TW201708475A - An adhesive composition, adhesive sheet and display body consisting of (meth) acrylate polymer, silane coupling agent, and hardening component - Google Patents

An adhesive composition, adhesive sheet and display body consisting of (meth) acrylate polymer, silane coupling agent, and hardening component Download PDF

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TW201708475A
TW201708475A TW105119070A TW105119070A TW201708475A TW 201708475 A TW201708475 A TW 201708475A TW 105119070 A TW105119070 A TW 105119070A TW 105119070 A TW105119070 A TW 105119070A TW 201708475 A TW201708475 A TW 201708475A
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adhesive
meth
adhesive composition
adhesive layer
acrylate
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TWI691570B (en
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Yuki Ozawa
Takayuki Arai
Yoichi Takahashi
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Lintec Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10Homopolymers or copolymers of methacrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/548Silicon-containing compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives 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
    • C09J4/06Organic 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Abstract

The present invention provides an adhesive composition, an adhesive sheet and a display member capable of effectively preventing and suppressing migration. The adhesive composition is formed into an adhesive for laminating a first display member and a second display member having a difference at the surface of the adhesive side; wherein, the first display member and/or the second display member have an electrode at least at the surface of the adhesive side, the adhesive composition contains a (meth) acrylate polymer (A), a silane coupling agent (B) having a mercapto group, and an active energy ray hardening component (C).

Description

黏著性組成物、黏著片及顯示體 Adhesive composition, adhesive sheet and display body

本發明係有關一種能夠使用於觸摸面板等顯示體之黏著性組成物及黏著片、以及使用該等之顯示體者。 The present invention relates to an adhesive composition and an adhesive sheet which can be used for a display body such as a touch panel, and a display body using the same.

近年來,智慧型手機、平板電腦等各種行動電子裝置中,多使用觸摸面板作為顯示器。作為觸摸面板的方式,有電阻膜方式、靜電容量方式等,在如上述之行動電子裝置中主要採用靜電容量方式。 In recent years, in various mobile electronic devices such as smart phones and tablet computers, a touch panel has been frequently used as a display. As a method of the touch panel, there are a resistive film method, an electrostatic capacitance method, and the like, and in the mobile electronic device as described above, a capacitance type is mainly employed.

最近謀求觸摸面板的大型化,作為該種觸摸面板用的電極材料,正在對網狀的金屬電極、例如銅電極或銀電極進行研究。但是,若使習知的黏著劑與金屬電極、尤其銅電極或銀電極接觸而使用,則有時會發生離子遷移(=電化學遷移(Electrochemical migration);以下,簡稱為“遷移”。)。具體而言,在正極中電極溶解而發生斷線,或者在負極中由正極成分的析出形成樹枝結晶而發生短路。 Recently, as the electrode material for such a touch panel has been demanded, the mesh metal electrode, for example, a copper electrode or a silver electrode, has been studied. However, when a conventional adhesive is used in contact with a metal electrode, particularly a copper electrode or a silver electrode, ion migration (=electrochemical migration; hereinafter, simply referred to as "migration") may occur. Specifically, in the positive electrode, the electrode is dissolved to cause disconnection, or in the negative electrode, a branch crystal is formed by precipitation of the positive electrode component to cause a short circuit.

在高溫高濕下對電極施加電壓時尤其容易發生該遷移。若發生該種遷移,則觸摸面板無法正常驅動。尤其最近,電極的微細化及窄間距化正在發展中,容易發生由遷移引起之電極的斷線、短路。 This migration is particularly likely to occur when a voltage is applied to the electrodes under high temperature and high humidity. If this kind of migration occurs, the touch panel will not drive properly. In particular, the miniaturization and narrow pitch of electrodes have been progressing recently, and disconnection and short-circuiting of electrodes due to migration are likely to occur.

然而,專利文獻1中已經揭示含有苯并三唑化合 物作為防鏽劑之觸摸面板用黏著劑組成物。 However, Patent Document 1 discloses that a benzotriazole compound is contained. An adhesive composition for a touch panel as a rust preventive.

【先前技術文獻】 [Previous Technical Literature] 【專利文獻】 [Patent Literature]

專利文獻1:日本特開2014-177611號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2014-177611

但是,作為防鏽劑之苯并三唑化合物即便具有金屬配線的防腐蝕效果,亦無法充分防止並抑制遷移。 However, the benzotriazole compound as a rust preventive agent cannot sufficiently prevent and inhibit migration even if it has an anticorrosive effect of metal wiring.

本發明係鑑於如上述之實際情況而完成者,其目的為提供一種能夠有效地防止並抑制遷移之黏著性組成物、黏著片及顯示體。 The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition, an adhesive sheet, and a display body which can effectively prevent and suppress migration.

為了實現上述目的,第一、本發明提供一種黏著性組成物,其形成用於將至少在貼合之側的面具有段差之第1顯示體構成構件與第2顯示體構成構件進行貼合之黏著劑,該黏著性組成物的特徵為:前述第1顯示體構成構件和/或前述第2顯示體構成構件至少在貼合之側的面具有電極,前述黏著性組成物含有(甲基)丙烯酸酯聚合物(A)、具有巰基之矽烷偶合劑(B)、及活性能量射線硬化性成分(C)(發明1)。 In order to achieve the above object, the present invention provides an adhesive composition which is formed by laminating a first display member constituting member having a step on at least a side of a bonding surface and a second display member constituting member. In the adhesive composition, the first display member constituting member and/or the second display member constituting member have electrodes on at least the surface on the side where they are bonded, and the adhesive composition contains (meth) An acrylate polymer (A), a decane coupling agent (B) having a mercapto group, and an active energy ray curable component (C) (Invention 1).

依由上述發明(發明1)之黏著性組成物得到之黏著劑,尤其藉由具有巰基之矽烷偶合劑(B)的作用,能夠有效地防止並抑制該黏著劑在所接觸之第1顯示體構成構件和/或第2顯示體構成構件的電極中之遷移。 The adhesive obtained by the adhesive composition of the above invention (Invention 1), particularly by the action of the decane coupling agent (B) having a mercapto group, can effectively prevent and suppress the adhesion of the first display body to be contacted The migration in the electrodes of the constituent members and/or the second display constituent members.

上述發明(發明1)中,前述具有巰基之矽烷偶合 劑(B)係含巰基之寡聚物型矽烷偶合劑為較佳(發明2)。 In the above invention (Invention 1), the aforementioned decane coupling having a mercapto group The agent (B) is preferably a thiol-containing oligomer-type decane coupling agent (Invention 2).

上述發明(發明1、2)中,構成前述具有巰基之矽烷偶合劑(B)之有機矽化合物的巰基當量為100g/莫爾以上且1000g/莫爾以下為較佳(發明3)。 In the above inventions (Inventions 1 and 2), the sulfhydryl equivalent of the organic ruthenium compound constituting the decane coupling agent (B) having a mercapto group is preferably 100 g/mol or more and 1000 g/mole or less (Invention 3).

上述發明(發明1~3)中,前述黏著性組成物中之前述具有巰基之矽烷偶合劑(B)的含有量相對於前述(甲基)丙烯酸酯聚合物(A)100質量份為0.01質量份以上且5質量份以下為較佳(發明4)。 In the above invention (Inventions 1 to 3), the content of the decane coupling agent (B) having a mercapto group in the adhesive composition is 0.01 by mass based on 100 parts by mass of the (meth)acrylate polymer (A). More than 5 parts by weight or less is preferred (Invention 4).

上述發明(發明1~4)中,前述黏著性組成物中之前述活性能量射線硬化性成分(C)的含有量相對於前述(甲基)丙烯酸酯聚合物(A)100質量份為0.5質量份以上且50質量份以下為較佳(發明5)。 In the above invention (Inventions 1 to 4), the content of the active energy ray-curable component (C) in the adhesive composition is 0.5 mass based on 100 parts by mass of the (meth) acrylate polymer (A). More than 50 parts by weight or less is preferred (Invention 5).

上述發明(發明1~5)中,前述(甲基)丙烯酸酯聚合物(A)含有3質量%以上且35質量%以下的含羥基單體來作為構成該聚合物之單體單元為較佳(發明6)。 In the above invention (Inventions 1 to 5), it is preferred that the (meth) acrylate polymer (A) contains 3% by mass or more and 35% by mass or less of a hydroxyl group-containing monomer as a monomer unit constituting the polymer. (Invention 6).

上述發明(發明1~6)中,前述黏著性組成物還含有交聯劑(D)為較佳(發明7)。 In the above invention (Inventions 1 to 6), it is preferred that the adhesive composition further contains a crosslinking agent (D) (Invention 7).

第二、本發明提供一種黏著片,其特徵為:具有使前述黏著性組成物(發明1~7)熱交聯而成之硬化前黏著劑層(發明8)。 Secondly, the present invention provides an adhesive sheet comprising a pre-curing adhesive layer obtained by thermally crosslinking the above-mentioned adhesive composition (Inventions 1 to 7) (Invention 8).

上述發明(發明8)中,前述黏著片包括兩片剝離片,前述黏著劑層以與前述兩片剝離片的剝離面接觸之方式被前述剝離片所夾持為較佳(發明9)。 In the above invention (Invention 8), the pressure-sensitive adhesive sheet includes two release sheets, and the pressure-sensitive adhesive layer is preferably sandwiched between the release sheets in contact with the release surfaces of the two release sheets (Invention 9).

第三、本發明提供一種顯示體,其包括:至少在 貼合之側的面具有段差之第1顯示體構成構件;第2顯示體構成構件;及將前述第1顯示體構成構件與前述第2顯示體構成構件相互貼合之黏著劑層,該顯示體的特徵為:前述第1顯示體構成構件和/或前述第2顯示體構成構件至少在貼合之側的面具有電極,前述黏著劑層係藉由活性能量射線的照射使前述黏著片(發明8、9)的硬化前黏著劑層硬化而得到者(發明10)。 Third, the present invention provides a display body including: at least a first display body constituting member having a step on the side of the bonding; a second display constituting member; and an adhesive layer that bonds the first display constituting member and the second display constituting member to each other, and the display The first display body constituent member and/or the second display body constituent member have electrodes on at least the surface on the side where the bonding is performed, and the adhesive layer is caused by irradiation of active energy rays to cause the adhesive sheet ( Inventions 8 and 9) are obtained by hardening the adhesive layer before curing (Invention 10).

依本發明之黏著性組成物、黏著片及顯示體,能夠有效地防止並抑制遷移。 According to the adhesive composition, the adhesive sheet and the display body of the present invention, migration can be effectively prevented and suppressed.

1‧‧‧黏著片 1‧‧‧Adhesive film

10‧‧‧硬化前黏著劑層 10‧‧‧Adhesive layer before hardening

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

2‧‧‧觸控面板 2‧‧‧ touch panel

3‧‧‧顯示體模組 3‧‧‧Display body module

4、11‧‧‧黏著劑層 4, 11‧‧‧ adhesive layer

5a‧‧‧第1薄膜感測器 5a‧‧‧1st film sensor

5b‧‧‧第2薄膜感測器 5b‧‧‧2nd film sensor

51‧‧‧基材薄膜 51‧‧‧Substrate film

52‧‧‧印刷層 52‧‧‧Printing layer

6‧‧‧覆蓋材 6‧‧‧ Covering materials

7‧‧‧印刷層 7‧‧‧Printing layer

第1圖係本發明的一實施形態之黏著片的剖面圖。 Fig. 1 is a cross-sectional view showing an adhesive sheet according to an embodiment of the present invention.

第2圖係表示觸摸面板的一構成例之剖面圖。 Fig. 2 is a cross-sectional view showing a configuration example of a touch panel.

第3圖係試驗例3的遷移防止效果評價中之評價基準的參考圖像。 Fig. 3 is a reference image of the evaluation criteria in the evaluation of the migration prevention effect of Test Example 3.

以下,對本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.

〔黏著性組成物〕 [adhesive composition]

本實施形態之黏著性組成物(以下,有時稱為“黏著性組成物P”。)係形成於將至少在貼合之側的面具有段差之第1顯示體構成構件與第2顯示體構成構件進行貼合之黏著劑之黏著性組成物,第1顯示體構成構件和/或第2顯示體構成構件至少在貼合之側的面具有電極。並且,黏著性組成物P含有(甲 基)丙烯酸酯聚合物(A)、具有巰基之矽烷偶合劑(B)、及活性能量射線硬化性成分(C),還含有交聯劑(D)為較佳。 The adhesive composition of the present embodiment (hereinafter sometimes referred to as "adhesive composition P") is formed on the first display member constituting member and the second display body having a step on at least the surface on the bonding side. The adhesive composition of the adhesive that bonds the constituent members, the first display constituent member and/or the second display constituent member have electrodes on at least the side on which the bonding is performed. Also, the adhesive composition P contains (A The acrylate polymer (A), the decane coupling agent (B) having a mercapto group, and the active energy ray curable component (C) further preferably contain a crosslinking agent (D).

其中,本發明中之“黏著劑”係指使黏著性組成物熱交聯而得到之硬化前黏著劑藉由活性能量射線的照射硬化者。同樣地,“黏著劑層”係指使黏著性組成物熱交聯而形成之硬化前黏著劑層藉由活性能量射線的照射硬化之層。並且,本說明書中,(甲基)丙烯酸酯係指丙烯酸酯及甲基丙烯酸酯這兩者。其他類似術語亦相同。另外,“聚合物”中亦包含“共聚物”的概念。另外,關於顯示體及顯示體構成構件將於後述。 Here, the "adhesive" in the present invention means a person which is hardened by irradiation of an active energy ray before the curing of the adhesive composition obtained by thermally crosslinking the adhesive composition. Similarly, the "adhesive layer" means a layer which is hardened by irradiation of active energy rays before the hardening of the adhesive layer formed by thermally crosslinking the adhesive composition. Further, in the present specification, (meth) acrylate means both acrylate and methacrylate. Other similar terms are also the same. In addition, the concept of "copolymer" is also included in "polymer". In addition, the display body and the display body constituent member will be described later.

藉由本實施形態之黏著性組成物P含有具有巰基之矽烷偶合劑(B),當由黏著性組成物P得到之黏著劑與電極接觸時,在正極中可以防止並抑制電極溶解,在負極中可以防止並抑制形成樹枝結晶。亦即,可以有效地防止並抑制在電極中之遷移(有時將本效果稱為“遷移防止效果”)。藉此,即使上述黏著劑與例如被微細化、窄間距化之電極接觸時,亦可以防止電極的斷線及短路。尤其,當上述電極為觸摸面板的電極時,可以防止由電極的斷線及短路引起之觸摸面板的驅動不良。 The adhesive composition P of the present embodiment contains a decane coupling agent (B) having a mercapto group. When the adhesive obtained from the adhesive composition P is in contact with the electrode, the electrode can be prevented from being dissolved and suppressed in the negative electrode. Formation of dendrite crystals can be prevented and suppressed. That is, migration in the electrode can be effectively prevented and suppressed (this effect is sometimes referred to as "migration prevention effect"). Thereby, even when the above-mentioned adhesive is brought into contact with, for example, a finely divided and narrow-pitched electrode, disconnection and short-circuiting of the electrode can be prevented. In particular, when the electrode is an electrode of a touch panel, it is possible to prevent driving failure of the touch panel caused by disconnection and short circuit of the electrode.

其中,作為上述電極,例如可以舉出由銅、銀等構成之金屬電極(包括網狀、柵狀者)、由錫摻雜氧化銦(ITO)等構成之透明導電膜(包含圖案化者)等。在上述電極中,將以未氧化之金屬為主成分之金屬電極、具體而言由銅或銀構成之金屬電極為較佳。與ITO等金屬氧化物相比,未氧化之金屬 的離子化傾向較高,但依由本實施形態之黏著性組成物P得到之黏著劑,即使在該情況下,亦可以有效地防止電極的斷線及短路。 In addition, examples of the electrode include a metal electrode (including a mesh or a grid) made of copper or silver, and a transparent conductive film made of tin-doped indium oxide (ITO) or the like (including a pattern). Wait. Among the above electrodes, a metal electrode mainly composed of an unoxidized metal, specifically a metal electrode composed of copper or silver is preferable. Unoxidized metal compared to metal oxides such as ITO The ionization tendency is high, but the adhesive obtained by the adhesive composition P of the present embodiment can effectively prevent the disconnection and short-circuit of the electrode even in this case.

並且,由含有具有巰基之矽烷偶合劑(B)之黏著性組成物P得到之黏著劑層在與作為被黏物之顯示體構成構件之界面存在源自具有巰基之矽烷偶合劑(B)之成分,藉此成為與顯示體構成構件之黏附性較高且段差追隨性優異者。具體而言,即使在將使黏著性組成物P熱交聯而形成之硬化前黏著劑層貼附於具有段差之顯示體構成構件並使該硬化前黏著劑層藉由活性能量射線的照射硬化而作為黏著劑層之後,暴露在高溫高濕條件(例如,在85℃、85%RH下72小時)之情況下,亦可以抑制在段差附近產生氣泡、浮起、剝離等(高溫高濕條件下之段差追隨性優異)。藉此,可以抑制在段差附近產生光的反射損失,能夠良好地維持顯示體的畫質。 Further, the adhesive layer obtained from the adhesive composition P containing the decane coupling agent (B) having a mercapto group is derived from the decane coupling agent (B) having a mercapto group at the interface with the constituent member constituting the adherend. The component is thus excellent in adhesion to the display member constituting member and excellent in step followability. Specifically, the pre-curing adhesive layer formed by thermally crosslinking the adhesive composition P is attached to the display member constituting member having a step, and the pre-curing adhesive layer is hardened by irradiation with an active energy ray. After exposure to high temperature and high humidity conditions (for example, at 85 ° C, 85% RH for 72 hours), it is also possible to suppress the generation of bubbles, floating, peeling, etc. in the vicinity of the step (high temperature and high humidity conditions). The next step is excellent in follow-up.) Thereby, it is possible to suppress the reflection loss of light generated in the vicinity of the step, and it is possible to satisfactorily maintain the image quality of the display.

