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TWI733728B - Adhesive sheet for conductive member, conductive member laminate, and image display device - Google Patents

Adhesive sheet for conductive member, conductive member laminate, and image display device Download PDF

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TWI733728B
TWI733728B TW105143067A TW105143067A TWI733728B TW I733728 B TWI733728 B TW I733728B TW 105143067 A TW105143067 A TW 105143067A TW 105143067 A TW105143067 A TW 105143067A TW I733728 B TWI733728 B TW I733728B
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meth
adhesive sheet
conductive member
conductive
adhesive
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TW201726858A (en
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新美可保留
山本亮太
稲永誠
吉川秀次郎
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日商三菱化學股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

本發明提供一種不會腐蝕導電構件、例如透明導電層且具有防氧化劣化性及良好之硬化特性之導電構件用黏著片材、導電構件積層體及圖像顯示裝置。本發明尤其提供一種適合於電漿顯示器(PDP)、液晶顯示器(LCD)、有機EL顯示器(OLED)等使用圖像顯示面板之圖像顯示裝置中貼合透明導電層等導電構件之導電構件用黏著片材。 本發明之導電構件用黏著片材包含黏著劑層，該黏著劑層包含含有(甲基)丙烯酸系共聚物、金屬腐蝕防止劑及亞磷酸酯化合物之黏著劑組合物。The present invention provides an adhesive sheet for a conductive member, a laminated body of a conductive member, and an image display device that does not corrode conductive members, such as a transparent conductive layer, has oxidation degradation resistance and good curing characteristics. In particular, the present invention provides a conductive member suitable for laminating conductive members such as transparent conductive layers in image display devices such as plasma displays (PDP), liquid crystal displays (LCD), organic EL displays (OLED) and other image display panels. Adhesive sheet. The adhesive sheet for a conductive member of the present invention includes an adhesive layer including an adhesive composition containing a (meth)acrylic copolymer, a metal corrosion inhibitor, and a phosphite compound.

Description

導電構件用黏著片材、導電構件積層體及圖像顯示裝置Adhesive sheet for conductive member, conductive member laminate, and image display device

本發明係關於一種導電構件用黏著片材及使用該黏著片材之導電構件積層體等。本發明尤其關於一種適合於電漿顯示器(PDP)、液晶顯示器(LCD)、有機EL(Electroluminescence，電致發光)顯示器(OLED)、無機EL顯示器、電泳顯示器(EPD)、干擾調變顯示器(IMOD)等使用圖像顯示面板之圖像顯示裝置中貼合透明導電層等導電構件之導電構件用黏著片材等。The present invention relates to an adhesive sheet for a conductive member, a conductive member laminate using the adhesive sheet, and the like. The present invention particularly relates to a plasma display (PDP), liquid crystal display (LCD), organic EL (Electroluminescence, electroluminescence) display (OLED), inorganic EL display, electrophoretic display (EPD), interference modulation display (IMOD) ) Adhesive sheets for conductive members, etc., in image display devices using image display panels, such as transparent conductive layers and other conductive members.

於個人電腦、行動設備終端(PDA)、遊戲機、電視(TV)、汽車導航系統、觸控面板、手寫板等之圖像顯示裝置、例如電漿顯示器(PDP)、液晶顯示器(LCD)、有機EL顯示器(OLED)、無機EL顯示器、電泳顯示器(EPD)、干擾調變顯示器(IMOD)等平面型或使用具有曲面之圖像顯示面板之圖像顯示裝置中，為了確保視認性或防止破損等，未於各構成構件間設置空隙並利用黏著片材或液狀黏著劑將各構成物材間貼合而一體化。 例如，於具備於液晶模組之視認側與表面保護面板之間插入有觸控面板而成之構成之圖像顯示裝置中，於表面保護面板與液晶模組之視認側之間配置黏著片材或液狀黏著劑，將觸控面板與另一構成構件、例如將觸控面板與液晶模組、觸控面板與表面保護面板貼合而一體化。 觸控面板通常具備由摻錫之氧化銦(ITO)、銦-鎵-鋅複合氧化物(IGZO)、摻Ga之氧化鋅(GZO)等金屬氧化物或銀、銅、鉬等金屬材料形成之微細配線或具有由銀奈米線、奈米碳管等形成之透明導電層之上部電極板及下部電極板。又，為了彙集透明導電層所檢測出之手指或觸摸筆等之位置資訊並進行通信，將由金屬材料形成之導體圖案(配線圖案)形成於透明導電層與IC(Integrated Circuit，積體電路)等控制機構之間。該等由各種材料形成之透明導電層或導體圖案通常係以表面與黏著劑相接之方式固定。該透明導電層或導體圖案存在如下顧慮：對腐蝕脆弱，於高溫或濕熱環境下會因黏著材之釋氣或源自溶出成分之酸成分等而腐蝕，視情形會斷線等。 然而，於決定黏著片材或液狀黏著劑等之組成或製備方法時，為了賦予接著力或凝集力等作為黏著材之基本物性，通常導入羧基等高極性成分作為共聚合成分或添加劑。然而，由於此種高極性成分具有氧化作用，故而存在因處於高溫高濕等環境下或長期保管而黏著片材導致被黏著體之氧化劣化等之情況。於貼合具備包含如ITO膜或IGZO膜等導電構件之部分之導電構件之情形時，需要特別注意此種被黏著體之氧化劣化。 因此，鑒於此種問題點，提出有不將羧基等酸性成分導入至黏著劑組合物中，藉此抑制被黏著體之氧化劣化。例如，於專利文獻1等中揭示有包含將丙烯酸烷氧基烷基酯(成分A)及具有羥基之丙烯酸系單體(成分B)作為必須之單體成分而構成之質量平均分子量40萬～160萬之丙烯酸系聚合物之黏著劑組合物。 又，例如，於專利文獻2中揭示有含有作為金屬腐蝕防止劑之苯并三唑及/或其衍生物之金屬貼附用黏著片材。 進而，例如，於專利文獻3中揭示有如下透明導電膜固定用兩面黏著片材：使兩面黏著片材之黏著劑層之酸成分含有特定量之含氮原子成分，藉此降低對透明導電膜之腐蝕性，並兼具較高之黏著劑層之凝集力及對透明導電膜之較高之接著性。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2010-215923號公報 [專利文獻2]日本專利特開2006-45315號公報 [專利文獻3]日本專利特開2010-144002號公報Image display devices used in personal computers, mobile device terminals (PDA), game consoles, televisions (TV), car navigation systems, touch panels, handwriting boards, etc., such as plasma displays (PDP), liquid crystal displays (LCD), Organic EL displays (OLED), inorganic EL displays, electrophoretic displays (EPD), interference modulation displays (IMOD) and other flat-type or image display devices using curved image display panels, in order to ensure visibility or prevent damage Etc., without providing a gap between the constituent members, and integrating the constituent materials with an adhesive sheet or a liquid adhesive. For example, in an image display device with a touch panel inserted between the viewing side of the liquid crystal module and the surface protection panel, an adhesive sheet is placed between the surface protection panel and the viewing side of the liquid crystal module Or a liquid adhesive, which integrates the touch panel and another constituent member, such as the touch panel and the liquid crystal module, and the touch panel and the surface protection panel. Touch panels are usually made of tin-doped indium oxide (ITO), indium-gallium-zinc composite oxide (IGZO), Ga-doped zinc oxide (GZO) and other metal oxides or silver, copper, molybdenum and other metal materials. The fine wiring may have an upper electrode plate and a lower electrode plate with a transparent conductive layer formed by silver nanowires, carbon nanotubes, etc. In addition, in order to collect and communicate the position information of the finger or touch pen detected by the transparent conductive layer, a conductive pattern (wiring pattern) formed of a metal material is formed on the transparent conductive layer and IC (Integrated Circuit), etc. Between control agencies. The transparent conductive layers or conductive patterns formed of various materials are usually fixed by the way the surface is connected with the adhesive. The transparent conductive layer or the conductive pattern has the following concerns: it is vulnerable to corrosion, will corrode due to the outgassing of the adhesive material or the acid component derived from the eluted component under high temperature or humid environment, and may break the wire depending on the situation. However, when determining the composition or preparation method of adhesive sheets or liquid adhesives, in order to impart adhesion or cohesive force as the basic physical properties of the adhesive, high-polarity components such as carboxyl groups are usually introduced as copolymerization components or additives. However, since such a highly polar component has an oxidizing effect, there are cases where the adhered body is oxidized and deteriorated due to the adhesion of the sheet under the environment such as high temperature and high humidity or long-term storage. When bonding a conductive member that includes a conductive member such as an ITO film or an IGZO film, it is necessary to pay special attention to the oxidation degradation of the adherend. Therefore, in view of such problems, it has been proposed not to introduce acidic components such as carboxyl groups into the adhesive composition, thereby suppressing the oxidative degradation of the adherend. For example, Patent Document 1 and the like disclose a mass average molecular weight comprising alkoxyalkyl acrylate (component A) and an acrylic monomer having a hydroxyl group (component B) as essential monomer components. 1.6 million acrylic polymer adhesive composition. In addition, for example, Patent Document 2 discloses an adhesive sheet for metal attachment containing benzotriazole and/or a derivative thereof as a metal corrosion inhibitor. Furthermore, for example, Patent Document 3 discloses a double-sided adhesive sheet for fixing a transparent conductive film: the acid component of the adhesive layer of the double-sided adhesive sheet contains a specific amount of nitrogen-containing atomic components, thereby reducing the resistance to the transparent conductive film It is corrosive, and has both higher cohesive force of the adhesive layer and higher adhesion to the transparent conductive film. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2010-215923 [Patent Document 2] Japanese Patent Laid-Open No. 2006-45315 [Patent Document 3] Japanese Patent Laid-Open No. 2010-144002 Bulletin

[發明所欲解決之問題] 若如上述專利文獻1所揭示般不將羧基等酸性成分導入至黏著劑組合物中，則黏著特性降低，於高溫高濕下白化而透明性等光學特性降低，故而難以維持含有羧基等酸性成分之先前之黏著劑組合物之特性。 又，上述專利文獻2之含有金屬腐蝕防止劑之兩面黏著片材存在金屬腐蝕防止劑於耐久性試驗中變色而光學特性降低等問題點。 進而，上述專利文獻3之透明導電膜固定用兩面黏著片材存在因含羧基之(甲基)丙烯酸酯共聚物之酸成分而導致ITO之電阻值變化之問題點。 因此，本發明所欲解決之問題亦在於提供一種不會腐蝕導電構件，又，即便黏著劑組合物包含羧基等酸性成分，於貼合於作為導電構件之透明導電層等時，亦可防止該等被黏著體之氧化劣化之防氧化劣化性優異之新穎之導電構件用黏著片材。更具體而言，提供一種即便與透明導電層之導電層面或由金屬材料形成之導體圖案(配線圖案)直接貼合，亦不會腐蝕該等，又，即便隔著絕緣保護膜(鈍化膜)與透明導電層之導電層面貼合，亦不會腐蝕透明導電層之導電構件用黏著片材。 [解決問題之技術手段] 本發明之主要特徵在於：其具有包含含有(甲基)丙烯酸系共聚物、金屬腐蝕防止劑及亞磷酸酯化合物之黏著劑組合物之黏著劑層。 [發明之效果] 本發明之導電構件用黏著片材可具有針對導電構件之耐腐蝕可靠性，並且亦可具有作為黏著片材之耐發泡可靠性及良好之硬化特性。因此，本發明之導電構件用黏著片材可用作適合貼合具有透明導電層及/或由包含銅或者銀之金屬材料形成之導體圖案之導電構件等各種導電構件。尤其可較佳地用作具有觸控面板之圖像顯示裝置用之黏著片材。[Problems to be Solved by the Invention] If acidic components such as carboxyl groups are not introduced into the adhesive composition as disclosed in Patent Document 1, the adhesive properties will decrease, whitening at high temperature and high humidity, and optical properties such as transparency will decrease. Therefore, it is difficult to maintain the characteristics of the previous adhesive composition containing acidic components such as carboxyl groups. In addition, the double-sided adhesive sheet containing a metal corrosion inhibitor of Patent Document 2 has a problem that the metal corrosion inhibitor discolors during the durability test and the optical properties are reduced. Furthermore, the double-sided adhesive sheet for fixing a transparent conductive film of Patent Document 3 described above has a problem that the resistance value of ITO changes due to the acid component of the carboxyl group-containing (meth)acrylate copolymer. Therefore, the problem to be solved by the present invention is also to provide a conductive member that does not corrode, and even if the adhesive composition contains acidic components such as carboxyl groups, it can also prevent the adhesive composition when it is attached to a transparent conductive layer as a conductive member. It is a novel adhesive sheet for conductive members with excellent resistance to oxidation degradation of the adherend. More specifically, there is provided a method that does not corrode even if it is directly attached to the conductive layer of the transparent conductive layer or the conductive pattern (wiring pattern) formed of a metal material, and even if an insulating protective film (passivation film) is interposed It is attached to the conductive surface of the transparent conductive layer without corroding the conductive member of the transparent conductive layer. [Technical Means to Solve the Problem] The main feature of the present invention is that it has an adhesive layer containing an adhesive composition containing a (meth)acrylic copolymer, a metal corrosion inhibitor, and a phosphite compound. [Effects of the invention] The adhesive sheet for conductive members of the present invention can have corrosion resistance reliability for conductive members, and can also have foaming resistance reliability and good hardening characteristics as an adhesive sheet. Therefore, the adhesive sheet for conductive members of the present invention can be used as various conductive members suitable for bonding conductive members having a transparent conductive layer and/or a conductive pattern formed of a metal material containing copper or silver. In particular, it can be preferably used as an adhesive sheet for an image display device with a touch panel.

