201041994 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種接著劑之組成物及其應用。 【先前技術】 一般用於軟性印刷電路板的背膠膜（coverlay)可分為 高分子保護膜層與接著劑膜層兩部份，高分子保護膜層用 於提供保護的功能，而接著劑膜層則用於黏合在電路板 上。背膠膜在商品化時，通常會再貼合一層離型紙於接著 劑膜層上。 在軟性印刷電路板中，背膠膜位於電路板層與層之間 或上下層的區域，用以作為電路板的保護膜。在印刷電路 板的製程中，通常會涉及高温製程，因此背膠膜需要有相 當好的熱穩定性。由於背膠膜的高分子保護膜一般多選用 具有良好熱性質的聚酸亞胺，因此在熱穩定性例如玻璃轉 移温度與熱膨脹係數的改良上，就需由接著劑的改良方向 著手。 此外，由於背膠膜係位於多層電路板中的層與層之 間，因此在介電性質上背膠膜需具有較低的介電係數與介 電損失，用於避免訊號傳遞的延遲與能量的損失。因此， 一種具有良好的熱穩定性以及較低介電係數與介電損失的 環氧樹脂接著劑為目前所需。 【發明内容】 因此，本發明之一目的係提供一種接著劑之組成物， 4 201041994 以合乎製程之需求，同時具有熱穩定性以及較低介電係數 與介電損失’可克服或改善前述先前技術的問題。 根據本發明之上述目的，提供一種接著劑之組成物包 含35,230咖重量之具有半互穿型網狀結構之聚合物、 1〇phr〜55Phr ί量份之聚_脂以& iph卜重量份之 橡膠彈性體’本發明之—係指重量份㈣匕per hundred)， 其中該具有半互穿型網狀結構之聚合物係由卿fphr 重量之丁一烯-苯乙稀-二乙稀笨共聚物、5phr〜80phr重量份 〇 增韌劑以及適量過氧化物觸媒進行一預聚合反應所得，且 該半互穿型網狀結構之聚合物之分子量介於350〜10000。 根據本發明之一實施例，此組成物更包含一無機填充 物用以維持接著劑之尺寸安定性。 根據本發明之一實施例，此組成物更包含一硬化劑以 使該接著劑組成物產生交聯作用。 根據本發明之上述目的，提供一種接著劑組成物之製 備方法，此方法包含先提供丁二烯_苯乙烯_二乙烯笨共聚 〇 物、一增韌劑及一觸媒。接著進行一預聚合反應以得一具 有半互穿型網狀結構之聚合物。最後加入聚酿樹脂以及橡 膠彈性體以完成製備該接著劑組成物。 根據本發明之另一目的’提供一種背膠膜，其包含聚 醢亞胺基材、位於聚醯亞胺基材上的接著層，以及貼附於 接著層上的離型層，其中接著層包含前述接著劑之組成物。 - 根據本發明之再一目的，提供一種接著膠片，其包含 玻纖基材以及一包覆玻纖基材的接著層，其中接著層包含 前述接著劑之組成物。 根據本發明之再一目的，提供一種雙面覆金屬積層 5 201041994 板’至少包含一基板、二硬化接著層以及一第一金屬箱與 一第二金屬箔。二硬化接著層分別位於基板相對之兩側 面，而第一金屬箔與第二金屬箔則分別黏著於兩硬化接著 • 層背對基板之表面上。其中二硬化接著層係由前述接著劑 組成物硬化而成。 本發明實施例所提供具有前述接著劑組成物的一種接 著劑’可塗佈於一薄膜之上而形成接著劑薄膜。 由上述可知’本發明中的接著劑組成物具有較高的玻 〇 璃轉移温度與低介電特性，具有較佳的熱穩定性，可將此 接著劑組成物用於高温製程上。而在接著的性質上，通過 組成物成份的調整，可使此接著劑組成物具有與習知接著 劑組成物相當之接著性。 【實施方式】 本發明係有關於一種接著劑組成物，該接著劑組成物 包含35phr〜230phr之具有半互穿型網狀結構之聚合物、 〇 l〇phr〜55phr之聚酯樹脂、lphr〜35phr之橡膠彈性體。本發 明之phr係指重量份(parts per hundred)。該具有半互穿型 網狀結構之聚合物係由30phr〜150phr之丁二稀-苯乙烯-二 乙烯苯共聚物、5phr〜80phr增韌劑以及適量過氧化物觸媒 進行一預聚合反應所得，且該半互穿型網狀結構之聚合物 之分子量介於350〜10000。 • 前述之增韌劑（toughener)用以改變接著劑組成物之韌 性。適用於本發明之增韌劑包含，但不限於，羧基化丁腈 橡膠（Carboxylterminated Butadiene Acrylonitrile, CTBN)或 6 201041994 丁腈橡膠(NitrileButadiene Rubber)。如果前述增韌劑之含 量未滿lOphr，則會使得接著劑組成物之勃性不足’如果增 韌劑含量高於70% ’則會使得接著劑組成物紂熱性下降。 Ο201041994 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composition of an adhesive and an application thereof. [Prior Art] A coverlay generally used for a flexible printed circuit board can be divided into two parts: a polymer protective film layer and an adhesive film layer, and a polymer protective film layer is used for providing a protective function, and an adhesive The film is then used to bond to the board. When the adhesive film is commercialized, a release paper is usually applied to the adhesive film layer. In a flexible printed circuit board, the adhesive film is located between the circuit board layer and the layer or in the upper and lower layers to serve as a protective film for the circuit board. In the manufacturing process of printed circuit boards, high temperature processes are usually involved, so the backing film needs to have relatively good thermal stability. Since the polymer protective film of the adhesive film is generally selected from polyimine having good thermal properties, it