer component constituting the main component refers to a polymer obtained by copolymerizing only the monomer components constituting the main component of the acrylic copolymer (1-A1). the glass transition temperature. Specifically, it refers to the value calculated by Fox's calculation formula from the glass transition temperature and composition ratio of the polymer obtained from the homopolymer of the respective components of the copolymer.

再者，所謂Fox之計算式係指藉由下式而求得之計算值，可使用聚合物手冊[Polymer HandBook,J.Brandrup,Interscience,1989]中記載之值而求得。 In addition, the calculation formula of Fox means the calculated value obtained by the following formula, and can be obtained using the value described in the polymer handbook [Polymer Handbook, J. Brandrup, Interscience, 1989].

1/(273+Tg)=Σ(Wi/(273+Tgi)) 1/(273+Tg)=Σ(Wi/(273+Tgi))

[式中，Wi表示單體i之重量分率，Tgi表示單體i之均聚物之Tg(℃)] [Where, Wi represents the weight fraction of monomer i, and Tgi represents the Tg (°C) of the homopolymer of monomer i]

構成上述丙烯酸系共聚物(1-A1)之主幹成分之共聚物成分之玻璃轉移溫度會對室溫狀態下之黏著劑組合物(1-I)之柔軟性，或黏著劑組合物(1-I)對被黏著體之潤濕性，即接著性產生影響，故而為使黏著劑組合物(1-I)於室溫狀態下獲得適度之接著性(黏性)，該玻璃轉移溫度較佳為-80℃~0℃，其中更佳為-75℃以上或-5℃以下，其中尤佳為-70℃以上或-10℃以下。 The glass transition temperature of the copolymer component constituting the main component of the acrylic copolymer (1-A1) affects the flexibility of the adhesive composition (1-I) at room temperature, or the adhesive composition (1-A1) I) It affects the wettability of the adherend, that is, the adhesiveness, so in order to make the adhesive composition (1-I) obtain moderate adhesiveness (viscosity) at room temperature, the glass transition temperature is better -80°C to 0°C, more preferably -75°C or higher or -5°C or lower, particularly preferably -70°C or higher or -10°C or lower.

其中，即使該共聚物成分之玻璃轉移溫度為相同溫度，亦可藉由調整分子量而調整黏彈性。例如藉由減小共聚物成分之分子量，可使之更柔軟化。 Among them, even if the glass transition temperature of the copolymer components is the same temperature, the viscoelasticity can be adjusted by adjusting the molecular weight. For example, by reducing the molecular weight of the copolymer component, it can be made more flexible.

作為上述丙烯酸系共聚物(1-A1)之主幹成分所含有之(甲基)丙烯酸酯單體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(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)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山崳酯、(甲基)丙烯酸異

Figure 110106505-A0305-02-0014-6
基酯、(甲基)丙烯酸2-苯氧基乙酯、丙烯酸3,5,5-三甲基環己酯、對異丙苯基苯酚EO改性(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸苄酯等。亦可使用該等中具有親水基或有機官能基等之(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、(甲基)丙烯酸甘油酯等含羥基之(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)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、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、反丁烯二酸、順丁烯二酸、伊康酸、順丁烯二酸單甲酯、伊康酸單甲酯等含羧基之單體，順丁烯二酸酐、伊康酸酐等含酸酐基之單體，(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-環氧丁酯等含環氧基之單體，(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯等含胺基之(甲基)丙烯酸酯系單體，(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-羥甲基(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、二丙酮丙烯醯胺、順丁烯二醯胺、順丁烯二醯亞胺等含醯胺基之單體，乙烯基吡咯啶酮、乙烯基吡啶、乙烯基咔唑等雜環系鹼性單體等。 Examples of the (meth)acrylate monomer contained in the main component of the acrylic copolymer (1-A1) include: methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate Propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 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 ester, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, Decyl (meth)acrylate, Isodecyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate, Cetyl (meth)acrylate, (Meth)acrylate ) stearyl acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, iso(meth)acrylate
Figure 110106505-A0305-02-0014-6
Base ester, 2-phenoxyethyl (meth)acrylate, 3,5,5-trimethylcyclohexyl acrylate, p-cumylphenol EO modified (meth)acrylate, (meth) Dicyclopentyl acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, and the like. Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycerin (meth)acrylate etc. which have a hydrophilic group or an organic functional group etc. can also be used Hydroxyl-containing (meth)acrylate, or (meth)acrylic acid, 2-(meth)acryloxyethylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydro Phthalic acid, 2-(meth)acryloxyethylphthalic acid, 2-(meth)acryloxypropylphthalic acid, 2-(meth)acryloxyethylphthalic acid 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxyethylsuccinic acid, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxypropylmaleic acid Carboxyl group-containing monomers such as propyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate, etc. Monomers containing acid anhydride groups such as diacid anhydride and itaconic anhydride, glycidyl (meth)acrylate, α-glycidyl ethacrylate, 3,4-epoxybutyl (meth)acrylate, etc. containing epoxy groups Monomers, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and other amino-containing (meth)acrylate monomers, (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl ( Meth)acrylamide, diacetoneacrylamide, maleimide, maleimide and other amido-containing monomers, vinylpyrrolidone, vinylpyridine, vinylcarbazole Heterocyclic basic monomers, etc.

又，亦可適當使用可與上述丙烯酸系單體或甲基丙烯酸系單體共聚 合之苯乙烯、第三丁基苯乙烯、α-甲基苯乙烯、乙烯基甲苯、丙烯腈、甲基丙烯腈、乙酸乙烯酯、丙酸乙烯酯、烷基乙烯基醚、羥基烷基乙烯基醚、烷基乙烯基單體等各種乙烯基單體。 Moreover, it is also possible to appropriately use Combined styrene, tertiary butyl styrene, α-methyl styrene, vinyl toluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl ethylene Various vinyl monomers such as base ethers and alkyl vinyl monomers.

又，丙烯酸系共聚物(1-A1)之主幹成分較佳為含有疏水性之(甲基)丙烯酸酯單體與親水性之(甲基)丙烯酸酯單體作為構成單元。 Moreover, it is preferable that the backbone component of an acryl-type copolymer (1-A1) contains a hydrophobic (meth)acrylate monomer and a hydrophilic (meth)acrylate monomer as a structural unit.

若丙烯酸系共聚物(1-A1)之主幹成分僅由疏水性單體構成，則確認存在濕熱白化之傾向，故而較佳為將親水性單體亦導入主幹成分而防止濕熱白化。 If the main component of the acrylic copolymer (1-A1) is composed of only hydrophobic monomers, it is confirmed that there is a tendency of wet heat whitening. Therefore, it is preferable to introduce a hydrophilic monomer into the main component to prevent wet heat whitening.

具體而言，作為上述丙烯酸系共聚物(1-A1)之主幹成分，可列舉：使疏水性之(甲基)丙烯酸酯單體與親水性之(甲基)丙烯酸酯單體與巨單體之末端之聚合性官能基無規共聚合而成之共聚物成分。 Specifically, as the main component of the above-mentioned acrylic copolymer (1-A1), a combination of a hydrophobic (meth)acrylate monomer, a hydrophilic (meth)acrylate monomer, and a macromonomer can be mentioned. A copolymer component formed by random copolymerization of polymerizable functional groups at the terminal.

此處，作為上述疏水性之(甲基)丙烯酸酯單體，較佳為不具有極性基之烷基酯(其中，不包括丙烯酸甲酯)，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、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)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山崳酯、(甲基)丙烯酸異

Figure 110106505-A0305-02-0015-8
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。 Here, as the above-mentioned hydrophobic (meth)acrylate monomer, alkyl esters having no polar groups (among which, methyl acrylate is not included) are preferred, for example, n-butyl (meth)acrylate , Isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, (meth) ) Neopentyl acrylate, (meth)hexyl acrylate, (meth)cyclohexyl acrylate, (meth)heptyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, ( Nonyl methacrylate, isononyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth) Undecyl acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, (meth)acrylic acid Behenyl Ester, (Meth) Acrylic Iso
Figure 110106505-A0305-02-0015-8
base ester, cyclohexyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, methyl methacrylate.

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。 In addition, examples of hydrophobic vinyl monomers include vinyl acetate, styrene ene, tertiary butylstyrene, α-methylstyrene, vinyltoluene, alkyl vinyl monomers, etc.

作為上述親水性之(甲基)丙烯酸酯單體，較佳為丙烯酸甲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)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、(甲基)丙烯酸甘油酯等含羥基之(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)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、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、反丁烯二酸、順丁烯二酸、伊康酸、順丁烯二酸單甲酯、伊康酸單甲酯等含羧基之單體，順丁烯二酸酐、伊康酸酐等含酸酐基之單體，(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、羥乙基丙烯醯胺等。 As the above-mentioned hydrophilic (meth)acrylate monomer, methyl acrylate or an ester having a polar group is preferable, for example, methyl acrylate, (meth)acrylic acid, tetrahydrofurfuryl (meth)acrylate Or (meth)acrylate or (meth)acrylate containing hydroxyl groups such as hydroxyethyl (meth)acrylate, (meth)hydroxypropyl Acrylic acid, 2-(meth)acryloxyethyl hexahydrophthalate, 2-(meth)acryloxypropyl hexahydrophthalate, 2-(meth)acryloxy Ethylphthalate, 2-(meth)acryloxypropylphthalate, 2-(meth)acryloxyethylmaleic acid, 2-(meth)acrylyl Oxypropylmaleic 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, ( Epoxy group-containing monomers such as glycidyl methacrylate, glycidyl α-ethacrylate, 3,4-epoxybutyl (meth)acrylate, etc., methoxypolyethylene glycol (methyl) Alkoxy polyalkylene glycol (meth)acrylate such as acrylate, N,N-dimethylacrylamide, hydroxyethylacrylamide, etc.

(分枝成分：巨單體) (branch components: macromonomer)

丙烯酸系共聚物(1-A1)較佳為導入巨單體作為接枝共聚物之分枝成分，含有源自巨單體之重複單元。 The acrylic copolymer (1-A1) preferably introduces a macromonomer as a branch component of the graft copolymer and contains repeating units derived from the macromonomer.

所謂巨單體係指具有末端之聚合性官能基與高分子量骨架成分之高分子單體。 The so-called macromonomer system refers to a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.

巨單體之玻璃轉移溫度(Tg)較佳為高於構成上述丙烯酸系共聚物(1-A1)之共聚物成分之玻璃轉移溫度。 The glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer components constituting the above-mentioned acrylic copolymer (1-A1).

具體而言，巨單體之玻璃轉移溫度(Tg)會對黏著劑組合物(1-I)之加 熱熔融溫度(熱熔溫度)產生影響，故而巨單體之玻璃轉移溫度(Tg)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。 Specifically, the glass transition temperature (Tg) of the macromonomer will add to the adhesive composition (1-I). The thermal melting temperature (hot melting temperature) has an influence, so the glass transition temperature (Tg) of the macromonomer is preferably 30°C~120°C, more preferably 40°C or higher or 110°C or lower, and even more preferably 50°C above or below 100°C.

若為此種玻璃轉移溫度(Tg)，則藉由調整分子量，可保持優異之加工性或保存穩定性，並且可調整為於80℃附近熱熔。 If it is such a glass transition temperature (Tg), by adjusting the molecular weight, it is possible to maintain excellent processability and storage stability, and it can be adjusted to heat-melt around 80°C.

所謂巨單體之玻璃轉移溫度係表示該巨單體本身之玻璃轉移溫度，可藉由示差掃描熱量計(DSC)而測定(升溫速度：5℃/分鐘，根據基準線位移之反曲點而測定Tg)。 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) (heating rate: 5°C/min, based on the inflection point of the baseline displacement Determination of Tg).

又，為達成於室溫狀態下可維持分枝成分彼此相互拉近，作為黏著劑組合物進行物理***聯之狀態，並且藉由加熱至適度之溫度可使上述物理***聯解開而獲得流動性，亦較佳為調整巨單體之分子量或含量。 In addition, in order to maintain the branched components close to each other at room temperature, as the adhesive composition undergoes physical cross-linking, and by heating to a moderate temperature, the above-mentioned physical cross-linking can be released to obtain fluidity It is also preferable to adjust the molecular weight or content of the macromonomer.

就該觀點而言，巨單體較佳為以5質量%~30質量%之比率含有於丙烯酸系共聚物(1-A1)中，其中更佳為6質量%以上或25質量%以下，其中進而較佳為8質量%以上或20質量%以下。 From this point of view, the macromonomer is preferably contained in the acrylic copolymer (1-A1) at a ratio of 5 mass % to 30 mass %, more preferably 6 mass % or more or 25 mass % or less, wherein More preferably, it is 8 mass % or more or 20 mass % or less.

又，巨單體之數量平均分子量較佳為500以上且未達8000，其中更佳為800以上或未達7500，其中進而較佳為1000以上或未達7000。 Also, the number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and still more preferably 1000 or more and less than 7000.

巨單體可適當使用通常製造者(例如東亞合成公司製造之巨單體等)。 As the macromonomer, a general manufacturer (for example, a macromonomer manufactured by Toagosei Co., Ltd., etc.) can be used appropriately.

巨單體之高分子量骨架成分較佳為包含丙烯酸系聚合物或乙烯系聚合物。 The high molecular weight skeleton component of the macromonomer preferably comprises an acrylic polymer or a vinyl polymer.

作為上述巨單體之高分子量骨架成分，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(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)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山崳酯、(甲基)丙烯酸異

Figure 110106505-A0305-02-0018-9
基酯、(甲基)丙烯酸2-苯氧基乙酯、丙烯酸3,5,5-三甲基環己酯、對異丙苯基苯酚EO改性(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸羥基烷基酯、(甲基)丙烯酸、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、(甲基)丙烯腈、(甲基)丙烯酸烷氧基烷基酯、烷氧基聚伸烷基二醇(甲基)丙烯酸酯等(甲基)丙烯酸酯單體或苯乙烯、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、乙酸乙烯酯、烷基乙烯基醚、羥基烷基乙烯基醚等各種乙烯基單體，該等可單獨使用或組合兩種以上使用。 Examples of the high-molecular-weight skeleton component of the macromonomer include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate base) n-butyl acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate Pentyl, 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 ester, undecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate , Behenyl (meth)acrylate, Iso(meth)acrylate
Figure 110106505-A0305-02-0018-9
Base ester, 2-phenoxyethyl (meth)acrylate, 3,5,5-trimethylcyclohexyl acrylate, p-cumylphenol EO modified (meth)acrylate, (meth) Dicyclopentyl acrylate, Dicyclopentenyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, Benzyl (meth)acrylate, Hydroxyalkyl (meth)acrylate, ( Meth)acrylic acid, glycidyl (meth)acrylate, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acrylonitrile, (meth)acrylamide (meth)acrylate monomers such as oxyalkyl esters, alkoxy polyalkylene glycol (meth)acrylates, or styrene, tert-butylstyrene, α-methylstyrene, vinyl Various vinyl monomers such as toluene, alkyl vinyl monomers, vinyl acetate, alkyl vinyl ethers, and hydroxyalkyl vinyl ethers may be used alone or in combination of two or more.

作為上述巨單體之末端聚合性官能基，例如可列舉：甲基丙烯醯基、丙烯醯基、乙烯基等。 As a terminal polymerizable functional group of the said macromonomer, a methacryl group, an acryl group, a vinyl group etc. are mentioned, for example.

(交聯劑(1-B1)) (Crosslinking agent (1-B1))

作為交聯劑(1-B1)，例如可適宜選擇具有2個以上之環氧基或異氰酸酯基、氧雜環丁烷基、矽烷醇基、(甲基)丙烯醯基等交聯性基之交聯劑。其中，就反應性或所得硬化物之強度之方面而言，較佳為具有2個以上之(甲基)丙烯醯基，其中更佳為具有3個以上之(甲基)丙烯醯基的多官能(甲基)丙烯酸酯或具有環氧基或異氰酸酯基等的(甲基)丙烯酸酯。 As the crosslinking agent (1-B1), for example, one having two or more crosslinkable groups such as epoxy groups or isocyanate groups, oxetanyl groups, silanol groups, (meth)acryl groups, etc. crosslinking agent. Among them, in terms of reactivity or the strength of the obtained hardened product, polyamides having 2 or more (meth)acryl groups are preferred, and polyamides having 3 or more (meth)acryl groups are more preferred. A functional (meth)acrylate or a (meth)acrylate having an epoxy group, an isocyanate group, or the like.

將圖像顯示裝置構成構件貼合一體化後，使交聯劑(1-B1)於黏著材中交聯，藉此可使該片材失去熱熔性，取而代之於高溫環境下表現較高之凝集力，獲得優異之耐發泡可靠性。 After laminating and integrating the components of the image display device, the cross-linking agent (1-B1) is cross-linked in the adhesive material, so that the sheet loses its heat-meltability and is replaced by one that exhibits higher performance in high-temperature environments. Cohesion, to obtain excellent reliability against foaming.

作為此種(甲基)丙烯酸酯，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、甘油二(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聚烷氧基二(甲基)丙烯酸酯、雙酚F聚烷氧基二(甲基)丙烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、三羥甲基丙烷三氧基乙基(甲基)丙烯酸酯、ε-己內酯改性三(2-羥基乙基)異氰尿酸酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、丙氧化季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、丙氧化季戊四醇四(甲基)丙烯酸酯、乙氧化季戊四醇四(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、三(丙烯醯氧基乙基)異氰尿酸酯、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、烷氧化三羥甲基丙烷三(甲基)丙烯酸酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯等紫外線硬化型多官能單體類，另外亦可列舉：聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能丙烯酸酯低聚物類或異氰酸酯(甲基)丙烯酸酯、1,1-(雙(甲基)丙烯醯氧基甲基)乙基異氰酸酯、2-(2-(甲基)丙烯醯氧 基乙基氧基)乙基異氰酸酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥乙酯縮水甘油醚、(甲基)丙烯酸羥丙酯縮水甘油醚、(甲基)丙烯酸羥丁酯縮水甘油醚等。 Examples of such (meth)acrylates include 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, Glycerin glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di( Meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol A polyalkoxy di(meth)acrylate, bisphenol F polyalkoxy di(meth)acrylate , polyalkylene glycol di(meth)acrylate, trimethylolpropane trioxyethyl(meth)acrylate, ε-caprolactone modified tris(2-hydroxyethyl)isocyanurate ester 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(acryloxy Ethyl) isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol Penta(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, di(meth)acrylate of ε-caprolactone adduct of hydroxypivalate neopentyl glycol , trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, etc. Monomers, in addition, polyfunctional acrylic acid such as polyester (meth)acrylate, epoxy (meth)acrylate, (meth)acrylate urethane, polyether (meth)acrylate, etc. Ester oligomers or isocyanate (meth)acrylate, 1,1-(bis(meth)acryloxymethyl)ethyl isocyanate, 2-(2-(meth)acryloxy (ethyloxy) ethyl isocyanate, (meth) glycidyl acrylate, (meth) hydroxyethyl acrylate glycidyl ether, (meth) hydroxypropyl acrylate glycidyl ether, (meth) hydroxybutyl acrylate Ester glycidyl ether etc.

上述所列舉之中，就提高對被黏著體之密接性或濕熱白化之抑制效果的觀點而言，較佳為含有羥基等極性官能基之多官能單體或低聚物。 Among those listed above, polyfunctional monomers or oligomers containing polar functional groups such as hydroxyl groups are preferred from the viewpoint of improving the adhesion to the adherend or the effect of suppressing wet heat whitening.

其中，較佳為使用具有羥基或羧基之多官能(甲基)丙烯酸酯。 Among them, it is preferable to use a polyfunctional (meth)acrylate having a hydroxyl group or a carboxyl group.

因此，就防止濕熱白化之觀點而言，作為上述丙烯酸系共聚物(1-A1)，即接枝共聚物之主幹成分，較佳為含有疏水性之丙烯酸酯單體與親水性之丙烯酸酯單體，進而，作為交聯劑(1-B)，較佳為使用具有羥基之多官能(甲基)丙烯酸酯。 Therefore, from the viewpoint of preventing whitening under heat and humidity, it is preferable to contain a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as the main component of the above-mentioned acrylic copolymer (1-A1), that is, a graft copolymer. Furthermore, it is preferable to use a polyfunctional (meth)acrylate which has a hydroxyl group as a crosslinking agent (1-B).

交聯劑(1-B1)之含量並無特別限制。作為標準，較佳為相對於丙烯酸系共聚物(1-A1)100質量份為0.5~20質量份，其中更佳為1質量份以上或15質量份以下，其中進而較佳為2質量份以上或10質量份以下之比率。 The content of the crosslinking agent (1-B1) is not particularly limited. As a standard, it is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the acrylic copolymer (1-A1), more preferably at least 1 part by mass and at most 15 parts by mass, and even more preferably at least 2 parts by mass Or a ratio of 10 parts by mass or less.

藉由於上述範圍內含有交聯劑(1-B1)，可同時實現未交聯狀態之本黏著片材1之形狀穩定性與交聯後之黏著材之耐發泡可靠性。其中，就與其他要素之平衡性而言，亦可超出該範圍。 By containing the crosslinking agent (1-B1) within the above range, the shape stability of the adhesive sheet 1 in the uncrosslinked state and the foaming resistance reliability of the crosslinked adhesive can be simultaneously realized. Among them, in terms of balance with other elements, it may also exceed this range.

(光聚合起始劑(1-C1)) (Photopolymerization Initiator (1-C1))

光聚合起始劑(1-C1)係發揮作為上述交聯劑(1-B1)之交聯反應之反應起始助劑的功能者。 The photopolymerization initiator (1-C1) functions as a reaction initiation aid for the crosslinking reaction of the above-mentioned crosslinking agent (1-B1).

光聚合起始劑可適當使用現今公知者。其中，就易於控制交聯反應之觀點而言，較佳為與波長380nm以下之紫外線感應之光聚合起始劑。 As the photopolymerization initiator, conventionally known ones can be appropriately used. Among them, a photopolymerization initiator responsive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.

另一方面，與較波長380nm長波長之光感應之光聚合起始劑於感應之光容易到達本黏著片材1之深部之方面而言較佳。 On the other hand, a photopolymerization initiator that responds to light with a wavelength longer than 380 nm is preferable in that the induced light easily reaches the deep portion of the adhesive sheet 1 .

光聚合起始劑根據自由基產生機制而大體分為兩類，大致分為：可使光聚合性起始劑本身之單鍵發生斷裂分解而產生自由基的裂解型光聚合起始劑、以及光激發之起始劑與系統中之氫供與體形成激發錯合物而可使氫供與體之氫轉移的奪氫型光聚合起始劑。 Photopolymerization initiators are roughly divided into two categories according to the mechanism of free radical generation, roughly divided into: cleavage-type photopolymerization initiators that can break and decompose the single bond of the photopolymerization initiator itself to generate free radicals, and The photoexcited initiator and the hydrogen donor and donor in the system form an excited complex, which can transfer the hydrogen of the hydrogen donor and donor to the hydrogen abstraction type photopolymerization initiator.

作為該等之中的裂解型光聚合起始劑，藉由光照射而產生自由基時分解而成為其他化合物，若一旦被激發則失去作為反應起始劑之功能。因此，不會於交聯反應結束後之黏著材中作為活性物質而殘存，不存在對黏著材造成未預期之光劣化等之可能性，故而較佳。 As the cleavage-type photopolymerization initiator among these, it decomposes into other compounds when free radicals are generated by light irradiation, and loses its function as a reaction initiator once it is excited. Therefore, it is preferable because it does not remain as an active material in the adhesive material after the crosslinking reaction is completed, and there is no possibility of causing unexpected photodegradation to the adhesive material.

另一方面，關於奪氫型光聚合起始劑，藉由紫外線等活性能量線照射而產生自由基反應時，不會產生如裂解型光聚合起始劑之分解物，故而反應結束後難以成為揮發成分，可減少對被黏著體之損傷，就該方面而言較為有用。 On the other hand, when a hydrogen abstraction photopolymerization initiator is irradiated with active energy rays such as ultraviolet rays to generate a free radical reaction, no decomposition product such as a cracking photopolymerization initiator is generated, so it is difficult to become Volatile components can reduce the damage to the adherend and are more useful in this respect.

作為上述裂解型光起始劑，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-

Figure 110106505-A0305-02-0021-11
啉基苯基)丁烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-
Figure 110106505-A0305-02-0021-13
啉基丙烷-1-酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-
Figure 110106505-A0305-02-0021-17
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或該等之衍生物等。 Examples of the cleavage-type photoinitiator 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-propan-1-one, 2 -Hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}phenyl]-2-methyl-propan-1-one, oligo(2-hydroxy- 2-methyl-1-(4-(1-methylvinyl)phenyl)acetone), methyl phenylglyoxylate, 2-benzyl-2-dimethylamino-1-(4-
Figure 110106505-A0305-02-0021-11
Linylphenyl) butane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-
Figure 110106505-A0305-02-0021-13
Linyl propan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-
Figure 110106505-A0305-02-0021-17
Phenyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide or their derivatives, etc.

作為上述奪氫型光起始劑，例如可列舉：二苯甲酮、4-甲基-二苯甲酮、2,4,6-三甲基二苯甲酮、4-苯基二苯甲酮、3,3'-二甲基-4-甲氧基二苯 甲酮、4-(甲基)丙烯醯氧基二苯甲酮、2-苯甲醯基苯甲酸甲酯、苯甲醯基甲酸甲酯、雙(2-苯基-2-乙醛酸)氧基雙乙烯、4-(1,3-丙烯醯基-1,4,7,10,13-五氧代十三烷基)二苯甲酮、9-氧硫

Figure 110106505-A0305-02-0022-18
、2-氯-9-氧硫
Figure 110106505-A0305-02-0022-19
、3-甲基-9-氧硫
Figure 110106505-A0305-02-0022-20
、2,4-二甲基-9-氧硫
Figure 110106505-A0305-02-0022-21
、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌或其衍生物等。 Examples of the hydrogen abstraction type photoinitiator include: benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone Ketone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloxybenzophenone, methyl 2-benzoylbenzoate, benzoyl Methyl methanoate, bis(2-phenyl-2-glyoxylate)oxybisethylene, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxotridecane base) benzophenone, 9-oxosulfur
Figure 110106505-A0305-02-0022-18
, 2-Chloro-9-oxosulfur
Figure 110106505-A0305-02-0022-19
, 3-methyl-9-oxosulfur
Figure 110106505-A0305-02-0022-20
, 2,4-Dimethyl-9-oxosulfur
Figure 110106505-A0305-02-0022-21
, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone or its derivatives, etc.

其中，並不限定於作為光聚合起始劑而於上述列舉之物質。可使用上述列舉之裂解型光聚合起始劑及奪氫型光聚合起始劑中之任一種，或組合兩種以上使用。 However, it is not limited to what was listed above as a photoinitiator. Any of the cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators listed above may be used, or two or more of them may be used in combination.

光聚合起始劑(1-C1)之含量並無特別限制。作為標準，較佳為以相對於丙烯酸系共聚物(1-A1)100質量份為0.1~10質量份，其中更佳為0.5質量份以上或5質量份以下，其中進而較佳為1質量份以上或3質量份以下之比率含有。 The content of the photopolymerization initiator (1-C1) is not particularly limited. As a standard, it is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the acrylic copolymer (1-A1), more preferably 0.5 parts by mass or more or less than 5 parts by mass, and even more preferably 1 part by mass More than or equal to 3 parts by mass or less.

藉由將光聚合起始劑(1-C1)之含量設為上述範圍，可獲得對活性能量線之適度之反應感度。 Moderate reaction sensitivity to active energy rays can be obtained by making content of a photoinitiator (1-C1) into the said range.

(其他成分) (other ingredients)

黏著劑組合物(1-I)可含有通常之黏著劑組合物中所調配之公知之成分作為上述以外之成分。例如可視需要適當含有黏著賦予樹脂或抗氧化劑、光穩定化劑、金屬減活劑、抗老化劑、吸濕劑、聚合抑制劑、紫外線吸收劑、防銹劑、矽烷偶合劑、無機粒子等各種添加劑。 The adhesive composition (1-I) may contain, as components other than the above, known components formulated in ordinary adhesive compositions. For example, if necessary, various types such as adhesion-imparting resins, antioxidants, photostabilizers, metal deactivators, anti-aging agents, moisture absorbers, polymerization inhibitors, ultraviolet absorbers, rust inhibitors, silane coupling agents, and inorganic particles can be appropriately contained. additive.

又，亦可視需要適當含有反應觸媒(三級胺系化合物、四級銨系化合物、月桂酸錫化合物等)。 Moreover, a reaction catalyst (tertiary amine type compound, quaternary ammonium type compound, tin laurate compound, etc.) may be contained suitably as needed.

<黏著劑組合物(1-II)> <Adhesive composition (1-II)>

作為黏著劑組合物(1-II)，可列舉：包含含有使玻璃轉移溫度(Tg)未 達0℃之單體a1、玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體a2及玻璃轉移溫度(Tg)為80℃以上之單體a3，以a1：a2：a3=10~40：90~35：0~25之莫耳比率共聚合而成且重量平均分子量為50000~400000之(甲基)丙烯酸酯共聚物或乙烯系共聚物之(甲基)丙烯酸系共聚物(1-A2)；交聯劑(1-B2)及光聚合起始劑(1-C2)的黏著劑組合物。 Examples of the adhesive composition (1-II) include: Monomer a1 with a glass transition temperature (Tg) of 0°C or higher, monomer a2 with a glass transition temperature (Tg) of 80°C or higher and monomer a3 with a glass transition temperature (Tg) of 80°C or higher, a1:a2:a3= 10~40: 90~35: 0~25 molar ratio copolymerized (meth)acrylic acid ester copolymer or vinyl copolymer (meth)acrylic copolymer with a weight average molecular weight of 50000~400000 (1-A2); an adhesive composition of a crosslinking agent (1-B2) and a photopolymerization initiator (1-C2).

((甲基)丙烯酸系共聚物(1-A2)) ((meth)acrylic copolymer (1-A2))

作為基礎聚合物之(甲基)丙烯酸系共聚物(1-A2)較佳為(甲基)丙烯酸酯共聚物或乙烯系共聚物。 The (meth)acrylic copolymer (1-A2) as the base polymer is preferably a (meth)acrylate copolymer or vinyl copolymer.

就同時實現室溫狀態下之形狀保持性與熱熔性之觀點而言，上述(甲基)丙烯酸酯共聚物或乙烯系共聚物之重量平均分子量較佳為50000~500000，其中更佳為60000以上或450000以下，其中進而較佳為70000以上或400000以下。 From the point of view of achieving both shape retention and heat-fusibility at room temperature, the weight average molecular weight of the (meth)acrylate copolymer or vinyl copolymer is preferably 50,000 to 500,000, more preferably 60,000 It is more than or equal to 450,000, and more preferably, it is more than or equal to 70,000 or less than 400,000.

對丙烯酸酯系共聚物而言，藉由適宜選擇用以調製其之丙烯酸系單體或甲基丙烯酸系單體之種類、組成比率，進而聚合條件等，可適宜調整玻璃轉移溫度(Tg)或分子量等物性。 For acrylate copolymers, the glass transition temperature (Tg) or properties such as molecular weight.

此時，作為構成丙烯酸酯共聚物之丙烯酸系單體，例如可列舉丙烯酸2-乙基己酯、丙烯酸正辛酯、丙烯酸異辛酯、丙烯酸正丁酯、丙烯酸乙酯等作為主原料。 In this case, as an acrylic monomer which comprises an acrylate copolymer, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, etc. are mentioned as a main raw material, for example.

該等之外，可以賦予凝集力或賦予極性等為目的而使具有各種官能基之(甲基)丙烯酸單體與上述丙烯酸系單體共聚合。 In addition to these, a (meth)acrylic monomer having various functional groups may be copolymerized with the above-mentioned acrylic monomer for the purpose of imparting cohesive force, imparting polarity, or the like.

作為該具有官能基之(甲基)丙烯酸單體，例如可列舉：甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸羥基乙酯、丙烯酸、丙烯酸縮水甘油酯、N-取代丙烯醯胺、丙烯腈、甲基丙烯腈、丙烯酸含氟烷基酯、含有機矽烷氧基之 丙烯酸酯等。 Examples of the (meth)acrylic monomer having a functional group include methyl methacrylate, methyl acrylate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, N-substituted acrylamide, acrylonitrile, Methacrylonitrile, fluorine-containing alkyl acrylate, organosilicon alkoxy Acrylic etc.

另一方面，作為乙烯系共聚物，可列舉：可與上述丙烯酸系單體或甲基丙烯酸系單體共聚合之乙酸乙烯酯或烷基乙烯基醚、羥基烷基乙烯基醚等各種乙烯基單體亦適宜聚合而成之乙烯系共聚物。 On the other hand, examples of vinyl copolymers include various vinyl copolymers such as vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether, which can be copolymerized with the above-mentioned acrylic monomer or methacrylic monomer. Monomers are also suitable for polymerization of vinyl copolymers.

作為本黏著片材1之(甲基)丙烯酸系共聚物(1-A2)，較佳為使玻璃轉移溫度(Tg)未達0℃之單體a1、玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體a2及玻璃轉移溫度(Tg)為80℃以上之單體a3，以a1：a2：a3=10~40：90~35：0~25之莫耳比率共聚合而成之(甲基)丙烯酸酯共聚物或乙烯系共聚物。 The (meth)acrylic copolymer (1-A2) of this adhesive sheet 1 is preferably a monomer a1 whose glass transition temperature (Tg) does not reach 0°C, and whose glass transition temperature (Tg) is 0°C or higher And the monomer a2 which is less than 80°C and the monomer a3 whose glass transition temperature (Tg) is above 80°C are copolymerized at a molar ratio of a1:a2:a3=10~40:90~35:0~25 into (meth)acrylate copolymers or vinyl copolymers.

此時，單體a1、a2及a3之各玻璃轉移溫度(Tg)係自該單體製作聚合物時(均聚物化)之各玻璃轉移溫度(Tg)。 At this time, the respective glass transition temperatures (Tg) of the monomers a1, a2, and a3 are obtained from the respective glass transition temperatures (Tg) when the monomers are produced into polymers (homopolymerization).

上述單體a1例如較佳為具有具有碳數4以上之側鏈之烷基結構之(甲基)丙烯酸酯單體。 The above-mentioned monomer a1 is preferably, for example, a (meth)acrylate monomer having an alkyl structure having a side chain having 4 or more carbon atoms.

此時，碳數4以上之側鏈可為包含直鏈者，亦可為包含分支之碳鏈者。 In this case, the side chain having 4 or more carbon atoms may include a straight chain or a branched carbon chain.

更具體而言，上述單體a1較佳為具有碳數4~10之直鏈烷基結構之(甲基)丙烯酸酯單體或具有碳數6~18之支鏈烷基結構之(甲基)丙烯酸酯單體。 More specifically, the above-mentioned monomer a1 is preferably a (meth)acrylate monomer having a linear alkyl structure with 4 to 10 carbons or a (meth)acrylate monomer having a branched alkyl structure with 6 to 18 carbons. ) acrylate monomer.

此處，作為「具有碳數4~10之直鏈烷基結構之(甲基)丙烯酸酯單體」，可列舉：丙烯酸正丁酯、丙烯酸正己酯、丙烯酸正辛酯、丙烯酸正壬酯、丙烯酸正癸酯等。 Here, examples of the "(meth)acrylate monomer having a linear alkyl structure having 4 to 10 carbon atoms" include n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-nonyl acrylate, N-decyl acrylate, etc.

另一方面，作為「具有碳數6~18之支鏈烷基結構之(甲基)丙烯酸酯單體」，可列舉：丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸2- 甲基己酯、丙烯酸異辛酯、丙烯酸異壬酯、丙烯酸異癸酯、甲基丙烯酸異癸酯等。 On the other hand, examples of "(meth)acrylate monomers having a branched chain alkyl structure having 6 to 18 carbon atoms" include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Acrylic 2- Methylhexyl, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, isodecyl methacrylate, etc.

上述單體a2較佳為碳數4以下之(甲基)丙烯酸酯單體、側鏈具有環狀骨架之(甲基)丙烯酸酯單體、碳數4以下之乙烯基單體或側鏈具有環狀骨架之乙烯基單體。 The above-mentioned monomer a2 is preferably a (meth)acrylate monomer with 4 or less carbon atoms, a (meth)acrylate monomer with a ring skeleton in the side chain, a vinyl monomer with 4 or less carbon atoms, or a vinyl monomer with a carbon number of 4 or less. Vinyl monomer with ring skeleton.

其中，上述單體a2尤佳為側鏈之碳數為4以下之乙烯基單體。 Among them, the above-mentioned monomer a2 is particularly preferably a vinyl monomer having 4 or less carbon atoms in the side chain.

此處，作為「碳數4以下之(甲基)丙烯酸酯單體」，可列舉：丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、丙烯酸第三丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯等。 Here, examples of the "(meth)acrylate monomer having 4 or less carbon atoms" include methyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, Isopropyl methacrylate, n-butyl methacrylate, tert-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, etc.

作為「側鏈具有環狀骨架之(甲基)丙烯酸酯單體」，可列舉：丙烯酸異

Figure 110106505-A0305-02-0025-22
基酯、丙烯酸環己酯、甲基丙烯酸環己酯、1,4-環己烷二甲醇單丙烯酸酯、甲基丙烯酸四氫糠酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸苯氧基乙酯、甲基丙烯酸苯氧基乙酯、丙烯酸2-羥基-3-苯氧基丙酯、3,3,5-三甲基環己醇丙烯酸酯、環狀三羥甲基丙烷甲縮醛丙烯酸酯、4-乙氧化異丙苯基苯酚丙烯酸酯、丙烯酸二環戊烯氧基乙酯、甲基丙烯酸二環戊烯氧基乙酯、丙烯酸二環戊烯酯等。 Examples of the "(meth)acrylate monomer having a cyclic skeleton in the side chain" include:
Figure 110106505-A0305-02-0025-22
methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, tetrahydrofurfuryl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate Ethyl ester, phenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, cyclic trimethylolpropane formal Acrylates, 4-ethoxylated cumylphenol acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, and the like.

作為「碳數4以下之乙烯基單體」，可列舉：乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、正丙基乙烯醚、異丙基乙烯醚、正丁基乙烯醚、異丁基乙烯醚等。 Examples of "vinyl monomers having 4 or less carbon atoms" include: vinyl acetate, vinyl propionate, vinyl butyrate, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, vinyl ether etc.

作為「側鏈具有環狀骨架之乙烯基單體」，可列舉：苯乙烯、環己基乙烯醚、降

Figure 110106505-A0305-02-0025-23
基乙烯醚、降
Figure 110106505-A0305-02-0025-25
烯基乙烯醚等。其中，尤佳為側鏈之碳數為4以下之乙烯基單體或側鏈之碳數為4以下之丙烯酸酯單體。 Examples of the "vinyl monomer having a cyclic skeleton in the side chain" include styrene, cyclohexyl vinyl ether, nor
Figure 110106505-A0305-02-0025-23
Vinyl ether, nor
Figure 110106505-A0305-02-0025-25
Alkenyl vinyl ether, etc. Among them, a vinyl monomer having 4 or less carbon atoms in the side chain or an acrylate monomer having 4 or less carbon atoms in the side chain is particularly preferable.

上述單體a3較佳為側鏈之碳數為1以下之(甲基)丙烯酸酯單體或側鏈具有環狀骨架之(甲基)丙烯酸酯單體。 The above-mentioned monomer a3 is preferably a (meth)acrylate monomer having 1 or less carbon atoms in the side chain or a (meth)acrylate monomer having a cyclic skeleton in the side chain.

此處，作為「側鏈之碳數為1以下之(甲基)丙烯酸酯單體」，可列舉：甲基丙烯酸甲酯、丙烯酸、甲基丙烯酸等。 Here, examples of the "(meth)acrylate monomer having one or less carbon atoms in the side chain" include methyl methacrylate, acrylic acid, methacrylic acid, and the like.

作為「側鏈具有環狀骨架之(甲基)丙烯酸酯單體」，可列舉：甲基丙烯酸異

Figure 110106505-A0305-02-0026-26
基酯、甲基丙烯酸3,3,5-三甲基環己酯、丙烯酸二環戊酯、甲基丙烯酸二環戊酯、甲基丙烯酸二環戊烯酯等。 Examples of the "(meth)acrylate monomer having a cyclic skeleton in the side chain" include:
Figure 110106505-A0305-02-0026-26
Base ester, 3,3,5-trimethylcyclohexyl methacrylate, dicyclopentyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, etc.

若(甲基)丙烯酸系共聚物(1-A2)含有使單體a1、單體a2與單體a3以a1：a2：a3=10~40：90~35：0~25之莫耳比率共聚合而成之(甲基)丙烯酸酯共聚物或乙烯系共聚物，則可將Tanδ之波峰調整為0~20℃，於通常狀態，即，室溫狀態下，可保持片狀之形狀。並且，具有以較輕之力短時間接著於被黏著體上之性質(稱為“黏性”)。又，若加熱至可熱熔之溫度，則表現出流動性，可追隨貼合面之階差部而填充至各角落。 If the (meth)acrylic copolymer (1-A2) contains monomer a1, monomer a2 and monomer a3 in a molar ratio of a1:a2:a3=10~40:90~35:0~25 The polymerized (meth)acrylate copolymer or ethylene-based copolymer can adjust the peak of Tanδ to 0~20°C, and can maintain the shape of a sheet in the normal state, that is, at room temperature. Also, it has the property of sticking to the adherend with light force for a short time (called "adhesive"). In addition, when heated to a heat-melting temperature, it exhibits fluidity and can be filled to every corner following the step of the bonding surface.

因此，就該觀點而言，構成(甲基)丙烯酸系共聚物(1-A2)之(甲基)丙烯酸酯共聚物或乙烯系共聚物中之單體a1、單體a2與單體a3之莫耳比率較佳為a1：a2：a3=10~40：90~35：0~25，其中更佳為13~40：87~35：0~23，其中進而較佳為15~40：85~38：2~20。 Therefore, from this point of view, the difference between monomer a1, monomer a2 and monomer a3 in the (meth)acrylate copolymer or vinyl copolymer constituting the (meth)acrylic copolymer (1-A2) The molar ratio is preferably a1:a2:a3=10~40:90~35:0~25, more preferably 13~40:87~35:0~23, and more preferably 15~40:85 ~38:2~20.

又，就與上述相同之觀點而言，構成(甲基)丙烯酸系共聚物(1-A2)之(甲基)丙烯酸酯共聚物或乙烯系共聚物中之單體a1、單體a2與單體a3之莫耳比率較佳為a2>a1>a3。 Also, from the same viewpoint as above, monomer a1, monomer a2 and monomer The molar ratio of body a3 is preferably a2>a1>a3.

(交聯劑(1-B2)) (Crosslinking agent (1-B2))

藉由於本黏著片材1中使交聯劑(1-B2)交聯，本黏著片材1於高溫環境下表現較高之凝集力，可獲得優異之耐發泡可靠性。 By crosslinking the crosslinking agent (1-B2) in the adhesive sheet 1, the adhesive sheet 1 exhibits high cohesive force under high temperature environment, and can obtain excellent reliability against foaming.

作為此種交聯劑(1-B2)，例如可適宜選擇具有2個以上之環氧基或異氰酸酯基、氧雜環丁烷基、矽烷醇基、(甲基)丙烯醯基等交聯性基之交聯劑。其中，就反應性或所得硬化物之強度之方面而言，較佳為具有2個以上之(甲基)丙烯醯基，其中更佳為具有3個以上之(甲基)丙烯醯基的多官能(甲基)丙烯酸酯或具有環氧基或異氰酸酯基等之(甲基)丙烯酸酯。 As such a crosslinking agent (1-B2), for example, crosslinking properties such as epoxy groups or isocyanate groups, oxetanyl groups, silanol groups, (meth)acryl groups, etc. can be appropriately selected. base crosslinking agent. Among them, in terms of reactivity or the strength of the obtained hardened product, polyamides having 2 or more (meth)acryl groups are preferred, and polyamides having 3 or more (meth)acryl groups are more preferred. Functional (meth)acrylates or (meth)acrylates having epoxy groups, isocyanate groups, etc.