以下，對本發明之實施形態之一例詳細地進行說明。但是，本發明並不限定於下述實施形態。 ＜導電構件用黏著片材＞ 本發明之實施形態之一例之導電構件用黏著片材(以下，亦省略後稱為「本黏著片材」)具有包含含有(甲基)丙烯酸系(共)聚合物、金屬腐蝕防止劑及亞磷酸酯化合物之黏著劑組合物之黏著劑層。 該黏著劑層既可為單層，亦可為多層，又，於為多層之情形時，亦可介存如所謂之基材層之其他層。於黏著劑層為具有其他層之多層構成之情形時，較佳為本黏著片材之表面層為包含上述黏著劑組合物之黏著劑層。 於本黏著片材為多層之情形時，包含上述黏著劑組合物之黏著劑層之厚度並無限定，相對於本黏著片材整體之厚度，較佳為10%以上，更佳為30%以上，進而較佳為50%以上。若包含上述黏著劑組合物之黏著劑層之厚度為上述範圍，則對導電構件之耐腐蝕可靠性、耐發泡可靠性、硬化特性變得良好，故而較佳。 再者，於本發明中，所謂「(共)聚合物」，係包括均聚物及共聚物之意義，所謂「(甲基)丙烯酸酯」係包括丙烯酸酯及甲基丙烯酸酯之意義。 [黏著劑組合物] 本黏著片材所使用之黏著劑組合物(以下，省略後稱為「本組合物」)含有(甲基)丙烯酸系(共)聚合物、金屬腐蝕防止劑及亞磷酸酯化合物。 本組合物亦可進而含有交聯劑、光聚合起始劑、抗氧化劑、其他成分。 本組合物較佳為光硬化性之組合物。 ((甲基)丙烯酸系(共)聚合物) 作為(甲基)丙烯酸系(共)聚合物，例如除(甲基)丙烯酸烷基酯之均聚物以外，亦可列舉藉由將其與具有共聚性之單體成分進行聚合而獲得之共聚物，更佳為列舉包含自(甲基)丙烯酸烷基酯、可與其共聚合之含羧基單體、含羥基單體、含胺基單體、含環氧基單體、含醯胺基單體及其他乙烯基單體中選擇之一種以上之單體作為結構單元之共聚物。 (甲基)丙烯酸系(共)聚合物可藉由常規方法視需要使用聚合起始劑對以下所例示之單體等進行製造。 於(甲基)丙烯酸系(共)聚合物為包含含羧基單體作為結構單元之共聚物之情形時，就獲得優異之黏著物性之觀點而言，(甲基)丙烯酸系(共)聚合物較佳為含有1.2～15質量%之含羧基單體，其中含有1.5質量%以上或者10質量%以下，其中進而較佳為含有2.0質量%以上或者8質量%以下。 作為更具體之(甲基)丙烯酸系(共)聚合物之一例，可列舉由側鏈之碳數為4～18之直鏈或支鏈(甲基)丙烯酸烷基酯(以下亦稱為「共聚性單體A」)與可與其共聚合之自以下之群中選擇之任一種以上之單體成分構成之共聚物。 ・含羧基單體(以下亦稱為「共聚性單體B」) ・巨單體(以下亦稱為「共聚性單體C」) ・側鏈之碳數為1～3之(甲基)丙烯酸酯(以下亦稱為「共聚性單體D」) ・含羥基單體(以下亦稱為「共聚性單體E」) ・其他乙烯基單體(以下亦稱為「共聚性單體F」) 又，作為(甲基)丙烯酸系(共)聚合物之一例，亦可列舉：(a)由包含共聚性單體A、共聚性單體B及/或共聚性單體C之單體成分構成之共聚物或(b)由包含共聚性單體A、共聚性單體B及/或共聚性單體C、共聚性單體D及/或共聚性單體E之單體成分構成之共聚物作為尤佳之例示。 作為上述側鏈之碳數4～18之直鏈或支鏈(甲基)丙烯酸烷基酯(共聚性單體A)，例如可列舉：(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山萮酯、(甲基)丙烯酸異𦯉基酯、3,5,5-三甲基環己烷(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸苄酯等。該等可使用1種，或亦可將2種以上組合使用。 上述共聚性單體A於共聚物之總單體成分中，較佳為含有30質量%以上且90質量%以下，其中，進而較佳為於35質量%以上或者88質量%以下之範圍內含有，其中，尤其進而較佳為於40質量%以上或者85質量%以下之範圍內含有。 作為上述含羧基單體(共聚性單體B)，例如可列舉：(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基丙基琥珀酸、丁烯酸、反丁烯二酸、順丁烯二酸、伊康酸。該等可使用1種，或亦可將2種以上組合。再者，「(甲基)丙烯酸基」係包括丙烯酸基及甲基丙烯酸基之意義。同樣地，「(甲基)丙烯醯基」係包括丙烯醯基及甲基丙烯醯基之意義。 上述共聚性單體B於共聚物之總單體成分中，較佳為於1.2質量%以上且15質量%以下之範圍內含有，其中，就獲得優異之黏著物性之觀點而言，較佳為於1.5質量%以上或者10質量%以下之範圍內含有，其中，尤佳為於2質量%以上或者8質量%以下之範圍內含有。   上述巨單體(共聚性單體C)係於藉由聚合而成為(甲基)丙烯酸系(共)聚合物時側鏈之碳數成為20以上之單體。藉由使用共聚性單體C，可將(甲基)丙烯酸系(共)聚合物製成接枝共聚物。因此，可根據共聚性單體C與除此以外之單體之選擇或調配比率使接枝共聚物之主鏈與側鏈之特性變化。 作為上述巨單體(共聚性單體C)，較佳為骨架成分係由丙烯酸系聚合物或乙烯系聚合物構成者。作為巨單體之骨架成分，例如可列舉上述共聚性單體A、上述共聚性單體B、下述共聚性單體D、下述共聚性單體E等所例示者，該等可單獨使用，或將2種以上組合使用。 巨單體係具有自由基聚合性基或羥基、異氰酸酯基、環氧基、羧基、胺基、醯胺基、硫醇基等官能基者。作為巨單體，較佳為具有可與其他單體共聚合之自由基聚合性基者。自由基聚合性基可含有一個或者兩個以上，其中，尤佳為一個。於巨單體具有官能基之情形時，官能基亦可含有一個或者兩個以上，其中，尤佳為一個。又，既可含有自由基聚合性基與官能基中之任一者，亦可含有兩者。 共聚性單體C之數量平均分子量較佳為500～2萬，其中，較佳為800以上或者8000以下，其中，較佳為1000以上或者7000以下。 巨單體可適當地使用以一般方式製造而成者(例如東亞合成公司製造之巨單體等)。 上述共聚性單體C於共聚物之總單體成分中，較佳為於5質量%以上且30質量%以下之範圍內含有，其中，較佳為於6質量%以上或者25質量%以下之範圍內含有，其中，尤佳為於8質量%以上或者20質量%以下之範圍內含有。 作為上述側鏈之碳數為1～3之(甲基)丙烯酸酯(共聚性單體D)，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯等。該等可使用1種，或亦可將2種以上組合。 上述共聚性單體D於共聚物之總單體成分中，較佳為含有0質量%以上且70質量%以下，其中，進而較佳為於3質量%以上或者65質量%以下之範圍內含有，其中，尤其進而較佳為於5質量%以上或者60質量%以下之範圍內含有。 作為上述含羥基單體(共聚性單體E)，可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯等(甲基)丙烯酸羥基烷基酯類。該等可使用1種，或亦可將2種以上組合。 上述共聚性單體E於共聚物之總單體成分中，較佳為含有0質量%以上且30質量%以下，其中，進而較佳為於0質量%以上或者25質量%以下之範圍內含有，其中，尤其進而較佳為於0質量%以上或者20質量%以下之範圍內含有。 作為上述其他乙烯基單體(共聚性單體F)，除共聚性單體A～E以外，亦可列舉分子內具有乙烯基之化合物。作為此種化合物，可例示：分子內具有醯胺基或烷氧基烷基等官能基之官能性單體類；以及聚伸烷基二醇二(甲基)丙烯酸酯類；以及乙酸乙烯酯、丙酸乙烯酯及月桂酸乙烯酯等乙烯酯單體；以及苯乙烯、氯苯乙烯、氯甲基苯乙烯、α-甲基苯乙烯及其他取代苯乙烯等芳香族乙烯基單體。該等可使用1種，或亦可將2種以上組合。 上述共聚性單體F於共聚物之總單體成分中，較佳為含有0質量%以上且30質量%以下，其中，進而較佳為於0質量%以上或者25質量%以下之範圍內含有，其中，尤其進而較佳為於0質量%以上或者20質量%以下之範圍內含有。 除上述所揭示者以外，亦可視需要適當地使用：順丁烯二酸酐、伊康酸酐等含酸酐基單體；(甲基)丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、(甲基)丙烯酸-3,4-環氧基丁酯等含環氧基單體；(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯等含胺基(甲基)丙烯酸酯系單體；(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、雙丙酮(甲基)丙烯醯胺、順丁烯二酸醯胺、順丁烯二醯胺等含有醯胺基或醯亞胺基之單體；乙烯基吡咯啶酮、乙烯基吡啶、乙烯咔唑等雜環系鹼性單體等。 作為(甲基)丙烯酸系(共)聚合物之最典型之例，例如可列舉使(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯等單體成分(a)、具有羧基之(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基丙基琥珀酸、丁烯酸、反丁烯二酸、順丁烯二酸、伊康酸等單體成分(b)、及具有有機官能基等之(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、(甲基)丙烯酸甘油酯、順丁烯二酸單甲酯、伊康酸單甲酯、乙酸乙烯酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯醯胺、(甲基)丙烯腈、氟化(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯等單體成分(c)共聚合所得之(甲基)丙烯酸酯共聚物。 (甲基)丙烯酸系(共)聚合物之質量平均分子量較佳為10萬以上且150萬以下，其中，較佳為15萬以上或者130萬以下，其中，尤佳為20萬以上或者120萬以下。 於欲獲得凝集力較高之黏著組合物之情形時，就分子量越大，越可藉由分子鏈之交聯而獲得凝集力之觀點而言，(甲基)丙烯酸系(共)聚合物之質量平均分子量較佳為70萬以上且150萬以下，尤佳為80萬以上或者130萬以下。另一方面，於欲獲得流動性或應力緩和性較高之黏著組合物之情形時，質量平均分子量較佳為10萬以上且70萬以下，尤佳為15萬以上或者60萬以下。 另一方面，於使黏著片材等成形時不使用溶劑之情形時，由於不易使用分子量較大之聚合物，故而(甲基)丙烯酸系(共)聚合物之質量平均分子量較佳為10萬以上且70萬以下，尤佳為15萬以上或者60萬以下，其中，尤佳為20萬以上或者50萬以下。 (金屬腐蝕防止劑) 本組合物含有金屬腐蝕防止劑。 作為金屬腐蝕防止劑，可列舉：苯并三唑系化合物、苯并咪唑化合物、苯并噻唑化合物、其他三唑衍生物等。 作為金屬腐蝕防止劑，較理想為自較佳為苯并三唑系化合物、1,2,3-三唑及1,2,4-三唑中選擇之任一種以上。其中，就除金屬腐蝕防止性以外，作為黏著片材之耐發泡可靠性亦優異之方面而言，較佳為1,2,3-三唑或1,2,4-三唑等三唑衍生物，尤佳為1,2,3-三唑。其原因在於推測可藉由於由包含銅之金屬材料形成之導體圖案表面形成銅原子與三唑之分子化學鍵結而成之保護皮膜而防止腐蝕。又，於具有由包含銀之金屬材料形成之導體圖案之導電構件中，亦可同樣地實現利用三唑所得之保護皮膜之效果。 再者，1,2,4-三唑係熔點約為120℃之固體，另一方面，1,2,3-三唑之熔點約為20℃，於室溫下大致為液體狀態。因此，與1,2,4-三唑相比，1,2,3-三唑具有混合於黏著劑組合物中時之分散性優異而可均勻地混合，又，容易母料化等優異之優勢。 於本組合物中，就金屬腐蝕防止劑之滲出或金屬腐蝕防止效果等觀點而言，較佳為以相對於(甲基)丙烯酸系(共)聚合物100質量份而為0.01質量份以上且5質量份以下之比率含有金屬腐蝕防止劑，其中，進一步較佳為以0.1質量份以上或者1質量份以下之比率含有，其中，進一步較佳為以0.2質量份以上或者0.5質量份以下之比率含有。 再者，本組合物亦可將2種以上之金屬腐蝕防止劑併用。具體而言，亦可將1,2,3-三唑與1,2,4-三唑併用。又，亦可將苯并三唑系化合物與1,2,3-三唑及/或1,2,4-三唑併用。 (亞磷酸酯化合物) 本組合物含有亞磷酸酯化合物。 亞磷酸酯化合物不僅本身不具有腐蝕性，並且可使羧基等酸成分穩定。因此，藉由於包含特定之(甲基)丙烯酸系(共)聚合物之本組合物中調配亞磷酸酯化合物，即便本組合物包含酸成分，亦可防止被黏著體、即導電構件之氧化劣化，於本組合物不包含酸成分之情形時，理所當然，可防止被黏著體、即導電構件之氧化劣化。 因此，若利用含有亞磷酸酯化合物之本組合物形成黏著片材，則可具有對導電構件(典型而言，具有包含ITO之透明導電層及/或由包含銅或銀之金屬材料形成之導體圖案之導電構件)之耐腐蝕可靠性，並且可防止導電構件之氧化劣化。因此，例如可較佳地用作具有觸控面板之圖像顯示裝置用之黏著片材。 本組合物所含有之亞磷酸酯化合物並無限定。其中，較佳為下述式(1)所示之亞磷酸酯化合物。 式(1)・・P[-OR]3 (式中之R為烴，具體而言，可列舉經取代或未經取代芳香族、脂肪環及烷基等；複數個R可彼此相同，亦可不同，相鄰之複數個R亦可彼此鍵結而形成飽和或不飽和之環結構) 又，亦可為包含2個以上之上述式(1)所表示之結構單元之化合物。 於包含特定之(甲基)丙烯酸系(共)聚合物及金屬腐蝕防止劑之本組合物中調配上述式(1)所示之各種亞磷酸酯化合物，結果確認到任一亞磷酸酯化合物均顯示出防氧化劣化效果，且確認到尤其是對包含ITO之透明導電層之防氧化劣化效果優異。 作為本組合物所含有之亞磷酸酯化合物，例如可列舉：亞磷酸三苯酯、亞磷酸三(壬基苯基)酯、亞磷酸三甲酚酯、亞磷酸三硬脂酯、亞磷酸三乙酯、亞磷酸三(2-乙基己基)酯、亞磷酸三癸酯、亞磷酸三月桂酯、亞磷酸三(十三烷基)酯、亞磷酸三油酯、亞磷酸二苯酯(2-乙基己基)酯、亞磷酸二苯酯單癸酯、亞磷酸二苯酯單(十三烷基)酯、四苯基二伸丙基二丙二醇二亞磷酸酯、四苯基(四-十三烷基)季戊四醇四亞磷酸酯、四(C12～C15烷基)-4,4-亞異丙基二苯基二亞磷酸酯、亞磷酸三(2,4-二第三丁基苯基)酯、亞磷酸三(4-壬基苯基)酯、3,9-雙(壬基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、3,9-雙(4-壬基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、3,9-雙(癸氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、3,9-雙(十三烷氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、3,9-雙(硬脂氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、3,9-雙(2,6-二第三丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、3,9-雙(2,4-二第三丁基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、3,9-雙{2,4-雙(1-甲基-1-苯基乙基)苯氧基}-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、亞磷酸2,2'-亞甲基雙(4,6-二第三丁基-1-苯基)酯、4,4'-亞異丙基二苯酚C12-15醇亞磷酸酯、二硬脂基季戊四醇二亞磷酸酯、2,4,8,10-四(1,1-二甲基乙基)-6-{(2-乙基己基)氧基}-12H-二苯并[d,g][1,3,2]二氧磷雜八環、2,4,8,10-四(1,1-二甲基乙基)-6-(十三烷氧基)-12H-二苯并[d,g][1,3,2]二氧磷雜八環、1,1'-聯苯基-4,4'-二基雙[亞磷酸雙(2,4-二第三丁基苯基)酯]、氫化雙酚A-季戊四醇亞磷酸酯聚合物、氫化雙酚A亞磷酸酯聚合物、亞磷酸二乙酯、亞磷酸雙(2-乙基己基)酯、亞磷酸二月桂酯、亞磷酸二油酯、亞磷酸二苯酯等。 其中，作為本組合物所含有之亞磷酸酯化合物，例如若考慮到與本組合物之相溶性，則較佳為脂肪族亞磷酸酯(例如，作為實施例2之亞磷酸酯化合物之亞磷酸三癸酯或實施例3之3,9-雙(癸氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷等)。又，若考慮到耐水解性，則較佳為芳香族亞磷酸酯(例如，作為實施例1之亞磷酸酯化合物之亞磷酸三(2,4-二第三丁基苯基)酯等)。又，若考慮到溶解性與耐水解性之平衡性，則較佳為亞磷酸二苯酯單(十三烷基)酯等兼具脂肪族酯基與芳香族酯基之亞磷酸酯。 於本組合物中，關於亞磷酸酯化合物之含有比率，就無損黏著性能且可更有效地抑制ITO等導電構件之氧化劣化之觀點而言，較佳為以相對於(甲基)丙烯酸系(共)聚合物100質量份而為0.0001(1×10-4 )質量份以上且2.0質量份以下之比率含有亞磷酸酯化合物，其中，進一步較佳為以0.0005質量份以上或者0.8質量份以下之比率含有，其中，進一步較佳為以0.001質量份以上或者0.7質量份以下之比率含有，尤其進一步較佳為以0.01質量份以上或者0.6質量份以下之比率含有。 (交聯劑) 本組合物亦可視需要包含交聯劑。 例如，作為對上述(甲基)丙烯酸系(共)聚合物進行交聯之方法，可列舉：添加可與導入至(甲基)丙烯酸系(共)聚合物中之羥基或羧基等反應性基化學鍵結之交聯劑，並藉由加熱或熟化使之反應之方法，或添加作為交聯劑之具有2個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸酯及光聚合起始劑等反應起始劑，並藉由紫外線照射等使之交聯之方法。其中，就不會因反應而消耗本組合物中之羧基等極性官能基，從而可維持源自極性成分之較高之凝集力或黏著物性之觀點而言，較佳為藉由紫外線等光照射之交聯方法。 作為上述交聯劑，例如可列舉具有選自(甲基)丙烯醯基、環氧基、異氰酸酯基、羧基、羥基、碳二醯亞胺基、㗁唑啉基、氮丙啶基、乙烯基、胺基、亞胺基、醯胺基、N-取代(甲基)丙烯醯胺基、烷氧基矽烷基中之至少1種交聯性官能基之交聯劑，可使用1種，或亦可將2種以上組合使用。再者，交聯性官能基亦可由可脫保護之保護基保護。 其中，就交聯反應之控制之容易性之觀點而言，較佳為多官能(甲基)丙烯酸酯。 作為此種多官能(甲基)丙烯酸酯，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇五(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、異氰尿酸三(丙烯醯氧基乙基)酯等紫外線硬化型之多官能單體類，以及聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚醚(甲基)丙烯酸酯等多官能丙烯酸系低聚物類或多官能丙烯醯胺等。 又，作為具有2種以上之交聯性官能基之交聯劑，例如可列舉：(甲基)丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、(甲基)丙烯酸-3,4-環氧丁酯、4-羥基丁基(甲基)丙烯酸酯縮水甘油醚等含環氧基單體；(甲基)丙烯酸2-異氰酸酯基乙酯、異氰酸2-(2-(甲基)丙烯醯氧基乙氧基)乙酯、(甲基)丙烯酸2-(0-[1'-甲基亞丙基胺基]羧基胺基)乙酯、(甲基)丙烯酸2-[(3,5-二甲基吡唑基)羰基胺基]乙酯等含異氰酸酯基或封端異氰酸酯基之單體；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷等各種矽烷偶合劑。 具有2種以上之交聯性官能基之交聯劑亦可採用使一官能基與(甲基)丙烯酸系(共)聚合物反應而鍵結於(甲基)丙烯酸系(共)聚合物所成之結構。藉由採用此種結構，可使例如(甲基)丙烯醯基或乙烯基等雙鍵性之交聯性官能基化學鍵結於(甲基)丙烯酸系(共)聚合物。又，藉由使交聯劑鍵結於(甲基)丙烯酸系(共)聚合物，有可抑制交聯劑之滲出或本黏著片材之意外之塑化之傾向。又，藉由使交聯劑鍵結於(甲基)丙烯酸系(共)聚合物而促進光交聯反應之反應效率，因此有可獲得凝集力更高之硬化物之傾向。 本組合物亦可進而含有可與交聯劑之交聯性官能基反應之單官能單體。作為此種單官能單體，例如可列舉：丙烯酸甲酯等(甲基)丙烯酸烷基酯；(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯、聚伸烷基二醇(甲基)丙烯酸酯等含羥基(甲基)丙烯酸酯；(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基順丁烯二酸、2-(甲基)丙烯醯氧基丙基順丁烯二酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基丙基琥珀酸、丁烯酸、反丁烯二酸、順丁烯二酸、伊康酸等含羧基單體；順丁烯二酸酐、伊康酸酐等含酸酐基單體；(甲基)丙烯酸四氫糠酯、甲氧基聚乙二醇(甲基)丙烯酸酯等含醚基(甲基)丙烯酸酯；(甲基)丙烯醯胺、二甲基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、異丙基(甲基)丙烯醯胺、二甲胺基丙基(甲基)丙烯醯胺、苯基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺等(甲基)丙烯醯胺系單體等。 其中，就提高對被黏著體之密接性或濕熱白化抑制之效果之觀點而言，較佳為使用含羥基(甲基)丙烯酸酯或(甲基)丙烯醯胺系單體。 關於交聯劑之含量，就使本組合物之柔軟性與凝集力平衡之觀點而言，較佳為以相對於上述(甲基)丙烯酸系(共)聚合物100質量份而為0.01以上且10質量份以下之比率調配，其中，尤佳為0.05質量份以上或者8質量份以下，其中，尤佳為0.1質量份以上或者5質量份以下。 再者，於本黏著片材為多層之情形時，關於構成黏著片材之層中之中間層或成為基材之層，交聯劑之含量亦可超過上述範圍。中間層或成為基材之層中之交聯劑之含量較佳為以相對於上述(甲基)丙烯酸系(共)聚合物100質量份而為0.01以上且40質量份以下之比率調配，其中，尤佳為1質量份以上或者30質量份以下，其中，尤佳為2質量份以上或者25質量份以下。 (光聚合起始劑) 於藉由光照射進行交聯之情形時，較佳為含有光聚合起始劑。 基於光聚合起始劑之自由基產生機構被分為2大類，有將自身之單鍵裂解並分解而產生自由基之α裂解型、及自系統中之化合物中使氫激發而產生自由基之脫氫型。該等之中，較佳為使用脫氫型光交聯起始劑。 其中，於使用具有(甲基)丙烯醯基之有機系交聯劑作為交聯劑之情形時，尤佳為進而添加光聚合起始劑。原因在於藉由光照射產生自由基而成為系統中之聚合反應之起點。 光聚合起始劑可適當使用目前公知者。其中，就交聯反應之控制之容易性之觀點而言，較佳為感應到波長380 nm以下之紫外線之光聚合起始劑。 另一方面，就可獲得較高之光反應性之方面及所感應之光容易到達至本黏著片材之深部之方面而言，較佳為感應到長於波長380 nm之波長之光之光聚合起始劑。 光聚合起始劑根據自由基產生機構而被分成2大類，大致分成可將光聚合起始劑自身之單鍵裂解分解而產生自由基之裂解型光聚合起始劑、及經光激發之起始劑與系統中之氫供與體形成激發錯合物並可使氫供與體之氫轉移之脫氫型光聚合起始劑。 該等中之裂解型光聚合起始劑於藉由光照射產生自由基時會分解而成為另一化合物，一旦被激發，則會失去作為交聯起始劑之功能。因此，不會以活性種之形式殘存於交聯反應結束後之黏著材中，從而不可能使黏著材產生意外之光劣化等，故而較佳。 另一方面，脫氫型光聚合起始劑於藉由紫外線等活性能量線照射產生自由基之反應時，不會產生如裂解型光聚合起始劑之分解物，因此就反應結束後不易成為揮發成分，從而可降低對被黏著體之損傷之方面而言有用。 作為上述裂解型光聚合起始劑，就對光之感應性較高且反應後成為分解物並脫色之方面而言，較佳為雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、(2,4,6-三甲基苯甲醯基)乙氧基苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)2,4,4-三甲基戊基氧化膦等醯基氧化膦系光聚合起始劑。 作為上述脫氫型光聚合起始劑，例如可列舉：二苯甲酮、4-甲基-二苯甲酮、2,4,6-三甲基二苯甲酮、4-苯基二苯甲酮、3,3'-二甲基-4-甲氧基二苯甲酮、4-(甲基)丙烯醯氧基二苯甲酮、4-[2-((甲基)丙烯醯氧基)乙氧基]二苯甲酮、4-(甲基)丙烯醯氧基-4'-甲氧基二苯甲酮、2-苯甲醯苯甲酸甲酯、苯甲醯甲酸甲酯、二乙二醇雙(2-苯基-2-側氧基乙酸酯)、4-(1,3-丙烯醯基-1,4,7,10,13-五氧雜十三烷基)二苯甲酮、9-氧硫𠮿

Figure 105143067-A0304-12-0019-3
、2-氯-9-氧硫𠮿
Figure 105143067-A0304-12-0019-3
、3-甲基-9-氧硫𠮿
Figure 105143067-A0304-12-0019-3
、2,4-二甲基-9-氧硫𠮿
Figure 105143067-A0304-12-0019-3
、蒽醌、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、樟腦醌或其衍生物等。 該等之中，較佳為二苯甲酮、4-甲基-二苯甲酮、2,4,6-三甲基二苯甲酮、4-苯基二苯甲酮、3,3'-二甲基-4-甲氧基二苯甲酮、4-(甲基)丙烯醯氧基二苯甲酮、4-[2-((甲基)丙烯醯氧基)乙氧基]二苯甲酮、4-(甲基)丙烯醯氧基-4'-甲氧基二苯甲酮、2-苯甲醯苯甲酸甲基、苯甲醯基甲酸甲基。 再者，上述所列舉之光聚合起始劑既可使用任1種或其衍生物，亦可將該等之2種以上組合使用。 進而，除光聚合起始劑以外，亦可使用增感劑。作為增感劑，並無特別限定，只要為光聚合起始劑所使用之增感劑，則可無問題地使用。例如可列舉：芳香族胺或蒽衍生物、蒽醌衍生物、香豆素衍生物、9-氧硫
Figure 105143067-A0304-12-0019-3
衍生物、酞菁衍生物等或二苯甲酮、𠮿酮、9-氧硫𠮿
Figure 105143067-A0304-12-0019-3