is necessary to improve the thermal stability such as the glass transition temperature and the thermal expansion coefficient from the improvement of the adhesive. In addition, since the adhesive film is located between the layers in the multilayer circuit board, the dielectric film has a lower dielectric constant and dielectric loss in terms of dielectric properties, and is used to avoid delay and energy of signal transmission. Loss. Therefore, an epoxy resin adhesive having good thermal stability and a low dielectric constant and dielectric loss is currently required. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a composition of an adhesive, 4 201041994 to meet the needs of the process, while having thermal stability and a lower dielectric constant and dielectric loss 'overcoming or improving the foregoing Technical issues. According to the above object of the present invention, there is provided a composition comprising an adhesive comprising 35,230 coffee by weight of a polymer having a semi-interpenetrating network structure, and a poly-lipid of 1 phr to 55 Phr Å by weight of & iph The rubber elastomer 'in the present invention' means a part by weight of (four) hundredper hundred), wherein the polymer having a semi-interpenetrating network structure is a butylene-styrene-diethylene The copolymer, 5 phr to 80 phr parts by weight of the cerium toughening agent and a suitable amount of peroxide catalyst are obtained by a prepolymerization reaction, and the polymer of the semi-interpenetrating network structure has a molecular weight of 350 to 10,000. According to an embodiment of the invention, the composition further comprises an inorganic filler for maintaining the dimensional stability of the adhesive. According to an embodiment of the present invention, the composition further comprises a hardener to cause cross-linking of the adhesive composition. According to the above object of the present invention, there is provided a process for the preparation of an adhesive composition which comprises first providing a butadiene-styrene-diethylene stupid copolymer, a toughening agent and a catalyst. A prepolymerization is then carried out to obtain a polymer having a semi-interpenetrating network structure. Finally, a binder resin and a rubber elastomer are added to complete the preparation of the adhesive composition. According to another object of the present invention, there is provided a backing film comprising a polyimide substrate, an adhesive layer on a polyimide substrate, and a release layer attached to the adhesive layer, wherein the adhesive layer A composition comprising the aforementioned adhesive. - According to still another object of the present invention, there is provided a film comprising a glass substrate and an adhesive layer of a coated glass substrate, wherein the adhesive layer comprises the composition of the foregoing adhesive. According to still another