作為此種(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、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、三羥甲基丙烷三氧基乙基(甲基)丙烯酸酯、ε-己內酯改性三(2-羥基乙基)異氰尿酸酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、丙氧化季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、丙氧化季戊四醇四(甲基)丙烯酸酯、乙氧化季戊四醇四(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、三(丙烯醯氧基乙基)異氰尿酸酯、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多官能單體類，另外亦可列舉：聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能丙烯酸酯低聚物類或異氰酸酯(甲基)丙 烯酸酯、1,1-(雙(甲基)丙烯醯氧基甲基)乙基異氰酸酯、2-(2-(甲基)丙烯醯氧基乙基氧基)乙基異氰酸酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥乙酯縮水甘油醚、(甲基)丙烯酸羥丙酯縮水甘油醚、(甲基)丙烯酸羥丁酯縮水甘油醚等。 Examples of such (meth)acrylates include 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, 1,6-hexanediol di(methyl) Acrylates, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol A Polypropoxy di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane trioxyethyl(methyl) ) acrylate, ε-caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate ester, ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylate, polyethylene glycol di(meth)acrylate, tris(acryloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, hydroxypivalic acid Di(meth)acrylate of ε-caprolactone adduct of neopentyl glycol ester, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate Acrylate, bis(trimethylolpropane)tetra(meth)acrylate and other ultraviolet curable polyfunctional monomers, and also polyester (meth)acrylate, epoxy (meth)acrylate , (meth)acrylate urethane, polyether (meth)acrylate and other multifunctional acrylate oligomers or isocyanate (meth)acrylic enoate, 1,1-(bis(meth)acryloxymethyl)ethyl isocyanate, 2-(2-(meth)acryloxyethyloxy)ethyl isocyanate, (methyl ) glycidyl acrylate, (meth)hydroxyethyl acrylate glycidyl ether, (meth)hydroxypropyl acrylate glycidyl ether, (meth)hydroxybutyl acrylate glycidyl ether, etc.

上述所列舉之中，就提高對被黏著體之密接性或耐熱性、濕熱白化抑制之效果的觀點而言，較佳為含有極性官能基之多官能單體或低聚物。其中，較佳為使用具有異三聚氰酸環骨架之多官能(甲基)丙烯酸酯。 Among those listed above, from the viewpoint of improving the adhesiveness to the adherend, the heat resistance, and the effect of suppressing wet heat whitening, polyfunctional monomers or oligomers containing polar functional groups are preferred. Among them, it is preferable to use a polyfunctional (meth)acrylate having an isocyanuric acid ring skeleton.

交聯劑(1-B2)之含量並無特別限制。作為標準，較佳為相對於(甲基)丙烯酸系共聚物(1-A2)100質量份為0.5~20質量份，其中更佳為1質量份以上或15質量份以下，其中進而較佳為2質量份以上或10質量份以下之比率。 The content of the crosslinking agent (1-B2) is not particularly limited. As a standard, it is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (meth)acrylic copolymer (1-A2), more preferably 1 part by mass or more and 15 parts by mass or less, and even more preferably 0.5 to 20 parts by mass The ratio of 2 mass parts or more or 10 mass parts or less.

藉由於上述範圍內含有交聯劑(1-B2)，可同時實現未交聯狀態之本黏著片材1之形狀穩定性與交聯後之黏著材之耐發泡可靠性。其中，就與其他要素之平衡性而言，亦可超出該範圍。 By containing the crosslinking agent (1-B2) within the above range, the shape stability of the adhesive sheet 1 in the uncrosslinked state and the foaming resistance reliability of the crosslinked adhesive can be simultaneously realized. Among them, in terms of balance with other elements, it may also exceed this range.

(光聚合起始劑(1-C2)) (Photopolymerization Initiator (1-C2))

光聚合起始劑(1-C2)係發揮作為上述交聯劑(1-B2)之交聯反應之反應起始助劑的功能者，可適當使用上述光聚合起始劑(1-C1)所記載者。 The photopolymerization initiator (1-C2) functions as a reaction initiation aid for the crosslinking reaction of the above-mentioned crosslinking agent (1-B2), and the above-mentioned photopolymerization initiator (1-C1) can be used appropriately recorded.

光聚合起始劑(1-C2)之含量並無特別限制。作為標準，較佳為以相對於(甲基)丙烯酸系共聚物(1-A2)100質量份為0.1~10質量份，其中更佳為0.5質量份以上或5質量份以下，其中進而較佳為1質量份以上或3質量份以下之比率含有。 The content of the photopolymerization initiator (1-C2) is not particularly limited. As a standard, it is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylic copolymer (1-A2), more preferably at least 0.5 parts by mass or less than 5 parts by mass, and even more preferably It is contained in the ratio of 1 mass part or more or 3 mass parts or less.

藉由將光聚合起始劑(1-C2)之含量設為上述範圍，可獲得對活性能量線之適度之反應感度。 Moderate reaction sensitivity to active energy rays can be obtained by making content of a photoinitiator (1-C2) into the said range.

(其他成分) (other ingredients)

黏著劑組合物(1-II)可含有通常之黏著劑組合物中所調配之公知之成分作為上述以外之成分。例如可視需要適當含有黏著賦予樹脂或抗氧化劑、光穩定化劑、金屬減活劑、抗老化劑、吸濕劑、聚合抑制劑、紫外線吸收劑、防銹劑、矽烷偶合劑、無機粒子等各種添加劑。 The adhesive composition (1-II) may contain, as components other than the above, known components formulated in ordinary adhesive compositions. For example, if necessary, various types such as adhesion-imparting resins, antioxidants, photostabilizers, metal deactivators, anti-aging agents, moisture absorbers, polymerization inhibitors, ultraviolet absorbers, rust inhibitors, silane coupling agents, and inorganic particles can be appropriately contained. additive.

又，亦可視需要適當含有反應觸媒(三級胺系化合物、四級銨系化合物、月桂酸錫化合物等)。 Moreover, a reaction catalyst (tertiary amine type compound, quaternary ammonium type compound, tin laurate compound, etc.) may be contained suitably as needed.

<積層構造> <Laminated structure>

本黏著片材1可為包含單一層之片材，亦可為2層以上積層而成之多層片材。 The adhesive sheet 1 may be a sheet comprising a single layer, or may be a multilayer sheet formed by laminating two or more layers.

於本黏著片材1為多層黏著片材之情形時，只要具備由本黏著劑組合物1形成之黏著層(稱為「本黏著層1」)即可，例如於形成具備中間層與最外層之積層構造之黏著片材之情形時，較佳為由本黏著劑組合物1，其中更佳為由黏著劑組合物(1-I)(1-II)形成該最外層。 When the adhesive sheet 1 is a multi-layer adhesive sheet, it only needs to have an adhesive layer formed from the adhesive composition 1 (referred to as "the adhesive layer 1"), for example, when forming a layer having an intermediate layer and an outermost layer In the case of an adhesive sheet having a laminated structure, it is preferable to form the outermost layer from the present adhesive composition 1, and it is more preferable to form the outermost layer from the adhesive composition (1-I) (1-II).

又，本黏著片材1亦可為具備使由本黏著劑組合物1形成之本黏著層1形成於脫模膜上而成之構成者，又，亦可為具備於被黏著體例如如下述之圖像顯示裝置用構成構件上形成上述本黏著層1而成之構成者。又，例如，可為具備於基材上形成上述本黏著層1而成之構成之附基材黏著片材，亦可為不具有基材之無基材黏著片材。進而，可為上下兩側具有本黏著層1之雙面黏著片材，亦可為僅於上下單面側具有本黏著層1之單面黏著片材。 In addition, the present adhesive sheet 1 may be provided with a structure in which the present adhesive layer 1 formed from the present adhesive composition 1 is formed on a release film, and may be provided on an adherend such as the following A structure in which the above-mentioned adhesive layer 1 is formed on a constituent member for an image display device. Also, for example, it may be a base-attached adhesive sheet having a structure in which the above-mentioned present adhesive layer 1 is formed on a base material, or may be a base-less adhesive sheet not having a base material. Furthermore, it may be a double-sided adhesive sheet having the present adhesive layer 1 on both upper and lower sides, or a single-sided adhesive sheet having the present adhesive layer 1 only on the upper and lower sides.

<厚度> <thickness>

作為本黏著片材1之厚度，就不妨礙圖像顯示裝置之薄化之觀點而 言，最大厚度部分之厚度較佳為250μm以下。換言之，本黏著片材1可為厚度均勻之片材，亦可為部分厚度不同之不均勻之片材，於厚度不均勻之片材之情形時，厚度最大之部分之厚度較佳為250μm以下。 As the thickness of the adhesive sheet 1, it is determined not to hinder the thinning of the image display device. In other words, the thickness of the maximum thickness portion is preferably 250 μm or less. In other words, the adhesive sheet 1 may be a sheet with a uniform thickness, or a non-uniform sheet with parts having different thicknesses. In the case of a sheet with non-uniform thickness, the thickness of the thickest part is preferably 250 μm or less .

又，就不妨礙與被黏著體之密接力或減震性之觀點而言，最大厚度部分之厚度較佳為5μm以上，更佳為10μm以上，進而較佳為15μm以上。 Also, the thickness of the maximum thickness portion is preferably at least 5 μm, more preferably at least 10 μm, and still more preferably at least 15 μm, from the viewpoint of not hindering the adhesion with the adherend or shock absorption.

<用途> <purpose>

本黏著片材1可於其原本之形態下使用，亦可以如下方式使用。但並不限定本黏著片材1之利用方法。 This adhesive sheet 1 can be used in its original form, and can also be used in the following manner. However, the utilization method of the adhesive sheet 1 is not limited.

本黏著片材1例如可作為具備於本黏著片材1之一面或雙面積層脫模膜而成之構成之黏著片材積層體而提供。 This adhesive sheet 1 can be provided, for example as an adhesive sheet laminate including a release film on one side of this adhesive sheet 1 or a double-sided layer.

<本圖像顯示裝置構成用積層體1> <Laminate 1 for constituting the present image display device>

又，可製作而提供具備介隔本黏著片材1而積層2個圖像顯示裝置用構成構件間而成之構成之圖像顯示裝置構成用積層體(以下，稱為「本圖像顯示裝置構成用積層體1」)。 In addition, a laminated body for constituting an image display device (hereinafter referred to as "this image display device") having a structure in which two constituting members for an image display device are laminated via this adhesive sheet 1 can be produced and provided. Laminated body for constituting 1").

本圖像顯示裝置構成用積層體1例如可藉由如下方式製作：介隔上述本黏著片材1積層圖像顯示裝置用構成構件與其他圖像顯示裝置用構成構件，介隔前者之圖像顯示裝置構成構件對上述本黏著片材1進行光照射，使該黏著片材光硬化。 The laminate 1 for constituting an image display device can be produced, for example, by interposing the above-mentioned adhesive sheet 1 to laminate the constituent members for an image display device and other constituent members for an image display device, and interposing the image of the former The display device constituting members irradiate the above-mentioned adhesive sheet 1 with light to photocure the adhesive sheet.

作為本圖像顯示裝置構成用積層體1之一例，除包含保護面板/本黏著片材1/偏光膜之構成之積層體外，例如亦可列舉：圖像顯示面板/本黏著片材1/觸控面板、圖像顯示面板/本黏著片材1/保護面板、圖像顯示面板/本黏著片材1/觸控面板/本黏著片材1/保護面板、偏光膜/本黏著片材1/觸 控面板、偏光膜/本黏著片材1/觸控面板/本黏著片材1/保護面板等構成例。 As an example of the laminate 1 for constituting the image display device, in addition to the laminate including the protective panel/this adhesive sheet 1/polarizing film, for example, image display panel/this adhesive sheet 1/touch Control panel, image display panel/this adhesive sheet 1/protective panel, image display panel/this adhesive sheet 1/touch panel/this adhesive sheet 1/protective panel, polarizing film/this adhesive sheet 1/ touch Control panel, polarizing film/adhesive sheet 1/touch panel/adhesive sheet 1/protective panel.

保護面板及圖像顯示面板亦可為於保護面板或圖像顯示面板本身中組入有觸控面板感測器者。 The protection panel and the image display panel may also be those in which a touch panel sensor is incorporated in the protection panel or the image display panel itself.

<本圖像顯示裝置1> <This image display device 1>

亦可使用本黏著片材1或本圖像顯示裝置構成用積層體而構成圖像顯示裝置(以下，稱為「本圖像顯示裝置1」)。 An image display device (hereinafter referred to as "the present image display device 1") can also be configured using the adhesive sheet 1 or the laminate for constituting the image display device.

對本圖像顯示裝置1之較佳之製法之一例加以說明。 An example of a preferable manufacturing method of the present image display device 1 will be described.

首先，加熱上述本黏著片材1使之熱熔，介隔上述本黏著片材1積層圖像顯示裝置用構成構件與其他圖像顯示裝置用構成構件。於該階段，本黏著片材1適度柔軟，故而可於維持保存穩定性之同時而充分追隨階差。 First, the above-mentioned adhesive sheet 1 is heated to be thermally fused, and the constituent members for an image display device and other constituent members for an image display device are laminated with the adhesive sheet 1 interposed therebetween. At this stage, since the present adhesive sheet 1 is moderately soft, it can sufficiently follow a step difference while maintaining storage stability.

並且其次，自圖像顯示裝置用構成構件之外側照射紫外線等光。由此，可進行交聯反應而使之光硬化，可實現優異之耐剝離性及耐發泡性。 Then, light such as ultraviolet rays is irradiated from the outside of the constituent member for an image display device. As a result, cross-linking reaction can be carried out to make it photocurable, and excellent peeling resistance and foaming resistance can be realized.

作為上述2個圖像顯示裝置用構成構件，例如可列舉：電腦、移動終端(PDA)、遊戲機、電視(TV)、汽車導航、觸控面板、手寫板等LCD、PDP或EL等圖像顯示裝置之構成構件。更具體而言，例如可列舉由觸控面板、圖像顯示面板、表面保護面板及偏光膜所組成之群中之任一種或包含兩種以上之組合之積層體。 As the constituent members for the above two image display devices, for example, computer, mobile terminal (PDA), game machine, television (TV), car navigation, touch panel, tablet and other LCD, PDP or EL etc. Components of display devices. More specifically, for example, any one of the group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film, or a laminate including a combination of two or more thereof can be used.

[本黏著片材2] [this adhesive sheet 2]

本發明之另一實施形態之一例之黏著片材(稱為「本黏著片材2」)係含有(甲基)丙烯酸系共聚物(A)作為基礎聚合物且部分光硬化而成之黏著片材，並且黏著片材之任一個中具有凝膠分率未達1%之片材部(稱為「軟質部」)與凝膠分率為40%以上之片材部(稱為「硬質部」)。 An adhesive sheet (referred to as "the present adhesive sheet 2"), which is an example of another embodiment of the present invention, is an adhesive sheet that contains a (meth)acrylic copolymer (A) as a base polymer and is partially photocured material, and any one of the adhesive sheets has a sheet part with a gel fraction of less than 1% (called "soft part") and a sheet part with a gel fraction of 40% or more (called "hard part") ").

作為凝膠分率之測定方法，可列舉藉由溶劑之萃取。具體而言，於構成黏著片材之聚合物未交聯之情形時選擇溶解該聚合物之溶劑(良溶劑)，繼而，使用該溶劑萃取黏著片材。作為萃取時之溶劑，例如可列舉：乙酸乙酯、丙酮、甲苯、二甲苯、低級醇、四氫呋喃等。 As a method for measuring the gel fraction, extraction with a solvent is exemplified. Specifically, when the polymer constituting the adhesive sheet is not cross-linked, a solvent (good solvent) that dissolves the polymer is selected, and then, the adhesive sheet is extracted using the solvent. As a solvent at the time of extraction, ethyl acetate, acetone, toluene, xylene, lower alcohol, tetrahydrofuran etc. are mentioned, for example.

萃取時之溫度或時間可任意設定。進行萃取操作後，回收不溶解於該溶劑中之成分(膨潤成分)，加以乾燥後，測定該重量分率即可。作為具體之萃取方法，可列舉索氏萃取或下述實施例中記載之方法等。 The temperature or time during extraction can be set arbitrarily. After the extraction operation, recover the insoluble component (swelling component) in the solvent, dry it, and measure the weight fraction. As a specific extraction method, Soxhlet extraction or the method described in the following examples etc. are mentioned.

再者，於凝膠分率較高之情形時，可適宜將黏著片材破碎而供於萃取。 Furthermore, when the gel fraction is relatively high, it may be appropriate to crush the adhesive sheet for extraction.

例如於行動電話之顯示畫面等中，採用於液晶面板顯示器(LCD)上積層偏光膜等，於其上介隔黏著劑或片材積層塑膠製之保護面板的構成，通常於該保護面板之背面之周緣部附設有印刷部等不透光部。 For example, in the display screen of a mobile phone, a liquid crystal panel display (LCD) is laminated with a polarizing film, etc., and a protective panel made of adhesive or sheet-laminated plastic is interposed thereon, usually on the back of the protective panel. The peripheral part is provided with opaque parts such as printing parts.

於將此種附設有印刷部之保護面板介隔黏著片材與觸控面板等其他圖像顯示裝置構成構件貼合之情形時，若該黏著片材可追隨印刷階差而填充至各角落，並且黏著片材之表面不平滑，則貼合圖像顯示構成構件時於黏著片材中產生應變或變形，成為顯示不均所導致之視認性下降之原因，故而要求該黏著片材具有柔軟性。並且，存在因印刷階差等而使黏著片材內易於產生應變或變形之課題。 When the protective panel with the printing part is bonded to other components of the image display device such as the touch panel through the adhesive sheet, if the adhesive sheet can follow the printing steps and fill to every corner, Moreover, if the surface of the adhesive sheet is not smooth, strain or deformation will occur in the adhesive sheet when the image display components are pasted, which will cause the decrease in visibility caused by uneven display. Therefore, the adhesive sheet is required to have flexibility. . In addition, there is a problem that strain and deformation are likely to occur in the adhesive sheet due to printing steps and the like.

另一方面，要求即使於高溫高濕下等嚴酷之環境下，露出之黏著面亦不發黏。不僅如此，亦要求介隔黏著片材貼合圖像顯示裝置構成構件後之黏著片材具有不產生剝離或發泡之較高之凝集力。 On the other hand, it is required that the exposed adhesive surface is not sticky even in severe environments such as high temperature and high humidity. Not only that, it is also required that the adhesive sheet bonded to the components of the image display device through the adhesive sheet has a high cohesive force without peeling or foaming.

因此本發明欲提供一種例如即使於貼合於貼合面內具有印刷部等不透光部與透光部之圖像顯示裝置用構成構件之情形時，亦可獲得對階差部 等之追隨性或表面平坦性，於不透光部中亦不會產生應變或變形，並且可具有較高之凝集力而將被黏著物彼此牢固地貼合，進而，即使於高溫高濕下等嚴酷之環境下，亦可使露出之黏著面不發黏的新穎的黏著片材2。 Therefore, the present invention intends to provide a step difference portion even when it is bonded to a constituent member for an image display device having an opaque portion such as a printed portion and a light-transmitting portion in the bonding surface, for example. The followability or flatness of the surface will not produce strain or deformation in the opaque part, and it can have high cohesion to firmly bond the adherends to each other, and even under high temperature and high humidity Novel adhesive sheet 2 that can also make the exposed adhesive surface not sticky under harsh environments.

對本黏著片材2而言，藉由凝膠分率未達1%之軟質部，可獲得對階差部等之追隨性或表面平坦性，可緩和片材內之應變或變形，另一方面藉由凝膠分率為40%以上之硬質部，不僅可使黏著面不發黏，亦可具有較高之凝集力而使被黏著物彼此牢固地接著。 In this adhesive sheet 2, the soft part with a gel fraction of less than 1% can obtain followability or surface flatness to the step part, etc., and can relieve strain or deformation in the sheet. On the other hand, With the hard part with a gel fraction of 40% or more, not only can the adhesive surface not be sticky, but it can also have a high cohesive force so that the adherends can be firmly bonded to each other.

因此，例如，即使於貼合於貼合面內具有印刷部等不透光部與透光部之圖像顯示裝置用構成構件之情形時，亦可作為黏著片材整體而獲得對印刷階差部之追隨性或表面平坦性，於不透光部中亦不會產生應變或變形，進而，可具有較高之凝集力而將被黏著物彼此牢固地貼合。又，藉由將露出之黏著面作為硬質部，即使於高溫高濕下等嚴酷之環境下，亦可使露出之黏著面不發黏。 Therefore, for example, even in the case of bonding to a constituent member for an image display device having an opaque portion such as a printed portion and a light-transmitting portion in the bonding surface, it is possible to obtain a print level difference as a whole of the adhesive sheet. The followability or surface flatness of the part does not cause strain or deformation in the opaque part, and furthermore, it can have a high cohesive force to firmly bond the adherends to each other. Also, by using the exposed adhesive surface as a hard portion, the exposed adhesive surface can be kept from sticking even under severe environments such as high temperature and high humidity.

本黏著片材2例如可為如圖1或圖2所示，於黏著片材之片材面內具有上述軟質部與硬質部之形態，又，亦可為如圖3(A)(B)或圖5所示，於黏著片材之至少一側之端面部具有上述硬質部之形態。此時，黏著片材之片材面可為軟質部，亦可為硬質部。又，亦可為如圖5所示，於卷為捲筒狀之黏著片材之至少一側之端面部具有上述硬質部之形態。 The adhesive sheet 2 can be, for example, as shown in Figure 1 or Figure 2, with the above-mentioned soft part and hard part in the sheet surface of the adhesive sheet, and can also be as shown in Figure 3 (A) (B). Or as shown in FIG. 5 , at least one end surface of the adhesive sheet has the form of the above-mentioned hard portion. In this case, the sheet surface of the adhesive sheet may be a soft part or a hard part. Moreover, as shown in FIG. 5, the said hard part may be provided in the end surface part of at least one side of the roll-shaped adhesive sheet.

所謂本發明之「基礎聚合物」係指成為形成各層之黏著劑組合物之主成分的樹脂。並不規定基礎聚合物之具體含量，但作為標準，較佳為占形成各層之黏著劑組合物中所含樹脂之50質量%以上，其中更佳為80質量%以上，其中進而較佳為90質量%以上(包含100質量%)之樹脂。再者，於基礎聚合物為兩種以上之情形時，該等之總量為上述含量。 The "base polymer" in the present invention refers to a resin that becomes the main component of the adhesive composition forming each layer. The specific content of the base polymer is not specified, but as a standard, it is preferably at least 50% by mass of the resin contained in the adhesive composition forming each layer, more preferably at least 80% by mass, and even more preferably at least 90% by mass. Resin of mass % or more (including 100 mass %). Furthermore, when there are two or more base polymers, the total amount thereof is the above-mentioned content.

就對階差部之追隨性、表面平坦性、進而可緩和片材內之應變或變形之觀點而言，上述軟質部之凝膠分率較佳為未達1%，其中更佳為未達0.8%，其中尤佳為未達0.5%。 From the standpoint of followability of the step portion, surface flatness, and relaxation of strain or deformation in the sheet, the gel fraction of the soft portion is preferably less than 1%, and more preferably less than 1%. 0.8%, of which the best is less than 0.5%.

另一方面，就發揮較高之凝集力而提高接著性，即使於高溫高濕下等嚴酷之環境下亦不會使黏著面發黏的觀點而言，上述硬質部之凝膠分率較佳為40%以上，其中更佳為45%以上，其中尤佳為50%以上。 On the other hand, the gel fraction of the above-mentioned hard part is preferable from the viewpoint of exerting a higher cohesive force to improve adhesiveness, and not making the adhesive surface sticky even in severe environments such as high temperature and high humidity. More than 40%, more preferably more than 45%, and especially more than 50%.

又，若使用示差掃描熱量計(DSC)而測定之上述軟質部之玻璃轉移溫度(Tg[S])為-70~-10℃，則於常溫範圍具有適度之柔軟性與自黏著性，因此軟質部之Tg較佳為-70~-10℃，其中更佳為-65℃以上或-15℃以下，其中尤佳為-60℃以上或-20℃以下。 In addition, if the glass transition temperature (Tg[S]) of the above-mentioned soft part measured by using a differential scanning calorimeter (DSC) is -70~-10°C, it has moderate flexibility and self-adhesiveness in the normal temperature range, so The Tg of the soft part is preferably -70~-10°C, more preferably above -65°C or below -15°C, especially preferably above -60°C or below -20°C.

另一方面，若使用示差掃描熱量計(DSC)而測定之上述硬質部之玻璃轉移溫度(Tg[H])為-60~+10℃，則可獲得較高之凝集力，因此硬質部之Tg較佳為-60~+20℃，其中更佳為-55℃以上或+15℃以下，其中尤佳為-50℃以上或+10℃以下。 On the other hand, if the glass transition temperature (Tg[H]) of the above-mentioned hard part measured by using a differential scanning calorimeter (DSC) is -60~+10°C, a higher cohesive force can be obtained, so the hard part Tg is preferably -60 to +20°C, more preferably above -55°C or below +15°C, especially preferably above -50°C or below +10°C.

又，若軟質部之玻璃轉移溫度(Tg[S])與硬質部之玻璃轉移溫度(Tg[H])之差(Tg[H]-Tg[S])為3℃以上，則可以更高水準同時實現柔軟性與凝集力之相反品質，其結果，可同時實現貼合時對被黏著面之追隨性與積層體後之優異之耐發泡可靠性，故而較佳。因此，硬質部之玻璃轉移溫度(Tg[H])之差(Tg[H]-Tg[S])較佳為3℃以上，其中更佳為5℃以上，其中尤佳為7℃以上。 In addition, if the difference (Tg[H]-Tg[S]) between the glass transition temperature (Tg[S]) of the soft part and the glass transition temperature (Tg[H]) of the hard part is 3 °C or more, it can be higher The level achieves the opposite qualities of softness and cohesive force at the same time. As a result, it can simultaneously realize the followability of the adhered surface during lamination and the excellent foaming resistance reliability of the laminated body, so it is preferable. Therefore, the difference (Tg[H]-Tg[S]) of the glass transition temperature (Tg[H]) of the hard portion is preferably 3°C or higher, more preferably 5°C or higher, and particularly preferably 7°C or higher.

(軟質部之阿斯卡硬度(Asker hardness)) (Asker hardness of the soft part)

藉由使本黏著片材2之軟質部之阿斯卡硬度(c)為10以上，可獲得對剪裁加工性或處理之容易性而言適度之硬度，故而較佳。又，藉由使上述阿 斯卡硬度(c)未達60，可獲得適度之柔軟性與對被黏著體之附著性，故而較佳。 Since the Ascal hardness (c) of the soft part of this adhesive sheet 2 is 10 or more, moderate hardness can be obtained with respect to the easiness of cutting processability and handling, and it is preferable. Also, by making the above The Ska hardness (c) is less than 60, which can obtain moderate flexibility and adhesion to the adherend, so it is preferable.

就該觀點而言，本黏著片材2之軟質部之阿斯卡硬度(c)較佳為10以上且未達60，其中更佳為15以上或55以下，其中尤佳為20以上或50以下。 From this point of view, the Ascal hardness (c) of the soft part of the adhesive sheet 2 is preferably 10 or more and less than 60, more preferably 15 or more or 55 or less, especially preferably 20 or more or 50 the following.

(硬質部之阿斯卡硬度) (Ascal hardness of the hard part)

藉由使本黏著片材2之硬質部之阿斯卡硬度(d)為40以上，可獲得較高之凝集力，可獲得形狀穩定性或耐發泡可靠性優異之積層體。又，藉由使上述阿斯卡硬度(d)未達90，可獲得不會變得過脆，耐衝擊性優異之積層體，故而較佳。 By setting the Asker's hardness (d) of the hard portion of the adhesive sheet 2 to 40 or more, a high cohesive force can be obtained, and a laminate excellent in shape stability and foaming resistance reliability can be obtained. Moreover, since the laminated body excellent in impact resistance can be obtained without becoming too brittle by making the above-mentioned Ascal hardness (d) less than 90, it is preferable.

就該觀點而言，本黏著片材2之硬質部之阿斯卡硬度(d)較佳為40以上且未達90，其中較佳為43以上或88以下，其中尤佳為45以上或85以下。 From this point of view, the Ascal hardness (d) of the hard portion of the adhesive sheet 2 is preferably 40 or more and less than 90, preferably 43 or more or 88 or less, and particularly preferably 45 or more or 85 or less. the following.

進而於本黏著片材2中，藉由使上述(d)-(c)為20以上，可同時實現貼合時對被黏著面之追隨性與積層體後之優異之耐發泡可靠性，故而較佳。 Furthermore, in this adhesive sheet 2, by setting the above-mentioned (d)-(c) to be 20 or more, it is possible to achieve both followability to the surface to be adhered during lamination and excellent foaming resistance reliability after the laminate, Therefore better.

就該觀點而言，於本黏著片材2中，軟質部之阿斯卡硬度(c)與硬質部之阿斯卡硬度(d)之差((d)-(c))較佳為20以上，其中更佳為20以上或80以下，其中尤佳為25以上或75以下。 From this point of view, in this adhesive sheet 2, the difference ((d)-(c)) between the Asker's hardness (c) of the soft part and the Asker's hardness (d) of the hard part is preferably 20. or more, more preferably 20 or more or 80 or less, especially preferably 25 or more or 75 or less.

於本黏著片材2中，為調整軟質部之阿斯卡硬度(c)及硬質部之阿斯卡硬度(d)，於組成或製法中，調整交聯劑或光聚合起始劑之組成比，或調整對黏著劑組合物之光照射量即可。但並不限定於此種方法。 In this adhesive sheet 2, in order to adjust the Asker's hardness (c) of the soft part and the Asker's hardness (d) of the hard part, the composition of the crosslinking agent or photopolymerization initiator is adjusted in the composition or manufacturing method ratio, or adjust the amount of light exposure to the adhesive composition. However, it is not limited to this method.

(軟質部之180°剝離力) (180°peel force of the soft part)

藉由使本黏著片材2之軟質部之180°剝離力為3N/cm以上，可具有常 溫下對被黏著體之適度之附著性，貼合作業性優異，故而較佳。 By making the 180° peeling force of the soft portion of the adhesive sheet 2 3 N/cm or more, it can have a constant Moderate adhesion to the adherend at low temperature and excellent lamination workability, so it is better.

就該觀點而言，本黏著片材2之軟質部之180°剝離力較佳為3N/cm以上，其中較佳為20N/cm以下，其中尤佳為4N/cm以上或15N/cm以下。 From this point of view, the 180° peel force of the soft portion of the adhesive sheet 2 is preferably 3 N/cm or more, preferably 20 N/cm or less, and particularly preferably 4 N/cm or more or 15 N/cm or less.

(硬質部之180°剝離力) (180°peel force of hard part)

藉由使本黏著片材2之硬質部之180°剝離力為5N/cm以上，可獲得優異之耐發泡、剝離性，故而較佳。 Since the 180° peeling force of the hard portion of the present adhesive sheet 2 is 5 N/cm or more, excellent foaming resistance and peeling properties can be obtained, which is preferable.

就該觀點而言，本黏著片材2之硬質部之180°剝離力較佳為5N/cm以上，其中較佳為25N/cm以下，其中尤佳為6N/cm以上或20N/cm以下。 From this point of view, the 180° peel force of the hard portion of the adhesive sheet 2 is preferably 5 N/cm or more, preferably 25 N/cm or less, and particularly preferably 6 N/cm or more or 20 N/cm or less.

於本黏著片材2中，為調整軟質部及硬質部之180°剝離力，於組成或製法中，調整交聯劑或光聚合起始劑之種類或組成比，或調整貼合時之加熱、加壓條件或貼合後之光照射條件即可。但並不限定於此種方法。 In this adhesive sheet 2, in order to adjust the 180° peeling force of the soft part and the hard part, in the composition or manufacturing method, the type or composition ratio of the crosslinking agent or photopolymerization initiator is adjusted, or the heating during lamination is adjusted. , pressurized conditions or light irradiation conditions after bonding. However, it is not limited to this method.

(軟質部之40℃保持力) (40°C holding power of the soft part)

藉由使本黏著片材2之軟質部之溫度40℃下之保持力為偏移長度未達10mm，可獲得優異之加工性或保存穩定性。 By making the holding force of the soft portion of the present adhesive sheet 2 at a temperature of 40° C. such that the offset length does not reach 10 mm, excellent processability and storage stability can be obtained.

就該觀點而言，本黏著片材2之軟質部之溫度40℃下之保持力較佳為偏移長度未達10mm，其中更佳為未達8mm，其中進而較佳為未達5mm。 From this point of view, the retention force of the soft portion of the present adhesive sheet 2 at a temperature of 40° C. is preferably less than 10 mm, more preferably less than 8 mm, and still more preferably less than 5 mm.

(軟質部之70℃保持力) (70°C holding power of the soft part)

又，關於本黏著片材2之軟質部之溫度70℃下之保持力，若未達10分鐘貼著面偏移且砝碼落下，則獲得貼合時對被黏著體之優異之密接性或凹凸吸收性，故而較佳。 Also, regarding the holding power of the soft part of the present adhesive sheet 2 at a temperature of 70°C, if the sticking surface deviates and the weight falls within 10 minutes, then excellent adhesion to the adherend can be obtained during sticking or Bump absorbency, so better.

就該觀點而言，關於本黏著片材2之軟質部之溫度70℃下之保持力，較佳為未達10分鐘貼著面偏移且砝碼落下，其中更佳為未達8分鐘貼著面 偏移且砝碼落下，其中進而較佳為未達6分鐘貼著面偏移且砝碼落下。 From this point of view, the holding power of the soft part of the adhesive sheet 2 at a temperature of 70°C is preferably less than 10 minutes when the sticking surface shifts and the weight falls, and more preferably less than 8 minutes. face to face Offset and the weight falls, and it is further preferably less than 6 minutes to face-to-face offset and the weight to drop.

(硬質部之40℃或70℃保持力) (40℃ or 70℃ holding force of hard part)

本黏著片材2之硬質部之溫度40℃以及70℃之保持力較佳均為偏移長度未達1mm，更佳為未達0.7mm，進而較佳為未達0.5mm。 The retention force of the hard portion of the adhesive sheet 2 at temperatures of 40°C and 70°C is preferably less than 1 mm in offset length, more preferably less than 0.7 mm, and still more preferably less than 0.5 mm.

藉由使本黏著片材2之硬質部之溫度40℃以及70℃之保持力為上述範圍，可獲得較高之凝集力，可獲得濕熱環境下之形狀穩定性或耐發泡可靠性。 By setting the holding power of the hard part of the adhesive sheet 2 at temperatures of 40° C. and 70° C. within the above-mentioned ranges, a high cohesive force can be obtained, and shape stability and foaming resistance reliability in hot and humid environments can be obtained.

<本黏著片材2之製作方法> <How to make this adhesive sheet 2>

本黏著片材2可藉由如下方式製作。 This adhesive sheet 2 can be produced as follows.

(1)對可光硬化之黏著片材，將成為軟質部之部位以不透光構件，即用於光硬化之光不透過之構件隱蔽，並且照射光，則可使以不透光構件被覆之部分成為軟質部，使未以不透光構件被覆之部分，即照射光之部分光硬化，則可成為硬質部。 (1) For the photocurable adhesive sheet, the part that will become the soft part is covered with a light-impermeable member, that is, a member that does not pass through light for photohardening, and the light is irradiated, so that the part can be covered with a light-impermeable member The part becomes the soft part, and the part not covered with the opaque member, that is, the part irradiated with light, is photohardened to become the hard part.

(2)又，若對黏著片材之端面部照射光，對該端面部以外之部分不照射光，則可使該端面部成為硬質部，其他部分成為軟質部。 (2) Also, if light is irradiated to the end surface of the adhesive sheet and no light is irradiated to the portion other than the end surface, the end surface can be made into a hard portion and the other portions can be made into a soft portion.

例如，可對黏著片材之端面部(將片材之正面及背面於垂直上下方向配置)自垂直方向或水平方向或傾斜上下方向照射光，又，亦可於黏著片材之正面及背面一側或兩側，預先積層用於光硬化之光不透過之片材，自垂直方向或水平方向或傾斜上下方向照射光。若如此進行光照射，則可使黏著片材之端面部光硬化。此時，作為用於光硬化之光不透過之上述片材，尤佳為使用以聚對苯二甲酸乙二酯為基礎聚合物之脫模片材；或者使用於聚對苯二甲酸乙二酯膜或聚烯烴膜中混練紫外線吸收劑，或於表面塗佈紫外線吸收劑之膜的脫模片材等，用於光硬化之光不透過之脫模片材。 For example, light can be irradiated on the end surface of the adhesive sheet (the front and back of the sheet are arranged vertically and vertically) from a vertical direction, a horizontal direction, or an inclined up and down direction, and the front and back of the adhesive sheet can also be illuminated together On one side or both sides, pre-laminated sheets for light hardening that do not pass through the light, and irradiate light from vertical or horizontal directions or obliquely up and down directions. By irradiating light in this way, the end surface of the adhesive sheet can be photohardened. At this time, as the above-mentioned light-proof sheet for photocuring, it is particularly preferable to use a release sheet based on polyethylene terephthalate; or to use polyethylene terephthalate UV absorber kneaded into ester film or polyolefin film, or release sheet of film coated with UV absorber on the surface, etc., used for light-proof release sheet for light hardening.

再者，照射光時端面部及其周邊部可成為硬質部。 In addition, when light is irradiated, the end face part and its peripheral part can become a hard part.

(3)又，亦可藉由分別預先製作具有各自所期望之凝膠分率之黏著片材，將兩者一體化，而於黏著片材內形成軟質部與硬質部。 (3) Also, the soft part and the hard part can be formed in the adhesive sheet by prefabricating the adhesive sheets each having a desired gel fraction and integrating the two.

<黏著片材X> <Adhesive sheet X>

本黏著片材2可使用如下之黏著片材X進行部分光硬化而形成。但並不限定於使用以下之黏著片材X而形成本黏著片材2。 The present adhesive sheet 2 can be formed by partially photocuring the following adhesive sheet X. However, it is not limited to use the following adhesive sheet X to form the present adhesive sheet 2 .

就於光硬化前之狀態下可表現熱熔性之觀點而言，黏著片材X於光硬化前之凝膠分率(a)為未達1%，其中較佳為未達0.8%，其中尤佳為未達0.5%。 From the point of view of expressing hot-melt properties in the state before photohardening, the gel fraction (a) of the adhesive sheet X before photohardening is less than 1%, preferably less than 0.8%. Preferably it is less than 0.5%.

又，就可於光硬化後獲得較高之凝集力，獲得於濕熱環境下之耐發泡可靠性的觀點而言，黏著片材X於光硬化後之凝膠分率(b)較佳為40%以上，其中更佳為45%以上或95%以下，其中尤佳為50%以上或90%以下。 Also, from the standpoint of obtaining higher cohesive force after photocuring and the reliability of foaming resistance in hot and humid environments, the gel fraction (b) of the adhesive sheet X after photocuring is preferably More than 40%, more preferably more than 45% or less than 95%, especially more than 50% or less than 90%.

為如上述方式調整光硬化前之凝膠分率(a)及光硬化後之凝膠分率(b)，於組成或製法中，調整交聯劑或光聚合起始劑之組成比，或調整加工時之溫度或光照射量即可。但並不限定於此種方法。 In order to adjust the gel fraction (a) before photohardening and the gel fraction (b) after photohardening as described above, adjust the composition ratio of the crosslinking agent or photopolymerization initiator in the composition or manufacturing method, or Just adjust the temperature or light exposure during processing. However, it is not limited to this method.

<本黏著劑組合物2> <This adhesive composition 2>

對可較佳用於形成上述黏著片材X之樹脂組合物(以下，稱為「本黏著劑組合物2」)加以說明。但僅為一例，並不限定於此。 A resin composition (hereinafter, referred to as "this adhesive composition 2") that can be preferably used to form the above-mentioned adhesive sheet X will be described. However, it is only an example and is not limited thereto.

作為本黏著劑組合物2，較佳為光硬化型黏著劑組合物。其中，較佳為含有(甲基)丙烯酸系共聚物(2-A)、交聯劑(2-B)與光聚合起始劑(2-C)之樹脂組合物。 As this adhesive composition 2, a photocurable adhesive composition is preferable. Among them, a resin composition containing a (meth)acrylic copolymer (2-A), a crosslinking agent (2-B) and a photopolymerization initiator (2-C) is preferable.

其中，如上所述，若可根據黏著片材內之部位而使貼著後之凝膠分率不同，則不限定用以形成本黏著片材2之黏著劑組合物之組成。 However, as mentioned above, the composition of the adhesive composition for forming the adhesive sheet 2 is not limited as long as the gel fraction after adhesion can be varied depending on the location in the adhesive sheet.

此處，本黏著片材2尤佳為可於常態下保持片狀，具有當於未交聯狀態下加熱時發生熔融或流動之熱熔性，且具有可光硬化之光硬化性的黏著片材。 Here, the present adhesive sheet 2 is particularly preferably an adhesive sheet that can maintain a sheet shape under normal conditions, has hot melt properties that melt or flow when heated in an uncrosslinked state, and has photocurable adhesive sheet that can be photocured. material.

若可於常態下保持片狀，則與液狀之接著劑相比，操作更容易，並且可省略填充液體之作業，因此生產性尤其優異。 If the sheet can be kept in a normal state, it is easier to handle than a liquid adhesive, and the work of filling the liquid can be omitted, so the productivity is particularly excellent.

進而，若於常態、即室溫附近具備適度之黏著性，即以較輕之力短時間接著於被黏著體上之性質(稱為“黏性”)，則易於進行貼著時之定位，作業性優異，因此較佳為於常態、即室溫附近具備黏性，若於-5℃至20℃之較低氣溫範圍亦具備黏性則更佳。 Furthermore, if it has moderate adhesiveness in the normal state, that is, around room temperature, that is, the property of sticking to the adherend with a relatively light force for a short time (called "stickiness"), it is easy to position when sticking, It is excellent in workability, so it is preferable to have viscosity in the normal state, that is, around room temperature, and it is better if it also has viscosity in the lower temperature range from -5°C to 20°C.

又，具備加熱時發生熔融或流動之熱熔性，則藉由加熱使之軟化或流動化，可追隨印刷階差等凹凸部而填充黏著劑，因此可於不產生發泡等之狀態下填充。 In addition, since it has a hot-melt property that melts or flows when heated, it can be softened or fluidized by heating, and the adhesive can be filled with uneven parts such as printing steps, so it can be filled without foaming, etc. .

進而若具有光硬化性，則藉由最終使之光硬化，可牢固地接著。 Furthermore, if it has photocurability, it can stick firmly by finally photocuring it.

如此，為製作可於常態下保持片狀，具有當於未交聯狀態下加熱時發生熔融或流動之熱熔性，且可光硬化之黏著片材，例如若為單層之黏著片材，則只要由以下說明之黏著劑組合物(2-I)或(2-II)製作單層之黏著片材即可。另一方面，於製為多層之黏著片材之情形時，例如可列舉：將包含黏著劑組合物(2-I)或(2-II)之黏著層與包含其他黏著劑組合物之黏著層積層而成之2種2層構造，或介隔中間樹脂層於正面及背面配置包含黏著劑組合物(2-I)或(2-II)之黏著層之2種3層構造，或依序積層包含黏著劑組合物(2-I)或(2-II)之黏著層、包含中間樹脂組合物之中間層及包含其他黏著劑組合物之黏著層而成的3種3層構造等。 In this way, in order to make a photocurable adhesive sheet that can maintain a sheet shape under normal conditions, has a heat-melt property that melts or flows when heated in an uncrosslinked state, for example, if it is a single-layer adhesive sheet, Then, it is only necessary to produce a single-layer adhesive sheet from the adhesive composition (2-I) or (2-II) described below. On the other hand, in the case of making a multilayer adhesive sheet, for example, an adhesive layer containing the adhesive composition (2-I) or (2-II) and an adhesive layer containing another adhesive composition can be mentioned. Two kinds of two-layer structures formed by lamination, or two kinds of three-layer structures in which an adhesive layer comprising the adhesive composition (2-I) or (2-II) is arranged on the front and back through an intermediate resin layer, or sequentially Three types of three-layer structures such as a laminate including an adhesive layer of the adhesive composition (2-I) or (2-II), an intermediate layer including an intermediate resin composition, and an adhesive layer including another adhesive composition.