另外,使上述硬化前黏著劑層藉由活性能量射線的照射硬化而成之黏著劑層由於內聚力較高,且顯示比較高的彈性模量,因此抗起泡性優異。並且,在該黏著劑層的與被黏物之界面存在源自具有巰基之矽烷偶合劑(B)之成分,與顯示體構成構件之黏附性較高,因此成為上述抗起泡性更加優異者。例如,即使籍由上述黏著劑層貼合顯示體構成構件之顯示體置於高溫高濕條件下(例如,在85℃、85%RH下72小時)且從由塑膠板等構成之顯示體構成構件產生逸氣之情況下,亦可以抑制在黏著劑層與顯示體構成構件的界面上產生氣泡、浮起、剝離等起泡現象(blister)。 Further, the adhesive layer obtained by curing the pre-curing adhesive layer by irradiation with active energy rays has a high cohesive force and exhibits a relatively high elastic modulus, and thus is excellent in anti-foaming property. Further, since the component derived from the decane coupling agent (B) having a mercapto group is present at the interface between the adhesive layer and the adherend, and the adhesion to the display constituent member is high, the antifoaming property is further excellent. . For example, even if the display body in which the display body constituent member is bonded by the above-mentioned adhesive layer is placed under high temperature and high humidity conditions (for example, at 85 ° C, 85% RH for 72 hours) and formed of a display body composed of a plastic plate or the like. When the member is out of gas, it is possible to suppress occurrence of blister such as bubbles, floating, and peeling at the interface between the adhesive layer and the display member.

(1)(甲基)丙烯酸酯聚合物(A) (1) (meth) acrylate polymer (A)

(甲基)丙烯酸酯聚合物(A)藉由含有烷基的碳數為1~20的(甲基)丙烯酸烷基酯來作為構成該聚合物之單體單元,能夠顯現較佳的黏著性。從該種觀點考慮,(甲基)丙烯酸酯聚合物(A)含有下限值為50質量%以上的烷基的碳數為1~20的(甲基)丙烯酸烷基酯來作為構成該聚合物之單體單元為較佳,含有60質量%以上尤為佳,含有70質量%以上為進一步較佳。若含有50質量%以上的上述(甲基)丙烯酸烷基酯,則(甲基)丙烯酸酯聚合物(A)能夠發揮較佳的黏著性。並且,(甲基)丙烯酸酯聚合物(A)含有上限值為97質量%以下的上述(甲基)丙烯酸烷基酯來作為構成該聚合物之單體單元為較佳,含有90質量%以下尤為佳,含有85質量%以下為進一步較佳。藉由含有97質量%以下的上述(甲基)丙烯酸烷基酯,能夠將較佳量的其他單體成分導入到(甲基)丙烯酸酯聚合物(A)中。 The (meth) acrylate polymer (A) can exhibit a good adhesion by using an alkyl (meth) acrylate having an alkyl group and having 1 to 20 carbon atoms as a monomer unit constituting the polymer. . From such a viewpoint, the (meth) acrylate polymer (A) contains an alkyl (meth) acrylate having an alkyl group having a lower limit of 50% by mass or more and a carbon number of 1 to 20 as a constituent of the polymerization. The monomer unit is preferably contained in an amount of 60% by mass or more, and more preferably 70% by mass or more. When the (meth)acrylic acid alkyl ester is contained in an amount of 50% by mass or more, the (meth)acrylate polymer (A) can exhibit better adhesion. Further, the (meth) acrylate polymer (A) contains the above (meth)acrylic acid alkyl ester having an upper limit of 97% by mass or less, preferably as a monomer unit constituting the polymer, and contains 90% by mass. The following is particularly preferable, and it is further preferable to contain 85% by mass or less. A preferred amount of the other monomer component can be introduced into the (meth) acrylate polymer (A) by containing 97% by mass or less of the above alkyl (meth) acrylate.

作為烷基的碳數為1~20的(甲基)丙烯酸烷基酯,例如可以舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛脂、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷基酯等,其中,從進一步提高黏著性之觀點考慮,含有烷基 的碳數為4~8的(甲基)丙烯酸酯為較佳。該等可以單獨使用,亦可以組合兩種以上使用。另外,烷基的碳數為1~20的(甲基)丙烯酸烷基酯中之烷基係指直鏈狀、支鏈狀或環狀的烷基。 Examples of the (meth)acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. N-butyl acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid N-decyl ester, n-dodecyl (meth)acrylate, tetradecyl (meth)acrylate, cetyl (meth)acrylate, octadecyl (meth)acrylate, ( Methyl)cyclohexyl acrylate, isobornyl (meth)acrylate, adamantyl (meth) acrylate, etc., wherein an alkyl group is contained from the viewpoint of further improving the adhesion. A (meth) acrylate having a carbon number of 4 to 8 is preferred. These may be used singly or in combination of two or more. Further, the alkyl group in the alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group means a linear, branched or cyclic alkyl group.

並且,作為烷基的碳數為1~20的(甲基)丙烯酸烷基酯,組合使用作為均聚物之玻璃轉變溫度(Tg)超過0℃之(70℃以上為較佳的)硬單體和作為均聚物之玻璃轉變溫度(Tg)為0℃以下的軟單體亦為較佳。這是因為,籍由軟單體保持黏著性及柔軟性,並且由硬單體提高內聚力,藉此能夠設為顯示器面板(觸摸面板)中之段差追隨性及抗起泡性更加優異者。 Further, as the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, a glass transition temperature (Tg) which is a homopolymer is used in combination with a hard one (more preferably 70 ° C or higher). A soft monomer having a glass transition temperature (Tg) of 0 ° C or less as a homopolymer is also preferred. This is because the soft monomer maintains adhesion and flexibility, and the cohesive force is increased by the hard monomer, whereby the step difference in tracking performance and the anti-foaming property in the display panel (touch panel) can be further improved.

上述硬單體與軟單體的質量比係5:95~40:60為較佳,20:80~30:70尤為佳。 The mass ratio of the above hard monomer to the soft monomer is preferably 5:95 to 40:60, and particularly preferably 20:80 to 30:70.

作為上述硬單體,例如可以舉出丙烯酸甲酯(Tg10℃)、甲基丙烯酸甲酯(Tg105℃)、丙烯酸異冰片酯(Tg94℃)、甲基丙烯酸異冰片酯(Tg180℃)、丙烯酸金剛烷基酯(Tg115℃)、甲基丙烯酸金剛烷基酯(Tg141℃)等。該等可以單獨使用,亦可以組合兩種以上使用。 Examples of the hard monomer include methyl acrylate (Tg 10 ° C), methyl methacrylate (Tg 105 ° C), isobornyl acrylate (Tg 94 ° C), isobornyl methacrylate (Tg 180 ° C), and acrylic acid. Alkyl ester (Tg 115 ° C), adamantyl methacrylate (Tg 141 ° C), and the like. These may be used singly or in combination of two or more.

在上述硬單體中,從防止對黏著性及透明性等其他特性之悪影響並且進一步發揮硬單體的性能之觀點考慮,丙烯酸甲酯、甲基丙烯酸甲酯及丙烯酸異冰片酯為較佳。若還考慮黏著性,則丙烯酸甲酯及甲基丙烯酸甲酯更為佳,甲基丙烯酸甲酯尤為佳。 Among the above hard monomers, methyl acrylate, methyl methacrylate and isobornyl acrylate are preferred from the viewpoint of preventing the influence on other properties such as adhesion and transparency and further exhibiting the performance of the hard monomer. Methyl acrylate and methyl methacrylate are more preferred if adhesion is also considered, and methyl methacrylate is particularly preferred.

作為上述軟單體,較佳地可以舉出具有碳數為2 ~12的直鏈狀或支鏈狀的烷基之丙烯酸烷基酯。例如,較佳地可以舉出丙烯酸2-乙基己酯(Tg-70℃)、丙烯酸正丁酯(Tg-54℃)等。該等可以單獨使用,亦可以組合兩種以上使用。 As the soft monomer, preferably, the carbon number is 2 ~12 linear or branched alkyl alkyl acrylate. For example, 2-ethylhexyl acrylate (Tg-70 ° C), n-butyl acrylate (Tg-54 ° C), and the like are preferable. These may be used singly or in combination of two or more.

(甲基)丙烯酸酯聚合物(A)含有含反應性官能基單體來作為構成該聚合物之單體單元為較佳。源自該含反應性官能基單體之反應性官能基與後述之交聯劑(D)進行反應,藉此形成交聯結構(三維網狀結構),可以得到具有所希望的內聚力之硬化前黏著劑。 The (meth) acrylate polymer (A) preferably contains a reactive functional group-containing monomer as a monomer unit constituting the polymer. The reactive functional group derived from the reactive functional group-containing monomer is reacted with a crosslinking agent (D) described later to form a crosslinked structure (three-dimensional network structure), and a pre-hardening property having a desired cohesive force can be obtained. Adhesive.

作為(甲基)丙烯酸酯聚合物(A)中作為構成該聚合物之單體單元而含有之含反應性官能基單體,較佳地可以舉出在分子內具有羥基之單體(含羥基單體)、在分子內具有羧基之單體(含羧基單體)、在分子內具有胺基之單體(含胺基單體)等。在該等之中,與交聯劑(D)之反應性及耐濕熱白化性優異且對電極之悪影響較少的含羥基單體尤為佳。 The reactive functional group monomer contained as the monomer unit constituting the polymer in the (meth) acrylate polymer (A) is preferably a monomer having a hydroxyl group in the molecule (hydroxy group-containing) Monomer), a monomer having a carboxyl group in a molecule (a carboxyl group-containing monomer), a monomer having an amine group in a molecule (an amine group-containing monomer), and the like. Among these, a hydroxyl group-containing monomer which is excellent in reactivity with a crosslinking agent (D) and wet heat whitening resistance and which has little influence on the electrode is particularly preferable.

作為含羥基單體,例如可以舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯等。其中,從所得到之(甲基)丙烯酸酯聚合物(A)中之羥基與交聯劑(D)之反應性及與其他單體之共聚性的觀點考慮,(甲基)丙烯酸2-羥基乙酯或(甲基)丙烯酸4-羥基丁酯為較佳。該等可以單獨使用,亦可以組合使用兩種以上。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-(meth)acrylate. A hydroxyalkyl (meth)acrylate such as hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate. Among them, from the viewpoint of the reactivity of the hydroxyl group in the obtained (meth)acrylate polymer (A) with the crosslinking agent (D) and the copolymerizability with other monomers, 2-hydroxyl (meth)acrylate Ethyl ester or 4-hydroxybutyl (meth)acrylate is preferred. These may be used alone or in combination of two or more.

作為含羧基單體,例如可以舉出丙烯酸、甲基丙 烯酸、巴豆酸、馬來酸、衣康酸、檸康酸等乙烯性不飽和羧酸。其中,從所得到之(甲基)丙烯酸酯聚合物(A)中之羧基與交聯劑(D)之反應性及與其他單體之共聚性的觀點考慮,丙烯酸為較佳。該等可以單獨使用,亦可以組合使用兩種以上。 Examples of the carboxyl group-containing monomer include acrylic acid and methyl propyl acrylate. An ethylenically unsaturated carboxylic acid such as an acid, a crotonic acid, a maleic acid, an itaconic acid or a citraconic acid. Among them, acrylic acid is preferred from the viewpoints of the reactivity of the carboxyl group in the obtained (meth)acrylate polymer (A) with the crosslinking agent (D) and the copolymerizability with other monomers. These may be used alone or in combination of two or more.

作為含胺基單體,例如可以舉出(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸正丁基胺基乙酯等。該等可以單獨使用,亦可以組合兩種以上使用。 Examples of the amine group-containing monomer include aminoethyl (meth)acrylate and n-butylaminoethyl (meth)acrylate. These may be used singly or in combination of two or more.

(甲基)丙烯酸酯聚合物(A)含有下限值為3質量%以上的含羥基單體來作為構成該聚合物之單體單元為較佳,含有10質量%以上尤為佳,含有15質量%以上為進一步較佳。並且,(甲基)丙烯酸酯聚合物(A)含有上限值為35質量%以下的含羥基單體來作為構成該聚合物之單體單元為較佳,含有30質量%以下尤為佳,含有25質量%以下為進一步較佳。若(甲基)丙烯酸酯聚合物(A)以上述量含有含羥基單體來作為單體單元,則在所得到之黏著劑中會殘留既定量的羥基。羥基係親水性基,若該種親水性基在黏著劑中存在既定量,則即使在黏著劑置於高溫高濕條件下之情況下,與在該高溫高濕條件下浸入黏著劑中之水分之相容性亦良好,其結果,可以抑制恢復常溫常濕時的黏著劑的白化(耐濕熱白化性優異)。 The (meth) acrylate polymer (A) contains a hydroxyl group-containing monomer having a lower limit of 3% by mass or more, preferably as a monomer unit constituting the polymer, more preferably 10% by mass or more, and particularly preferably 15% by mass. More than % is further preferred. In addition, the (meth) acrylate polymer (A) contains a hydroxyl group-containing monomer having an upper limit of 35% by mass or less, and is preferably a monomer unit constituting the polymer, and particularly preferably contains 30% by mass or less. 25 mass% or less is further preferable. When the (meth) acrylate polymer (A) contains a hydroxyl group-containing monomer as a monomer unit in the above amount, a predetermined amount of a hydroxyl group remains in the obtained adhesive. a hydroxy-based hydrophilic group, if the hydrophilic group is present in the adhesive, even if the adhesive is placed under high temperature and high humidity conditions, and immersed in the adhesive under the high temperature and high humidity conditions The compatibility is also good, and as a result, it is possible to suppress whitening (excellent resistance to moist heat whitening) of the adhesive when the normal temperature and normal humidity are restored.

作為白化抑制程度,施加高溫高濕條件之後恢復常溫常濕時的黏著劑層的霧度值(按照JIS K7136:2000測定之值)係1.0%以下為較佳,0.9%以下尤為佳,0.8%以下為進一步較佳。另外,黏著劑層在常態時亦具有如上述般的霧度值 為較佳。若霧度值為1.0%以下,則透明性非常高,成為適合用於光學用途者。 The degree of whitening inhibition is preferably 1.0% or less, more preferably 0.9% or less, and 0.8% or less, in the case where the temperature of the adhesive layer after normal temperature and high humidity is applied after the application of the high temperature and high humidity conditions (the value measured according to JIS K7136:2000) is preferably 1.0% or less. The following is further preferred. In addition, the adhesive layer also has a haze value as described above in a normal state. It is better. When the haze value is 1.0% or less, the transparency is extremely high, and it is suitable for use in optical applications.

但是,若如上所述般親水性基在黏著劑中存在既定量,則黏著劑容易吸進水,與該黏著劑接觸之電極中容易發生遷移。但是,本實施形態之黏著性組成物P藉由含有具有巰基之矽烷偶合劑(B),能夠有效地防止並抑制所接觸之電極中發生遷移。 However, if the hydrophilic group is present in the adhesive as described above, the adhesive easily absorbs water, and migration is likely to occur in the electrode in contact with the adhesive. However, the adhesive composition P of the present embodiment can effectively prevent and suppress migration in the electrode to be contacted by containing the decane coupling agent (B) having a mercapto group.

(甲基)丙烯酸酯聚合物(A)不含含羧基單體來作為構成該聚合物之單體單元為較佳,但容許含有既定量。這是因為,羧基係酸成分,因此通常擔心對象構件的遷移,但由含有具有巰基之矽烷偶合劑(B)之黏著性組成物P得到之黏著劑,即使存在羧基,亦能夠發揮遷移防止效果。具體而言,容許在(甲基)丙烯酸酯聚合物(A)中以5質量%以下、較佳地以2質量%以下的量含有含羧基單體來作為單體單元。 The (meth) acrylate polymer (A) does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer, but it is allowed to contain a predetermined amount. This is because the carboxyl group-based acid component is generally worried about the migration of the target member. However, the adhesive obtained from the adhesive composition P containing the decane coupling agent (B) having a mercapto group can exhibit a migration prevention effect even if a carboxyl group is present. . Specifically, the carboxyl group-containing monomer is contained in the (meth) acrylate polymer (A) in an amount of 5 mass% or less, preferably 2 mass% or less, as a monomer unit.

(甲基)丙烯酸酯聚合物(A)根據需要可以含有其他單體來作為構成該聚合物之單體單元。作為其他單體,還為了不妨礙含反應性官能基單體的作用,係不含具有反應性之官能基之單體為較佳。作為該種其他單體,例如可以舉出(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯、(甲基)丙烯醯基嗎啉等具有非交聯性的3級胺基之(甲基)丙烯酸酯、(甲基)丙烯醯胺、二甲基丙烯醯胺、乙酸乙烯酯、苯乙烯等。該等可以單獨使用,亦可以組合兩種以上使用。 The (meth) acrylate polymer (A) may contain other monomers as a monomer unit constituting the polymer, as needed. As the other monomer, in order not to hinder the action of the reactive functional group-containing monomer, a monomer having no reactive functional group is preferable. Examples of such other monomers include (meth)acrylic acid alkoxyalkyl esters such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate, and (meth)acrylic acid. Non-crosslinkable tertiary amine group such as N,N-dimethylaminoethyl ester, N,N-dimethylaminopropyl (meth)acrylate, or (meth)propenylmorpholine (Meth) acrylate, (meth) acrylamide, dimethyl methacrylate, vinyl acetate, styrene, and the like. These may be used singly or in combination of two or more.

