TW200806771A - Adhesive composition and transparent laminate - Google Patents

Abstract

To provide an adhesive composition having excellent transparency, a heat resistance, adhesiveness, a moisture resistance and anti-insulating property as well, as compared with a conventional epoxy resin type adhesive agent for a print circuit board. An adhesive composition for a laminate comprising a silane-modified epoxy resin containing a methoxy group (A) which is obtained by subjecting a bisphenol type epoxy resin (a-1) and a partially condensed methoxy silane (a-2) to de-alcoholizing reaction, an acryl polymer which contains a carboxyl group, shows a glass transition point of not higher than 20 DEG C, an acid value of 2 to 10 (mgKOH/g) and a number average molecular weight of 150,000 to 300,000 (B), and a cross-linking agent for an epoxy resin (C).

Description

200806771 九、發明說明： 【發明所屬之技術領域】 本發明係關於接著劑組合物。該接著劑組合物，係適 合用於印刷電路㈣接著劑，⑽〗是，軟性印刷基板，或 覆蓋層膜、稱為TAB(TaPe Aut〇mated B〇nding :捲帶式自 動接合）方式之半導體積體電路構裝用捲帶（以下，略稱為 「TAB帶」）、觸控面板用基板、1(：卡、i(：標籤用基板: 電子紙用基板、軟性顯示器用基板等之金屬層與塑膠膜之 接著劑組合物。 【先前技術】 軟性印刷電路板’-般係將以耐熱性及電絕緣性優广 的聚亞醯胺、液晶高分子等作為素材之'耐熱性有機絕緣膜又 經由接著劑接著銅ϋ或ITG膜等導體—體化者，惟作為該 接著劑由於接著性良好使用環氧樹脂系接著劑。但是：;: 著近年的配線密度或構裝密度的顯著的增加，*求印刷= 路板之耐熱性、耐濕性、接著性、作業性之更佳提升。又， TAB帶基板上係與軟性印刷電路板相同者，材料構成 要求的諸特性基板上共通’惟現狀係按照要求特性水準將 兩者區分使用。對於如此之市場要求，特別是要求作業性 或成本耐濕性之用途，開始使用聚對苯二甲酸乙二醇酉t (PET)或聚萘二甲酸乙二醇酯(pEN)等聚酯膜隻印刷雞板。曰 該等膜，由於較聚亞醯胺.液晶高分子廉價，透明性佳， 製作印刷電路板時之加工容易，且比聚亞醯胺耐濕性佳。 2066-89l4-PF;Ahddub 6 200806771 然而’使用環氧樹脂與硬化劑所組成之接著劑將該等 接著’則因熱循環使接著劑硬化劑產生很大的歪曲，有破 壞接合部之情形。而有為將如此之内部歪曲吸收，防止產 生内部應力使接著劑硬化物具有撓曲性之嘗試。例如，揭 不有於接著劑組合物中添加合成橡膠等之方法（參照專利 文獻1 )，於環氧樹脂添加合成橡膠之接著劑組合物雖剝離 強度佳’但在於耐熱性並不是可以滿足者。200806771 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an adhesive composition. The adhesive composition is suitable for use in a printed circuit (4) adhesive, (10) is a flexible printed substrate, or a cover film, a semiconductor called TAB (TaPe Aut〇mated B〇nding) Tape for integrated circuit assembly (hereinafter, abbreviated as "TAB tape"), substrate for touch panel, 1 (: card, i (: substrate for label: substrate for electronic paper, substrate for flexible display, etc.) The adhesive composition of the layer and the plastic film. [Prior Art] The flexible printed circuit board is a 'heat-resistant organic insulation material that uses heat-sensitive and electrically insulating polyacrylamide, liquid crystal polymer, etc. as a material. The film is further bonded to a conductor such as a copper beryllium or an ITG film via an adhesive, and an epoxy resin-based adhesive is used as the adhesive because of good adhesion. However, the wiring density or the density of the structure is remarkable in recent years. Increase, *Seeking printing = better heat resistance, moisture resistance, adhesion, and workability of the board. Also, the TAB tape substrate is the same as the flexible printed circuit board, and the material composition is required on the substrate. Common Use the two according to the required characteristic level. For such market requirements, especially for applications requiring workability or cost moisture resistance, start using polyethylene terephthalate PETt (PET) or polyethylene naphthalate. Polyester film such as diol ester (pEN) only prints chicken plates. These films are cheaper than polyimidamide. Liquid crystal polymers, good transparency, easy processing when making printed circuit boards, and more than polyaluminium The amine has good moisture resistance. 2066-89l4-PF; Ahddub 6 200806771 However, 'the use of an adhesive composed of an epoxy resin and a hardener to continue the same' causes a large distortion of the adhesive hardener due to thermal cycling. In the case of damaging the joint, there is an attempt to absorb such internal distortion and prevent internal stress from causing flexibility of the adhesive. For example, a method of adding synthetic rubber or the like to the adhesive composition is not disclosed ( According to Patent Document 1), the adhesive composition in which the synthetic rubber is added to the epoxy resin has good peeling strength, but the heat resistance is not satisfactory.

本案申請人，為解決該等問題，提案了一種環氧樹脂 組合物，其特徵在於包含··含有甲氧基之矽烷變性環氧樹 脂、含有環氧基之合成橡膠及環氧樹脂用硬化劑，惟該組 口物雖對聚亞醯胺膜之接著性良好，但對等聚醋膜 之接著性並不充分。（參照專利文獻2) 因此，本案申請人，反覆改良提案了一種接著劑組合 物八特徵在於包合·丙烯酸高分子，其具有缓基及/或窥 玻璃轉移點為2Gt以下；及環氧樹脂用硬化劑。該接 著劑組合物，不僅對聚亞醯胺膜，對S PEN、液晶高分子 :示優良的接著性，並且相較於印刷電路板用接著劑之先 則之環氧職系接著劑，顯示更佳優良的耐熱性等，惟由 於適顯示器或光學用丈伞笼田面七、杜 . 用途4用，要求進一步改良透明性者（參 知專利文獻3 )。 [專利文獻1]日本特開平1〇—335768號公報 [專利文獻2]日本特開2003-246838號公報 [專利文獻3]日本特開2005-179408號公報 2066-8914-PF;Ahddub 7 200806771 【發明内容】 [發明所欲解決的課題] 本發明之目的係在於提供相較於印刷電路板用接著劑 之先前之環氧樹脂系接著劑，可賦予兼具更佳的透明性， 及耐熱性、接著性、耐濕性、絕緣性等之接著層之接 組合物〇 月 [用以解決課題的手段] ^本發明者為解決上述課題，反覆銳意研究結果，發現 2由使用以：含有甲氧基之矽烷變性環氧樹脂，其係將特 定的環氧樹脂以特定的甲氧矽烷化合物變性而纟；特定的 =性體；及環氧樹脂用硬化劑作為必須構成成分之樹脂組 合物’可得合於上述目的之接著劑組合物，達至完成本發 々即，本發明係關於一種層積體用接著劑組合物，其特 徵在於包含：含有甲氧基之石夕烧變性環氧樹脂（A)，其係使 雙紛型環氧樹脂（a-ι)及甲氧耗部分縮合物（a—2)脫醇反 應而得者；丙烯酸高分子（B)，其具有羧基，玻璃轉移點為 j〇°C以下，酸償為2〜1〇(mgK〇H/g)，平均分子量數目為15 萬3 0萬，環氧樹脂用硬化劑（c)。一種透明層積體，其係 將聚萘二甲酸乙二醇酷或聚對苯二甲酸乙二醇醋使用該層 積體用接著劑組合物接著者，該層積體之霧度值為2⑽。 [發明效果] 本發明之接著劑組合物，不僅接著性、耐熱性、耐濕 性、絕緣性等優良，透明性亦優良，特別示可充分使用於 2〇66-8914-PF;Ahddub 8 200806771 . 光學用途者。因此，根據本發明之接著劑組合物，有用於 作為用於軟性印刷電路板、TAB帶、觸控面板用基扳、IC 卡、1C標籤用基板、電子紙用基板、軟性顯示器用基板、 電磁遮蔽用層積體等之金屬層與塑膠膜之接著劑組合物。 【實施方式】 用於本發明之含有甲氧基之矽烷變性環氧樹脂（A)，係 由雙酚型環氧樹脂（a-1)(以下稱為成分）及甲氧矽垸 _部分縮合物（a-2)(以下稱為（a_2)成分）所構成。該(a_n 成分，係由雙酚類與環氧氯丙烷或沒_甲基環氧氯丙烷等 之鹵代環氧化物之反應而得者。作為雙酚類，可舉酚或2, 6一 一鹵化酚，與甲醛、乙醛、丙酮、乙醯苯、環己酮、二苯 酮等醛類或酮類反應之外，以過酸氧化二羥苯硫醚/對苯 二酚相互之酯化反應等而得者。 又，（a-ι)成分，係具有可與（a_2)成分脫甲醇反應之 _ m基者。該經基，並不需要含於構成U-1)成分之所有的分 子’只要作為（a-1)成分’具有經基即可。 (a-1)成分之環氧當量，由於拼旁r 田於根據Ca-1)成分之構造而 異，可按照用途適宜選擇使用褕# μ卢与火3丄 中從用適當的裱氧當量者，以350 以上1000g/eq以下者為佳。去、戈QRn / al ^ 禾滿350g/eq，則有降低所得 接著層於高溫下之密著性之俩Α ^ ^ ^ 貝向’又’超過l〇Q〇a/eq，則 有降低含有曱氧基之石夕燒變性環氧樹脂之保存安定性之傾 向。於該等（a-1)成分之中，牲它|斗 将別式以雙分A型環氧樹脂， 最被廣用且低償格而佳。 2066-8914-PF;Ahddub 9 200806771 —a又/作為構成（A)成分之（a — 2)成分，可使用一般用於 一多疑豚去，將甲氧矽烷部分水解，縮合之募聚物。可例 ，] 以通式：RpSl(0CH3)4-P(式中，p表示0或1的整 數R表不碳數6以下的低級烧基或苯基。）所表示之化合 物，部分縮合物等。再者，P為2〜4日寺，由於不會發生3 ' 對於最終所得接著劑硬化物並不會賦予所期望的 耐熱性。In order to solve such problems, the applicant of the present application proposed an epoxy resin composition characterized by comprising a methoxy-containing decane-modified epoxy resin, an epoxy-containing synthetic rubber, and an epoxy resin hardener. However, although the group of mouth materials has good adhesion to the polyimide film, the adhesion of the equivalent polyester film is not sufficient. (Refer to Patent Document 2) Therefore, the applicant of the present invention has proposed an adhesive composition which is characterized by comprising an acrylic polymer having a slow base and/or a glass transition point of 2 Gt or less; and an epoxy resin. Use a hardener. The adhesive composition exhibits excellent adhesion not only to the polyimide film but also to S PEN and liquid crystal polymer, and is displayed in comparison with the epoxy adhesive adhesive of the adhesive for printed circuit boards. For better heat resistance, etc., it is required to further improve the transparency (for example, Patent Document 3), because it is suitable for display or optical use. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-246838 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei No. 2005-179408 No. 2066-8914-PF; Ahddub 7 200806771 Disclosure of the Invention [Problems to be Solved by the Invention] An object of the present invention is to provide a prior art epoxy resin-based adhesive which is compatible with a bonding agent for a printed circuit board, and which can provide both better transparency and heat resistance. In the inventors, in order to solve the above problems, the inventors have tried to solve the above problems and found that 2 is used to: contain a An oxy-decane-modified epoxy resin which denatures a specific epoxy resin with a specific methoxydecane compound; a specific = physical body; and a resin composition for an epoxy resin as an essential constituent resin' An adhesive composition for the above purpose can be obtained, and the present invention relates to a laminate composition for a laminate, characterized by comprising: a methoxy-containing cerium-degraded epoxy Resin (A), which is obtained by de-alcoholization reaction of a double-type epoxy resin (a-ι) and a methoxy-consuming partial condensate (a-2); an acrylic polymer (B) having a carboxyl group and a glass transition The point is below j〇°C, the acid is 2~1〇 (mgK〇H/g), the average molecular weight is 153,000, and the hardener for epoxy resin (c). A transparent laminate comprising polyethylene naphthalate or polyethylene terephthalate using the laminate adhesive composition, the laminate having a haze value of 2 (10) . [Effect of the Invention] The adhesive composition of the present invention is excellent not only in adhesion, heat resistance, moisture resistance, insulating properties, etc., but also excellent in transparency, and particularly can be sufficiently used in 2〇66-8914-PF; Ahddub 8 200806771 Optical use. Therefore, the adhesive composition according to the present invention is useful as a substrate for a flexible printed circuit board, a TAB tape, a touch panel, an IC card, a 1C label substrate, an electronic paper substrate, a flexible display substrate, and an electromagnetic An adhesive composition of a metal layer such as a laminate for shielding and a plastic film. [Embodiment] The methoxy-containing decane-modified epoxy resin (A) used in the present invention is a bisphenol-type epoxy resin (a-1) (hereinafter referred to as a component) and a methoxy hydrazine-partial condensation. The substance (a-2) (hereinafter referred to as (a_2) component) is composed. The component (a_n) is obtained by reacting a bisphenol with a halogenated epoxide such as epichlorohydrin or non-methylepichlorohydrin. Examples of the bisphenol include phenol or 2, 6 Monohalogenated phenol, which is reacted with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone, etc., by peracid oxidation of dihydroxyphenyl sulfide/hydroquinone Further, the (a-ι) component has a _ m base which can be demethylated with the component (a_2). The radical does not need to be contained in all of the components constituting U-1). The molecule 'as long as the component (a-1)' has a radical. The epoxy equivalent of the component (a-1) varies depending on the structure of the component according to Ca-1), and may be appropriately selected according to the use of 褕#μ卢和火3丄 from the appropriate oxime equivalent. It is preferable to use 350 or more and 1000 g/eq or less. Go, QRn / al ^ Wo 350g / eq, there is a reduction in the adhesion of the resulting layer under high temperature Α ^ ^ ^ Bay to 'again' more than l〇Q〇a / eq, there is a reduction in containment The tendency of the decyloxy group to oxidize the epoxy resin to preserve stability. Among these (a-1) ingredients, it is best to use double-type A-type epoxy resin, which is the most widely used and low-compensation. 2066-8914-PF; Ahddub 9 200806771 - a / as a component (a - 2) constituting the component (A), it is possible to use a condensate which is generally used for the hydrolysis of a methoxysilane and a condensation . For example, a compound represented by the formula: RpSl(0CH3)4-P (wherein p represents an integer R of 0 or 1 and a lower alkyl group having a carbon number of 6 or less or a phenyl group), a partial condensate Wait. Further, P is a 2 to 4 day temple, and since 3' does not occur, the desired heat resistance is not imparted to the finally obtained adhesive.