其中，用以形成本黏著片材2之黏著劑組合物並不限定於黏著劑組合 物(2-I)或(2-II)。 Wherein, the adhesive composition used to form the adhesive sheet 2 is not limited to the adhesive combination Object (2-I) or (2-II).

<黏著劑組合物(2-I)> <Adhesive composition (2-I)>

作為黏著劑組合物(2-I)，可列舉：包含具備巨單體作為分枝成分之接枝共聚物之丙烯酸系共聚物(2-A1)、交聯劑(2-B1)及光聚合起始劑(2-C1)之樹脂組合物。 Examples of the adhesive composition (2-I) include: an acrylic copolymer (2-A1) comprising a graft copolymer having a macromonomer as a branch component, a crosslinking agent (2-B1), and a photopolymerization agent (2-B1). The resin composition of the initiator (2-C1).

(丙烯酸系共聚物(2-A1)) (Acrylic Copolymer (2-A1))

作為基礎聚合物之丙烯酸系共聚物(2-A1)若為具備巨單體作為分枝成分之接枝共聚物即可。 The acrylic copolymer (2-A1) as the base polymer may be a graft copolymer having a macromonomer as a branch component.

(主幹成分) (main ingredient)

上述丙烯酸系共聚物(2-A1)之主幹成分較佳為包含含有源自(甲基)丙烯酸酯之重複單元之共聚物成分。 It is preferable that the backbone component of the said acrylic-type copolymer (2-A1) contains the copolymer component containing the repeating unit derived from (meth)acrylate.

構成上述丙烯酸系共聚物(2-A1)之主幹成分之共聚物之玻璃轉移溫度較佳為-70~0℃。 The glass transition temperature of the copolymer constituting the main component of the acrylic copolymer (2-A1) is preferably -70 to 0°C.

此時，所謂構成主幹成分之共聚物成分之玻璃轉移溫度，係指僅將組成丙烯酸系共聚物(2-A1)之主幹成分之單體成分共聚合而獲得之聚合物之玻璃轉移溫度。具體而言，係指由自該共聚物各成分之均聚物獲得之聚合物之玻璃轉移溫度與構成比率，藉由Fox之計算式而算出之值。 In this case, the glass transition temperature of the copolymer component constituting the main component refers to the glass transition temperature of a polymer obtained by copolymerizing only the monomer components constituting the main component of the acrylic copolymer (2-A1). Specifically, it refers to the value calculated by Fox's calculation formula from the glass transition temperature and composition ratio of the polymer obtained from the homopolymer of the respective components of the copolymer.

再者，所謂Fox之計算式係指藉由下式而求得之計算值，可使用聚合物手冊[Polymer HandBook,J.Brandrup,Interscience,1989]中記載之值而求得。 In addition, the calculation formula of Fox means the calculated value obtained by the following formula, and can be obtained using the value described in the polymer handbook [Polymer Handbook, J. Brandrup, Interscience, 1989].

1/(273+Tg)=Σ(Wi/(273+Tgi)) 1/(273+Tg)=Σ(Wi/(273+Tgi))

[式中，Wi表示單體i之重量分率，Tgi表示單體i之均聚物之Tg(℃)] [Where, Wi represents the weight fraction of monomer i, and Tgi represents the Tg (°C) of the homopolymer of monomer i]

構成上述丙烯酸系共聚物(2-A1)之主幹成分之共聚物成分之玻璃轉 移溫度會對室溫狀態下之黏著劑組合物(2-I)之柔軟性，或黏著劑組合物(2-I)對被黏著體之潤濕性，即接著性產生影響，故而為使黏著劑組合物(2-I)於室溫狀態下獲得適度之接著性(黏性)，該玻璃轉移溫度較佳為-70℃~0℃，其中更佳為-65℃以上或-5℃以下，其中尤佳為-60℃以上或-10℃以下。 Glass transition of the copolymer component constituting the main component of the above-mentioned acrylic copolymer (2-A1) The temperature change will affect the flexibility of the adhesive composition (2-I) at room temperature, or the wettability of the adhesive composition (2-I) to the adherend, that is, the adhesiveness. Adhesive composition (2-I) obtains moderate adhesiveness (viscosity) at room temperature, and the glass transition temperature is preferably -70°C~0°C, more preferably -65°C or above or -5°C below, especially preferably above -60°C or below -10°C.

其中，即使該共聚物成分之玻璃轉移溫度為相同溫度，亦可藉由調整分子量而調整黏彈性。例如藉由減小共聚物成分之分子量，可使之更柔軟化。 Among them, even if the glass transition temperature of the copolymer components is the same temperature, the viscoelasticity can be adjusted by adjusting the molecular weight. For example, by reducing the molecular weight of the copolymer component, it can be made more flexible.

作為上述丙烯酸系共聚物(2-A1)之主幹成分所含有之(甲基)丙烯酸酯單體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(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)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山崳酯、(甲基)丙烯酸異

Figure 110106505-A0305-02-0041-27
基酯、(甲基)丙烯酸2-苯氧基乙酯、丙烯酸3,5,5-三甲基環己酯、對異丙苯基苯酚EO改性(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸苄酯等。亦可使用該等中具有親水基或有機官能基等之(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、(甲基)丙烯酸甘油酯 等含羥基之(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)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、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、反丁烯二酸、順丁烯二酸、伊康酸、順丁烯二酸單甲酯、伊康酸單甲酯等含羧基之單體，順丁烯二酸酐、伊康酸酐等含酸酐基之單體，(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-環氧丁酯等含環氧基之單體，(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯等含胺基之(甲基)丙烯酸酯系單體，(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-羥甲基(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、二丙酮丙烯醯胺、順丁烯二醯胺、順丁烯二醯亞胺等含醯胺基之單體，乙烯基吡咯啶酮、乙烯基吡啶、乙烯基咔唑等雜環系鹼性單體等。 Examples of the (meth)acrylate monomer contained in the main component of the acrylic copolymer (2-A1) include methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate Propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 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 ester, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, Decyl (meth)acrylate, Isodecyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate, Cetyl (meth)acrylate, (Meth)acrylate ) stearyl acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, iso(meth)acrylate
Figure 110106505-A0305-02-0041-27
Base ester, 2-phenoxyethyl (meth)acrylate, 3,5,5-trimethylcyclohexyl acrylate, p-cumylphenol EO modified (meth)acrylate, (meth) Dicyclopentyl acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, and the like. Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycerin (meth)acrylate etc. which have a hydrophilic group or an organic functional group etc. can also be used Hydroxyl-containing (meth)acrylate, or (meth)acrylic acid, 2-(meth)acryloxyethylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydro Phthalic acid, 2-(meth)acryloxyethylphthalic acid, 2-(meth)acryloxypropylphthalic acid, 2-(meth)acryloxyethylphthalic acid 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxyethylsuccinic acid, 2-(meth)acryloxypropylmaleic acid, 2-(meth)acryloxypropylmaleic acid Carboxyl group-containing monomers such as propyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate, etc. Monomers containing acid anhydride groups such as diacid anhydride and itaconic anhydride, glycidyl (meth)acrylate, α-glycidyl ethacrylate, 3,4-epoxybutyl (meth)acrylate, etc. containing epoxy groups Monomers, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and other amino-containing (meth)acrylate monomers, (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl ( Meth)acrylamide, diacetoneacrylamide, maleimide, maleimide and other amido-containing monomers, vinylpyrrolidone, vinylpyridine, vinylcarbazole Heterocyclic basic monomers, etc.

又，亦可適當使用可與上述丙烯酸系單體或甲基丙烯酸系單體共聚合之苯乙烯、第三丁基苯乙烯、α-甲基苯乙烯、乙烯基甲苯、丙烯腈、甲基丙烯腈、乙酸乙烯酯、丙酸乙烯酯、烷基乙烯基醚、羥基烷基乙烯基醚、烷基乙烯基單體等各種乙烯基單體。 In addition, styrene, tert-butylstyrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylic acid copolymerizable with the above-mentioned acrylic monomer or methacrylic monomer can also be suitably used. Various vinyl monomers such as nitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, alkyl vinyl monomer, etc.

又，丙烯酸系共聚物(2-A1)之主幹成分較佳為含有疏水性之(甲基)丙烯酸酯單體與親水性之(甲基)丙烯酸酯單體作為構成單元。 Moreover, it is preferable that the backbone component of an acryl-type copolymer (2-A1) contains a hydrophobic (meth)acrylate monomer and a hydrophilic (meth)acrylate monomer as a structural unit.

若丙烯酸系共聚物(2-A1)之主幹成分僅由疏水性單體構成，則確認存在濕熱白化之傾向，故而較佳為將親水性單體亦導入主幹成分而防止濕熱白化。 If the main component of the acrylic copolymer (2-A1) is composed of only hydrophobic monomers, it is confirmed that there is a tendency of wet heat whitening. Therefore, it is preferable to introduce a hydrophilic monomer into the main component to prevent wet heat whitening.

具體而言，作為上述丙烯酸系共聚物(2-A1)之主幹成分，可列舉：使疏水性之(甲基)丙烯酸酯單體與親水性之(甲基)丙烯酸酯單體與巨單體之末端之聚合性官能基無規共聚合而成之共聚物成分。 Specifically, as the main component of the above-mentioned acrylic copolymer (2-A1), a combination of a hydrophobic (meth)acrylate monomer, a hydrophilic (meth)acrylate monomer, and a macromonomer can be mentioned. A copolymer component formed by random copolymerization of polymerizable functional groups at the terminal.

此處，作為上述疏水性之(甲基)丙烯酸酯單體，較佳為不具有極性基之烷基酯(其中，不包括丙烯酸甲酯)，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、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)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山崳酯、(甲基)丙烯酸異

Figure 110106505-A0305-02-0043-28
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。 Here, as the above-mentioned hydrophobic (meth)acrylate monomer, alkyl esters having no polar groups (among which, methyl acrylate is not included) are preferred, for example, n-butyl (meth)acrylate , Isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, (meth) ) Neopentyl acrylate, (meth)hexyl acrylate, (meth)cyclohexyl acrylate, (meth)heptyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, ( Nonyl methacrylate, isononyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth) Undecyl acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, (meth)acrylic acid Behenyl Ester, (Meth) Acrylic Iso
Figure 110106505-A0305-02-0043-28
base ester, cyclohexyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, methyl methacrylate.

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。 Moreover, as a hydrophobic vinyl monomer, vinyl acetate, styrene, tert-butylstyrene, (alpha)-methylstyrene, vinyl toluene, an alkyl vinyl monomer, etc. are mentioned, for example.

作為上述親水性之(甲基)丙烯酸酯單體，較佳為丙烯酸甲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)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、(甲基)丙烯酸甘油酯等含羥基之(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)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧 基丙基順丁烯二酸、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、反丁烯二酸、順丁烯二酸、伊康酸、順丁烯二酸單甲酯、伊康酸單甲酯等含羧基之單體，順丁烯二酸酐、伊康酸酐等含酸酐基之單體，(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、羥乙基丙烯醯胺等。 As the above-mentioned hydrophilic (meth)acrylate monomer, methyl acrylate or an ester having a polar group is preferable, for example, methyl acrylate, (meth)acrylic acid, tetrahydrofurfuryl (meth)acrylate Or (meth)acrylate or (meth)acrylate containing hydroxyl groups such as hydroxyethyl (meth)acrylate, (meth)hydroxypropyl Acrylic acid, 2-(meth)acryloxyethyl hexahydrophthalate, 2-(meth)acryloxypropyl hexahydrophthalate, 2-(meth)acryloxy Ethylphthalate, 2-(meth)acryloxypropylphthalate, 2-(meth)acryloxyethylmaleic acid, 2-(meth)acrylyl oxygen propylmaleic acid, 2-(meth)acryloxyethylsuccinic acid, 2-(meth)acryloxypropylmaleic acid, crotonic acid, fumaric acid, cisuccinic acid Carboxyl-containing monomers such as butenedioic acid, itaconic acid, monomethyl maleate, and monomethyl itaconate, monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride, (form Base) glycidyl acrylate, α-glycidyl ethacrylate, 3,4-epoxybutyl (meth)acrylate and other monomers containing epoxy groups, methoxypolyethylene glycol (meth)acrylic acid Alkoxy polyalkylene glycol (meth)acrylate such as ester, N,N-dimethylacrylamide, hydroxyethylacrylamide, etc.

(分枝成分：巨單體) (branch components: macromonomer)

丙烯酸系共聚物(2-A1)較佳為導入巨單體作為接枝共聚物之分枝成分，含有源自巨單體之重複單元。 The acrylic copolymer (2-A1) preferably introduces a macromonomer as a branch component of the graft copolymer and contains repeating units derived from the macromonomer.

所謂巨單體係指具有末端之聚合性官能基與高分子量骨架成分之高分子單體。 The so-called macromonomer system refers to a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.

巨單體之玻璃轉移溫度(Tg)較佳為高於構成上述丙烯酸系共聚物(2-A1)之共聚物成分之玻璃轉移溫度。 The glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer components constituting the above-mentioned acrylic copolymer (2-A1).

具體而言，巨單體之玻璃轉移溫度(Tg)會對黏著劑組合物(2-I)之加熱熔融溫度(熱熔溫度)產生影響，故而巨單體之玻璃轉移溫度(Tg)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。 Specifically, the glass transition temperature (Tg) of the macromonomer will affect the heating and melting temperature (melt temperature) of the adhesive composition (2-I), so the glass transition temperature (Tg) of the macromonomer is better 30° C. to 120° C., more preferably 40° C. or higher or 110° C. or lower, and more preferably 50° C. or higher or 100° C. or lower.

若為此種玻璃轉移溫度(Tg)，則藉由調整分子量，可保持優異之加工性或保存穩定性，並且可調整為於80℃附近熱熔。 If it is such a glass transition temperature (Tg), by adjusting the molecular weight, it is possible to maintain excellent processability and storage stability, and it can be adjusted to heat-melt around 80°C.

所謂巨單體之玻璃轉移溫度係表示該巨單體本身之玻璃轉移溫度，可藉由示差掃描熱量計(DSC)而測定。(升溫速度：5℃/分鐘，根據基準線位移之反曲點而測定Tg) 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). (Heating rate: 5°C/min, Tg is measured according to the inflection point of the baseline displacement)

又，為達成於室溫狀態下可維持分枝成分彼此相互拉近，作為黏著劑組合物進行物理***聯之狀態，並且藉由加熱至適度之溫度可使上述物理***聯解開而獲得流動性，亦較佳為調整巨單體之分子量或含量。 In addition, in order to maintain the branched components close to each other at room temperature, as the adhesive composition undergoes physical cross-linking, and by heating to a moderate temperature, the above-mentioned physical cross-linking can be released to obtain fluidity It is also preferable to adjust the molecular weight or content of the macromonomer.

就該觀點而言，巨單體較佳為以5質量%~30質量%之比率含有於丙烯酸系共聚物(2-A1)中，其中更佳為6質量%以上或25質量%以下，其中進而較佳為8質量%以上或20質量%以下。 From this point of view, the macromonomer is preferably contained in the acrylic copolymer (2-A1) at a ratio of 5% by mass to 30% by mass, more preferably at least 6% by mass and at most 25% by mass, wherein More preferably, it is 8 mass % or more or 20 mass % or less.

又，巨單體之數量平均分子量較佳為500以上且未達8000，其中更佳為800以上或未達7500，其中進而較佳為1000以上或未達7000。 Also, the number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and still more preferably 1000 or more and less than 7000.

巨單體可適當使用通常製造者(例如東亞合成公司製造之巨單體等)。 As the macromonomer, a general manufacturer (for example, a macromonomer manufactured by Toagosei Co., Ltd., etc.) can be used appropriately.

巨單體之高分子量骨架成分較佳為包含丙烯酸系聚合物或乙烯系聚合物。 The high molecular weight skeleton component of the macromonomer preferably comprises an acrylic polymer or a vinyl polymer.

作為上述巨單體之高分子量骨架成分，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(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)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山崳酯、(甲基)丙烯酸異

Figure 110106505-A0305-02-0045-29
基酯、(甲基)丙烯酸2-苯氧基乙酯、丙烯酸3,5,5-三甲基環己酯、對異丙苯基苯酚EO改性(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯 酸二環戊烯氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸羥基烷基酯、(甲基)丙烯酸、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、(甲基)丙烯腈、(甲基)丙烯酸烷氧基烷基酯、烷氧基聚伸烷基二醇(甲基)丙烯酸酯等(甲基)丙烯酸酯單體或苯乙烯、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、乙酸乙烯酯、烷基乙烯基醚、羥基烷基乙烯基醚等各種乙烯基單體等，該等可單獨使用或組合兩種以上使用。 Examples of the high-molecular-weight skeleton component of the macromonomer include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate base) n-butyl acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate Pentyl, 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 ester, undecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate , Behenyl (meth)acrylate, Iso(meth)acrylate
Figure 110106505-A0305-02-0045-29
Base ester, 2-phenoxyethyl (meth)acrylate, 3,5,5-trimethylcyclohexyl acrylate, p-cumylphenol EO modified (meth)acrylate, (meth) Dicyclopentyl acrylate, Dicyclopentenyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, Benzyl (meth)acrylate, Hydroxyalkyl (meth)acrylate, ( Meth)acrylic acid, glycidyl (meth)acrylate, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acrylonitrile, (meth)acrylamide (meth)acrylate monomers such as oxyalkyl esters, alkoxy polyalkylene glycol (meth)acrylates, or styrene, tert-butylstyrene, α-methylstyrene, vinyl Various vinyl monomers such as toluene, alkyl vinyl monomers, vinyl acetate, alkyl vinyl ethers, and hydroxyalkyl vinyl ethers can be used alone or in combination of two or more.

作為上述巨單體之末端聚合性官能基，例如可列舉：甲基丙烯醯基、丙烯醯基、乙烯基等。 As a terminal polymerizable functional group of the said macromonomer, a methacryl group, an acryl group, a vinyl group etc. are mentioned, for example.

(交聯劑(2-B1)) (Crosslinking agent (2-B1))

作為交聯劑(2-B1)，例如可適宜選擇具有2個以上之環氧基或異氰酸酯基、氧雜環丁烷基、矽烷醇基、(甲基)丙烯醯基等交聯性基之交聯劑。其中，就反應性或所得硬化物之強度之方面而言，較佳為具有2個以上之(甲基)丙烯醯基，其中更佳為具有3個以上之(甲基)丙烯醯基的多官能(甲基)丙烯酸酯或具有環氧基或異氰酸酯基、矽烷醇基之(甲基)丙烯酸酯。 As the cross-linking agent (2-B1), for example, one having two or more cross-linking groups such as epoxy groups or isocyanate groups, oxetanyl groups, silanol groups, and (meth)acryl groups can be appropriately selected. crosslinking agent. Among them, in terms of reactivity or the strength of the obtained hardened product, polyamides having 2 or more (meth)acryl groups are preferred, and polyamides having 3 or more (meth)acryl groups are more preferred. Functional (meth)acrylates or (meth)acrylates with epoxy groups, isocyanate groups, and silanol groups.

將圖像顯示裝置構成構件貼合一體化後，使交聯劑(2-B1)於黏著材中交聯，藉此可使該片材失去熱熔性，取而代之於高溫環境下表現較高之凝集力，獲得優異之耐發泡可靠性。 After laminating and integrating the components of the image display device, the cross-linking agent (2-B1) is cross-linked in the adhesive material, so that the sheet loses its heat-meltability and is replaced by one that exhibits higher performance in high-temperature environments. Cohesion, to obtain excellent reliability against foaming.

作為此種(甲基)丙烯酸酯，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、甘油二(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聚烷氧基二(甲基)丙烯酸酯、雙酚F聚烷氧基二(甲基)丙 烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、三羥甲基丙烷三氧基乙基(甲基)丙烯酸酯、ε-己內酯改性三(2-羥基乙基)異氰尿酸酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、丙氧化季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、丙氧化季戊四醇四(甲基)丙烯酸酯、乙氧化季戊四醇四(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、三(丙烯醯氧基乙基)異氰尿酸酯、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、烷氧化三羥甲基丙烷三(甲基)丙烯酸酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯等紫外線硬化型多官能單體類，另外亦可列舉：聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能丙烯酸酯低聚物類或異氰酸酯(甲基)丙烯酸酯、1,1-(雙(甲基)丙烯醯氧基甲基)乙基異氰酸酯、2-(2-(甲基)丙烯醯氧基乙基氧基)乙基異氰酸酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥乙酯縮水甘油醚、(甲基)丙烯酸羥丙酯縮水甘油醚、(甲基)丙烯酸羥丁酯縮水甘油醚等。 Examples of such (meth)acrylates include 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, Glycerin glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di( Meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol A polyalkoxy di(meth)acrylate, bisphenol F polyalkoxy di(meth)acrylate Acrylic acid ester, polyalkylene 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 Acrylates, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, tri(propylene Acyloxyethyl) isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate , tripentaerythritol penta(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, ε-caprolactone adduct of hydroxypivalate neopentyl glycol two (methyl ) acrylate, trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, etc. Type polyfunctional monomers, in addition: polyester (meth)acrylate, epoxy (meth)acrylate, (meth)acrylate urethane, polyether (meth)acrylate, etc. Polyfunctional acrylate oligomers or isocyanate (meth)acrylate, 1,1-(bis(meth)acryloxymethyl)ethyl isocyanate, 2-(2-(meth)acryloxy (ethyloxy) ethyl isocyanate, (meth) glycidyl acrylate, (meth) hydroxyethyl acrylate glycidyl ether, (meth) hydroxypropyl acrylate glycidyl ether, (meth) hydroxybutyl acrylate Ester glycidyl ether etc.

上述所列舉之中，就提高對被黏著體之密接性或濕熱白化之抑制效果的觀點而言，較佳為含有羥基等極性官能基之多官能單體或低聚物。 Among those listed above, polyfunctional monomers or oligomers containing polar functional groups such as hydroxyl groups are preferred from the viewpoint of improving the adhesion to the adherend or the effect of suppressing wet heat whitening.

其中，較佳為使用具有羥基或羧基之多官能(甲基)丙烯酸酯。 Among them, it is preferable to use a polyfunctional (meth)acrylate having a hydroxyl group or a carboxyl group.

因此，就防止濕熱白化之觀點而言，作為上述丙烯酸系共聚物(2-A1)，即接枝共聚物之主幹成分，較佳為含有疏水性之丙烯酸酯單體與親 水性之丙烯酸酯單體，進而，作為交聯劑(2-B)，較佳為使用具有羥基之多官能(甲基)丙烯酸酯。 Therefore, from the viewpoint of preventing wet heat whitening, as the above-mentioned acrylic copolymer (2-A1), that is, the main component of the graft copolymer, it is preferable to contain a hydrophobic acrylate monomer and an As the aqueous acrylate monomer, and furthermore, as the crosslinking agent (2-B), it is preferable to use a polyfunctional (meth)acrylate having a hydroxyl group.

交聯劑(2-B1)之含量並無特別限制。作為標準，較佳為相對於丙烯酸系共聚物(2-A1)100質量份為0.5~20質量份，其中更佳為1質量份以上或15質量份以下，其中進而較佳為2質量份以上或10質量份以下之比率。 The content of the crosslinking agent (2-B1) is not particularly limited. As a standard, it is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer (2-A1), more preferably at least 1 part by mass and at most 15 parts by mass, and even more preferably at least 2 parts by mass Or a ratio of 10 parts by mass or less.

藉由於上述範圍內含有交聯劑(2-B1)，可同時實現未交聯狀態之本黏著片材2之形狀穩定性與交聯後之黏著材之耐發泡可靠性。其中，就與其他要素之平衡性而言，亦可超出該範圍。 By containing the crosslinking agent (2-B1) within the above range, the shape stability of the adhesive sheet 2 in the uncrosslinked state and the foaming resistance reliability of the crosslinked adhesive can be simultaneously realized. Among them, in terms of balance with other elements, it may also exceed this range.

(光聚合起始劑(2-C1)) (Photopolymerization Initiator (2-C1))

光聚合起始劑(2-C1)係發揮作為上述交聯劑(2-B1)之交聯反應之反應起始助劑的功能者。 The photopolymerization initiator (2-C1) functions as a reaction initiation aid for the crosslinking reaction of the above-mentioned crosslinking agent (2-B1).

光聚合起始劑可適當使用現今公知者。其中，就易於控制交聯反應之觀點而言，較佳為與波長380nm以下之紫外線感應之光聚合起始劑。 As the photopolymerization initiator, conventionally known ones can be appropriately used. Among them, a photopolymerization initiator responsive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.

另一方面，與較波長380nm長波長之光感應之光聚合起始劑於感應之光容易到達本黏著片材2之深部之方面而言較佳。 On the other hand, a photopolymerization initiator that responds to light with a wavelength longer than 380 nm is preferable in that the induced light easily reaches the deep portion of the adhesive sheet 2 .

光聚合起始劑根據自由基產生機制而大體分為兩類，大致分為：可使光聚合性起始劑本身之單鍵發生斷裂分解而產生自由基的裂解型光聚合起始劑、以及光激發之起始劑與系統中之氫供與體形成激發錯合物而可使氫供與體之氫轉移的奪氫型光聚合起始劑。 Photopolymerization initiators are roughly divided into two categories according to the mechanism of free radical generation, roughly divided into: cleavage-type photopolymerization initiators that can break and decompose the single bond of the photopolymerization initiator itself to generate free radicals, and The photoexcited initiator and the hydrogen donor and donor in the system form an excited complex, which can transfer the hydrogen of the hydrogen donor and donor to the hydrogen abstraction type photopolymerization initiator.

作為該等之中的裂解型光聚合起始劑，藉由光照射而產生自由基時分解而成為其他化合物，若一旦被激發則失去作為反應起始劑之功能。因此，不會於交聯反應結束後之黏著材中作為活性物質而殘存，不存在對黏著材造成未預期之光劣化等之可能性，故而較佳。 As the cleavage-type photopolymerization initiator among these, it decomposes into other compounds when free radicals are generated by light irradiation, and loses its function as a reaction initiator once it is excited. Therefore, it is preferable because it does not remain as an active material in the adhesive material after the crosslinking reaction is completed, and there is no possibility of causing unexpected photodegradation to the adhesive material.

另一方面，關於奪氫型光聚合起始劑，藉由紫外線等活性能量線照射而產生自由基反應時，不會產生如裂解型光聚合起始劑之分解物，故而反應結束後難以成為揮發成分，可減少對被黏著體之損傷，就該方面而言較為有用。 On the other hand, when a hydrogen abstraction photopolymerization initiator is irradiated with active energy rays such as ultraviolet rays to generate a free radical reaction, no decomposition product such as a cracking photopolymerization initiator is generated, so it is difficult to become Volatile components can reduce the damage to the adherend and are more useful in this respect.

作為上述裂解型光起始劑，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-

Figure 110106505-A0305-02-0049-30
啉基苯基)丁烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-
Figure 110106505-A0305-02-0049-31
啉基丙烷-1-酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-
Figure 110106505-A0305-02-0049-32
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或該等之衍生物等。 Examples of the cleavage-type photoinitiator 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-propan-1-one, 2 -Hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}phenyl]-2-methyl-propan-1-one, oligo(2-hydroxy- 2-methyl-1-(4-(1-methylvinyl)phenyl)acetone), methyl phenylglyoxylate, 2-benzyl-2-dimethylamino-1-(4-
Figure 110106505-A0305-02-0049-30
Linylphenyl) butane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-
Figure 110106505-A0305-02-0049-31
Linyl propan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-
Figure 110106505-A0305-02-0049-32
Phenyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide or their derivatives, etc.

作為上述奪氫型光起始劑，例如可列舉：二苯甲酮、4-甲基-二苯甲酮、2,4,6-三甲基二苯甲酮、4-苯基二苯甲酮、3,3'-二甲基-4-甲氧基二苯甲酮、4-(甲基)丙烯醯氧基二苯甲酮、2-苯甲醯基苯甲酸甲酯、苯甲醯基甲酸甲酯、雙(2-苯基-2-乙醛酸)氧基雙乙烯、4-(1,3-丙烯醯基-1,4,7,10,13-五氧代十三烷基)二苯甲酮、9-氧硫

Figure 110106505-A0305-02-0049-33
、2-氯-9-氧硫
Figure 110106505-A0305-02-0049-34
、3-甲基-9-氧硫
Figure 110106505-A0305-02-0049-35
、2,4-二甲基-9-氧硫
Figure 110106505-A0305-02-0049-36
、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌或其衍生物等。 Examples of the hydrogen abstraction type photoinitiator include: benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone Ketone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloxybenzophenone, methyl 2-benzoylbenzoate, benzoyl Methyl methanoate, bis(2-phenyl-2-glyoxylate)oxybisethylene, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxotridecane base) benzophenone, 9-oxosulfur
Figure 110106505-A0305-02-0049-33
, 2-Chloro-9-oxosulfur
Figure 110106505-A0305-02-0049-34
, 3-methyl-9-oxosulfur
Figure 110106505-A0305-02-0049-35
, 2,4-Dimethyl-9-oxosulfur
Figure 110106505-A0305-02-0049-36
, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone or its derivatives, etc.

其中，並不限定於作為光聚合起始劑而於上述列舉之物質。可使用上述列舉之裂解型光聚合起始劑及奪氫型光聚合起始劑中之任一種，或組合兩種以上使用。 However, it is not limited to what was listed above as a photoinitiator. Any of the cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators listed above may be used, or two or more of them may be used in combination.

光聚合起始劑(2-C1)之含量並無特別限制。作為標準，較佳為以相對於丙烯酸系共聚物(2-A1)100質量份為0.1~10質量份，其中更佳為0.5質量份以上或5質量份以下，其中進而較佳為1質量份以上或3質量份以下之比率含有。 The content of the photopolymerization initiator (2-C1) is not particularly limited. As a standard, it is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the acrylic copolymer (2-A1), more preferably at least 0.5 parts by mass or less than 5 parts by mass, and even more preferably 1 part by mass More than or equal to 3 parts by mass or less.

藉由將光聚合起始劑(2-C1)之含量設為上述範圍，可獲得對活性能量線之適度之反應感度。 Moderate reaction sensitivity to active energy rays can be obtained by making content of a photoinitiator (2-C1) into the said range.

(其他成分) (other ingredients)

黏著劑組合物(2-I)可含有通常之黏著劑組合物中所調配之公知之成分作為上述以外之成分。例如可視需要適當含有黏著賦予樹脂或抗氧化劑、光穩定化劑、金屬減活劑、抗老化劑、吸濕劑、聚合抑制劑、紫外線吸收劑、防銹劑、矽烷偶合劑、無機粒子等各種添加劑。 The adhesive composition (2-I) may contain, as components other than the above, known components formulated in ordinary adhesive compositions. For example, if necessary, various types such as adhesion-imparting resins, antioxidants, photostabilizers, metal deactivators, anti-aging agents, moisture absorbers, polymerization inhibitors, ultraviolet absorbers, rust inhibitors, silane coupling agents, and inorganic particles can be appropriately contained. additive.

又，亦可視需要適當含有反應觸媒(三級胺系化合物、四級銨系化合物、月桂酸錫化合物等)。 Moreover, a reaction catalyst (tertiary amine type compound, quaternary ammonium type compound, tin laurate compound, etc.) may be contained suitably as needed.

<黏著劑組合物(2-II)> <Adhesive composition (2-II)>

作為黏著劑組合物(2-II)，可列舉：包含含有使玻璃轉移溫度(Tg)未達0℃之單體a與玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體b與玻璃轉移溫度(Tg)為80℃以上之單體c，以a：b：c=10~40：90~35：0~25之莫耳比率共聚合而成且重量平均分子量為50000~400000之(甲基)丙烯酸酯共聚物或乙烯系共聚物之(甲基)丙烯酸系共聚物(2-A2)；交聯劑(2-B2)及光聚合起始劑(2-C2)的樹脂組合物。 Examples of the adhesive composition (2-II) include monomers having a glass transition temperature (Tg) of less than 0°C and monomers having a glass transition temperature (Tg) of 0°C to less than 80°C. b and monomer c with a glass transition temperature (Tg) above 80°C are copolymerized at a molar ratio of a:b:c=10~40:90~35:0~25 and the weight average molecular weight is 50000~ 400000 (meth)acrylic copolymer (2-A2) of (meth)acrylate copolymer or vinyl copolymer; crosslinking agent (2-B2) and photopolymerization initiator (2-C2) resin composition.

再者，數量平均分子量及重量平均分子量係使用凝膠滲透層析儀(GPC)，採用使用聚苯乙烯作為標準物質之換算值。 In addition, the number average molecular weight and weight average molecular weight are conversion values using polystyrene as a standard substance using gel permeation chromatography (GPC).

((甲基)丙烯酸系共聚物(2-A2)) ((meth)acrylic copolymer (2-A2))

作為基礎聚合物之(甲基)丙烯酸系共聚物(2-A2)較佳為(甲基)丙烯酸酯共聚物或乙烯系共聚物。 The (meth)acrylic copolymer (2-A2) as the base polymer is preferably a (meth)acrylate copolymer or vinyl copolymer.

就同時實現室溫狀態下之形狀保持性與熱熔性之觀點而言，上述(甲基)丙烯酸酯共聚物或乙烯系共聚物之重量平均分子量較佳為50000~400000，其中更佳為60000以上或350000以下，其中進而較佳為70000以上或300000以下。 From the point of view of achieving both shape retention and heat-fusibility at room temperature, the weight-average molecular weight of the above-mentioned (meth)acrylate copolymer or vinyl copolymer is preferably 50,000 to 400,000, more preferably 60,000 It is more than or equal to 350,000, and more preferably more than or equal to 70,000 or less than 300,000.

對丙烯酸酯系共聚物而言，藉由適宜選擇用以調製其之丙烯酸系單體或甲基丙烯酸系單體之種類、組成比率，進而聚合條件等，可適宜調整玻璃轉移溫度(Tg)或分子量等物性。 For acrylate copolymers, the glass transition temperature (Tg) or properties such as molecular weight.

此時，作為構成丙烯酸酯共聚物之丙烯酸系單體，例如可列舉丙烯酸2-乙基己酯、丙烯酸正辛酯、丙烯酸異辛酯、丙烯酸正丁酯、丙烯酸乙酯等作為主原料。 In this case, as an acrylic monomer which comprises an acrylate copolymer, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, etc. are mentioned as a main raw material, for example.

該等之外，可以賦予凝集力或賦予極性等為目的而使具有各種官能基之(甲基)丙烯酸單體與上述丙烯酸系單體共聚合。 In addition to these, a (meth)acrylic monomer having various functional groups may be copolymerized with the above-mentioned acrylic monomer for the purpose of imparting cohesive force, imparting polarity, or the like.

作為該具有官能基之(甲基)丙烯酸單體，例如可列舉：甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸羥基乙酯、丙烯酸、丙烯酸縮水甘油酯、N-取代丙烯醯胺、丙烯腈、甲基丙烯腈、丙烯酸含氟烷基酯、含有機矽烷氧基之丙烯酸酯等。 Examples of the (meth)acrylic monomer having a functional group include methyl methacrylate, methyl acrylate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, N-substituted acrylamide, acrylonitrile, Methacrylonitrile, fluorine-containing alkyl acrylate, acrylate containing organosilyloxyl group, etc.

另一方面，作為乙烯系共聚物，可列舉：可與上述丙烯酸系單體或甲基丙烯酸系單體共聚合之乙酸乙烯酯或烷基乙烯基醚、羥基烷基乙烯基醚等各種乙烯基單體亦適宜聚合而成之乙烯系共聚物。 On the other hand, examples of vinyl copolymers include various vinyl copolymers such as vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether, which can be copolymerized with the above-mentioned acrylic monomer or methacrylic monomer. Monomers are also suitable for polymerization of vinyl copolymers.

作為本黏著片材2之(甲基)丙烯酸系共聚物(2-A2)，較佳為使玻璃轉移溫度(Tg)未達0℃之單體a與玻璃轉移溫度(Tg)為0℃以上且未達80℃之 單體b與玻璃轉移溫度(Tg)為80℃以上之單體c，以a：b：c=10~40：90~35：0~25之莫耳比率共聚合而成之(甲基)丙烯酸酯共聚物或乙烯系共聚物。 As the (meth)acrylic copolymer (2-A2) of this adhesive sheet 2, it is preferable that the monomer a whose glass transition temperature (Tg) is less than 0°C and the glass transition temperature (Tg) be 0°C or higher and below 80°C Monomer b and monomer c with a glass transition temperature (Tg) above 80°C are copolymerized at a molar ratio of a:b:c=10~40:90~35:0~25 (methyl) Acrylate copolymer or vinyl copolymer.

此時，單體a、b及c之各玻璃轉移溫度(Tg)係自該單體製作聚合物時(均聚物化)之各玻璃轉移溫度(Tg)。 In this case, each glass transition temperature (Tg) of the monomers a, b, and c is the respective glass transition temperature (Tg) when the monomer is produced into a polymer (homopolymerization).

上述單體a例如較佳為具有具有碳數4以上之側鏈之烷基結構之(甲基)丙烯酸酯單體。 The above-mentioned monomer a is preferably, for example, a (meth)acrylate monomer having an alkyl structure having a side chain having 4 or more carbon atoms.

此時，碳數4以上之側鏈可為包含直鏈者，亦可為包含分支之碳鏈者。 In this case, the side chain having 4 or more carbon atoms may include a straight chain or a branched carbon chain.

更具體而言，上述單體a較佳為具有碳數4~10之直鏈烷基結構之(甲基)丙烯酸酯單體或具有碳數6~18之支鏈烷基結構之(甲基)丙烯酸酯單體。 More specifically, the above-mentioned monomer a is preferably a (meth)acrylate monomer having a straight-chain alkyl structure with 4 to 10 carbons or a (meth)acrylate monomer having a branched alkyl structure with 6 to 18 carbons. ) acrylate monomer.

此處，作為「具有碳數4~10之直鏈烷基結構之(甲基)丙烯酸酯單體」，可列舉：丙烯酸正丁酯、丙烯酸正己酯、丙烯酸正辛酯、丙烯酸正壬酯、丙烯酸正癸酯等。 Here, examples of the "(meth)acrylate monomer having a linear alkyl structure having 4 to 10 carbon atoms" include n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-nonyl acrylate, N-decyl acrylate, etc.

另一方面，作為「具有碳數6~18之支鏈烷基結構之(甲基)丙烯酸酯單體」，可列舉：丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸2-甲基己酯、丙烯酸異辛酯、丙烯酸異壬酯、丙烯酸異癸酯、甲基丙烯酸異癸酯等。 On the other hand, examples of "(meth)acrylate monomers having a branched chain alkyl structure having 6 to 18 carbon atoms" include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-methylhexyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, isodecyl methacrylate, and the like.

上述單體b較佳為碳數4以下之(甲基)丙烯酸酯單體、側鏈具有環狀骨架之(甲基)丙烯酸酯單體、碳數4以下之乙烯基單體或側鏈具有環狀骨架之乙烯基單體。 The above-mentioned monomer b is preferably a (meth)acrylate monomer with 4 or less carbon atoms, a (meth)acrylate monomer with a ring skeleton in the side chain, a vinyl monomer with 4 or less carbon atoms, or a vinyl monomer with a side chain with Vinyl monomer with ring skeleton.

其中，上述單體b尤佳為側鏈之碳數為4以下之乙烯基單體。 Among them, the above-mentioned monomer b is particularly preferably a vinyl monomer having 4 or less carbon atoms in the side chain.

此處，作為「碳數4以下之(甲基)丙烯酸酯單體」，可列舉：丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、丙烯酸第三丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯等。 Here, examples of the "(meth)acrylate monomer having 4 or less carbon atoms" include methyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, Isopropyl methacrylate, n-butyl methacrylate, tert-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, etc.

作為「側鏈具有環狀骨架之(甲基)丙烯酸酯單體」，可列舉：丙烯酸異

Figure 110106505-A0305-02-0053-37
基酯、丙烯酸環己酯、甲基丙烯酸環己酯、1,4-環己烷二甲醇單丙烯酸酯、甲基丙烯酸四氫糠酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸苯氧基乙酯、甲基丙烯酸苯氧基乙酯、丙烯酸2-羥基-3-苯氧基丙酯、3,3,5-三甲基環己醇丙烯酸酯、環狀三羥甲基丙烷甲縮醛丙烯酸酯、4-乙氧化異丙苯基苯酚丙烯酸酯、丙烯酸二環戊烯氧基乙酯、甲基丙烯酸二環戊烯氧基乙酯、丙烯酸二環戊烯酯等。 Examples of the "(meth)acrylate monomer having a cyclic skeleton in the side chain" include:
Figure 110106505-A0305-02-0053-37
methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, tetrahydrofurfuryl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate Ethyl ester, phenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, cyclic trimethylolpropane formal Acrylates, 4-ethoxylated cumylphenol acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, and the like.

作為「碳數4以下之乙烯基單體」，可列舉：乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、正丙基乙烯醚、異丙基乙烯醚、正丁基乙烯醚、異丁基乙烯醚等。 Examples of "vinyl monomers having 4 or less carbon atoms" include: vinyl acetate, vinyl propionate, vinyl butyrate, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, vinyl ether etc.

作為「側鏈具有環狀骨架之乙烯基單體」，可列舉：苯乙烯、環己基乙烯醚、降

Figure 110106505-A0305-02-0053-38
基乙烯醚、降
Figure 110106505-A0305-02-0053-39
烯基乙烯醚等。其中，尤佳為側鏈之碳數為4以下之乙烯基單體或側鏈之碳數為4以下之丙烯酸酯單體。 Examples of the "vinyl monomer having a cyclic skeleton in the side chain" include styrene, cyclohexyl vinyl ether, nor
Figure 110106505-A0305-02-0053-38
Vinyl ether, nor
Figure 110106505-A0305-02-0053-39
Alkenyl vinyl ether, etc. Among them, a vinyl monomer having 4 or less carbon atoms in the side chain or an acrylate monomer having 4 or less carbon atoms in the side chain is particularly preferable.

上述單體c較佳為側鏈之碳數為1以下之(甲基)丙烯酸酯單體或側鏈具有環狀骨架之(甲基)丙烯酸酯單體。 The above-mentioned monomer c is preferably a (meth)acrylate monomer having one or less carbon atoms in the side chain or a (meth)acrylate monomer having a ring skeleton in the side chain.

此處，作為「側鏈之碳數為1以下之(甲基)丙烯酸酯單體」，可列舉：甲基丙烯酸甲酯、丙烯酸、甲基丙烯酸等。 Here, examples of the "(meth)acrylate monomer having one or less carbon atoms in the side chain" include methyl methacrylate, acrylic acid, methacrylic acid, and the like.

作為「側鏈具有環狀骨架之(甲基)丙烯酸酯單體」，可列舉：甲基丙烯酸異

Figure 110106505-A0305-02-0053-40
基酯、甲基丙烯酸3,3,5-三甲基環己酯、丙烯酸二環戊酯、甲基 丙烯酸二環戊酯、甲基丙烯酸二環戊烯酯等。 Examples of the "(meth)acrylate monomer having a cyclic skeleton in the side chain" include:
Figure 110106505-A0305-02-0053-40
Base ester, 3,3,5-trimethylcyclohexyl methacrylate, dicyclopentyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, etc.

若(甲基)丙烯酸系共聚物(2-A2)含有使單體a與單體b與單體c以a：b：c=10~40：90~35：0~25之莫耳比率共聚合而成之(甲基)丙烯酸酯共聚物或乙烯系共聚物，則可將Tanδ之波峰調整為0~20℃，於通常狀態，即，室溫狀態下，可保持片狀之形狀。並且，具有以較輕之力短時間接著於被黏著體上之性質(稱為“黏性”)。又，若加熱至可熱熔之溫度，則表現出流動性，可追隨貼合面之階差部而填充至各角落。 If the (meth)acrylic copolymer (2-A2) contains monomer a, monomer b and monomer c at a molar ratio of a:b:c=10~40:90~35:0~25 The polymerized (meth)acrylate copolymer or ethylene-based copolymer can adjust the peak of Tanδ to 0~20°C, and can maintain the shape of a sheet in the normal state, that is, at room temperature. Also, it has the property of sticking to the adherend with light force for a short time (called "adhesive"). In addition, when heated to a heat-melting temperature, it exhibits fluidity and can be filled to every corner following the step of the bonding surface.