(甲基)丙烯酸酯聚合物(A)的聚合形態可以係無規共聚物,亦可以係嵌段共聚物。 The polymerization form of the (meth) acrylate polymer (A) may be a random copolymer or a block copolymer.

(甲基)丙烯酸酯聚合物(A)的重量平均分子量的下限值係20萬以上為較佳,30萬以上尤為佳,40萬以上為進一步較佳。若(甲基)丙烯酸酯聚合物(A)的重量平均分子量的下限值為上述以上,則所得到之黏著劑成為高溫高濕條件下之段差追隨性更加優異者。另外,本說明書中之重量平均分子量係藉由凝膠滲透層析(GPC)法測定之標準聚苯乙烯換算的值。 The lower limit of the weight average molecular weight of the (meth) acrylate polymer (A) is preferably 200,000 or more, more preferably 300,000 or more, and still more preferably 400,000 or more. When the lower limit of the weight average molecular weight of the (meth) acrylate polymer (A) is at least the above, the obtained adhesive is more excellent in the step-following property under high-temperature and high-humidity conditions. Further, the weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.

並且,(甲基)丙烯酸酯聚合物(A)的重量平均分子量的上限值係100萬以下為較佳,90萬以下尤為佳,70萬以下為進一步較佳。若(甲基)丙烯酸酯聚合物(A)的重量平均分子量的上限值為上述以下,則所得到之硬化前黏著劑層成為貼附時的段差追隨性更加優異者。 Further, the upper limit of the weight average molecular weight of the (meth) acrylate polymer (A) is preferably 1,000,000 or less, more preferably 900,000 or less, and still more preferably 700,000 or less. When the upper limit of the weight average molecular weight of the (meth) acrylate polymer (A) is at most the above, the obtained adhesive layer before curing becomes more excellent in the step-following property at the time of attachment.

另外,在黏著性組成物P中,(甲基)丙烯酸酯聚合物(A)可以單獨使用一種,亦可以組合使用兩種以上。 Further, in the adhesive composition P, the (meth) acrylate polymer (A) may be used alone or in combination of two or more.

(2)具有巰基之矽烷偶合劑(B) (2) a decane coupling agent having a mercapto group (B)

具有巰基之矽烷偶合劑(B)由在分子內具有至少1個巰基、具有至少1個烷氧基矽烷基之有機矽化合物構成。若考慮所得到之黏著劑的用途,則具有巰基之矽烷偶合劑(B)係具有光透過性者、例如實質上透明者為較佳。 The decane coupling agent (B) having a mercapto group is composed of an organic ruthenium compound having at least one mercapto group in the molecule and having at least one alkoxyalkyl group. In consideration of the use of the obtained adhesive, it is preferred that the decyl coupling agent (B) having a mercapto group is light transmissive, for example, substantially transparent.

作為具有巰基之矽烷偶合劑(B)的具體例,可以舉出3-巰丙基三甲氧基矽烷、3-巰丙基三乙氧基矽烷、3-巰丙基二甲氧基甲基矽烷等含巰基之低分子型矽烷偶合劑;3-巰丙 基三甲氧基矽烷、3-巰丙基三乙氧基矽烷、3-巰丙基二甲氧基甲基矽烷等含巰基之矽烷化合物與甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等含烷基之矽烷化合物的共縮合物等含巰基之寡聚物型矽烷偶合劑等。其中,遷移防止效果更加優異且作業性亦良好的含巰基之寡聚物型矽烷偶合劑為較佳,含巰基之矽烷化合物與含烷基之矽烷化合物的共縮合物尤為佳,3-巰丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮合物為進一步較佳。該等可以單獨使用一種,亦可以組合兩種以上使用。 Specific examples of the decane coupling agent (B) having a mercapto group include 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, and 3-mercaptopropyldimethoxymethylnonane. a low molecular weight decane coupling agent containing a thiol group; A decyl-containing decane compound such as trimethoxy decane, 3-mercaptopropyltriethoxy decane or 3-mercaptopropyldimethoxymethyl decane, and methyltriethoxy decane, ethyltriethoxy A sulfhydryl group-containing oligomer-type decane coupling agent such as a cocondensate of an alkyl group-containing decane compound such as decane, methyltrimethoxydecane or ethyltrimethoxydecane. Among them, a mercapto group-containing oligomer-type decane coupling agent which is more excellent in migration prevention effect and workability is preferable, and a co-condensation product of a mercapto group-containing decane compound and an alkyl group-containing decane compound is particularly preferable. A cocondensate of a trimethoxy decane and methyl triethoxy decane is further preferred. These may be used alone or in combination of two or more.

構成具有巰基之矽烷偶合劑(B)之有機矽化合物的巰基當量的下限值係100g/莫爾以上為較佳,120g/莫爾以上尤為佳,150g/莫爾以上為進一步較佳。藉由如上述設定下限值,將與(甲基)丙烯酸酯聚合物(A)之極性差設在適當的範圍內,從而能夠設為上述矽烷偶合劑(B)在黏著性組成物P中之分散性較佳者。 The lower limit of the thiol equivalent of the organic hydrazine compound constituting the decane coupling agent (B) having a mercapto group is preferably 100 g/mole or more, more preferably 120 g/mole or more, and still more preferably 150 g/mole or more. By setting the lower limit as described above, the polarity difference from the (meth) acrylate polymer (A) is set to an appropriate range, whereby the decane coupling agent (B) can be used as the viscous composition P. The dispersion is better.

構成具有巰基之矽烷偶合劑(B)之有機矽化合物的巰基當量的上限值係1000g/莫爾以下為較佳,800g/莫爾以下尤為佳,500g/莫爾以下為進一步較佳。藉由如上述設定上限值,能夠防止由與(甲基)丙烯酸酯聚合物(A)之相分離引起之光學特性的惡化。 The upper limit of the thiol equivalent of the organic hydrazine compound constituting the decane coupling agent (B) having a mercapto group is preferably 1000 g/mole or less, more preferably 800 g/mole or less, and further preferably 500 g/mole or less. By setting the upper limit as described above, deterioration of optical characteristics due to phase separation from the (meth) acrylate polymer (A) can be prevented.

黏著性組成物P中之具有巰基之矽烷偶合劑(B)的含有量相對於(甲基)丙烯酸酯聚合物(A)100質量份,下限值係0.01質量份以上為較佳,0.05質量份以上尤為佳,0.1質量份以上為進一步較佳。並且,上限值係5質量份以下 為較佳,1.5質量份以下尤為佳,1.0質量份以下為進一步較佳。藉由具有巰基之矽烷偶合劑(B)的含有量在上述範圍,成為遷移防止效果更加優異者。 The content of the decane coupling agent (B) having a mercapto group in the adhesive composition P is preferably 0.01 parts by mass or less, and preferably 0.05 parts by mass based on 100 parts by mass of the (meth) acrylate polymer (A). More preferably, it is more preferably 0.1 part by mass or more. Further, the upper limit is 5 parts by mass or less. Preferably, it is especially preferably 1.5 parts by mass or less, and more preferably 1.0 part by mass or less. When the content of the decane coupling agent (B) having a mercapto group is in the above range, the migration preventing effect is further excellent.

並且,(甲基)丙烯酸酯聚合物(A)每100g的、矽烷偶合劑(B)中之巰基的莫爾數(巰基量)的下限值係0.01mmol以上為較佳,0.1mmol以上尤為佳,0.2mmol以上為進一步較佳。並且,上述莫爾數的上限值係30mmol以下為較佳,5mmol以下尤為佳,1.5mmol以下為進一步較佳。藉由矽烷偶合劑(B)的巰基相對於(甲基)丙烯酸酯聚合物(A)之莫爾數在上述範圍,能夠設為遷移防止效果更加優異者。 Further, the lower limit of the molar number (the amount of sulfhydryl groups) of the fluorenyl group in the decane coupling agent (B) per 100 g of the (meth) acrylate polymer (A) is preferably 0.01 mmol or more, and particularly preferably 0.1 mmol or more. Preferably, 0.2 mmol or more is further preferred. Further, the upper limit of the molar number is preferably 30 mmol or less, more preferably 5 mmol or less, and still more preferably 1.5 mmol or less. When the molar ratio of the fluorenyl group of the decane coupling agent (B) to the (meth) acrylate polymer (A) is in the above range, it is possible to further improve the migration prevention effect.

(3)活性能量射線硬化性成分(C) (3) Active energy ray hardening component (C)

若黏著性組成物P含有活性能量射線硬化性成分(C),則使該黏著性組成物P熱交聯而成之硬化前黏著劑藉由活性能量射線的照射硬化時,活性能量射線硬化性成分(C)相互聚合,推斷該聚合之活性能量射線硬化性成分(C)係纏繞於(甲基)丙烯酸酯聚合物(A)的交聯結構(三維網狀結構)者。具有該種高次結構之黏著劑由於內聚力較高且顯示比較高的彈性模量,因此抗起泡性優異。 When the adhesive composition P contains the active energy ray-curable component (C), the adhesive agent P is thermally crosslinked and the pre-curing adhesive is cured by irradiation with active energy rays, and the active energy ray hardenability is obtained. The component (C) is polymerized with each other, and it is estimated that the polymerized active energy ray-curable component (C) is entangled in the crosslinked structure (three-dimensional network structure) of the (meth) acrylate polymer (A). The adhesive having such a high-order structure is excellent in anti-foaming property because it has a high cohesive force and exhibits a relatively high elastic modulus.

活性能量射線硬化性成分(C)只要係藉由活性能量射線的照射而硬化從而得到上述效果之成分,則並沒有特別限制,可以係單體、寡聚物或聚合物中的任何一種,亦可以係該等的混合物。其中,較佳地可以舉出與(甲基)丙烯酸酯聚合物(A)等之相容性優異之分子量小於1000的多官能丙烯酸酯系單體。 The active energy ray-curable component (C) is not particularly limited as long as it is cured by irradiation with an active energy ray to obtain the above-described effects, and may be any of a monomer, an oligomer, or a polymer. These mixtures can be used. Among them, a polyfunctional acrylate monomer having a molecular weight of less than 1,000 which is excellent in compatibility with a (meth) acrylate polymer (A) or the like is preferably used.

作為分子量小於1000的多官能丙烯酸酯系單體,例如可以舉出1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸酯二(甲基)丙烯酸酯、羥基新戊酸新戊二醇二(甲基)丙烯酸酯、二環戊酯二(甲基)丙烯酸酯、己內酯改性二環戊基二(甲基)丙烯酸酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、二(丙烯醯氧基乙基)異氰脲酸酯、烯丙基化環己基二(甲基)丙烯酸酯、乙氧基化雙酚A二丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀等2官能型;三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改性二季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、三(丙烯醯氧基乙基)異氰脲酸酯、ε-己內酯改性三-(2-(甲基)丙烯醯氧基乙基)異氰脲酸酯等3官能型;二甘油四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等4官能型;丙酸改性二季戊四醇五(甲基)丙烯酸酯等5官能型;二季戊四醇六(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等6官能型等。在上述之中,從所得到之黏著劑的抗起泡性的觀點考慮,季戊四醇三(甲基)丙烯酸酯及ε-己內酯改性三-(2-(甲基)丙烯醯氧基乙基)異氰脲酸酯為較佳。該等可以單獨使用一種,亦可以組合使用兩種以上。 Examples of the polyfunctional acrylate monomer having a molecular weight of less than 1,000 include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopenta-2. Alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(methyl) Acrylate, dicyclopentyl ester di(meth)acrylate, caprolactone modified dicyclopentyl di(meth)acrylate, ethylene oxide modified di(meth)acrylate, di(propylene) Ethoxyethyl)isocyanurate, allylated cyclohexyl di(meth)acrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-propene oxime) 2-functional type such as oxyethoxy)phenyl]anthracene; trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylic acid Ester, pentaerythritol tri(meth) acrylate, propylene oxide modified trimethylolpropane tri(meth) acrylate, tris(propylene decyloxyethyl) isocyanurate, ε-caprolactone Tris-(2-(methyl)propenyloxy a trifunctional type such as isocyanurate; a tetrafunctional type such as diglycerin tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; propionic acid-modified dipentaerythritol penta(meth)acrylate, etc. 5 Functional type; dipentaerythritol hexa(meth) acrylate, caprolactone-modified dipentaerythritol hexa(meth) acrylate, etc., etc. Among the above, pentaerythritol tri(meth)acrylate and ε-caprolactone-modified tris-(2-(methyl)acryloxyloxy B are considered from the viewpoint of antifoaming property of the obtained adhesive. Isocyanurate is preferred. These may be used alone or in combination of two or more.

作為活性能量射線硬化性成分(C),亦可以使用活性能量射線硬化型的丙烯酸酯系寡聚物。該丙烯酸酯系寡聚物為重量平均分子量50,000以下者為較佳。作為該種丙烯酸 酯系寡聚物的例子,可以舉出聚酯丙烯酸酯系、環氧丙烯酸酯系、胺基甲酸酯丙烯酸酯系、聚醚丙烯酸酯系、聚丁二烯丙烯酸酯系、矽酮丙烯酸酯系等。 As the active energy ray-curable component (C), an active energy ray-curable acrylate-based oligomer can also be used. The acrylate-based oligomer is preferably a weight average molecular weight of 50,000 or less. As the kind of acrylic acid Examples of the ester-based oligomer include a polyester acrylate type, an epoxy acrylate type, an urethane acrylate type, a polyether acrylate type, a polybutadiene acrylate type, and an anthrone acrylate. Department and so on.

上述丙烯酸酯系寡聚物的重量平均分子量為50,000以下為較佳,500~50,000尤為佳,3,000~40,000為進一步較佳。該等丙烯酸酯系寡聚物可以單獨使用一種,亦可以組合使用兩種以上。 The acrylate-based oligomer preferably has a weight average molecular weight of 50,000 or less, more preferably 500 to 50,000, and still more preferably 3,000 to 40,000. These acrylate-based oligomers may be used alone or in combination of two or more.

並且,作為活性能量射線硬化性成分(C),亦可以使用在側鏈中導入有具有(甲基)丙烯醯基之基團之加成丙烯酸酯系聚合物。該種加成丙烯酸酯系聚合物可藉由使用(甲基)丙烯酸酯與在分子內具有交聯性官能基之單體的共聚物,並使該共聚物的交聯性官能基的一部分、與具有能與(甲基)丙烯醯基以及交聯性官能基發生反應的基團之化合物進行反應來得到。 Further, as the active energy ray-curable component (C), an addition acrylate-based polymer having a group having a (meth)acryl fluorenyl group introduced into a side chain can also be used. The addition acrylate polymer can be a copolymer of a (meth) acrylate and a monomer having a crosslinkable functional group in a molecule, and a part of the crosslinkable functional group of the copolymer, It is obtained by reacting with a compound having a group reactive with a (meth) acrylonitrile group and a crosslinkable functional group.

上述加成丙烯酸酯系聚合物的重量平均分子量為5萬~90萬左右為較佳,10萬~50萬左右尤為佳。 The weight average molecular weight of the above-mentioned addition acrylate-based polymer is preferably from 50,000 to 900,000, particularly preferably from about 100,000 to about 500,000.

活性能量射線硬化性成分(C)既可以從前述多官能丙烯酸酯系單體、丙烯酸酯系寡聚物及加成丙烯酸酯系聚合物中選擇使用一種,亦可以組合使用兩種以上,亦可以與該等以外的活性能量射線硬化性成分組合使用。 The active energy ray-curable component (C) may be selected from the above-mentioned polyfunctional acrylate-based monomer, acrylate-based oligomer, and addition acrylate-based polymer, or two or more types may be used in combination. It is used in combination with active energy ray curable components other than these.

從提高所得到之黏著劑的內聚力而設為抗起泡性優異者之觀點考慮,黏著性組成物P中之活性能量射線硬化性成分(C)的含有量相對於(甲基)丙烯酸酯聚合物(A)100質量份,下限值係0.5質量份以上為較佳,1.0質量份以上更 為佳,3.0質量份以上尤為佳。另一方面,從防止活性能量射線硬化性成分(C)與(甲基)丙烯酸酯聚合物(A)相分離之觀點考慮,上述含有量的上限值係50質量份以下為較佳,20質量份以下更為佳,若進一步考慮使抗起泡性變得更加良好之觀點,則12質量份以下尤為佳。 The content of the active energy ray-curable component (C) in the adhesive composition P is increased relative to the (meth) acrylate polymerization, from the viewpoint of improving the cohesive force of the obtained adhesive and improving the foaming resistance. 100 parts by mass of the substance (A), and the lower limit is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more. Preferably, 3.0 parts by mass or more is particularly preferred. On the other hand, from the viewpoint of preventing separation of the active energy ray-curable component (C) from the (meth) acrylate polymer (A), the upper limit of the content is preferably 50 parts by mass or less, and 20 is preferable. It is more preferably equal to or less than the mass part, and further preferably 12 parts by mass or less, from the viewpoint of further improving the anti-foaming property.

(4)交聯劑(D) (4) Crosslinking agent (D)

黏著性組成物P含有交聯劑(D)為較佳。黏著性組成物P藉由含有交聯劑(D),使(甲基)丙烯酸酯聚合物(A)交聯而形成三維網狀結構,能夠進一步提高所得到之黏著劑的內聚力,從而進一步提高高溫高濕條件下之段差追隨性。 It is preferred that the adhesive composition P contains a crosslinking agent (D). The adhesive composition P crosslinks the (meth) acrylate polymer (A) by the crosslinking agent (D) to form a three-dimensional network structure, and the cohesive force of the obtained adhesive can be further improved, thereby further improving Segmental follow-up under high temperature and high humidity conditions.