: 比（a 2)成分之具體例，可舉四甲氧基石夕烧之部 分縮合物；甲基三甲氧基石夕烷、乙基三甲氧基矽烷…丙 ”矽烷、異丙基三甲氧基矽烷、乙烯基三甲氧基 、、苯基一甲氧基矽烷等之三甲氧基矽烷類之部分縮合 物或5亥等之混合物。該等之中，目甲氧基矽烷、甲基三甲 乳基矽烷等之部分縮合物，及該等之混合物，由於溶膠— 凝膠硬化速度大而佳。 乂 (a-2)成分，係由上述物質之中適宜選擇！種或2種以 尸可惟1分子當量的Si之平均個數以3〜12為佳。^ ，平均個數未滿3,則由於與㈤）成分作脫醇反應時，與 ]產之醇起流出系外之有毒之甲氧基系烧類之量會增加 =佳°又’超過12 ’則與（a])成分之反應性降低，而 為得目的之（A)成分需要很長的時間。 特別式，作為（a-2)成分，使用包含通式： [化1] 2066-89l4-PF；Ahddub 10 200806771Specific examples of the component (a 2) include a partial condensate of tetramethoxy sulphate; methyltrimethoxy oxalate, ethyltrimethoxy decane, propyl decane, and isopropyl trimethoxy decane. a partial condensate of a trimethoxynonane such as vinyltrimethoxy or phenylmonomethoxynonane or a mixture of 5H, etc. Among them, methyl methoxy decane, methyl dimethyl decyl decane The partial condensate, and the mixture of these, are preferred because of the high rate of sol-gel hardening. The component (a-2) is suitably selected from the above substances or two species of corpse one molecule. The average number of equivalent Si is preferably from 3 to 12. ^, the average number is less than 3, because the (f)) component is used for dealcoholization reaction, and the alcohol produced by the alcohol is out of the toxic methoxy group. The amount of the burning type will increase = good ° and 'more than 12 ' will reduce the reactivity with the component (a), and the desired component (A) will take a long time. Special formula, as (a-2) Ingredients, use inclusion formula: [Chemical 1] 2066-89l4-PF; Ahddub 10 200806771

Me MeMe Me

MeO 一$i—0 一^Si'〇Me OMe OMe —* ·— fi-1 (式中，Me表示曱基、n之平均反覆單位數位3〜8。） 所表示之甲基三甲氧基矽烷部分縮合物70重量％以上者， 則接著性、耐濕性、彎曲性等支點佳。MeO - $i - 0 - ^ Si ' 〇 Me OMe OMe — * · — fi-1 (wherein Me represents the sulfhydryl group, and the average repeating unit number of n is 3 to 8.) The methyltrimethoxydecane represented by When the partial condensate is 70% by weight or more, the fulcrum such as adhesion, moisture resistance, and flexibility is preferable.