因此，就該觀點而言，構成(甲基)丙烯酸系共聚物(2-A2)之(甲基)丙烯酸酯共聚物或乙烯系共聚物中之單體a與單體b與單體c之莫耳比率較佳為a：b：c=10~40：90~35：0~25，其中更佳為13~40：87~35：0~23，其中進而較佳為15~40：85~38：2~20。 Therefore, from this point of view, the difference between monomer a, monomer b, and monomer c in the (meth)acrylate copolymer or vinyl copolymer constituting the (meth)acrylic copolymer (2-A2) The molar ratio is preferably a:b:c=10~40:90~35:0~25, more preferably 13~40:87~35:0~23, and more preferably 15~40:85 ~38:2~20.

又，就與上述相同之觀點而言，構成(甲基)丙烯酸系共聚物(2-A2)之(甲基)丙烯酸酯共聚物或乙烯系共聚物中之單體a與單體b與單體c之莫耳比率較佳為b>a>c。 Also, from the same viewpoint as above, monomer a, monomer b, and monomer in the (meth)acrylate copolymer or vinyl copolymer constituting the (meth)acrylic copolymer (2-A2) The molar ratio of body c is preferably b>a>c.

(交聯劑(2-B2)) (Crosslinking agent (2-B2))

藉由於本黏著片材2中使交聯劑(2-B2)交聯，本黏著片材2於高溫環境下表現較高之凝集力，可獲得優異之耐發泡可靠性。 By crosslinking the crosslinking agent (2-B2) in the adhesive sheet 2, the adhesive sheet 2 exhibits high cohesive force under high temperature environment, and can obtain excellent reliability against foaming.

作為此種交聯劑(2-B2)，例如可適宜選擇具有2個以上之環氧基或異氰酸酯基、氧雜環丁烷基、矽烷醇基、(甲基)丙烯醯基等交聯性基之交聯劑。其中，就反應性或所得硬化物之強度之方面而言，較佳為具有2個以上之(甲基)丙烯醯基，其中更佳為具有3個以上之(甲基)丙烯醯基的多官能(甲基)丙烯酸酯或具有環氧基或異氰酸酯基、矽烷醇基之(甲基)丙烯酸酯。 As such a crosslinking agent (2-B2), for example, one having two or more epoxy groups or isocyanate groups, oxetanyl groups, silanol groups, (meth)acryl groups and other crosslinking properties can be selected appropriately. base crosslinking agent. Among them, in terms of reactivity or the strength of the obtained hardened product, polyamides having 2 or more (meth)acryl groups are preferred, and polyamides having 3 or more (meth)acryl groups are more preferred. Functional (meth)acrylates or (meth)acrylates with epoxy groups, isocyanate groups, and silanol groups.

作為此種(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、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、三羥甲基丙烷三氧基乙基(甲基)丙烯酸酯、ε-己內酯改性三(2-羥基乙基)異氰尿酸酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、丙氧化季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、丙氧化季戊四醇四(甲基)丙烯酸酯、乙氧化季戊四醇四(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、三(丙烯醯氧基乙基)異氰尿酸酯、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多官能單體類，另外亦可列舉：聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能丙烯酸酯低聚物類或異氰酸酯(甲基)丙烯酸酯、1,1-(雙(甲基)丙烯醯氧基甲基)乙基異氰酸酯、2-(2-(甲基)丙烯醯氧基乙基氧基)乙基異氰酸酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥乙酯縮水甘油醚、(甲基)丙烯酸羥丙酯縮水甘油醚、(甲基)丙烯酸羥丁酯縮水甘油醚等。 Examples of such (meth)acrylates include 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, 1,6-hexanediol di(methyl) Acrylates, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol A Polypropoxy di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane trioxyethyl(methyl) ) acrylate, ε-caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate ester, ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylate, polyethylene glycol di(meth)acrylate, tris(acryloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, hydroxypivalic acid Di(meth)acrylate of ε-caprolactone adduct of neopentyl glycol ester, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate Acrylate, bis(trimethylolpropane)tetra(meth)acrylate and other ultraviolet curable polyfunctional monomers, and also polyester (meth)acrylate, epoxy (meth)acrylate , (meth)acrylate urethane, polyether (meth)acrylate and other polyfunctional acrylate oligomers or isocyanate (meth)acrylate, 1,1-(bis(meth)acryl Oxymethyl)ethylisocyanate, 2-(2-(meth)acryloxyethyloxy)ethylisocyanate, glycidyl (meth)acrylate, glycidyl (meth)hydroxyethylacrylate Ether, hydroxypropyl (meth)acrylate glycidyl ether, hydroxybutyl (meth)acrylate glycidyl ether, etc.

上述所列舉之中，就提高對被黏著體之密接性或耐熱性、濕熱白化 抑制之效果的觀點而言，較佳為含有極性官能基之多官能單體或低聚物。其中，較佳為使用具有異三聚氰酸環骨架之多官能(甲基)丙烯酸酯。 Among the above listed, it is to improve the adhesion or heat resistance to the adherend, and to improve the heat and humidity whitening. From the viewpoint of the inhibitory effect, polyfunctional monomers or oligomers containing polar functional groups are preferred. Among them, it is preferable to use a polyfunctional (meth)acrylate having an isocyanuric acid ring skeleton.

交聯劑(2-B2)之含量並無特別限制。作為標準，較佳為相對於(甲基)丙烯酸系共聚物(2-A2)100質量份為0.5~20質量份，其中更佳為1質量份以上或15質量份以下，其中進而較佳為2質量份以上或10質量份以下之比率。 The content of the crosslinking agent (2-B2) is not particularly limited. As a standard, it is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the (meth)acrylic copolymer (2-A2), more preferably at least 1 part by mass and at most 15 parts by mass, and even more preferably 0.5 to 20 parts by mass The ratio of 2 mass parts or more or 10 mass parts or less.

藉由於上述範圍內含有交聯劑(2-B2)，可同時實現未交聯狀態之本黏著片材2之形狀穩定性與交聯後之黏著材之耐發泡可靠性。其中，就與其他要素之平衡性而言，亦可超出該範圍。 By containing the crosslinking agent (2-B2) within the above range, the shape stability of the adhesive sheet 2 in the uncrosslinked state and the foaming resistance reliability of the crosslinked adhesive can be simultaneously realized. Among them, in terms of balance with other elements, it may also exceed this range.

(光聚合起始劑(2-C2)) (Photopolymerization Initiator (2-C2))

光聚合起始劑(2-C2)係發揮作為上述交聯劑(2-B2)之交聯反應之反應起始助劑的功能者，可適當使用上述光聚合起始劑(2-C1)所記載者。 The photopolymerization initiator (2-C2) functions as a reaction initiation aid for the crosslinking reaction of the above-mentioned crosslinking agent (2-B2), and the above-mentioned photopolymerization initiator (2-C1) can be used appropriately recorded.

光聚合起始劑(2-C2)之含量並無特別限制。作為標準，較佳為以相對於(甲基)丙烯酸系共聚物(2-A2)100質量份為0.1~10質量份，其中更佳為0.5質量份以上或5質量份以下，其中進而較佳為1質量份以上或3質量份以下之比率含有。 The content of the photopolymerization initiator (2-C2) is not particularly limited. As a standard, it is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylic copolymer (2-A2), more preferably not less than 0.5 parts by mass and not more than 5 parts by mass, and even more preferably It is contained in the ratio of 1 mass part or more or 3 mass parts or less.

藉由將光聚合起始劑(2-C2)之含量設為上述範圍，可獲得對活性能量線之適度之反應感度。 Moderate reaction sensitivity to active energy rays can be obtained by making content of a photoinitiator (2-C2) into the said range.

(其他成分) (other ingredients)

黏著劑組合物(2-II)可含有通常之黏著劑組合物中所調配之公知之成分作為上述以外之成分。例如可視需要適當含有黏著賦予樹脂或抗氧化劑、光穩定化劑、金屬減活劑、抗老化劑、吸濕劑、聚合抑制劑、紫外線吸收劑、防銹劑、矽烷偶合劑、無機粒子等各種添加劑。 The adhesive composition (2-II) may contain, as components other than the above, known components formulated in ordinary adhesive compositions. For example, if necessary, various types such as adhesion-imparting resins, antioxidants, photostabilizers, metal deactivators, anti-aging agents, moisture absorbers, polymerization inhibitors, ultraviolet absorbers, rust inhibitors, silane coupling agents, and inorganic particles can be appropriately contained. additive.

又，亦可視需要適當含有反應觸媒(三級胺系化合物、四級銨系化合物、月桂酸錫化合物等)。 Moreover, a reaction catalyst (tertiary amine type compound, quaternary ammonium type compound, tin laurate compound, etc.) may be contained suitably as needed.

<黏著片材X之製作方法> <Manufacturing method of adhesive sheet X>

製作黏著片材X之方法可列舉：使藉由公知之方法而調製之黏著劑組合物(2-I)、(2-II)溶於溶劑並塗佈之溶液塗佈法；或使該黏著劑組合物加熱熔融並塗佈之熱熔塗佈法等。其中，只要可獲得目標黏著片材，則並無特別限制，可藉由公知之方法而製作。 The method for producing the adhesive sheet X includes: a solution coating method in which the adhesive composition (2-I) and (2-II) prepared by a known method are dissolved in a solvent and applied; or the adhesive composition The hot-melt coating method in which the agent composition is heated, melted and coated, etc. Among these, it will not specifically limit as long as the objective adhesive sheet can be obtained, It can manufacture by a well-known method.

再者，上述黏著劑組合物(2-I)、(2-II)中，形成厚度為50μm以下之薄膜品時，就厚度控制之容易性而言，較佳為採用溶液塗佈法。另一方面，形成厚度為50μm以上之黏著片材時，就環境污染或厚膜成形之容易性而言，較佳為採用熱熔塗佈法。 Furthermore, in the above-mentioned adhesive compositions (2-I) and (2-II), when forming a thin film with a thickness of 50 μm or less, it is preferable to use a solution coating method in terms of the ease of thickness control. On the other hand, when forming an adhesive sheet with a thickness of 50 μm or more, it is preferable to use a hot-melt coating method in terms of environmental pollution and ease of forming a thick film.

<積層構造> <Laminated structure>

本黏著片材2可為包含單一層之片材，亦可為2層以上積層而成之多層片材。 The adhesive sheet 2 may be a sheet comprising a single layer, or a multi-layer sheet formed by laminating two or more layers.

於將本黏著片材2製成多層之透明雙面黏著材之情形時，作為積層構造，具體而言，可列舉：將本黏著劑組合物2與其他黏著劑樹脂組合物積層而成之2種2層構造、或介隔中間樹脂層於正面及背面配置本黏著劑組合物2之2種3層構造、或依序積層本黏著劑組合物2與中間樹脂組合物及其他黏著劑樹脂組合物而成之3種3層構造等。其中，較佳為最外層自本黏著劑組合物2，例如上述黏著劑組合物(2-I)(2-II)形成。 When this adhesive sheet 2 is made into a multi-layered transparent double-sided adhesive, as a laminated structure, specifically, there may be mentioned: 2 laminated with this adhesive composition 2 and another adhesive resin composition. 2-layer structure, or 2 types of 3-layer structure in which this adhesive composition 2 is placed on the front and back via an intermediate resin layer, or this adhesive composition 2, intermediate resin composition, and other adhesive resin combinations are laminated sequentially There are three kinds of three-layer structures made of things. Among them, it is preferable that the outermost layer is formed from the present adhesive composition 2, such as the above-mentioned adhesive composition (2-I) (2-II).

又，亦可將本黏著劑組合物2與其他黏著劑樹脂組合物以片狀成形於分別不同之脫模膜或圖像顯示裝置構成構件上，積層兩黏著面而獲得本黏著片材2，又，亦可依序將本黏著劑組合物2與中間樹脂組合物及黏著劑樹 脂組合物共擠出而獲得2種3層之本黏著片材2，又，亦可於中間樹脂層之正面及背面積層本黏著劑組合物2或其他黏著劑樹脂組合物而獲得本黏著片材2。 In addition, the present adhesive composition 2 and other adhesive resin compositions may be molded in a sheet form on separate release films or image display device components, and both adhesive surfaces may be laminated to obtain the present adhesive sheet 2. In addition, the present adhesive composition 2, the intermediate resin composition and the adhesive tree can also be used in sequence. The resin composition is co-extruded to obtain the adhesive sheet 2 of two types and three layers. In addition, the adhesive composition 2 or other adhesive resin compositions can be laminated on the front and back of the middle resin layer to obtain the adhesive sheet. Material 2.

又，例如可為於基材上具備自本黏著劑組合物2形成之黏著層(稱為「本黏著層2」)之附基材黏著片材，亦可為不具有基材之無基材黏著片材。進而，可為上下兩側具有上述本黏著層2之雙面黏著片材，亦可為僅於上下單面側具有上述本黏著層2之單面黏著片材。 Also, for example, it may be a substrate-attached adhesive sheet having an adhesive layer formed from the present adhesive composition 2 (referred to as "this adhesive layer 2") on the substrate, or may be a substrate-free sheet without a substrate. Adhesive sheet. Furthermore, it may be a double-sided adhesive sheet having the above-mentioned present adhesive layer 2 on both upper and lower sides, or a single-sided adhesive sheet having the above-mentioned present adhesive layer 2 only on one side of the upper and lower sides.

<厚度> <thickness>

作為本黏著片材2之厚度，就不妨礙圖像顯示裝置之薄化之觀點而言，最大厚度部分之厚度較佳為250μm以下。換言之，本黏著片材2可為厚度均勻之片材，亦可為部分厚度不同之不均勻之片材，於厚度不均勻之片材之情形時，厚度最大之部分之厚度較佳為250μm以下。 As the thickness of the adhesive sheet 2, the thickness of the maximum thickness portion is preferably 250 μm or less from the viewpoint of not hindering the thinning of the image display device. In other words, the adhesive sheet 2 can be a sheet with a uniform thickness, or a non-uniform sheet with parts of different thicknesses. In the case of a sheet with non-uniform thickness, the thickness of the thickest part is preferably 250 μm or less .

又，就不妨礙與被黏著體之密接力或減震性之觀點而言，最大厚度部分之厚度較佳為5μm以上，更佳為10μm以上，進而較佳為15μm以上。 Also, the thickness of the maximum thickness portion is preferably at least 5 μm, more preferably at least 10 μm, and still more preferably at least 15 μm, from the viewpoint of not hindering the adhesion with the adherend or shock absorption.

<用途> <purpose>

本黏著片材2可於其原本之形態下使用，亦可以如下方式使用。但並不限定本黏著片材2之利用方法。 This adhesive sheet 2 can be used in its original form, and can also be used as follows. However, the utilization method of the adhesive sheet 2 is not limited.

(黏著片材積層體2) (adhesive sheet laminate 2)

本黏著片材2例如可作為具備於本黏著片材2之一面或雙面積層脫模膜而成之構成之黏著片材積層體2而提供。 This adhesive sheet 2 can be provided as the adhesive sheet laminated body 2 provided with the structure which consists of one side of this adhesive sheet 2, or a double-layer release film, for example.

此時，本黏著片材2例如可為如圖1或圖2所示，於片材面內具有上述軟質部與硬質部之形態，又，亦可為如圖3(A)(B)所示，於黏著片材之至 少一側之端面部具有上述硬質部之形態。此時，可為該端面部整面為上述硬質部，亦可為該端面部一部分為上述硬質部。又，亦可於端面及面內具有硬質部分。 At this time, the adhesive sheet 2 can be, for example, as shown in Fig. 1 or Fig. 2, with the above-mentioned soft part and hard part in the sheet surface, and also can be as shown in Fig. 3 (A) (B). show, in the adhesive sheet to The end face on one side has the form of the above-mentioned hard part. In this case, the entire surface of the end surface may be the hard portion, or a part of the end surface may be the hard portion. In addition, hard parts may be provided on the end surface and inside the surface.

若為圖4(A)(B)所示，本黏著片材2之端面部為硬質部之形態，則例如即使於高溫高濕下等嚴酷之環境下，亦可使露出之端面部不發黏，因此可較佳地保管。 As shown in Fig. 4 (A) (B), the end face of the adhesive sheet 2 is in the form of a hard part, for example, even in severe environments such as high temperature and high humidity, the exposed end face can not be exposed. Sticky, so it can be stored better.

(本圖像顯示裝置構成用積層體2) (Laminate 2 for constituting the image display device)

於本黏著片材2於片材面內具有上述軟質部與上述硬質部之情形時，例如可製作而提供具備介隔該本黏著片材2積層2個圖像顯示裝置用構成構件間而成之構成的圖像顯示裝置構成用積層體(以下，稱為「本圖像顯示裝置構成用積層體2」)。 In the case where the present adhesive sheet 2 has the aforementioned soft portion and the aforementioned hard portion on the surface of the sheet, for example, it can be produced and provided with a space between two image display device constituent members interposed therebetween. The laminated body for constituting an image display device (hereinafter referred to as "the laminated body 2 for constituting an image display device") having the above-mentioned configuration.

本圖像顯示裝置構成用積層體2例如可以如下方式製作：介隔上述黏著片材X積層於貼合面具有不透光部與透光部之圖像顯示裝置用構成構件與其他圖像顯示裝置用構成構件，介隔前者之圖像顯示裝置構成構件對上述黏著片材X進行光照射，使該黏著片材部分光硬化。 The laminate 2 for constituting an image display device can be produced, for example, by laminating a constituent member for an image display device having an opaque portion and a light-transmitting portion on the bonding surface through the above-mentioned adhesive sheet X and other image display components. The device component irradiates the above-mentioned adhesive sheet X with light through the former image display device component, and partially photocures the adhesive sheet.

作為本圖像顯示裝置構成用積層體2之一例，除包含保護面板/本黏著片材2/偏光膜之構成之積層體外，例如亦可列舉：圖像顯示面板/本黏著片材2/觸控面板、圖像顯示面板/本黏著片材2/保護面板、圖像顯示面板/本黏著片材2/觸控面板/本黏著片材2/保護面板、偏光膜/本黏著片材2/觸控面板、偏光膜/本黏著片材2/觸控面板/本黏著片材2/保護面板等構成例。 As an example of the laminate 2 for constituting the image display device, in addition to the laminate including the protective panel/this adhesive sheet 2/polarizing film, for example: image display panel/this adhesive sheet 2/touch Control panel, image display panel/this adhesive sheet 2/protective panel, image display panel/this adhesive sheet 2/touch panel/this adhesive sheet 2/protective panel, polarizing film/this adhesive sheet 2/ Configuration example of touch panel, polarizing film/this adhesive sheet 2/touch panel/this adhesive sheet 2/protection panel.

保護面板及圖像顯示面板亦可為於保護面板或圖像顯示面板本身中組入有觸控面板感測器者。 The protection panel and the image display panel may also be those in which a touch panel sensor is incorporated in the protection panel or the image display panel itself.

(本圖像顯示裝置2) (this image display device 2)

亦可使用本黏著片材2或上述圖像顯示裝置構成用積層體構成圖像顯示裝置(以下，稱為「本圖像顯示裝置2」)。 An image display device (hereinafter referred to as "this image display device 2") can also be configured using the adhesive sheet 2 or the above-mentioned image display device constituting laminate.

即，本圖像顯示裝置2係至少具備面對面之2個圖像顯示裝置用構成構件，至少其中一個圖像顯示裝置用構成構件於貼合面具有不透光部與透光部之圖像顯示裝置，該圖像顯示裝置可作為具有以下特徵之圖像顯示裝置而構成：其係具備於上述2個圖像顯示裝置用構成構件間以黏著片材填充而成之構成之圖像顯示裝置，上述黏著片材之與上述透光部相接之位置之凝膠分率為40%以上，且與上述不透光部相接之位置之凝膠分率未達1%。 That is, the image display device 2 is provided with at least two face-to-face constituent members for an image display device, and at least one of the constituent members for an image display device has an opaque portion and a light-transmitting portion on the bonding surface. A device, the image display device may be configured as an image display device having the following characteristics: it is an image display device having a structure in which an adhesive sheet is filled between the above-mentioned two constituent members for an image display device, The gel fraction of the above-mentioned adhesive sheet in contact with the above-mentioned light-transmitting portion is 40% or more, and the gel fraction of the position in contact with the above-mentioned opaque portion is less than 1%.

於上述本圖像顯示裝置構成用積層體2及本圖像顯示裝置2中，將於貼合面具有畫面周圍之印刷部分等光硬化所需之波長之光不透過之部分(本發明中稱為「不透光部」)及光硬化所需之波長之光透過之部分(本發明中稱為「透光部」)的圖像顯示裝置用構成構件與其他圖像顯示裝置用構成構件貼合時，使與上述不透光部相接之位置之凝膠分率未達1%，與上述透光部相接之位置之凝膠分率為40%以上，藉此可緩和因不透光部壓迫而承受之應力，減小該部分產生之應變，並且亦可具有較高之凝集力而使被黏著物彼此牢固地接著。 In the above-mentioned laminated body 2 for constituting the image display device and the image display device 2, the bonded surface has a portion that does not transmit light of a wavelength required for light hardening such as the printed portion around the screen (referred to in the present invention as A component member for an image display device that is the “opaque portion”) and a portion through which light of a wavelength required for photocuring (referred to as a “transmittance portion” in the present invention) is bonded to other component members for an image display device. When appropriate, make the gel fraction of the position in contact with the above-mentioned opaque part less than 1%, and the gel fraction of the position in contact with the above-mentioned light-transmitting part is more than 40%, so as to alleviate the problem caused by the opacity. The stress borne by the light part can reduce the strain generated by the part, and it can also have a higher cohesive force so that the adherends can be firmly bonded to each other.

再者，與不透光部相接之位置之凝膠分率較佳為未達1%，其中更佳為未達0.8%。 Furthermore, the gel fraction at the position in contact with the opaque portion is preferably less than 1%, more preferably less than 0.8%.

另一方面，與透光部相接之位置之凝膠分率尤佳為40%以上，其中進而較佳為45%以上。 On the other hand, the gel fraction at the position in contact with the light-transmitting portion is more preferably 40% or more, and more preferably 45% or more.

對本圖像顯示裝置2之較佳製法之一例加以說明。 An example of a preferable manufacturing method of the image display device 2 will be described.

首先，將上述黏著片材X加熱使之熱熔，介隔上述黏著片材X積層具有印刷部(1)之圖像顯示裝置用構成構件1與圖像顯示裝置用構成構件3。於該階段，黏著片材X適度柔軟，故而可於維持保存穩定性之同時而充分追隨階差。 First, the above-mentioned adhesive sheet X is heated to be thermally fused, and the constituent member for image display device 1 and the constituent member for image display device 3 having the printed portion (1) are laminated through the above-mentioned adhesive sheet X. At this stage, since the adhesive sheet X is moderately soft, it can fully follow a step difference, maintaining storage stability.

並且其次，自圖像顯示裝置用構成構件1之外側照射紫外線等光。由此，因印刷部(1)遮蔽光，故而光無法到達與印刷部(1)相接之部分，或到達之光顯著受到限制，另一方面光充分到達與無印刷部(1)之透光部(3)相接之部分，該部分可進行交聯反應而光硬化，可實現優異之耐剝離性及耐發泡性。 Then, light such as ultraviolet rays is irradiated from the outside of the constituent member 1 for an image display device. Thus, because the printing part (1) shields the light, the light cannot reach the part that is in contact with the printing part (1), or the light that reaches is significantly restricted. The contact part of the optical part (3) can undergo a crosslinking reaction and be photohardened, which can achieve excellent peeling resistance and foaming resistance.

作為上述2個圖像顯示裝置用構成構件，例如可列舉：電腦、移動終端(PDA)、遊戲機、電視(TV)、汽車導航、觸控面板、手寫板等LCD、PDP或EL等圖像顯示裝置之構成構件。更具體而言，例如可列舉由觸控面板、圖像顯示面板、表面保護面板及偏光膜所組成之群中之任一種或包含兩種以上之組合之積層體。 As the constituent members for the above two image display devices, for example, computer, mobile terminal (PDA), game machine, television (TV), car navigation, touch panel, tablet and other LCD, PDP or EL etc. Components of display devices. More specifically, for example, any one of the group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film, or a laminate including a combination of two or more thereof can be used.

(黏著片材捲筒) (adhesive sheet reel)

本黏著片材2如圖5所示，可為卷為捲筒狀之形態。例如可將黏著片材X卷為捲筒狀後，僅對其端面進行光照射使之光硬化而製作，亦可將僅使端面光硬化之本黏著片材2卷為捲筒狀而製作。無論何種，若卷為捲筒狀之形態之黏著片材之端面成為光硬化部，則例如即使於高溫高濕下等嚴酷之環境下，露出之捲筒端面亦不發黏，因此可較佳地保管。 As shown in FIG. 5, the adhesive sheet 2 can be rolled into a roll shape. For example, the adhesive sheet X may be rolled into a roll, and only the end surface thereof may be irradiated with light to make it photocured, or the original adhesive sheet 2 , which is light-cured only on the end surface, may be rolled into a roll. In any case, if the end surface of the adhesive sheet rolled into a roll form is a light-hardened portion, the exposed roll end surface will not be sticky even in severe environments such as high temperature and high humidity, so it can be compared Keep well.

<本黏著片材3> <This adhesive sheet 3>

本發明之實施形態之另外一例之雙面黏著片材(以下稱為「本黏著片材3」)之特徵在於：其係包含含有(甲基)丙烯酸系共聚物(3-A)100質量 份、交聯劑(3-B)0.5~20質量份及光聚合起始劑(3-C)0.1~5質量份之黏著劑樹脂組合物(以下，稱為「本黏著劑樹脂組合物3」)者，並且關於拉伸彈性模數，光交聯前之拉伸彈性模數(X1)與光交聯後之拉伸彈性模數(X2)之比(X1/X2)成為3以上。 Another example of the embodiment of the present invention is a double-sided adhesive sheet (hereinafter referred to as "this adhesive sheet 3") characterized in that it contains 100 parts by mass of (meth)acrylic copolymer (3-A) , an adhesive resin composition comprising 0.5 to 20 parts by mass of a crosslinking agent (3-B) and 0.1 to 5 parts by mass of a photopolymerization initiator (3-C) (hereinafter referred to as "this adhesive resin composition 3") ), and regarding the tensile modulus, the ratio ( X 1 / X 2 ) of the tensile modulus (X 1 ) before photocrosslinking to the tensile modulus (X 2 ) after photocrosslinking becomes 3 or more.

於以行動電話或移動終端等為中心之圖像顯示裝置之領域中，除薄化、高精密化外，設計之多樣化亦不斷發展，伴隨於此而產生了新課題。例如，通常於表面保護面板之周緣部印刷有框狀之黑色隱蔽部。因此，對用以貼合具備此種印刷部之構成構件之黏著片材要求具有可追隨印刷階差而填充至各角落之印刷階差追隨性。此時，於光交聯前無黏著性(黏性)之情形時，貼合作業不容易， In the field of image display devices centered on mobile phones and mobile terminals, in addition to thinning and high precision, the diversification of design is also progressing, and new issues have arisen along with it. For example, a frame-shaped black concealed portion is usually printed on the periphery of the surface protection panel. Therefore, an adhesive sheet for bonding components having such a printed portion is required to have printing level followability that can follow the printing level and fill to every corner. At this time, when there is no adhesiveness (stickiness) before photocrosslinking, the bonding operation is not easy,

因此本發明欲提供一種可光交聯之黏著片材，即使於光交聯前亦具有黏著性，貼合時黏著材不會過於流動而使黏著劑樹脂組合物溢出或潰縮，進而光交聯後可獲得充分之硬度的本黏著片材3。 Therefore, the present invention intends to provide a photocrosslinkable adhesive sheet, which has adhesiveness even before photocrosslinking. After bonding, the adhesive sheet 3 with sufficient hardness can be obtained.

本黏著片材3具有光交聯前後之拉伸彈性模數(X1)之差顯著較大的特徵，即使於光交聯前亦具有黏著性，貼合時黏著材不會過於流動而使黏著劑樹脂組合物溢出或潰縮，進而光交聯後可獲得充分之硬度。 This adhesive sheet 3 has the characteristic that the difference in tensile elastic modulus (X 1 ) before and after photo-crosslinking is significantly large, and it has adhesiveness even before photo-crosslinking, and the adhesive material will not flow too much when laminating. The adhesive resin composition overflows or collapses, and then obtains sufficient hardness after photo-crosslinking.

<本黏著劑樹脂組合物3> <This adhesive resin composition 3>

本黏著劑樹脂組合物3係如上所述含有(甲基)丙烯酸系共聚物(3-A)、交聯劑(3-B)及光聚合起始劑(3-C)之樹脂組合物。 This adhesive resin composition 3 is a resin composition containing a (meth)acrylic copolymer (3-A), a crosslinking agent (3-B), and a photopolymerization initiator (3-C) as described above.

<(甲基)丙烯酸系共聚物(3-A)> <(Meth)acrylic copolymer (3-A)>

作為基礎聚合物之(甲基)丙烯酸系共聚物(3-A)較佳為具備巨單體作為分枝成分之接枝共聚物(3-A1)。 The (meth)acrylic copolymer (3-A) as the base polymer is preferably a graft copolymer (3-A1) having a macromonomer as a branch component.

此處，所謂「基礎聚合物」係指成為本黏著劑樹脂組合物3之主成分 之樹脂。並不規定基礎聚合物之具體含量，但作為標準，較佳為占本黏著劑樹脂組合物3中所含樹脂之50質量%以上，其中更佳為80質量%以上，其中進而較佳為90質量%以上(包含100質量%)之樹脂。再者，於基礎聚合物為兩種以上之情形時，該等之總量為上述含量。 Here, the so-called "base polymer" refers to the main component of this adhesive resin composition 3 of resin. The specific content of the base polymer is not specified, but as a standard, it is preferably at least 50% by mass of the resin contained in the present adhesive resin composition 3, more preferably at least 80% by mass, and even more preferably at least 90% by mass. Resin of mass % or more (including 100 mass %). Furthermore, when there are two or more base polymers, the total amount thereof is the above-mentioned content.

(主幹成分) (main ingredient)

上述接枝共聚物(3-A1)之主幹成分較佳為包含含有源自(甲基)丙烯酸酯之重複單元之共聚物成分。 It is preferable that the backbone component of the said graft copolymer (3-A1) contains the copolymer component containing the repeating unit derived from (meth)acrylate.

構成上述接枝共聚物(3-A1)之主幹成分之共聚物之玻璃轉移溫度較佳為-70~0℃。 The glass transition temperature of the copolymer constituting the main component of the graft copolymer (3-A1) is preferably -70 to 0°C.

此時，所謂構成主幹成分之共聚物成分之玻璃轉移溫度，係指僅將組成接枝共聚物(3-A1)之主幹成分之單體成分共聚合而獲得之聚合物之玻璃轉移溫度。具體而言，係指由自該共聚物各成分之均聚物獲得之聚合物之玻璃轉移溫度與構成比率，藉由Fox之計算式而算出之值。 In this case, the glass transition temperature of the copolymer component constituting the backbone component means the glass transition temperature of a polymer obtained by copolymerizing only the monomer components constituting the backbone component of the graft copolymer (3-A1). Specifically, it refers to the value calculated by Fox's calculation formula from the glass transition temperature and composition ratio of the polymer obtained from the homopolymer of the respective components of the copolymer.

再者，所謂Fox之計算式係指藉由下式而求得之計算值，可使用聚合物手冊[Polymer HandBook,J.Brandrup,Interscience,1989]中記載之值而求得。 In addition, the calculation formula of Fox means the calculated value obtained by the following formula, and can be obtained using the value described in the polymer handbook [Polymer Handbook, J. Brandrup, Interscience, 1989].

1/(273+Tg)=Σ(Wi/(273+Tgi)) 1/(273+Tg)=Σ(Wi/(273+Tgi))

[式中，Wi表示單體i之重量分率，Tgi表示單體i之均聚物之Tg(℃)] [Where, Wi represents the weight fraction of monomer i, and Tgi represents the Tg (°C) of the homopolymer of monomer i]

構成上述接枝共聚物(3-A1)之主幹成分之共聚物成分之玻璃轉移溫度會對室溫狀態下之本黏著劑樹脂組合物3之柔軟性，或本黏著劑樹脂組合物3對被黏著體之潤濕性，即接著性產生影響，故而為使本黏著劑樹脂組合物3於室溫狀態下獲得適度之接著性(黏性)，該玻璃轉移溫度較佳為-70℃~0℃，其中更佳為-65℃以上或-5℃以下，其中尤佳為-60℃以上或- 10℃以下。 The glass transition temperature of the copolymer component constituting the main component of the above-mentioned graft copolymer (3-A1) affects the flexibility of the present adhesive resin composition 3 at room temperature, or the present adhesive resin composition 3 affects the flexibility of the substrate. The wettability of the adhesive, that is, the adhesiveness affects, so in order to make the adhesive resin composition 3 obtain moderate adhesiveness (viscosity) at room temperature, the glass transition temperature is preferably -70°C~0 °C, more preferably above -65°C or below -5°C, especially preferably above -60°C or below - Below 10°C.

其中，即使該共聚物成分之玻璃轉移溫度為相同溫度，亦可藉由調整分子量而調整黏彈性。例如藉由減小共聚物成分之分子量，可使之更柔軟化。 Among them, even if the glass transition temperature of the copolymer components is the same temperature, the viscoelasticity can be adjusted by adjusting the molecular weight. For example, by reducing the molecular weight of the copolymer component, it can be made more flexible.

作為上述接枝共聚物(3-A1)之主幹成分所含有之(甲基)丙烯酸酯單體，例如可列舉：丙烯酸2-乙基己酯、丙烯酸正辛酯、丙烯酸異辛酯、丙烯酸正丁酯、丙烯酸乙酯、甲基丙烯酸甲酯、丙烯酸甲酯等。亦可使用該等中具有親水基或有機官能基等之丙烯酸羥乙酯、甲基丙烯酸羥乙酯、丙烯酸羥丙酯、甲基丙烯酸羥丙酯、丙烯酸、甲基丙烯酸、丙烯酸縮水甘油酯、丙烯醯胺、N,N-二甲基丙烯醯胺、丙烯腈、甲基丙烯腈等。 Examples of the (meth)acrylate monomer contained in the main component of the graft copolymer (3-A1) include: 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-octyl acrylate Butyl ester, ethyl acrylate, methyl methacrylate, methyl acrylate, etc. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, Acrylamide, N,N-dimethylacrylamide, acrylonitrile, methacrylonitrile, etc.

又，亦可適當使用可與上述丙烯酸系單體或甲基丙烯酸系單體共聚合之乙酸乙烯酯或烷基乙烯基醚、羥基烷基乙烯基醚等各種乙烯基單體。 In addition, various vinyl monomers such as vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether, which are copolymerizable with the above-mentioned acrylic monomer or methacrylic monomer, can also be suitably used.

又，接枝共聚物(3-A1)之主幹成分較佳為含有疏水性之(甲基)丙烯酸酯單體與親水性之(甲基)丙烯酸酯單體作為構成單元。 In addition, the main component of the graft copolymer (3-A1) preferably contains a hydrophobic (meth)acrylate monomer and a hydrophilic (meth)acrylate monomer as constituent units.

若接枝共聚物(3-A1)之主幹成分僅由疏水性單體構成，則確認存在濕熱白化之傾向，故而較佳為將親水性單體亦導入主幹成分而防止濕熱白化。 If the main component of the graft copolymer (3-A1) is composed of only hydrophobic monomers, it is confirmed that there is a tendency of wet heat whitening, so it is preferable to introduce a hydrophilic monomer into the main component to prevent wet heat whitening.

具體而言，作為上述接枝共聚物(3-A1)之主幹成分，可列舉：使疏水性之(甲基)丙烯酸酯單體與親水性之(甲基)丙烯酸酯單體與巨單體之末端之聚合性官能基無規共聚合而成之共聚物成分。 Specifically, as the main component of the above-mentioned graft copolymer (3-A1), a mixture of a hydrophobic (meth)acrylate monomer, a hydrophilic (meth)acrylate monomer, and a macromonomer can be mentioned. A copolymer component formed by random copolymerization of polymerizable functional groups at the terminal.

此處，作為上述疏水性之(甲基)丙烯酸酯單體，較佳為不具有極性基之烷基酯(其中，不包括丙烯酸甲酯)，例如可列舉：(甲基)丙烯酸正丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、 (甲基)丙烯酸正癸酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-甲基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸異

Figure 110106505-A0305-02-0065-43
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、乙酸乙烯酯等。 Here, as the above-mentioned hydrophobic (meth)acrylate monomer, alkyl esters having no polar groups (among which, methyl acrylate is not included) are preferred, for example, n-butyl (meth)acrylate , n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate base) 2-methylhexyl acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid n-propyl, isopropyl (meth)acrylate, tertiary butyl (meth)acrylate, isobutyl (meth)acrylate, iso(meth)acrylate
Figure 110106505-A0305-02-0065-43
base ester, cyclohexyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, methyl methacrylate, vinyl acetate, etc.

作為上述親水性之(甲基)丙烯酸酯單體，較佳為丙烯酸甲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、2-(甲基)丙烯酸羥乙酯、甲氧基聚乙二醇(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、N,N-二甲基丙烯醯胺、羥乙基丙烯醯胺等。 As the above-mentioned hydrophilic (meth)acrylate monomer, methyl acrylate or an ester having a polar group is preferable, for example, methyl acrylate, (meth)acrylic acid, tetrahydrofurfuryl (meth)acrylate , 2-(meth)hydroxyethyl acrylate, methoxy polyethylene glycol (meth)acrylate, 2-(meth)acryloxyethyl succinic acid, 2-(meth)acryloxy Ethyl phthalic acid, 2-(meth)acryloxypropyl hexahydrophthalic acid, N,N-dimethylacrylamide, hydroxyethylacrylamide, etc.

(分枝成分：巨單體) (branch components: macromonomer)

作為接枝共聚物(3-A1)之分枝成分，較佳為導入巨單體，含有源自巨單體之重複單元。 As the branch component of the graft copolymer (3-A1), it is preferable to introduce a macromonomer and contain repeating units derived from the macromonomer.

所謂巨單體係指具有末端之聚合性官能基與高分子量骨架成分之高分子單體。 The so-called macromonomer system refers to a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.

巨單體之玻璃轉移溫度(Tg)較佳為高於構成上述接枝共聚物(3-A1)之共聚物成分之玻璃轉移溫度。 The glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer components constituting the graft copolymer (3-A1).

具體而言，巨單體之玻璃轉移溫度(Tg)會對本黏著劑樹脂組合物3之加熱熔融溫度(熱熔溫度)產生影響，故而巨單體之玻璃轉移溫度(Tg)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。 Specifically, the glass transition temperature (Tg) of the macromonomer will affect the heating and melting temperature (melt temperature) of the adhesive resin composition 3, so the glass transition temperature (Tg) of the macromonomer is preferably 30°C ~120°C, more preferably above 40°C or below 110°C, more preferably above 50°C or below 100°C.

若為此種玻璃轉移溫度(Tg)，則藉由調整分子量，可保持優異之加工性或保存穩定性，並且可調整為於80℃附近熱熔。 If it is such a glass transition temperature (Tg), by adjusting the molecular weight, it is possible to maintain excellent processability and storage stability, and it can be adjusted to heat-melt around 80°C.

所謂巨單體之玻璃轉移溫度係表示該巨單體本身之玻璃轉移溫度，可藉由示差掃描熱量計(DSC)而測定。(升溫速度：5℃/分鐘，根據基準線位移之反曲點而測定Tg) 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). (Heating rate: 5°C/min, Tg is measured according to the inflection point of the baseline displacement)

又，為達成於室溫狀態下可維持分枝成分彼此相互拉近，作為本黏著劑樹脂組合物3進行物理***聯之狀態，並且藉由加熱至適度之溫度可使上述物理***聯解開而獲得流動性，亦較佳為調整巨單體之分子量或含量。 In addition, in order to keep the branch components close to each other at room temperature, the adhesive resin composition 3 is in a state of physical crosslinking, and the above physical crosslinking can be released by heating to a moderate temperature. To obtain fluidity, it is also preferable to adjust the molecular weight or content of the macromonomer.

就該觀點而言，巨單體較佳為以5質量%~30質量%之比率含有於接枝共聚物(3-A1)中，其中更佳為6質量%以上或25質量%以下，其中進而較佳為8質量%以上或20質量%以下。 From this point of view, the macromonomer is preferably contained in the graft copolymer (3-A1) at a ratio of 5 mass % to 30 mass %, more preferably 6 mass % or more or 25 mass % or less, wherein More preferably, it is 8 mass % or more or 20 mass % or less.

又，巨單體之數量平均分子量較佳為500以上且未達8000，其中更佳為800以上或未達7500，其中進而較佳為1000以上或未達7000。 Also, the number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and still more preferably 1000 or more and less than 7000.

巨單體可適當使用通常製造者(例如東亞合成公司製造之巨單體等)。 As the macromonomer, a general manufacturer (for example, a macromonomer manufactured by Toagosei Co., Ltd., etc.) can be used appropriately.

巨單體之高分子量骨架成分較佳為包含丙烯酸系聚合物或乙烯系聚合物。 The high molecular weight skeleton component of the macromonomer preferably comprises an acrylic polymer or a vinyl polymer.

作為上述巨單體之高分子量骨架成分，例如可列舉：聚苯乙烯、苯乙烯及丙烯腈之共聚物、聚(第三丁基苯乙烯)、聚(α-甲基苯乙烯)、聚乙烯基甲苯、聚甲基丙烯酸甲酯等。 Examples of the high-molecular-weight skeleton component of the macromonomer include polystyrene, copolymers of styrene and acrylonitrile, poly(tert-butylstyrene), poly(α-methylstyrene), polyethylene methyl toluene, polymethyl methacrylate, etc.

作為上述巨單體之末端聚合性官能基，例如可列舉：甲基丙烯醯基、丙烯醯基、乙烯基等。 As a terminal polymerizable functional group of the said macromonomer, a methacryl group, an acryl group, a vinyl group etc. are mentioned, for example.

((甲基)丙烯酸系共聚物(3-A)之物性) (Physical properties of (meth)acrylic copolymer (3-A))

上述(甲基)丙烯酸系共聚物(3-A)於溫度130℃，頻率0.02Hz下之複黏度較佳為100~800Pa‧s，更佳為150~700Pa‧s，進而較佳為170~600Pa‧s。 The complex viscosity of the above-mentioned (meth)acrylic copolymer (3-A) at a temperature of 130°C and a frequency of 0.02 Hz is preferably 100~800Pa‧s, more preferably 150~700Pa‧s, and more preferably 170~ 600Pa‧s.

上述(甲基)丙烯酸系共聚物(3-A)之溫度130℃下之複黏度會對使該透明雙面黏著材熱熔而使用時之黏著劑樹脂組合物之流動性產生影響，因此若該複黏度為100~800Pa‧s，則可具有優異之熱熔適性。 The complex viscosity of the above-mentioned (meth)acrylic copolymer (3-A) at a temperature of 130°C will affect the fluidity of the adhesive resin composition when the transparent double-sided adhesive is melted and used, so if If the complex viscosity is 100~800Pa‧s, it can have excellent hot-melt suitability.

為將上述(甲基)丙烯酸系共聚物(3-A)之複黏度調整為上述範圍，例如可列舉調整構成接枝共聚物(3-A1)之主幹成分之共聚物成分之玻璃轉移溫度。可列舉藉由調整為-70℃~0℃，其中更佳為-65℃以上或-5℃以下，其中尤佳為-60℃以上或-10℃以下並且調整該共聚物成分之分子量而調整黏彈性的方法。但並不限定於該方法。 In order to adjust the complex viscosity of the (meth)acrylic copolymer (3-A) to the above range, for example, adjusting the glass transition temperature of the copolymer component constituting the main component of the graft copolymer (3-A1) can be exemplified. It can be adjusted by adjusting to -70°C to 0°C, more preferably -65°C or higher or -5°C or lower, especially preferably -60°C or higher or -10°C or lower, and adjusting the molecular weight of the copolymer component Viscoelastic method. However, it is not limited to this method.