作為交聯劑(D),只要係與(甲基)丙烯酸酯聚合物(A)所具有之反應性基進行反應者即可,例如可以舉出異氰酸酯系交聯劑、環氧系交聯劑、胺系交聯劑、三聚氰胺系交聯劑、氮丙啶系交聯劑、聯胺系交聯劑、醛系交聯劑、噁唑啉系交聯劑、金屬醇鹽系交聯劑、金屬螯合系交聯劑、金屬鹽系交聯劑、銨鹽系交聯劑等。當(甲基)丙烯酸酯聚合物(A)含有含羥基單體來作為構成該聚合物之單體單元時,使用與該羥基之反應性優異之異氰酸酯系交聯劑為較佳。另外,交聯劑(D)可以單獨使用一種,或者組合兩種以上使用。 The crosslinking agent (D) may be reacted with a reactive group of the (meth) acrylate polymer (A), and examples thereof include an isocyanate crosslinking agent and an epoxy crosslinking agent. , an amine crosslinking agent, a melamine crosslinking agent, an aziridine crosslinking agent, a hydrazine crosslinking agent, an aldehyde crosslinking agent, an oxazoline crosslinking agent, a metal alkoxide crosslinking agent, A metal chelate crosslinking agent, a metal salt crosslinking agent, an ammonium salt crosslinking agent, and the like. When the (meth) acrylate polymer (A) contains a hydroxyl group-containing monomer as a monomer unit constituting the polymer, an isocyanate crosslinking agent excellent in reactivity with the hydroxy group is preferably used. Further, the crosslinking agent (D) may be used alone or in combination of two or more.

異氰酸酯系交聯劑係至少含有聚異氰酸酯化合物者。作為聚異氰酸酯化合物,例如可以舉出甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族聚異氰酸酯、六亞甲基二異氰酸酯等脂肪族聚異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯等脂環式聚異氰酸酯等 及該等的縮二脲體、異氰脲酸酯體、以及乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等作為與含低分子活性氫化合物之反應物之加成物等。其中,從與羥基之反應性的觀點考慮,三羥甲基丙烷改性的芳香族聚異氰酸酯為較佳,三羥甲基丙烷改性甲苯二異氰酸酯尤為佳。 The isocyanate crosslinking agent is a compound containing at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate and benzodimethyl diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; and isophorone diisocyanate. And alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate And the biuret, isocyanurate, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. as a reaction with a low molecular weight active hydrogen compound Adults and so on. Among them, trimethylolpropane-modified aromatic polyisocyanate is preferred from the viewpoint of reactivity with a hydroxyl group, and trimethylolpropane-modified toluene diisocyanate is particularly preferred.

黏著性組成物P中之交聯劑(D)的含有量相對於(甲基)丙烯酸酯聚合物(A)100質量份,下限值係0.001質量份以上為較佳,0.01質量份以上尤為佳,0.02質量份以上為進一步較佳。並且,上限值係10質量份以下為較佳,5質量份以下尤為佳,1質量份以下為進一步較佳。 The content of the crosslinking agent (D) in the adhesive composition P is preferably 0.001 part by mass or more based on 100 parts by mass of the (meth) acrylate polymer (A), and more preferably 0.01 part by mass or more. Preferably, 0.02 parts by mass or more is further preferred. Further, the upper limit is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less.

藉由交聯劑(D)的含有量在上述範圍,成為所得到之黏著劑的內聚力較佳者,黏著劑的高溫高濕條件下之段差追隨性進一步得到提高。 When the content of the crosslinking agent (D) is in the above range, the cohesive force of the obtained adhesive is preferable, and the step followability of the adhesive under high temperature and high humidity conditions is further improved.

(5)光聚合起始劑(E) (5) Photopolymerization initiator (E)

當使硬化前黏著劑硬化時使用紫外線來作為對硬化前黏著劑照射之活性能量射線時,黏著性組成物P還含有光聚合起始劑(E)為較佳。如此,藉由含有光聚合起始劑(E),能夠使活性能量射線硬化性成分(C)高效地聚合,並且能夠減少聚合硬化時間及活性能量射線的照射量。 When the ultraviolet ray is used as the active energy ray for irradiating the adhesive before curing, the adhesive composition P further contains a photopolymerization initiator (E). By containing the photopolymerization initiator (E), the active energy ray-curable component (C) can be efficiently polymerized, and the polymerization hardening time and the amount of irradiation of the active energy ray can be reduced.

作為該種光聚合起始劑(E),例如可以舉出安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香正丁醚、安息香異丁醚、苯乙酮、二甲基胺基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基) 苯基]-2-嗎啉代-丙-1-酮、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、二苯甲酮、對苯基二苯甲酮、4,4’-二乙基胺基二苯甲酮、二氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、2-胺基蒽醌、2-甲基噻噸酮、2-乙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、苄基二甲基縮酮、苯乙酮二甲基縮酮、對二甲基胺基苯甲酸酯、寡聚[2-羥基-2-甲基-1[4-(1-甲基乙烯基)苯基]丙酮]、2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。該等可以單獨使用,亦可以組合使用兩種以上。 Examples of such a photopolymerization initiator (E) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, and dimethylaminobenzene. Ethyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)one, benzophenone, p-phenylene Benzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylindole, 2-ethylhydrazine, 2-tert-butylfluorene, 2- Aminoguanidine, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoate, oligomeric [2-hydroxy-2-methyl-1[4-(1-methylethylene) Phenyl]acetone], 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, and the like. These may be used alone or in combination of two or more.

黏著性組成物P中之光聚合起始劑(E)的含有量相對於活性能量射線硬化性成分(C)100質量份,下限值係0.1質量份以上為較佳,1質量份以上尤為佳。並且,上限值係30質量份以下為較佳,10質量份以下尤為佳。 The content of the photopolymerization initiator (E) in the adhesive composition P is preferably 0.1 part by mass or less based on 100 parts by mass of the active energy ray-curable component (C), and more preferably 1 part by mass or more. good. Further, the upper limit is preferably 30 parts by mass or less, more preferably 10 parts by mass or less.

(6)各種添加劑 (6) Various additives

黏著性組成物P中根據需要可以添加在丙烯酸系黏著劑中通常使用之各種添加劑、例如抗靜電劑、增黏劑、抗氧化劑、紫外線吸收劑、光穩定劑、軟化劑、填充劑、折射率調整劑、具有巰基之矽烷偶合劑(B)以外的其他矽烷偶合劑等。但是,防鏽劑尤其苯并三唑系防鏽劑具有阻礙黏著性組成物P的交聯之作用,因此不含為較佳。 The adhesive composition P may be added with various additives commonly used in acrylic adhesives, such as an antistatic agent, a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, a filler, and a refractive index, as needed. The adjusting agent, a decane coupling agent other than the decyl coupling agent (B), and the like. However, the rust preventive agent, particularly the benzotriazole-based rust preventive agent, has an effect of inhibiting the crosslinking of the adhesive composition P, and therefore it is preferably not contained.

另外,黏著性組成物P係表示在黏著劑層中以原狀態或反應之狀態殘存之各種成分的混合物者,在乾燥製程等中被去除之成分例如後述的聚合溶劑及稀釋溶劑不含於黏著性組成物P中。 In addition, the adhesive composition P is a mixture of various components remaining in the original state or the reaction state in the adhesive layer, and the component removed in the drying process or the like, for example, a polymerization solvent and a diluent solvent to be described later are not contained in the adhesive. In the composition P.

(7)黏著性組成物的製造 (7) Manufacture of adhesive composition

黏著性組成物P能夠藉由製造(甲基)丙烯酸酯聚合物(A)並將所得到之(甲基)丙烯酸酯聚合物(A)、具有巰基之矽烷偶合劑(B)及活性能量射線硬化性成分(C)混合,並且根據需要加入交聯劑(D)、光聚合起始劑(E)及添加劑而製造。 The adhesive composition P can be produced by producing a (meth) acrylate polymer (A) and obtaining the (meth) acrylate polymer (A), a decane coupling agent (B) having a mercapto group, and an active energy ray. The curable component (C) is mixed, and if necessary, a crosslinking agent (D), a photopolymerization initiator (E), and an additive are added to produce.

(甲基)丙烯酸酯聚合物(A)能夠藉由將構成聚合物之單體單元的混合物利用通常的自由基聚合法進行聚合而製造。(甲基)丙烯酸酯聚合物(A)的聚合根據需要能夠使用聚合起始劑並藉由溶液聚合法等來進行。作為聚合溶劑,例如可以舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲苯、丙酮、己烷、甲乙酮等,亦可以並用兩種以上。 The (meth) acrylate polymer (A) can be produced by polymerizing a mixture of monomer units constituting the polymer by a usual radical polymerization method. The polymerization of the (meth) acrylate polymer (A) can be carried out by a solution polymerization method or the like using a polymerization initiator as needed. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and two or more kinds thereof may be used in combination.

作為聚合起始劑,可以舉出偶氮系化合物、有機過氧化物等,亦可以並用兩種類以上。作為偶氮系化合物,例如可以舉出2,2'-偶氮二異丁腈、2,2'-偶氮二(2-甲基丁腈)、1,1'-偶氮二(環己烷1-甲腈)、2,2'-偶氮二(2,4-二甲基戊腈)、2,2'-偶氮二(2,4-二甲基-4-甲氧基戊腈)、二甲基2,2'-偶氮二(2-甲基丙酸酯)、4,4'-偶氮二(4-氰基戊酸)、2,2'-偶氮二(2-羥基甲基丙腈)、2,2'-偶氮二[2-(2-咪唑啉-2-基)丙烷]等。 Examples of the polymerization initiator include an azo compound, an organic peroxide, and the like, and two or more types may be used in combination. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis (cyclohexane). Alkane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypentyl) Nitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis 2-hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane, and the like.

作為有機過氧化物,例如可以舉出過氧化苯甲醯、過氧苯甲酸叔丁酯、氫過氧化異丙苯、過氧化二碳酸二異丙酯、過氧化二碳酸二正丙酯、二(2-乙氧基乙基)過氧化二碳酸酯、過氧化新癸酸叔丁酯、過氧化新戊酸叔丁酯、(3,5,5-三甲基己醯)過氧化物、二丙醯過氧化物、二乙醯過氧化物等。 Examples of the organic peroxide include benzammonium peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and (2-ethoxyethyl)peroxydicarbonate, tert-butyl peroxy neodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexyl) peroxide, Dipropylene peroxide, diethyl hydrazine peroxide, etc.

另外,在上述聚合製程中,藉由配合2-巰基乙醇等鏈轉移劑,能夠調節所得到之聚合物的重量平均分子量。 Further, in the above polymerization process, the weight average molecular weight of the obtained polymer can be adjusted by blending a chain transfer agent such as 2-mercaptoethanol.

若得到(甲基)丙烯酸酯聚合物(A),則在(甲基)丙烯酸酯聚合物(A)的溶液中添加具有巰基之矽烷偶合劑(B)、活性能量射線硬化性成分(C)以及根據需要之交聯劑(D)、光聚合起始劑(E)、添加劑及稀釋溶劑並充分混合,藉此得到由溶劑稀釋之黏著性組成物P(塗佈溶液)。 When the (meth) acrylate polymer (A) is obtained, a decane coupling agent (B) having a mercapto group and an active energy ray curable component (C) are added to the solution of the (meth) acrylate polymer (A). The crosslinking agent (D), the photopolymerization initiator (E), the additive, and the diluent solvent are mixed as needed, and the mixture is sufficiently mixed, whereby an adhesive composition P (coating solution) diluted with a solvent is obtained.

作為上述稀釋溶劑,例如使用己烷、庚烷、環己烷等脂肪族烴、甲苯、二甲苯等芳香族烴、二氯甲烷、二氯乙烷等鹵代烴、甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等醇、丙酮、甲乙酮、2-戊酮、異佛爾酮、環己酮等酮、乙酸乙酯、乙酸丁酯等酯、乙基溶纖劑等溶纖劑系溶劑等。 Examples of the diluent solvent include an aliphatic hydrocarbon such as hexane, heptane or cyclohexane, an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as dichloromethane or dichloroethane, methanol, ethanol or propanol. Alcohols such as butanol and 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, ethyl acetate, butyl acetate, etc. A cellosolve such as a solvent is a solvent or the like.

作為如此製備之塗佈溶液的濃度、黏度,只要在可塗層之範圍即可,並沒有特別限制,可以根據狀況適當選定。例如,稀釋成黏著性組成物P的濃度成為10~40質量%。另外,當得到塗佈溶液時,稀釋溶劑等的添加並非必要條件,只要黏著性組成物P為可塗層之黏度等,則亦可以不添加稀釋溶劑。此時,黏著性組成物P成為將(甲基)丙烯酸酯聚合物(A)的聚合溶劑直接作為稀釋溶劑之塗佈溶液。 The concentration and viscosity of the coating solution thus prepared are not particularly limited as long as they are within the range of the coatable layer, and may be appropriately selected depending on the situation. For example, the concentration of the adhesive composition P diluted is 10 to 40% by mass. Further, when the coating solution is obtained, the addition of a diluent solvent or the like is not a requirement, and the diluent solvent may not be added as long as the adhesive composition P is a coatable viscosity or the like. At this time, the adhesive composition P is a coating solution in which the polymerization solvent of the (meth) acrylate polymer (A) is directly used as a diluent solvent.

〔黏著片〕 [adhesive sheet]

如第1圖所示,本實施形態之黏著片1由如下構成:兩片剝離片12a、12b;及以與該等兩片剝離片12a、12b的剝離面接觸之方式被該兩片剝離片12a、12b所夾持之硬化前黏著劑層10。但是,在黏著片1中剝離片12a、12b並非必須構成要 件,係在使用黏著片1時被剝離、去除者。另外,本說明書中之剝離片的剝離面係指在剝離片中具有剝離性之面,係包含實施剝離處理之面及即使未實施剝離處理亦顯示剝離性之面這兩者。 As shown in Fig. 1, the adhesive sheet 1 of the present embodiment is composed of two release sheets 12a and 12b and two release sheets which are in contact with the peeling surfaces of the two release sheets 12a and 12b. The pre-hardening adhesive layer 10 held by 12a, 12b. However, in the adhesive sheet 1, the release sheets 12a, 12b do not have to be formed. The parts are peeled off and removed when the adhesive sheet 1 is used. In addition, the peeling surface of the peeling sheet in this specification is the surface which has the peeling property in the peeling sheet, and is the surface which carried out the peeling process, and the surface which shows the peeling-

(1)硬化前黏著劑層 (1) Adhesive layer before hardening

硬化前黏著劑層10係使前述黏著性組成物P熱交聯而形成為層狀者,係籍由活性能量射線的照射而硬化之前階段者。硬化前黏著劑層10的厚度(按照JIS K7130測定之值)的下限值係10μm以上為較佳,25μm以上尤為佳,50μm以上為進一步較佳。藉由硬化前黏著劑層10的厚度的下限值為上述以上,在使硬化前黏著劑層10硬化而得到之黏著劑層中可以充分發揮優異之黏著力。並且,硬化前黏著劑層10的厚度的上限值係300μm以下為較佳,250μm以下尤為佳,100μm以下為進一步較佳。藉由硬化前黏著劑層10的厚度的上限值為上述以下,加工性變得良好。另外,硬化前黏著劑層10可以以單層形成,亦可以將複數層積層而形成。 The pre-hardening adhesive layer 10 is formed by laminating the above-mentioned adhesive composition P to form a layer, and is a stage before curing by irradiation with an active energy ray. The lower limit of the thickness of the adhesive layer 10 before curing (value measured in accordance with JIS K7130) is preferably 10 μm or more, more preferably 25 μm or more, and still more preferably 50 μm or more. The lower limit of the thickness of the adhesive layer 10 before curing is more than the above, and an excellent adhesive force can be sufficiently exhibited in the adhesive layer obtained by curing the adhesive layer 10 before curing. Further, the upper limit of the thickness of the adhesive layer 10 before curing is preferably 300 μm or less, more preferably 250 μm or less, and further preferably 100 μm or less. The upper limit of the thickness of the adhesive layer 10 before curing is the above-described value, and the workability is good. Further, the adhesive layer 10 may be formed in a single layer before curing, or may be formed by laminating a plurality of layers.

(2)剝離片 (2) peeling sheet

作為剝離片12a、12b並沒有特別限定,可以使用公知的塑膠薄膜。例如,可以使用聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚氨酯薄膜、乙烯乙酸乙烯酯薄膜、離聚物樹脂薄膜、乙烯.(甲基)丙烯酸共聚物薄膜、乙烯.(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸 酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等。並且,亦可以使用該等的交聯薄膜。另外,亦可以係該等的積層薄膜。 The release sheets 12a and 12b are not particularly limited, and a known plastic film can be used. For example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, or a polyethylene terephthalate film can be used. , polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene. (Meth)acrylic copolymer film, ethylene. (Meth)acrylate copolymer film, polystyrene film, polycarbonate An ester film, a polyimide film, a fluororesin film, or the like. Further, these crosslinked films can also be used. Alternatively, these laminated films may be used.

上述剝離片12a、12b的剝離面(尤其與硬化前黏著劑層10接觸之面)實施有剝離處理為較佳。作為剝離處理中所使用之剝離劑,例如可以舉出醇酸系、矽酮系、氟系、不飽和聚酯系、聚烯烴系、蠟系的剝離劑。另外,在剝離片12a、12b中,將一個剝離片設為剝離力較大的重剝離型剝離片,將另一個剝離片設為剝離力較小的輕剝離型剝離片為較佳。 It is preferable that the release surface of the release sheets 12a and 12b (especially the surface in contact with the adhesive layer 10 before curing) is subjected to a release treatment. Examples of the release agent used in the release treatment include an alkyd type, an anthrone type, a fluorine type, an unsaturated polyester type, a polyolefin type, and a wax type release agent. Further, in the release sheets 12a and 12b, one release sheet is a heavy release type release sheet having a large peeling force, and the other release sheet is preferably a light release type release sheet having a small peeling force.