用於本發明之（A)成分，係藉由上述（a-j)成分與（a—2) 之脫醇反應而得。（a-1)成分與（a—2)成分之使用比例，只 要於所侍（A )成分中，甲氧基會殘存之比例即並無特別限 制，惟（a-2)成分之二氧化矽換算重量成分之重量 (重篁比）以0. 25〜1. 2的範圍，在耐熱性或密著性之點佳。 再者，對於一般的彈性體（B)(以下，稱為（B)成分），僅由 (a-Ι)成分與環氧樹脂硬化劑（〇(以下稱為（c)成分）所得 之硬化膜之折射率高…（a-2)成分之二氧化矽換算重量 /(a-1)成分之重量（重量比）變大，則僅由成分與（c)成 分所得之硬化膜之折射率減少，而接近（B)成分之折射率， 故使上述重量比為〇.5()以上，可擴大可使用之⑻成分之 選擇性而特別佳。 關於⑴成分之製造，例如將（a-Ι)成分與U-2)成分放 入’藉由加熱將副產之醇潑除或以冷凝管回流送回系内而 進行。反應溫度為5{M3{rc程度，以為佳，全反 應時間為1〜15小時程度。該反應，為防止U-2)成分本身 2 0 6 6-8 914-PF;Ahddub 11 200806771 的聚縮合反應，大體上在無水條件下進行為彳土。 又，於上述脫醇反應時，為促進反應於先前習知之觸 媒之中，可使用不會環氧開環者。作為該觸媒，例如，鋰、 鈉、鉀、铷、鉋、鎂'鈣、鋇、锶、鋅、鋁、鈦、鈷、鍺、 錫、鉛、録、石申、鈽、删、鑛、鐘等金屬；該等金屬之氧 化物、有機酸鹽、鹵化物、甲氧化物等。該等之中，特別 是有機錫、有機酸錫為佳’具體而言，二月桂酸二丁基錫’、 辛酸錫等為有效。 又，上述反應可於溶劑中，亦可在無溶劑進行。作為 溶劑，只要是可輯解（a])成分及（a_2)成分，間兮等 為惰性之有機溶劑即無特別限制。作為如此之有機溶劑， 可舉例如’甲基乙基_、甲基異丁基酮、環己酮、異佛爾 酮等之酮系；醋酸乙醋、醋酸丁醋等醋系；甲苯、二甲苯 等芳香族系；乙二醇丁喊醋酸西旨、甲基乙二醇丁㈣_ 等溶纖系；四氫咬喃、二乙二醇二甲基縫等謎系；異丙醇、 正丁醇等醇類；二甲基甲醯胺等非質子性極性溶劑。該等 之中，以甲基乙基酮等於常壓的沸點為70」1〇。。者因以下 的理由而特別佳1 ’該接著劑組合物，係經於PEN等基 材膜上形成半硬化絲態（B_Stage)(接著$ )，將銅箱等導 體層壓’又，熱壓接之後，進一步加熱形成硬化層 (士c-stage)(本接著劑硬化）之製造過程，而接著導體後加熱 時’產生大量的揮發分（溶劑等）則會在導體與接著劑硬化 塢之間產生氣泡，而引起於導體表面形成凹凸等問題。因 此，製作上述接薯1 者月#，盡I減低溶劑等之揮發分之殘存 2066-8914-PF;Ahdciub 12 200806771 •量，使硬化層（C—Stage)之硬化殘分鐘的揮發分殘存率為5 重s %以下地調整為佳。使用沸點超過u 〇c>c之溶劑時，為 降低溶劑殘存率需要使接著片之形成溫度過度地上升，結 果，有使接續之硬化層（c — stage)與導體之層間密著性不充 分之傾向而不佳。又，使用溶劑之沸點未滿7(TC時，於（a-i ) 成分與（a-2)成分之脫醇反應所需之時間長而不佳。 如此所得之（A)成分，係以（a-1)成分中的羥基，矽烷 艾1^之％氧樹脂作為主成分，惟該（A)成分中亦可含有為反 _應之（a-1)成分或未反應之（a —2)成分。 (A)成分，於其分子中具有來自（a-2)成分之曱氧矽基 P位及來自雙分型環氧樹脂之環氧基。該甲氧石夕基部位， 係藉由溶劑的蒸發或加熱處理，或與水分（濕氣）之反應， 成互相結合之硬化物。所關硬化物，係具有凝膠化之細 微的二氧化矽部位（矽氧烷之高維網狀構造）者。因此，含 ;(A)成刀中的甲氧基，以保持使用之（a - 2)成分之甲氧基 # 之60莫耳％以上者為佳。又，環氧基係與後述之（C)成分反 應者。 作為用於本發明之（B)成分，需要選擇，具有羧基，玻 璃轉移點為20t以下，酸價為2〜1〇(mgK〇H/g)，數目平均 刀子里為15萬〜30萬，賦予接著劑硬化物柔軟性，且不會 在銲錫溶岫溫度（23〇〜2 6 〇。[)發生分解物，對p题或pm等 透明膜之密著力強者。 由於藉由使（β)成分之玻璃轉移溫度，為-50〜20°C，可 使之“（A)成分等之其他成成之混合容易，可減少溶劑（d) 2066-8914-PF；Ahddub 13 200806771 之使用里又黏度调整容易而佳，再者，使之為〜〇 C ’則不易受到季節因素等氣溫影響而特別佳。玻璃轉移 溫度超過201，則接著劑硬化物之柔軟性惡化，於黏貼時 使壓接溫度上升而不佳。The component (A) used in the present invention is obtained by a dealcoholization reaction of the above (a-j) component with (a-2). The ratio of the (a-1) component to the (a-2) component is not particularly limited as long as the methoxy group remains in the component (A), but the (a-2) component is oxidized.重量。 The weight of the weight component (weight ratio) in the range of 0. 25~1. 2, in the heat resistance or adhesion point. In addition, in the general elastomer (B) (hereinafter referred to as component (B)), only the (a-Ι) component and the epoxy resin curing agent (hereinafter referred to as component (c)) are hardened. When the refractive index of the film is high, the weight (weight ratio) of the (a-1) component is increased, and the refractive index of the cured film obtained only from the component and the component (c) is high. The reduction is close to the refractive index of the component (B), so that the above weight ratio is 〇.5 () or more, and the selectivity of the component (8) which can be used can be expanded, and it is particularly preferable. For the manufacture of the component (1), for example, (a- The Ι) component and the component U-2) are placed by 'removing the by-produced alcohol by heating or returning it to the inside of the system by refluxing the condensing tube. The reaction temperature is preferably 5 {M3{rc, preferably, and the total reaction time is about 1 to 15 hours. This reaction, in order to prevent the U-2) component itself 2 0 6 6-8 914-PF; Ahddub 11 200806771, is a polycondensation reaction, which is carried out substantially under anhydrous conditions. Further, in the above dealcoholization reaction, in order to promote the reaction among the conventionally used catalysts, those which do not open the epoxy ring can be used. As the catalyst, for example, lithium, sodium, potassium, rubidium, planer, magnesium 'calcium, barium, strontium, zinc, aluminum, titanium, cobalt, strontium, tin, lead, lithography, shishen, bismuth, deletion, ore, a metal such as a clock; an oxide of such a metal, an organic acid salt, a halide, a methoxide or the like. Among these, in particular, organic tin and organic acid tin are preferable. Specifically, dibutyltin dilaurate and tin octylate are effective. Further, the above reaction may be carried out in a solvent or in the absence of a solvent. The solvent is not particularly limited as long as it is an organic solvent which is inert to the component (a) and the component (a_2). Examples of such an organic solvent include ketone systems such as 'methylethyl group, methyl isobutyl ketone, cyclohexanone, and isophorone; vinegar systems such as ethyl acetate and butyl acetate; toluene and An aromatic system such as toluene; ethylene glycol butyl ketone acetate, methyl glycol butyl (tetra) _ such a fibrinolytic system; tetrahydroanthracene, diethylene glycol dimethyl sedan and other mysteries; isopropanol, n-butyl An alcohol such as an alcohol; an aprotic polar solvent such as dimethylformamide. Among these, methyl ethyl ketone is equal to the boiling point of atmospheric pressure of 70"1〇. . It is particularly preferable for the following reasons: 1] The adhesive composition is formed by forming a semi-hardened filament state (B_Stage) on a substrate film such as PEN (and then $), and laminating a conductor such as a copper box. After the connection, further heating to form a hardened layer (c-stage) (the present adhesive hardening) manufacturing process, and then heating after the conductor 'generates a large amount of volatile matter (solvent, etc.) will be in the conductor and the adhesive hardened dock Air bubbles are generated at the same time, causing problems such as unevenness on the surface of the conductor. Therefore, the above-mentioned potato 1 will be produced, and the remaining volatiles of the solvent and the like will be reduced by 2066-8914-PF; Ahdciub 12 200806771 • The amount of residual volatiles of the hardened layer (C-Stage) It is better to adjust below 5 s %. When a solvent having a boiling point of more than u 〇 c > c is used, it is necessary to excessively increase the temperature at which the formation of the succeeding sheet is lowered in order to lower the solvent residual ratio, and as a result, the adhesion between the cured layer (c-stage) and the conductor is insufficient. The tendency is not good. Further, when the boiling point of the solvent is less than 7 (TC, the time required for the dealcoholization reaction between the (ai) component and the (a-2) component is not good. The component (A) thus obtained is (a). -1) The hydroxyl group in the component, the oxyalkylene oxime% oxygen resin as the main component, but the component (A) may also contain the (a-1) component or the unreacted component (a-2). The component (A) has an oxohydrazide P site derived from the component (a-2) and an epoxy group derived from a bipartite epoxy resin in the molecule. Evaporation or heat treatment of the solvent, or reaction with moisture (moisture), forming a hardened substance bonded to each other. The cured product is a gelled fine ceria site (high-dimensional network of decane) Therefore, it is preferable to contain (A) a methoxy group in a knife to maintain 60 mol% or more of the methoxy group # of the (a - 2) component to be used. Reacting with the component (C) described later. As the component (B) used in the present invention, it is necessary to select a carboxyl group, a glass transition point of 20 t or less, and an acid value of 2 to 1 〇 (mgK〇H/g). The average knife is 150,000 to 300,000, which imparts softness to the hardener of the adhesive, and does not melt at the temperature of the solder (23〇~2 6 〇.[), and it is densely formed on the transparent film of p or pm. Because the glass transition temperature of the (β) component is -50 to 20 ° C, it is easy to mix the other components such as (A), and the solvent can be reduced (d) 2066-8914 -PF;Ahddub 13 200806771 The viscosity adjustment is easy and good, and it is better to make it ~〇C', which is not easy to be affected by seasonal factors such as temperature. When the glass transition temperature exceeds 201, the adhesive hardener The softness is deteriorated, and the crimping temperature is not improved when it is pasted.