、米其勒酮、9,10-菲醌等芳香族酮及該等之衍生物等。 再者，光聚合起始劑或增感劑亦可以鍵結於(甲基)丙烯酸系(共)聚合物之狀態包含。作為使光聚合起始劑或增感劑鍵結於(甲基)丙烯酸系(共)聚合物之方法，可採用與使上述交聯劑鍵結於(甲基)丙烯酸系(共)聚合物之情形時相同之方法。 光聚合起始劑之含量並無特別限制，典型而言，尤佳為以相對於(甲基)丙烯酸系(共)聚合物100質量份而為0.1以上且10質量份以下之比率調整，其中，尤佳為以0.2質量份以上或者5質量份以下之比率調整，其中，尤佳為以0.5質量份以上或者3質量份以下之比率調整。其中，亦可因與其他要素之平衡性而超出該範圍。 (抗氧化劑) 除上述以外，本組合物亦可視需要含有抗氧化劑。 作為抗氧化劑，例如可列舉：2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、己二醇-雙(3,5-二第三丁基-4-羥基氫化肉桂酸酯)、四[亞甲基(3,5-二第三丁基-4-羥基氫化肉桂酸酯)]甲烷、三乙二醇-雙-3-(3-第三丁基-4-羥基-5-甲基苯基)丙酸酯、1,3,5-三甲基-2,4,6-三(3,5-二第三丁基-4-羥基-苄基)苯、3-(4'-羥基-3',5'-二第三丁基苯酚基)丙酸正十八烷基酯、4,4'-亞甲基雙(2,6-二第三丁基苯酚)、4,4'-亞丁基-雙-(6-第三丁基-3-甲基-苯酚)等受阻酚系抗氧化劑或硫系、胺系等各種抗氧化劑。 (其他成分) 進而，本組合物亦可適當含有通常之黏著劑組合物中所調配之公知之成分。例如，可適當含有光穩定劑、紫外線吸收劑、金屬鈍化劑、防銹劑(上述金屬腐蝕防止劑除外)、抗老化劑、抗靜電劑、吸濕劑、發泡劑、消泡劑、無機粒子、黏度調整劑、黏著賦予樹脂、光敏劑、螢光劑等各種添加劑，或反應觸媒(三級胺系化合物、四級銨系化合物、月桂酸錫化合物等)。 (黏著劑組合物之調整) 本黏著片材所使用之黏著劑組合物(本組合物)可藉由將(甲基)丙烯酸系(共)聚合物、金屬腐蝕防止劑及亞磷酸酯化合物以及視需要之其他成分分別以特定量進行混合而獲得。 作為該等之混合方法，並無特別限制，各成分之混合順序亦無特別限定。又，亦可於製造本組合物時添加熱處理步驟，於此情形時，較理想為預先將本組合物之各成分進行混合後進行熱處理。亦可使用將各種混合成分濃縮後母料化而成者。 又，混合時之裝置亦並無特別限制，例如可使用萬能混練機、行星式攪拌機、班布里混合機、捏合機、框式混合機、加壓捏合機、三輥研磨機、雙輥研磨機。亦可視需要使用溶劑進行混合。又，本組合物亦可用作不包含溶劑之無溶劑系。藉由用作無溶劑系，可具備不會殘存溶劑而耐熱性及耐光性增高之優勢。 進而，本組合物亦可以如下方式使用：預先製成包含構成(甲基)丙烯酸系(共)聚合物之單體成分、1,2,3-三唑、光聚合起始劑及其他任意成分之組合物，於將其用作導電構件用黏著片材時，進行光照射以進行聚合反應而生成(甲基)丙烯酸系(共)聚合物。 ＜導電構件用黏著片材之形態＞ 本黏著片材除可將本組合物直接塗佈於被黏著體並形成為片狀後使用以外，亦可製成於脫模膜上成型為單層或多層之片狀之附脫模膜之黏著片材。 作為該脫模膜之材質，例如可列舉：聚酯膜、聚烯烴膜、聚碳酸酯膜、聚苯乙烯膜、丙烯酸膜、三乙醯纖維素膜、氟樹脂膜等。該等之中，尤佳為聚酯膜及聚烯烴膜。 脫模膜之厚度並無特別限制。其中，例如就加工性及操作性之觀點而言，較佳為25 μm～500 μm，其中，進而較佳為38 μm以上或者250 μm以下，其中，進而較佳為50 μm以上或者200 μm以下。 再者，本黏著片材亦可採用未如上所述般使用被黏著體或脫模膜而將本組合物直接擠出成形之方法或藉由注入至模具中成形之方法。進而，藉由將本組合物直接填充至導電構件等構件間，亦可製成黏著片材之態樣。 ＜導電構件用黏著片材之物性＞ (對導電構件之導電層之防腐效果) 本黏著片材具有對導電構件、尤其是透明導電層或由包含銅之金屬材料形成之導體圖案之防腐性。因此，可將利用以下之(1)～(2)之方法所測得之ITO電阻值之變化率[((Ω/Ω0)－1)×100]設為未達5%，其中，可設為未達3%。又，可將利用以下之(3)～(4)之方法所測得之銅電阻值之變化率[((Ω/Ω0)－1)×100]設為未達20%，其中，可設為未達10%，進而可設為未達5%，尤其可設為未達3%。 (1)將導電構件用黏著劑組合物(本組合物)製膜成厚度150 μm之片狀而製成黏著片材，並將上述黏著片材貼合於包含氧化銦(ITO)之ITO配線形成於玻璃基板上而成之評價用ITO玻璃基板而製作附黏著片材之ITO配線。 (2)預先測定上述附黏著片材之ITO配線中之ITO配線之室溫下之電阻值(Ω0)，並於65℃・90%RH環境下將上述附黏著片材之ITO配線保管500小時，測定上述附黏著片材之ITO配線中之ITO配線之上述保管後之電阻值(Ω)。 (3)將導電構件用黏著劑組合物(本組合物)製膜成厚度150 μm之片狀而製成黏著片材，並將上述黏著片材貼合於銅配線形成於玻璃基板上而成之評價用銅玻璃基板而製作附黏著片材之銅配線。 (4)預先測定上述附黏著片材之銅配線中之銅配線之室溫下之電阻值(Ω0)，並於65℃・90%RH環境下將上述附黏著片材之銅配線保管500小時，測定上述附黏著片材之銅配線中之銅配線之上述保管後之電阻值(Ω)。 (透明性) 本黏著片材較佳為光學透明。即，較佳為透明黏著片材。此處，所謂「光學透明」，意在總光線透過率為80%以上，較佳為85%以上，更佳為90%以上。 (厚度) 本黏著片材之厚度較佳為10 μm以上且500 μm以下，其中，更佳為15 μm以上或者400 μm以下，其中，尤其進而較佳為20 μm以上或者350 μm以下。 ＜導電構件用黏著片材之用途＞ 本黏著片材於例如個人電腦、行動設備終端(PDA)、遊戲機、電視(TV)、汽車導航系統、觸控面板、手寫板等圖像顯示裝置、例如電漿顯示器(PDP)、液晶顯示器(LCD)、有機EL顯示器(OLED)、無機EL顯示器、電泳顯示器(EPD)、干擾調變顯示器(IMOD)等使用圖像顯示面板之圖像顯示裝置中，適合貼合各構成構件、其中導電構件、其中具有透明導電層及/或由包含銅之金屬材料形成之導體圖案之導電構件。又，亦適合貼合包含含有ITO或者IGZO之透明導電層及/或具有由包含銅或銀之金屬材料形成之導體圖案之透明導電層之導電構件。 ＜導電構件積層體＞ 本發明之導電構件積層體(以下，亦省略後稱為「本積層體」)可藉由將本黏著片材與導電構件、例如透明導電層之導電層面貼合而獲得。 本積層體只要具有至少將本黏著片材之任一黏著劑層面與透明導電層之導電層面貼合而成之構成即可。 於本黏著片材為兩面黏著片材之情形時，本積層體亦可具有將本黏著片材之兩黏著劑層面與透明導電層之導電層面貼合而成之構成。 上述透明導電層亦可以覆蓋其導電膜之導電層面之方式形成利用烯烴系聚合物、胺基甲酸酯系聚合物、環氧系聚合物、丙烯酸系聚合物、聚矽氧系聚合物、或者無機玻璃等而形成之絕緣保護膜(鈍化膜)。 與導電層面貼合所得之本積層體可較佳地用於觸控面板。作為觸控面板，可列舉電阻膜方式、靜電電容方式、電磁感應方式等方式者，較佳為靜電電容方式。 作為上述透明導電層，只要為至少於單面之表層具有導電層者即可，可列舉藉由蒸鍍或濺鍍、塗佈等於透明基材之表層設置有導電物質而成之透明導電層。 透明導電層之導電層所使用之導電物質並無特別限定。具體而言，除氧化銦、銦-鎵-鋅複合氧化物、摻錫之氧化銦(ITO)、氧化鋅、氧化鎵、氧化鈦等金屬氧化物以外，亦可列舉銀、銅、鉬、鋁等金屬材料。其中，可較佳地使用透明性優異之摻錫之氧化銦(ITO)及銦-鎵-鋅複合氧化物(IGZO)。又，就導電性優異之觀點而言，亦可較佳地使用銅或銀。 於透明導電層中，作為欲利用導電物質形成圖案之基材，並無特別限定，可列舉玻璃、樹脂膜等。 典型而言，透明導電層至少於單面之表層具有導電層。又，典型而言，於透明導電層以引繞周邊部之方式形成有將銅或銀作為主成分之導體圖案(配線圖案)。1,2,3-三唑對其中之銅之耐腐蝕可靠性較高，因此包含其之本黏著片材可尤其較佳地用於具備由包含銅之金屬材料形成之導體圖案之導電構件。 作為其他本積層體之具體例，例如可列舉：脫模膜/本黏著片材/觸控面板、脫模膜/本黏著片材/保護面板、脫模膜/本黏著片材/圖像顯示面板、圖像顯示面板/本黏著片材/觸控面板、圖像顯示面板/本黏著片材/保護面板、圖像顯示面板/本黏著片材/觸控面板/本黏著片材/保護面板、偏光膜/本黏著片材/觸控面板、偏光膜/本黏著片材/觸控面板/本黏著片材/保護面板等構成。又，於上述構成中，可列舉於本黏著片材與和其相鄰之觸控面板、保護面板、圖像顯示面板、偏光膜等構件之間介置有上述導電層之所有構成。但是，並不限定於該等積層例。 再者，上述觸控面板亦包含使觸控面板功能內置於保護面板而成之結構體或使觸控面板功能內置於圖像顯示面板而成之結構體。 ＜圖像顯示裝置＞ 本發明之圖像顯示裝置(以下，亦省略後稱為「本裝置」)至少具有本積層體、圖像顯示面板及表面保護面板作為構成構件。 更具體而言，可列舉將本黏著片材與透明導電層之導電層面貼合而得之本積層體插入至圖像顯示面板與表面保護面板之間之構成之圖像顯示裝置。此時，於圖像顯示面板側亦使用本黏著片材。 作為表面保護面板之材質，除玻璃以外，亦可為丙烯酸系樹脂、聚碳酸酯系樹脂、環烯烴聚合物等脂環式聚烯烴系樹脂、苯乙烯系樹脂、聚氯乙烯系樹脂、酚系樹脂、三聚氰胺系樹脂、環氧系樹脂等塑膠。 圖像顯示面板係由除偏光膜以外之相位差膜等其他光學膜、液晶材料及背光光源系統構成(通常，本組合物或黏著物品對圖像顯示面板之被接著面成為光學膜)，根據液晶材料之控制方式而存在STN(Super Twisted Nematic，超扭轉向列)方式或VA(Vertical Aligned，垂直配向)方式或IPS(In-Plane Switching，橫向電場效應)方式等，可為任何方式。 作為本圖像顯示裝置，例如可構成液晶顯示器、有機EL顯示器、無機EL顯示器、電子紙、電漿顯示器及微機電系統(MEMS)顯示器等圖像顯示裝置。 ＜語句之說明＞ 於本說明書中，於表述為「X～Y」(X、Y為任意之數字)之情形時，只要未特別說明，則包含「X以上且Y以下」之意義，並且包含「較佳為大於X」或者「較佳為小於Y」之意義。 又，於表述為「X以上」(X為任意之數字)或者「Y以下」(Y為任意之數字)之情形時，包含「較佳為大於X」或者「較佳為未達Y」之意圖。 一般而言，所謂「片材」，於JIS中之定義中，係指較薄、其厚度小於長度與寬度之商且平坦之製品，一般而言，所謂「膜」，係與長度及寬度相比厚度極小且最大厚度被任意地限定之較薄且平坦之製品，通常係指以輥之形供給者(日本工業標準JIS K6900)。然而，片材與膜之交界並不確定，於本發明中，無需於語言上對兩者進行區別，因此，於本發明中，於稱為「膜」之情形時亦包含「片材」，於稱為「片材」之情形時亦包含「膜」。 [實施例] 以下，藉由實施例及比較例進而詳細地進行說明。但是，本發明並不限定於該等實施例。 [實施例1] 向包含丙烯酸2-乙基己酯76質量份、乙酸乙烯酯20質量份及丙烯酸4質量份之共聚物(A-1，質量平均分子量40萬)1 kg中添加丙氧化季戊四醇聚丙烯酸酯(新中村化學工業公司製造，商品名「ATM-4PL」)200 g作為交聯劑、及4-甲基二苯甲酮與2,4,6-三甲基二苯甲酮之混合物(Lamberti公司製造，商品名「Esacure TZT」)10 g作為光聚合起始劑並均勻混合，獲得中間層用樹脂組合物。 將中間層用樹脂組合物夾於經剝離處理之2片聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，商品名「DIAFOIL MRF」，厚度75 μm及三菱樹脂公司製造，商品名「DIAFOIL MRT」，厚度38 μm)之間，並以黏著片材之厚度成為80 μm之方式賦形成片狀，製作中間層用樹脂片(α)。 向上述丙烯酸酯共聚物(A-1)1 kg中添加1,2,3-三唑1.5 g作為金屬腐蝕防止劑、亞磷酸三(2,4-二第三丁基苯基)酯(BASF公司製造，商品名「Irgafos 168」)5 g作為亞磷酸酯化合物、及4-甲基二苯甲酮與2,4,6-三甲基二苯甲酮之混合物(Lamberti公司製造、商品名「Esacure TZT」)15 g作為光聚合起始劑並均勻混合，獲得黏著劑層用樹脂組合物。 將上述黏著劑層用樹脂組合物夾於經剝離處理之2片聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，商品名「DIAFOIL MRV」，厚度100 μm及三菱樹脂公司製造，商品名「DIAFOIL MRT」，厚度38 μm)之間，並以黏著片材之厚度成為35 μm之方式賦形成片狀，製作黏著劑層用樹脂片(β)。 進而，將上述黏著劑層用樹脂組合物夾於經剝離處理之2片聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，商品名「DIAFOIL MRQ」，厚度75 μm及三菱樹脂公司製造，商品名「DIAFOIL MRT」，厚度38 μm)之間，並以黏著片材之厚度成為35 μm之方式賦形成片狀，製作黏著劑層用樹脂片(β')。 將上述中間層用片材(α)之兩側之PET膜依序剝離去除，並且將黏著劑層用樹脂片(β)及(β')之一側之PET膜剝離，將所露出之黏著面依序貼合於中間層用片材(β)之兩表面，製作包含(β)/(α)/(β')之積層體。 隔著殘留於上述(β)及(β')之表面之PET膜，以波長365 nm之累計光量成為2000 mJ/cm2 之方式利用高壓水銀燈照射紫外線，使(α)、(β)及(β')進行紫外線交聯，製作黏著片材積層體(厚度150 μm)。針對該黏著片材積層體，進行下述各種評價。結果示於表1。 [實施例2] 向包含丙烯酸丁酯81質量份、甲基丙烯酸甲酯15質量份及丙烯酸4質量份之共聚物(A-2，質量平均分子量20萬)1 kg中添加1,2,3-三唑3 g作為金屬腐蝕防止劑、亞磷酸三癸酯(ADEKA公司製造，商品名「Adekastab 3010」)3 g作為亞磷酸酯化合物、季戊四醇三及四丙烯酸酯(東亞合成公司製造，「ARONIXM-306」)20 g作為交聯劑、以及1-羥基-環己基苯基酮(BASF公司製造，Irgacure 184)10 g作為光聚合起始劑並均勻混合，獲得黏著劑層用樹脂組合物。 繼而，將上述黏著劑層用樹脂組合物於經剝離處理之聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，DIAFOIL MRV，厚度100 μm)上以厚度成為150 μm之方式成形為片狀後，被覆經剝離處理之聚對苯二甲酸乙二酯膜(三菱樹脂公司製造，商品名「DIAFOIL MRQ」，厚度75 μm)。隔著經剝離處理之聚對苯二甲酸乙二酯膜，以波長365 nm之累計光量成為1000 mJ/cm2 之方式利用高壓水銀燈照射紫外線使黏著劑層用樹脂組合物進行紫外線交聯，製作黏著片材積層體2。針對該黏著片材積層體2，進行下述各種評價。結果示於表1。 [實施例3] 使用3,9-雙(癸氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷(城北化學公司製造，商品名「JPE-10」)3 g作為亞磷酸酯化合物，除此以外，以與實施例2相同之方式製作黏著片材積層體3。針對該黏著片材積層體3，進行下述各種評價。結果示於表1。 [比較例1] 未添加作為金屬腐蝕防止劑之1,2,3-三唑及作為亞磷酸酯化合物之亞磷酸三(2,4-二第三丁基苯基)酯(BASF公司製造，商品名「Irgafos 168」)，除此以外，以與實施例2相同之方式製作黏著片材積層體4。針對該黏著片材積層體4，進行下述各種評價。結果示於表1。 [比較例2] 未添加作為金屬腐蝕防止劑之1,2,3-三唑，除此以外，以與實施例1相同之方式製作黏著片材積層體5。針對該黏著片材積層體5，進行下述各種評價。結果示於表1。 [比較例3] 添加苯并三唑(城北化學公司製造，商品名「BT120」)1.5 g代替1,2,3-三唑作為金屬腐蝕防止劑，且未添加亞磷酸酯化合物，除此以外，以與實施例1相同之方式製作黏著片材積層體6。針對該黏著片材積層體6，進行下述各種評價。結果示於表1。 ＜各種評價＞ (1)防氧化劣化性 於玻璃基板(60 mm×45 mm)上以厚度150～200 Å、線寬70 μm、線長度46 mm、線間隔30 μm並以往返10.5次之方式形成氧化銦(ITO)之往返線，並且於該往返線之兩末端形成包含ITO之2 mm見方之正方形而形成ITO圖案(長度約97 cm)，製作防氧化劣化性評價用ITO玻璃基板(參照圖1(A))。 將於上述實施例及比較例中製作之黏著片材積層體1～6(厚度150 μm)之單面之剝離膜剝離，並利用手壓輥將PET膜(東洋紡織公司製造，商品名「COSMOSHINE A4100」，125 μm)貼附於其露出面。繼而，將上述附PET膜之黏著片材切成52 mm×45 mm後，將剩餘之剝離膜剝離，如圖1(B)所示，以將ITO之往返線上被覆之方式利用手壓輥將該黏著片材貼附於防氧化劣化性評價用ITO玻璃基板，製作防氧化劣化性評價用樣品(附黏著片材之ITO配線)(參照圖1(C))。 預先測定該防氧化劣化性評價用樣品(附黏著片材之ITO配線)中之ITO配線之室溫下之電阻值(Ω0)。 另一方面，將該防氧化劣化性評價用樣品(附黏著片材之ITO配線)於65℃・90%RH環境下保管500小時，保管後，測定耐防氧化劣化性評價用樣品(附黏著片材之ITO配線)中之ITO配線之電阻值(Ω)。 並且，算出ITO電阻值、即線末端間電阻值之變化率(%)[((Ω/Ω0)－1)×100]，於表1中表示成「電阻值變化」。 關於防氧化劣化性，將電阻值之變化率為5%以上者判定為「×(poor)」，將未達5%判定為「○(good)」。結果示於表1。 (2)耐腐蝕可靠性 於玻璃基板(60 mm×45 mm)上以線寬70 μm、線長度46 mm、線間隔30 μm並以往返10.5次之方式形成將厚度1300 Å之ITO、厚度3000 Å之銅膜依序積層而成之金屬膜之往返線，並且於該往返線之兩末端形成2 mm見方之正方形而形成銅圖案(長度約97 cm)，製作耐腐蝕可靠性評價用銅玻璃基板(參照圖1(A))。 將於上述實施例及比較例中製作之黏著片材積層體1～6(厚度150 μm)之單面之剝離膜剝離，並利用手壓輥將PET膜(東洋紡織公司製造，商品名「COSMOSHINE A4100」，125 μm)貼附於其露出面。繼而，將上述附PET膜之黏著片材切成52 mm×45 mm後，將剩餘之剝離膜剝離，如圖1(B)所示，以將金屬膜之往返線上被覆之方式利用手壓輥將黏著片材貼附於耐腐蝕可靠性評價用銅玻璃基板，製作耐腐蝕可靠性評價用樣品(附黏著片材之銅配線)(參照圖1(D))。 預先測定該耐腐蝕可靠性評價用樣品(附黏著片材之銅配線)中之銅配線之室溫下之電阻值(Ω0)。 另一方面，將該耐腐蝕可靠性評價用樣品(附黏著片材之銅配線)於65℃・90%RH環境下保管500小時，保管後，測定耐腐蝕可靠性評價用樣品(附黏著片材之銅配線)中之銅配線之電阻值(Ω)。 並且，算出銅電阻值、即線末端間電阻值之變化率(%)[((Ω/Ω0)－1)×100]，於表1中表示成「電阻值變化」。 關於耐腐蝕可靠性，將電阻值之變化率為20%以上者判定為「×(poor)」，將未達20%判定為「○(good)」。結果示於表1。 [表1]
Figure 105143067-A0304-0001
 (評價結果) 實施例1～3之黏著片材包含金屬腐蝕防止劑與亞磷酸酯，藉此ITO配線、銅配線均為電阻值之變化較少且耐腐蝕可靠性及防氧化劣化性優異者。 另一方面，比較例1均不包含亞磷酸酯化合物及金屬腐蝕防止劑，而耐腐蝕可靠性及防氧化劣化性較差。 比較例2由於不包含金屬腐蝕防止劑，故而銅配線之腐蝕尤其顯著。 比較例3不包含亞磷酸酯化合物，而對ITO配線之防氧化劣化性較差。 [產業上之可利用性] 本發明之導電構件用黏著片材可具有對導電構件(典型而言，具有透明導電層及/或由包含銅或者銀之金屬材料形成之導體圖案之導電構件)之耐腐蝕可靠性，並且可具有防氧化劣化性，因此可用作適合貼合各種導電構件之黏著片材。尤其可較佳地用作具有觸控面板之圖像顯示裝置用之黏著片材。Hereinafter, an example of an embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. <Adhesive sheet for conductive members> The adhesive sheet for conductive members of an example of the embodiment of the present invention (hereinafter, also referred to as "the adhesive sheet" after abbreviation) has a composition containing (meth)acrylic (co)polymer It is the adhesive layer of the adhesive composition of the compound, metal corrosion inhibitor and phosphite compound. The adhesive layer may be a single layer or multiple layers, and in the case of multiple layers, other layers such as the so-called substrate layer may also be interposed. When the adhesive layer has a multilayer structure with other layers, it is preferable that the surface layer of the adhesive sheet is an adhesive layer containing the above-mentioned adhesive composition. When the adhesive sheet is multi-layered, the thickness of the adhesive layer containing the adhesive composition is not limited. Relative to the thickness of the entire adhesive sheet, it is preferably 10% or more, more preferably 30% or more , More preferably 50% or more. If the thickness of the adhesive layer containing the adhesive composition is in the above range, the corrosion resistance reliability, foaming resistance reliability, and hardening characteristics of the conductive member become good, which is preferable. Furthermore, in the present invention, the so-called "(co)polymer" includes the meaning of homopolymer and copolymer, and the so-called "(meth)acrylate" includes the meaning of acrylate and methacrylate. [Adhesive composition] The adhesive composition used in this adhesive sheet (hereinafter referred to as "this composition") contains (meth)acrylic (co)polymer, metal corrosion inhibitor and phosphorous acid Ester compound. This composition may further contain a crosslinking agent, a photopolymerization initiator, an antioxidant, and other components. This composition is preferably a photocurable composition. ((Meth)acrylic (co)polymer) As the (meth)acrylic (co)polymer, for example, in addition to the homopolymer of (meth)acrylic acid alkyl ester, it can also be exemplified by combining it with Copolymers obtained by polymerizing monomer components with copolymerizable properties, more preferably, carboxyl group-containing monomers, hydroxyl group-containing monomers, and amine group-containing monomers that can be copolymerized with alkyl (meth)acrylates are included , A copolymer containing more than one monomer selected from epoxy group-containing monomers, amide group-containing monomers and other vinyl monomers as structural units. The (meth)acrylic (co)polymer can be produced by a conventional method using a polymerization initiator as needed, using monomers and the like exemplified below. When the (meth)acrylic (co)polymer is a copolymer containing a carboxyl group-containing monomer as a structural unit, from the viewpoint of obtaining excellent adhesive properties, the (meth)acrylic (co)polymer It is preferable to contain 1.2 to 15% by mass of the carboxyl group-containing monomer, 1.5% by mass or more or 10% by mass or less in it, and more preferably 2.0% by mass or more or 8% by mass or less. As an example of a more specific (meth)acrylic (co)polymer, a linear or branched alkyl (meth)acrylate having 4 to 18 carbon atoms in the side chain (hereinafter also referred to as " Copolymerizable monomer A") is a copolymer composed of any one or more monomer components selected from the following group that can be copolymerized therewith.