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

(3)黏著片的製造 (3) Manufacture of adhesive sheets

作為黏著片1的一製造例,在一個剝離片12a(或12b)的剝離面塗佈上述黏著性組成物P的塗佈液,並進行加熱處理而使黏著性組成物P熱交聯來形成塗佈層之後,在該塗佈層上重疊另一個剝離片12b(或12a)的剝離面。當需要熟化期間時,上述塗佈層藉由經過熟化期間而成為硬化前黏著劑層10,當不需要熟化期間時,上述塗佈層直接成為硬化前黏著劑層10。藉此,得到上述黏著片1。另外,亦可以由使塗佈之黏著性組成物P的稀釋溶劑等揮發時的乾燥處理兼作加熱處理。 As a production example of the adhesive sheet 1, the coating liquid of the above-mentioned adhesive composition P is applied to the peeling surface of one release sheet 12a (or 12b), and heat treatment is performed to thermally crosslink the adhesive composition P. After the coating layer is applied, the peeling surface of the other release sheet 12b (or 12a) is superposed on the coating layer. When the aging period is required, the coating layer becomes the pre-hardening adhesive layer 10 by the aging period, and when the aging period is not required, the coating layer directly becomes the pre-hardening adhesive layer 10. Thereby, the above-mentioned adhesive sheet 1 is obtained. In addition, the drying treatment at the time of volatilizing the diluted solvent or the like of the applied adhesive composition P may also serve as a heat treatment.

當進行加熱處理時,加熱溫度係50~150℃為較佳,70~120℃尤為佳。並且,加熱時間係30秒~10分鐘為較佳,50秒~2分鐘尤為佳。當設置熟化期間時,作為其條件,例如在常溫(例如,23℃、50%RH)下1~2周左右為較佳。 When the heat treatment is performed, the heating temperature is preferably 50 to 150 ° C, and particularly preferably 70 to 120 ° C. Further, the heating time is preferably 30 seconds to 10 minutes, and particularly preferably 50 seconds to 2 minutes. When the ripening period is set, as a condition thereof, for example, about 1 to 2 weeks at normal temperature (for example, 23 ° C, 50% RH) is preferable.

作為塗佈上述黏著性組成物P的塗佈液之方法, 例如可以利用棒塗佈法、刮刀塗佈法、輥塗佈法、刮板塗佈法、模具塗佈法、凹版塗佈法等。 As a method of applying the coating liquid of the above-described adhesive composition P, For example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.

作為黏著片1的另一製造例,在一個剝離片12a的剝離面塗佈上述黏著性組成物P的塗佈液,並進行加熱處理而使黏著性組成物P進行交聯來形成塗佈層,從而得到帶塗佈層之剝離片12a。並且,在另一個剝離片12b的剝離面塗佈上述黏著性組成物P的塗佈液,並進行加熱處理而使黏著性組成物P進行交聯來形成塗佈層,從而得到帶塗佈層之剝離片12b。並且,將帶塗佈層之剝離片12a與帶塗佈層之剝離片12b以兩個塗佈層相互接觸之方式進行貼合。當需要熟化期間時,上述積層之塗佈層經由熟化期間而成為硬化前黏著劑層10,當不需要熟化期間時,上述積層之塗佈層直接成為硬化前黏著劑層10。藉比,可以得到上述黏著片1。根據該製造例,即使在硬化前黏著劑層10較厚的情況下,亦能夠穩定地進行製造。 In another example of the production of the adhesive sheet 1, the coating liquid of the adhesive composition P is applied onto the peeling surface of one of the release sheets 12a, and heat treatment is performed to crosslink the adhesive composition P to form a coating layer. Thus, a release sheet 12a with a coating layer was obtained. Then, the coating liquid of the adhesive composition P is applied onto the peeling surface of the other release sheet 12b, and heat treatment is performed to crosslink the adhesive composition P to form a coating layer, thereby obtaining a coating layer. The peeling sheet 12b. Further, the release sheet 12a with the coating layer and the release sheet 12b with the coating layer are bonded to each other so that the two coating layers are in contact with each other. When the aging period is required, the above-mentioned laminated coating layer becomes the pre-curing adhesive layer 10 via the aging period, and when the aging period is not required, the laminated coating layer directly becomes the pre-curing adhesive layer 10. The above adhesive sheet 1 can be obtained by the ratio. According to this production example, even when the adhesive layer 10 is thick before curing, it can be stably manufactured.

(4)凝膠分率 (4) Gel fraction

使黏著性組成物P熱交聯而成之硬化前黏著劑的凝膠分率的下限值係20%以上為較佳,30%以上尤為佳,40%以上為進一步較佳。若硬化前黏著劑的凝膠分率的下限值為上述以上,則藉由活性能量射線照射硬化而成之黏著劑的內聚力變高,成為抗起泡性更加優異者。並且,上述凝膠分率的上限值係90%以下為較佳,80%以下尤為佳,75%以下為進一步較佳。若硬化前黏著劑的凝膠分率的上限值為上述以下,則硬化前黏著劑層10不會變得過硬,成為貼附時的段差追隨性優異者。 The lower limit of the gel fraction of the pre-curing adhesive which is obtained by thermally crosslinking the adhesive composition P is preferably 20% or more, more preferably 30% or more, and still more preferably 40% or more. When the lower limit of the gel fraction of the adhesive before curing is at least the above, the cohesive force of the adhesive which is cured by irradiation with active energy rays is increased, and the antifoaming property is further improved. Further, the upper limit of the gel fraction is preferably 90% or less, more preferably 80% or less, and still more preferably 75% or less. When the upper limit of the gel fraction of the adhesive before curing is not more than the above, the adhesive layer 10 does not become excessively hard before curing, and is excellent in step followability at the time of attachment.

另一方面,使上述硬化前黏著劑藉由活性能量射 線的照射硬化而成之黏著劑的凝膠分率的下限值係50%以上為較佳,60%以上尤為佳,70%以上為進一步較佳。若黏著劑的凝膠分率的下限值為上述以上,則該黏著劑的內聚力變高,成為抗起泡性更加優異者。並且,上述凝膠分率的上限值係99%以下為較佳,96%以下尤為佳,94%以下為進一步較佳。若黏著劑的凝膠分率的上限值為上述以下,則能夠維持適當的黏著力,並能夠維持良好的起泡性能。另外,硬化前黏著劑及黏著劑的凝膠分率的測定方法如後述之試驗例所示。 On the other hand, the pre-hardening adhesive is irradiated by active energy. The lower limit of the gel fraction of the adhesive which is cured by irradiation of the wire is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more. When the lower limit of the gel fraction of the adhesive is at least the above, the cohesive force of the adhesive becomes high, and the anti-foaming property is further improved. Further, the upper limit of the gel fraction is preferably 99% or less, more preferably 96% or less, and even more preferably 94% or less. When the upper limit of the gel fraction of the adhesive is at most the above, it is possible to maintain an appropriate adhesive force and maintain good foaming performance. Further, the method for measuring the gel fraction of the adhesive and the adhesive before curing is as shown in the test examples described later.

(5)黏著力 (5) Adhesion

本實施形態之黏著片1對鈉鈣玻璃之黏著力的下限值係5N/25mm以上為較佳,7N/25mm以上尤為佳,10N/25mm以上為進一步較佳。若黏著片1的黏著力的下限值為上述以上,則能夠有效地防止在保管中剝離片剝離,或者在搬送製程中與被黏物之間產生剝離等。另一方面,上述黏著力的上限值並沒有特別限制,若考慮使用時之剝離片12a、12b從硬化前黏著劑層10之剝離容易度等,則50N/25mm以下為較佳,30N/25mm以下尤為佳。若還進一步考慮再加工性,則26N/25mm以下為較佳。在該情況下,即使發生誤貼合,亦可以輕鬆地再利用顯示體構成構件。 The lower limit of the adhesion of the adhesive sheet 1 to the soda lime glass of the present embodiment is preferably 5 N/25 mm or more, more preferably 7 N/25 mm or more, and still more preferably 10 N/25 mm or more. When the lower limit of the adhesive force of the pressure-sensitive adhesive sheet 1 is at least the above, it is possible to effectively prevent the release sheet from being peeled off during storage or to cause peeling or the like between the adherend and the adherend. On the other hand, the upper limit of the adhesive force is not particularly limited, and in consideration of easiness of peeling of the release sheets 12a and 12b from the adhesive layer 10 before curing, 50 N/25 mm or less is preferable, and 30 N/ is preferable. Especially below 25mm. If reworkability is further considered, 26 N/25 mm or less is preferable. In this case, even if a misfit occurs, the display body constituent member can be easily reused.

上述黏著力基本上係指藉由按照JIS Z0237:2009之180度剝離法測定之黏著力,係將測定樣品設為25mm寬度、100mm長度,將該測定樣品貼附於被黏物,並在0.5MPa、50℃下加壓20分鐘之後,在常壓、23℃、50%RH的條件下放置24小時,其後以剝離速度300mm/min測定者。 The above-mentioned adhesive force basically means an adhesive force measured by a 180-degree peeling method according to JIS Z0237:2009, and the measurement sample is set to a width of 25 mm and a length of 100 mm, and the measurement sample is attached to the adherend, and is 0.5. After pressurizing at 50 ° C for 20 minutes at MPa, the mixture was allowed to stand under normal pressure, 23 ° C, and 50% RH for 24 hours, and then measured at a peeling speed of 300 mm/min.

並且,使本實施形態之黏著片1的硬化前黏著劑層10藉由活性能量射線的照射硬化而作為黏著劑層時之、該黏著片對鈉鈣玻璃之黏著力的下限值係5N/25mm以上為較佳,7N/25mm以上尤為佳,10N/25mm以上為進一步較佳。若黏著片1的黏著力的下限值為上述以上,則成為抗起泡性更加優異者。另一方面,上述黏著力的上限值並沒有特別限制,通常係50N/25mm以下。 Further, when the pre-curing adhesive layer 10 of the adhesive sheet 1 of the present embodiment is cured by irradiation with an active energy ray as an adhesive layer, the lower limit of the adhesion of the adhesive sheet to the soda lime glass is 5N/ 25 mm or more is preferable, 7N/25 mm or more is particularly preferable, and 10N/25 mm or more is further preferable. When the lower limit of the adhesive force of the adhesive sheet 1 is more than the above, the anti-foaming property is further excellent. On the other hand, the upper limit of the above-mentioned adhesive force is not particularly limited, and is usually 50 N/25 mm or less.

上述黏著力基本上係指藉由按照JIS Z0237:2009之180度剝離法測定之黏著力,係將測定樣品設為25mm寬度、100mm長度,將該測定樣品貼附於被黏物,並在0.5MPa、50℃下加壓20分鐘之後,藉由活性能量射線的照射使硬化前黏著劑層硬化而作為黏著劑層,接著,在常壓、23℃、50%RH的條件下放置24小時之後,以剝離速度300mm/min測定者。 The above-mentioned adhesive force basically means an adhesive force measured by a 180-degree peeling method according to JIS Z0237:2009, and the measurement sample is set to a width of 25 mm and a length of 100 mm, and the measurement sample is attached to the adherend, and is 0.5. After pressurizing at MPa and 50 ° C for 20 minutes, the adhesive layer was hardened as an adhesive layer by irradiation with active energy rays, and then placed under normal pressure, 23 ° C, and 50% RH for 24 hours. The tester was measured at a peeling speed of 300 mm/min.

〔顯示體〕 [display body]

本實施形態之顯示體包括:至少在貼合之側的面具有段差之第1顯示體構成構件;第2顯示體構成構件;及將第1顯示體構成構件與第2顯示體構成構件相互貼合之黏著劑層。第1顯示體構成構件和/或第2顯示體構成構件至少在貼合之側(黏著劑層側)的面具有電極。作為較佳的構成,第2顯示體構成構件至少在貼合之側的面具有電極。 The display body of the present embodiment includes a first display body constituent member having a step on at least the surface on the side of the bonding, a second display body constituent member, and a first display member and a second display member. Adhesive layer. The first display body constituent member and/or the second display body constituent member have electrodes on at least the side of the bonding side (adhesive layer side). In a preferred configuration, the second display member constituting member has an electrode on at least the surface on the side to which it is bonded.

上述黏著劑層係使前述硬化前黏著劑層藉由活性能量射線的照射而硬化者。其中,活性能量射線係指在電磁波或帶電粒子束中具有能量子者,具體而言,可以舉出紫外線、電子束等。在活性能量射線中,操作輕鬆的紫外線尤為佳。 The adhesive layer is obtained by curing the pre-curing adhesive layer by irradiation with active energy rays. Here, the active energy ray means an energy source having an electromagnetic wave or a charged particle beam, and specific examples thereof include ultraviolet rays, electron beams, and the like. In active energy ray, it is especially good to operate with easy UV rays.

紫外線的照射能夠藉由高壓水銀燈、融合H燈、氙燈等來進行,關於紫外線的照射量,照度為50~1000mW/cm2左右為較佳。並且,光量為50~10000mJ/cm2為較佳,80~5000mJ/cm2更為佳,200~2000mJ/cm2尤為佳。另一方面,電子束的照射能够藉由電子束加速器等來進行,電子束的照射量為10~1000krad左右為較佳。 The irradiation of ultraviolet rays can be carried out by a high pressure mercury lamp, a fused H lamp, a xenon lamp or the like, and the illuminance is preferably about 50 to 1000 mW/cm 2 with respect to the amount of ultraviolet rays. Further, the light amount is preferably 50 to 10000 mJ/cm 2 , more preferably 80 to 5,000 mJ/cm 2 , and particularly preferably 200 to 2000 mJ/cm 2 . On the other hand, the irradiation of the electron beam can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably about 10 to 1000 krad.

對硬化前黏著劑層之活性能量射線的照射係籍由該硬化前黏著劑層將第1顯示體構成構件與第2顯示體構成構件相互貼合之後,隔著第1顯示體構成構件及第2顯示體構成構件中的使活性能量射線透過之構件而進行為較佳。 The irradiation of the active energy ray of the adhesive layer before the curing is performed by bonding the first display constituent member and the second display constituent member to each other by the pre-curing adhesive layer, and then the first display constituent member and the first member are interposed therebetween. It is preferable to display a member that transmits an active energy ray in the body constituent member.

若對硬化前黏著劑層照射活性能量射線,則活性能量射線硬化性成分(B)聚合而硬化。藉由活性能量射線的照射使硬化前黏著劑層硬化而得到之黏著劑層成為抗起泡性非常優異者。 When the active energy ray is irradiated to the adhesive layer before curing, the active energy ray curable component (B) is polymerized and hardened. The adhesive layer obtained by hardening the adhesive layer before hardening by irradiation with active energy rays is excellent in anti-foaming property.

作為顯示體,例如可以舉出液晶(LCD)顯示器、發光二極體(LED)顯示器、有機電致發光(有機EL)顯示器、電子紙等,亦可以係觸摸面板。並且,作為顯示體,亦可以係構成該等的一部分之構件。 Examples of the display body include a liquid crystal (LCD) display, a light-emitting diode (LED) display, an organic electroluminescence (organic EL) display, electronic paper, and the like, and may be a touch panel. Further, the display body may be a member constituting a part of the components.

第1顯示體構成構件可以係玻璃板、塑膠板等,此外,係由包含該等之積層體等構成之保護面板為較佳。第1顯示體構成構件在黏著劑層側的面具有段差,具體而言,具有由印刷層形成之段差為較佳。該印刷層一般形成為邊框狀。 The first display member constituting member may be a glass plate, a plastic plate or the like, and is preferably a protective panel including a laminate or the like. The first display member constituting member has a step on the surface on the side of the adhesive layer, and specifically, a step formed by the printed layer is preferable. The printed layer is generally formed in a frame shape.

作為上述玻璃板並沒有特別限定,例如可以舉出化學強化玻璃、無鹼性玻璃、石英玻璃、鈉鈣玻璃、含鋇、鍶 玻璃、鋁矽酸鹽玻璃、鉛玻璃、硼矽酸鹽玻璃、鋇硼矽酸鹽玻璃等。玻璃板的厚度並沒有特別限定,通常係0.1~5mm,0.2~2mm為較佳。 The glass plate is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, and barium and strontium. Glass, aluminosilicate glass, lead glass, borosilicate glass, barium borate glass, and the like. The thickness of the glass plate is not particularly limited, and is usually 0.1 to 5 mm, preferably 0.2 to 2 mm.

作為上述塑膠板並沒有特別限定,例如可以舉出丙烯酸板、聚碳酸酯板等。塑膠板的厚度並沒有特別限定,通常係0.2~5mm,0.4~3mm為較佳。 The plastic plate is not particularly limited, and examples thereof include an acrylic plate and a polycarbonate plate. The thickness of the plastic plate is not particularly limited, and is usually 0.2 to 5 mm, and 0.4 to 3 mm is preferable.

另外,在上述玻璃板或塑膠板的一面或兩面可以設置各種功能層(電極層、矽氧層、硬塗層、防眩層等),亦可以積層光學構件。 Further, various functional layers (electrode layer, silicon oxide layer, hard coat layer, antiglare layer, etc.) may be provided on one or both sides of the glass plate or the plastic plate, or an optical member may be laminated.