為對PEN $ PET等透明膜得到密著力，可舉具有選自 由叛基、經基所組成之群之至少一個官能基者，一般，以 (1)丙烯酸酯、α-取代丙烯酸s旨為主成分，於此作為架橋 點含有上述官能基之至少丨個而成之聚合物，或（2)至少具 有1個上述官能基之單體之上述主成分之單體或接枝聚合 之高分子。具體而言，以丙烯酸酯或α —取代丙烯酸酯 (Β -1)(以下稱為（Β-υ成分）之丨種作為主成分之構成成 分，與選自由，含有環氧基之單體（Β—2)(以下稱為（Β-2) 成分、含有羧基之單體（B-3)(以下稱為（Β-3)成分）、含有 羥基之單體（Β-4)(以下稱為（Β—4)成分）所組成之群之至少 具有一個官能基之單體共聚合者。作為成分，可舉丙 基酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯 酸辛知等，不具有環氧基、羧基及羥基之單體。作為（β-2) 成分，可舉於（B-1)成分以外，不具有羧基及羥基之，乙烯 基縮水甘油醚、丙烯基縮水甘油醚等縮水甘油醚類、丙烯 酸縮水甘油酯、曱基丙烯酸縮水甘油酯等。作為（B_3)成 分’可舉於（B-1)成分、（B-2)成分以外，不具有羥基之丙 烯酸、甲基丙烯酸、衣康酸、馬來酸、馬來酐等。作為（B-4) 成分’可舉（B-1)〜（B-3)成分以外之甲基丙烯酸—2-羥基乙 酯、甲基丙烯酸-2-羥基丙酯、二曱基丙烯酸乙二醇酯、二 2066-8914-PF;Ahddub 14 200806771 甲基丙烯酸丙二醇酯、二甲基丙烯酸聚乙二醇酯等之多價 醇之二甲基丙烯酸酯類；丙烯酸曱氧基甲酯等之丙烯酸= 氧基酯等。該等可單獨或混合2種以上使用。再者，按酽 需要，亦可與其他的乙烯基單體，例如氯乙烯、偏氯乙烯二 笨乙烯、丙烯腈、醋酸乙烯酯等共聚合。 作為用於本發明之（B)成分，酸價需為 2〜10(mgKOH/g)。超過此範圍，則與（A)成分之相溶性化， 無法得到均勻的接著劑組合物，有降低透明性之傾向。又， 超過10，則有降低接著劑組合物之吸水率、電氣特性之傾 向0 又，用於本發明之（B )成分之數目平均分子量，兩為 15萬〜30萬。超過此範圍，則與（几）成分之相溶性惡化而無 法得到均勻的接著劑組合物，有使由接著劑組合物所得2 硬化膜之透明性惡化之傾向。 於本發明，特別是在於得到透明性優良的接著劑層之 目的’重要的是減少(A)成分與(c)成分所得之硬化膜與⑻ 成分之折射率差，因此，需要選擇折射率為1.45〜1.54之 彈性體。當折射率為U5以下、1<54以上，則與⑴成分 與（C)成分所得之硬化膜之折射率差會變大，而容易在接著 劑層產生霧，失去透明性之傾向強。在者，作為上述⑻ 成分，可直接使用市售者。作為市售之丙烯酸高分子，可 舉例如，以特森樹脂SG-70L(商品名Nagase ChemteX(股） 么司製）等為主成分之方法。 用於本發明之接著劑組合物之（B)成分於與其他的成 2〇66-8914-PF;Ahddub 15 200806771 & 〇之月』/合解於'谷劑為佳。作為可使用於溶解（B)成分之 命J可舉與用於製造（A)成分時所使用相同者。考慮混合 之容易度，則以固形分，以1〇〜3〇重量％程度，黏度以 100〜lOOOOmPa · s程度為佳。 作為用於本發明之（C )成分，並無特別限定，可使用習 知之環氧樹脂用硬化劑之廣樹脂系硬化劑、聚胺系硬化 劑、？請酸硬化劑等。具體而言，作為齡樹脂系硬化劑， 可舉盼酸樹脂、甲㈣樹脂、雙㈣樹脂、聚對乙稀基盼 _ t ;作為聚胺系、硬化劑·，可舉二亞乙基三胺、三亞乙基四 版四亞乙基五如、雙氰胺、聚醯胺一胺（聚醯胺樹脂）、酮 亞胺化合物、異佛爾酮二胺、間二甲苯二胺。間苯二胺、 1，3-雙（胺基甲基）環己烷、N 一胺基乙基哌嗪、4,4, _二胺 基二苯甲烷、4,4,—二胺基—3,3,—二乙基二苯甲烷、二安 基二苯基砜等；作為聚羧酸硬化劑，可舉鄰苯二曱酸酐、 四氫鄰苯二曱酸酐、甲基四氫鄰苯二甲酸酐、3,6一内亞甲 φ 基四氫鄰苯二甲酸酐、六氯内亞甲基四氫鄰苯二甲酸酐、 甲基-3, 6-内亞甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲 -文酐等該等之中，藉由使用選自由芳香族胺及酚醛樹脂 所組成之群之至少一種，可使接著劑組合物之可兼具使用 時間（Pot-Life)與低溫硬化而佳。再者，用於本發明之接 著4彳組合物之（C )成分於室溫為固形時，於與其他成分混合 之鈾，>谷解於溶劑為佳。作為可使用於溶解（◦)成分之溶 劑’可舉與用於製造（A)成分時之相同者。又，本發明之接 著劑組合物，根據塗佈機之種類等塗佈條件，以溶劑稀釋， 2066-8914-PF；Ahddub 16 200806771 周整#度為佳。作為稀釋溶劑’可舉與用於製造（A)成分時 之相同者。 八本^明之接著劑組合物，係、調合上述各種必須構成成 、P (A)成分、（b)成分、及（c)成分而調製。（b)成分對 ' 、刀之凋0比例，由透明性、接著劑硬化物與聚酯膜 等之透明臈之層間密著性之點，對U)成分之硬化殘分需要 為9〇 200重量％。該調合比例未滿90重量％，則硬化層對 於導體之㉖、著性將不充分，並且無法得到透明的接著劑硬 物又超過20 0重量％，則耐熱性有降低之傾向。在者， (A)成分之硬化殘分可如下求得，，將⑷成分與ι當量 的二亞乙基四胺混合，將該混合液約lg秤取於鋁杯(50mm 控）（計量⑴），將此以小時，接著以·r乾燥2 小時，使之硬化再計量（計量（ii))，由下式算出。 硬化殘分（％) =(計量（i i 三亞乙基四胺重量〇 量⑴ 又，（C)成分之調合比例，對於存在於接著劑組合物中 的環氧基1當量，（C)成分中具有活性氫之官能基以 〇·1〜1·2當量程度之範圍為佳。 又，於上述接著劑組合物，使之含有環氧硬化促進劑， 促進裱氧樹脂與硬化技之硬化反應，降低於與鋼落等之基 材黏貼後所進行之硬化劑組合物之硬化之溫度，可縮短硬 化時間。例如，1，8-二氮—雙環[5.4.〇]十_碳—7-烯、三亞 乙基二胺、节基二甲基胺、2乙醇胺、二甲基胺基乙醇、 三（二甲基胺基甲基）酚等三級胺類；2_甲基咪唑、2_苯基 2066-8914-PF/Ahddub 17 200806771 咪唑、2-苯基甲基咪唑、2-十七烷基咪唑等咪唑類；三 丁基膦、甲基二苯基膦、三苯基膦、二苯基膦、苯基膦等 有機膦類；四苯基硼·四苯基鱗、四苯基爛· 2—乙基—4一 甲基咪唑、四苯基硼· N-甲基嗎琳等四苯基硼鹽等。該硬 化促進劑，對（A)成分之硬化殘分，以〇· 〇5~5重量％之比例 使用為佳。 又，由於在曱氧矽基部位之溶勝—凝膠硬化反應會產生 醇，故於（A)成分中的環氧基，與（C)成分之間，進行環氧 _ 基之開環·架橋反應之硬化後產生該醇時，有於接著劑硬 化物產生發泡或龜裂之虞。因此，有添加有機錫觸媒等之 溶膠-凝膠硬化促進劑之需要，惟該促進劑有與含於丙烯酸 高分子之羧酸、基等官能基錯合，#果有使接著劑組合 物之使用時間（Pot-Life)變短之虞。因此，於（c)成分，使 用或併用亦可作為溶膠—凝膠硬化促進劑之作用之芳香族 胺為佳。 ' 本發明之接著劑組合物之組成’可按照其用途適宜調 整’惟通常，系由㈣接㈣組合物所得之接著劑硬化物 中的二氧化石夕換算重量成7〜41重量％地調合為佳。再者， 同換算重量為15〜25重量叫’接著劑硬化物之耐埶性，盥 歸之密著性優良，而特別佳。在此，所對二氧化石夕換算 重f ’係指將含於接著劑組合物中用於（A)成分之製造之 U-2)成分溶膠-凝膠硬化反應而得之二氧化矽之重量。作 為由該接著劑組合物所得之接著劑硬化物中之：氧化石夕換 算重量之調整方法，在將⑴成分、⑻成分、(C)成分之調 2066-8914~PF；Ahddub 18 200806771 合比調整為上述記載之比例範圍之方法之外 其他的固形成分之古、土 + 有使之含有 ， 成刀於雙分型環氧樹脂（a-Ι)之外，可兴弈 ㈣U 絲樹脂等之環氧樹脂、 ΓΓΓ 接著劑組合物作為覆蓋層用接著劑 : 用時，由於需要填埋電路之凹凸，需要對於00 硬化殘分使用20〜400重«之環氧樹月旨。未滿20重 "’則接著劑缺乏流動性，無法填埋電路，超過彻重量 %，則对熱性降低’有使滲出性惡化之傾向。作為如此之環 氧樹脂之種類，可舉用於製造（Α)成分時之（a])相同者， 惟在室溫為固體者，作為覆蓋層膜較容易操作。 於本^明之接著劑組合物，在不損本發明之效果之範 圍’可按照需要’調合脫模劑、表面處理劑、難燃劑、黏 度調節劑、可塑劑、抗菌劑、防霉劑、平滑劑、消泡劑、 著色劑、安定劑、偶合劑等。 如此所得之接著劑組合物，可作為用於軟性印刷電路 板、TAB帶、觸控面板用基板、Ic卡、κ標籤用基板、電 子紙用基板、軟性顯示器用基板、電磁遮蔽用層積體等之 金屬層與塑膠膜之接著劑組合物。 、 為由本發明之接著劑組合物，得到軟性印刷電路板、 TAB帶、觸控面板用基板、I c卡、IC標籤用基板、電子紙 用基板、軟性顯示器用基板、電磁遮蔽用層積體，將本發 明之接著劑組合物，以硬化膜厚5〜5 0 /z m程度塗佈於基板 膜上’以70〜15(TC乾燥30秒〜15分程度之後，將銅箔等金 19 2066-8914-PF;Ahddub 200806771 屬箔以50〜100°C程度熱壓接，之後以40〜150°C程度後處理 1〜3小時程度，完全硬化成硬化層（〇Stage)之方法。於半 硬化成膠態（B-Stage)，需要藉由減低接著劑組合物之揮發 分（（A)成分中的製造用溶劑、（A)成分之甲氧矽基部位之溶 膠-凝膠硬化反應所副產之甲醇，接著劑組合物中的溶劑） 之殘存率，防止接著在硬化層（C-Stage)發生氣泡。覆蓋層 膜’係於基材膜上使接著劑組合物乾燥硬化作成半硬化成 膠態（B-Stage)時完成製造，惟之後對印刷基板，以 馨 〇· 5〜，80〜150°C、1〜3小時程度之熱壓接。 作為塗佈本接著劑組合物之基材膜，並無特別限制， 可技照用途使用可無限制地使用習知者，惟如觸控面板用 基板、IC卡、I c標籤用基板、電子紙用基板、軟性顯示器 用基板，作為層積體特別重視光穿透性時，使用無色的基 材之膜為佳，以PEN、PET等聚酯膜特別佳。如軟性印刷基 板、覆蓋層膜、TAB帶，作為層積體特別需要耐熱性時， • 使用選自由PEN、聚亞醯胺所組成之群之任何一種所構成 之基材，由耐熱性等之觀點為佳。 又，作為金屬箔，可按照該層積體之用途使用各種習 知2具體而言，金荡、IT0箱、銀箱、鋼落、錄絡箱、 銘箱等’惟特別是使用於印刷電路板或ΤΑΒ料時，以銅 箔、鎳鉻箔、鋁箔為佳。 由本發明之接著劑組合物構成之硬化物，具有耐孰 性、密著性、㈣性、絕緣性，特別是透明性佳。由 著劑組合物所得之15㈣程度之接著劑，通常，作為料 20 2066»8914-PF;Ahddub 200806771In order to obtain a close adhesion to a transparent film such as PEN $PET, it is possible to have at least one functional group selected from the group consisting of a thiol group and a thiol group. Generally, (1) acrylate, α-substituted acrylic acid s The component is a polymer obtained by containing at least one of the above functional groups as a bridging point, or (2) a monomer having the above main component of a monomer having at least one functional group or a polymer obtained by graft polymerization. Specifically, a constituent component containing an acrylate or an α-substituted acrylate (Β -1) (hereinafter referred to as a "Β-υ component") as a main component, and a monomer selected from the group consisting of an epoxy group ( Β—2) (hereinafter referred to as (Β-2) component, carboxyl group-containing monomer (B-3) (hereinafter referred to as (Β-3) component), and hydroxyl group-containing monomer (Β-4) (hereinafter referred to as a monomer copolymerized with at least one functional group of the group consisting of (Β-4) component. Examples of the component include methyl propylate, ethyl acrylate, propyl acrylate, butyl acrylate, and octyl acrylate. A monomer having no epoxy group, a carboxyl group, or a hydroxyl group, and a (β-2) component, other than the component (B-1), having no carboxyl group or a hydroxyl group, vinyl glycidyl ether or propylene group Glycidyl ethers such as glycidyl ether, glycidyl acrylate, glycidyl methacrylate, etc. The (B-3) component 'is not limited to the (B-1) component or the (B-2) component, and has no hydroxyl group. Acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, etc. As (B-4) component, it can be mentioned as (B-1)~( B-3) methacrylic acid other than the component - 2-hydroxyethyl ester, 2-hydroxypropyl methacrylate, ethylene glycol dimercaptoacrylate, two 2066-8914-PF; Ahddub 14 200806771 propylene glycol methacrylate A dimethic acid ester of a polyvalent alcohol such as an ester or a polyethylene glycol dimethacrylate; an acrylic acid such as a methoxymethyl acrylate; an oxyester; and the like. These may be used alone or in combination of two or more. Further, it may be copolymerized with other vinyl monomers such as vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate or the like as needed. As the component (B) used in the present invention, acid The price is required to be 2 to 10 (mgKOH/g). When it exceeds this range, it is compatible with the component (A), and a uniform adhesive composition cannot be obtained, which tends to lower the transparency. Further, if it exceeds 10, The tendency to reduce the water absorption rate and electrical characteristics of the adhesive composition is 0. The number average molecular weight of the component (B) used in the present invention is 250,000 to 300,000. If it exceeds this range, the phase(s) are The solubility is deteriorated and a uniform adhesive composition cannot be obtained. The transparency of the cured film obtained by the composition of the composition tends to deteriorate. In the present invention, in particular, the purpose of obtaining an adhesive layer having excellent transparency is to reduce the cured film obtained by the component (A) and the component (c). (8) The refractive index difference of the components, therefore, it is necessary to select an elastomer having a refractive index of 1.45 to 1.54. When the refractive index is U5 or less and 1 < 54 or more, the refractive index difference between the cured film obtained from the components (1) and (C) is In the case of the above-mentioned (8) component, it is possible to use a commercially available person as a commercially available acrylic polymer, for example, A method in which a resin SG-70L (trade name: Nagase ChemteX Co., Ltd.) is used as a main component. The component (B) used in the adhesive composition of the present invention is preferably combined with other granules in the form of 2〇66-8914-PF; Ahddub 15 200806771 & The life J which can be used for dissolving the component (B) can be the same as that used for the production of the component (A). In consideration of the ease of mixing, the solid content is preferably from about 1 to about 3 % by weight, and the viscosity is preferably from 100 to 100 mPa · s. The component (C) used in the present invention is not particularly limited, and a conventional resin-based curing agent or a polyamine-based curing agent for a curing agent for an epoxy resin can be used. Please use acid hardener and so on. Specifically, as an aged resin-based curing agent, an acid resin, a nail resin, a bis(tetra) resin, a polyethylene terephthalate, or a polyamine-based or a curing agent may be mentioned. Amine, triethylene tetratype tetraethylene quinone, dicyandiamide, polyamidamine-amine (polyamine resin), ketimine compound, isophorone diamine, m-xylene diamine. M-phenylenediamine, 1,3-bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, 4,4,diaminodiphenylmethane, 4,4,-diamino- 3,3,-diethyldiphenylmethane, diampenyldiphenyl sulfone, etc.; as a polycarboxylic acid hardener, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydroortylene Dicarboxylic anhydride, 3,6-internal ylidene tetrahydrophthalic anhydride, hexachloromethylenetetrahydrophthalic anhydride, methyl-3,6-endomethylenetetrahydroortylene Among the dicarboxylic anhydride, methylhexahydrophthalic acid-formic anhydride, etc., by using at least one selected from the group consisting of an aromatic amine and a phenol resin, the adhesive composition can be combined It is better to use time (Pot-Life) and low temperature hardening. Further, when the component (C) used in the composition of the present invention of the present invention is solid at room temperature, uranium mixed with other components is preferably dissolved in a solvent. The solvent which can be used for dissolving the component is the same as that used for the production of the component (A). Further, the adhesive composition of the present invention is diluted with a solvent according to the coating conditions such as the type of the coater, 2066-8914-PF; Ahddub 16 200806771 is preferably #度. The diluent solvent is the same as that used in the production of the component (A). The adhesive composition of the present invention is prepared by blending the above various components, P (A) component, (b) component, and (c) component. (b) The ratio of the component to the 'knife', the ratio of the transparentness, the adhesion between the cured material of the adhesive and the polyester film, and the hardening residue of the U) component is 9〇200. weight%. When the blending ratio is less than 90% by weight, the hardened layer is insufficient for the conductor 26, and if the transparent adhesive hard material is not more than 20% by weight, the heat resistance tends to be lowered. Further, the hardening residue of the component (A) can be obtained by mixing the component (4) with 1 part by weight of diethylenetetramine, and weighing the mixture about lg in an aluminum cup (50 mm control) (metering (1) This was dried in 2 hours, followed by drying for 2 hours, and hardened and metered (meter (ii)), and was calculated from the following formula. Hardening residue (%) = (Metric (ii) Triethylenetetramine weight ( (1) Further, the blending ratio of the component (C) is 1 equivalent of the epoxy group present in the adhesive composition, in the component (C) The functional group having an active hydrogen is preferably in a range of from about 1 to about 1.2 equivalents. Further, the above-mentioned adhesive composition contains an epoxy hardening accelerator to promote a hardening reaction between the epoxy resin and the hardening technique. The hardening time can be shortened by lowering the hardening temperature of the hardener composition which is carried out after adhering to the substrate such as steel falling, etc. For example, 1,8-diaza-bicyclo[5.4.〇]d-carbon-7-ene , tertiary amines such as triethylenediamine, benzyldimethylamine, 2ethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2_methylimidazole, 2-phenylene Base 2066-8914-PF/Ahddub 17 200806771 Imidazoles such as imidazole, 2-phenylmethylimidazole, 2-heptadecylimidazole, etc.; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenyl Organic phosphines such as phosphine, phenylphosphine, etc.; tetraphenylboron tetraphenyl sulphate, tetraphenyl sulphide-2-ethyl-4-methylimidazole, tetraphenylboron N-methyl a tetraphenylboron salt such as morphine, etc. The hardening accelerator is preferably used in a ratio of 5% to 5% by weight of the hardening residue of the component (A). When the melt-gel hardening reaction generates alcohol, when the epoxy group is formed by the ring-opening/branched reaction of the epoxy group in the epoxy group in the component (A), There is a problem that foaming or cracking occurs in the cured product of the adhesive. Therefore, there is a need to add a sol-gel hardening accelerator such as an organic tin catalyst, but the accelerator has a carboxylic acid contained in the acrylic polymer. The functional groups of the base are misaligned, and the use of the adhesive composition is shortened. Therefore, the component (c) may be used as a sol-gel hardening accelerator. The aromatic amine to be used is preferred. The composition of the adhesive composition of the present invention can be suitably adjusted according to the use thereof, but usually, the weight of the silica in the hardener of the adhesive obtained from the composition of the (iv) (iv) composition is converted into a weight. It is better to blend 7 to 41% by weight. Furthermore, the weight of the conversion is 15 to 25 It is called 'the hardenability of the hardener of the adhesive, and the adhesion is excellent, and it is especially good. Here, the weight of the dioxide is converted to the binder composition for (A) The weight of the cerium oxide obtained by the sol-gel hardening reaction of the component U-2). The method of adjusting the weight of the oxide in the adhesive of the adhesive obtained from the adhesive composition, In addition to the method of adjusting the ratio of (1) component, (8) component, and (C) component 2066-8914 to PF; Ahddub 18 200806771 to the above-described ratio range, other solid components and soil + are contained, In addition to the double-type epoxy resin (a-Ι), the epoxy resin and the ruthenium composition of the U-wire resin can be used as an adhesive for the cover layer: when used, it is necessary to fill the circuit. Bump, need to use 20~400 heavy « epoxide tree for 00 hardening residue. Less than 20 weights "' The adhesive lacks fluidity and cannot fill the circuit. If the weight exceeds %, the heat is reduced, which tends to deteriorate the exudation. The type of such an epoxy resin is the same as (a)) when the component is produced, but it is easy to handle as a cover film when it is solid at room temperature. The adhesive composition of the present invention can be blended with a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, an antibacterial agent, an antifungal agent, etc., as long as the effect of the present invention is not impaired. A smoothing agent, an antifoaming agent, a coloring agent, a stabilizer, a coupling agent, and the like. The adhesive composition thus obtained can be used as a flexible printed circuit board, a TAB tape, a touch panel substrate, an Ic card, a κ label substrate, an electronic paper substrate, a flexible display substrate, and an electromagnetic shielding laminate. An adhesive composition of a metal layer and a plastic film. In the adhesive composition of the present invention, a flexible printed circuit board, a TAB tape, a touch panel substrate, an IC card, an IC tag substrate, an electronic paper substrate, a flexible display substrate, and an electromagnetic shielding laminate are obtained. The adhesive composition of the present invention is applied to the substrate film to a thickness of 5 to 5 0 /zm in a cured film thickness of 70 to 15 (TC is dried for 30 seconds to 15 minutes, and then copper foil and the like 19 2066 -8914-PF; Ahddub 200806771 is a method in which the foil is thermocompression-bonded at a temperature of 50 to 100 ° C, and then treated to a degree of 40 to 150 ° C for 1 to 3 hours to completely harden into a hardened layer (〇tage). To harden into a colloidal state (B-Stage), it is necessary to reduce the volatile matter of the adhesive composition (the solvent for the production of the component (A), and the sol-gel hardening reaction of the methoxy group of the component (A). The residual ratio of the by-product methanol and the solvent in the adhesive composition prevents the occurrence of bubbles in the hardened layer (C-Stage). The cover film is attached to the substrate film to dry and harden the adhesive composition to form a semi-hardening. Finishing in the form of a gel (B-Stage), but then on the printed substrate, 〇 〇 5 5 80 80 80 80 80 80 80 80 80 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 。 作为 。 。 。 。 。 。 。 。 。 。 In the case of a touch panel substrate, an IC card, an Ic label substrate, an electronic paper substrate, and a flexible display substrate, when a light-transmitting property is particularly emphasized as a laminate, a colorless substrate film is used. Preferably, a polyester film such as PEN or PET is particularly preferable, such as a flexible printed substrate, a cover film, and a TAB tape, and when heat resistance is particularly required as a laminate, • a group selected from PEN and polyamidones is used. The base material of any one of them is preferable from the viewpoint of heat resistance, etc. Further, as the metal foil, various conventional uses can be used according to the use of the laminate. Specifically, Jindang, IT0 box, silver box, Steel drop, record box, name box, etc. 'When used especially for printed circuit boards or dips, copper foil, nickel chrome foil, aluminum foil is preferred. The cured product composed of the adhesive composition of the present invention has resistance孰, adhesion, (4), insulation, especially transparency Preferably, the 15 (four) degree of the adhesive obtained from the composition, usually as a material 20 2066»8914-PF; Ahddub 200806771