<交聯劑(3-B)> <Crosslinking agent (3-B)>

作為交聯劑(3-B)，例如可適宜選擇具有2個以上之環氧基或異氰酸酯基、氧雜環丁烷基、矽烷醇基、(甲基)丙烯醯基等交聯性基之交聯劑。其中，就反應性或所得硬化物之強度之方面而言，較佳為具有2個以上之(甲基)丙烯醯基，其中更佳為具有3個以上之(甲基)丙烯醯基的多官能(甲基)丙烯酸酯或具有環氧基或異氰酸酯基、矽烷醇基之(甲基)丙烯酸酯。 As the cross-linking agent (3-B), for example, one having two or more cross-linking groups such as epoxy groups or isocyanate groups, oxetanyl groups, silanol groups, (meth)acryl groups, etc. can be appropriately selected. crosslinking agent. Among them, in terms of reactivity or the strength of the obtained hardened product, polyamides having 2 or more (meth)acryl groups are preferred, and polyamides having 3 or more (meth)acryl groups are more preferred. Functional (meth)acrylates or (meth)acrylates with epoxy groups, isocyanate groups, and silanol groups.

作為此種多官能(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、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、三羥甲基丙烷三氧基乙基(甲基)丙烯酸酯、ε-己內酯改性三(2- 羥基乙基)異氰尿酸酯三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、丙氧化季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、丙氧化季戊四醇四(甲基)丙烯酸酯、乙氧化季戊四醇四(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、三(丙烯醯氧基乙基)異氰尿酸酯、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多官能單體類，另外亦可列舉：聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能丙烯酸酯低聚物類或異氰酸酯(甲基)丙烯酸酯、1,1-(雙(甲基)丙烯醯氧基甲基)乙基異氰酸酯、2-(2-(甲基)丙烯醯氧基乙基氧基)乙基異氰酸酯、(甲基)丙烯酸縮水甘油酯、丙烯酸羥乙酯縮水甘油醚、(甲基)丙烯酸羥丙酯縮水甘油醚、(甲基)丙烯酸羥丁酯縮水甘油醚。 Examples of such polyfunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, glycerin glycidyl ether di(meth)acrylate ester, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A poly Ethoxylated Di(meth)acrylate, Bisphenol A Polypropoxylated Di(meth)acrylate, Bisphenol F Polyethoxylated Di(meth)acrylate, Ethylene Glycol Di(meth)acrylate , trimethylolpropane trioxyethyl (meth)acrylate, ε-caprolactone modified three (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, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate Base) acrylate, tripentaerythritol penta(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, ε-caprolactone adduct of hydroxypivalate neopentyl glycol Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, bis(trimethylolpropane)tetra(methyl) ) acrylates and other UV curable polyfunctional monomers, in addition: polyester (meth)acrylate, epoxy (meth)acrylate, (meth)acrylate urethane, polyether ( Polyfunctional acrylate oligomers such as meth)acrylate or isocyanate (meth)acrylate, 1,1-(bis(meth)acryloxymethyl)ethyl isocyanate, 2-(2-( Meth)acryloxyethyloxy)ethyl isocyanate, glycidyl (meth)acrylate, glycidyl hydroxyethyl acrylate, glycidyl hydroxypropyl (meth)acrylate, (meth)acrylic acid Hydroxybutyl Glycidyl Ether.

上述所列舉之中，就提高對被黏著體之密接性或濕熱白化之抑制效果的觀點而言，較佳為含有羥基等極性官能基之多官能單體或低聚物。 Among those listed above, polyfunctional monomers or oligomers containing polar functional groups such as hydroxyl groups are preferred from the viewpoint of improving the adhesion to the adherend or the effect of suppressing wet heat whitening.

其中，較佳為使用具有羥基之多官能(甲基)丙烯酸酯。 Among them, it is preferable to use a polyfunctional (meth)acrylate having a hydroxyl group.

因此，就防止濕熱白化之觀點而言，作為上述接枝共聚物(3-A1)之主幹成分，較佳為含有疏水性之丙烯酸酯單體與親水性之丙烯酸酯單體，進而，作為交聯劑(3-B)，較佳為使用具有羥基之多官能(甲基)丙烯酸酯。 Therefore, from the viewpoint of preventing wet heat whitening, it is preferable to contain a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as the main component of the above-mentioned graft copolymer (3-A1). As the coupling agent (3-B), it is preferable to use a polyfunctional (meth)acrylate having a hydroxyl group.

交聯劑(3-B)之含量較佳為以相對於(甲基)丙烯酸系共聚物(3-A)100 質量份為0.5~20質量份之比率含有，其中更佳為1質量份以上或15質量份以下，其中進而較佳為2質量份以上或10質量份以下之比率。 The content of the crosslinking agent (3-B) is preferably 100% relative to the (meth)acrylic copolymer (3-A) The ratio of 0.5 to 20 parts by mass is included, more preferably at least 1 part by mass or less than 15 parts by mass, and even more preferably at least 2 parts by mass or less than 10 parts by mass.

藉由於上述範圍內含有交聯劑(3-B)，可同時實現未交聯狀態之本黏著片材3之形狀穩定性與交聯後之黏著材之耐發泡可靠性。其中，就與其他要素之平衡性而言，亦可超出該範圍。 By containing the crosslinking agent (3-B) within the above range, the shape stability of the adhesive sheet 3 in the uncrosslinked state and the foaming resistance reliability of the crosslinked adhesive can be simultaneously realized. Among them, in terms of balance with other elements, it may also exceed this range.

<光聚合起始劑(3-C)> <Photopolymerization Initiator (3-C)>

光聚合起始劑(3-C)係發揮作為上述交聯劑(3-B)之交聯反應之反應起始助劑的功能者。 The photopolymerization initiator (3-C) functions as a reaction initiation aid for the crosslinking reaction of the above-mentioned crosslinking agent (3-B).

光聚合起始劑可適當使用現今公知者。其中，就易於控制交聯反應之觀點而言，較佳為與波長380nm以下之紫外線感應之光聚合起始劑。 As the photopolymerization initiator, conventionally known ones can be appropriately used. Among them, a photopolymerization initiator responsive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.

另一方面，與較波長380nm長波長之光感應之光聚合起始劑於感應之光容易到達本黏著片材3之深部之方面而言較佳。 On the other hand, a photopolymerization initiator that responds to light with a wavelength longer than 380 nm is preferable because the induced light easily reaches the deep portion of the adhesive sheet 3 .

光聚合起始劑根據自由基產生機制而大體分為兩類，大致分為：可使光聚合性起始劑本身之單鍵發生斷裂分解而產生自由基的裂解型光聚合起始劑、以及光激發之起始劑與系統中之氫供與體形成激發錯合物而可使氫供與體之氫轉移的奪氫型光聚合起始劑。 Photopolymerization initiators are roughly divided into two categories according to the mechanism of free radical generation, roughly divided into: cleavage-type photopolymerization initiators that can break and decompose the single bond of the photopolymerization initiator itself to generate free radicals, and The photoexcited initiator and the hydrogen donor and donor in the system form an excited complex, which can transfer the hydrogen of the hydrogen donor and donor to the hydrogen abstraction type photopolymerization initiator.

關於該等之中的裂解型光聚合起始劑，藉由光照射而產生自由基時分解而成為其他化合物，若一旦被激發則失去作為反應起始劑之功能。因此，不會於交聯反應結束後之黏著材中作為活性物質而殘存，不存在對黏著材造成未預期之光劣化等之可能性，故而較佳。 Among them, the cleavage-type photopolymerization initiator decomposes into other compounds when free radicals are generated by light irradiation, and loses its function as a reaction initiator once it is excited. Therefore, it is preferable because it does not remain as an active material in the adhesive material after the crosslinking reaction is completed, and there is no possibility of causing unexpected photodegradation to the adhesive material.

另一方面，關於奪氫型光聚合起始劑，藉由紫外線等活性能量線照射而產生自由基反應時，不會產生如裂解型光聚合起始劑之分解物，故而反應結束後難以成為揮發成分，可減少對被黏著體之損傷，就該方面而言 較為有用。 On the other hand, when a hydrogen abstraction photopolymerization initiator is irradiated with active energy rays such as ultraviolet rays to generate a free radical reaction, no decomposition product such as a cracking photopolymerization initiator is generated, so it is difficult to become Volatile components can reduce the damage to the adherend, in this respect more useful.

作為上述裂解型光起始劑，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-

Figure 110106505-A0305-02-0070-44
啉基苯基)丁烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-
Figure 110106505-A0305-02-0070-45
啉基丙烷-1-酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-
Figure 110106505-A0305-02-0070-46
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或該等之衍生物等。 Examples of the cleavage-type photoinitiator 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-propan-1-one, 2 -Hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}phenyl]-2-methyl-propan-1-one, oligo(2-hydroxy- 2-methyl-1-(4-(1-methylvinyl)phenyl)acetone), methyl phenylglyoxylate, 2-benzyl-2-dimethylamino-1-(4-
Figure 110106505-A0305-02-0070-44
Linylphenyl) butane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-
Figure 110106505-A0305-02-0070-45
Linyl propan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-
Figure 110106505-A0305-02-0070-46
Phenyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide or their derivatives, etc.

作為上述奪氫型光起始劑，例如可列舉：二苯甲酮、4-甲基-二苯甲酮、2,4,6-三甲基二苯甲酮、4-苯基二苯甲酮、3,3'-二甲基-4-甲氧基二苯甲酮、4-(甲基)丙烯醯氧基二苯甲酮、2-苯甲醯基苯甲酸甲酯、苯甲醯基甲酸甲酯、雙(2-苯基-2-乙醛酸)氧基雙乙烯、4-(1,3-丙烯醯基-1,4,7,10,13-五氧代十三烷基)二苯甲酮、9-氧硫

Figure 110106505-A0305-02-0070-53
、2-氯-9-氧硫
Figure 110106505-A0305-02-0070-52
、3-甲基-9-氧硫
Figure 110106505-A0305-02-0070-49
、2,4-二甲基-9-氧硫
Figure 110106505-A0305-02-0070-50
、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌或其衍生物等。 Examples of the hydrogen abstraction type photoinitiator include: benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone Ketone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloxybenzophenone, methyl 2-benzoylbenzoate, benzoyl Methyl methanoate, bis(2-phenyl-2-glyoxylate)oxybisethylene, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxotridecane base) benzophenone, 9-oxosulfur
Figure 110106505-A0305-02-0070-53
, 2-Chloro-9-oxosulfur
Figure 110106505-A0305-02-0070-52
, 3-methyl-9-oxosulfur
Figure 110106505-A0305-02-0070-49
, 2,4-Dimethyl-9-oxosulfur
Figure 110106505-A0305-02-0070-50
, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone or its derivatives, etc.

其中，並不限定於作為光聚合起始劑而於上述列舉之物質。可使用上述列舉之裂解型光聚合起始劑及奪氫型光聚合起始劑中之任一種，或組合兩種以上使用。 However, it is not limited to what was listed above as a photoinitiator. Any of the cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators listed above may be used, or two or more of them may be used in combination.

光聚合起始劑(3-C)之含量較佳為以相對於(甲基)丙烯酸系共聚物(3-A)100質量份為0.1~5質量份之比率含有，其中更佳為以0.5質量份以上或3質量份以下，其中進而較佳為以1質量份以上之比率含有。 The content of the photopolymerization initiator (3-C) is preferably contained in a ratio of 0.1 to 5 parts by mass relative to 100 parts by mass of the (meth)acrylic copolymer (3-A), more preferably 0.5 parts by mass. It is more than or equal to 3 parts by mass, and it is more preferable to contain it in the ratio of 1 part by mass or more.

藉由將光聚合起始劑(3-C)之含量設為上述範圍，可獲得對活性能量線之適度之反應感度。 Moderate reaction sensitivity to active energy rays can be obtained by making content of a photoinitiator (3-C) into the said range.

<其他成分> <other ingredients>

本黏著劑樹脂組合物3可含有通常之黏著劑組合物中所調配之公知之成分作為上述以外之成分。例如可視需要適當含有黏著賦予樹脂或抗氧化劑、光穩定化劑、金屬減活劑、抗老化劑、吸濕劑、聚合抑制劑、紫外線吸收劑、防銹劑、矽烷偶合劑、無機粒子等各種添加劑。 The present adhesive resin composition 3 may contain, as components other than the above, known components formulated in ordinary adhesive compositions. For example, if necessary, various types such as adhesion-imparting resins, antioxidants, photostabilizers, metal deactivators, anti-aging agents, moisture absorbers, polymerization inhibitors, ultraviolet absorbers, rust inhibitors, silane coupling agents, and inorganic particles can be appropriately contained. additive.

又，亦可視需要適當含有反應觸媒(三級胺系化合物、四級銨系化合物、月桂酸錫化合物等)。 Moreover, a reaction catalyst (tertiary amine type compound, quaternary ammonium type compound, tin laurate compound, etc.) may be contained suitably as needed.

<本黏著片材3之特徵> <Features of this adhesive sheet 3>

本黏著片材3可設為如下黏著片材：可於常態下保持片狀，具有當於未交聯狀態下加熱時發生熔融或流動之熱熔性，且具有可光硬化之光硬化性。 The present adhesive sheet 3 may be an adhesive sheet that can maintain a sheet shape under normal conditions, has heat-melt property that melts or flows when heated in an uncrosslinked state, and has photocurable property that can be photocured.

若可於常態下保持片狀，則與液狀之接著劑相比，操作更容易，並且可省略填充液體之作業，因此生產性尤其優異。此時，若進而於常態、即室溫附近具備適度之黏著性，即以較輕之力短時間接著於被黏著體上之性質(稱為“黏性”)，則易於進行貼著時之定位，作業性優異，因此較佳為於常態、即室溫附近具備黏性，若於-5℃至20℃之較低氣溫範圍亦具備黏性則更佳。藉由使用上述接枝共聚物(3-A1)作為(甲基)丙烯酸系共聚物(3-A)，可獲得此種黏性。 If the sheet can be kept in a normal state, it is easier to handle than a liquid adhesive, and the work of filling the liquid can be omitted, so the productivity is particularly excellent. At this time, if it has moderate adhesiveness in the normal state, that is, around room temperature, that is, the property of sticking to the adherend with a light force for a short time (called "stickiness"), it will be easy to stick. Positioning and workability are excellent, so it is better to have viscosity in the normal state, that is, around room temperature, and it is better if it also has viscosity in the lower temperature range from -5°C to 20°C. Such tackiness can be obtained by using the above-mentioned graft copolymer (3-A1) as the (meth)acrylic copolymer (3-A).

又，若具備加熱時發生熔融或流動之熱熔性，則藉由加熱使之軟化或流動化，可追隨印刷階差等凹凸部而填充黏著劑，因此可於不產生發泡等之狀態下填充。 In addition, if it has a hot-melt property that melts or flows when heated, it can be softened or fluidized by heating, and the adhesive can be filled with uneven parts such as printing steps, so it can be used without foaming. filling.

進而若具有光硬化性，則藉由最終使之光硬化，可牢固地接著。 Furthermore, if it has photocurability, it can stick firmly by finally photocuring it.

如上所述，為製作可於常態下保持片狀，具有當於未交聯狀態下加熱時發生熔融或流動之熱熔性，且可光硬化之黏著片材，例如若為單層之黏著片材，則只要由上述本黏著劑樹脂組合物3製作單層之黏著片材即可。另一方面，於製為多層之黏著片材之情形時，例如可列舉：將包含本黏著劑樹脂組合物3之黏著層與包含其他黏著劑樹脂組合物之黏著層積層而成之2種2層構造，或介隔中間樹脂層於正面及背面配置包含本黏著劑樹脂組合物3之黏著層之2種3層構造，或依序積層包含本黏著劑樹脂組合物3之黏著層與包含中間樹脂組合物之中間層及包含其他黏著劑樹脂組合物之黏著層而成之3種3層構造等。 As mentioned above, in order to produce a photohardenable adhesive sheet that can maintain a sheet shape under normal conditions, has a heat-melt property that melts or flows when heated in an uncrosslinked state, for example, if it is a single-layer adhesive sheet material, it is only necessary to make a single-layer adhesive sheet from the above-mentioned adhesive resin composition 3. On the other hand, in the case of making a multi-layered adhesive sheet, for example, two types 2 in which an adhesive layer composed of this adhesive resin composition 3 and an adhesive layer composed of another adhesive resin composition are laminated. Layer structure, or two types of 3-layer structure in which an adhesive layer containing this adhesive resin composition 3 is arranged on the front and back through an intermediate resin layer, or an adhesive layer containing this adhesive resin composition 3 and an adhesive layer containing this adhesive resin composition 3 are sequentially laminated. Three types of 3-layer structures formed by the middle layer of the resin composition and the adhesive layer of the resin composition containing other adhesives, etc.

其中，用以形成本黏著片材3之黏著劑樹脂組合物並不限定於本黏著劑樹脂組合物3。 Wherein, the adhesive resin composition used to form the adhesive sheet 3 is not limited to the adhesive resin composition 3 .

(凝膠分率) (gel fraction)

就可於光硬化前之狀態下表現熱熔性之觀點而言，本黏著片材3於光硬化前之凝膠分率(a)為5%以下，其中較佳為4%以下，其中尤佳為2%以下。 From the point of view of expressing hot-melt property in the state before photohardening, the gel fraction (a) of the adhesive sheet 3 before photohardening is 5% or less, preferably 4% or less, especially Preferably less than 2%.

又，就光硬化後可獲得較高之凝集力，可獲得濕熱環境下之耐發泡可靠性的觀點而言，本黏著片材3於光硬化後之凝膠分率(b)較佳為50%以上，其中更佳為60%以上或90%以下，其中尤佳為65%以上或80%以下。 Also, from the standpoint of obtaining higher cohesive force after photocuring and the reliability of foaming resistance in hot and humid environments, the gel fraction (b) of the adhesive sheet 3 after photocuring is preferably More than 50%, more preferably more than 60% or less than 90%, especially more than 65% or less than 80%.

為如上所述調整光硬化前之凝膠分率(a)及光硬化後之凝膠分率(b)，例如只要使用具備巨單體作為分枝成分之接枝共聚物(A1)作為(甲基)丙烯酸系共聚物(3-A)，並且調整交聯劑或光聚合起始劑之組成比，或調整加工時之溫度或光照射量即可。但並不限定於此種方法。 In order to adjust the gel fraction (a) before photohardening and the gel fraction (b) after photohardening as described above, for example, a graft copolymer (A1) having a macromonomer as a branch component is used as ( The meth)acrylic copolymer (3-A) may be adjusted by adjusting the composition ratio of the crosslinking agent or photopolymerization initiator, or adjusting the temperature or light irradiation amount during processing. However, it is not limited to this method.

(拉伸彈性模數) (tensile modulus of elasticity)

關於本黏著片材3，若光交聯前之拉伸彈性模數(X1)與光交聯後之拉伸彈性模數(X2)之比(X1/X2)成為3以上，則可獲得良好之階差吸收性或耐發泡可靠性。 Regarding this adhesive sheet 3, if the ratio ( X 1 /X 2 ) of the tensile modulus (X 1 ) before photocrosslinking to the tensile modulus (X 2 ) after photocrosslinking becomes 3 or more, Then, good step absorption or foaming resistance reliability can be obtained.

就該觀點而言，光交聯前之拉伸彈性模數(X1)與光交聯後之拉伸彈性模數(X2)之比(X1/X2)較佳為3以上，其中更佳為5以上或30以下，其中進而較佳為10以上或27以下。 From this point of view, the ratio (X 1 /X 2 ) of the tensile modulus of elasticity (X 1 ) before photocrosslinking to the tensile modulus of elasticity (X 2 ) after photocrosslinking is preferably 3 or more, Among them, 5 or more or 30 or less are more preferable, and 10 or more or 27 or less are still more preferable.

光交聯前之拉伸彈性模數(X1)較佳為0.01MPa以上且0.2MPa以下，其中更佳為0.05MPa以上或0.1MPa以下。 The tensile elastic modulus (X 1 ) before photocrosslinking is preferably from 0.01 MPa to 0.2 MPa, more preferably from 0.05 MPa to 0.1 MPa.

另一方面，光交聯後之拉伸彈性模數(X2)較佳為0.8MPa以上且2.0MPa以下，其中更佳為1.0MPa以上或1.8MPa以下。 On the other hand, the tensile elastic modulus (X 2 ) after photocrosslinking is preferably from 0.8 MPa to 2.0 MPa, more preferably from 1.0 MPa to 1.8 MPa.

(拉伸最大應力(Y)) (Maximum tensile stress (Y))

關於本黏著片材3，若光交聯前之拉伸最大應力(Y1)與光交聯後之拉伸最大應力(Y2)之比(Y1/Y2)為5以上且20以下，則可獲得良好之階差吸收性或耐發泡可靠性。 Regarding this adhesive sheet 3, if the ratio (Y 1 /Y 2 ) of the maximum tensile stress (Y 1 ) before photocrosslinking to the maximum tensile stress (Y 2 ) after photocrosslinking is 5 or more and 20 or less , you can get good step absorption or anti-foaming reliability.

就該觀點而言，本黏著片材3之光交聯前之拉伸最大應力(Y1)與光交聯後之拉伸最大應力(Y2)之比(Y1/Y2)較佳為5以上且20以下，其中更佳為8以上或15以下。 From this viewpoint, the ratio (Y 1 /Y 2 ) of the maximum tensile stress (Y 1 ) before photocrosslinking to the maximum tensile stress (Y 2 ) after photocrosslinking of the present adhesive sheet 3 is preferable 5 or more and 20 or less, and more preferably 8 or more or 15 or less.

光交聯前之拉伸最大應力(Y1)較佳為0.5N以上且5N以下，其中尤佳為0.8N以上或2N以下。 The maximum tensile stress (Y 1 ) before photocrosslinking is preferably not less than 0.5N and not more than 5N, particularly preferably not less than 0.8N and not more than 2N.

另一方面，光交聯後之拉伸最大應力(Y2)較佳為7N以上且15N以下，其中尤佳為9N以上或12N以下。 On the other hand, the maximum tensile stress (Y 2 ) after photocrosslinking is preferably not less than 7N and not more than 15N, particularly preferably not less than 9N and not more than 12N.

(拉伸斷裂應力(Z)) (tensile stress at break (Z))

關於本黏著片材3，若光交聯前之拉伸斷裂應力(Z1)與光交聯後之拉伸斷裂應力(Z2)之比(Z1/Z2)為10以上且50以下，則可獲得良好之階差吸收性或耐發泡可靠性。 Regarding this adhesive sheet 3, if the ratio (Z 1 /Z 2 ) of the tensile breaking stress (Z 1 ) before photocrosslinking to the tensile breaking stress (Z 2 ) after photocrosslinking is 10 or more and 50 or less , you can get good step absorption or anti-foaming reliability.

就該觀點而言，本黏著片材3之光交聯前之拉伸斷裂應力(Z1)與光交聯後之拉伸斷裂應力(Z2)之比(Z1/Z2)較佳為10以上且50以下，其中尤佳為15以上或40以下。 From this point of view, the ratio (Z 1 /Z 2 ) of the tensile breaking stress before photocrosslinking (Z 1 ) to the tensile breaking stress (Z 2 ) after photocrosslinking of the present adhesive sheet 3 is preferable It is 10 or more and 50 or less, especially preferably 15 or more or 40 or less.

光交聯前之拉伸斷裂應力(Z1)較佳為0.1N以上且2N以下，其中尤佳為0.2N以上或0.6N以下。 The tensile breaking stress (Z 1 ) before photocrosslinking is preferably from 0.1N to 2N, particularly preferably from 0.2N to 0.6N.

另一方面，光交聯後之拉伸斷裂應力(Z2)較佳為7N以上且16N以下，其中尤佳為9N以上或12N以下。 On the other hand, the tensile breaking stress (Z 2 ) after photocrosslinking is preferably not less than 7N and not more than 16N, particularly preferably not less than 9N and not more than 12N.

於本黏著片材3中，為將拉伸彈性模數、拉伸最大應力及拉伸斷裂應力調整為上述範圍內，例如只要使用具備巨單體作為分枝成分之接枝共聚物(3-A1)作為(甲基)丙烯酸系共聚物(3-A)，並且調整該巨單體之種類或份數即可。但並不限定於該方法。 In this adhesive sheet 3, in order to adjust the tensile elastic modulus, maximum tensile stress and tensile breaking stress within the above ranges, for example, a graft copolymer (3- A1) As the (meth)acrylic copolymer (3-A), the type or number of parts of the macromonomer may be adjusted. However, it is not limited to this method.

若使用具備巨單體作為分枝成分之接枝共聚物(3-A1)作為(甲基)丙烯酸系共聚物(3-A)，則於通常狀態下亦可保持片材形狀，藉由加熱可發揮流動性而滿足階差追隨性，藉由進行紫外線交聯可推進硬化反應而獲得優異之接著可靠性。 If a graft copolymer (3-A1) having a macromonomer as a branch component is used as the (meth)acrylic copolymer (3-A), the shape of the sheet can be maintained under normal conditions. It can exert fluidity and meet the step followability, and the hardening reaction can be promoted by ultraviolet crosslinking to obtain excellent bonding reliability.

<積層構造> <Laminated structure>

本黏著片材3可為包含單一層之片材，亦可為2層以上積層而成之多層片材。 The adhesive sheet 3 may be a sheet comprising a single layer, or a multi-layer sheet formed by laminating two or more layers.

於將本黏著片材3製成多層之透明雙面黏著材之情形時，最外層較佳為與上述單層之情形相同同時實現凹凸追隨性與耐發泡可靠性，因此，較 佳為使用上述本黏著劑樹脂組合物3而成形。 When the present adhesive sheet 3 is made into a multi-layer transparent double-sided adhesive material, the outermost layer is preferably the same as the case of the above-mentioned single layer, and at the same time realizes concave-convex followability and foam resistance reliability. Preferably, it is molded using the present adhesive resin composition 3 described above.

另一方面，中間層由於對與圖像顯示裝置構成構件之黏著不起到助益，故而較佳為不損害透明性，且具有不妨礙最外層之2次硬化反應之程度之透光性，且具有提高削減性及處理性之性質。 On the other hand, since the intermediate layer does not contribute to the adhesion with the constituent members of the image display device, it is preferable not to impair the transparency, and to have light transmittance to the extent that the secondary curing reaction of the outermost layer is not hindered. And it has the property of improving reduction and handling.

形成中間層之基礎聚合物之種類只要為透明樹脂，則並無特別限定。形成中間層之基礎聚合物可為與最外層之基礎聚合物相同之樹脂亦可為不同之樹脂。其中，就透明性之確保或製作容易性，進而防止於積層邊界面之光之折射的觀點而言，較佳為使用與最外層之基礎聚合物相同之丙烯酸系樹脂。 The type of the base polymer forming the intermediate layer is not particularly limited as long as it is a transparent resin. The base polymer forming the middle layer may be the same resin as the base polymer of the outermost layer or a different resin. Among them, it is preferable to use the same acrylic resin as the base polymer of the outermost layer from the viewpoint of ensuring transparency, ease of manufacture, and preventing refraction of light at the boundary surface of the laminate.

中間層及其他樹脂層可具有活性能量線硬化性亦可不具有活性能量線硬化性。例如可形成為藉由紫外線交聯而硬化，亦可形成為藉由熱而硬化。又，尤其可形成為不進行後硬化。其中，若考慮與最外層之密接性，則較佳為形成為進行後硬化，尤佳為形成為進行紫外線交聯。 The intermediate layer and other resin layers may or may not have active energy ray curability. For example, it may be cured by ultraviolet crosslinking, or it may be cured by heat. In addition, in particular, post-hardening may not be performed. Among them, in consideration of the adhesiveness with the outermost layer, it is preferably formed so as to be post-cured, and particularly preferably formed so as to be ultraviolet crosslinked.

此時，若交聯起始劑之含量變多則透光率下降，故而較佳為以中間層之交聯起始劑較外層之含有率低之含有率含有紫外線交聯劑。 At this time, as the content of the crosslinking initiator increases, the light transmittance decreases, so it is preferable to contain the ultraviolet crosslinking agent at a lower content of the crosslinking initiator in the middle layer than in the outer layer.

於將本黏著片材3製成多層之透明雙面黏著材之情形時，作為積層構造，具體可列舉：將本黏著劑樹脂組合物3與其他黏著劑樹脂組合物積層而成之2種2層構造，或介隔中間樹脂層於正面及背面配置本黏著劑樹脂組合物3之2種3層構造，或依序積層本黏著劑樹脂組合物3與中間樹脂組合物及其他黏著劑樹脂組合物而成之3種3層構造等。 When this adhesive sheet 3 is made into a multi-layered transparent double-sided adhesive, as a laminated structure, specifically, two types 2 in which this adhesive resin composition 3 and another adhesive resin composition are laminated are listed. Layer structure, or two types of three-layer structure in which this adhesive resin composition 3 is arranged on the front and back through an intermediate resin layer, or this adhesive resin composition 3, intermediate resin composition, and other adhesive resin combinations are laminated sequentially There are three kinds of three-layer structures made of things.

又，可將本黏著劑樹脂組合物3與其他黏著劑樹脂組合物以片狀成形於分別不同之脫模膜或圖像顯示裝置構成構件上，積層兩黏著面而獲得本黏著片材3，又，亦可依序將本黏著劑組合物3與中間樹脂組合物及黏著劑 樹脂組合物共擠出而獲得2種3層之本黏著片材3，又，亦可於中間樹脂層之正面及背面積層本黏著劑組合物3或其他黏著劑樹脂組合物而獲得本黏著片材3。 In addition, this adhesive resin composition 3 and other adhesive resin compositions can be molded in a sheet form on different release films or image display device constituent members, and both adhesive surfaces can be laminated to obtain this adhesive sheet 3, In addition, the present adhesive composition 3, the intermediate resin composition and the adhesive can also be used in sequence. The resin composition is co-extruded to obtain the adhesive sheet 3 of two types and three layers. In addition, the adhesive composition 3 or other adhesive resin compositions can be laminated on the front and back of the middle resin layer to obtain the adhesive sheet. Material 3.

又，例如，可為具備於基材形成上述本黏著層3而成之構成之附基材黏著片材，亦可為不具有基材之無基材黏著片材。進而，可為上下兩側具有上述本黏著層3之雙面黏著片材，亦可為僅於上下單面側具有上述本黏著層3之單面黏著片材。 Also, for example, it may be a substrate-attached adhesive sheet having a structure in which the above-mentioned adhesive layer 3 is formed on a substrate, or may be a substrate-less adhesive sheet that does not have a substrate. Furthermore, it may be a double-sided adhesive sheet having the above-mentioned present adhesive layer 3 on both upper and lower sides, or a single-sided adhesive sheet having the above-mentioned present adhesive layer 3 only on one side of the upper and lower sides.

<厚度> <thickness>

就不妨礙圖像顯示裝置之薄化之觀點及階差吸收性之觀點而言，本黏著片材3之厚度，即總厚度較佳為50μm~1mm，其中更佳為75μm以上或500μm以下。 The thickness of the adhesive sheet 3 , that is, the total thickness is preferably 50 μm to 1 mm, more preferably 75 μm or more or 500 μm or less from the viewpoint of not hindering the thinning of the image display device and the viewpoint of step absorption.

若本黏著片材3之總厚度為50μm以上，則可追隨高印刷階差等凹凸，若為1mm以下，則可應對薄化之要求。 If the total thickness of the adhesive sheet 3 is 50 μm or more, it can follow unevenness such as high printing steps, and if it is 1 mm or less, it can meet the requirement of thinning.

進而，就先前之圖像顯示裝置之周緣之隱蔽層之印刷高度更高，具體而言可填埋達到80μm左右之階差的觀點而言，本黏著片材3之厚度較佳為75μm以上，尤佳為100μm以上。另一方面，就應對薄化之要求之觀點而言，較佳為500μm以下，尤佳為350μm以下。 Furthermore, the thickness of the adhesive sheet 3 is preferably 75 μm or more from the viewpoint that the printing height of the concealing layer on the periphery of the conventional image display device is higher, specifically, a level difference of about 80 μm can be filled. More preferably, it is 100 μm or more. On the other hand, it is preferably 500 μm or less, particularly preferably 350 μm or less, from the viewpoint of meeting the demand for thinning.

又，就不妨礙與被黏著體之密接力或減震性之觀點而言，最大厚度部分之厚度較佳為5μm以上，更佳為10μm以上，進而較佳為15μm以上。 Also, the thickness of the maximum thickness portion is preferably at least 5 μm, more preferably at least 10 μm, and still more preferably at least 15 μm, from the viewpoint of not hindering the adhesion with the adherend or shock absorption.

於多層構造之情形時，各最外層之厚度與中間層之厚度之比率較佳為1：1~1：20，其中更佳為1：2~1：10。 In the case of a multilayer structure, the ratio of the thickness of each outermost layer to the thickness of the middle layer is preferably 1:1 to 1:20, more preferably 1:2 to 1:10.

若中間層之厚度為上述範圍，則不會對積層體之黏著材層之厚度給 予過多影響，不會過於柔軟而使剪裁或處理之作業性變差，故而較佳。 If the thickness of the intermediate layer is within the above range, there will be no impact on the thickness of the adhesive layer of the laminate. It is better to give too much influence, and it will not be too soft to make the workability of cutting or handling worse.

又，若最外層為上述範圍，則對凹凸或彎曲之面之追隨性不會變差，可維持對被黏著體之接著力或潤濕性，故而較佳。 Moreover, if the outermost layer is within the above range, the conformability to uneven or curved surfaces will not be deteriorated, and the adhesion and wettability to the adherend can be maintained, which is preferable.

又，本黏著片材3之最大厚度部分之厚度較佳為250μm以下。換言之，本黏著片材3可為厚度均勻之片材，亦可為部分厚度不同之不均勻之片材，於厚度不均勻之片材之情形時，厚度最大之部分之厚度較佳為250μm以下。 In addition, the thickness of the maximum thickness portion of the present adhesive sheet 3 is preferably 250 μm or less. In other words, the adhesive sheet 3 can be a sheet with a uniform thickness, or a non-uniform sheet with parts of different thicknesses. In the case of a sheet with non-uniform thickness, the thickness of the thickest part is preferably 250 μm or less .

<用途> <purpose>

本黏著片材3可於其原本之形態下使用，亦可以如下方式使用。但並不限定本黏著片材3之利用方法。 This adhesive sheet 3 can be used in its original form, and can also be used in the following manner. However, the utilization method of the adhesive sheet 3 is not limited.

(黏著片材積層體) (adhesive sheet laminate)

本黏著片材3例如可作為具備於本黏著片材3之一面或雙面積層脫模膜而成之構成之黏著片材積層體而提供。 This adhesive sheet 3 can be provided, for example as an adhesive sheet laminate including a release film on one side of this adhesive sheet 3 or a double-layered release film.

(本圖像顯示裝置構成用積層體3) (Laminate 3 for constituting the present image display device)

作為本黏著片材3之用途之一例，可製作具備介隔本黏著片材3積層2個圖像顯示裝置用構成構件間而成之構成的圖像顯示裝置構成用積層體(以下，稱為「本圖像顯示裝置構成用積層體3」)。 As an example of the use of this adhesive sheet 3, a laminated body for image display device (hereinafter referred to as a laminate) having a structure in which two constituent members for an image display device are laminated with this adhesive sheet 3 interposed can be produced. "Laminate 3 for constituting the present image display device").

本圖像顯示裝置構成用積層體3例如可列舉如下圖像顯示裝置構成用積層體：至少具備面對面之2個圖像顯示裝置用構成構件，至少其中一個圖像顯示裝置用構成構件於貼合面具有不透光部與透光部；具備於上述2個圖像顯示裝置用構成構件間填充本黏著片材3而成之構成；具備介隔上述圖像顯示裝置用構成構件對上述黏著片材進行光照射，可使該黏著片材部分光硬化而成之構成。 The laminated body 3 for constituting an image display device includes, for example, a laminated body for constituting an image display device that includes at least two constituting members for an image display device facing each other, and at least one of the constituting members for an image display device is bonded together. The surface has an opaque portion and a light-transmitting portion; it has a structure in which the adhesive sheet 3 is filled between the above-mentioned two constituent members for an image display device; The adhesive sheet is irradiated with light to partially light-harden the adhesive sheet.

此時，上述黏著片材之與上述透光部相接之位置之凝膠分率可為50%以上，且與上述不透光部相接之位置之凝膠分率可未達5%。 In this case, the gel fraction of the position of the above-mentioned adhesive sheet in contact with the above-mentioned light-transmitting part may be more than 50%, and the gel fraction of the position in contact with the above-mentioned opaque part may be less than 5%.

此處，作為上述圖像顯示裝置用構成構件，可列舉：由觸控面板、圖像顯示面板、表面保護面板及偏光膜所組成之群中之任一種或包含兩種以上之組合之積層體。 Here, as the constituent member for the above-mentioned image display device, any one of the group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film, or a laminate including a combination of two or more .

作為本圖像顯示裝置構成用積層體3之一例，除包含保護面板/本黏著片材3/偏光膜之構成之積層體外，例如可列舉：圖像顯示面板/本黏著片材3/觸控面板、圖像顯示面板/本黏著片材3/保護面板、圖像顯示面板/本黏著片材3/觸控面板/本黏著片材3/保護面板、偏光膜/本黏著片材3/觸控面板、偏光膜/本黏著片材3/觸控面板/本黏著片材3/保護面板等構成例。 As an example of the laminate 3 for constituting the image display device, in addition to the laminate including the protective panel/this adhesive sheet 3/polarizing film, for example: image display panel/this adhesive sheet 3/touch panel Panel, image display panel/this adhesive sheet 3/protective panel, image display panel/this adhesive sheet 3/touch panel/this adhesive sheet 3/protective panel, polarizing film/this adhesive sheet 3/touch Control panel, polarizing film/adhesive sheet 3/touch panel/adhesive sheet 3/protective panel.

保護面板及圖像顯示面板亦可為於保護面板或圖像顯示面板本身中組入有觸控面板感測器者。 The protection panel and the image display panel may also be those in which a touch panel sensor is incorporated in the protection panel or the image display panel itself.

本圖像顯示裝置構成用積層體3例如可經過以下(1)~(3)之步驟而製造。 The laminate 3 for constituting an image display device can be manufactured, for example, through the following steps (1) to (3).

其中，本圖像顯示裝置構成用積層體3之製造方法具有至少以下(1)~(3)之步驟即可，因此可追加其他步驟或於各步驟間***其他步驟。 Here, the manufacturing method of the laminated body 3 for constituting an image display device should only have at least the following steps (1) to (3), so other steps may be added or inserted between each step.

(1)製備含有(甲基)丙烯酸系共聚物(3-A)、交聯劑(B)及光聚合起始劑(C)之黏著劑樹脂組合物，使用該黏著劑樹脂組合物成形為單層或多層之片狀，製作本黏著片材3的步驟。 (1) Prepare an adhesive resin composition containing a (meth)acrylic copolymer (3-A), a crosslinking agent (B) and a photopolymerization initiator (C), and mold the adhesive resin composition into Single-layer or multi-layer sheet, the steps of making this adhesive sheet 3.

(2)介隔本黏著片材3貼著2個圖像顯示裝置構成構件而積層的步驟。 (2) A step of laminating two image display device constituent members through the adhesive sheet 3 .

(3)於至少其中一個圖像顯示裝置構成構件之外側對本黏著片材3照射活性能量線，使本黏著片材3交聯，使2個圖像顯示裝置構成構件接著的步驟。 (3) A step of irradiating the adhesive sheet 3 with active energy rays on the outside of at least one of the image display device constituent members to crosslink the present adhesive sheet 3 and bond the two image display device constituent members.

(步驟(1)) (step 1))

於步驟(1)中，藉由公知之方法製備本黏著劑樹脂組合物3，成形為具備包含該黏著劑樹脂組合物之黏著層之單層或多層之未交聯狀態之片狀，製作本黏著片材3。 In step (1), the present adhesive resin composition 3 is prepared by a known method, and formed into a single-layer or multi-layer uncrosslinked sheet with an adhesive layer comprising the adhesive resin composition to produce this adhesive resin composition. Adhesive sheet 3.

使本黏著劑樹脂組合物3成形為片狀的方法可任意採用現今公知之方法。 As a method for forming the present adhesive resin composition 3 into a sheet shape, conventionally known methods can be arbitrarily adopted.

此時，亦可使本黏著劑樹脂組合物3於脫模膜上成形為單層或多層之片狀，從而製作具備黏著層之單層或多層之透明雙面黏著材。 At this time, the present adhesive resin composition 3 can also be formed into a single-layer or multi-layer sheet on a release film to produce a single-layer or multi-layer transparent double-sided adhesive material with an adhesive layer.

又，亦可使本黏著劑樹脂組合物3於圖像顯示裝置構成構件上成形為單層或多層之片狀，從而製作於該圖像顯示裝置構成構件上具備黏著層之單層或多層之透明雙面黏著材。 In addition, the present adhesive resin composition 3 can also be formed into a single-layer or multi-layer sheet on the image display device component, thereby producing a single-layer or multi-layer sheet having an adhesive layer on the image display device component. Transparent double-sided adhesive material.

(步驟(2)) (step (2))

於步驟(2)中，可介隔上述本黏著片材3貼著2個圖像顯示裝置構成構件而積層。 In step (2), two image display device constituent members can be laminated by adhering the above-mentioned adhesive sheet 3 .

此時，若使用上述接枝共聚物(A1)作為本黏著片材3之基礎聚合物，則於通常狀態，即室溫狀態下，該巨單體彼此凝集而形成物理***聯結構，可對本黏著片材3賦予優異之保存穩定性或剪裁加工性。 At this time, if the above-mentioned graft copolymer (A1) is used as the base polymer of the adhesive sheet 3, in the normal state, that is, at room temperature, the macromonomers aggregate to form a physically cross-linked structure, which can be used in this adhesive sheet. The adhesive sheet 3 imparts excellent storage stability and cutting processability.

又，若(甲基)丙烯酸系共聚物(3-A)於溫度130℃，頻率0.02Hz下之複黏度為100~800Pa‧s，則於貼合時用作熱熔片材時，可享受優異之作業性。 Also, if the (meth)acrylic copolymer (3-A) has a complex viscosity of 100-800 Pa‧s at a temperature of 130°C and a frequency of 0.02 Hz, it can enjoy Excellent workability.

如此於步驟(2)中，可介隔本黏著片材3貼著2個圖像顯示裝置構成構件而積層。如此，則僅將本黏著片材3壓抵於被黏著體上即可簡單地獲得可貼附程度之黏著性，因此易於進行貼著黏著材之定位，作業上非常便 利。 Thus, in step (2), two image display device constituent members can be laminated by adhering through this adhesive sheet 3 . In this way, only by pressing the adhesive sheet 3 against the adherend can simply obtain the adhesiveness of the adhesive level, so it is easy to position the adhesive material, and it is very convenient in operation profit.

又，本黏著片材3之形狀保持性優異，可提前預先加工為任意形狀，因此亦可依照積層之圖像顯示裝置構成構件之尺寸預先將成形於脫模膜上之本黏著片材3進行剪裁。 In addition, the adhesive sheet 3 has excellent shape retention and can be pre-processed into any shape in advance. Therefore, the adhesive sheet 3 formed on the release film can also be processed in advance according to the size of the components of the image display device to be laminated. tailoring.

此時之剪裁方法通常為藉由湯姆生刀之沖切、藉由超級切割機或雷射之剪裁，更佳為以易於剝離脫模膜之方式將正面及背面任一者之脫模膜以邊框狀留下而半剪裁。 The cutting method at this time is usually punching with a Thomson knife, cutting with a super cutter or laser, and it is better to use either the release film on the front and the back in a way that is easy to peel off the release film. Borders are left and half cropped.

於步驟(2)中，本黏著片材3，即透明雙面黏著材亦為未交聯狀態。 In step (2), the adhesive sheet 3, that is, the transparent double-sided adhesive material is also in an uncrosslinked state.

(步驟(3)) (step (3))

於步驟(3)中，自至少其中一個圖像顯示裝置構成構件之外側對本黏著片材3之上述黏著層照射活性能量線，使該黏著層交聯，使2個圖像顯示裝置構成構件接著，從而可製造本圖像顯示裝置構成用積層體3。 In step (3), active energy rays are irradiated to the above-mentioned adhesive layer of the adhesive sheet 3 from the outside of at least one of the image display device constituent members to cross-link the adhesive layer and bond the two image display device constituent members. , and thus the laminated body 3 for constituting the image display device can be manufactured.