構成印刷層之材料並沒有特別限定,可以使用印刷用的公知的材料。印刷層的厚度亦即段差的高度的下限值係3μm以上為較佳,5μm以上更為佳,7μm以上尤為佳,10μm以上最為佳。若下限值為上述以上,則使得電配線難以從視認者側觀察到等能夠充分確保隱蔽性。並且,上限值係50μm以下為較佳,35μm以下更為佳,25μm以下尤為佳,20μm以下為進一步較佳。藉由上限值為上述以下,能夠防止黏著劑層對該印刷層之段差追隨性惡化。 The material constituting the printing layer is not particularly limited, and a known material for printing can be used. The thickness of the printed layer, that is, the lower limit of the height of the step is preferably 3 μm or more, more preferably 5 μm or more, particularly preferably 7 μm or more, and most preferably 10 μm or more. When the lower limit value is equal to or higher than the above, the electrical wiring is difficult to be observed from the viewer side, and the concealability can be sufficiently ensured. Further, the upper limit is preferably 50 μm or less, more preferably 35 μm or less, particularly preferably 25 μm or less, and further preferably 20 μm or less. By the upper limit being the above value, it is possible to prevent deterioration of the step followability of the adhesive layer to the printed layer.

第2顯示體構成構件係應貼合於第1顯示體構成構件之光學構件、顯示體模組(例如,液晶(LCD)模組、發光二極體(LED)模組、有機電致發光(有機EL)模組等)、作為顯示體模組的一部分之光學構件、或包含顯示體模組之積層體,係至少在黏著劑層側的面具有電極者為較佳。 The second display member is a member to be bonded to the optical member and the display module of the first display member (for example, a liquid crystal (LCD) module, a light emitting diode (LED) module, or an organic electroluminescence ( The organic EL module or the like, the optical member which is a part of the display body module, or the laminated body including the display body module is preferably an electrode having at least the surface on the side of the adhesive layer.

作為上述光學構件,例如可以舉出電極薄膜、透明導電性薄膜、薄膜感測器、金屬奈米線薄膜、線柵偏光薄膜 等。 Examples of the optical member include an electrode film, a transparent conductive film, a film sensor, a metal nanowire film, and a wire grid polarizing film. Wait.

作為上述電極,例如可以舉出由銅、銀等構成之金屬電極(包括網狀、柵狀者)、由錫摻雜氧化銦(ITO)等構成之透明導電膜(包括圖案化者)等。如上所述,在上述電極中,以未氧化之金屬為主成分之金屬電極、具體而言由銅或銀構成之金屬電極為較佳。 Examples of the electrode include a metal electrode (including a mesh or a grid) made of copper or silver, a transparent conductive film (including a pattern) made of tin-doped indium oxide (ITO), or the like. As described above, among the above electrodes, a metal electrode mainly composed of an unoxidized metal, specifically, a metal electrode composed of copper or silver is preferable.

作為本實施形態之顯示體的一例,在第2圖中示出靜電容量方式的觸摸面板2。觸摸面板2構成為包括:顯示體模組3;在之上經由黏著劑層4而積層之第1薄膜感測器5a;在之上經由第1黏著劑層11而積層之第2薄膜感測器5b;在之上經由第2黏著劑層11而積層之覆蓋材6。在覆蓋材6的第2黏著劑層11側的面形成有印刷層7,因此存在由印刷層7的有無而形成之段差。本實施形態中,覆蓋材6相當於上述第1顯示體構成構件,第2薄膜感測器5b相當於上述第2顯示體構成構件。 As an example of the display body of the present embodiment, a capacitive touch panel 2 is shown in FIG. 2 . The touch panel 2 is configured to include a display body module 3, a first film sensor 5a laminated thereon via an adhesive layer 4, and a second film sensing layered thereon via the first adhesive layer 11. The cover 5 is laminated on the second adhesive layer 11 above. Since the printed layer 7 is formed on the surface of the cover material 6 on the side of the second adhesive layer 11, there is a step formed by the presence or absence of the printed layer 7. In the present embodiment, the cover member 6 corresponds to the first display member constituting member, and the second film sensor 5b corresponds to the second display member constituting member.

本實施形態中之第1黏著劑層11及第2黏著劑層11考慮該等的遷移防止效果,兩者均設為使上述黏著片1的硬化前黏著劑層10藉由活性能量射線的照射而硬化者。但是,本發明並不限定於此,第1黏著劑層11亦可以由其他黏著劑或黏著片形成。作為該情況的黏著劑,可以舉出丙烯酸系黏著劑、橡膠系黏著劑、矽酮系黏著劑、胺基甲酸酯系黏著劑、聚酯系黏著劑、聚乙烯醚系黏著劑等,其中,丙烯酸系黏著劑為較佳。 The first adhesive layer 11 and the second adhesive layer 11 in the present embodiment are considered to have such a migration preventing effect, and both are used to irradiate the adhesive layer 10 before curing of the adhesive sheet 1 with active energy rays. And hardened. However, the present invention is not limited thereto, and the first adhesive layer 11 may be formed of another adhesive or an adhesive sheet. Examples of the adhesive in this case include an acrylic adhesive, a rubber-based adhesive, an anthrone-based adhesive, an urethane-based adhesive, a polyester-based adhesive, and a polyvinyl ether-based adhesive. An acrylic adhesive is preferred.

黏著劑層4可以由上述黏著片1的硬化前黏著劑 層10形成,亦可以由其他黏著劑或黏著片形成。在後者的情況下,作為構成黏著劑層4之黏著劑,可以舉出丙烯酸系黏著劑、橡膠系黏著劑、矽酮系黏著劑、氨基甲酸酯系黏著劑、聚酯系黏著劑、聚乙烯醚系黏著劑等,其中,丙烯酸系黏著劑為較佳。 The adhesive layer 4 may be a pre-hardening adhesive of the above-mentioned adhesive sheet 1 Layer 10 is formed and may also be formed from other adhesives or adhesive sheets. In the latter case, examples of the adhesive constituting the adhesive layer 4 include an acrylic adhesive, a rubber adhesive, an anthrone adhesive, a urethane adhesive, a polyester adhesive, and a poly A vinyl ether adhesive or the like is preferred, and an acrylic adhesive is preferred.

本實施形態中之第1薄膜感測器5a及第2薄膜感測器5b分別包括基材薄膜51及形成於基材薄膜51之電極52。作為基材薄膜51並沒有特別限定,例如可以使用聚對苯二甲酸乙二酯薄膜、丙烯酸薄膜、聚碳酸酯薄膜等。 The first film sensor 5a and the second film sensor 5b in the present embodiment each include a base film 51 and an electrode 52 formed on the base film 51. The base film 51 is not particularly limited, and for example, a polyethylene terephthalate film, an acrylic film, a polycarbonate film, or the like can be used.

電極52例如由金屬電極和圖案化透明導電膜等構成,該金屬電極由銅、銀等構成,該圖案化透明導電膜由錫摻雜氧化銦(ITO)等構成。 The electrode 52 is composed of, for example, a metal electrode, a patterned transparent conductive film, or the like, and the metal electrode is made of copper, silver, or the like, and the patterned transparent conductive film is made of tin-doped indium oxide (ITO) or the like.

第1薄膜感測器5a的電極52及第2薄膜感測器5b的電極52通常係一個構成X軸方向的電路圖案,另一個構成Y軸方向的電路圖案。 The electrode 52 of the first thin film sensor 5a and the electrode 52 of the second thin film sensor 5b are generally one circuit pattern constituting the X-axis direction, and the other is a circuit pattern in the Y-axis direction.

本實施形態中之第2薄膜感測器5b的電極52在第2圖中位於第2薄膜感測器5b的上側。另一方面,第1薄膜感測器5a的電極52在第2圖中位於第1薄膜感測器5a的上側,但並不限定於此,亦可以位於第1薄膜感測器5a的下側。 The electrode 52 of the second thin film sensor 5b in the present embodiment is located on the upper side of the second thin film sensor 5b in Fig. 2 . On the other hand, the electrode 52 of the first thin film sensor 5a is located above the first thin film sensor 5a in Fig. 2, but the invention is not limited thereto, and may be located on the lower side of the first thin film sensor 5a. .

以下,對上述觸摸面板2的製造方法的一例進行說明。 Hereinafter, an example of the method of manufacturing the touch panel 2 will be described.

作為黏著片1,準備第1黏著片1及第2黏著片1。從第1黏著片1剝離一個剝離片12a,並將露出之硬化前黏著劑層10 (第1硬化前黏著劑層10)以與第1薄膜感測器5a的電極52接觸之方式與該第1薄膜感測器5a貼合。並且,從第2黏著片1剝離一個剝離片12a,並將露出之硬化前黏著劑層10(第2硬化前黏著劑層10)以與第2薄膜感測器5b的電極52接觸之方式與該第2薄膜感測器5b貼合。 As the adhesive sheet 1, the first adhesive sheet 1 and the second adhesive sheet 1 are prepared. A release sheet 12a is peeled off from the first adhesive sheet 1, and the pre-hardened adhesive layer 10 is exposed. (The first adhesive layer 10 before curing) is bonded to the first thin film sensor 5a so as to be in contact with the electrode 52 of the first thin film sensor 5a. Then, one release sheet 12a is peeled off from the second adhesive sheet 1, and the exposed pre-curing adhesive layer 10 (the second pre-curing adhesive layer 10) is brought into contact with the electrode 52 of the second thin film sensor 5b. The second film sensor 5b is bonded to each other.

並且,剝離第1黏著片中之另一個剝離片12b,並以露出之第1硬化前黏著劑層10與上述第2薄膜感測器5b中之與積層有第2硬化前黏著劑層10之側相反側的面(第1薄膜感測器5b的基材薄膜51的露出面)接觸之方式將兩者貼合。藉此,得到剝離片12b、第2硬化前黏著劑層10、第2薄膜感測器5b、第1硬化前黏著劑層10及第1薄膜感測器5a依次積層而成之積層體。 Then, the other peeling sheet 12b of the first adhesive sheet is peeled off, and the first pre-curing adhesive layer 10 and the second thin film sensor 5b are laminated with the second pre-hardening adhesive layer 10 The surface on the opposite side (the exposed surface of the base film 51 of the first film sensor 5b) is brought into contact with each other. Thereby, a laminate in which the release sheet 12b, the second pre-curing adhesive layer 10, the second thin film sensor 5b, the first pre-curing adhesive layer 10, and the first thin film sensor 5a are laminated is obtained.

接著,在上述積層體的第1薄膜感測器5a側的面(第1薄膜感測器5a的基材薄膜51的露出面)貼合設置於剝離片上之黏著劑層4。接著,從上述積層體剝離剝離片12b,並對露出之第2硬化前黏著劑層10以覆蓋材6的印刷層7側與該第2硬化前黏著劑層10接觸之方式貼合該覆蓋材6。此時,第2硬化前黏著劑層10由於貼附時的段差追隨性優異,因此可以抑制在籍由印刷層7形成之段差附近產生間隙及浮起。藉由上述貼合,可以得到覆蓋材6、第2硬化前黏著劑層10、第2薄膜感測器5b、第1硬化前黏著劑層10、第1薄膜感測器5a、黏著劑層4及剝離片依次積層而成之構成體。 Then, the adhesive layer 4 provided on the release sheet is bonded to the surface of the laminate on the side of the first thin film sensor 5a (the exposed surface of the base film 51 of the first thin film sensor 5a). Then, the release sheet 12b is peeled off from the laminated body, and the exposed pre-adhesive adhesive layer 10 is bonded to the cover layer 7 so that the printed layer 7 side of the cover material 6 comes into contact with the second pre-curing adhesive layer 10 6. At this time, since the adhesion layer 10 before the second hardening is excellent in the step-following property at the time of attaching, it is possible to suppress the occurrence of a gap and the floating in the vicinity of the step formed by the printed layer 7. By the above bonding, the covering material 6, the second pre-curing adhesive layer 10, the second thin film sensor 5b, the first pre-curing adhesive layer 10, the first thin film sensor 5a, and the adhesive layer 4 can be obtained. And a structure in which the release sheets are laminated in this order.

接著,從上述構成體的任一側、較佳地從覆蓋材6側對第2硬化前黏著劑層10及第1硬化前黏著劑層10照射活 性能量射線,使第2硬化前黏著劑層10及第1硬化前黏著劑層10硬化來分別作為第2黏著劑層11及第1黏著劑層11。 Next, the second pre-curing adhesive layer 10 and the first pre-curing adhesive layer 10 are irradiated from either side of the above-mentioned constituent body, preferably from the side of the covering material 6 The first amount of the pre-curing adhesive layer 10 and the first pre-curing adhesive layer 10 are cured as the second adhesive layer 11 and the first adhesive layer 11, respectively.

最後,從上述構成體剝離剝離片,並以露出之黏著劑層4與顯示體模組3接觸之方式將該構成體貼合於顯示體模組3。藉此,製造第2圖所示之觸摸面板2。 Finally, the release sheet is peeled off from the above-described constituent body, and the exposed adhesive layer 4 is brought into contact with the display module 3 so that the constituent body is bonded to the display module 3. Thereby, the touch panel 2 shown in FIG. 2 is manufactured.

即使在上述觸摸面板2置於高溫高濕條件下並以該狀態對電極52施加電壓之情況下,藉由與電極52接觸之黏著劑層11含有源自具有巰基之矽烷偶合劑(B)之成分,可以有效地抑制電極52的遷移。藉此,可以防止由電極52的斷線及短路引起之觸摸面板2的驅動不良。 Even in the case where the touch panel 2 is placed under high temperature and high humidity conditions and a voltage is applied to the electrode 52 in this state, the adhesive layer 11 in contact with the electrode 52 contains a decane coupling agent (B) derived from a mercapto group. The composition can effectively suppress the migration of the electrode 52. Thereby, it is possible to prevent the driving failure of the touch panel 2 caused by the disconnection and short circuit of the electrode 52.

並且,上述黏著劑層11即使在高溫高濕條件下段差追隨性亦優異,因此即使在觸摸面板2在高溫高濕條件下暴露既定時間之情況下,亦可以有效地抑制在籍由印刷層7形成之段差附近產生氣泡、浮起、剝離等。 Further, the pressure-sensitive adhesive layer 11 is excellent in step-followability even under high-temperature and high-humidity conditions, and therefore can be effectively suppressed from being formed by the printed layer 7 even when the touch panel 2 is exposed to a predetermined time under high-temperature and high-humidity conditions. Bubbles, floating, peeling, and the like occur in the vicinity of the step.

另外,即便上述觸摸面板2置於高溫高濕條件下而從覆蓋材6、第2薄膜感測器5b或第1薄膜感測器5a產生逸氣,由於黏著劑層11的抗起泡性優異,因此亦可以抑制在黏著劑層11與覆蓋材6、第2薄膜感測器5b或第1薄膜感測器5a的界面上產生氣泡、浮起、剝離等起泡。 Further, even if the touch panel 2 is placed under high temperature and high humidity conditions to generate outgassing from the cover material 6, the second thin film sensor 5b or the first thin film sensor 5a, the adhesive layer 11 is excellent in anti-foaming property. Therefore, it is also possible to suppress generation of bubbles such as bubbles, floating, and peeling at the interface between the adhesive layer 11 and the cover member 6, the second thin film sensor 5b, or the first thin film sensor 5a.

以上說明之實施形態係為了便於理解本發明而記載者,並非為了限定本發明而記載者。因此,上述實施形態中所揭示之各要件係還包含本發明的技術技範圍所屬之所有設計變更和均等物之趣旨。 The embodiments described above are described in order to facilitate the understanding of the present invention, and are not intended to limit the present invention. Therefore, the various embodiments disclosed in the above embodiments are intended to encompass all design changes and equivalents of the technical scope of the invention.

例如,可以省略黏著片1中之剝離片12a、12b中 的任一個。 For example, the peeling sheets 12a, 12b in the adhesive sheet 1 can be omitted. Any one.

【實施例】 [Examples]

以下,藉由實施例對本發明進行進一步具體的說明,但本發明的範圍並非限定於該等實施例者。 Hereinafter, the present invention will be specifically described by way of examples, but the scope of the invention is not limited to the embodiments.

〔實施例1〕 [Example 1]

1.(甲基)丙烯酸酯共聚物的製備 1. Preparation of (meth) acrylate copolymer

使丙烯酸2-乙基己酯60質量份、甲基丙烯酸甲酯20質量份及丙烯酸2-羥基乙酯20質量份共聚而製備(甲基)丙烯酸酯聚合物(A)。利用後述之方法測定該(甲基)丙烯酸酯聚合物(A)的分子量之結果,重量平均分子量(Mw)為60萬。 The (meth) acrylate polymer (A) was prepared by copolymerizing 60 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl methacrylate, and 20 parts by mass of 2-hydroxyethyl acrylate. The molecular weight of the (meth) acrylate polymer (A) was measured by the method described later, and the weight average molecular weight (Mw) was 600,000.