耐熱性具有230 C〜260 C ’又作為密著性，例如以pen · pet 作為基材膜，以電解銅箔作為金屬層使用時，具有 以上之剝離強度。又，吸水率，通常為〇·5%以下，耐濕性 佳，於上述用途通常評價之溫度8(rc，濕度85%環境下保 管12小時後之焊接耐熱性試驗亦並未特別發生問題。又， 通常具有體積電阻1 Ο13 Ω · cm以上而絕緣性亦佳。關於最 重要的透明性，以15//m之接著劑層之膜厚之霧度值，通 常為5%以下，在500 # m之厚膜以1〇%以下為佳。此時，製 _ 作於PEN或PET上設接著材層於接著材層上層積pen或PET 之層積體時，可抑制霧度值之上升，通常霧度值成20%以 下。 [實施例] 以下’舉實施例及比較例具體說明本發明。再者，於 各例t，若無特別提及，％為重量基準。 製造例1(含有甲氧基之矽烷變性環氧樹脂（A—i)之製造） 於具備攪拌機、冷卻管、溫度計之反應裝置，加入雙 紛A型環氧樹脂（日本環氧樹脂（股）製，商品名 「 JER1001 」，環氧當量 480g/eq)(a-1)800.0g 及 MEK960.0g，以8(rc溶解。再者，加入曱基三甲氧矽烷 (ClhSiCOCH3)3)之部分縮合物si之平均個數為3· 5之聚（甲 基二甲氧矽烷）（多摩化學（股）製，商品名r MTMS一 A」 (a-2)605. 〇g與作為觸媒之月桂酸二丁基錫2· 3g，以8〇〇c 使之脫醇反應5小時，得到有效成分（硬化後）5 〇%，二氧化 石夕換算重量/雙酚型環氧樹脂（1)之重量（重量比）為〇51， 2066-8914-PF;Ahddub 21 200806771 環氧當量1400g/eq之含有甲氧基之矽烷變性環氧樹脂 (A-1)。又，以I-匪R確認到，甲基三甲氧石夕烧之部分縮 合成份之甲氧基保持87莫耳％。 製造例2(含有曱氧基之矽烷變性環氧樹脂（A_2)之製造） 於具備攪拌機、冷卻管、溫度計之反應裝置，加入 JER1001(a-l)400· Og 及 MEK334· 8g，以 8〇°C 溶解。再者， 加入四甲氧石夕烧（S i (0CH3)4) (a-2 )之部分縮合物S i之平均 個數為4· 0之聚（四曱氧矽烷）（多摩化學（股）製，商品名 「MS-51」429· lg與作為觸媒之月桂酸二丁基錫〇· 35g，以 80°C使之脫醇反應5小時，得到有效成分（硬化後）50%，二 氧化石夕換算重量/雙酚型環氧樹脂（丨）之重量（重量比）為 0· 55,環氧當量1400g/eq之含有甲氧基之矽烷變性環氡樹 脂（A-2)。又，以1H-NMR確認到，四甲氧石夕烧之部分縮合 成份之甲氧基保持87莫耳％。 實施例1 (接著劑組合物之製造） 將製造例1所得之含有甲氧基之矽烷變性環氧樹脂 (A-l)20· Og ; Nagase ChemteX(股）公司製，商品名「特森 樹脂SG-70L」（固形分12· 5%MEK清漆，玻璃轉移點-i7°C， 酸價5mgK0H/g，數目平均分子量2〇萬）（成分B)64 〇g;芳 香胺（三菱氣體化學（股）製，商品名「GASKAMINE 24〇」， 活性氫當罝103g/eq)(成分C)l· l〇g ;甲基乙基酮1〇. 〇g加 入均勻溶解調製接著劑組合物。（B)成分之調合比例，以固 形殘分對（A)成分之硬化殘分為重量％。存在於接著劑組 合物令的環氧基1當量，（C)成分中具有活性氫之官能基為 2066-8914-PF/Ahddub 22 200806771 1當量。接著劑硬化物中的二氧切換算重量為i8重量％。 實施例2(接著劑組合物之製造） 將製造例1所得之含有曱氧基之矽烷變性環氧樹脂 (A-l)11.5g;製造例2所得之含有甲氧基之石夕烧變性環氧 樹脂（A-2)1.0g;特森樹脂SG_7〇L(成分B)68 〇g; GASKAMINE 240(成分 c)0. lg ; jeriooi 2· 3g ;以及甲基乙 基酮10. Og加入均勻溶解調製接著劑組合物。（b)成分之調The heat resistance has a density of 230 C to 260 C ', and for example, pen·pet is used as a base film, and when an electrolytic copper foil is used as a metal layer, the above peel strength is obtained. Further, the water absorption rate is usually 5% or less, and the moisture resistance is good, and the solder heat resistance test after storage for 12 hours in an environment generally evaluated for the above-mentioned use of 8 (rc, humidity 85%) is not particularly problematic. Further, it generally has a volume resistance of 1 Ο13 Ω·cm or more and good insulation properties. For the most important transparency, the haze value of the film thickness of the adhesive layer of 15/m is usually 5% or less at 500. The thickness of the #m thick film is preferably 1% or less. In this case, when the laminate layer of the pen or PET is laminated on the adhesive layer on the PEN or PET, the increase in the haze value can be suppressed. In general, the haze value is 20% or less. [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples. Further, in each Example t, unless otherwise specified, % is based on the weight. Manufacture of a methoxy-containing decane-modified epoxy resin (A-i)) A reaction apparatus equipped with a stirrer, a cooling tube, and a thermometer, and a double-type A-type epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name) "JER1001", epoxy equivalent 480g/eq) (a-1) 800.0g and MEK960.0g, dissolved in 8 (rc). , a poly(methyl dimethoxy decane) having a total number of partial condensates si of decyltrimethoxy decane (ClhSiCOCH3) 3) (manufactured by Tama Chemical Co., Ltd., trade name r MTMS-A) (a-2) 605. 〇g and dibutyltin laurate as a catalyst, 2·3g, de-alcoholic reaction at 8〇〇c for 5 hours, to obtain an active ingredient (after hardening) 5 〇%, dioxide dioxide The weight (weight ratio) of the converted weight/bisphenol type epoxy resin (1) is 〇51, 2066-8914-PF; Ahddub 21 200806771 epoxy equivalent 1400 g/eq of methoxy-containing decane-modified epoxy resin (A) -1) Further, it was confirmed by I-匪R that the methoxy group of the partial condensation component of methyl methoxide was maintained at 87 mol%. Production Example 2 (decyl epoxidized epoxy resin containing decyloxy group) Production of A_2) In a reaction apparatus equipped with a stirrer, a cooling tube, and a thermometer, JER1001 (al) 400·Og and MEK334·8g were added and dissolved at 8 ° C. Further, tetramethoxine was added (S i (0CH3)4) The average number of partial condensates S i of (a-2) is 4·0 poly(tetraoxaxane) (manufactured by Tama Chemical Co., Ltd., trade name "MS- 51 429 · lg and dibutyltin laurate as a catalyst, 35g, de-alcoholic reaction at 80 ° C for 5 hours, to obtain 50% of the active ingredient (after hardening), weight loss of bismuth dioxide / bisphenol type The weight (weight ratio) of the epoxy resin (丨) was 0·55, and the methoxy group-containing decane-modified cyclic oxime resin (A-2) having an epoxy equivalent of 1400 g/eq. Further, it was confirmed by 1H-NMR that the methoxy group of the partial condensation component of the tetramethoxine was maintained at 87 mol%. Example 1 (Production of adhesive composition) The methoxy-containing decane-modified epoxy resin (Al) obtained in Production Example 1 was 20·Og; Nagase ChemteX Co., Ltd., trade name "Terson resin SG- 70L" (solid content 12 · 5% MEK varnish, glass transfer point - i7 ° C, acid value 5 mg K0H / g, number average molecular weight 2 million) (ingredient B) 64 〇 g; aromatic amine (Mitsubishi Gas Chemicals Co., Ltd.) The product name is "GASKAMINE 24", active hydrogen is 罝103g/eq) (component C) l·l〇g; methyl ethyl ketone 1 〇. 〇g is added to the homogeneous dissolution-adjusting adhesive composition. The blending ratio of the component (B) is determined by the solid residue to the hardening residue of the component (A). The epoxy group present in the adhesive composition is 1 equivalent, and the functional group having active hydrogen in the component (C) is 2066-8914-PF/Ahddub 22 200806771 1 equivalent. The dioxin switching weight in the subsequent hardened material was i8 wt%. Example 2 (Production of an adhesive composition) 11.5 g of a decyl-containing decene-modified epoxy resin (Al) obtained in Production Example 1; a methoxy-containing cerium-modified epoxy resin obtained in Production Example 2 (A-2) 1.0 g; Texen resin SG_7〇L (ingredient B) 68 〇g; GASKAMINE 240 (ingredient c) 0. lg; jeriooi 2·3g; and methyl ethyl ketone 10. Og added to uniform dissolution modulation The composition of the subsequent agent. (b) the adjustment of ingredients