・Carboxyl group-containing monomer (hereinafter also referred to as "copolymerizable monomer B") · Macromonomer (hereinafter also referred to as "copolymerizable monomer C") · Side chain carbon number of 1 to 3 (methyl) Acrylate (hereinafter also referred to as "copolymerizable monomer D") ・Hydroxy-containing monomer (hereinafter also referred to as "copolymerizable monomer E") ・Other vinyl monomers (hereinafter also referred to as "copolymerizable monomer F") ") In addition, as an example of the (meth)acrylic (co)polymer, (a) a monomer comprising a copolymerizable monomer A, a copolymerizable monomer B, and/or a copolymerizable monomer C can also be cited Copolymer composed of components or (b) composed of monomer components including comonomer A, comonomer B and/or comonomer C, comonomer D and/or comonomer E Copolymers are particularly preferred examples. Examples of linear or branched alkyl (meth)acrylates having 4 to 18 carbon atoms in the side chain (copolymerizable monomer A) include n-butyl (meth)acrylate and (meth)acrylic acid Isobutyl ester, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, neopentyl (meth)acrylate, Hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, (meth) Isooctyl acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate Esters, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, cetyl (meth)acrylate Ester, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, isopropyl (meth)acrylate, 3,5,5-trimethyl ring Hexane (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, benzyl (meth)acrylate Ester etc. These can be used singly or in combination of two or more kinds. The above-mentioned copolymerizable monomer A is preferably contained in the total monomer components of the copolymer at 30% by mass or more and 90% by mass or less, and among them, it is more preferably contained within the range of 35% by mass or more or 88% by mass or less Among them, it is more preferable to contain in the range of 40% by mass or more or 85% by mass or less. Examples of the carboxyl group-containing monomer (copolymerizable monomer B) include (meth)acrylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, and 2-(meth)propylene Glyoxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(methyl) Yl)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropylmaleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-( (Meth)acryloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid. These may use 1 type, or may combine 2 or more types. Furthermore, "(meth)acrylic group" includes the meaning of acrylic acid group and methacrylic acid group. Similarly, "(meth)acryloyl" refers to the meaning of acryloyl and methacryloyl. The above-mentioned copolymerizable monomer B is preferably contained in the range of 1.2% by mass to 15% by mass in the total monomer components of the copolymer, and among them, from the viewpoint of obtaining excellent adhesive properties, it is preferably It is contained in the range of 1.5% by mass or more or 10% by mass or less, and it is particularly preferably contained in the range of 2% by mass or more or 8% by mass or less. The above-mentioned macromonomer (copolymerizable monomer C) is a monomer whose side chain carbon number becomes 20 or more when it becomes a (meth)acrylic (co)polymer by polymerization. By using the copolymerizable monomer C, the (meth)acrylic (co)polymer can be made into a graft copolymer. Therefore, the characteristics of the main chain and the side chain of the graft copolymer can be changed according to the selection or blending ratio of the copolymerizable monomer C and other monomers. As the above-mentioned macromonomer (copolymerizable monomer C), it is preferable that the skeleton component is composed of an acrylic polymer or a vinyl polymer. As the skeleton component of the macromonomer, for example, the above-mentioned copolymerizable monomer A, the above-mentioned copolymerizable monomer B, the following copolymerizable monomer D, the following copolymerizable monomer E, etc. are exemplified, and these can be used alone , Or use a combination of two or more. The macromonomer system has a radical polymerizable group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, and a thiol group. The macromonomer is preferably one having a radical polymerizable group that can be copolymerized with other monomers. The radical polymerizable group may contain one or two or more, and among them, one is particularly preferred. When the macromonomer has a functional group, the functional group may also contain one or more than two, among which one is particularly preferred. Moreover, either one of a radical polymerizable group and a functional group may be contained, and both may be contained. The number average molecular weight of the comonomer C is preferably 500 to 20,000, and among them, it is preferably 800 or more or 8,000 or less, and among them, it is preferably 1,000 or more or 7,000 or less. The macromonomer can be appropriately manufactured by a general method (for example, the macromonomer manufactured by Toagosei Co., Ltd.). The above-mentioned comonomer C is preferably contained in the total monomer components of the copolymer in a range of 5% by mass or more and 30% by mass or less. Among them, it is preferably 6% by mass or more or 25% by mass or less. It is contained within the range, and among them, it is particularly preferably contained within the range of 8% by mass or more or 20% by mass or less. Examples of the (meth)acrylate (copolymerizable monomer D) having 1 to 3 carbon atoms in the side chain include: methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid N-propyl ester, isopropyl (meth)acrylate, etc. These may use 1 type, or may combine 2 or more types. The above-mentioned copolymerizable monomer D is preferably contained in the total monomer components of the copolymer from 0% by mass to 70% by mass, and among them, it is more preferably contained in the range of 3% by mass or more or 65% by mass. Among them, it is particularly preferable to contain in the range of 5% by mass or more or 60% by mass or less. Examples of the hydroxyl-containing monomer (copolymerizable monomer E) include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl (meth)acrylate. These may use 1 type, or may combine 2 or more types. The above-mentioned copolymerizable monomer E is preferably contained in the total monomer components of the copolymer from 0% by mass to 30% by mass, and among them, it is more preferably contained within the range of 0% by mass or more or 25% by mass. Among them, it is particularly preferable to contain in the range of 0% by mass or more or 20% by mass or less. As the above-mentioned other vinyl monomers (copolymerizable monomer F), in addition to the copolymerizable monomers A to E, compounds having a vinyl group in the molecule can also be cited. Examples of such compounds include: functional monomers having functional groups such as amide groups or alkoxyalkyl groups in the molecule; and polyalkylene glycol di(meth)acrylates; and vinyl acetate , Vinyl ester monomers such as vinyl propionate and vinyl laurate; and aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene and other substituted styrenes. These may use 1 type, or may combine 2 or more types. The above-mentioned comonomer F is preferably contained in the total monomer components of the copolymer from 0% by mass to 30% by mass, and among them, it is more preferably contained within the range of 0% by mass or more or 25% by mass. Among them, it is particularly preferable to contain in the range of 0% by mass or more or 20% by mass or less. In addition to what is disclosed above, it can also be appropriately used as needed: anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, (formaldehyde) Group) 3,4-epoxybutyl acrylate and other epoxy-containing monomers; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and other amine-containing monomers (former Yl)acrylate monomer; (meth)acrylamide, N-tert-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl (Meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone (meth)acrylamide, maleic acid amide, maleic acid amide, etc. Monomers of amino groups or imine groups; basic heterocyclic monomers such as vinylpyrrolidone, vinylpyridine, vinylcarbazole, etc. As the most typical example of the (meth)acrylic (co)polymer, for example, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, Isostearyl (meth)acrylate, butyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate and other monomer components (a), (meth)acrylic acid with carboxyl group, 2-(Meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl Phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxy Propyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid Monomer components (b) such as olefinic acid and itaconic acid, and hydroxyethyl (meth)acrylate having organic functional groups, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, ( (Meth) glyceryl acrylate, monomethyl maleate, monomethyl itconate, vinyl acetate, glycidyl (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile , Fluorinated (meth)acrylate, polysiloxane (meth)acrylate and other monomer components (c) copolymerized (meth)acrylate copolymer. The mass average molecular weight of the (meth)acrylic (co)polymer is preferably 100,000 or more and 1.5 million or less, among which, it is preferably 150,000 or more or 1.3 million or less, and particularly preferably 200,000 or more or 1.2 million the following. When it is desired to obtain an adhesive composition with higher cohesive force, the higher the molecular weight, the more cohesive force can be obtained by cross-linking of molecular chains. The mass average molecular weight is preferably 700,000 or more and 1.5 million or less, and more preferably 800,000 or more or 1.3 million or less. On the other hand, when it is desired to obtain an adhesive composition with high fluidity or stress relaxation properties, the mass average molecular weight is preferably 100,000 or more and 700,000 or less, and more preferably 150,000 or more or 600,000 or less. On the other hand, when a solvent is not used when forming an adhesive sheet, etc., since it is difficult to use a polymer with a larger molecular weight, the mass average molecular weight of the (meth)acrylic (co)polymer is preferably 100,000 Above and below 700,000, particularly preferably above 150,000 or below 600,000, among which, above 200,000 or below 500,000 are particularly preferred. (Metal corrosion inhibitor) This composition contains a metal corrosion inhibitor. Examples of metal corrosion inhibitors include benzotriazole-based compounds, benzimidazole compounds, benzothiazole compounds, and other triazole derivatives. As a metal corrosion inhibitor, it is more preferable to be any one or more selected from preferably a benzotriazole-based compound, 1,2,3-triazole, and 1,2,4-triazole. Among them, in terms of not only the metal corrosion prevention properties but also excellent foaming resistance reliability as an adhesive sheet, triazoles such as 1,2,3-triazole or 1,2,4-triazole are preferred. The derivative is particularly preferably 1,2,3-triazole. The reason is that it is presumed that corrosion can be prevented by forming a protective film formed by chemical bonding of copper atoms and molecules of triazole on the surface of a conductor pattern formed of a metal material containing copper. In addition, in a conductive member having a conductive pattern formed of a metal material containing silver, the effect of a protective film obtained by using triazole can also be achieved in the same way. Furthermore, 1,2,4-triazole is a solid with a melting point of approximately 120°C. On the other hand, 1,2,3-triazole has a melting point of approximately 20°C and is approximately liquid at room temperature. Therefore, compared with 1,2,4-triazole, 1,2,3-triazole has excellent dispersibility when mixed in the adhesive composition, can be uniformly mixed, and is easy to masterbatch. Advantage. In the present composition, from the viewpoint of the bleeding of the metal corrosion inhibitor or the metal corrosion prevention effect, it is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the (meth)acrylic (co)polymer and The metal corrosion inhibitor is contained in a ratio of 5 parts by mass or less. Among them, it is more preferably contained in a ratio of 0.1 parts by mass or more or 1 part by mass or less, and among them, it is more preferably in a ratio of 0.2 parts by mass or more or 0.5 parts by mass or less. contain. Furthermore, this composition can also use two or more kinds of metal corrosion inhibitors in combination. Specifically, 1,2,3-triazole and 1,2,4-triazole may be used in combination. In addition, a benzotriazole-based compound may be used in combination with 1,2,3-triazole and/or 1,2,4-triazole. (Phosphite compound) This composition contains a phosphite compound. The phosphite compound is not only non-corrosive, but also can stabilize acid components such as carboxyl groups. Therefore, by blending a phosphite compound in the composition containing a