2.黏著性組成物的製備 2. Preparation of adhesive composition

將上述製程1中所得到之(甲基)丙烯酸酯聚合物(A)100質量份(固形成分換算值;以下相同)、作為具有巰基之矽烷偶合劑(B)之3-巰丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮合物(Shin-Etsu Chemical Co.,Ltd.製,商品名“X-41-1810”,寡聚物型,巰基當量:450g/莫爾)0.20質量份、作為活性能量射線硬化性成分(C)之ε-己內酯改性三-(2-丙烯醯氧乙基)異氰脲酸酯(Shin-Nakamura Chemical Co.,Ltd.製,產品名“NK Ester A-9300-1CL”)2.5質量份、作為交聯劑(D)之三羥甲基丙烷改性甲苯二異氰酸酯(Nippon Polyurethane Industry Co.,Ltd.製,產品名“Coronate L”)0.23質量份、作為光聚合起始劑(E)之將二苯甲酮與1-羥基環己基苯基酮以1:1的質量比混合而成者(BASF公司製,產品名“IRGACURE 500“)0.25質量份進行混合並充分攪拌,並且利 用甲乙酮稀釋,藉此得到固形成分濃度36質量%的黏著性組成物的塗佈溶液。 100 parts by mass of the (meth) acrylate polymer (A) obtained in the above Process 1 (solid content conversion value; the same applies hereinafter), 3-mercaptopropyltrimethoxy which is a decane-based decane coupling agent (B) Co-condensation product of decane and methyltriethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-41-1810", oligomer type, thiol equivalent: 450 g/mole) 0.20 Ε-caprolactone-modified tris-(2-propenyloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.) as a component of the active energy ray-curable component (C) "NK Ester A-9300-1CL") 2.5 parts by mass of trimethylolpropane-modified toluene diisocyanate as a crosslinking agent (D) (manufactured by Nippon Polyurethane Industry Co., Ltd., product name "Coronate L" 0.23 parts by mass, as a photopolymerization initiator (E), a mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1:1 (manufactured by BASF Corporation, product name "IRGACURE 500" ") 0.25 parts by mass for mixing and stirring well, and It was diluted with methyl ethyl ketone to obtain a coating solution of an adhesive composition having a solid content concentration of 36% by mass.

其中,將(甲基)丙烯酸酯聚合物(A)設為100質量份(固形成分換算值)時的黏著性組成物的各配合(固形成分換算值)示於表1。另外,表1中所記載之縮寫等的詳細內容如下所示。 In the above, the respective components (solid content conversion values) of the adhesive composition when the (meth) acrylate polymer (A) is 100 parts by mass (solid content conversion value) are shown in Table 1. The details of the abbreviations and the like described in Table 1 are as follows.

[(甲基)丙烯酸酯聚合物(A)] [(Meth)acrylate polymer (A)]

2EHA:丙烯酸2-乙基己酯 2EHA: 2-ethylhexyl acrylate

MMA:甲基丙烯酸甲酯 MMA: Methyl methacrylate

HEA:丙烯酸2-羥基乙酯 HEA: 2-hydroxyethyl acrylate

[具有巰基之矽烷偶合劑(B)] [Centane coupling agent (B) having a mercapto group]

X-41-1810:3-巰丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮合物(Shin-Etsu Chemical Co.,Ltd.製,商品名“X-41-1810”,寡聚物型,巰基當量:450g/莫爾) X-41-1810: a cocondensate of 3-mercaptopropyltrimethoxydecane and methyltriethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-41-1810"), Polymer type, thiol equivalent: 450g/mole)

KBM-803:3-巰丙基三甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製,商品名“KBM-803”,低分子型,巰基當量:196.4g/莫爾) KBM-803: 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-803", low molecular weight, thiol equivalent: 196.4 g/mole)

[其他矽烷偶合劑] [Other decane coupling agents]

KBM-403:3-縮水甘油醚氧丙基三甲氧基矽烷(Shin-Etsu Silicone Co.,Ltd.製,商品名“KBM-403”,低分子型) KBM-403: 3-glycidyloxypropyltrimethoxydecane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name "KBM-403", low molecular type)

KBE-9007:3-異氰酸酯丙基三乙氧基矽烷(Shin-Etsu Silicone Co.,Ltd.製,商品名“KBE-9007”,低分子型) KBE-9007: 3-isocyanate propyl triethoxy decane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name "KBE-9007", low molecular type)

[活性能量射線硬化性成分(C)] [Active energy ray hardening component (C)]

NK Ester A-9300-1CL:ε-己內酯改性三-(2-丙烯醯氧乙 基)異氰脲酸酯(Shin-Nakamura Chemical Co.,Ltd.製,產品名“NK Ester A-9300-1CL”) NK Ester A-9300-1CL: ε-caprolactone modified tris-(2-propene oxyfluoride Isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "NK Ester A-9300-1CL")

NK Ester A-TMM-3L:季戊四醇三丙烯酸酯(三酯55質量%)(Shin-Nakamura Chemical Co.,Ltd.製,產品名“NK Ester A-TMM-3L”) NK Ester A-TMM-3L: pentaerythritol triacrylate (triester 55 mass%) (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "NK Ester A-TMM-3L")

3.黏著片的製造 3. Adhesive sheet manufacturing

在將聚對苯二甲酸乙二酯薄膜的一面利用矽酮系剝離劑進行剝離處理而得到之重剝離型剝離片(LINTEC Corporation製,商品名“SP-PET382150”,厚度:38μm)的剝離處理面上,利用刮刀式塗佈機塗佈上述製程2中所得到之黏著性組成物的塗佈溶液之後,在90℃下加熱處理1分鐘而形成塗佈層(厚度:25μm)。同樣地,在將聚對苯二甲酸乙二酯薄膜的一面利用矽酮系剝離劑進行剝離處理而得到之輕剝離型剝離片(LINTEC Corporation製,產品名“SP-PET382120”)的剝離處理面上,利用刮刀式塗佈機塗佈上述製程2中所得到之黏著性組成物的塗佈溶液之後,在90℃下加熱處理1分鐘而形成塗佈層(厚度:25μm)。 A peeling treatment of a heavy release type release sheet (manufactured by LINTEC Corporation, trade name "SP-PET382150", thickness: 38 μm) obtained by peeling one surface of a polyethylene terephthalate film with an anthrone-based release agent On the surface, the coating solution of the adhesive composition obtained in the above Process 2 was applied by a knife coater, and then heat-treated at 90 ° C for 1 minute to form a coating layer (thickness: 25 μm). In the same manner, a peeling-treated surface of a light-peelable release sheet (manufactured by LINTEC Corporation, product name "SP-PET382120") obtained by peeling one surface of a polyethylene terephthalate film with an anthrone-based release agent Then, the coating solution of the adhesive composition obtained in the above Process 2 was applied by a doctor blade coater, and then heat-treated at 90 ° C for 1 minute to form a coating layer (thickness: 25 μm).

接著,將上述中所得到之帶塗佈層之重剝離型剝離片與上述中所得到之帶塗佈層之輕剝離型剝離片以兩個塗佈層相互接觸之方式進行貼合,並在23℃、50%RH的條件下熟化7天,藉此製作由重剝離型剝離片/硬化前黏著劑層(厚度:50μm)/輕剝離型剝離片構成之黏著片。 Then, the heavy release release sheet with the coating layer obtained in the above and the light release release sheet with the coating layer obtained above are bonded together so that the two coating layers are in contact with each other, and The adhesive sheet consisting of a heavy peeling type release sheet / pre-hardening adhesive layer (thickness: 50 μm) / light release type release sheet was produced by aging for 7 days under conditions of 23 ° C and 50% RH.

〔實施例2~10、比較例1~10〕 [Examples 2 to 10, Comparative Examples 1 to 10]

如表1所示般改變矽烷偶合劑(具有巰基之矽烷偶合劑 (B)及其他矽烷偶合劑)的種類及比例、活性能量射線硬化性成分(C)的種類及比例、交聯劑(D)的比例、以及光聚合起始劑(E)的比例,除此以外,與實施例1同樣地製造黏著片。另外,對於比較例7~10,將N,N-雙(2-乙基己基)-(4或5)-甲基-1H-苯并三唑-1-甲胺(BASF公司製,商品名“IRGMET 39”)作為防鏽劑以表1所示之比例配合於黏著性組成物中。並且,比較例1~10的黏著性組成物係活性能量射線非硬化性,一般係使該黏著性組成物熱交聯而得到者成為黏著劑,但方便起見,有時由該黏著劑構成之層亦稱為“硬化前黏著劑層”。 Changing the decane coupling agent (the decane coupling agent having a mercapto group) as shown in Table 1. The type and ratio of (B) and other decane coupling agents, the type and ratio of active energy ray-curable component (C), the ratio of crosslinking agent (D), and the ratio of photopolymerization initiator (E), Otherwise, an adhesive sheet was produced in the same manner as in Example 1. Further, for Comparative Examples 7 to 10, N,N-bis(2-ethylhexyl)-(4 or 5)-methyl-1H-benzotriazole-1-methylamine (trade name, manufactured by BASF Corporation) "IRGMET 39") was incorporated as a rust inhibitor in the adhesive composition in the proportions shown in Table 1. Further, in the adhesive compositions of Comparative Examples 1 to 10, the active energy ray is non-hardening, and generally the adhesive composition is thermally crosslinked to obtain an adhesive. However, for convenience, the adhesive may be used. The layer is also referred to as the "adhesive layer before hardening".

其中,前述重量平均分子量(Mw)係使用凝膠滲透色譜(GPC)在以下條件下測定(GPC測定)之聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions (GPC measurement).

<測定條件> <Measurement conditions>

.GPC測定裝置:TOSOH CORPORATION製,HLC-8020 . GPC measuring device: manufactured by TOSOH CORPORATION, HLC-8020

.GPC柱(按以下順序通過):TOSOH CORPORATION製 . GPC column (passed in the following order): TOSOH CORPORATION

TSK guard column HXL-H TSK guard column HXL-H

TSK gel GMHXL(×2) TSK gel GMHXL (×2)

TSK gel G2000HXL TSK gel G2000HXL

.測定溶劑:四氫呋喃 . Determination of solvent: tetrahydrofuran

.測定溫度:40℃ . Measuring temperature: 40 ° C

〔試驗例1〕(凝膠分率的測定) [Test Example 1] (Measurement of gel fraction)

將實施例及比較例中所得到之黏著片裁剪為80mm×80mm的尺寸,將其硬化前黏著劑層包在聚酯製網(網眼尺寸200) 中,藉由精密天平秤取其質量,減去上述網單獨的質量,藉此計算硬化前黏著劑本身的質量。將此時的質量設為M1。 The adhesive sheets obtained in the examples and the comparative examples were cut into a size of 80 mm × 80 mm, and the adhesive layer before curing was wrapped in a polyester mesh (mesh size 200). In the middle, the mass of the above-mentioned net is subtracted by the precision balance, and the quality of the adhesive itself before hardening is calculated. Set the quality at this time to M1.

接著,在室溫下(23℃),將包在上述聚酯製網中之硬化前黏著劑在乙酸乙酯中浸漬24小時。其後,取出硬化前黏著劑,在溫度23℃、相對濕度50%的環境下風乾24小時,另外,在80℃的烘箱中乾燥12小時。乾燥後,藉由精密天平秤取其質量,減去上述網單獨的質量,藉此計算硬化前黏著劑本身的質量。將此時的質量設為M2。以(M2/M1)×100表示凝膠率(%)。將結果示於表2。 Next, the pre-curing adhesive wrapped in the above polyester web was immersed in ethyl acetate for 24 hours at room temperature (23 ° C). Thereafter, the pre-curing adhesive was taken out, air-dried for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 50%, and dried in an oven at 80 ° C for 12 hours. After drying, the mass of the above-mentioned net is subtracted by a precision balance to calculate the mass of the above-mentioned net, thereby calculating the quality of the adhesive itself before hardening. Set the quality at this time to M2. The gel fraction (%) is represented by (M2/M1) × 100. The results are shown in Table 2.

並且,對實施例中所得到之黏著片的硬化前黏著劑層,隔著輕剝離型剝離片籍由紫外線照射裝置(EYE GRAPHICS Co.,Ltd.製,產品名“Eye Grandage ECS-401GX型”)在下述條件下照射紫外線,使硬化前黏著劑層硬化而作為黏著劑層。對於該黏著劑層,與上述硬化前黏著劑層同樣地測定凝膠分率(%)。將結果示於表2。 Further, the pre-hardening adhesive layer of the adhesive sheet obtained in the examples was subjected to an ultraviolet irradiation apparatus (manufactured by EYE GRAPHICS Co., Ltd., product name "Eye Grandage ECS-401GX type") via a light-peelable release sheet. The ultraviolet ray is irradiated under the following conditions to harden the adhesive layer before curing as an adhesive layer. The gel fraction (%) was measured in the same manner as the pre-curing adhesive layer. The results are shown in Table 2.

[紫外線照射條件] [UV irradiation conditions]

.光源:高壓水銀燈 . Light source: high pressure mercury lamp

.光量:1000mJ/cm2 . Light quantity: 1000mJ/cm 2

.照度:200mW/cm2 . Illuminance: 200mW/cm 2

〔試驗例2〕(黏著力的測定) [Test Example 2] (Measurement of adhesion)

從實施例及比較例中所得到之黏著片上剝離輕剝離型剝離片,並將暴露之硬化前黏著劑層貼合於具有易接著層之聚對苯二甲酸乙二酯(PET)薄膜(TOYOBO CO.,LTD.製,產品名“PET A4300”,厚度:100μm)的易接著層,從而得到重剝離型 剝離片/硬化前黏著劑層/PET薄膜的積層體。將所得到之積層體裁斷為25mm宽度、100mm長度,將其作為樣品。 The light release release sheet was peeled off from the adhesive sheets obtained in the examples and the comparative examples, and the exposed pre-hardened adhesive layer was attached to a polyethylene terephthalate (PET) film having an easy adhesion layer (TOYOBO). CO.,LTD., product name "PET A4300", thickness: 100μm) easy adhesion layer, resulting in heavy peeling type A laminate of a release sheet/pre-curing adhesive layer/PET film. The obtained laminate was cut into a width of 25 mm and a length of 100 mm, and this was used as a sample.

在23℃、50%RH的環境下,從上述樣品剝離重剝離型剝離片,並將露出之硬化前黏著劑層貼附於鈉鈣玻璃(Nippon Sheet Glass Co.,Ltd.製)之後,利用KURIHARA CORPORATION製高壓釜在0.5MPa、50℃下加壓20分鐘。其後,在23℃、50%RH的條件下放置24小時之後,使用拉伸試驗機(ORIENTEC Co.,LTD.製,TENSILON)在剝離速度300mm/min、剝離角度180度的條件下測定黏著力(N/25mm)。在此所記載之以外的條件遵照JIS Z 0237:2009來進行測定。將結果示於表2。 The peeling-off release sheet was peeled off from the above-mentioned sample in an environment of 23° C. and 50% RH, and the exposed pre-curing adhesive layer was attached to soda lime glass (manufactured by Nippon Sheet Glass Co., Ltd.). The KURIHARA CORPORATION autoclave was pressurized at 0.5 MPa and 50 ° C for 20 minutes. Thereafter, the mixture was allowed to stand under the conditions of 23 ° C and 50% RH for 24 hours, and then the adhesion was measured under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180 degrees using a tensile tester (TENSILON, manufactured by ORIENTEC Co., LTD.). Force (N/25mm). The conditions other than those described herein were measured in accordance with JIS Z 0237:2009. The results are shown in Table 2.

並且,將上述樣品(僅對實施例)如上所述般貼附於鈉鈣玻璃,並利用KURIHARA CORPORATION製高壓釜在0.5MPa、50℃下加壓20分鐘之後,在與試驗例1相同的紫外線照射條件下,隔著PET薄膜而對硬化前黏著劑層照射紫外線,使硬化前黏著劑層硬化而作為黏著劑層。對於具有該黏著劑層之樣品,與上述同樣地測定黏著力(N/25mm)。將結果示於表2。 Furthermore, the above sample (only the examples) was attached to soda lime glass as described above, and the same ultraviolet rays as in Test Example 1 were applied after being pressurized at 0.5 MPa and 50 ° C for 20 minutes in an autoclave made of KURIHARA CORPORATION. Under the irradiation conditions, the adhesive layer before the curing is irradiated with ultraviolet rays through the PET film, and the adhesive layer before curing is cured to serve as an adhesive layer. The adhesion (N/25 mm) was measured in the same manner as above for the sample having the adhesive layer. The results are shown in Table 2.

〔試驗例3〕(遷移防止效果的評價) [Test Example 3] (Evaluation of migration prevention effect)

(1)配線基板的作製 (1) Manufacturing of wiring board

在將銅箔(厚度:18μm)與聚對苯二甲酸乙二酯薄膜(厚度:50μm)積層而成之敷銅積層板(NIKKAN INDUSTRIES Co.,Ltd.製,產品名“NIKAFLEX”)的銅箔表面上,利用網版印刷法印刷蝕刻抗蝕劑圖案。其後,藉由蝕刻去除不需要的銅箔 而形成梳形電極。各電極的線寬為300μm,電極相互間的間隙為50μm。 A copper-clad laminate (manufactured by NIKKAN INDUSTRIES Co., Ltd., product name "NIKAFLEX") laminated with a copper foil (thickness: 18 μm) and a polyethylene terephthalate film (thickness: 50 μm) On the foil surface, an etch resist pattern is printed by screen printing. Thereafter, the unnecessary copper foil is removed by etching A comb electrode is formed. The line width of each electrode was 300 μm, and the gap between the electrodes was 50 μm.

(2)遷移防止效果的評價 (2) Evaluation of migration prevention effect

從實施例及比較例中所得到之黏著片剝離輕剝離型剝離片,並將露出之硬化前黏著劑層貼合於具有易接著層之聚對苯二甲酸乙二酯(PET)薄膜(TOYOBO CO.,LTD.製,產品名“PET A4300”,厚度:100μm)的易接著層,從而得到重剝離型剝離片/硬化前黏著劑層/PET薄膜的積層體。接著,從上述積層體剝離重剝離型剝離片,並將露出之硬化前黏著劑層貼附於上述梳形電極上。 The light release release sheet was peeled off from the adhesive sheets obtained in the examples and the comparative examples, and the exposed pre-hardened adhesive layer was attached to a polyethylene terephthalate (PET) film having an easy adhesion layer (TOYOBO). An easy-adhesion layer of a product of "CO., LTD., product name "PET A4300", thickness: 100 μm) was obtained, thereby obtaining a laminate of a heavy release type release sheet/pre-curing adhesive layer/PET film. Next, the heavy release type release sheet is peeled off from the laminated body, and the exposed pre-curing adhesive layer is attached to the comb-shaped electrode.