object of the present invention, there is provided a double-sided metal-clad laminate 5 201041994 which comprises at least one substrate, two hardened back layers, and a first metal case and a second metal foil. The two hardened adhesive layers are respectively located on opposite sides of the substrate, and the first metal foil and the second metal foil are respectively adhered to the surfaces of the two hardened layers which are opposite to the substrate. The two hardened adhesive layers are formed by hardening the aforementioned adhesive composition. An adhesive agent provided in the embodiment of the present invention having the foregoing adhesive composition can be coated on a film to form an adhesive film. From the above, it is known that the adhesive composition of the present invention has a high glass transition temperature and low dielectric properties, and has excellent heat stability, and this adhesive composition can be used for a high temperature process. On the basis of the subsequent properties, the composition of the adhesive can be made to have an adhesive property comparable to that of the conventional adhesive composition by adjustment of the composition of the composition. [Embodiment] The present invention relates to an adhesive composition comprising 35 phr to 230 phr of a polymer having a semi-interpenetrating network structure, a polyester resin of 〇l〇phr to 55 phr, and a lphr~ 35 phr of rubber elastomer. The phr of the present invention refers to parts per hundred. The polymer having a semi-interpenetrating network structure is obtained by prepolymerization of 30 phr to 150 phr of butyl succinyl-styrene-divinylbenzene copolymer, 5 phr to 80 phr of toughening agent, and appropriate amount of peroxide catalyst. And the molecular weight of the polymer of the semi-interpenetrating network structure is between 350 and 10,000. • The aforementioned toughener is used to alter the toughness of the adhesive composition. Toughening agents suitable for use in the present invention include, but are not limited to, Carboxylterminated Butadiene Acrylonitrile (CTBN) or 6 201041994 Nitrile Butadiene Rubber. If the content of the above-mentioned toughening agent is less than 10 phr, the boring property of the adhesive composition is insufficient. If the content of the toughening agent is higher than 70%, the heat resistance of the adhesive composition is lowered. Ο
前述之具有半互穿型網狀結構之聚合物的添加是用以 降低接著劑組成物的介電常數。如果前述之具有半互穿型 網狀結構之聚合物含量未滿3 Ophr，則介電常數無法小於 3.7 ’且介電損失無法小於〇.〇〇8，如果前述厶具有半互穿 型網狀結構之聚合物含量高於15〇phr，則會造成無法加工 接著劑組成物。 聚酯樹脂係為不飽和酯類包含，但不限於，異氰酸酯 樹脂或環氧化聚丁二烯樹脂等環氧樹脂。 如果前述之橡膠彈性體之含量未滿2phr，則使得接著 劑組成物柔軟性不足，如果橡膠彈性體含量高於20phr，則 使得接著劑組成物耐熱性不足。適用於本發明之橡膠彈性 體包含甲基醚化樹脂。 在特定實施例中，本發明之接著劑組成物可更包含硬 化劑的加入是為了使接著劑分子產生交聯，以增加接著劑 的耐熱性與内聚力。硬化劑可為酚醛硬化劑GPH78或4,4-二胺基-二笨基砜(4,4-DDS)或其組合。 在特定實施例中，本發明之接著劑組成物可更包含無 ，，充劑。藉由無機填充物的加入，可提昇接著劑的尺 ，定I"生與影響接著劑組成物的熱傳係數。無機填充劑可為 氫氧化鉬、氧化鋁或其組合。 在特定實施例中，本發明之接著劑組成物可更包含觸 媒用以加速反應進行。