specific (meth)acrylic (co)polymer, even if the composition contains an acid component, it is possible to prevent the oxidative deterioration of the adherend, that is, the conductive member When the composition does not contain an acid component, it is of course possible to prevent the oxidative deterioration of the adherend, that is, the conductive member. Therefore, if the adhesive sheet is formed using the present composition containing a phosphite compound, it may have a conductive member (typically, a transparent conductive layer containing ITO and/or a conductor formed of a metal material containing copper or silver). The patterned conductive member) has corrosion resistance and reliability, and can prevent the conductive member from oxidizing and deteriorating. Therefore, for example, it can be preferably used as an adhesive sheet for an image display device with a touch panel. The phosphite compound contained in this composition is not limited. Among them, the phosphite compound represented by the following formula (1) is preferred. Formula (1)··P[-OR] 3 (where R is a hydrocarbon, specifically, substituted or unsubstituted aromatics, aliphatic rings, and alkyl groups, etc.; multiple Rs may be the same as each other, or It may be different, and adjacent plural R may be bonded to each other to form a saturated or unsaturated ring structure), and may also be a compound containing two or more structural units represented by the above formula (1). Various phosphite compounds represented by the above formula (1) were blended in the present composition containing a specific (meth)acrylic (co)polymer and a metal corrosion inhibitor. As a result, it was confirmed that any phosphite compound was It exhibits an anti-oxidation degradation effect, and it has been confirmed that the anti-oxidation degradation effect is particularly excellent for a transparent conductive layer containing ITO. Examples of the phosphite compound contained in the composition include triphenyl phosphite, tris(nonylphenyl) phosphite, tricresol phosphite, tristearyl phosphite, and triethyl phosphite Ester, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl phosphite (2 -Ethylhexyl) ester, diphenyl phosphite monodecyl ester, diphenyl phosphite mono(tridecyl) ester, tetraphenyl dipropylene glycol diphosphite, tetraphenyl (tetra- Tridecyl) pentaerythritol tetraphosphite, tetra(C12～C15 alkyl)-4,4-isopropylidene diphenyl diphosphite, phosphite tris(2,4-di-tertiary butylbenzene) Yl) ester, tris(4-nonylphenyl) phosphite, 3,9-bis(nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5]Undecane, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]十Monoalkane, 3,9-bis(decyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-bis(ten Trialkoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-bis(stearyloxy)-2,4 ,8,10-Tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-Tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)- 2,4,8,10-Tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-bis{2,4-bis(1-methyl-1-phenyl) Ethyl)phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, phosphite 2,2'-methylenebis(4 ,6-Di-tert-butyl-1-phenyl) ester, 4,4'-isopropylidene diphenol C12-15 alcohol phosphite, distearyl pentaerythritol diphosphite, 2,4,8 ,10-Tetra(1,1-dimethylethyl)-6-{(2-ethylhexyl)oxy}-12H-dibenzo[d,g][1,3,2]phosphorus Heterooctacyclic, 2,4,8,10-tetra(1,1-dimethylethyl)-6-(tridecyloxy)-12H-dibenzo[d,g][1,3, 2] Dioxaphosphate, 1,1'-biphenyl-4,4'-diylbis[bis(2,4-di-tert-butylphenyl) phosphite], hydrogenated bisphenol A -Pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, diethyl phosphite, bis(2-ethylhexyl) phosphite, dilauryl phosphite, dioleyl phosphite, phosphorous acid Diphenyl esters and so on. Among them, as the phosphite compound contained in the present composition, for example, in consideration of compatibility with the present composition, an aliphatic phosphite (for example, the phosphorous acid as the phosphite compound of Example 2) is preferred. Tridecyl ester or 3,9-bis(decyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane of Example 3). In addition, in consideration of hydrolysis resistance, aromatic phosphites are preferable (for example, tris(2,4-di-tert-butylphenyl) phosphite, etc., as the phosphite compound of Example 1) . Moreover, in consideration of the balance between solubility and hydrolysis resistance, phosphites having both aliphatic ester groups and aromatic ester groups, such as diphenyl phosphite mono(tridecyl) ester, are preferred. In the present composition, the content ratio of the phosphite compound is preferably relative to the (meth)acrylic (meth)acrylic ( Co) 100 parts by mass of the polymer contains a phosphite compound in a ratio of 0.0001 (1×10 -4 ) parts by mass or more and 2.0 parts by mass or less. Among them, it is more preferably 0.0005 parts by mass or more or 0.8 parts by mass or less. Among them, it is more preferably contained in a ratio of 0.001 parts by mass or more or 0.7 parts by mass or less, and particularly more preferably contained in a ratio of 0.01 parts by mass or more or 0.6 parts by mass or less. (Crosslinking agent) The composition may optionally contain a crosslinking agent. For example, as a method of crosslinking the above-mentioned (meth)acrylic (co)polymer, it is possible to add a reactive group such as a hydroxyl group or a carboxyl group that can be introduced into the (meth)acrylic (co)polymer. A method of chemically bonding crosslinking agent and reacting by heating or aging, or adding as a crosslinking agent a multifunctional (meth)acrylate with two or more (meth)acrylic groups and photopolymerization A method of reacting initiators such as initiators and cross-linking them by ultraviolet irradiation or the like. Among them, from the viewpoint of not consuming polar functional groups such as carboxyl groups in the composition due to the reaction, and maintaining high cohesion or adhesion properties derived from polar components, it is preferable to irradiate light with ultraviolet rays or the like. The cross-linking method. Examples of the above-mentioned crosslinking agent include those having a (meth)acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a carbodiimide group, an azolinyl group, an aziridinyl group, and a vinyl group. A crosslinking agent of at least one crosslinkable functional group among, amine, imino, amide, N-substituted (meth)acrylamido, and alkoxysilyl group, one can be used, or Two or more types can also be used in combination. Furthermore, the cross-linkable functional group may also be protected by a protective group that can be deprotected. Among them, from the viewpoint of the ease of control of the crosslinking reaction, a polyfunctional (meth)acrylate is preferred. As such polyfunctional (meth)acrylates, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate Base) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid UV-curing multifunctional monomers such as tris(acryloxyethyl) ester, as well as polyester (meth)acrylate, epoxy (meth)acrylate, (meth)acrylate urethane , Polyether (meth)acrylate and other polyfunctional acrylic oligomers or polyfunctional acrylamide, etc. In addition, as a crosslinking agent having two or more types of crosslinkable functional groups, for example, glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, and 3,4-(meth)acrylate Epoxy butyl ester, 4-hydroxybutyl (meth)acrylate glycidyl ether and other epoxy-containing monomers; 2-isocyanatoethyl (meth)acrylate, 2-(2-(methyl) isocyanate )Acrylic oxyethoxy) ethyl ester, (meth)acrylic acid 2-(0-[1'-methylpropyleneamino]carboxyamino)ethyl, (meth)acrylic acid 2-[( 3,5-Dimethylpyrazolyl)carbonylamino]ethyl and other monomers containing isocyanate groups or blocked isocyanate groups; vinyl trimethoxysilane, vinyl triethoxysilane, 3-glycidoxy 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane and other silane coupling agents. A crosslinking agent with two or more crosslinkable functional groups can also be used to react a functional group with a (meth)acrylic (co)polymer to bond to the (meth)acrylic (co)polymer. Into the structure. By adopting such a structure, a double-bonded crosslinkable functional group such as a (meth)acryloyl group or a vinyl group can be chemically bonded to the (meth)acrylic (co)polymer. In addition, by bonding the crosslinking agent to the (meth)acrylic (co)polymer, there is a tendency that the bleeding of the crosslinking agent or the unexpected plasticization of the adhesive sheet can be suppressed. In addition, the reaction efficiency of the photo-crosslinking reaction is promoted by bonding the crosslinking agent to the (meth)acrylic (co)polymer, so there is a tendency to obtain a cured product with higher cohesive force. The composition may further contain a monofunctional monomer that can react with the crosslinkable functional group of the crosslinking agent. Examples of such monofunctional monomers include alkyl (meth)acrylates such as methyl acrylate; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. Hydroxyl-containing (meth)acrylates such as esters, polyalkylene glycol (meth)acrylates, etc.; (meth)acrylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2 -(Meth)acryloxypropylhexahydrophthalic acid, 2-(meth)acryloxyethyl phthalic acid, 2-(meth)acryloxyethyl maleate Diacid, 2-(meth)acryloxypropyl maleic acid, 2-(meth)acryloxyethyl succinic acid, 2-(meth)acryloxypropyl succinic acid , Crotonic acid, fumaric acid, maleic acid, itaconic acid and other carboxyl group-containing monomers; maleic anhydride, itaconic anhydride and other acid anhydride group-containing monomers; (meth)acrylic acid tetrahydrofuran Ester, methoxy polyethylene glycol (meth) acrylate and other ether group-containing (meth)acrylates; (meth)acrylamide, dimethyl(meth)acrylamide, diethyl(meth)acrylate (Methyl)acrylamide, (meth)acrylamide, (meth)acrylamide, isopropyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, phenyl(meth)acrylamide , N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide and other (meth)acrylamide monomers. Among them, it is preferable to use a hydroxyl group-containing (meth)acrylate or (meth)acrylamide-based monomer from the viewpoint of improving the adhesiveness to the adherend or the effect of suppressing moist heat whitening. Regarding the content of the crosslinking agent, from the viewpoint of balancing the flexibility and cohesive force of the composition, it is preferably 0.01 or more with respect to 100 parts by mass of the above-mentioned (meth)acrylic (co)polymer. It is formulated at a ratio of 10 parts by mass or less, among which, 0.05 parts by mass or more or 8 parts by mass or less is particularly preferred, and among them, 0.1 parts by mass or more or 5 parts by mass or less is particularly preferred. Furthermore, when the adhesive sheet is multi-layered, the content of the cross-linking agent may exceed the above-mentioned range with regard to the intermediate layer among the layers constituting the adhesive sheet or the layer that becomes the base material. The content of the crosslinking agent in the intermediate layer or the substrate layer is preferably formulated at a ratio of 0.01 to 40 parts by mass relative to 100 parts by mass of the (meth)acrylic (co)polymer, wherein , Particularly preferably 1 part by mass or more or 30 parts by mass or less, and particularly preferably 2 parts by mass or more or 25 parts by mass or less. (Photopolymerization initiator) In the case of crosslinking by light irradiation, it is preferable to contain a photopolymerization initiator. Free radical generation mechanisms based on photopolymerization initiators are divided into two categories. There are α-cleavage types that cleave and decompose their own single bonds to generate free radicals, and those that generate free radicals by exciting hydrogen from compounds in the system. Dehydrogenation type. Among these, it is preferable to use a dehydrogenation type photocrosslinking initiator. Among them, when an organic crosslinking agent having a (meth)acryloyl group is used as the crosslinking agent, it is particularly