本黏著片材3含有交聯劑(B)及光聚合起始劑(C)，因此對本黏著片材3之上述黏著層照射活性能量線，可使該黏著層交聯而硬化，可使2個圖像顯示裝置構成構件牢固地貼著。 This adhesive sheet 3 contains a crosslinking agent (B) and a photopolymerization initiator (C). Therefore, the above-mentioned adhesive layer of this adhesive sheet 3 is irradiated with active energy rays to crosslink and harden the adhesive layer, and 2 The components of the image display device are firmly attached.

此時，作為活性能量線，若照射熱線、X射線、電子束、紫外線、可見光線等使聚合起始劑感應之能量線即可。其中，就抑制對圖像顯示裝置構成構件之損傷或反應控制之容易性的觀點而言，較佳為照射紫外線，尤其波長380nm以下之紫外線。 At this time, as the active energy ray, it is sufficient to irradiate the energy ray that induces the polymerization initiator, such as heat rays, X-rays, electron beams, ultraviolet rays, and visible rays. Among them, from the viewpoint of suppressing damage to constituent members of an image display device or easiness of reaction control, irradiation with ultraviolet rays, especially ultraviolet rays with a wavelength of 380 nm or less is preferred.

關於紫外線照射條件並無特別限制。就保持作業性並且使交聯反應充分進行之觀點而言，例如較佳為以到達黏著材之紫外線之累計光量於波長365nm下成為500~5000mJ/cm2之方式進行照射。 There are no particular restrictions on the ultraviolet irradiation conditions. From the standpoint of maintaining workability and fully advancing the crosslinking reaction, for example, it is preferable to irradiate so that the cumulative light intensity of ultraviolet rays reaching the adhesive material becomes 500 to 5000 mJ/cm 2 at a wavelength of 365 nm.

其中，於照射紫外線時介隔之圖像顯示裝置構成構件阻斷上述波長 之光線之情形時，較佳為配合介隔之構件，根據聚合起始劑之種類適宜調整黏著材所感應之能量線之種類。 Among them, when ultraviolet rays are irradiated, the components of the image display device interrupted by blocking the above-mentioned wavelengths In the case of light, it is better to match the components of the spacer, and adjust the type of energy rays sensed by the adhesive according to the type of polymerization initiator.

(其他步驟) (additional steps)

可於上述步驟(2)與上述步驟(3)中間***加熱上述步驟(2)中所得之積層物而使透明雙面黏著材之黏著層加熱熔融的步驟。即，可加熱步驟(2)中貼著之積層物而使本黏著片材3之黏著層加熱熔融(熱熔)。 A step of heating the laminate obtained in the above step (2) to heat and melt the adhesive layer of the transparent double-sided adhesive material may be inserted between the above step (2) and the above step (3). That is, the laminate attached in step (2) can be heated to heat-melt (hot-melt) the adhesive layer of the present adhesive sheet 3 .

對本黏著片材3而言，若加熱，則可使巨單體彼此之上述凝集瓦解從而使物理***聯結構解開而表現高流動性。因此，於著面具有印刷階差等凹凸之情形時，積層2個圖像顯示裝置構成構件時，藉由加熱本黏著片材3使之流動(熱熔)，可提高黏著材之凹凸追隨性或對被黏著體之潤濕性，可不殘留應變，使構件彼此更牢固地一體化。 In this adhesive sheet 3, when heated, the above-mentioned aggregation of macromonomers can be disintegrated, and the physical cross-linked structure can be released to express high fluidity. Therefore, when the adhesive surface has unevenness such as printing steps, when laminating two image display device components, the adhesive sheet 3 can be heated to make it flow (heat-melt), and the unevenness followability of the adhesive can be improved. Or the wettability of the adherend can leave no strain and make the components more firmly integrated.

此時，較佳為加熱至60~100℃使之熱熔。若為60℃以上，則可充分賦予黏著材之流動性，可充分對凹凸部填充黏著劑樹脂組合物。另一方面，若為100℃以下，則不僅可抑制對作為被黏著體之圖像顯示裝置構成構件造成熱損傷，亦可防止黏著材過於流動而產生黏著劑樹脂組合物之溢出或潰縮。 At this time, it is preferable to heat to 60-100 degreeC and heat-melt it. If it is 60° C. or higher, the fluidity of the adhesive material can be sufficiently imparted, and the adhesive resin composition can be sufficiently filled into the concavo-convex portion. On the other hand, if the temperature is below 100°C, not only thermal damage to the components of the image display device as the adherend can be suppressed, but also overflow or collapse of the adhesive resin composition caused by excessive fluidity of the adhesive can be prevented.

就此種觀點而言，熱熔溫度較佳為60~100℃，其中更佳為62℃以上或95℃以下，其中進而較佳為65℃以上或90℃以下。 From this point of view, the hot-melt temperature is preferably 60 to 100°C, more preferably 62°C or higher or 95°C or lower, and even more preferably 65°C or higher or 90°C or lower.

(本圖像顯示裝置3) (this image display device 3)

亦可使用本黏著片材3或上述圖像顯示裝置構成用積層體而構成圖像顯示裝置(以下，稱為「本圖像顯示裝置3」)。 An image display device (hereinafter referred to as "this image display device 3") can also be configured using the adhesive sheet 3 or the above-mentioned image display device constituting laminate.

例如，本圖像顯示裝置3可列舉如下之圖像顯示裝置：至少具備面對面之2個圖像顯示裝置用構成構件，至少其中一個圖像顯示裝置用構成構 件於貼合面具有不透光部與透光部，並且具備於上述2個圖像顯示裝置用構成構件間以黏著片材填充而成之構成。此時，上述黏著片材之與上述透光部相接之位置之凝膠分率可為50%以上，且與上述不透光部相接之位置之凝膠分率可未達5%。 For example, the image display device 3 can include an image display device that includes at least two face-to-face constituent members for an image display device, and at least one of the constituent members for an image display device The material has an opaque portion and a light-transmitting portion on the bonding surface, and has a structure in which an adhesive sheet is filled between the above-mentioned two constituent members for an image display device. In this case, the gel fraction of the position of the above-mentioned adhesive sheet in contact with the above-mentioned light-transmitting part may be more than 50%, and the gel fraction of the position in contact with the above-mentioned opaque part may be less than 5%.

於上述本圖像顯示裝置構成用積層體3及本圖像顯示裝置3中，將於貼合面具有畫面周圍之印刷部分等光硬化所需之波長之光不透過之部分(本發明中稱為「不透光部」)及光硬化所需之波長之光透過之部分(本發明中稱為「透光部」)的圖像顯示裝置用構成構件與其他圖像顯示裝置用構成構件貼合時，使與上述不透光部相接之位置之凝膠分率未達1%，與上述透光部相接之位置之凝膠分率為40%以上，藉此可緩和因不透光部壓迫而承受之應力，減小該部分產生之應變，並且亦可具有較高之凝集力而使被黏著物彼此牢固地接著。 In the above-mentioned laminated body 3 for constituting the image display device and the image display device 3, the bonded surface has a portion that does not transmit light of a wavelength required for light hardening such as the printed portion around the screen (referred to as “in the present invention”). A component member for an image display device that is the “opaque portion”) and a portion through which light of a wavelength required for photocuring (referred to as a “transmittance portion” in the present invention) is bonded to other component members for an image display device. When appropriate, make the gel fraction of the position in contact with the above-mentioned opaque part less than 1%, and the gel fraction of the position in contact with the above-mentioned light-transmitting part is more than 40%, so as to alleviate the problem caused by the opacity. The stress borne by the light part can reduce the strain generated by the part, and it can also have a higher cohesive force so that the adherends can be firmly bonded to each other.

對本圖像顯示裝置3之較佳製法之具體例之一例加以說明。 One example of a specific example of a preferable manufacturing method of the present image display device 3 will be described.

首先，加熱本黏著片材3使之熱熔，介隔上述本黏著片材3積層具有印刷部即不透光部之圖像顯示裝置用構成構件與圖像顯示裝置用構成構件。於該階段，本黏著片材3適度柔軟，故而可於維持保存穩定性之同時而充分追隨階差。 First, the adhesive sheet 3 is heated to be thermally fused, and the constituent members for the image display device having the printed portion, that is, the opaque portion, and the constituent members for the image display device are laminated through the adhesive sheet 3 . At this stage, since the present adhesive sheet 3 is moderately soft, it can fully follow a step difference while maintaining storage stability.

並且其次，自圖像顯示裝置用構成構件之外側照射紫外線等光。由此，因印刷部遮蔽光，故而光無法到達與印刷部相接之部分，或到達之光顯著受到限制，另一方面光充分到達與無印刷部之透光部相接之部分，該部分可進行交聯反應而光硬化，可實現優異之耐剝離性及耐發泡性。 Then, light such as ultraviolet rays is irradiated from the outside of the constituent member for an image display device. Therefore, because the printed part blocks the light, the light cannot reach the part that is in contact with the printed part, or the light that reaches is significantly restricted. It can undergo cross-linking reaction and light curing, and can achieve excellent peeling resistance and foaming resistance.

作為上述2個圖像顯示裝置用構成構件，例如可列舉：電腦、移動終端(PDA)、遊戲機、電視(TV)、汽車導航、觸控面板、手寫板等LCD、 PDP或EL等圖像顯示裝置之構成構件。更具體而言，例如可列舉由觸控面板、圖像顯示面板、表面保護面板及偏光膜所組成之群中之任一種或包含兩種以上之組合之積層體。 As the constituent members for the above two image display devices, for example, LCDs such as computers, mobile terminals (PDAs), game machines, televisions (TVs), car navigations, touch panels, and handwriting tablets, A component of an image display device such as a PDP or EL. More specifically, for example, any one of the group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film, or a laminate including a combination of two or more thereof can be used.

[語句之說明等] [Explanation of sentences, etc.]

通常所謂「片材」，根據JIS中之定義，係指較薄，其厚度較長度與寬度而言較小且扁平之製品，通常所謂「膜」係指與長度及寬度相比厚度極小，最大厚度任意限定之薄且扁平之製品，通常係指以捲筒之形態供給者(日本工業規格JISK6900)。然而，片材與膜之邊界並不確定，於本發明中不必於文語上將兩者區別，故而於本發明中，稱為「膜」之情形時亦包含「片材」，稱為「片材」之情形時亦包含「膜」。 Generally, the so-called "sheet", according to the definition in JIS, refers to a thinner and flat product whose thickness is smaller than the length and width. Thin and flat products with arbitrarily limited thickness are usually supplied in the form of rolls (Japanese Industrial Standard JISK6900). However, the boundary between a sheet and a film is not certain, and it is not necessary to distinguish the two in terms of language in the present invention. Therefore, in the present invention, a "film" also includes a "sheet", and it is called a "sheet". In the case of "material", "film" is also included.

又，於表達如圖像顯示面板、保護面板等「面板」之情形時，係包含板體、片材及膜或該等之積層體者。 In addition, when expressing a "panel" such as an image display panel and a protective panel, it includes a board, a sheet, a film, or a laminate of these.

於本說明書中，記為「X~Y」(X、Y為任意之數字)之情形時，若無特別說明則表示「X以上且Y以下」，並且亦包含「較佳為大於X」或「較佳為小於Y」之含義。 In this specification, when described as "X~Y" (X, Y are arbitrary numbers), unless otherwise specified, it means "more than X and less than Y", and also includes "preferably greater than X" or The meaning of "preferably less than Y".

又，記為「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，記為「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。 Also, when it is described as "more than X" (X is an arbitrary number), it includes the meaning of "preferably greater than X" unless otherwise specified, and when it is described as "below Y" (Y is an arbitrary number) When , it includes the meaning of "preferably smaller than Y" unless otherwise specified.

[實施例] [Example]

以下，以實施例進一步詳細說明。但本發明不受該等任何限制。 Hereinafter, it will be further described in detail with examples. But the present invention is not limited by any of these.

[實施例1-1] [Example 1-1]

均勻混合作為(甲基)丙烯酸系共聚物(1-A)之由數量平均分子量為2400之聚甲基丙烯酸甲酯巨單體(Tg：105℃)15質量份(18mol%)與丙烯 酸丁酯(Tg：-55℃)81質量份(75mol%)與丙烯酸(Tg：106℃)4質量份(7mol%)無規共聚合而成之丙烯酸系共聚物(1-A-1)(重量平均分子量：23萬)1kg、作為交聯劑(1-B)之甘油二甲基丙烯酸酯(日油公司製造，製品名：GMR)(1-B-1)75g、及作為光聚合起始劑(1-C)之2,4,6-三甲基二苯甲酮與4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)(1-C-1)15g，製作黏著劑組合物1-1。 Uniformly mix 15 parts by mass (18 mol%) of polymethyl methacrylate macromonomer (Tg: 105°C) with a number average molecular weight of 2400 and propylene as a (meth)acrylic copolymer (1-A) An acrylic copolymer (1-A-1) obtained by random copolymerization of 81 parts by mass (75mol%) of butyl ester (Tg: -55°C) and 4 parts by mass (7mol%) of acrylic acid (Tg: 106°C) (weight average molecular weight: 230,000) 1 kg, 75 g of glycerol dimethacrylate (manufactured by NOF Corporation, product name: GMR) (1-B-1) as a crosslinking agent (1-B), and 75 g as a photopolymerization A mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone as an initiator (1-C) (manufactured by Lanberti, product name: Esacure TZT) (1-C-1 ) 15g to make adhesive composition 1-1.

將上述組合物1-1以2張脫模膜即經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造「DIAFOIL MRV-V06」，厚度100μm/三菱樹脂公司製造「DIAFOIL MRQ」，厚度75μm)夾持，使用貼合機以厚度成為150μm之方式賦形為片狀，製作黏著片材1-1(厚度150μm)。 The above-mentioned composition 1-1 was used as two release films, that is, two polyethylene terephthalate films ("DIAFOIL MRV-V06" manufactured by Mitsubishi Plastics Co., Ltd., thickness 100 μm) and "DIAFOIL MRQ", with a thickness of 75 μm), and shaped into a sheet using a laminating machine so as to have a thickness of 150 μm to produce an adhesive sheet 1-1 (thickness 150 μm).

準備附印刷階差之玻璃板，該玻璃板係對238mm×182mm×厚度0.8mm之玻璃之周緣部(長邊側20mm，短邊側17mm)實施厚度60μm之紫外光不透過之印刷，非印刷部為198mm×148mm。 Prepare a glass plate with a printed step. The glass plate is printed with a thickness of 60 μm and does not pass through ultraviolet light on the peripheral part of the glass (long side 20 mm, short side 17 mm) of 238 mm x 182 mm x thickness 0.8 mm. The upper part is 198mm×148mm.

剝離黏著片材1-1之其中一張脫模膜，輥壓貼合於150mm×200mm×厚度1mm之鈉鈣玻璃上。 Peel off one of the release films of the adhesive sheet 1-1, and roll it onto the soda-lime glass of 150mm×200mm×thickness 1mm.

繼而，剝離剩餘之脫模膜，於附印刷階差之玻璃板之印刷面上，以黏著面之四邊覆蓋在印刷階差上之方式使用真空加壓機加壓壓接後(絕對壓力5kPa，溫度80℃，加壓壓力0.04MPa)，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著。自實施有印刷之玻璃側，藉由高壓水銀燈以波長365nm之紫外線以2000mJ/cm2到達黏著片材1-1之方式照射紫外線，使黏著片材1-1硬化，製作積層體1-1。 Then, peel off the remaining release film, and use a vacuum press to press and crimp the printed surface of the glass plate with printed steps in such a way that the four sides of the adhesive surface cover the printed steps (absolute pressure 5kPa, Temperature 80°C, pressurized pressure 0.04MPa), and autoclave treatment (80°C, gauge pressure 0.2MPa, 20 minutes) for final sticking. From the printed glass side, ultraviolet rays with a wavelength of 365nm and 2000mJ/cm 2 were irradiated to the adhesive sheet 1-1 by a high-pressure mercury lamp so that the adhesive sheet 1-1 was hardened to produce a laminate 1-1.

[實施例1-2] [Example 1-2]

均勻混合作為(甲基)丙烯酸系共聚物(1-A)之由丙烯酸2-乙基己酯 (Tg：-70℃)55質量份(36mol%)與乙酸乙烯酯(Tg：32℃)40質量份(56mol%)與丙烯酸(Tg：106℃)5質量份(8mol%)無規共聚合而成之丙烯酸系共聚物(1-A-2)(重量平均分子量：17萬)1kg、作為交聯劑(1-B)之ε己內酯改性異三聚氰酸酸三丙烯酸酯(1-B-2)(新中村化學公司製造，製品名：A9300-1CL)75g及作為光聚合起始劑(1-C)之Esacure KTO46(1-C-2)(Lanberti公司製造)5g，製作黏著劑組合物1-2。 Homogenously mix 2-ethylhexyl acrylate as (meth)acrylic copolymer (1-A) (Tg: -70°C) 55 parts by mass (36mol%) and vinyl acetate (Tg: 32°C) 40 parts by mass (56mol%) and acrylic acid (Tg: 106°C) 5 parts by mass (8mol%) random copolymerization Formed acrylic copolymer (1-A-2) (weight average molecular weight: 170,000) 1kg, ε caprolactone modified isocyanuric acid triacrylate ( 1-B-2) (manufactured by Shin Nakamura Chemical Co., Ltd., product name: A9300-1CL) 75 g and Esacure KTO46 (1-C-2) (manufactured by Lanberti) as a photopolymerization initiator (1-C) 5 g, Adhesive composition 1-2 was produced.

以與實施例1-1相同之方式將上述組合物1-2賦形為片狀，製作黏著片材1-2(厚度150μm)。 The above-mentioned composition 1-2 was shaped into a sheet in the same manner as in Example 1-1 to prepare an adhesive sheet 1-2 (thickness: 150 μm).

除使用黏著片材1-2以外，以與實施例1-1相同之方式製作積層體1-2。 Except having used the adhesive sheet 1-2, the laminated body 1-2 was produced in the same manner as Example 1-1.

[實施例1-3] [Example 1-3]

均勻混合作為(甲基)丙烯酸系共聚物(1-A)之由數量平均分子量為1400之聚甲基丙烯酸甲酯巨單體(Tg：105℃)10質量份(17mol%)與丙烯酸2-乙基己酯(Tg：-70℃)90質量份(83mol%)無規共聚合而成之丙烯酸系共聚物(1-A-3)(重量平均分子量：23萬)1kg、作為交聯劑(1-B)之丙氧化季戊四醇三丙烯酸酯(新中村化學公司製造，製品名：ATM-4PL)(1-B-3)50g、及作為光聚合起始劑(1-C)之4-甲基二苯甲酮(1-C-3)15g，製作黏著劑組合物1-3。 Uniformly mix 10 parts by mass (17mol%) of polymethyl methacrylate macromonomer (Tg: 105°C) with a number average molecular weight of 1400 as a (meth)acrylic copolymer (1-A) and acrylic acid 2- 1 kg of acrylic copolymer (1-A-3) (weight average molecular weight: 230,000) obtained by random copolymerization of 90 parts by mass (83 mol%) of ethylhexyl ester (Tg: -70°C) as a crosslinking agent Propoxylated pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: ATM-4PL) (1-B-3) 50 g of (1-B), and 4-4 as a photopolymerization initiator (1-C) Methyl benzophenone (1-C-3) 15g, make adhesive composition 1-3.

以與實施例1-1相同之方式將上述組合物1-3賦形為片狀，製作黏著片材1-3(厚度150μm)。 The above-mentioned composition 1-3 was shaped into a sheet in the same manner as in Example 1-1, and an adhesive sheet 1-3 (thickness 150 μm) was produced.

除使用黏著片材1-3以外，以與實施例1-1相同之方式製作積層體1-3。 Except having used the adhesive sheet 1-3, the laminated body 1-3 was produced in the same manner as Example 1-1.

[實施例1-4] [Example 1-4]

均勻混合作為(甲基)丙烯酸系共聚物(1-A)之由數量平均分子量為2400之聚甲基丙烯酸甲酯巨單體(Tg：105℃)12質量份(19mol%)與丙烯酸2-乙基己酯(Tg：-70℃)85質量份(74mol%)與丙烯酸(Tg：106℃)3質量份(7mol%)無規共聚合而成之丙烯酸系共聚物(1-A-4)(重量平均分子量：8萬)1kg、作為交聯劑(1-B)之甘油二甲基丙烯酸酯(日油公司製造，製品名：GMR)(1-B-1)90g、及作為光聚合起始劑(1-C)之Esacure KTO46(1-C-2)(Lanberti公司製造)5g，製作黏著劑組合物1-4。 Uniformly mix 12 parts by mass (19mol%) of polymethyl methacrylate macromonomer (Tg: 105°C) with a number average molecular weight of 2400 as a (meth)acrylic copolymer (1-A) and acrylic acid 2- Acrylic copolymer (1-A-4 ) (weight average molecular weight: 80,000) 1 kg, glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (1-B-1) 90 g as a crosslinking agent (1-B), and 90 g as a photo 5 g of Esacure KTO46 (1-C-2) (manufactured by Lanberti) as a polymerization initiator (1-C) was used to prepare adhesive composition 1-4.

以與實施例1-1相同之方式將上述組合物1-4賦形為片狀，製作黏著片材1-4(厚度150μm)。 The above-mentioned composition 1-4 was shaped into a sheet in the same manner as in Example 1-1, and an adhesive sheet 1-4 (thickness 150 μm) was produced.

除使用黏著片材1-4以外，以與實施例1-1相同之方式製作積層體1-4。 Except having used the adhesive sheet 1-4, the laminated body 1-4 was produced in the same manner as Example 1-1.

[比較例1-1] [Comparative Example 1-1]

以相當於國際公開2012/032995號公報之實施例之方式，如下所述製作積層體5。 In a manner corresponding to the embodiment of WO2012/032995A, the laminate 5 was produced as follows.

於作為(甲基)丙烯酸系共聚物(1-A)之由丙烯酸2-乙基己酯(Tg：-70℃)75質量份(57mol%)與乙酸乙烯酯(Tg：32℃)20質量份(33mol%)與丙烯酸(Tg：106℃)5質量份(10mol%)無規共聚合而成之丙烯酸系共聚物(1-A-5)1kg中，混合添加作為交聯劑(1-B)之三羥甲基丙烷三丙烯酸酯(1-B-4)200g及作為光聚合起始劑(1-C)之4-甲基二苯甲酮(1-C-3)10g，製備中間層用樹脂組合物。將上述中間層用樹脂組合物以經剝離處理之2張聚對苯二甲酸乙二酯膜(Panac公司製造，NP75Z01，厚度75μm/東洋紡織公司製造，E7006，厚度38μm)夾持，以厚度成為80μm之方式賦形為片狀，製作中間層用片材(α)。 In (meth)acrylic copolymer (1-A), 75 parts by mass (57mol%) of 2-ethylhexyl acrylate (Tg: -70°C) and 20 parts by mass of vinyl acetate (Tg: 32°C) Part (33mol%) and 5 parts by mass (10mol%) of acrylic acid (Tg: 106°C) were randomly copolymerized into 1 kg of acrylic copolymer (1-A-5), mixed and added as a crosslinking agent (1- B) 200g of trimethylolpropane triacrylate (1-B-4) and 10g of 4-methylbenzophenone (1-C-3) as photopolymerization initiator (1-C), prepared Resin composition for an intermediate layer. The resin composition for the intermediate layer was interposed between two peeled polyethylene terephthalate films (manufactured by Panac, NP75Z01, thickness 75 μm/manufactured by Toyobo Co., Ltd., E7006, thickness 38 μm), with a thickness of Shaped into a sheet with a thickness of 80 μm, the intermediate layer sheet (α) was produced.

繼而，對上述丙烯酸系共聚物(1-A-5)1kg添加混合作為光聚合起始劑(1-C)之4-甲基二苯甲酮(1-C-3)20g，製備接著層用樹脂組合物。 Next, add and mix 20 g of 4-methylbenzophenone (1-C-3) as a photopolymerization initiator (1-C) to 1 kg of the above-mentioned acrylic copolymer (1-A-5) to prepare an adhesive layer Use a resin composition.

將上述接著層用樹脂組合物以2張脫模膜即經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造「DIAFOIL MRA」，厚度75μm/東洋紡織公司製造「E7006」，厚度38μm)夾持，以厚度成為35μm之方式賦形為片狀，製作接著層用樹脂片材(β)。 The resin composition for the adhesive layer is used as two release films, that is, two polyethylene terephthalate films ("DIAFOIL MRA" manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 μm/"E7006" manufactured by Toyobo Co., Ltd.) , thickness 38 μm) sandwiched, and formed into a sheet shape so that the thickness becomes 35 μm, and the resin sheet (β) for an adhesive layer was produced.

進而將接著層用樹脂組合物以經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，DIAFOIL MRF，厚度75μm/東洋紡織公司製造，E7006，厚度38μm)夾持，以厚度成為35μm之方式賦形為片狀，製作接著層用樹脂片材(β')。 Furthermore, the resin composition for the adhesive layer was sandwiched between two peeled polyethylene terephthalate films (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRF, thickness 75 μm/manufactured by Toyobo Co., Ltd., E7006, thickness 38 μm), and It shaped into a sheet shape so that thickness might become 35 micrometers, and produced the resin sheet (β') for adhesive layers.

依序剝離去除中間層用片材(α)之兩側之PET膜，並且剝離接著層用樹脂片材(β)及(β')之一側之PET膜，將露出之黏著面依序貼合於中間層用片材(α)之兩表面，製作包含(β)/(α)/(β')之3層黏著片材。 Sequentially peel and remove the PET film on both sides of the middle layer sheet (α), and peel off the PET film on one side of the adhesive layer resin sheet (β) and (β'), and stick the exposed adhesive surface in sequence A 3-layer adhesive sheet consisting of (β)/(α)/(β') was prepared by attaching to both surfaces of the sheet (α) for the intermediate layer.

介隔(β)及(β')之表面殘留之PET膜，以波長365nm之累計光量成為1000mJ/cm2之方式藉由高壓水銀燈照射紫外線，使(α)、(β)及(β')進行紫外線交聯，製作黏著片材1-5(厚度150μm)。 The remaining PET film on the surface of (β) and (β') is irradiated with ultraviolet rays by a high-pressure mercury lamp in such a way that the cumulative light intensity at a wavelength of 365nm becomes 1000mJ/ cm2 , so that (α), (β) and (β') Ultraviolet crosslinking was carried out to produce adhesive sheets 1-5 (thickness 150 μm).

除使用黏著片材1-5以外，以與實施例1-1相同之方式製作積層體1-5。 Except having used the adhesive sheet 1-5, the laminated body 1-5 was produced in the same manner as Example 1-1.

[比較例1-2] [Comparative example 1-2]

對作為(甲基)丙烯酸系共聚物(1-A)之市售之丙烯酸系黏著劑(1-A-6)(綜研化學公司製造，商品名「SK DYNE 1882」)1kg，均勻混合異氰酸酯系硬化劑(綜研化學公司製造，商品名「L-45」)1.85g及環氧系硬化劑(綜研化學公司製造，商品名「E-5XM」)0.5g，製備黏著劑組合物1- 6。 To 1 kg of a commercially available acrylic adhesive (1-A-6) (manufactured by Soken Chemical Co., Ltd., trade name "SK DYNE 1882") which is a (meth)acrylic copolymer (1-A), uniformly mix isocyanate Adhesive composition 1- 6.

將上述組合物1-6以乾燥後之厚度成為75μm之方式塗佈於厚度50μm之脫模膜即經剝離處理之聚對苯二甲酸乙二酯膜(三菱樹脂公司製造「MRF75」：厚度75μm)之脫模面上，藉由加熱使溶劑乾燥，製作厚度75μm之黏著片材。 The above composition 1-6 was coated on a release film with a thickness of 50 μm, that is, a peel-treated polyethylene terephthalate film (“MRF75” manufactured by Mitsubishi Plastics Co., Ltd.: thickness 75 μm) so that the thickness after drying became 75 μm ) on the release surface, the solvent was dried by heating to produce an adhesive sheet with a thickness of 75 μm.

進而，將上述組合物1-6以乾燥後之厚度成為75μm之方式塗佈於脫模膜即經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-V06」，厚度100μm)之脫模面上，藉由加熱使溶劑乾燥，製作厚度75μm之黏著片材。 Furthermore, the above composition 1-6 was coated on a release film, that is, a release-treated polyethylene terephthalate film ("DIAFOIL MRV-V06" manufactured by Mitsubishi Plastics Co., Ltd. On the release surface with a thickness of 100 μm), the solvent was dried by heating to produce an adhesive sheet with a thickness of 75 μm.

對製作之2張黏著片材，貼著各自之黏著面使之熟化1週，藉此製作黏著片材1-6(厚度150μm)。 Adhesive sheets 1-6 (thickness 150 μm) were produced by sticking the adhesive surfaces of the two produced adhesive sheets and aging them for one week.

準備附印刷階差之玻璃板，該玻璃板係對238mm×182mm×厚度0.8mm之玻璃之周緣部(長邊側20mm，短邊側17mm)實施厚度60μm之紫外光不透過之印刷，非印刷部為198mm×148mm。 Prepare a glass plate with a printed step. The glass plate is printed with a thickness of 60 μm and does not pass through ultraviolet light on the peripheral part of the glass (long side 20 mm, short side 17 mm) of 238 mm x 182 mm x thickness 0.8 mm. The upper part is 198mm×148mm.

剝離黏著片材1-6之其中一張脫模膜，輥壓貼合於150mm×200mm×厚度1mm之鈉鈣玻璃上。 Peel off one of the release films of the adhesive sheets 1-6, and roll it onto the soda-lime glass of 150mm×200mm×thickness 1mm.

繼而，剝離剩餘之脫模膜，於附印刷階差之玻璃板之印刷面上，以黏著面之四邊覆蓋在印刷階差上之方式使用真空加壓機加壓壓接後(絕對壓力5kPa，溫度80℃，加壓壓力0.04MPa)，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著，製作積層體1-6。 Then, peel off the remaining release film, and use a vacuum press to press and crimp the printed surface of the glass plate with printed steps in such a way that the four sides of the adhesive surface cover the printed steps (absolute pressure 5kPa, temperature 80°C, pressurized pressure 0.04MPa), and autoclave treatment (80°C, gauge pressure 0.2MPa, 20 minutes) for final bonding to produce laminates 1-6.

[比較例1-3] [Comparative example 1-3]

以相當於WO2010038366號之實施例之方式，如下所述製作積層體1-7。 In a manner corresponding to the embodiment of WO2010038366, laminates 1-7 were produced as follows.

均勻混合作為(甲基)丙烯酸系共聚物(1-A)之替代之苯氧樹脂(1-A-7)(InChem公司製造，PKHH，重量平均分子量5.2萬)650g、作為交聯劑(1-B)之替代之具有碳酸酯骨架之聚丙烯酸胺基甲酸酯(1-B-4)(根上工業公司製造，UN5500，重量平均分子量6.7萬)1kg、及作為光聚合起始劑(1-C)之1-環己基苯基酮(1-C-4)(BASF公司製造，Irgacure184)43g，製作黏著劑組合物1-7。 Uniformly mix 650 g of phenoxy resin (1-A-7) (manufactured by InChem, PKHH, weight average molecular weight: 52,000) as a substitute for (meth)acrylic copolymer (1-A), and 650 g of crosslinking agent (1 -1 kg of urethane polyacrylate (1-B-4) (manufactured by Negami Kogyo Co., Ltd., UN5500, weight average molecular weight: 67,000) with a carbonate skeleton as an alternative to B), and as a photopolymerization initiator (1 -C) 43 g of 1-cyclohexyl phenyl ketone (1-C-4) (manufactured by BASF, Irgacure 184) was used to prepare adhesive composition 1-7.

以與實施例1-1相同之方式將上述組合物1-7賦形為片狀，製作黏著片材1-7(厚度150μm)。 The above-mentioned composition 1-7 was shaped into a sheet in the same manner as in Example 1-1, and an adhesive sheet 1-7 (thickness 150 μm) was produced.

準備附印刷階差之玻璃板，該玻璃板係對238mm×182mm×厚度0.8mm之玻璃之周緣部(長邊側20mm，短邊側17mm)實施厚度60μm之紫外光不透過之印刷，非印刷部為198mm×148mm。 Prepare a glass plate with a printed step. The glass plate is printed with a thickness of 60 μm and does not pass through ultraviolet light on the peripheral part of the glass (long side 20 mm, short side 17 mm) of 238 mm x 182 mm x thickness 0.8 mm. The upper part is 198mm×148mm.

剝離黏著片材1-7之其中一張脫模膜，一面加熱80℃一面輥壓貼合於150mm×200mm×厚度1mm之鈉鈣玻璃上。 Peel off one of the release films of the adhesive sheets 1-7, heat it at 80°C and roll it on the soda-lime glass of 150mm×200mm×thickness 1mm.

繼而，剝離剩餘之脫模膜，於附印刷階差之玻璃板之印刷面上，以黏著面之四邊覆蓋在印刷階差上之方式使用真空加壓機加壓壓接後(絕對壓力5kPa，溫度80℃，加壓壓力0.04MPa)，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著。自實施有印刷之玻璃側，藉由高壓水銀燈以波長365nm之紫外線以2000mJ/cm2到達黏著片材之方式照射紫外線，使黏著片材1-7硬化，製作積層體1-7。 Then, peel off the remaining release film, and use a vacuum press to press and crimp the printed surface of the glass plate with printed steps in such a way that the four sides of the adhesive surface cover the printed steps (absolute pressure 5kPa, Temperature 80°C, pressurized pressure 0.04MPa), and autoclave treatment (80°C, gauge pressure 0.2MPa, 20 minutes) for final sticking. From the side of the glass on which the printing was performed, ultraviolet rays with a wavelength of 365nm and 2000mJ/cm 2 were irradiated to the adhesive sheet by a high-pressure mercury lamp to harden the adhesive sheet 1-7 to produce laminates 1-7.

[評價] [evaluate]

對實施例及比較例中製成之黏著片材及積層體以如下方式進行評價。 The adhesive sheets and laminates produced in Examples and Comparative Examples were evaluated as follows.

(黏度測定) (viscosity measurement)

分別使用複數張實施例及比較例中製成之黏著片材1-1~1-7，以成為1mm~2mm之厚度之方式積層，製作沖切為直徑20mm之圓狀者。 A plurality of adhesive sheets 1-1 to 1-7 prepared in the examples and comparative examples were used respectively, laminated so as to have a thickness of 1 mm to 2 mm, and punched into a circular shape with a diameter of 20 mm.

使用流變計(英弘精機股份有限公司製造「MARS」)，以黏著夾具：Φ 25mm平行板，應變：0.5%，頻率：1Hz，升溫速度：3℃/分鐘，測定70℃至120℃之光硬化前之黏著片材之複黏度。 Using a rheometer (manufactured by Yinghong Seiki Co., Ltd. "MARS"), with an adhesive fixture: Φ 25mm parallel plate, strain: 0.5%, frequency: 1Hz, heating rate: 3°C/min, measure the light from 70°C to 120°C The complex viscosity of the adhesive sheet before hardening.

對黏著片材1-1~1-5及1-7，使用高壓水銀燈，以365nm之累計光量成為2000mJ/cm2之方式，介隔聚對苯二甲酸乙二酯膜對黏著片材照射紫外線，使黏著片材硬化。將硬化後之黏著片材以成為1mm~2mm之厚度之方式積層，製作沖切為直徑20mm之圓狀者。 For the adhesive sheets 1-1~1-5 and 1-7, use a high-pressure mercury lamp to irradiate the adhesive sheets with ultraviolet rays through polyethylene terephthalate film in such a way that the cumulative light intensity at 365nm becomes 2000mJ/ cm2 , to harden the adhesive sheet. The hardened adhesive sheets are laminated so as to have a thickness of 1 mm to 2 mm, and are punched into circular shapes with a diameter of 20 mm.

使用流變計(英弘精機股份有限公司製造「MARS」)，以黏著夾具：Φ 25mm平行板，應變：0.5%，頻率：1Hz，升溫速度：3℃/分鐘，測定70℃至120℃之光硬化後之黏著片材之複黏度。 Using a rheometer (manufactured by Yinghong Seiki Co., Ltd. "MARS"), with an adhesive fixture: Φ 25mm parallel plate, strain: 0.5%, frequency: 1Hz, heating rate: 3°C/min, measure the light from 70°C to 120°C The complex viscosity of the adhesive sheet after hardening.

(硬化後接著力) (adhesion after hardening)

將實施例及比較例中製作之黏著片材1-1~1-7之其中一個脫模膜剝離，貼合作為襯底膜之50μm之PET膜(三菱樹脂公司製造，DIAFOIL T100，厚度50μm)而準備積層品。 Peel off one of the release films of the adhesive sheets 1-1 to 1-7 produced in Examples and Comparative Examples, and attach a 50 μm PET film (manufactured by Mitsubishi Plastics Corporation, DIAFOIL T100, thickness 50 μm) as a substrate film And prepare laminated product.

將上述積層品剪裁為長150mm、寬10mm後，剝離剩餘之脫模膜，將露出之黏著面以2kg之輥進行1個往復而輥壓接於鈉鈣玻璃上。對貼合品實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著後，以365nm之累計光量成為2000mJ/cm2之方式照射紫外線使黏著片材硬化，熟化15小時，製為剝離力測定試樣。 After cutting the above-mentioned laminated product to a length of 150 mm and a width of 10 mm, the remaining release film was peeled off, and the exposed adhesive surface was reciprocated with a 2 kg roller, and the roller was crimped on the soda-lime glass. After performing autoclave treatment (80°C, gauge pressure 0.2MPa, 20 minutes) on the laminated product for final bonding, irradiate ultraviolet light so that the cumulative light intensity at 365nm becomes 2000mJ/ cm2 to harden the adhesive sheet, and cure it for 15 hours. Prepare a peel force measurement sample.

測定將上述剝離力測定樣品於23℃、40%RH及80℃、10%RH之環境下，以剝離角180°，剝離速度60mm/分鐘剝離時之對玻璃之剝離力 (N/cm)，求得硬化後之接著力。 Determination of the peeling force of the above-mentioned peeling force test sample to glass when it is peeled off at a peeling angle of 180° and a peeling speed of 60mm/min under the environment of 23°C, 40%RH and 80°C, 10%RH (N/cm), obtain the adhesive force after hardening.

(硬化前接著力) (adhesion before hardening)

將實施例及比較例中製作之黏著片材1-1~1-7之其中一個脫模膜剝離，貼合作為襯底膜之50μm之PET膜(三菱樹脂公司製造，DIAFOIL T100，厚度50μm)而準備積層品。 Peel off one of the release films of the adhesive sheets 1-1 to 1-7 produced in Examples and Comparative Examples, and attach a 50 μm PET film (manufactured by Mitsubishi Plastics Corporation, DIAFOIL T100, thickness 50 μm) as a substrate film And prepare laminated product.

將上述積層品剪裁為長150mm、寬10mm後，剝離剩餘之脫模膜，將露出之黏著面以2kg之輥進行1個往復而將上述黏著片材輥壓接於鈉鈣玻璃上。 After cutting the above-mentioned laminated product to a length of 150 mm and a width of 10 mm, the remaining release film was peeled off, and the exposed adhesive surface was reciprocated once with a 2 kg roller to press-bond the above-mentioned adhesive sheet to the soda-lime glass.

測定將該接著力測定樣品於23℃、40%RH及80℃、10%RH之環境下，以剝離角180°，剝離速度60mm/分鐘剝離時之對玻璃之剝離力(N/cm)，求得硬化前之接著力。 Measure the peeling force (N/cm) of the adhesion test sample to glass when it is peeled at 23°C, 40%RH and 80°C, 10%RH at a peeling angle of 180° and a peeling speed of 60mm/min. Obtain the adhesion force before hardening.

再者，關於於80℃、10%RH環境下進行剝離時之剝離模式，將凝集破壞者於表中記為「CF」，將界面剝離者於表中記為「AF」。 In addition, regarding the peeling mode when peeling was carried out under the environment of 80 degreeC and 10%RH, the thing which broke coagulation was shown as "CF" in the table, and the thing which peeled at the interface was shown as "AF" in the table.

(透明性) (transparency)

將實施例及比較例中製作之黏著片材1-1~1-7之其中一個脫模膜剝離，將露出之黏著面輥壓貼合於2塊鈉鈣玻璃(82mm×53mm×0.5mm厚)上後，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著，製作光學評價用積層體。 Peel off one of the release films of the adhesive sheets 1-1~1-7 produced in the examples and comparative examples, and roll the exposed adhesive surface onto two pieces of soda-lime glass (82mm×53mm×0.5mm thick ) was applied, autoclave treatment (80° C., gauge pressure 0.2 MPa, 20 minutes) was carried out for final bonding to prepare a laminate for optical evaluation.

對上述積層體，使用霧度計(日本電色工業公司製造，NDH5000)，求得依據JIS K7136之霧度值以及依據JIS K7361-1之全光線透過率(%)。 About the said laminated body, the haze value based on JIS K7136 and the total light transmittance (%) based on JIS K7361-1 were calculated|required using the haze meter (Nippon Denshoku Kogyo Co., Ltd. make, NDH5000).

(貼合作業性) (suitable for business)

於上述光學評價用積層體之製作中，將實施例及比較例中製作之片材貼合於鈉鈣玻璃上時，於23℃、40%之環境下進行輥壓貼合，將可與玻 璃板密接固定者記為「○(好)」，將玻璃板與片材無法於23℃、40%之環境下密接，輥壓貼合時需要加熱者記為「×(差)」。 In the production of the above-mentioned laminated body for optical evaluation, when laminating the sheets produced in Examples and Comparative Examples on soda-lime glass, roll-bonding is carried out at 23°C and 40% of the environment, and the sheet can be bonded to the glass. If the glass plate is tightly bonded and fixed, it is marked as "○ (good)", and if the glass plate and the sheet cannot be tightly bonded at 23°C and 40% of the environment, and heat is required for roll bonding, it is marked as "× (poor)".

(釋氣分析) (outgassing analysis)

所謂本發明之光照射後之釋氣係指藉由下述分析方法而檢測者。 The outgassing after light irradiation in the present invention refers to the one detected by the following analysis method.

(釋氣產生方法) (Outgassing method)

使用高壓水銀燈，對於實施例及比較例中製作之黏著片材1-1~1-5及1-7，以365nm之累計光量成為2000mJ/cm2之方式，介隔聚對苯二甲酸乙二酯膜對黏著片材照射紫外線，製作相當於光硬化後之黏著片材。將光硬化後之黏著片材剪裁為1cm×3cm，裝入20ml之小瓶中密閉。將該小瓶裝入氙氣UV照射裝置(SUNTEST CPS：東洋精機製造)中，以照度765W/m2，溫度60℃實施24小時UV照射處理。 Using a high-pressure mercury lamp, for the adhesive sheets 1-1 to 1-5 and 1-7 produced in the examples and comparative examples, the cumulative light intensity at 365nm becomes 2000mJ/cm 2 , through polyethylene terephthalate The ester film irradiates ultraviolet rays to the adhesive sheet to produce an adhesive sheet equivalent to photohardening. Cut the light-cured adhesive sheet into 1cm×3cm, put it into a 20ml vial and seal it tightly. This vial was placed in a xenon UV irradiation device (SUNTEST CPS: manufactured by Toyo Seiki), and UV irradiation treatment was performed at a temperature of 60° C. for 24 hours at an illuminance of 765 W/m 2 .

將比較例1-2之黏著片材1-6剪裁為1cm×3cm，裝入20ml之小瓶中密閉。將該小瓶裝入氙氣UV照射裝置(SUNTEST CPS：東洋精機製造)中，以照度765W/m2，溫度60℃實施24小時UV照射處理。 Cut the adhesive sheet 1-6 of Comparative Example 1-2 into 1 cm×3 cm, put it into a 20 ml vial and seal it. This vial was placed in a xenon UV irradiation device (SUNTEST CPS: manufactured by Toyo Seiki), and UV irradiation treatment was performed at a temperature of 60° C. for 24 hours at an illuminance of 765 W/m 2 .