合比例，以固形殘分對（A)成分之硬化殘分為1〇〇重量 存在於接著劑組合物中的環氧基i當量，（c)成分中具有活 性氫之官能基為(M當量。接著劑硬化物中的二氧切換 算重量為12. 8重量％。 實施例3(接著劑組合物之製造） 將特森樹脂SG-70L之使用量改為8〇 〇g以外，與實施 例1同樣的調合量進行相同操作，調製接著劑組合物/(B) 成分之調合比例’以固形殘分對⑴成分之硬化殘分為1〇〇 重量％。接著劑硬化物中的二氧化矽換算重量為166重量 %。 實施例4(接著劑組合物之製造） 將特森樹脂SG-70L之使用量改為81.5g以外，與實施 例1同樣的調合量進行相同操作，調製接著劑組合物/⑻ 成分之調合比例，以固形殘分對（A)成分之硬化殘分為12〇 重量％。接著劑硬化物中的二氧化矽換算重量為η· 7重量 %。 (比較例1) 2066-8914-PF;Ahddub 23 200806771 ^ JER1001 l〇.Og ; GASKAMINE 240 1.10g^SG-70L 64. Og、甲基乙基酮2〇 〇g加入均勻溶解調製接著劑組合 物。⑻成分之調合比例，以目形殘分對（A)成分之硬化殘 分為80重量％。存在於接著劑組合物中的環氧基i當量， (C)成分中具有活性氫之官能基為〇 . π當量。 (比較例2)In proportion, the hardening residue of the component (A) is 1 part by weight of the epoxy group i equivalent in the adhesive composition, and the functional group having active hydrogen in the component (c) is (M equivalent) The amount of the dioxin switching weight in the adhesive hardened material was 12.8% by weight. Example 3 (manufacture of the adhesive composition) The amount of the use of the Texen resin SG-70L was changed to 8 〇〇g, and the implementation was carried out. Example 1 The same blending amount was carried out in the same manner, and the blending ratio of the adhesive composition/(B) component was adjusted to be 1% by weight of the hard residue of the solid residue to the component (1). The conversion weight was 166% by weight. Example 4 (Production of adhesive composition) The same operation as in Example 1 was carried out except that the amount of use of the Texen resin SG-70L was changed to 81.5 g, and the adhesive was prepared. The blending ratio of the composition/(8) component was 12% by weight of the hard residue of the component (A) in the solid residue, and the weight of the binder in the cured product was η·7% by weight. ) 2066-8914-PF; Ahddub 23 200806771 ^ JER1001 l〇.Og ; GASKAMINE 240 1 .10g^SG-70L 64. Og, methyl ethyl ketone 2〇〇g is added to the homogeneous dissolution-adjusting adhesive composition. (8) The blending ratio of the components, the hardening residue of the (A) component is 80 % by weight of the epoxy group i equivalent present in the adhesive composition, and the functional group having active hydrogen in the component (C) is 〇. π equivalent. (Comparative Example 2)