preferable to further add a photopolymerization initiator. The reason is that free radicals are generated by light irradiation and become the starting point of the polymerization reaction in the system. As the photopolymerization initiator, conventionally known ones can be used as appropriate. Among them, from the viewpoint of the ease of control of the crosslinking reaction, a photopolymerization initiator that senses ultraviolet rays having a wavelength of 380 nm or less is preferred. On the other hand, in terms of obtaining higher photoreactivity and the aspect that the induced light can easily reach the deep part of the adhesive sheet, it is preferable to induce the photopolymerization initiation of light with a wavelength longer than 380 nm Agent. Photopolymerization initiators are divided into two categories according to the free radical generating mechanism, which can be roughly divided into cleavage-type photopolymerization initiators that can cleave and decompose single bonds of the photopolymerization initiator itself to generate free radicals, and photopolymerization initiators that are excited by light. The initiator and the hydrogen donor in the system form a dehydrogenation type photopolymerization initiator that excites the complex and can transfer the hydrogen from the hydrogen donor. The cleavage-type photopolymerization initiator among them decomposes when generating free radicals by light irradiation and becomes another compound. Once excited, it loses its function as a crosslinking initiator. Therefore, it does not remain in the adhesive material after the cross-linking reaction is completed in the form of active species, so that it is impossible to cause unexpected light deterioration of the adhesive material, etc., so it is preferable. On the other hand, dehydrogenation-type photopolymerization initiators do not generate decomposition products such as cleavage-type photopolymerization initiators when they are irradiated with active energy rays such as ultraviolet rays to generate free radicals. Therefore, they are not easy to become Volatile components are useful in terms of reducing damage to the adherend. As the above-mentioned cleavage-type photopolymerization initiator, bis(2,4,6-trimethylbenzyl) is preferred in terms of its high sensitivity to light and the decomposition and decolorization after the reaction. -Phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, (2,4,6-trimethylbenzyl)ethoxyphenylphosphine oxide, bis( 2,6-Dimethoxybenzyl) 2,4,4-trimethylpentyl phosphine oxide and other phosphine oxide-based photopolymerization initiators. As the dehydrogenation-type photopolymerization initiator, for example, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenyldiphenyl Methyl ketone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(meth)acryloxybenzophenone, 4-[2-((meth)acryloxy Yl)ethoxy)benzophenone, 4-(meth)acryloyloxy-4'-methoxybenzophenone, 2-benzyl benzoate, methyl benzoate, Diethylene glycol bis(2-phenyl-2-oxoacetate), 4-(1,3-propenyl-1,4,7,10,13-pentaoxatridecyl) Benzophenone, 9-oxysulfur 𠮿
Figure 105143067-A0304-12-0019-3
, 2-chloro-9-oxysulfur 𠮿
Figure 105143067-A0304-12-0019-3
, 3-Methyl-9-oxysulfur 𠮿
Figure 105143067-A0304-12-0019-3
, 2,4-Dimethyl-9-oxysulfur 𠮿
Figure 105143067-A0304-12-0019-3
, Anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, camphorquinone or its derivatives, etc. Among them, preferred are benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3' -Dimethyl-4-methoxybenzophenone, 4-(meth)acryloyloxybenzophenone, 4-[2-((meth)acryloyloxy)ethoxy] two Benzophenone, 4-(meth)acryloyloxy-4'-methoxybenzophenone, 2-benzylbenzoic acid methyl, and benzylcarboxylic acid methyl. In addition, any one of the photopolymerization initiators listed above or a derivative thereof may be used, or two or more of these may be used in combination. Furthermore, in addition to the photopolymerization initiator, a sensitizer may also be used. The sensitizer is not particularly limited, and as long as it is a sensitizer used in the photopolymerization initiator, it can be used without problems. Examples include: aromatic amines or anthracene derivatives, anthraquinone derivatives, coumarin derivatives, 9-oxysulfur
Figure 105143067-A0304-12-0019-3
Derivatives, phthalocyanine derivatives, etc. or benzophenone, ketone, 9-oxysulfur
Figure 105143067-A0304-12-0019-3
Aromatic ketones such as Michele ketone, 9,10-phenanthrenequinone, and their derivatives. In addition, the photopolymerization initiator or sensitizer may be contained in a state bonded to the (meth)acrylic (co)polymer. As a method for bonding the photopolymerization initiator or sensitizer to the (meth)acrylic (co)polymer, it is possible to use the same method as bonding the above-mentioned crosslinking agent to the (meth)acrylic (co)polymer. In the case of the situation, the same method. The content of the photopolymerization initiator is not particularly limited. Typically, it is particularly preferred to adjust at a ratio of 0.1 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylic (co)polymer. It is particularly preferable to adjust at a ratio of 0.2 parts by mass or more or 5 parts by mass or less, among which, it is particularly preferable to adjust at a ratio of 0.5 parts by mass or more or 3 parts by mass or less. Among them, the range may be exceeded due to the balance with other elements. (Antioxidant) In addition to the above, the composition may optionally contain an antioxidant. Examples of antioxidants include 2,2'-methylenebis(4-methyl-6-tert-butylphenol), hexanediol-bis(3,5-di-tert-butyl-4- Hydroxyhydrocinnamate), tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, triethylene glycol-bis-3-(3-tert-butyl -4-hydroxy-5-methylphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl )Benzene, 3-(4'-hydroxy-3',5'-di-tert-butylphenol) n-octadecyl propionate, 4,4'-methylene bis(2,6-di Hindered phenol-based antioxidants such as tributylphenol), 4,4'-butylene-bis-(6-tert-butyl-3-methyl-phenol) or various antioxidants such as sulfur-based and amine-based antioxidants. (Other components) Furthermore, this composition may contain well-known components which are blended in a normal adhesive composition as appropriate. For example, light stabilizers, ultraviolet absorbers, metal deactivators, rust inhibitors (except the above-mentioned metal corrosion inhibitors), anti-aging agents, antistatic agents, moisture absorbers, foaming agents, defoamers, inorganic Various additives such as particles, viscosity modifiers, adhesion imparting resins, photosensitizers, fluorescent agents, etc., or reaction catalysts (tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, etc.). (Adjustment of Adhesive Composition) The adhesive composition (this composition) used in this adhesive sheet can be prepared by combining (meth)acrylic (co)polymers, metal corrosion inhibitors, and phosphite compounds, and If necessary, other ingredients are mixed in specific amounts to obtain them. There are no particular restrictions on these mixing methods, and the mixing order of the components is also not particularly limited. In addition, a heat treatment step may be added during the production of the present composition. In this case, it is preferable to mix the components of the present composition in advance and then perform the heat treatment. It is also possible to use a masterbatch after concentrating various mixed components. In addition, there are no special restrictions on the mixing device. For example, universal kneaders, planetary mixers, Bamburi mixers, kneaders, frame mixers, pressure kneaders, three-roll mills, and two-roll mills can be used. machine. A solvent can also be used for mixing as needed. Moreover, this composition can also be used as a solvent-free system which does not contain a solvent. By using it as a solvent-free system, it has the advantage of not remaining solvents and increased heat resistance and light resistance. Furthermore, the composition can also be used in the following manner: it is prepared in advance to contain monomer components constituting the (meth)acrylic (co)polymer, 1,2,3-triazole, photopolymerization initiator and other optional components When the composition is used as an adhesive sheet for a conductive member, it is irradiated with light to undergo a polymerization reaction to produce a (meth)acrylic (co)polymer. <The form of the adhesive sheet for conductive members> In addition to applying the composition directly to the adherend and forming it into a sheet, this adhesive sheet can also be formed on a release film and formed into a single layer or Multi-layer sheet-like adhesive sheet with release film. As the material of the release film, for example, a polyester film, a polyolefin film, a polycarbonate film, a polystyrene film, an acrylic film, a triacetyl cellulose film, a fluororesin film, etc. may be mentioned. Among them, polyester films and polyolefin films are particularly preferred. The thickness of the release film is not particularly limited. Among them, for example, from the viewpoint of processability and operability, it is preferably 25 μm to 500 μm, and among them, it is more preferably 38 μm or more or 250 μm or less, and among them, it is more preferably 50 μm or more or 200 μm or less. . Furthermore, the adhesive sheet can also be formed by directly extruding the composition without using the adherend or release film as described above, or by injecting it into a mold. Furthermore, by directly filling the composition between conductive members and other members, it can also be made into an adhesive sheet. <Physical properties of the adhesive sheet for conductive members> (Anticorrosive effect on conductive layer of conductive member) This adhesive sheet has corrosion resistance to conductive members, especially transparent conductive layers or conductive patterns formed by metal materials containing copper. Therefore, the change rate of the ITO resistance value [((Ω/Ω0)-1)×100] measured by the following methods (1)～(2) can be set to less than 5%, among which, you can set It is less than 3%. In addition, the rate of change of the copper resistance measured by the following methods (3) to (4) [((Ω/Ω0)-1)×100] can be set to less than 20%, among which, you can set It is less than 10%, and can be set to less than 5%, especially less than 3%. (1) The adhesive composition for conductive members (this composition) is formed into a sheet with a thickness of 150 μm to form an adhesive sheet, and the adhesive sheet is attached to an ITO wiring containing indium oxide (ITO) An ITO glass substrate for evaluation formed on a glass substrate was used to produce ITO wiring with an adhesive sheet. (2) Pre-measure the resistance value (Ω0) of the ITO wiring in the above-mentioned adhesive sheet-attached ITO wiring at room temperature, and store the above-mentioned adhesive sheet-attached ITO wiring at 65°C and 90%RH for 500 hours Measure the resistance value (Ω) of the ITO wiring in the ITO wiring with the adhesive sheet after the storage. (3) The adhesive composition for conductive members (this composition) is formed into a sheet with a thickness of 150 μm to form an adhesive sheet, and the adhesive sheet is bonded to copper wiring and formed on a glass substrate. For the evaluation, a copper glass substrate was used to produce copper wiring with an adhesive sheet. (4) Pre-measure the resistance value (Ω0) of the copper wiring in the copper wiring with the adhesive sheet at room temperature, and store the copper wiring with the adhesive sheet for 500 hours at 65°C and 90%RH Measure the resistance value (Ω) of the copper wiring in the copper wiring with the adhesive sheet after the storage. (Transparency) The adhesive sheet is preferably optically transparent. That is, it is preferably a transparent adhesive sheet. Here, the term "optically transparent" means that the total light transmittance is 80% or more, preferably 85% or more, and more preferably 90% or more. (Thickness) The thickness of the adhesive sheet is preferably 10 μm or more and 500 μm or less, among them, 15 μm or