在與試驗例1相同的紫外線照射條件下,隔著PET薄膜而對上述硬化前黏著劑層(僅對實施例)照射紫外線,使硬化前黏著劑層硬化而作為黏著劑層。 Under the ultraviolet irradiation conditions similar to those in Test Example 1, the pre-curing adhesive layer (only the examples) was irradiated with ultraviolet rays through a PET film, and the adhesive layer before curing was cured to serve as an adhesive layer.

在85℃、85%RH的濕熱條件下靜置如上述所得之樣品,以該狀態對電極間施加5V的電壓來進行遷移試驗。自試驗開始起8小時後、24小時後及48小時後,利用光學顯微鏡(倍率:10倍)對梳形電極進行觀察,並基於以下所示之評價基準評價遷移防止效果。將結果示於表2。 The sample obtained as described above was allowed to stand under humid heat conditions of 85 ° C and 85% RH, and a voltage of 5 V was applied between the electrodes in this state to carry out a migration test. The comb-shaped electrode was observed by an optical microscope (magnification: 10 times) 8 hours, 24 hours, and 48 hours after the start of the test, and the migration prevention effect was evaluated based on the evaluation criteria shown below. The results are shown in Table 2.

◎:完全未觀察到電極(正極)的溶解及在電極(負極)中形成樹枝結晶。 ◎: Dissolution of the electrode (positive electrode) and formation of dendrite crystals in the electrode (negative electrode) were not observed at all.

○:僅在電極(正極)的端部觀察到溶解,未觀察到在電極(負極)中形成樹枝結晶。 ○: Dissolution was observed only at the end of the electrode (positive electrode), and no branch crystal was observed in the electrode (negative electrode).

×:觀察到電極(正極)的溶解及在電極(負極)中形成樹枝結晶。 ×: Dissolution of the electrode (positive electrode) and formation of dendrite crystals in the electrode (negative electrode) were observed.

另外,將上述評價基準的參考圖像示於第3圖。 In addition, the reference image of the above evaluation criteria is shown in FIG.

〔試驗例4〕(段差追隨性的評價) [Test Example 4] (Evaluation of the step followability)

(a)評價用樣品的製作 (a) Production of samples for evaluation

在玻璃板(NSG Precision Co.,Ltd.製造,產品名“Corning Glass EAGLE XG”,縱90mm×橫50mm×厚度0.5mm)的表面網版印刷紫外線硬化型油墨(Teikoku Printing Inks Mfg.Co.,Ltd.製造,產品名“POS-911油墨”),使得塗佈厚度成為5μm、10μm、15μm及20μm中的任意一種的邊框狀(外形:縱90mm×橫50mm,寬5mm)。接著,照射紫外線(80W/cm2,金屬鹵化物燈兩個,燈高為15cm,帶速為10~15m/分鐘),以使印刷之上述紫外線硬化型油墨硬化,從而製作藉由印刷而具有段差(段差的高度:5μm、10μm、15μm及20μm中的任意一種)之附帶段差之玻璃板。 Surface-printing UV-curable ink (Teikoku Printing Inks Mfg. Co., manufactured by NSG Precision Co., Ltd., product name "Corning Glass EAGLE XG", vertical 90 mm × width 50 mm × thickness 0.5 mm) The product name "POS-911 Ink" manufactured by Ltd. is such that the coating thickness is a frame shape of any of 5 μm, 10 μm, 15 μm, and 20 μm (outer shape: vertical 90 mm × width 50 mm, width 5 mm). Next, ultraviolet rays (80 W/cm 2 , two metal halide lamps, a lamp height of 15 cm, and a belt speed of 10 to 15 m/min) were irradiated to harden the printed ultraviolet curable ink, thereby producing by printing. A glass plate with a step difference (the height of the step: any one of 5 μm, 10 μm, 15 μm, and 20 μm).

從在實施例及比較例中所得之黏著片剝離輕剝離型剝離片,並將所露出之硬化前黏著劑層貼合於具有易接著層之聚對苯二甲酸乙二酯(PET)薄膜(TOYOBO Co.,Ltd.製造,PET A4300,厚度:100μm)的易接著層。接著,剝離重剝離型剝離片,並揭開硬化前黏著劑層。之後,使用積層機(FUJIPLA Inc.製造,產品名“LPD3214”)以硬化前黏著劑層覆蓋邊框狀的整個印刷面之方式將上述積層體積層到各附帶段差的玻璃板上。 The light release-type release sheet was peeled off from the adhesive sheets obtained in the examples and the comparative examples, and the exposed pre-hardened adhesive layer was attached to a polyethylene terephthalate (PET) film having an easy-to-attach layer ( Manufactured by TOYOBO Co., Ltd., PET A4300, thickness: 100 μm). Next, the heavy release type release sheet was peeled off, and the adhesive layer before hardening was peeled off. Thereafter, the laminated volume layer was applied to each of the glass plates with the stepped surface so that the pre-hardening adhesive layer covered the entire printing surface of the frame by using a laminator (manufactured by FUJIPLA Inc., product name "LPD3214").

在與試驗例1相同的紫外線照射條件下,隔著PET薄膜而對上述硬化前黏著劑層(僅對實施例)照射紫外線,使硬化前黏著劑層硬化而作為黏著劑層。 Under the ultraviolet irradiation conditions similar to those in Test Example 1, the pre-curing adhesive layer (only the examples) was irradiated with ultraviolet rays through a PET film, and the adhesive layer before curing was cured to serve as an adhesive layer.

(b)評價用樣品的評價 (b) Evaluation of samples for evaluation

在50℃、0.5MPa的條件下,對如上述所得之評價用樣品進行30分鐘高壓釜處理之後,在常壓、23℃、50%RH下放置24小時。接著,在85℃、85%RH的耐久條件下保管72小時。其後,目視確認黏著劑層(尤其由印刷層形成之段差的附近),並依照以下基準評價段差追隨性。將結果示於表2。 The sample for evaluation obtained as described above was subjected to an autoclave treatment at 50 ° C and 0.5 MPa for 30 minutes, and then left at normal pressure, 23 ° C, and 50% RH for 24 hours. Next, it was stored under the endurance conditions of 85 ° C and 85% RH for 72 hours. Thereafter, the adhesive layer (especially in the vicinity of the step formed by the printed layer) was visually confirmed, and the step followability was evaluated in accordance with the following criteria. The results are shown in Table 2.

◎:完全沒有氣泡及浮起。 ◎: There are no bubbles at all and floating.

○:在段差附近觀察到少於10個的氣泡。 ○: Less than 10 bubbles were observed in the vicinity of the step.

×:存在氣泡和/或浮起。 ×: There are bubbles and/or floating.

〔試驗例5〕(抗起泡性的評價) [Test Example 5] (Evaluation of anti-foaming property)

將實施例及比較例中所得到之黏著片的硬化前黏著劑層夾在一面設有由錫摻雜氧化銦(ITO)構成之透明導電膜之聚對苯二甲酸乙二酯(PET)薄膜(OIKE & Co.,Ltd.製,ITO薄膜,厚度:125μm)的透明導電膜與聚碳酸酯板(Mitsubishi Gas Chemical Company,Inc.製,產品名“Iupilon.sheet MR58”,厚度:1mm)之間而得到積層體。 The pre-hardening adhesive layer of the adhesive sheet obtained in the examples and the comparative examples was sandwiched between polyethylene terephthalate (PET) films provided with a transparent conductive film made of tin-doped indium oxide (ITO). A transparent conductive film (manufactured by Oike & Co., Ltd., ITO film, thickness: 125 μm) and a polycarbonate plate (manufactured by Mitsubishi Gas Chemical Company, Inc., product name "Iupilon.sheet MR58", thickness: 1 mm) A layered body is obtained.

在50℃、0.5MPa的條件下,對所得到之積層體進行30分鐘高壓釜處理。並且,對於實施例的積層體,在與試驗例1相同的紫外線照射條件下,隔著PET薄膜而照射紫外線,使硬化前黏著劑層硬化而作為黏著劑層。 The obtained laminate was subjected to autoclave treatment at 50 ° C and 0.5 MPa for 30 minutes. Further, in the laminate of the example, under the same ultraviolet irradiation conditions as in Test Example 1, ultraviolet rays were irradiated through the PET film, and the adhesive layer before curing was cured to serve as an adhesive layer.

將如上述所得之樣品在常壓、23℃、50%RH下放置15小時之後,在85℃、85%RH的高溫高濕條件下保管72小時。其後,目視確認黏著劑層與被黏物的界面上之氣泡、浮起或剝離,並依照以下基準評價抗起泡性。將結果示於表2。 The sample obtained as described above was allowed to stand under normal pressure, 23 ° C, and 50% RH for 15 hours, and then stored under high temperature and high humidity conditions of 85 ° C and 85% RH for 72 hours. Thereafter, bubbles, floating or peeling at the interface between the adhesive layer and the adherend were visually confirmed, and the anti-foaming property was evaluated in accordance with the following criteria. The results are shown in Table 2.

◎......完全沒有氣泡、浮起及剝離。 ◎...... There are no bubbles, floats and peels at all.

○......僅產生直径0.2mm以下的氣泡。 ○ ... Only bubbles having a diameter of 0.2 mm or less were produced.

×......產生直怪超過0.2mm的氣泡、浮起或剝離。 ×... Produces a bubble that floats more than 0.2 mm, floats or peels off.

〔試驗例6〕(耐濕熱白化性的評價) [Test Example 6] (Evaluation of resistance to wet heat whitening)

將實施例或比較例中所得到之黏著片的硬化前黏著劑層利用厚度1.1mm的兩片無鹼性玻璃夾住而得到積層體。並且,對於實施例的積層體,在與試驗例1相同的紫外線照射條件下,隔著一個玻璃而照射紫外線,使硬化前黏著劑層硬化而作為黏著劑層。 The pre-curing adhesive layer of the adhesive sheet obtained in the example or the comparative example was sandwiched between two sheets of alkali-free glass having a thickness of 1.1 mm to obtain a laminate. Further, in the laminate of the example, under the same ultraviolet irradiation conditions as in Test Example 1, ultraviolet rays were irradiated through one glass, and the adhesive layer before curing was cured to serve as an adhesive layer.

在85℃、85%RH的條件下,將如上述所得之樣品保管120小時。其後,恢復23℃、50%RH的常溫常濕,依照以下基準目視確認白化的有無來,評價耐濕熱白化性,並且測定黏著劑層的霧度值。關於霧度值,使樣品恢復常溫常濕之後在30分鐘以內,使用霧度計(NIPPON DENSHOKU INDUSTRIES Co.,LTD.製,產品名“NDH2000”)按照JIS K7136:2000進行測定。將結果示於表2。 The sample obtained as described above was stored for 120 hours under conditions of 85 ° C and 85% RH. Thereafter, normal temperature and humidity of 23° C. and 50% RH were recovered, and the presence or absence of whitening was visually observed according to the following criteria, and the wet heat whitening resistance was evaluated, and the haze value of the adhesive layer was measured. With respect to the haze value, the sample was returned to normal temperature and humidity, and the measurement was carried out in accordance with JIS K7136:2000 using a haze meter (manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD., product name "NDH2000") within 30 minutes. The results are shown in Table 2.

○:即使恢復常溫常濕亦未確認到白化。或者,一部分發生白化,但在30分鐘以內消失。 ○: Whitening was not confirmed even after returning to normal temperature and humidity. Or, part of it will be whitened, but it will disappear within 30 minutes.

×:整體發生白化。或者,一部分發生白化之後,即使在常溫常濕下保管亦無法恢復原狀態。 ×: The overall whitening occurred. Or, after a part of whitening occurs, it cannot be restored to its original state even if it is stored under normal temperature and humidity.

【表1】 【Table 1】

由表2可知,實施例中所得到之黏著片係遷移防止效果、段差追隨性、抗起泡性及耐濕熱白化性中的任一個均 優異者。 As can be seen from Table 2, any of the adhesive sheet migration prevention effect, the step followability, the anti-foaming property, and the moist heat whitening property obtained in the examples were all observed. Excellent.

【產業上的可利用性】 [Industrial availability]

本發明之黏著性組成物及黏著片例如可以較佳地用於使用銅電極或銀電極之靜電容量方式的觸摸面板。並且,本發明之顯示體例如較佳地作為使用銅電極或銀電極之靜電容量方式的觸摸面板。 The adhesive composition and the adhesive sheet of the present invention can be preferably used, for example, in a capacitive touch panel using a copper electrode or a silver electrode. Further, the display body of the present invention is preferably used as a capacitive touch panel using a copper electrode or a silver electrode, for example.

1‧‧‧黏著片 1‧‧‧Adhesive film

10‧‧‧硬化前黏著劑層 10‧‧‧Adhesive layer before hardening

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

Claims (10)

一種黏著性組成物,其形成用於將至少在貼合之側的面具有段差之第1顯示體構成構件與第2顯示體構成構件進行貼合之黏著劑,該黏著性組成物的特徵為:前述第1顯示體構成構件和/或前述第2顯示體構成構件至少在貼合之側的面具有電極,前述黏著性組成物含有:(甲基)丙烯酸酯聚合物(A);具有巰基之矽烷偶合劑(B);及活性能量射線硬化性成分(C)。 An adhesive composition which forms an adhesive for bonding a first display constituent member and a second display constituent member having a step at least on the side of the bonding, and the adhesive composition is characterized by The first display member constituting member and/or the second display member constituting member have an electrode on at least a surface on which the bonding is performed, and the adhesive composition contains a (meth) acrylate polymer (A); a decane coupling agent (B); and an active energy ray hardening component (C). 如申請專利範圍第1項所述之黏著性組成物,其中,前述具有巰基之矽烷偶合劑(B)係含巰基之寡聚物型矽烷偶合劑。 The adhesive composition according to claim 1, wherein the decane coupling agent (B) having a mercapto group is a fluorenyl group-containing oligomer-type decane coupling agent. 如申請專利範圍第1項所述之黏著性組成物,其中,構成前述具有巰基之矽烷偶合劑(B)之有機矽化合物的巰基當量為100g/莫爾以上且1000g/莫爾以下。 The adhesive composition according to claim 1, wherein the sulfhydryl equivalent of the organic hydrazine compound constituting the decane coupling agent (B) having a mercapto group is 100 g/mole or more and 1000 g/mole or less. 如申請專利範圍第1項所述之黏著性組成物,其中,前述黏著性組成物中之前述具有巰基之矽烷偶合劑(B)的含有量相對於前述(甲基)丙烯酸酯聚合物(A)100質量份為0.01質量份以上且5質量份以下。 The adhesive composition according to claim 1, wherein the content of the decane coupling agent (B) having a mercapto group in the adhesive composition is relative to the (meth) acrylate polymer (A). 100 parts by mass is 0.01 parts by mass or more and 5 parts by mass or less. 如申請專利範圍第1項所述之黏著性組成物,其中,前述黏著性組成物中之前述活性能量射線硬化性成分(C)的含有量相對於前述(甲基)丙烯酸酯聚合物(A)100質量份為0.5質量份以上且50質量份以下。 The adhesive composition according to the first aspect of the invention, wherein the content of the active energy ray-curable component (C) in the adhesive composition is relative to the (meth) acrylate polymer (A) 100 parts by mass is 0.5 parts by mass or more and 50 parts by mass or less. 如申請專利範圍第1項所述之黏著性組成物,其中,前述(甲基)丙烯酸酯聚合物(A)含有3質量%以上且35質量%以下的含羥基單體來作為構成該聚合物之單體單元。 The adhesive composition according to claim 1, wherein the (meth) acrylate polymer (A) contains 3% by mass or more and 35% by mass or less of a hydroxyl group-containing monomer as a constituent of the polymer. Monomer unit. 如申請專利範圍第1項所述之黏著性組成物,其中,前述黏著性組成物還含有交聯劑(D)。 The adhesive composition according to claim 1, wherein the adhesive composition further contains a crosslinking agent (D). 一種黏著片,其特徵為:具有使申請專利範圍第1至7項中任一項所述之黏著性組成物熱交聯而成之硬化前黏著劑層。 An adhesive sheet comprising a pre-curing adhesive layer obtained by thermally crosslinking an adhesive composition according to any one of claims 1 to 7. 如申請專利範圍第8項所述之黏著片,其中,前述黏著片包括兩片剝離片,前述硬化前黏著劑層以與前述兩片剝離片的剝離面接觸之方式被前述剝離片所夾持。 The adhesive sheet according to claim 8, wherein the adhesive sheet comprises two release sheets, and the pre-curing adhesive layer is held by the release sheet in contact with the peeling surface of the two release sheets. . 一種顯示體,其包括:至少在貼合之側的面具有段差之第1顯示體構成構件;第2顯示體構成構件;及將前述第1顯示體構成構件與前述第2顯示體構成構件相互貼合之黏著劑層,其特徵為:前述第1顯示體構成構件和/或前述第2顯示體構成構件至少在貼合之側的面具有電極,前述黏著劑層係藉由活性能量射線的照射使申請專利範圍第8項所述之黏著片的硬化前黏著劑層硬化而得到者。 A display body comprising: a first display body constituting member having a step at least on a side of the bonding; a second display constituting member; and the first display constituting member and the second display constituting member The adhesive layer to be bonded is characterized in that the first display constituent member and/or the second display constituent member have electrodes on at least the surface on the side where the bonding is performed, and the adhesive layer is composed of active energy rays. Irradiation is obtained by hardening the pre-hardening adhesive layer of the adhesive sheet according to item 8 of the patent application.
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