(釋氣分析方法) (Outgassing analysis method)

自如上所述進行UV處理之樹脂組合物產生之氣體可藉由安裝有頂空取樣器之氣相層析分析法(HS-GC)而測定。 Gas generation from the resin composition subjected to UV treatment as described above can be measured by gas chromatography (HS-GC) equipped with a headspace sampler.

(1)分析氣體之捕集 (1) Capture of analytical gas

利用以下條件捕集上述黏著片材之產生氣體。 Gas generated from the above-mentioned adhesive sheet was collected under the following conditions.

1.HS取樣器：TuboMatri×40(Perkin Elmer公司製造) 1. HS sampler: TuboMatri×40 (manufactured by Perkin Elmer)

2.加熱溫度：80℃ 2. Heating temperature: 80°C

3.加熱時間：30分鐘 3. Heating time: 30 minutes

4.針溫度：110℃ 4. Needle temperature: 110°C

5.轉移溫度：170℃ 5. Transfer temperature: 170°C

6.注入時間：0.1分鐘 6. Injection time: 0.1 minute

7.管柱壓力：16.0psi 7. Column pressure: 16.0psi

(2)GC分析 (2) GC analysis

藉由GC(Perkin Elmer公司製造：Clarus580)分析產生之氣體，將檢測出之釋氣產生量以十六烷換算進行定量。 The generated gas was analyzed by GC (manufactured by Perkin Elmer: Clarus 580), and the detected amount of outgassing was quantified in terms of hexadecane.

(凹凸吸收性) (concave-convex absorptivity)

以目視觀察實施例及比較例中製作之積層體1-1~1-7，將印刷階差附近黏著材未追隨而殘留氣泡者判定為「×(差)」，將階差附近可見源自黏著片材之殘留應變之不均者判定為「△」，將無氣泡而平滑貼合者判定為「○(好)」。 Visually observe the laminates 1-1 to 1-7 produced in the examples and comparative examples, judge as "× (poor)" if the adhesive material does not follow the adhesive material near the printing step and leave air bubbles, and judge it as "× (poor)" if the adhesive material near the step is not followed. The unevenness of the residual strain of the adhesive sheet was judged as "△", and the case of smooth bonding without air bubbles was judged as "○ (good)".

(耐發泡可靠性) (reliability against foaming)

將實施例及比較例中製作之積層體1-1~1-7裝入氙氣UV照射裝置(SUNTEST CPS：東洋精機製造)，觀察以照度765W/m2，溫度60℃實施24小時UV照射處理後之外觀。 Put the laminates 1-1 to 1-7 produced in Examples and Comparative Examples into a xenon UV irradiation device (SUNTEST CPS: manufactured by Toyo Seiki) for observation, and perform UV irradiation treatment for 24 hours at an illumination intensity of 765W/m 2 and a temperature of 60°C after appearance.

將黏著片材中產生直徑5mm以上之氣泡者判定為「×(差)」，將可見直徑5mm以下之氣泡者判定為「△(普通)」，將無發泡且無外觀變化者判定為「○(好)」。 Those with bubbles with a diameter of 5 mm or more in the adhesive sheet were judged as "× (bad)", those with visible bubbles with a diameter of 5 mm or less were judged as "△ (normal)", and those with no foaming and no change in appearance were judged as " ○ (good)".

Figure 110106505-A0305-02-0094-1
Figure 110106505-A0305-02-0094-1

Figure 110106505-A0305-02-0094-2
Figure 110106505-A0305-02-0094-2

(考察) (investigation)

實施例1-1~1-4中製作之黏著片材於光硬化前之高溫下之剝離模式為凝集破壞，因此可知對被黏著面之潤濕性優異，對凹凸面之追隨性優異，不僅如此光硬化後之接著力亦較高。因此，使用實施例1-1~1-4中製作之黏著片材，可獲得即使於如高溫度下之長時間紫外線照射之嚴苛之環境試驗下亦不會產生剝離或發泡、變形，具有較高之可靠性之積層體。 The peeling mode of the adhesive sheets produced in Examples 1-1 to 1-4 at high temperature before photohardening is cohesion failure, so it can be seen that the wettability to the surface to be adhered is excellent, and the followability to the uneven surface is excellent, not only In this way, the adhesive force after light hardening is also higher. Therefore, using the adhesive sheets produced in Examples 1-1 to 1-4, even under severe environmental tests such as long-term ultraviolet radiation at high temperatures, no peeling, foaming, or deformation can be obtained. A laminate with high reliability.

又，實施例1-1~1-4中製作之黏著片材於0~40℃下可保持形狀，且顯示自黏著性。 In addition, the adhesive sheets produced in Examples 1-1 to 1-4 can maintain their shape at 0 to 40° C. and exhibit self-adhesiveness.

比較例1-1之黏著片材係藉由紫外線照射而使黏著劑樹脂組合物一部分交聯，即光硬化後之狀態，故而與附印刷階差之玻璃積層時，於印刷階差附近可見由黏著片材之殘留應變導致之不均，貼合外觀較差。又，使其再次光硬化後，接著力較低，凝集力較差，因此於紫外線照射試驗中可見發泡，貼合可靠性亦較差。 The adhesive sheet of Comparative Example 1-1 is partially crosslinked by ultraviolet irradiation, that is, the state after photohardening, so when it is laminated with glass with printed steps, it can be seen near the printed steps. The residual strain of the adhesive sheet causes unevenness and poor bonding appearance. In addition, after photocuring again, the adhesive force is low and the cohesive force is poor, so foaming can be seen in the ultraviolet irradiation test, and the bonding reliability is also poor.

比較例1-2中，黏著劑樹脂組合物之交聯反應於貼合於構件之前階段中已完成，故而即使照射紫外線，黏度或接著力亦不顯現變化。又，與附印刷階差之玻璃積層時，於印刷階差交叉之角部附近有一部分黏著劑未完全填充，結果殘留氣泡。又，由於階差附近之黏著材之應變，於紫外線照射試驗中可見氣泡之成長。 In Comparative Example 1-2, the cross-linking reaction of the adhesive resin composition was completed in the stage before bonding to the member, so the viscosity or adhesive force did not change even when ultraviolet rays were irradiated. Also, when laminated with glass with printed steps, some adhesive was not completely filled near the corners where the printed steps intersected, resulting in air bubbles remaining. Also, due to the strain of the adhesive material near the step difference, the growth of bubbles can be seen in the ultraviolet irradiation test.

比較例1-3未使用作為主成分之(甲基)丙烯酸系共聚物，係使用於室溫範圍內具有某種程度之剛性之接著性樹脂組合物的熱熔型接著片材。 Comparative Example 1-3 is a hot-melt adhesive sheet using an adhesive resin composition with a certain degree of rigidity at room temperature without using a (meth)acrylic copolymer as a main component.

比較例1-3之片材於光硬化前之接著力較低，由於可見與實施例之黏著片材相比，室溫附近之黏性非常低，0~40℃下之自黏著性不充分。比較例1-3之黏著片材於貼合時必須自定位之階段對被黏著體進行預熱，與僅以壓接即可常溫貼附之黏著片材相比，存在作業繁雜之缺陷。 The adhesive force of the sheets of Comparative Examples 1-3 before photohardening is low, because it can be seen that compared with the adhesive sheets of Examples, the viscosity around room temperature is very low, and the self-adhesiveness at 0-40°C is not sufficient . The adhesive sheets of Comparative Examples 1-3 have to preheat the adherend at the stage of self-positioning during lamination. Compared with the adhesive sheets that can be attached at room temperature only by crimping, there is a defect that the operation is complicated.

[實施例2-1] [Example 2-1]

均勻混合作為(甲基)丙烯酸系共聚物(2-A)之由包含聚甲基丙烯酸甲酯(Tg：105℃)之數量平均分子量為2900之巨單體15質量份(18mol%)與丙烯酸丁酯(Tg：-55℃)81質量份(75mol%)與丙烯酸(Tg：106℃)4質量份(7mol%)無規共聚合而成之丙烯酸系接枝共聚物(2-A-1)(重量平均分子 量：23萬)1kg、作為交聯劑(2-B)之甘油二甲基丙烯酸酯(日油公司製造，製品名：GMR)(2-B-1)90g、及作為光聚合起始劑(2-C)之2,4,6-三甲基二苯甲酮與4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)(2-C-1)15g，製作黏著樹脂組合物2-1。 Uniformly mix 15 parts by mass (18 mol%) of a macromonomer with a number average molecular weight of 2900 including polymethyl methacrylate (Tg: 105°C) and acrylic acid as a (meth)acrylic copolymer (2-A). Acrylic graft copolymer (2-A-1 ) (weight average molecule Quantity: 230,000) 1 kg, glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (2-B-1) 90 g as a crosslinking agent (2-B), and as a photopolymerization initiator (2-C) a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name: Esacure TZT) (2-C-1) 15g, Adhesive resin composition 2-1 was prepared.

以經剝離處理之聚對苯二甲酸乙二酯膜Y(三菱樹脂公司製造，DIAFOIL MRV-V06，厚度100μm，稱為「脫模膜Y」)與經剝離處理之聚對苯二甲酸乙二酯膜Z(三菱樹脂公司製造，DIAFOIL MRQ，厚度75μm，稱為「脫模膜Z」)夾持上述組合物2-1，使用貼合機以厚度成為150μm之方式賦形為片狀，製作黏著片材X1(厚度150μm)。 A peeled polyethylene terephthalate film Y (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRV-V06, thickness 100 μm, called "release film Y") and a peeled polyethylene terephthalate film Ester film Z (manufactured by Mitsubishi Plastics Co., Ltd., DIAFOIL MRQ, thickness 75 μm, called “release film Z”) sandwiches the above-mentioned composition 2-1, and forms it into a sheet with a laminating machine so that the thickness becomes 150 μm. Adhesive sheet X1 (thickness 150 μm).

將於黑色片材(LSL-8 Inoac公司製造透光率0%)之單面貼附雙面膠帶並剪裁為50mm×100mm者，貼合於積層於上述黏著片材X1之一側之脫模膜Z之表面形成不透光部，製作於片材面內具有透光部與不透光部之黏著片材積層體。 Attach a double-sided tape to one side of a black sheet (LSL-8 Inoac company with a light transmittance of 0%) and cut it to 50mm×100mm, and stick it to the mold release laminated on one side of the above-mentioned adhesive sheet X1 An opaque portion is formed on the surface of the film Z, and an adhesive sheet laminate having a light-transmitting portion and an opaque portion on the surface of the sheet is produced.

其次，使用高壓水銀燈，自如此製作之黏著片材積層體之黑色片材側，以波長365nm之累計光量成為2000mJ/cm2之方式照射紫外線，使黏著片材積層體之透光部硬化，製作具有軟質部與硬質部之黏著片材2-1。 Next, using a high-pressure mercury lamp, ultraviolet rays are irradiated from the black sheet side of the adhesive sheet laminate produced in this way so that the cumulative light intensity at a wavelength of 365 nm becomes 2000 mJ/cm 2 to harden the light-transmitting portion of the adhesive sheet laminate to produce Adhesive sheet 2-1 having a soft part and a hard part.

(參照圖2) (Refer to Figure 2)

此處，所謂軟質部係指以黑色片材遮蔽之黏著片材之部位，所謂硬質部係指未以黑色片材遮蔽之黏著片材之部位。 Here, the so-called soft portion refers to the portion of the adhesive sheet covered by the black sheet, and the so-called hard portion refers to the portion of the adhesive sheet not covered by the black sheet.

[實施例2-2] [Example 2-2]

均勻混合作為(甲基)丙烯酸系共聚物(2-A)之由丙烯酸2-乙基己酯(Tg：-70℃)55質量份(36mol%)與乙酸乙烯酯(Tg：32℃)40質量份(56mol%)與丙烯酸(Tg：106℃)5質量份(8mol%)無規共聚合而成之丙烯酸系 共聚物(2-A-2)(重量平均分子量：17萬)1kg、作為交聯劑(2-B)之異三聚氰酸酸EO改性二丙烯酸酯與異三聚氰酸酸EO改性三丙烯酸酯之混合物(2-B-2)(東亞合成公司製造，製品名：ARONIX M313)70g、及作為光聚合起始劑(2-C)之Esacure KTO46(2-C-2)(Lanberti公司製造)5g，製作黏著樹脂組合物2-2。 Uniformly mix 55 parts by mass (36mol%) of 2-ethylhexyl acrylate (Tg: -70°C) and 40% of vinyl acetate (Tg: 32°C) as a (meth)acrylic copolymer (2-A). An acrylic system made by random copolymerization of 5 parts by mass (56mol%) and 5 parts by mass (8mol%) of acrylic acid (Tg: 106°C) Copolymer (2-A-2) (weight average molecular weight: 170,000) 1kg, isocyanuric acid EO modified diacrylate and isocyanuric acid EO modified diacrylate as crosslinking agent (2-B) 70 g of a mixture (2-B-2) of permanent triacrylate (manufactured by Toagosei Co., Ltd., product name: ARONIX M313), and Esacure KTO46 (2-C-2) as a photopolymerization initiator (2-C) ( Lanberti company) 5g, and the adhesive resin composition 2-2 was produced.

以上述脫模膜Y、Z夾持上述組合物2-2，使用貼合機以厚度成為150μm之方式賦形為片狀，製作黏著片材X2(厚度150μm)。 The above-mentioned composition 2-2 was sandwiched between the above-mentioned release films Y and Z, and formed into a sheet shape using a laminating machine so as to have a thickness of 150 μm, thereby producing an adhesive sheet X2 (thickness 150 μm).

除使用黏著片材X2以外，以與實施例2-1相同之方式製作黏著片材積層體，進而以與實施例2-1相同之方式製作具有軟質部與硬質部之黏著片材2-2。 Except for using the adhesive sheet X2, an adhesive sheet laminate was produced in the same manner as in Example 2-1, and an adhesive sheet 2-2 having a soft part and a hard part was produced in the same manner as in Example 2-1. .

[實施例2-3] [Example 2-3]

均勻混合作為(甲基)丙烯酸系共聚物(2-A)之由數量平均分子量1400之聚甲基丙烯酸甲酯巨單體(Tg：105℃)10質量份(17mol%)與丙烯酸2-乙基己酯(Tg：-70℃)90質量份(83mol%)無規共聚合而成之丙烯酸系接枝共聚物(2-A-3)(重量平均分子量：23萬)1kg、作為交聯劑(2-B)之三環癸烷二甲基丙烯酸酯(新中村化學公司製造，製品名：DCP)(2-B-3)50g、及作為光聚合起始劑(2-C)之2,4,6-三甲基二苯甲酮與4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)(2-C-1)15g，製作黏著樹脂組合物2-3。 Uniformly mix 10 parts by mass (17mol%) of polymethyl methacrylate macromonomer (Tg: 105°C) with a number average molecular weight of 1400 as a (meth)acrylic copolymer (2-A) and 2-ethyl acrylic acid 1 kg of an acrylic graft copolymer (2-A-3) (weight average molecular weight: 230,000) obtained by random copolymerization of 90 parts by mass (83 mol%) of hexyl hexyl ester (Tg: -70°C) as a cross-linking Tricyclodecane dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: DCP) (2-B-3) 50 g of the agent (2-B), and as the photopolymerization initiator (2-C) 15 g of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name: Esacure TZT) (2-C-1) to prepare adhesive resin composition 2 -3.

以上述脫模膜Y、Z夾持上述組合物2-3，使用貼合機以厚度成為150μm之方式賦形為片狀，製作黏著片材X3(厚度150μm)。 The above-mentioned composition 2-3 was sandwiched between the above-mentioned release films Y and Z, and formed into a sheet shape using a laminating machine so as to have a thickness of 150 μm, thereby producing an adhesive sheet X3 (thickness 150 μm).

除使用黏著片材X3以外，以與實施例2-1相同之方式製作黏著片材積層體，進而以與實施例2-1相同之方式製作具有軟質部與硬質部之黏著片 材2-3。 Except for using the adhesive sheet X3, an adhesive sheet laminate was produced in the same manner as in Example 2-1, and an adhesive sheet having a soft part and a hard part was produced in the same manner as in Example 2-1. Material 2-3.

[實施例2-4] [Example 2-4]

均勻混合作為(甲基)丙烯酸系共聚物(2-A)之由數量平均分子量為2400之聚甲基丙烯酸甲酯巨單體(Tg：105℃)12質量份(19mol%)與丙烯酸2-乙基己酯(Tg：-70℃)85質量份(74mol%)與丙烯酸(Tg：106℃)3質量份(7mol%)無規共聚合而成之丙烯酸系接枝共聚物(2-A-4)(重量平均分子量：8萬)1kg、作為交聯劑(2-B)之甘油二甲基丙烯酸酯(日油公司製造，製品名：GMR)(2-B-1)90g、及作為光聚合起始劑(2-C)之2,4,6-三甲基二苯甲酮與4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)(2-C-1)15g，製作黏著樹脂組合物2-4。 Uniformly mix 12 parts by mass (19mol%) of polymethyl methacrylate macromonomer (Tg: 105°C) with a number average molecular weight of 2400 as a (meth)acrylic copolymer (2-A) and acrylic acid 2- Acrylic graft copolymer (2-A -4) (weight average molecular weight: 80,000) 1 kg, glycerol dimethacrylate (manufactured by NOF Corporation, product name: GMR) (2-B-1) 90 g as a crosslinking agent (2-B), and A mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone as a photopolymerization initiator (2-C) (manufactured by Lanberti, product name: Esacure TZT) (2- C-1) 15g, and the adhesive resin composition 2-4 was produced.

以上述脫模膜Y、Z夾持上述組合物2-4，使用貼合機以厚度成為150μm之方式賦形為片狀，製作黏著片材X4(厚度150μm)。 The above-mentioned composition 2-4 was sandwiched between the above-mentioned release films Y and Z, and formed into a sheet shape using a laminating machine so as to have a thickness of 150 μm, thereby producing an adhesive sheet X4 (thickness 150 μm).

除使用黏著片材X4以外，以與實施例2-1相同之方式製作黏著片材積層體，進而以與實施例2-1相同之方式製作具有軟質部與硬質部之黏著片材2-4。 Except for using the adhesive sheet X4, an adhesive sheet laminate was produced in the same manner as in Example 2-1, and an adhesive sheet 2-4 having a soft part and a hard part was produced in the same manner as in Example 2-1. .

[實施例2-5] [Example 2-5]

均勻混合實施例2-1中使用之丙烯酸系共聚物(2-A-1)(重量平均分子量：23萬)1kg、作為交聯劑(2-B)之三羥甲基丙烷三丙烯酸酯(2-B-4)70g、及作為光聚合起始劑(2-C)之2,4,6-三甲基二苯甲酮與4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)(2-C-1)8g，製作黏著樹脂組合物2-5。 Uniformly mix 1 kg of the acrylic copolymer (2-A-1) (weight average molecular weight: 230,000) used in Example 2-1, trimethylolpropane triacrylate ( 2-B-4) 70 g, and a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone as a photopolymerization initiator (2-C) (manufactured by Lanberti, Product name: Esacure TZT) (2-C-1) 8g, to make adhesive resin composition 2-5.

將以乙酸乙酯將黏著樹脂組合物2-5以固形物成分濃度成為40%之方式稀釋所得的溶液，以乾燥後之厚度成為25μm之方式塗佈於經剝離處理 之聚對苯二甲酸乙二酯膜Y(三菱樹脂公司製造，DIAFOIL MRV-V06，厚度100μm，稱為「脫模膜Y」)之剝離處理面上，加以乾燥後，於塗佈之黏著面上被覆經剝離處理之聚對苯二甲酸乙二酯膜Z(三菱樹脂公司製造，DIAFOIL MRQ，厚度75μm，稱為「脫模膜Z」)，製作黏著片材X5(厚度25μm)。 The solution obtained by diluting Adhesive Resin Composition 2-5 with ethyl acetate so that the solid content concentration becomes 40% is applied on the peeled surface so that the thickness after drying becomes 25 μm. The polyethylene terephthalate film Y (manufactured by Mitsubishi Plastics Co., Ltd., DIAFOIL MRV-V06, thickness 100 μm, called "release film Y") is dried on the peeled surface, and then applied to the coated adhesive surface The polyethylene terephthalate film Z (manufactured by Mitsubishi Plastics Co., Ltd., DIAFOIL MRQ, thickness 75 μm, called “release film Z”) was covered with a peeled polyethylene terephthalate film Z, and an adhesive sheet X5 (thickness 25 μm) was prepared.

除使用黏著片材X5以外，以與實施例2-1相同之方式製作黏著片材積層體，進而以與實施例2-1相同之方式製作具有軟質部與硬質部之黏著片材2-5。 Except for using the adhesive sheet X5, an adhesive sheet laminate was produced in the same manner as in Example 2-1, and an adhesive sheet 2-5 having a soft part and a hard part was produced in the same manner as in Example 2-1. .

[比較例2-1] [Comparative Example 2-1]

於由丙烯酸2-乙基己酯(Tg：-70℃)75質量份(57mol%)與乙酸乙烯酯(Tg：32℃)20質量份(33mol%)與丙烯酸(Tg：106℃)5質量份(10mol%)無規共聚合而成之(甲基)丙烯酸系共聚物(2-A-5)1kg中，混合添加三羥甲基丙烷三丙烯酸酯(2-B-4)200g及4-甲基二苯甲酮(2-C-3)10g，製備中間層用樹脂組合物。 Based on 75 parts by mass (57mol%) of 2-ethylhexyl acrylate (Tg: -70°C), 20 parts by mass (33mol%) of vinyl acetate (Tg: 32°C) and 5 parts by mass of acrylic acid (Tg: 106°C) part (10mol%) random copolymerization of (meth)acrylic copolymer (2-A-5) 1kg, mixed with trimethylolpropane triacrylate (2-B-4) 200g and 4 - 10 g of methylbenzophenone (2-C-3) to prepare a resin composition for an intermediate layer.

將上述中間層用樹脂組合物以經剝離處理之2張聚對苯二甲酸乙二酯膜(Panac公司製造，NP75Z01，厚度75μm/東洋紡織公司製造，E7006，厚度38μm)夾持，以厚度成為80μm之方式賦形為片狀，製作中間層用片材(α)。 The resin composition for the intermediate layer was interposed between two peeled polyethylene terephthalate films (manufactured by Panac, NP75Z01, thickness 75 μm/manufactured by Toyobo Co., Ltd., E7006, thickness 38 μm), with a thickness of Shaped into a sheet with a thickness of 80 μm, the intermediate layer sheet (α) was produced.

繼而，對上述丙烯酸系共聚物(2-A-5)1kg添加混合作為光聚合起始劑(2-C)之4-甲基二苯甲酮(2-C-3)20g，製備黏著層用樹脂組合物。 Next, 20 g of 4-methylbenzophenone (2-C-3) was added and mixed as a photopolymerization initiator (2-C) to 1 kg of the above-mentioned acrylic copolymer (2-A-5) to prepare an adhesive layer Use a resin composition.

將上述黏著層用樹脂組合物以經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，DIAFOIL MRA，厚度75μm/東洋紡織公司製造，E7006，厚度38μm)夾持，以厚度成為35μm之方式賦形為片狀，製 作黏著層用樹脂片材(β)。 The above resin composition for an adhesive layer was sandwiched between two peeled polyethylene terephthalate films (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRA, thickness 75 μm/manufactured by Toyobo Co., Ltd., E7006, thickness 38 μm), and It is shaped into a sheet so that the thickness becomes 35 μm, and the production Used as a resin sheet (β) for an adhesive layer.

另一方面，將黏著層用樹脂組合物以經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，DIAFOIL MRF，厚度75μm/東洋紡織公司製造，E7006，厚度38μm)夾持，以厚度成為35μm之方式賦形為片狀，製作黏著層用樹脂片材(β')。 On the other hand, the resin composition for the adhesive layer was sandwiched between two polyethylene terephthalate films (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRF, thickness 75 μm/manufactured by Toyobo Co., Ltd., E7006, thickness 38 μm) that had undergone peeling treatment. Hold, shape it into a sheet shape so that thickness may become 35 micrometers, and prepare the resin sheet (β') for adhesive layers.

依序剝離去除中間層用片材(α)之兩側之PET膜，並且剝離黏著層用樹脂片材(β)及(β')之一側之PET膜，將露出之黏著面依序貼合於中間層用片材(α)之兩表面，製作包含(β)/(α)/(β')之3層黏著片材。 Peel and remove the PET film on both sides of the middle layer sheet (α) in sequence, and peel off the PET film on one side of the adhesive layer resin sheet (β) and (β'), and stick the exposed adhesive surface sequentially A 3-layer adhesive sheet consisting of (β)/(α)/(β') was prepared by attaching to both surfaces of the sheet (α) for the intermediate layer.

介隔(β)及(β')之表面殘留之PET膜，以波長365nm之累計光量成為1000mJ/cm2之方式藉由高壓水銀燈照射紫外線，使(α)、(β)及(β')進行紫外線交聯，製作黏著片材X6(厚度150μm)。 The remaining PET film on the surface of (β) and (β') is irradiated with ultraviolet rays by a high-pressure mercury lamp in such a way that the cumulative light intensity at a wavelength of 365nm becomes 1000mJ/ cm2 , so that (α), (β) and (β') Ultraviolet crosslinking was carried out to produce an adhesive sheet X6 (thickness 150 μm).

將於黑色片材(LSL-8 Inoac公司製造透光率0%)之單面貼附雙面膠帶並剪裁為50mm×100mm者，貼合於上述黏著片材X6之其中一個經剝離處理之聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，DIAFOIL MRF)之表面形成不透光，製作於片材面內具有透光部與不透光部之黏著片材積層體。 A black sheet (LSL-8 manufactured by Inoac with a light transmittance of 0%) is affixed with double-sided tape on one side and cut to 50mm x 100mm, and attached to one of the above-mentioned adhesive sheets X6 that has been peeled off. The surface of the ethylene terephthalate film (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRF) is formed to be opaque, and an adhesive sheet laminate having a translucent portion and an opaque portion in the sheet surface is produced.

其次，使用高壓水銀燈，自如此製作黏著片材之黏著片材積層體之黑色片材側，以波長365nm之累計光量成為2000mJ/cm2之方式照射紫外線，對與積層體之透光部相接之部位之黏著材進而進行光照射，製作黏著片材2-6。 Next, using a high-pressure mercury lamp, irradiate ultraviolet rays from the black sheet side of the adhesive sheet laminate of the adhesive sheet produced in this way so that the cumulative light intensity at a wavelength of 365nm becomes 2000mJ/ cm2 , and the light-transmitting part of the laminate is in contact with The parts of the adhesive material are further irradiated with light to produce adhesive sheets 2-6.

[比較例2-2] [Comparative Example 2-2]

均勻混合苯氧樹脂(2-A-6)(InChem公司製造，PKHH，重量平均分子量5.2萬)650g、作為交聯劑(2-B)之替代之具有碳酸酯骨架之聚丙烯酸 胺基甲酸酯(2-B-4)(根上工業公司製造，UN5500，重量平均分子量6.7萬)1kg、作為光聚合起始劑(2-C)之1-環己基苯基酮(2-C-4)(BASF公司製造，Irgacure184)43g，製作黏著樹脂組合物2-7。 650 g of phenoxy resin (2-A-6) (manufactured by InChem, PKHH, weight average molecular weight 52,000) and polyacrylic acid having a carbonate skeleton as an alternative to the crosslinking agent (2-B) were uniformly mixed Urethane (2-B-4) (manufactured by Negami Industry Co., Ltd., UN5500, weight average molecular weight 67,000) 1 kg, 1-cyclohexyl phenyl ketone (2-cyclohexyl phenyl ketone) as photopolymerization initiator (2-C) C-4) (BASF company make, Irgacure184) 43g, and the adhesive resin composition 2-7 was produced.

將上述組合物2-7以經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，DIAFOIL MRV-V06，厚度100μm/三菱樹脂公司製造，DIAFOIL MRQ，厚度75μm)夾持，使用貼合機以厚度成為150μm之方式賦形為片狀，製作黏著片材X7(厚度150μm)。 The above compositions 2-7 were interposed between two peeled polyethylene terephthalate films (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRV-V06, thickness 100 μm / manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRQ, thickness 75 μm) , Shaped into a sheet shape using a laminating machine so as to have a thickness of 150 μm, and an adhesive sheet X7 (thickness 150 μm) was produced.

將於黑色片材(LSL-8 Inoac公司製造透光率0%)之單面貼附雙面膠帶並剪裁為50mm×100mm者，貼合於上述黏著片材X7之其中一個經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)之表面形成不透光，製作於片材面內具有透光部與不透光部之黏著片材積層體。 A black sheet (LSL-8 manufactured by Inoac with a light transmittance of 0%) is pasted with double-sided tape on one side and cut to 50mm x 100mm, and attached to one of the above-mentioned adhesive sheets X7 which has been peeled off. The surface of an ethylene terephthalate film (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRQ) is formed to be opaque, and an adhesive sheet laminate having a translucent portion and an opaque portion on the surface of the sheet is produced.

其次，使用高壓水銀燈，自如此製作之黏著片材積層體之黑色片材側，以波長365nm之累計光量成為2000mJ/cm2之方式照射紫外線，使黏著片材積層體之透光部硬化，製作黏著片材2-7。 Next, using a high-pressure mercury lamp, ultraviolet rays are irradiated from the black sheet side of the adhesive sheet laminate produced in this way so that the cumulative light intensity at a wavelength of 365 nm becomes 2000 mJ/cm 2 to harden the light-transmitting portion of the adhesive sheet laminate to produce Adhesive sheets 2-7.

[比較例2-3] [Comparative example 2-3]

對市售之丙烯酸系黏著劑(2-A-7)(綜研化學公司製造，商品名「SK DYNE 1882」)1kg均勻混合異氰酸酯系硬化劑(綜研化學公司製造，商品名「L-45」)1.85g及環氧系硬化劑(綜研化學公司製造，商品名「E-5XM」)0.5g，製備黏著樹脂組合物2-6。 1 kg of a commercially available acrylic adhesive (2-A-7) (manufactured by Soken Chemical Co., Ltd., trade name "SK DYNE 1882") was uniformly mixed with an isocyanate-based hardener (manufactured by Soken Chemical Co., Ltd., trade name "L-45") 1.85 g and 0.5 g of an epoxy-based hardener (manufactured by Soken Chemical Co., Ltd., trade name "E-5XM") were used to prepare Adhesive Resin Composition 2-6.

將上述組合物2-6以乾燥後之厚度成為75μm之方式塗佈於厚度50μm之經剝離處理之聚對苯二甲酸乙二酯膜(商品名「MRF75」：三菱樹脂公司製造)之脫模面上，藉由加熱使溶劑乾燥，製作厚度75μm之黏著片 材。 The above-mentioned composition 2-6 was applied to the mold release of a release-treated polyethylene terephthalate film (trade name "MRF75": manufactured by Mitsubishi Plastics Co., Ltd.) with a thickness of 50 μm so that the thickness after drying was 75 μm. On the surface, dry the solvent by heating to make an adhesive sheet with a thickness of 75 μm material.

進而，將上述組合物2-6以乾燥後之厚度成為75μm之方式塗佈於經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-V06，厚度100μm)之脫模面上，藉由加熱使溶劑乾燥，製作厚度75μm之黏著片材。 Furthermore, the above-mentioned composition 2-6 was coated on the release layer of a polyethylene terephthalate film (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRV-V06, thickness 100 μm) so that the thickness after drying became 75 μm. On the die surface, the solvent was dried by heating to produce an adhesive sheet with a thickness of 75 μm.

對製作之2張黏著片材，貼著各自之黏著面熟化1週，使硬化劑反應，製作黏著片材2-8(厚度150μm)。 For the two produced adhesive sheets, stick to the respective adhesive surfaces and cure for 1 week to allow the hardener to react to produce adhesive sheets 2-8 (thickness 150 μm).

[評價] [evaluate]

以如下方式測定並評價實施例及比較例中製作之黏著片材2-1~2-8之各種物性值。 Various physical property values of the adhesive sheets 2-1 to 2-8 produced in Examples and Comparative Examples were measured and evaluated as follows.

(凝膠分率) (gel fraction)

將實施例及比較例中製作之黏著片材2-1~2-7之與透光部相接之部位，即硬質部及與不透光部相接之部位，即軟質部分別取出，對取出者進行下述測定。 Take out the parts of the adhesive sheets 2-1~2-7 that are in contact with the light-transmitting part, that is, the hard part, and the part that is in contact with the opaque part, that is, the soft part, of the adhesive sheets 2-1~2-7 produced in the examples and comparative examples. Those who took out were subjected to the following measurements.

對比較例2-3之黏著片材2-8，對任意部位進行下述測定。 Regarding the adhesive sheet 2-8 of Comparative Example 2-3, the following measurement was performed on an arbitrary part.

1)稱量黏著劑組合物(W1)，包裹於預先測定重量之200網目之SUS篩網(W0)中。 1) Weigh the adhesive composition (W1) and wrap it in a 200-mesh SUS screen (W0) with a predetermined weight.

2)將上述SUS篩網浸漬於100mL之乙酸乙酯中24小時。 2) Immerse the above SUS mesh in 100 mL of ethyl acetate for 24 hours.

3)取出SUS篩網，於75℃下半乾燥4小時。 3) Take out the SUS screen and semi-dry at 75°C for 4 hours.

4)求得乾燥後之重量(W2)，藉由下述式測定黏著劑組合物之凝膠分率。 4) The weight (W2) after drying is obtained, and the gel fraction of the adhesive composition is determined by the following formula.

凝膠分率(%)=100×(W2-W0)/W1 Gel fraction (%)=100×(W2-W0)/W1

(玻璃轉移溫度(Tg)) (Glass transition temperature (Tg))

使用珀金埃爾默公司製造之示差掃描熱量測定裝置(DSC-8500)，依據JIS K-7121(ISO3146)以升溫速度5℃/分鐘進行升溫測定，根據所得熱譜，分別對黏著片材2-1~2-7之與透光部相接之部位，即硬質部及與不透光部相接之部位，即軟質部求得玻璃轉移溫度(Tg)。 Using a differential scanning calorimeter (DSC-8500) manufactured by PerkinElmer, the temperature was measured according to JIS K-7121 (ISO3146) at a heating rate of 5°C/min. According to the obtained thermal spectrum, each of the adhesive sheets 2 From -1 to 2-7, the glass transition temperature (Tg) is obtained for the part that is in contact with the light-transmitting part, that is, the hard part, and the part that is in contact with the opaque part, that is, the soft part.

對比較例2-3之黏著片材2-8，對任意部位進行同樣之測定。 For the adhesive sheet 2-8 of Comparative Example 2-3, the same measurement was performed on any part.

(阿斯卡硬度) (Ascal Hardness)

對實施例及比較例中製作之黏著片材2-1~2-7之與不透光部相接之部位，即軟質部，剝離片材之剝離膜，依序重疊露出之黏著面，以總厚度成為5mm~7mm之範圍內之方式積層複數張黏著片材。藉此可減低載置測定試樣之載置台之硬度之影響，可比較、測定材料特有之壓入硬度。繼而，對積層之黏著片材之露出之黏著面以荷重1kg以向垂直下方3mm/分鐘之速度壓抵ASKER C2L硬度計之前端端子，測定軟質部之C2阿斯卡硬度(c)。 For the parts of the adhesive sheets 2-1 to 2-7 produced in the examples and comparative examples that are in contact with the opaque part, that is, the soft part, the peeling film of the peeling sheet is overlapped sequentially on the exposed adhesive surface, and Laminate multiple adhesive sheets so that the total thickness falls within the range of 5mm to 7mm. This can reduce the impact of the hardness of the mounting table on which the test sample is placed, and can compare and measure the unique indentation hardness of the material. Then, the exposed adhesive surface of the laminated adhesive sheet is pressed against the front terminal of the Asker C2L hardness tester with a load of 1kg at a speed of 3mm/min vertically downward, and the C2 Asker hardness (c) of the soft part is measured.

對實施例及比較例中製作之黏著片材2-1~2-7之與透光部相接之部位，即硬質部，亦以與上述相同之方式以成為5mm~7mm之範圍內之方式積層黏著片材，測定硬質部之C2阿斯卡硬度(d)。 For the adhesive sheets 2-1 to 2-7 produced in Examples and Comparative Examples, the parts that are in contact with the light-transmitting parts, that is, the hard parts, are also in the same manner as above, so that they fall within the range of 5 mm to 7 mm. For laminated adhesive sheets, measure the C2 Ascal hardness (d) of the hard part.

對比較例2-3中製作之黏著片材2-8，對任意部位進行相同測定。 For the adhesive sheet 2-8 produced in Comparative Example 2-3, the same measurement was performed on an arbitrary part.

(軟質部之180°剝離力) (180°peel force of the soft part)

將實施例及比較例中製作之黏著片材2-1~2-7之與不透光部相接之部位，即軟質部切出後，剝離其中一個脫模膜，貼合作為襯底膜之50μm之PET膜(三菱樹脂公司製造，DIAFOIL T100，厚度50μm)準備積層品。 After cutting out the parts of the adhesive sheets 2-1~2-7 that are in contact with the opaque part, that is, the soft part, of the adhesive sheets 2-1~2-7 produced in the examples and comparative examples, peel off one of the release films and stick them together as the base film A 50 μm PET film (Mitsubishi Plastics Co., Ltd., DIAFOIL T100, thickness 50 μm) was prepared as a laminate.

將上述積層品剪裁為長150mm，寬10mm後，剝離剩餘之脫模膜，將露出之黏著面以2kg之輥進行1個往復而將上述黏著片材輥壓接於鈉鈣 玻璃上。 After cutting the above-mentioned laminated product to a length of 150mm and a width of 10mm, peel off the remaining release film, and use a 2kg roller to reciprocate the exposed adhesive surface to press-bond the above-mentioned adhesive sheet to the sodium calcium on the glass.

測定將該黏著力測定樣品於23℃、40%RH之環境下以剝離角180°，剝離速度60mm/分鐘剝離時之對玻璃之剝離力(N/cm)，求得與不透光部相接之部位，即軟質部之180°剝離力。 Measure the peeling force (N/cm) of the adhesion test sample to glass when it is peeled off at a peeling angle of 180° and a peeling speed of 60mm/min in an environment of 23°C and 40%RH. The joint part, that is, the 180° peel force of the soft part.

(硬質部之180°剝離力) (180°peel force of hard part)

對實施例2-2-1~4及比較例2-1、2-2中製作之光照射前之狀態之黏著片材X1~7剝離其中一個脫模膜，貼合作為襯底膜之50μm之PET膜(三菱樹脂公司製造，DIAFOIL T100，50μm)準備積層品。 Peel off one of the release films from the adhesive sheets X1 to 7 produced in Examples 2-2-1 to 4 and Comparative Examples 2-1 and 2-2 before light irradiation, and attach a 50 μm substrate film A PET film (manufactured by Mitsubishi Plastics Corporation, DIAFOIL T100, 50 μm) was prepared as a laminate.

將上述積層品剪裁為長150mm，寬10mm後，剝離剩餘之脫模膜，將露出之黏著面以2kg之輥進行1個往復而輥壓接於鈉鈣玻璃上。對貼合品實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著後，以365nm之累計光量成為2000mJ/cm2之方式照射紫外線使黏著片材硬化，熟化15小時，製為剝離力測定試樣。 After cutting the above-mentioned laminated product to a length of 150 mm and a width of 10 mm, the remaining release film was peeled off, and the exposed adhesive surface was reciprocated with a 2 kg roller, and the roller was crimped on the soda-lime glass. After performing autoclave treatment (80°C, gauge pressure 0.2MPa, 20 minutes) on the laminated product for final bonding, irradiate ultraviolet light so that the cumulative light intensity at 365nm becomes 2000mJ/ cm2 to harden the adhesive sheet, and cure it for 15 hours. Prepare a peel force measurement sample.

測定將上述剝離力測定樣品於23℃、40%RH之環境下，以剝離角180°，剝離速度60mm/分鐘剝離時之對玻璃之剝離力(N/cm)，作為與透光部相接之部位，即硬質部之180°剝離力。 Measure the peeling force (N/cm) to glass when the above-mentioned peeling force measurement sample is peeled at 23°C and 40%RH at a peeling angle of 180° and a peeling speed of 60mm/min, as the contact with the light-transmitting part The part, that is, the 180° peeling force of the hard part.

對比較例2-3中製作之黏著片材2-8，對任意部位切出黏著片材後，以與軟質部之180℃剝離力之順序相同之方式進行測定。 With respect to the adhesive sheet 2-8 produced in the comparative example 2-3, after cutting out the adhesive sheet to an arbitrary part, it measured in the same order as the 180 degreeC peeling force of a soft part.

(軟質部之保持力) (Retention force of soft part)

將實施例及比較例中製作之黏著片材2-1~2-7之與不透光部相接之部位，即軟質部剪裁為50mm×100mm後，剝離單面之剝離膜，以該黏著片材之單面重疊於襯底用之聚對苯二甲酸乙二酯膜(厚度38μm)上之方式以手動輥貼著，將其剪裁為寬25mm×長100mm之短條狀，作為試驗片。 Cut the parts of the adhesive sheets 2-1 to 2-7 that are in contact with the opaque part, that is, the soft part, into 50mm x 100mm of the adhesive sheets 2-1~2-7 produced in the examples and comparative examples, and then peel off the release film on one side to use the adhesive One side of the sheet is superimposed on the polyethylene terephthalate film (thickness 38μm) for the substrate, and it is pasted with a manual roller, and it is cut into a short strip with a width of 25mm x a length of 100mm, which is used as a test piece .

其次，剝離剩餘之剝離膜，對垂直立設之SUS板(厚度120mm，5mm×1.5mm)，以試驗片僅20mm之長度重疊之方式以手動輥貼著。此時，透明雙面黏著片材與SUS板之貼著面積成為25mm×20mm。 Next, peel off the remaining release film, and stick it with a manual roller in such a way that the length of the test piece overlaps only 20 mm to the vertically erected SUS board (thickness 120 mm, 5 mm x 1.5 mm). At this time, the sticking area of the transparent double-sided adhesive sheet and the SUS board was 25 mm x 20 mm.

其後，將試驗片於40℃及70℃之環境下熟化15分鐘後，對試驗片於垂直方向安裝懸掛4.9N之砝碼靜置30分鐘後，測定SUS與試驗片之貼著位置向下方偏移之長度(mm)。對於貼著面偏移且砝碼落下者，測定砝碼落下所需時間。 After that, the test piece was aged at 40°C and 70°C for 15 minutes, and the test piece was hung with a weight of 4.9N in the vertical direction and left to stand for 30 minutes, and the sticking position between SUS and the test piece was measured downward. Offset length (mm). For those whose sticking surface deviates and the weight falls, measure the time required for the weight to fall.

再者，比較例2-2之黏著片材2-7不具有自黏著性，因此將積層於SUS板上之試驗片於80℃下預熱5分鐘，與被黏著體密接後進行保持力測定。 Furthermore, the adhesive sheet 2-7 of Comparative Example 2-2 does not have self-adhesiveness, so the test piece laminated on the SUS board was preheated at 80°C for 5 minutes, and the holding force was measured after it was in close contact with the adherend .

(硬質部之保持力) (Retention force of hard part)

對實施例2-2-1~5及比較例2-1、2-2中製作之光照射前之狀態之黏著片材X1~7，以與光硬化前之保持力測定相同之方式，製作SUS與試驗片之積層體後，以波長365nm之紫外線以2000mJ/cm2到達黏著片材之方式，一面藉由光量計(牛尾電機公司製造，UNIMETER UIT250/感測器：UVD-C365)確認累計光量，一面使用高壓水銀燈自襯底用之聚對苯二甲酸乙二酯膜側照射紫外線，製作相當於與透光部相接之部位，即硬質部之黏著片材。 Adhesive sheets X1 to 7 in the state before light irradiation produced in Examples 2-2-1 to 5 and Comparative Examples 2-1 and 2-2 were prepared in the same manner as the retention force measurement before photohardening. After the laminated body of SUS and the test piece, ultraviolet light with a wavelength of 365nm reaches the adhesive sheet at 2000mJ/cm 2 , and the cumulative accumulation is confirmed by a light meter (manufactured by Ushio Electric Co., Ltd., UNIMETER UIT250/sensor: UVD-C365) For the amount of light, ultraviolet rays are irradiated from the side of the polyethylene terephthalate film for the substrate using a high-pressure mercury lamp, and an adhesive sheet corresponding to the part that is in contact with the light-transmitting part, that is, the hard part, is produced.