more or 400 μm or less is more preferable, and among them, 20 μm or more or 350 μm or less is more preferable. <Use of the adhesive sheet for conductive members> This adhesive sheet is used in image display devices such as personal computers, mobile device terminals (PDA), game consoles, televisions (TV), car navigation systems, touch panels, handwriting boards, etc. For example, plasma display (PDP), liquid crystal display (LCD), organic EL display (OLED), inorganic EL display, electrophoretic display (EPD), interference modulation display (IMOD) and other image display devices that use image display panels , Suitable for bonding each constituent member, the conductive member, the conductive member with a transparent conductive layer and/or a conductive pattern formed of a metal material containing copper. In addition, it is also suitable for bonding conductive members including a transparent conductive layer containing ITO or IGZO and/or a transparent conductive layer with a conductive pattern formed of a metal material containing copper or silver. <Conductive member laminate> The conductive member laminate of the present invention (hereinafter, also referred to as "the laminate") can be obtained by bonding the adhesive sheet to a conductive member, for example, a conductive layer of a transparent conductive layer . The laminated body only needs to have a structure in which at least any one of the adhesive layer of the adhesive sheet and the conductive layer of the transparent conductive layer are bonded together. When the adhesive sheet is a double-sided adhesive sheet, the laminate may also have a structure in which the two adhesive layers of the adhesive sheet and the conductive layer of the transparent conductive layer are bonded together. The above-mentioned transparent conductive layer can also be formed by covering the conductive layer of the conductive film using olefin-based polymers, urethane-based polymers, epoxy-based polymers, acrylic polymers, polysiloxane-based polymers, or Insulation protection film (passivation film) formed of inorganic glass. The laminated body obtained by bonding with the conductive layer can be preferably used in a touch panel. Examples of the touch panel include methods such as a resistive film method, an electrostatic capacitance method, and an electromagnetic induction method, and the electrostatic capacitance method is preferred. As the above-mentioned transparent conductive layer, any one having a conductive layer on at least one surface of the surface layer is sufficient, and examples thereof include a transparent conductive layer formed by vapor deposition, sputtering, or coating with a conductive material provided on the surface of a transparent substrate. The conductive material used in the conductive layer of the transparent conductive layer is not particularly limited. Specifically, in addition to metal oxides such as indium oxide, indium-gallium-zinc composite oxide, tin-doped indium oxide (ITO), zinc oxide, gallium oxide, titanium oxide, silver, copper, molybdenum, aluminum And other metal materials. Among them, tin-doped indium oxide (ITO) and indium-gallium-zinc composite oxide (IGZO) with excellent transparency can be preferably used. In addition, from the viewpoint of excellent conductivity, copper or silver can also be preferably used. In the transparent conductive layer, the base material to be patterned with the conductive material is not particularly limited, and glass, resin film, etc. can be mentioned. Typically, the transparent conductive layer has a conductive layer on at least one surface. In addition, typically, a conductive pattern (wiring pattern) mainly composed of copper or silver is formed on the transparent conductive layer so as to surround the peripheral portion. 1,2,3-triazole has high corrosion resistance to copper among them, so the original adhesive sheet containing it can be particularly preferably used for conductive members with conductor patterns formed of metal materials containing copper. As specific examples of other present laminates, for example, release film/main adhesive sheet/touch panel, release film/main adhesive sheet/protection panel, release film/main adhesive sheet/image display Panel, image display panel/this adhesive sheet/touch panel, image display panel/this adhesive sheet/protection panel, image display panel/this adhesive sheet/touch panel/this adhesive sheet/protection panel , Polarizing film/this adhesive sheet/touch panel, polarizing film/this adhesive sheet/touch panel/this adhesive sheet/protective panel, etc. In addition, in the above-mentioned configuration, all configurations in which the above-mentioned conductive layer is interposed between the present adhesive sheet and the adjacent touch panel, protective panel, image display panel, polarizing film, and other members can be cited. However, it is not limited to these laminated examples. Furthermore, the above-mentioned touch panel also includes a structure in which a touch panel function is built in a protective panel or a structure in which a touch panel function is built in an image display panel. <Image display device> The image display device of the present invention (hereinafter, also referred to as "this device" is omitted hereafter) has at least this laminate, an image display panel, and a surface protection panel as constituent members. More specifically, an image display device having a structure in which the present laminated body obtained by bonding the present adhesive sheet and the conductive layer of the transparent conductive layer is inserted between the image display panel and the surface protection panel can be cited. At this time, the adhesive sheet is also used on the image display panel side. As the material of the surface protection panel, in addition to glass, it can also be alicyclic polyolefin resins such as acrylic resins, polycarbonate resins, and cycloolefin polymers, styrene resins, polyvinyl chloride resins, and phenolic resins. Resin, melamine resin, epoxy resin and other plastics. The image display panel is composed of other optical films such as retardation films, liquid crystal materials, and backlight light source systems other than polarizing films (usually, this composition or adhesive article becomes an optical film on the surface of the image display panel to be bonded), according to There are STN (Super Twisted Nematic, super twisted nematic) method, VA (Vertical Aligned, vertical alignment) method, IPS (In-Plane Switching, lateral electric field effect) method, etc. for the control method of the liquid crystal material, which can be any method. As this image display device, for example, an image display device such as a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, a plasma display, and a microelectromechanical system (MEMS) display can be configured. <Explanation of sentences> In this manual, when it is expressed as "X～Y" (X and Y are arbitrary numbers), unless otherwise specified, it includes the meaning of "more than X and less than Y", and includes The meaning of "preferably larger than X" or "preferably smaller than Y". In addition, when the expression is "more than X" (X is any number) or "below Y" (Y is any number), it includes "preferably greater than X" or "preferably less than Y" intention. Generally speaking, the so-called "sheet", in the definition of JIS, refers to a product that is thinner, whose thickness is less than the quotient of the length and width, and is flat. Generally speaking, the so-called "film" is the same as the length and width. Thinner and flat products whose specific thickness is extremely small and the maximum thickness is arbitrarily limited are usually supplied in the shape of a roll (Japanese Industrial Standard JIS K6900). However, the boundary between the sheet and the film is not certain. In the present invention, there is no need to distinguish between the two in terms of language. Therefore, in the present invention, the term "film" also includes "sheet". It also includes "film" when it is called "sheet". [Examples] Hereinafter, examples and comparative examples will be further described in detail. However, the present invention is not limited to these embodiments. [Example 1] 1 kg of copolymer (A-1, mass average molecular weight 400,000) containing 76 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 4 parts by mass of acrylic acid was added to 1 kg of pentaerythritol propoxylate Polyacrylate (manufactured by Shinnakamura Chemical Industry Co., Ltd., trade name "ATM-4PL") 200 g as a crosslinking agent, and a combination of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone 10 g of the mixture (manufactured by Lamberti, trade name "Esacure TZT") was used as a photopolymerization initiator and uniformly mixed to obtain a resin composition for an intermediate layer. The resin composition for the intermediate layer was sandwiched between two peeled polyethylene terephthalate films (manufactured by Mitsubishi Plastics, trade name "DIAFOIL MRF", thickness 75 μm, and manufactured by Mitsubishi Plastics, trade name "DIAFOIL"MRT" with a thickness of 38 μm), and form a sheet so that the thickness of the adhesive sheet becomes 80 μm to produce a resin sheet (α) for the intermediate layer. To 1 kg of the above-mentioned acrylate copolymer (A-1), 1.5 g of 1,2,3-triazole was added as a metal corrosion inhibitor, tris(2,4-di-tert-butylphenyl) phosphite (BASF) Manufactured by the company, trade name "Irgafos 168") 5 g as a phosphite compound, and a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (manufactured by Lamberti, trade name "Esacure TZT") 15 g was used as a photopolymerization initiator and uniformly mixed to obtain a resin composition for an adhesive layer. The above-mentioned resin composition for the adhesive layer was sandwiched between two peeled polyethylene terephthalate films (manufactured by Mitsubishi Plastics, trade name "DIAFOIL MRV", thickness 100 μm, and manufactured by Mitsubishi Plastics, trade name). "DIAFOIL MRT", thickness 38 μm), and form a sheet so that the thickness of the adhesive sheet becomes 35 μm to produce a resin sheet (β) for the adhesive layer. Furthermore, the above-mentioned resin composition for the adhesive layer was sandwiched between two peeling-treated polyethylene terephthalate films (manufactured by Mitsubishi Plastics Corporation, brand name "DIAFOIL MRQ", thickness 75 μm, and manufactured by Mitsubishi Plastics Corporation, The product name is "DIAFOIL MRT", the thickness is 38 μm), and the adhesive sheet is formed into a sheet so that the thickness of the adhesive sheet becomes 35 μm to produce a resin sheet (β') for the adhesive layer. The PET film on both sides of the above-mentioned intermediate layer sheet (α) is peeled off in order, and the PET film on one side of the resin sheet (β) and (β') for the adhesive layer is peeled off, and the exposed adhesive The surfaces are sequentially attached to both surfaces of the intermediate layer sheet (β) to produce a laminate containing (β)/(α)/(β'). Through the PET film remaining on the surface of (β) and (β'), ultraviolet light is irradiated with a high-pressure mercury lamp so that the cumulative light intensity of the wavelength of 365 nm becomes 2000 mJ/cm 2 to make (α), (β) and ( β') was cross-linked by ultraviolet rays to produce an adhesive sheet laminate (thickness 150 μm). The following various evaluations were performed for this adhesive sheet laminate. The results are shown in Table 1. [Example 2] To 1 kg of copolymer (A-2, mass average molecular weight 200,000) containing 81 parts by mass of butyl acrylate, 15 parts by mass of methyl methacrylate, and 4 parts by mass of acrylic acid was added 1, 2, 3 -Triazole 3 g as a metal corrosion inhibitor, tridecyl phosphite (manufactured by ADEKA, trade name "Adekastab 3010") 3 g as a phosphite compound, pentaerythritol tri- and tetraacrylate (manufactured by Toagosei Co., Ltd., "ARONIXM -306") 20 g as a crosslinking agent, and 10 g of 1-hydroxy-cyclohexyl phenyl ketone (manufactured by BASF Corporation, Irgacure 184) as a