適用於本發明之觸媒包含過氧化觸 媒過氧化二異丙苯(Dicumyl Per〇xide, DCp)或一級胺或二 7 201041994 級胺觸媒。若觸媒添加量大於lphr，雖可縮短硬化反應時 間，但易生成副產物且對硬化反應的均一性產生不良的影 響；若觸媒添加量小於0.05phr，反應速度過慢，較無效率。 在特定實施例中，更包含加入一阻燃劑以使接著劑具 阻燃效果。其中阻燃劑係為奈米矽化物。 依據本發明一實施例所述之接著劑組成物的製備方 法，先將增韌劑以及一 丁二烯·苯乙烯-二乙烯苯共聚物溶 於丁嗣(Methyl-Ethyl Ketone ; MEK)溶劑中，並進行一預聚 〇 合反應’配製成增韌劑溶液。之後，在另一反應瓶中加入 聚醋樹脂以及橡膠彈性體。同時可加入一過氧化物觸媒以 加速反應速率，接著將前述的增韌劑溶液加入前述的反應 瓶中以完成製備分散的接著劑組成物。 在特定實施例中，可將上述接著劑組成物，塗佈於聚 醯亞胺基材上，再將溶劑去除，即可製成一背膠膜。於商 品化時，僅需於接著劑之表面再覆上一離型層即可，此離 型層可由聚對苯二曱酸乙二脂（polyethylene Q Terephthalate，PET)製成。 在特定實施例中，可將前述提及的接著劑，塗佈於聚 對笨二曱酸乙二酯，再將溶劑去除，同時將ρΕτ去除，即 可製成一具有本發明之接著劑原料的接著劑薄膜，此接著 劑薄膜具有-半互穿形網狀結構。在使用上，可直接將此 接著劑薄膜夾在欲固著的固體間，再以185ΐ的温度進行 ' 熱壓1小時，即可形成位於兩固體間的接著劑層。除了以 ㈣的方式形成接著劑薄料，亦可將玻纖基材浸泡於前 述接著劑組成物中，使接著劑纟域物包覆錢基材。之後， 再將玻纖基材取出，並去除接著劑組成物之溶劑 ，即可形 8 201041994 成具有玻纖基材之接著膠片。 在特定實施例中，上述之接著劑組成物或包含接著劑 組成物的接著膠片可用以製作雙面覆金屬積層板，其具有 一基板、二硬化接著層、第一金屬箔以及第二金屬箔。二 硬化接著層分別位於基板相對之兩側面上，硬化接著層係 由前述之接著劑組成物或包含接著劑組成物的接著膠片硬 =而成。第一金屬箔與第二金屬箔分別覆蓋於硬化接著層 背對基板之表面，並進行熱壓，以黏著於二硬化接著層上。 〇 在特定實施例中’前述接著膠片中的玻纖基材亦可直 接作為雙面覆金屬積層板取代基板的支撐基材，以製作雙 面覆金屬積層板，其包含第一金屬箔、硬化接著層與第二 金屬箔。、硬化接著層位於第一金屬箔上，其由前述接著劑 組成物或包含接著劑組成物的接著膠片硬化而成。第二金 屬箱位於硬化接著層背對第一金屬箔之表面上。 第1圖所示為本發明之一實施例之覆金屬積層板1〇〇 之剖面示意圖。在特定實施例中，前述接著膠片中的玻纖 〇 基材亦可直接作為雙面覆金屬積層板1〇〇取代基板的支撐 基材，以製作雙面覆金屬積層板100，其包含第一金屬箔 140、一硬化接著層120與第二金屬箔16〇。硬化接著層12〇 位於第一金屬箔14〇上，由前述之接著劑組成物或包含接 著劑組成物的接著膠片所硬化而成。第二金屬箔160位於 硬化接著層120背對第一金屬箔14〇之表面上。 • 第2圖所示為本發明之一實施例之液晶積層板200之 剖面示意圖。在特定實施例中’前述接著劑組成物可形成 液晶積層板200的接著層21〇, 22〇 ’中間層依序為聚亞醯 fe(Polyimide, Pi)層 23〇、液晶高分子層 24〇(Liquid Crystal 9 201041994The aforementioned polymer having a semi-interpenetrating network structure is added to lower the dielectric constant of the adhesive composition. If the aforementioned polymer having a semi-interpenetrating network structure is less than 3 Ophr, the dielectric constant cannot be less than 3.7 ′ and the dielectric loss cannot be less than 〇.〇〇8 if the bismuth has a semi-interpenetrating mesh A polymer content of the structure above 15 〇phr results in an inability to process the adhesive composition. The polyester resin is an unsaturated ester, but is not limited to an epoxy resin such as an isocyanate resin or an epoxidized polybutadiene resin. If the content of the aforementioned rubber elastomer is less than 2 phr, the adhesiveness of the adhesive composition is insufficient, and if the rubber elastomer content is more than 20 phr, the heat resistance of the adhesive composition is insufficient. The rubber elastomer suitable for use in the present invention contains a methyl etherified resin. In a particular embodiment, the adhesive composition of the present invention may further comprise a hardening agent added to cause cross-linking of the adhesive molecules to increase the heat resistance and cohesion of the adhesive. The hardener may be a phenolic hardener GPH78 or 4,4-diamino-diphenylsulfone (4,4-DDS) or a combination thereof. In a particular embodiment, the adhesive composition of the present invention may further comprise a no, a bulking agent. By the