其後，將試驗片於40℃及70℃之環境下熟化15分鐘後，對試驗片於垂直方向安裝懸掛4.9N之砝碼靜置30分鐘後，測定SUS與試驗片之貼著位置向下方偏移之長度(mm)。 After that, the test piece was aged at 40°C and 70°C for 15 minutes, and the test piece was hung with a weight of 4.9N in the vertical direction and left to stand for 30 minutes, and the sticking position between SUS and the test piece was measured downward. Offset length (mm).

將試驗片幾乎未動，偏移長度未達0.1mm者於表3中記為「<0.1mm」。 The test pieces were hardly moved, and those whose deviation length was less than 0.1mm were recorded as "<0.1mm" in Table 3.

對比較例2-3中製作之黏著片材2-8，對任意部位切出黏著片材後， 以與軟質部之保持力測定順序相同之方式進行測定。 For the adhesive sheet 2-8 produced in Comparative Example 2-3, after cutting out the adhesive sheet for any part, The measurement was performed in the same manner as the procedure for measuring the retention force of the soft part.

(透明性) (transparency)

對實施例及比較例中製作之黏著片材2-1~2-7之與透光部相接之部位，即硬質部剝離其中一個脫模膜，將露出之黏著面輥壓貼合於2張鈉鈣玻璃(82mm×53mm×0.5mm厚)上後，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著，製作光學評價用積層體。 For the parts of the adhesive sheets 2-1~2-7 produced in Examples and Comparative Examples that are in contact with the light-transmitting part, that is, the hard part, peel off one of the release films, and roll the exposed adhesive surface to the 2 Soda-lime glass (82mm×53mm×0.5mm thick) was laid on, and then autoclaved (80°C, gauge pressure 0.2MPa, 20 minutes) for final bonding to produce a laminate for optical evaluation.

對比較例2-3中製作之黏著片材2-8，對任意部位以同樣之方式製作樣品。 With respect to the adhesive sheet 2-8 produced in the comparative example 2-3, the sample was produced in the same manner for an arbitrary part.

對上述積層體，使用霧度計(日本電色工業公司製造，NDH5000)，求得依據JIS K7136之霧度值以及依據JIS K7361-1之全光線透過率(%)。 About the said laminated body, the haze value based on JIS K7136 and the total light transmittance (%) based on JIS K7361-1 were calculated|required using the haze meter (Nippon Denshoku Kogyo Co., Ltd. make, NDH5000).

(凹凸吸收性) (concave-convex absorptivity)

將實施例2-1~2-4及比較例2-1、2-2中製作之光照射前之狀態之黏著片材X1~4、6、7剪裁為50mm×80mm，剝離其中一個脫模膜，使用真空加壓機將露出之黏著面以黏著材之四邊覆蓋在印刷階差上之方式加壓壓接(絕對壓力5kPa，溫度80℃，加壓壓力0.04MPa)在於周緣部3mm實施有厚度80μm之印刷之鈉鈣玻璃(82mm×53mm×0.5mm厚)之印刷面上。繼而剝離剩餘之脫模膜，加壓貼合ZEONOR膜(日本ZEON公司製造，100μm厚)後，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著。自實施有印刷之鈉鈣玻璃側，以波長365nm之紫外線以2000mJ/cm2到達片材X之方式藉由高壓水銀燈照射紫外線，使未實施印刷之開口部，即與透光部相接之部位之片材硬化，製作評價用積層體2-1~2-6。 Cut the adhesive sheets X1~4, 6, and 7 prepared in Examples 2-1~2-4 and Comparative Examples 2-1, 2-2 before light irradiation to 50mm×80mm, and peel off one of them for demoulding For the film, use a vacuum press to press-bond the exposed adhesive surface so that the four sides of the adhesive material cover the printing step (absolute pressure 5kPa, temperature 80°C, pressurized pressure 0.04MPa) on the peripheral part 3mm Printing surface of printed soda-lime glass (82mm×53mm×0.5mm thick) with a thickness of 80 μm. Then the remaining release film was peeled off, and the ZEONOR film (manufactured by ZEON Japan, 100 μm thick) was pressure-bonded, followed by autoclave treatment (80°C, gauge pressure 0.2MPa, 20 minutes) for final bonding. From the side of the printed soda lime glass, ultraviolet rays with a wavelength of 365nm reach the sheet X at a rate of 2000mJ/cm 2 and irradiate ultraviolet rays with a high-pressure mercury lamp, so that the openings that are not printed, that is, the parts that are in contact with the light-transmitting parts The sheets were hardened to prepare laminates 2-1 to 2-6 for evaluation.

對實施例2-5中製作之黏著片材X5，使用實施印刷之鈉鈣玻璃之印刷厚度為15μm者，以相同之方式製作評價用積層體2-7。 With respect to the adhesive sheet X5 produced in Example 2-5, the printed thickness of the soda-lime glass used for printing was 15 micrometers, and the laminated body 2-7 for evaluation was produced in the same manner.

對比較例2-3中製作之黏著片材2-8，使用黏著片材2-7，以與上述相同之順序製作實施有印刷之鈉鈣玻璃與ZEONOR膜(日本ZEON公司製造，100μm厚)之積層體後，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著，作為評價用積層體2-8。 For the adhesive sheet 2-8 produced in Comparative Example 2-3, use the adhesive sheet 2-7 to produce printed soda lime glass and ZEONOR film (manufactured by ZEON Japan, 100 μm thick) in the same order as above. After forming the laminate, autoclave treatment (80°C, gauge pressure 0.2MPa, 20 minutes) was carried out for final sticking, which was used as laminate 2-8 for evaluation.

以目視觀察製作之積層體2-1~2-8，將於印刷階差附近黏著材未追隨而殘留氣泡者判定為「×」，將膜於階差附近彎曲，可見應變導致之凹凸不均者判定為「△」，將無氣泡而平滑貼合者判定為「○」。 Visually observe the produced laminates 2-1 to 2-8, judge as "×" if the adhesive material does not follow the adhesive material near the printing step and leave bubbles, and the film is bent near the step difference, and unevenness caused by strain can be seen Those who were judged as "△" were judged as "△", and those who adhered smoothly without air bubbles were judged as "◯".

(耐發泡可靠性) (reliability against foaming)

將凹凸吸收性評價中製作之評價用積層體2-1~2-8投入85℃、85%RH之恆溫恆濕槽中，觀察熟化100小時後之外觀。將黏著片材中產生氣泡者判定為「×」，將無外觀變化者判定為「○」。 Put the evaluation laminates 2-1 to 2-8 produced in the uneven absorbency evaluation into a constant temperature and humidity chamber at 85°C and 85%RH, and observe the appearance after aging for 100 hours. The case where air bubbles were generated in the adhesive sheet was judged as "x", and the case without appearance change was judged as "◯".

Figure 110106505-A0305-02-0107-3
Figure 110106505-A0305-02-0107-3

Figure 110106505-A0305-02-0108-4
Figure 110106505-A0305-02-0108-4

(考察) (investigation)

實施例2-1~2-5中製作之黏著片材之軟質部之凝膠分率未達1%，因此藉由加熱可表現較高之流動性。因此，藉由於貼合時加熱使之熔融，不僅對凹凸面之追隨性優異，並且即使被黏著體之一方為如膜之剛性較低之素材，亦不會於階差附近產生彎曲，可獲得平滑之積層體。進而，硬質部之凝膠分率為40%以上，因此即使於高溫高濕下等嚴苛之環境試驗下亦可表現較高之凝集力，不產生剝離或發泡、變形，可獲得具有較高之可靠性之積層體。 The gel fraction of the soft portion of the adhesive sheets produced in Examples 2-1 to 2-5 did not reach 1%, so they can exhibit higher fluidity by heating. Therefore, by heating and melting it at the time of lamination, not only is the followability to the uneven surface excellent, but also even if one of the adherends is a material with low rigidity such as a film, there is no bending near the step difference, and it can be obtained. Smooth laminate. Furthermore, the gel fraction of the hard part is more than 40%, so even under severe environmental tests such as high temperature and high humidity, it can exhibit high cohesion, without peeling, foaming, and deformation, and can obtain a more High reliability laminated body.

作為比較例2-1之黏著片材，藉由紫外線照射而使黏著劑樹脂組合物一部分交聯，故而積層附印刷階差之玻璃與膜時，於膜側轉印有印刷階差導致之凹凸從而無法獲得平滑之積層體。又，由於階差附近之黏著材之應變，於高溫高濕試驗下可見發泡，保存穩定性較差。 As the adhesive sheet of Comparative Example 2-1, part of the adhesive resin composition was cross-linked by ultraviolet irradiation, so when the glass and the film with printed steps were laminated, the unevenness caused by the printed steps was transferred to the film side Therefore, a smooth laminate cannot be obtained. In addition, due to the strain of the adhesive material near the step difference, foaming can be seen under the high temperature and high humidity test, and the storage stability is poor.

比較例2-2未使用(甲基)丙烯酸系共聚物，係使用於室溫範圍內具備某種程度之剛性之黏著性樹脂組合物的熱熔型黏著片材。 Comparative Example 2-2 is a hot-melt adhesive sheet using an adhesive resin composition with a certain degree of rigidity at room temperature without using a (meth)acrylic copolymer.

比較例2-2之片材與實施例之黏著片材相比，室溫附近之黏性非常低。積層附印刷階差之玻璃與片材時，加熱時之流動性較低，故而於片材側轉印有少許印刷階差導致之凹凸，與實施例之黏著片材相比，結果為積層體之平滑性較差。又，不透光部位之阿斯卡硬度較高，由此可知貼合作業時片材之剛性較高，不具有自黏著性，因此貼合時必須自定位之階段對被黏著體進行預熱，與僅以壓接即可常溫貼附之黏著片材相比，亦存在作業繁雜之課題。 The sheet of Comparative Example 2-2 had very low viscosity around room temperature compared to the adhesive sheet of the examples. When laminating glass and sheets with printing steps, the fluidity during heating is low, so a little unevenness caused by printing steps is transferred on the side of the sheet. Compared with the adhesive sheet of the embodiment, the result is a laminate. The smoothness is poor. In addition, the Ascar hardness of the opaque part is relatively high, so it can be seen that the rigidity of the sheet is relatively high during lamination, and it does not have self-adhesiveness. Therefore, it is necessary to preheat the adherend at the stage of self-positioning during lamination. , Compared with adhesive sheets that can be attached at room temperature only by crimping, there is also a problem of complicated work.

比較例2-3中，黏著片材2-7之黏著劑樹脂組合物之交聯反應已完成，故而黏著片材內不存在凝膠分率為1%以下之軟質部，於膜側轉印有印刷階差導致之凹凸從而無法獲得平滑之積層體，不僅如此於印刷階差交叉之角部附近有一部分黏著劑未完全填充，結果殘留氣泡。 In comparative example 2-3, the cross-linking reaction of the adhesive resin composition of adhesive sheet 2-7 has been completed, so there is no soft part with a gel fraction of 1% or less in the adhesive sheet, which is transferred to the film side There are irregularities caused by printing steps, so that a smooth laminate cannot be obtained. Not only that, part of the adhesive is not completely filled near the corners where the printing steps intersect, and as a result, air bubbles remain.

自以上之實施例之結果以及至今為止發明者所進行之試驗結果，可認為若使用具有凝膠分率未達1%之軟質部與凝膠分率為40%以上之硬質部且含有(甲基)丙烯酸系共聚物之光硬化性透明雙面黏著片材，則與實施例相同可使2個圖像顯示裝置構成構件較佳地接著。 From the results of the above examples and the test results carried out by the inventors so far, it can be considered that if the soft part with a gel fraction of less than 1% and the hard part with a gel fraction of 40% or more are used and contain (a The base) a photocurable transparent double-sided adhesive sheet of an acrylic copolymer can allow two image display device components to be preferably bonded in the same manner as in the examples.

又，可認為黏著片材面內之軟質部之凝膠分率較佳為未達1%，硬質部之凝膠分率較佳為40%以上。 In addition, it is considered that the gel fraction of the soft portion within the surface of the adhesive sheet is preferably less than 1%, and the gel fraction of the hard portion is preferably 40% or more.

又，可認為黏著片材面內之軟質部之玻璃轉移溫度(實測Tg)較佳為-70~-10℃，硬質部之玻璃轉移溫度(實測Tg)為-60~+20℃，硬質部之玻璃轉移溫度(Tg[H])與軟質部之玻璃轉移溫度(Tg[S])之差(Tg[H]-Tg[S])較佳為3℃以上。 In addition, it can be considered that the glass transition temperature (actually measured Tg) of the soft part in the surface of the adhesive sheet is preferably -70~-10°C, the glass transition temperature (actually measured Tg) of the hard part is -60~+20°C, and the hard part The difference (Tg[H]-Tg[S]) between the glass transition temperature (Tg[H]) of the soft part and the glass transition temperature (Tg[S]) of the soft part is preferably 3°C or more.

[實施例2-6] [Example 2-6]

對於實施例2-1中製作之黏著片材X1，將寬150mm，長100m之長 條之積層片材以初始捲繞張力70N，推拔比20%捲繞在直徑6英吋之塑膠製捲芯上，製作黏著片材捲筒。 For the adhesive sheet X1 made in Example 2-1, the width is 150mm, and the length is 100m. The laminated sheet of the strip is wound on a plastic core with a diameter of 6 inches with an initial winding tension of 70N and a push-pull ratio of 20%, to make an adhesive sheet roll.

使用高壓水銀燈，對製作之片材捲筒之端面部以波長365nm之累計光量以500mJ/cm2到達之方式進行光照射而使端面部光硬化，成為端面部具有硬質部之黏著片材捲筒。 Using a high-pressure mercury lamp, irradiate the end face of the produced sheet roll with a cumulative light intensity of 500mJ/ cm2 at a wavelength of 365nm to light-harden the end face and become an adhesive sheet roll with a hard part on the end face .

[比較例2-4] [Comparative example 2-4]

除未進行光照射以外，以與實施例2-6相同之方式製作黏著片材捲筒。 An adhesive sheet roll was produced in the same manner as in Example 2-6 except that light irradiation was not performed.

對如此製作之不具有硬質部之僅有軟質部之比較例2-4之黏著片材捲筒與端面部具有硬質部之實施例2-6之黏著片材捲筒，於40℃、90%RH之恆溫恆濕槽中保管2週後，以目視觀察黏著片材捲筒之端面部。 For the adhesive sheet rolls of Comparative Example 2-4 with no hard parts and only soft parts and the adhesive sheet rolls of Examples 2-6 with hard parts on the end face, they were tested at 40°C and 90% After storing in a constant temperature and humidity tank of RH for 2 weeks, visually observe the end face of the adhesive sheet roll.

作為端面部具有硬質部之實施例2-5之黏著片材捲筒，不會自端面部溢出漿糊，片材之捲出作業性良好，相對於此僅包含軟質部之比較例2-4之黏著片材捲筒之端面部溢出漿糊，從而導致端面部發黏，結果對捲出作業造成障礙。 As the adhesive sheet roll of Example 2-5, which has a hard part on the end part, the paste does not overflow from the end part, and the unwinding workability of the sheet is good, compared to Comparative Example 2-4 which only includes a soft part. The end face of the adhesive sheet reel overflows with paste, which causes the end face to become sticky, resulting in obstacles to the unwinding operation.

[實施例3-1] [Example 3-1]

作為(甲基)丙烯酸系共聚物(3-A)，使用由聚甲基丙烯酸甲酯巨單體(Tg：105℃，數量平均分子量為2400)15質量份(18mol%)與丙烯酸丁酯(Tg：-55℃)81質量份(75mol%)與丙烯酸(Tg：106℃)4質量份(7mol%)無規共聚合而成之接枝共聚物(3-A1)。 As the (meth)acrylic copolymer (3-A), 15 parts by mass (18 mol%) of polymethyl methacrylate macromonomer (Tg: 105°C, number average molecular weight 2400) and butyl acrylate ( A graft copolymer (3-A1) obtained by random copolymerization of 81 parts by mass (75mol%) of Tg: -55°C) and 4 parts by mass (7mol%) of acrylic acid (Tg: 106°C).

於該接枝共聚物(3-A1)中，構成主幹成分之共聚物之玻璃轉移溫度為-60℃，巨單體於接枝共聚物(3-A1)中之含量為15質量%，溫度130℃、頻率0.02Hz下之複黏度為260Pa‧s。 In this graft copolymer (3-A1), the glass transition temperature of the copolymer constituting the main component is -60°C, the content of the macromonomer in the graft copolymer (3-A1) is 15% by mass, and the temperature The complex viscosity at 130℃ and frequency 0.02Hz is 260Pa‧s.

均勻混合該接枝共聚物(3-A1)1kg、作為交聯劑(3-B)之甘油二甲基丙烯酸酯(日油公司製造，製品名：GMR)90g、及作為光聚合起始劑(3-C)之2,4,6-三甲基二苯甲酮及4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)15g，製作黏著劑樹脂組合物3-1。 1 kg of the graft copolymer (3-A1), 90 g of glycerol dimethacrylate (manufactured by NOF Corporation, product name: GMR) as a crosslinking agent (3-B), and 90 g of a photopolymerization initiator were uniformly mixed. (3-C) 15 g of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name: Esacure TZT) to prepare adhesive resin composition 3 -1.

將上述黏著劑樹脂組合物3-1以2張脫模膜即經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造「DIAFOIL MRV-V06」，厚度100μm/三菱樹脂公司製造「DIAFOIL MRQ」，厚度75μm)夾持，使用貼合機以厚度成為150μm之方式賦形為片狀，製作黏著片材3-1(厚度150μm)。 Use the above-mentioned adhesive resin composition 3-1 as two release films, that is, two polyethylene terephthalate films ("DIAFOIL MRV-V06" manufactured by Mitsubishi Plastics Co., Ltd., thickness 100 μm / Mitsubishi Plastics Co., Ltd.) after peeling treatment Manufacture "DIAFOIL MRQ" (thickness: 75 μm) sandwiched, and shaped into a sheet using a laminating machine so as to have a thickness of 150 μm, and an adhesive sheet 3-1 (thickness: 150 μm) was produced.

[實施例3-2] [Example 3-2]

除使用甘油二甲基丙烯酸酯(新中村化學工業公司製造，製品名：NK ester 701)(3-B-1)90g作為交聯劑(3-B)以外，以與實施例3-1相同之方式製作黏著劑樹脂組合物3-2。 Except using 90 g of glycerin dimethacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name: NK ester 701) (3-B-1) as the crosslinking agent (3-B), the same as in Example 3-1 Adhesive resin composition 3-2 was prepared in the same way.

使用上述黏著劑樹脂組合物3-2，以與實施例3-1相同之方式製作黏著片材3-2(厚度150μm)。 Using the above-mentioned adhesive resin composition 3-2, an adhesive sheet 3-2 (thickness 150 μm) was produced in the same manner as in Example 3-1.

[實施例3-3] [Example 3-3]

均勻混合與實施例3-1相同之接枝共聚物(3-A1)1kg、作為交聯劑(3-B)之甘油二甲基丙烯酸酯(日油公司製造，製品名：GMR)90g、及作為光聚合起始劑(3-C)之2,4,6-三甲基二苯甲酮及4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)15g、紫外線穩定化劑(Ciba Japan公司製造，製品名：TIN123)50g，製作黏著劑樹脂組合物3-3。 Uniformly mix 1 kg of the same graft copolymer (3-A1) as in Example 3-1, 90 g of glycerol dimethacrylate (manufactured by NOF Corporation, product name: GMR) as a crosslinking agent (3-B), and 15 g of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name: Esacure TZT) as a photopolymerization initiator (3-C), An ultraviolet stabilizer (manufactured by Ciba Japan, product name: TIN123) was 50 g, and an adhesive resin composition 3-3 was produced.

並且，使用該黏著劑樹脂組合物3-3以與實施例3-1相同之方式製作黏著片材3-3(厚度150μm)。 And the adhesive sheet 3-3 (150 micrometers in thickness) was produced in the same manner as Example 3-1 using this adhesive resin composition 3-3.

[實施例3-4] [Example 3-4]

作為(甲基)丙烯酸系共聚物(3-A)，使用由聚甲基丙烯酸甲酯巨單體(Tg：105℃，數量平均分子量為2500)10質量份(12mol%)與丙烯酸丁酯(Tg：-55℃)88質量份(84mol%)與丙烯酸(Tg：106℃)2質量份(7mol%)無規共聚合而成之接枝共聚物(3-A2)。 As the (meth)acrylic copolymer (3-A), 10 parts by mass (12 mol%) of polymethyl methacrylate macromonomer (Tg: 105°C, number average molecular weight 2500) and butyl acrylate ( A graft copolymer (3-A2) obtained by random copolymerization of 88 parts by mass (84mol%) of Tg: -55°C) and 2 parts by mass (7mol%) of acrylic acid (Tg: 106°C).

於該接枝共聚物(3-A2)中，構成主幹成分之共聚物之玻璃轉移溫度為-60℃，巨單體於接枝共聚物(3-A2)中之含量為10質量%，於溫度130℃、頻率0.02Hz下之複黏度為240Pa‧s。 In this graft copolymer (3-A2), the glass transition temperature of the copolymer constituting the main component is -60°C, and the content of the macromonomer in the graft copolymer (3-A2) is 10% by mass. The complex viscosity at a temperature of 130°C and a frequency of 0.02Hz is 240Pa‧s.

均勻混合該接枝共聚物(3-A2)1kg、作為交聯劑(3-B)之三羥甲基丙烷三丙烯酸酯(新中村化學工業公司製造，製品名：CLM400)50g、及作為光聚合起始劑(3-C)之2,4,6-三甲基二苯甲酮及4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)15g，製作黏著劑樹脂組合物3-4。 1 kg of the graft copolymer (3-A2), 50 g of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name: CLM400) as a crosslinking agent (3-B), and 50 g of a photopolymer (3-A2) were uniformly mixed. 15 g of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name: Esacure TZT) as a polymerization initiator (3-C) to make an adhesive Resin composition 3-4.

並且，使用該黏著劑樹脂組合物3-4以與實施例3-1相同之方式製作黏著片材3-4(厚度150μm)。 And, the adhesive sheet 3-4 (150 micrometers in thickness) was produced in the same manner as Example 3-1 using this adhesive resin composition 3-4.

[實施例3-5] [Example 3-5]

作為(甲基)丙烯酸系共聚物(3-A)，使用由聚甲基丙烯酸甲酯巨單體(Tg：105℃，數量平均分子量為2500)8質量份(10mol%)與丙烯酸丁酯(Tg：-55℃)89質量份(85mol%)與丙烯酸(Tg：106℃)3質量份(5mol%)無規共聚合而成之接枝共聚物(3-A3)。 As (meth)acrylic copolymer (3-A), 8 mass parts (10mol%) of polymethyl methacrylate macromonomer (Tg: 105°C, number average molecular weight of 2500) and butyl acrylate ( A graft copolymer (3-A3) obtained by random copolymerization of 89 parts by mass (85mol%) of Tg: -55°C) and 3 parts by mass (5mol%) of acrylic acid (Tg: 106°C).

於該接枝共聚物(3-A3)中，構成主幹成分之共聚物之玻璃轉移溫度為-40℃，巨單體於接枝共聚物(3-A3)中之含量為8質量%，於溫度130℃、頻率0.02Hz下之複黏度為220Pa‧s。 In this graft copolymer (3-A3), the glass transition temperature of the copolymer constituting the main component is -40°C, and the content of the macromonomer in the graft copolymer (3-A3) is 8% by mass. The complex viscosity at a temperature of 130°C and a frequency of 0.02Hz is 220Pa‧s.

均勻混合該接枝共聚物(3-A3)1kg、作為交聯劑(3-B)之甘油二甲基 丙烯酸酯(日油公司製造，製品名：GMR)90g、及作為光聚合起始劑(3-C)之2,4,6-三甲基二苯甲酮及4-甲基二苯甲酮之混合物(Lanberti公司製造，製品名：Esacure TZT)15g，製作黏著劑樹脂組合物3-5。 Uniformly mix 1kg of the graft copolymer (3-A3), glycerol dimethyl as crosslinking agent (3-B) 90 g of acrylate (manufactured by NOF Corporation, product name: GMR), and 2,4,6-trimethylbenzophenone and 4-methylbenzophenone as photopolymerization initiators (3-C) 15 g of the mixture (manufactured by Lanberti, product name: Esacure TZT) was used to prepare adhesive resin compositions 3-5.

並且，使用該黏著劑樹脂組合物3-5，以與實施例3-1相同之方式製作黏著片材3-5(厚度150μm)。 And using this adhesive resin composition 3-5, the adhesive sheet 3-5 (thickness 150 micrometers) was produced in the same manner as Example 3-1.

[比較例3-1] [Comparative Example 3-1]

以相當於國際公開2012/032995號公報之實施例之方式進行製作。 Produced in a manner equivalent to the embodiment of International Publication No. 2012/032995.

即，於作為(甲基)丙烯酸系共聚物(3-A)之由丙烯酸2-乙基己酯(Tg：-70℃)75質量份(57mol%)與乙酸乙烯酯(Tg：32℃)20質量份(33mol%)與丙烯酸(Tg：106℃)5質量份(10mol%)無規共聚合而成之丙烯酸系共聚物(3-A-5)1kg中，混合添加作為交聯劑(3-B)之三羥甲基丙烷三丙烯酸酯(3-B-4)200g及作為光聚合起始劑(3-C)之4-甲基二苯甲酮(3-C-3)10g製備中間層用樹脂組合物。 That is, in the (meth)acrylic copolymer (3-A), 75 parts by mass (57 mol%) of 2-ethylhexyl acrylate (Tg: -70°C) and vinyl acetate (Tg: 32°C) 20 parts by mass (33mol%) and 5 parts by mass (10mol%) of acrylic acid (Tg: 106°C) were randomly copolymerized into 1 kg of acrylic copolymer (3-A-5), mixed and added as a crosslinking agent ( 3-B) 200g of trimethylolpropane triacrylate (3-B-4) and 10g of 4-methylbenzophenone (3-C-3) as photopolymerization initiator (3-C) A resin composition for an intermediate layer was prepared.

將該中間層用樹脂組合物以經剝離處理之2張聚對苯二甲酸乙二酯膜(Panac公司製造，NP75Z01，厚度75μm/東洋紡織公司製造，E7006，厚度38μm)夾持，以厚度成為80μm之方式賦形為片狀，製作中間層用片材(α)。 The resin composition for the intermediate layer was sandwiched between two peeled polyethylene terephthalate films (manufactured by Panac, NP75Z01, thickness 75 μm/manufactured by Toyobo Co., Ltd., E7006, thickness 38 μm), with a thickness of Shaped into a sheet with a thickness of 80 μm, the intermediate layer sheet (α) was produced.

繼而，對上述丙烯酸系共聚物(3-A-5)1kg添加混合作為光聚合起始劑(3-C)之4-甲基二苯甲酮(3-C-3)20g，製備接著層用樹脂組合物。 Next, add and mix 20 g of 4-methylbenzophenone (3-C-3) as a photopolymerization initiator (3-C) to 1 kg of the above-mentioned acrylic copolymer (3-A-5) to prepare an adhesive layer Use a resin composition.

將上述接著層用樹脂組合物以2張脫模膜即經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造「DIAFOIL MRA」，厚度75μm/東洋紡織公司製造「E7006」，厚度38μm)夾持，以厚度成為35μm之方式賦形為片狀，製作接著層用樹脂片材(β)。 The resin composition for the adhesive layer is used as two release films, that is, two polyethylene terephthalate films ("DIAFOIL MRA" manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 μm/"E7006" manufactured by Toyobo Co., Ltd.) , thickness 38 μm) sandwiched, and formed into a sheet shape so that the thickness becomes 35 μm, and the resin sheet (β) for an adhesive layer was produced.

進而將接著層用樹脂組合物以經剝離處理之2張聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，DIAFOIL MRF，厚度75μm/東洋紡織公司製造，E7006，厚度38μm)夾持，以厚度成為35μm之方式賦形為片狀，製作接著層用樹脂片材(β')。 Furthermore, the resin composition for the adhesive layer was sandwiched between two peeled polyethylene terephthalate films (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRF, thickness 75 μm/manufactured by Toyobo Co., Ltd., E7006, thickness 38 μm), and It shaped into a sheet shape so that thickness might become 35 micrometers, and produced the resin sheet (β') for adhesive layers.

依序剝離去除中間層用片材(α)之兩側之PET膜，並且剝離接著層用樹脂片材(β)及(β')之一側之PET膜，將露出之黏著面依序貼合於中間層用片材(α)之兩表面，製作包含(β)/(α)/(β')之3層黏著片材。 Sequentially peel and remove the PET film on both sides of the middle layer sheet (α), and peel off the PET film on one side of the adhesive layer resin sheet (β) and (β'), and stick the exposed adhesive surface in sequence A 3-layer adhesive sheet consisting of (β)/(α)/(β') was prepared by attaching to both surfaces of the sheet (α) for the intermediate layer.

介隔(β)及(β')之表面殘留之PET膜，以波長365nm之累計光量成為1000mJ/cm2之方式藉由高壓水銀燈照射紫外線，使(α)、(β)及(β')進行紫外線交聯，製作黏著片材3-6(厚度150μm)。 The remaining PET film on the surface of (β) and (β') is irradiated with ultraviolet rays by a high-pressure mercury lamp in such a way that the cumulative light intensity at a wavelength of 365nm becomes 1000mJ/ cm2 , so that (α), (β) and (β') Ultraviolet crosslinking was carried out to produce an adhesive sheet 3-6 (thickness 150 μm).

[比較例3-2] [Comparative Example 3-2]

依據WO2010/038366之實施例6製作黏著片材。 The adhesive sheet was produced according to Example 6 of WO2010/038366.

即，均勻混合作為(甲基)丙烯酸系共聚物(3-A)之替代之苯氧樹脂(InChem公司製造，PKHH，重量平均分子量5.2萬)650g、作為交聯劑(3-B)之替代之具有碳酸酯骨架之聚丙烯酸胺基甲酸酯(根上工業公司製造，UN5500，重量平均分子量6.7萬)1kg、及作為光聚合起始劑(3-C)之1-環己基苯基酮(BASF公司製造，Irgacure184)43g，製作黏著劑樹脂組合物3-7。 That is, 650 g of a phenoxy resin (manufactured by InChem, PKHH, weight average molecular weight: 52,000) as a substitute for the (meth)acrylic copolymer (3-A) and 650 g as a substitute for the crosslinking agent (3-B) were uniformly mixed. 1 kg of polyacrylic urethane (manufactured by Negami Industrial Co., Ltd., UN5500, weight average molecular weight 67,000) with a carbonate skeleton, and 1-cyclohexyl phenyl ketone (3-C) as a photopolymerization initiator (3-C) Made by BASF Corporation, Irgacure 184) 43 g, and adhesive resin composition 3-7 was prepared.

上述組合物3-7以與實施例3-1相同之方法製作黏著片材3-7(厚度150μm)。 The above-mentioned composition 3-7 was prepared in the same manner as in Example 3-1 to produce an adhesive sheet 3-7 (thickness: 150 μm).

[評價] [evaluate]

對實施例及比較例中製作之黏著片材及積層體進行如下評價。 The adhesive sheets and laminates produced in Examples and Comparative Examples were evaluated as follows.

(拉伸彈性模數、斷裂強度、斷裂伸長率) (tensile elastic modulus, breaking strength, breaking elongation)

將黏著片材3-1~3-7剪裁為寬20mm，作為光交聯前之拉伸試驗測定試樣。 Adhesive sheets 3-1~3-7 were cut to a width of 20mm, and used as samples for tensile test before photocrosslinking.

將黏著片材3-1~3-7剪裁為寬20mm後，以365nm之累計光量成為2000mJ/cm2之方式，使用高壓水銀燈，自脫模PET側照射紫外線使黏著片材硬化，於23℃、50%RH下熟化15小時，作為光交聯後之拉伸試驗測定試樣。 After cutting the adhesive sheets 3-1 to 3-7 to a width of 20mm, use a high-pressure mercury lamp to irradiate ultraviolet light from the demoulding PET side to harden the adhesive sheet in such a way that the cumulative light intensity at 365nm becomes 2000mJ/cm 2 , at 23°C , Cured for 15 hours at 50% RH, used as a sample for tensile test after photocrosslinking.

對上述拉伸試驗測定試樣於23℃、50%RH之環境下，以試驗速度300mm/分鐘測定拉伸時之拉伸彈性模數、拉伸斷裂強度、拉伸斷裂伸長率。 For the above tensile test, the tensile modulus, tensile breaking strength and tensile breaking elongation of the sample were measured under the environment of 23°C and 50%RH at a test speed of 300mm/min.

再者，拉伸彈性模數之測定條件中，位移為30~50mm。 Furthermore, in the measurement conditions of the tensile elastic modulus, the displacement is 30 to 50 mm.

(凝膠分率) (gel fraction)

將實施例及比較例中製作之黏著片材3-1~3-7之與透光部相接之部位，即硬質部及與不透光部相接之部位，即軟質部分別取出，對取出者進行下述測定。 Take out the parts of the adhesive sheets 3-1 to 3-7 that are in contact with the light-transmitting part, that is, the hard part, and the part that is in contact with the opaque part, that is, the soft part, of the adhesive sheets 3-1~3-7 produced in the examples and comparative examples, respectively. Those who took out were subjected to the following measurements.

1)稱量黏著劑樹脂組合物(W1)，包裹於預先測定重量之200網目之SUS篩網(W0)中。 1) Weigh the adhesive resin composition (W1), and wrap it in a 200-mesh SUS screen (W0) with a predetermined weight.

2)將上述SUS篩網浸漬於100mL之乙酸乙酯中24小時。 2) Immerse the above SUS mesh in 100 mL of ethyl acetate for 24 hours.

3)取出SUS篩網，於75℃下半乾燥4小時。 3) Take out the SUS screen and semi-dry at 75°C for 4 hours.

4)求得乾燥後之重量(W2)，藉由下述式測定黏著劑組合物之凝膠分率。 4) The weight (W2) after drying is obtained, and the gel fraction of the adhesive composition is determined by the following formula.

凝膠分率(%)=100×(W2-W0)/W1 Gel fraction (%)=100×(W2-W0)/W1

(作業性(保管性)) (operability (storage))

將剪裁為50mm×50mm見方之黏著片材3-1~3-7夾持於100 mm×100mm見方且厚度2mm之玻璃板2張之間製作積層體。將500g之砝碼置於積層體上，於60℃之環境下放置24小時後，以目視觀察黏著劑是否自積層體溢出。 Clamp the adhesive sheets 3-1~3-7 cut into 50mm×50mm square in 100 A laminate is made between two glass plates with a square of mm×100mm and a thickness of 2mm. Place a 500g weight on the laminate, and place it at 60°C for 24 hours, then visually observe whether the adhesive overflows from the laminate.

以目視觀察製作之積層體，將黏著劑整體溢出者判定為「×」，將黏著劑僅自角部溢出者判定為「△」，將黏著劑未溢出者判定為「○」。 The produced laminate was visually observed, and the case where the adhesive overflowed as a whole was judged as "×", the case where the adhesive overflowed only from the corner was judged as "△", and the case where the adhesive did not overflow was judged as "○".

(階差吸收性) (step absorbency)

將實施例3-1~3-5及比較例3-1中製作之光照射前之狀態之黏著片材3-1~3-6剪裁為50mm×80mm，剝離其中一個脫模膜，使用真空加壓機將露出之黏著面以黏著材之四邊覆蓋在印刷階差上之方式加壓壓接(絕對壓力5kPa，溫度80℃，加壓壓力0.04MPa)在於周緣部3mm實施有厚度80μm之印刷之鈉鈣玻璃(82mm×53mm×0.5mm厚)之印刷面上。繼而剝離剩餘之脫模膜，加壓貼合ZEONOR膜(日本ZEON公司製造，100μm厚)後，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著。 Cut the adhesive sheets 3-1~3-6 produced in Examples 3-1~3-5 and Comparative Example 3-1 into 50mm×80mm before light irradiation, peel off one of the release films, and use a vacuum The press machine presses and presses the exposed adhesive surface with the four sides of the adhesive covering the printing step (absolute pressure 5kPa, temperature 80°C, pressurized pressure 0.04MPa) and prints with a thickness of 80μm on the peripheral part of 3mm The printing surface of soda lime glass (82mm×53mm×0.5mm thick). Then the remaining release film was peeled off, and the ZEONOR film (manufactured by ZEON Japan, 100 μm thick) was pressure-bonded, followed by autoclave treatment (80°C, gauge pressure 0.2MPa, 20 minutes) for final bonding.

其次，自實施有印刷之鈉鈣玻璃側，以波長365nm之紫外線以2000mJ/cm2到達片材X之方式藉由高壓水銀燈照射紫外線，使未實施印刷之開口部，即與透光部相接之部位之片材硬化，製作評價用積層體3-1~3-6。 Next, from the side of the printed soda lime glass, irradiate ultraviolet light with a wavelength of 365nm at 2000mJ/ cm2 to the sheet X by means of a high-pressure mercury lamp, so that the opening without printing is in contact with the transparent part The sheets at the parts were hardened to make laminates 3-1 to 3-6 for evaluation.

對比較例3-2中製作之黏著片材3-7，使用黏著片材3-7，以與上述相同之順序製作實施有印刷之鈉鈣玻璃與ZEONOR膜(日本ZEON公司製造，100μm厚)之積層體後，實施高壓釜處理(80℃，表壓0.2MPa，20分鐘)進行最終貼著，作為評價用積層體3-7。 For the adhesive sheet 3-7 produced in Comparative Example 3-2, use the adhesive sheet 3-7 to produce printed soda lime glass and ZEONOR film (manufactured by ZEON Japan, 100 μm thick) in the same order as above. After the laminated body was formed, autoclave treatment (80°C, gauge pressure 0.2 MPa, 20 minutes) was carried out for final sticking, which was used as laminated body 3-7 for evaluation.

以目視觀察製作之積層體3-1~3-7，將於印刷階差附近黏著材未追隨而殘留氣泡者判定為「×」，將膜於階差附近彎曲，可見應變導致之凹凸不均者判定為「△」，將無氣泡而平滑貼合者判定為「○」 Visually observe the produced laminates 3-1~3-7, judge as "×" if the adhesive material does not follow the adhesive material near the printing step and leave bubbles, and the film is bent near the step difference, and unevenness caused by strain can be seen Those who were judged as "△" and those who fit smoothly without air bubbles were judged as "○".

Figure 110106505-A0305-02-0117-5
Figure 110106505-A0305-02-0117-5

實施例3-1~3-5中製作之黏著片材係於光硬化前後拉伸特性變化較大者。因具有此種特性，故而確認實施例3-1~3-5中製作之黏著片材可於光硬化前具有優異之階差吸收性，另一方面可於光硬化後具有優異之耐發泡性。 The adhesive sheets produced in Examples 3-1 to 3-5 are those with large changes in tensile properties before and after photohardening. Because of this characteristic, it was confirmed that the adhesive sheets produced in Examples 3-1 to 3-5 have excellent step absorption before photocuring, and on the other hand have excellent foaming resistance after photocuring sex.

相對於此，於比較例中，於光硬化前後拉伸特性之變化不充分，故而因比較例3-1中光交聯後之變化不充分，因此成為可靠性較差之片材，比較例3-2中成為光交聯前作業性(保管性)較差之片材。 On the other hand, in Comparative Example, the change in tensile properties before and after photocuring was not sufficient, so the change after photocrosslinking in Comparative Example 3-1 was not sufficient, so it became a sheet with poor reliability. Comparative Example 3 In -2, the workability (storability) before photocrosslinking was poor.

Claims (9)

一種黏著片材，其特徵在於：其係含有(甲基)丙烯酸系共聚物(A)且經光硬化而成者，並且具有凝膠分率未達1%之片材部與凝膠分率為40%以上之片材部，上述凝膠分率未達1%之片材部之藉由示差掃描熱量計(DSC)而測定之玻璃轉移溫度(Tg[S])為-70~-10℃，凝膠分率為40%以上之片材部之藉由示差掃描熱量計(DSC)而測定之玻璃轉移溫度(Tg[H])為-60~+20℃，且凝膠分率為40%以上之片材部之玻璃轉移溫度與凝膠分率未達1%之片材部之玻璃轉移溫度的差(Tg[H]-Tg[S])為3℃以上。 An adhesive sheet, which is characterized in that it contains a (meth)acrylic copolymer (A) and is light-cured, and has a gel fraction of less than 1% of the sheet part and a gel fraction The glass transition temperature (Tg[S]) measured by a differential scanning calorimeter (DSC) for the sheet part with a gel fraction of less than 1% is -70~-10 The glass transition temperature (Tg[H]) of the sheet part with a gel fraction of 40% or more measured by a differential scanning calorimeter (DSC) is -60~+20°C, and the gel fraction is The difference (Tg[H]-Tg[S]) between the glass transition temperature of the sheet portion of 40% or more and the glass transition temperature of the sheet portion of less than 1% gel fraction is 3°C or more. 如請求項1之黏著片材，其係將由含有(甲基)丙烯酸系共聚物(A)、交聯劑(B)及光聚合起始劑(C)之樹脂組合物形成之片材進行部分光硬化而成。 The adhesive sheet according to claim 1, which is a part of a sheet formed from a resin composition containing a (meth)acrylic copolymer (A), a crosslinking agent (B) and a photopolymerization initiator (C) Light hardened. 如請求項1或2之黏著片材，其中上述(甲基)丙烯酸系共聚物(A)係具備巨單體作為分枝成分之接枝共聚物。 The adhesive sheet according to claim 1 or 2, wherein the (meth)acrylic copolymer (A) is a graft copolymer having a macromonomer as a branch component. 如請求項1或2之黏著片材，其中上述(甲基)丙烯酸系共聚物(A)係使玻璃轉移溫度(Tg)未達0℃之單體a1、玻璃轉移溫度(Tg)為0℃以上且未達80℃之單體a2及玻璃轉移溫度(Tg)為80℃以上之單體a3，以a1：a2：a3=10~40：90~35：0~25之莫耳比率進行共聚合而成，且重量平均分子 量為50000~400000之(甲基)丙烯酸系共聚物。 The adhesive sheet according to claim 1 or 2, wherein the above-mentioned (meth)acrylic copolymer (A) is a monomer a1 whose glass transition temperature (Tg) does not reach 0°C, and the glass transition temperature (Tg) is 0°C Monomer a2 above and below 80°C and monomer a3 with a glass transition temperature (Tg) above 80°C are combined at a molar ratio of a1:a2:a3=10~40:90~35:0~25 Polymerized, and the weight average molecule The amount is 50000~400000 (meth)acrylic copolymer. 如請求項1或2之黏著片材，其中於黏著片材之片材面內具有凝膠分率未達1%之片材部與凝膠分率為40%以上之片材部。 The adhesive sheet according to claim 1 or 2, wherein the adhesive sheet has a sheet portion with a gel fraction of less than 1% and a sheet portion with a gel fraction of 40% or more within the sheet surface of the adhesive sheet. 一種黏著片材積層體，其具備積層如請求項1至5中任一項之黏著片材與脫模膜而成之構成。 An adhesive sheet laminate, which is formed by laminating the adhesive sheet according to any one of Claims 1 to 5 and a release film. 一種圖像顯示裝置構成用積層體，其具備介隔如請求項1至5中任一項之黏著片材將2個圖像顯示裝置用構成構件間積層而成之構成。 A laminate for constituting an image display device, comprising a structure in which two constituting members for an image display device are laminated with the adhesive sheet according to any one of Claims 1 to 5 interposed therebetween. 如請求項7之圖像顯示裝置構成用積層體，其中上述圖像顯示裝置構成構件係由觸控面板、圖像顯示面板、表面保護面板及偏光膜所組成之群中選出之任一種或包含兩種以上之組合之積層體。 The laminated body for forming an image display device according to Claim 7, wherein the constituent member of the image display device is any one selected from the group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film or includes A laminate of two or more combinations. 一種圖像顯示裝置，其係使用如請求項7或8之圖像顯示裝置構成用積層體而構成。 An image display device constructed using the laminate for image display device construction according to claim 7 or 8.
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