photopolymerization initiator and uniformly mixed to obtain a resin composition for an adhesive layer. Next, the above-mentioned resin composition for the adhesive layer was formed into a sheet with a thickness of 150 μm on a polyethylene terephthalate film (manufactured by Mitsubishi Plastics Corporation, DIAFOIL MRV, thickness 100 μm) that was peeled off. Afterwards, a peel-off polyethylene terephthalate film (manufactured by Mitsubishi Plastics Corporation, trade name "DIAFOIL MRQ", thickness 75 μm) was coated. Through the peeled polyethylene terephthalate film, the resin composition for the adhesive layer is cross-linked by ultraviolet rays by irradiating ultraviolet rays with a high-pressure mercury lamp so that the cumulative amount of light at a wavelength of 365 nm becomes 1000 mJ/cm 2 Adhesive sheet laminate 2. The following various evaluations were performed for this adhesive sheet laminate 2. The results are shown in Table 1. [Example 3] 3,9-bis(decyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (manufactured by Johoku Chemical Co., Ltd., product (Name "JPE-10") 3 g was used as the phosphite compound, and except for that, an adhesive sheet laminate 3 was produced in the same manner as in Example 2. The following various evaluations were performed for this adhesive sheet laminate 3. The results are shown in Table 1. [Comparative Example 1] 1,2,3-triazole as a metal corrosion inhibitor and tris(2,4-di-tert-butylphenyl) phosphite (manufactured by BASF Corporation, as a phosphite compound) were not added Except for the trade name "Irgafos 168"), an adhesive sheet laminate 4 was produced in the same manner as in Example 2. The following various evaluations were performed for this adhesive sheet laminate 4. The results are shown in Table 1. [Comparative Example 2] An adhesive sheet laminate 5 was produced in the same manner as in Example 1 except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The following various evaluations were performed for this adhesive sheet laminate 5. The results are shown in Table 1. [Comparative Example 3] 1.5 g of benzotriazole (manufactured by Johoku Chemical Co., Ltd., trade name "BT120") was added instead of 1,2,3-triazole as a metal corrosion inhibitor, and no phosphite compound was added, except that , The adhesive sheet laminate 6 was produced in the same manner as in Example 1. The following various evaluations were performed for this adhesive sheet laminate 6. The results are shown in Table 1. <Various evaluations> (1) Oxidation and degradation resistance on a glass substrate (60 mm×45 mm) with a thickness of 150 to 200 Å, a line width of 70 μm, a line length of 46 mm, and a line interval of 30 μm, with 10.5 round trips Form a round-trip wire of indium oxide (ITO), and form a 2 mm square containing ITO at both ends of the round-trip wire to form an ITO pattern (length about 97 cm), and make an ITO glass substrate for evaluation of oxidation degradation resistance (refer to Figure 1(A)). The single-sided release film of the adhesive sheet laminates 1 to 6 (thickness 150 μm) produced in the above examples and comparative examples was peeled off, and the PET film (manufactured by Toyobo Co., Ltd., trade name "COSMOSHINE"A4100", 125 μm) is attached to the exposed surface. Then, after cutting the above adhesive sheet with PET film into 52 mm×45 mm, peel off the remaining release film, as shown in Figure 1(B), and use a hand roller to cover the ITO back and forth wires. This pressure-sensitive adhesive sheet was attached to an ITO glass substrate for evaluation of oxidation degradation resistance to prepare a sample for evaluation of oxidation degradation resistance (ITO wiring with adhesive sheet) (see FIG. 1(C)). The resistance value (Ω0) of the ITO wiring in the sample for evaluation of oxidation degradation resistance (ITO wiring with adhesive sheet) at room temperature was measured in advance. On the other hand, the sample for evaluation of oxidation degradation resistance (ITO wiring with adhesive sheet) was stored for 500 hours in an environment of 65°C and 90%RH. After storage, the sample for evaluation of oxidation degradation resistance (with adhesive) was measured. The resistance value (Ω) of the ITO wiring in the ITO wiring of the sheet. In addition, the ITO resistance value, that is, the rate of change (%) of the resistance value between the ends of the line (%) [((Ω/Ω0)-1)×100] was calculated and expressed as "resistance value change" in Table 1. Regarding the oxidation degradation resistance, the resistance value change rate of 5% or more is judged as "× (poor)", and the resistance value less than 5% is judged as "○ (good)". The results are shown in Table 1. (2) Corrosion resistance reliability is formed on a glass substrate (60 mm×45 mm) with a line width of 70 μm, a line length of 46 mm, a line interval of 30 μm, and 10.5 round trips to form ITO with a thickness of 1300 Å and a thickness of 3000. A round-trip wire of a metal film formed by sequential layers of copper films of Å, and a 2 mm square square is formed at both ends of the round-trip wire to form a copper pattern (length approximately 97 cm) to produce copper glass for corrosion resistance reliability evaluation Substrate (refer to Figure 1(A)). The single-sided release film of the adhesive sheet laminates 1 to 6 (thickness 150 μm) produced in the above examples and comparative examples was peeled off, and the PET film (manufactured by Toyobo Co., Ltd., trade name "COSMOSHINE"A4100", 125 μm) is attached to the exposed surface. Then, after cutting the above adhesive sheet with PET film into 52 mm×45 mm, peel off the remaining peeling film, as shown in Figure 1(B), and use a hand roller to cover the metal film on the return line The adhesive sheet was attached to a copper glass substrate for corrosion-resistant reliability evaluation to prepare a sample for corrosion-resistant reliability evaluation (copper wiring with adhesive sheet) (see Fig. 1(D)). The resistance value (Ω0) of the copper wiring in the corrosion resistance reliability evaluation sample (copper wiring with an adhesive sheet) at room temperature was measured in advance. On the other hand, the sample for corrosion resistance reliability evaluation (copper wiring with adhesive sheet) was stored at 65°C and 90%RH for 500 hours. After storage, the sample for corrosion resistance reliability evaluation (with adhesive sheet) was measured. The resistance value (Ω) of the copper wiring in the material of the copper wiring). In addition, the copper resistance value, that is, the rate of change (%) of the resistance value between the wire ends (%) [((Ω/Ω0)-1)×100] was calculated and expressed as "resistance value change" in Table 1. Regarding the corrosion resistance reliability, the resistance value change rate of 20% or more is judged as "× (poor)", and less than 20% is judged as "○ (good)". The results are shown in Table 1. [Table 1]
Figure 105143067-A0304-0001
 (Evaluation results) The adhesive sheets of Examples 1 to 3 contain metal corrosion inhibitors and phosphites, so that ITO wiring and copper wiring have less resistance value changes and are excellent in corrosion resistance reliability and oxidation degradation resistance . On the other hand, none of Comparative Example 1 contained a phosphite compound and a metal corrosion inhibitor, and had poor corrosion resistance reliability and oxidation degradation resistance. Since Comparative Example 2 does not contain a metal corrosion inhibitor, the corrosion of copper wiring is particularly remarkable. Comparative Example 3 does not contain a phosphite compound, and has poor resistance to oxidation degradation of ITO wiring. [Industrial Applicability] The adhesive sheet for a conductive member of the present invention may have a conductive member (typically, a conductive member having a transparent conductive layer and/or a conductive pattern formed of a metal material containing copper or silver) It has corrosion resistance and reliability, and can prevent oxidation and deterioration, so it can be used as an adhesive sheet suitable for laminating various conductive components. In particular, it can be preferably used as an adhesive sheet for an image display device with a touch panel.

圖1係用以對下述實施例中進行之耐腐蝕可靠性之評價試驗方法進行說明之圖，(A)係防氧化劣化性評價用ITO玻璃基板之ITO圖案之俯視圖或耐腐蝕可靠性評價用銅玻璃基板之銅圖案之俯視圖，(B)係表示於防氧化劣化性評價用ITO玻璃基板上被覆有黏著片材之狀態之俯視圖或表示於耐腐蝕可靠性評價用銅玻璃基板上被覆有黏著片材之狀態之俯視圖，(C)係防氧化劣化性評價用樣品之剖視圖，(D)係耐腐蝕可靠性評價用樣品之剖視圖。Figure 1 is a diagram for explaining the corrosion resistance reliability evaluation test method carried out in the following examples, (A) is the top view of the ITO pattern of the ITO glass substrate for the evaluation of oxidation degradation resistance or the corrosion resistance reliability evaluation The top view of the copper pattern on the copper glass substrate, (B) is the top view showing the state where the adhesive sheet is coated on the ITO glass substrate for the evaluation of oxidation degradation or the top view of the copper glass substrate for the evaluation of corrosion resistance reliability. The top view of the state of the adhesive sheet, (C) is a cross-sectional view of the sample for evaluation of anti-oxidation degradation, (D) is a cross-sectional view of the sample for evaluation of corrosion resistance reliability.

Claims (11)

一種導電構件用黏著片材，其包含黏著劑層，該黏著劑層包含含有(甲基)丙烯酸系共聚物、金屬腐蝕防止劑及亞磷酸酯化合物之黏著劑組合物，該金屬腐蝕防止劑包含選自1,2,3-三唑及1,2,4-三唑之任一種以上。 An adhesive sheet for conductive members, comprising an adhesive layer comprising an adhesive composition containing a (meth)acrylic copolymer, a metal corrosion inhibitor, and a phosphite compound, and the metal corrosion inhibitor includes Any one or more selected from 1,2,3-triazole and 1,2,4-triazole. 如請求項1之導電構件用黏著片材，其中上述亞磷酸酯化合物包含選自脂肪族亞磷酸酯、芳香族亞磷酸酯以及具有脂肪族酯基及芳香族酯基之亞磷酸酯之任一種以上。 The adhesive sheet for conductive members according to claim 1, wherein the phosphite compound includes any one selected from the group consisting of aliphatic phosphites, aromatic phosphites, and phosphites having aliphatic ester groups and aromatic ester groups above. 如請求項1或2之導電構件用黏著片材，其中上述(甲基)丙烯酸系共聚物包含含羧基單體作為結構單元。 The adhesive sheet for conductive members according to claim 1 or 2, wherein the (meth)acrylic copolymer includes a carboxyl group-containing monomer as a structural unit. 如請求項3之導電構件用黏著片材，其中上述(甲基)丙烯酸系共聚物含有1.2~15質量%之含羧基單體。 According to claim 3, the adhesive sheet for conductive members, wherein the (meth)acrylic copolymer contains 1.2 to 15% by mass of a carboxyl group-containing monomer. 如請求項1或2之導電構件用黏著片材，其中上述黏著劑組合物具有光硬化性。 The adhesive sheet for conductive members according to claim 1 or 2, wherein the adhesive composition has photocuring properties. 如請求項1或2之導電構件用黏著片材，其中上述黏著劑組合物包含交聯劑。 The adhesive sheet for conductive members according to claim 1 or 2, wherein the adhesive composition includes a crosslinking agent. 如請求項1或2之導電構件用黏著片材，其中上述導電構件具有透明導 電層。 The adhesive sheet for a conductive member of claim 1 or 2, wherein the conductive member has a transparent conductive Electric layer. 如請求項7之導電構件用黏著片材，其中上述導電構件具有包含摻錫之氧化銦之透明導電層及/或由包含銅之金屬材料形成之導體圖案。 The adhesive sheet for a conductive member of claim 7, wherein the conductive member has a transparent conductive layer containing tin-doped indium oxide and/or a conductive pattern formed of a metal material containing copper. 一種導電構件積層體，其具有將如請求項1至8中任一項之導電構件用黏著片材與導電構件貼合而成之構成。 A conductive member laminate having a structure in which the adhesive sheet for a conductive member according to any one of claims 1 to 8 and a conductive member are bonded together. 一種圖像顯示裝置，其包含如請求項9之導電構件積層體、圖像顯示面板及表面保護面板作為構成構件。 An image display device comprising the conductive member laminate as claimed in claim 9, an image display panel, and a surface protection panel as constituent members. 一種導電構件用黏著劑組合物，其含有(甲基)丙烯酸系共聚物、金屬腐蝕防止劑及亞磷酸酯化合物，該金屬腐蝕防止劑包含選自1,2,3-三唑及1,2,4-三唑之任一種以上。 An adhesive composition for conductive members, which contains a (meth)acrylic copolymer, a metal corrosion inhibitor and a phosphite compound, and the metal corrosion inhibitor includes 1,2,3-triazole and 1,2 Any one or more of 4-triazole.
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