將 JER1001 l(M9g;GASKAMINE 24〇 〇 23g、SG — 7〇L 81.5g、甲基乙基酮20.〇g加入均勻溶解調製接著劑組合 _ 物。（B)成分之調合比μ，以固形歹袭分對⑴成分之硬化殘 分為100重量％。存在於接著劑組合物中的環氧基丨當量， (C)成分中具有活性氫之官能基為〇· 1當量。 (比較例3) 作為丙烯酸高分子（Β)，將特森樹脂SG-7〇L改為 Nagase ChemteX(股）公司製，商品名「特森樹脂Ws — 〇23」 (玻璃轉移點-5°C ’酸價2〇mgKOH/g，數目平均分子量11 φ 萬），使用特森樹脂WS-023，加入甲基乙基酮32g以外 與貫施例1相同調合量進行相同操作，調製接著劑組合 物。（B)成分之調合比例，以固形殘分對（A)成分之硬化殘 分為8 0重量％。接著劑硬化物中的二氧化石夕換算重量為 18. 3重量％。 (比較例4) 作為丙烯酸高分子（B)，變更為使用6· 8g特森樹脂 WS-023，加入甲基乙基酮27· 2g以外與實施例1相同調合 量進行相同操作，調製接著劑組合物。（B)成分之調合比 2066-8914-PF;Ahddub 24 200806771 例，以固形殘分對（A)成分之締几我八a • 之硬化殘分為8 0重量％。接著劑 硬化物中的二氧化矽換算重量為14· 2重量％。 (比較例5) 作為丙烯酸高分子（B)，將特森樹脂SG-70L改為 NagaseChemteX(股）公司製，商品名「特森樹脂sG_p3」（固 形分15%MEK清漆’玻璃轉移點丨，酸價〇，數目平均分 子量25萬）’加入53.3g特森樹脂SG_p3,以外與實施例1 相同調合量進行相同操作，調製接著劑組合物。（b)成分之 » 調合比例，以固形殘分對（A)成分之硬化殘分為8〇重量％。 接著劑硬化物中的二氧化矽換算重量為18. 3重量％。 (比較例6 ) 作為丙烯酸高分子（B)，變更為使用453§特森樹脂 SG-P3以外與實施例1相同調合量進行相同操作，調製接 著劑組合物。（B)成分之調合比例，以固形殘分對（A)成分 之硬化殘分為8 0重ir %。接著劑硬化物中的二氧化石夕換算 g 重量為14.2重量％。 〈黏貼樣品之製造：使用實施例1、3、比較例1、3及5之 接著劑組合物〉 將實施例1、3、比較例1、3及5所得接著劑組合物 以輥輪塗佈機使乾燥後之厚度成15 μ m地塗佈乾燥於 50/zm之聚萘二曱酸乙二醇酯（PEN)膜（帝人杜邦膜（股） 製’商品名「TEONEX Q83」’之後使接著劑面，與；[g μ m 之銅箔（古河Circuit Foil(股）製，商品名「F2-WS」）之 處理面，重疊以12 0 °C之層壓輥輪壓接後，以烘箱1 〇 〇 處 2066-8914-PF;Ahddub 25 200806771 理3小時；說處理3小時；㈣處理3小時，使接著 劑硬化得到黏貼樣品（P E N /接著層/銅箱）。使用實施例i之 接著劑組合物所得之黏貼樣品作為H_卜使實施例3、比較 例1、3及5之接著劑組合物所得之接著片樣品分別為h_3、 G-卜G-3、G-5。將所得氧品之評價之剝離強度、焊接耐熱 性、耐濕性、測定體積電阻之結果示於表工。 剝離強度：根據JIS C-6481，測定銅箱與膜之剝離強 度。 知接耐熱性·將试驗片1 〇 〇 °C，加熱乾燥6 〇分後，於 2 6 0 C之和接浴中回焊3 0秒調查有無腫脹。 耐濕性（耐濕焊接耐熱性）：將試驗片置於8〇〇c、濕度 85%的環境下12小時後，實施焊接耐熱試驗。 體積電阻：根據JIS C-6481進行測定。 [表1] 接著劑組合物 實施例1 實施例3 比較例1 比較例3 比較例5 黏貼樣品 H-1 Η- 3 G-1 G-3 G-5 剝離強度(N/cm) 10 10 8 9 8 焊接耐熱性 〇 〇 X 〇 X 耐濕性 〇 〇 一 〇 體積電阻（Ω · cm) 2x1 〇14 2x1014 lxlO13 lxlO14 lxlO13 由以下結果’明顯可知實施例1及3之接著劑組合物 剝離強度·焊接耐熱性優良。 〈黏貼樣品之製造：使用實施例2、4、比較例2、4及6之 接著劑組合物〉 將實施例2、4、比較例2、4及6所得接著劑組合物 以輥輪塗佈機使乾燥後之厚度成2 5 /z m地塗佈乾燥於 2066-8914-PF;Ahddub 26 200806771 5〇Ρ之聚萘二甲酸乙二醇酯（PEN)膜（帝人杜邦膜（股） 製’ ^品名「T_X Q83」，得到接著樣品（pEN/接著層）。 使用只施例2之接著劑組合物所得之黏貼樣品作為H_2， 使貫％例4 tb車义例2、4及6之接著劑組合物所得之接著 片樣品分別為Η一4、g-2、G-4、G-6。 以前項所得片樣品之各種物性示於表2。測定方法如 下。 透明性：霧度值（暈價），根據JIS κ 7105測定。接著 片樣ασ係以接著層在半硬化成膠態（B-Si:age)之狀態測 定。 接著劑層之透明性，由上述層積體之霧度值扣除pEN 膜之霧度值之值。 剝離強度：接著片樣品之接著力測定用樣品，係將接 著片樣品之接著層侧，重疊於銅箔之鏡面侧，以熱壓製機 140 C、2· OMpa加熱加壓2小時壓接製作試驗片（pen/接著 層/銅箔）。 焊接耐熱性；將使用於上述剝離強度試驗之試驗片以 l〇〇°C ’加熱乾燥分後，於26〇。〇之和接浴中回悍30秒 調查有無腫脹。 [表2]JER1001 l (M9g; GASKAMINE 24〇〇23g, SG-7〇L 81.5g, methyl ethyl ketone 20. 〇g added to the homogeneous dissolution preparation adhesive composition. (B) composition of the mixing ratio μ, to solid form The hardening residue of the component (1) is 100% by weight, the epoxy group equivalent of the epoxy group present in the adhesive composition, and the functional group having active hydrogen in the component (C) is 〇·1 equivalent. As an acrylic polymer (Β), the Texen resin SG-7〇L was changed to Nagase ChemteX Co., Ltd. under the trade name "Terson resin Ws - 〇23" (glass transfer point -5 ° C 'acid price) 2 〇 mgKOH/g, number average molecular weight: 11 φ 10,000), and the same operation as in Example 1 except that 32% of methyl ethyl ketone was added, and the same composition was used to prepare an adhesive composition. The weight ratio of the solid residue to the hardening residue of the component (A) is 80% by weight. The weight of the sulfur dioxide in the adhesive hardener is 18.3% by weight. (Comparative Example 4) The acrylic polymer (B) was changed to use 6.8 g of Texen resin WS-023, and methyl ethyl ketone was added to 27.2 g. Example 1 The same blending amount was carried out to carry out the same operation to prepare an adhesive composition. The blending ratio of the component (B) was 2066-8914-PF; Ahddub 24 200806771, for example, the solid residue pair (A) component was The hardening residue was 80% by weight, and the weight of the cerium oxide in the cured product of the adhesive was 14.2% by weight. (Comparative Example 5) As the acrylic polymer (B), the SG-70L was changed to NagaseChemteX. (manufactured by the company), the product name "Terson resin sG_p3" (solid content 15% MEK varnish 'glass transfer point 酸, acid value 〇, number average molecular weight 250,000) 'add 53.3g Texen resin SG_p3, and examples 1 The same blending amount was carried out in the same manner to prepare the adhesive composition. (b) The blending ratio of the component was determined by the solid residue to the hardening residue of the component (A) by 8% by weight. (Comparative Example 6) The acrylic polymer (B) was changed to the same operation as in Example 1 except that 453 § tesson resin SG-P3 was used, and the adhesive composition was adjusted. (B) blending ratio of ingredients, to solid The hardening residue of the component (A) was 80% by weight ir %. The weight of the silica in the hardener of the adhesive was 14.2% by weight in terms of g. <Manufacture of the adhesive sample: Comparison using Examples 1, 3, Adhesive Compositions of Examples 1, 3, and 5> The adhesive compositions obtained in Examples 1, 3, and Comparative Examples 1, 3, and 5 were applied and dried by a roll coater to a thickness of 15 μm after drying. Polyethylene naphthalate (PEN) film at 50/zm (manufactured by Teijin DuPont Film Co., Ltd. 'trade name "TEONEX Q83"' to make the adhesive surface, and [g μ m copper foil ( The processing surface of Furukawa Circuit Foil (shares), trade name "F2-WS", overlapped with a laminating roller at 12 0 °C, and then oven 20 〇〇 at 2066-8914-PF; Ahddub 25 200806771 Treatment for 3 hours; said treatment for 3 hours; (d) treatment for 3 hours, the adhesive was hardened to obtain a paste sample (PEN / adhesive layer / copper box). The adhesive sample obtained by using the adhesive composition of Example i was used as H_b. The adhesive sheet samples obtained in the adhesive compositions of Example 3, Comparative Examples 1, 3 and 5 were respectively h_3, G-Bu G-3, G-5. The results of the evaluation of the peel strength, the solder heat resistance, the moisture resistance, and the volume resistance of the obtained oxygen product are shown in the table. Peel strength: The peel strength of the copper box and the film was measured in accordance with JIS C-6481. Knowing the heat resistance. The test piece was 〇 〇 ° C, heated and dried for 6 minutes, and then re-welded for 30 seconds in the bath of 260 ° C to investigate whether there was swelling. Moisture resistance (wet resistance to soldering heat resistance): After the test piece was placed in an environment of 8 ° C and a humidity of 85% for 12 hours, a solder heat resistance test was performed. Volume resistance: Measured in accordance with JIS C-6481. [Table 1] Adhesive Composition Example 1 Example 3 Comparative Example 1 Comparative Example 3 Comparative Example 5 Adhesion sample H-1 Η-3 G-1 G-3 G-5 Peel strength (N/cm) 10 10 8 9 8 Soldering heat resistance 〇X 〇X Moisture resistance 〇〇One volume resistance (Ω · cm) 2x1 〇14 2x1014 lxlO13 lxlO14 lxlO13 From the following results, it is apparent that the peeling strength of the adhesive compositions of Examples 1 and 3 is Excellent solder heat resistance. <Manufacture of Adhesive Sample: Using the Adhesive Compositions of Examples 2, 4, Comparative Examples 2, 4, and 6> The adhesive compositions obtained in Examples 2, 4, Comparative Examples 2, 4, and 6 were coated with a roller. The machine is dried and dried to a thickness of 2 5 /zm to 2066-8914-PF; Ahddub 26 200806771 5 聚 polyethylene naphthalate (PEN) film (Dynasty DuPont film (stock) system' ^ Product name "T_X Q83", the following sample (pEN/adhesive layer) was obtained. The adhesive sample obtained by using only the adhesive composition of Example 2 was used as H_2, so that the %4 tb car examples 2, 4 and 6 were followed. The film samples obtained by the composition of the composition were respectively Η4, g-2, G-4, and G-6. The various physical properties of the sample obtained in the previous paragraph are shown in Table 2. The measurement method was as follows. Transparency: haze value ( The halo is measured according to JIS κ 7105. Then, the sheet ασ is measured in a state in which the adhesive layer is semi-hardened to a colloidal state (B-Si:age). The transparency of the subsequent layer is determined by the haze of the above laminate. The value is deducted from the value of the haze value of the pEN film. Peel strength: the sample for the adhesion measurement of the next sample, which is the adhesive layer of the next sample. The side was superposed on the mirror side of the copper foil, and was heated and pressed by a hot press machine 140 C, 2·OMpa for 2 hours to prepare a test piece (pen/attach layer/copper foil). Solder heat resistance; used for the above peel strength The test piece of the test was heated and dried at 10 ° C. After 26 minutes, the sputum was taken back in the bath for 30 seconds to investigate whether there was swelling. [Table 2]

接著劑組合物 實施例2 實施例4 比較例2 比較例4 比較例6 黏貼片樣品 H-2 Η - 4 G- 2 G-4 G-6 透明性(％) 7 7 80 80 80 接著劑層之透明性 1 1 74 74 74 剝離強度(N/cm2) 8 8 6 7 6 焊接耐熱彳生(有無腫脹） 〇 〇 X 〇 X 2066-8914-PF;Ahddub 27 200806771 • I Γ260°(：χ30 秒)_ ]—' 厂~—r—~~^^--— 1 1 &quot; —___ ‘ 由以上結果，實施例2及4之接著劑組合物，透明性、 剝離強度、焊接耐熱性優良，有用於作為用於覆蓋層膜之 接著劑組合物。 〈層積膜樣品之製造〉 將實施例1、3、比較例1、3及5所得之黏貼樣品之 銅邊藉由氣化鐵水溶液將全面钱刻去除，分別將實施例2、 4、比較例2、4、6所得接著片樣聘之接著層側重疊，以熱 馨 壓製機l40°c、2· OMpa、加熱壓加壓壓接2小時，製作層 積膜樣品（PEN/接著片樣品接著層/黏貼樣品接著層 /PEN)。將所得各膜樣品之透明性根據上述JIS κ 71〇5測 定。結果示於表3。 [表3] 層積膜 F-1 F-2 Ε-1 E-3 黏貝占樣品 ΪΗ Η-3 G-1 G-3 G-5 接者片樣πα ~~ΙΓ2~~ Η-4 | G-4 G-6 透明性〇〇 18 18 83 83 83 由以上結果，由實施例1及3之接著劑組合物所得之 貼銅層基板與實施例2及4所得之覆蓋層膜之組合，可製 作透明性優良之軟性印刷電路板。 〈硬化膜樣品：使用實施例1、3、比較例1、3及5之接著 劑組合物〉 將實施例1、3、比較例1、3及5之接著劑組合物流 延於鋁杯，以50°C，12小時，15(TC，3小時使之硬化， 得到5 0 0 /z m厚之硬化膜。 硬化膜透明性：霧度值（暈價），根據jIS κ 71〇5測定。 2066-8914-PF;Ahddub 28 200806771 吸收率：將硬化膜以50°C，24小時，置於絕對乾燥狀 態後，浸潰於水2 4小時，求含水量。將結果示於表4。 [表4] 硬化膜 C-1 C-3 B~1 B-3 B-5 接著劑組合物 實施例1 實施例3 比較例1 比較例3 比較例5 硬化膜之透明性(％) 3 3 90 90 90 吸水率(％) 0.3 0.3 0.6 0.4 0.6 由以上結果，明顯可知實施例1及3之接著劑組合物， 透明性、耐濕性優良。 【圖式簡單說明】 無。 【主要元件符號說明】 無0 馨 2066-8914-PF;Ahddub 29Adhesive composition Example 2 Example 4 Comparative Example 2 Comparative Example 4 Comparative Example 6 Adhesive sheet sample H-2 Η - 4 G- 2 G-4 G-6 Transparency (%) 7 7 80 80 80 Adhesive layer Transparency 1 1 74 74 74 Peel strength (N/cm2) 8 8 6 7 6 Welding heat-resistant twins (with or without swelling) 〇〇X 〇X 2066-8914-PF; Ahddub 27 200806771 • I Γ260° (:χ30 seconds )_]-'Factory~-r-~~^^--- 1 1 &quot; —___ ' From the above results, the adhesive compositions of Examples 2 and 4 are excellent in transparency, peel strength, and solder heat resistance. It is used as an adhesive composition for a cover film. <Manufacturing of laminated film samples> The copper edges of the pasted samples obtained in Examples 1, 3, and Comparative Examples 1, 3, and 5 were thoroughly removed by an aqueous solution of iron oxide, and Examples 2, 4, and Comparative, respectively. The results obtained in Examples 2, 4, and 6 were then overlapped on the side of the film. The laminated film samples (PEN/Battery samples) were prepared by hot pressing presses l40°c, 2· OMpa, and hot pressing for 2 hours. Next layer/stick sample back layer/PEN). The transparency of each of the obtained film samples was measured in accordance with JIS κ 71〇5 described above. The results are shown in Table 3. [Table 3] Laminated film F-1 F-2 Ε-1 E-3 Adhesive occupies sample ΪΗ Η-3 G-1 G-3 G-5 接片样πα ~~ΙΓ2~~ Η-4 | G-4 G-6 transparency 〇〇18 18 83 83 83 From the above results, the combination of the copper-clad layer substrate obtained from the adhesive compositions of Examples 1 and 3 and the cover film obtained in Examples 2 and 4, A flexible printed circuit board with excellent transparency can be produced. <Cured film sample: Using the adhesive compositions of Examples 1, 3, Comparative Examples 1, 3, and 5> The adhesive composition streams of Examples 1, 3, Comparative Examples 1, 3, and 5 were extended to an aluminum cup to At 50 ° C, 12 hours, 15 (TC, 3 hours to harden it, to obtain a cured film of 5000 / zm thick. Curing film transparency: haze value (halo), measured according to jIS κ 71〇 5. 2066 -8914-PF; Ahddub 28 200806771 Absorption rate: After the cured film was placed in an absolute dry state at 50 ° C for 24 hours, it was immersed in water for 24 hours to obtain a water content. The results are shown in Table 4. 4] Cured film C-1 C-3 B~1 B-3 B-5 Adhesive composition Example 1 Example 3 Comparative Example 1 Comparative Example 3 Comparative Example 5 Transparency of cured film (%) 3 3 90 90 90 Water absorption ratio (%) 0.3 0.3 0.6 0.4 0.6 From the above results, it is apparent that the adhesive compositions of Examples 1 and 3 are excellent in transparency and moisture resistance. [Simplified description of the drawings] None. [Explanation of main component symbols] No 0 Xin 2066-8914-PF; Ahddub 29

Claims (1)

200806771 . 十、申請專利範圍： 1· 一種層積體用接著劑組合物，其特徵在於包含： ^含有甲氧基之矽烷變性環氧樹脂（A)，其係使雙酚型環 氧樹脂（a-ι)及曱氧石夕貌部分縮合物（a_2)脫肖反應而得 者； 丙烯fee间刀子（3)，其具有羧基，玻璃轉移點為2〇它 以下，酸價為2〜10(mgK〇H/g)，平均分子量數目為15萬〜3〇 萬；及 ^ 氧樹脂用硬化劑（C)。 2·如申請專利範圍第〗項所述的層積體用接著劑組合 物，其中上述曱氧矽烷部分縮合物（a—2)，係四曱氧矽烷及 /或甲基三甲氧矽烷之部分縮合物。 3·如申請專利範圍第丨或2項所述的層積體用接著劑 組合物，其中上述丙烯酸高分子（B)之調合量對於含有甲氧 基之矽烷變性環氧樹脂（A)之硬化殘分為9〇〜2〇〇%。 • 4·如申請專利範圍第1至3項中任一項所述的層積體 用接著劑組合物，其中環氧樹脂用硬化劑（c)，係選自由芳 香胺及紛駿樹脂所組成之群之至少一種。 5.如申請專利範圍第丨至4項中任一項所述的層積體 用接著劑組合物，其中作成15 // m之硬化膜時之霧度值為 5%以下。 6· —種透明層積體，將聚萘二曱酸乙二醇酯或聚對苯 .二甲酸乙二醇酯使用申請專利範圍第1至5項中任一項所 述層積體用接者劑組合物接著者，該層積體之霧度值為 2 0 6 6-8 914-P F;Ahddub 30 200806771 以下。200806771 . X. Patent Application Range: 1. A laminate composition for an adhesive comprising: a methoxy-containing decane-modified epoxy resin (A) which is a bisphenol type epoxy resin ( A-ι) and the oxidized stone partial condensate (a_2) obtained by decoupling reaction; propylene fee knife (3), which has a carboxyl group, the glass transition point is 2 〇 or less, and the acid value is 2 to 10 (mgK 〇 H / g), the average molecular weight number is 150,000 ~ 3 million; and ^ oxy resin hardener (C). The adhesive composition for a laminate according to the above aspect of the invention, wherein the above-mentioned oxime partial condensate (a-2) is a part of tetraoxoxane and/or methyltrimethoxy decane. Condensate. 3. The adhesive composition for a laminate according to the above or 2, wherein the blending amount of the above acrylic polymer (B) is hardened for the methoxy group-containing decene-modified epoxy resin (A). The residue is 9〇~2〇〇%. The adhesive composition for a laminate according to any one of claims 1 to 3, wherein the epoxy resin hardener (c) is selected from the group consisting of an aromatic amine and a rhodium resin. At least one of the groups. The laminate composition for a laminate according to any one of claims 4 to 4, wherein a haze value of the cured film of 15 // m is 5% or less. 6. A transparent laminate comprising polyethylene naphthalate or polyparaphenylene dicarboxylate using the laminate according to any one of claims 1 to 5. The composition of the composition is followed by a haze value of 2 0 6 6-8 914-PF; Ahddub 30 200806771 or less. 2 0 6 6-8 914-PF;Ahddub 31 200806771 七、指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明：無。 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無0 2066-8914-PF;Ahddub2 0 6 6-8 914-PF; Ahddub 31 200806771 VII. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0 2066-8914-PF; Ahddub