addition of the inorganic filler, the size of the adhesive can be increased, and the heat transfer coefficient of the composition of the adhesive is affected. The inorganic filler may be molybdenum hydroxide, aluminum oxide or a combination thereof. In a particular embodiment, the adhesive composition of the present invention may further comprise a catalyst to accelerate the reaction. Catalysts suitable for use in the present invention comprise a peroxygen peroxide dicumyl peroxixide (DCp) or a primary amine or a secondary amine catalyst of 201041994. If the amount of catalyst added is more than 1 phr, the hardening reaction time can be shortened, but by-products are easily formed and adversely affect the uniformity of the hardening reaction; if the amount of catalyst added is less than 0.05 phr, the reaction rate is too slow and inefficient. In a particular embodiment, a flame retardant is further included to provide a flame retardant effect to the adhesive. The flame retardant is a nano-telluride. According to a method for preparing an adhesive composition according to an embodiment of the present invention, a toughening agent and a butadiene styrene-divinylbenzene copolymer are first dissolved in a solvent of Methyl-Ethyl Ketone (MEK). And performing a prepolymerization reaction to prepare a toughening agent solution. Thereafter, a polyester resin and a rubber elastomer were added to the other reaction bottle. At the same time, a peroxide catalyst can be added to accelerate the reaction rate, and then the aforementioned toughening agent solution is added to the aforementioned reaction flask to complete the preparation of the dispersed adhesive composition. In a specific embodiment, the above adhesive composition can be applied to a polyimide substrate and the solvent removed to form a backing film. For commercialization, it is only necessary to apply a release layer to the surface of the adhesive. The release layer can be made of polyethylene Q Terephthalate (PET). In a specific embodiment, the above-mentioned adhesive can be applied to polyethylene terephthalate, and then the solvent is removed, and ρΕτ is removed to prepare a binder having the present invention. An adhesive film having a semi-interpenetrating network structure. In use, the adhesive film can be directly sandwiched between the solids to be fixed, and then subjected to 'hot pressing at 185 Torr for 1 hour to form an adhesive layer between the two solids. In addition to forming the adhesive thinner in the manner of (4), the glass fiber substrate may be immersed in the above-mentioned adhesive composition to coat the adhesive substrate with the adhesive substrate. Thereafter, the glass fiber substrate is taken out, and the solvent of the adhesive composition is removed, and then the film having the glass fiber substrate is formed in 201041994. In a particular embodiment, the above-described adhesive composition or the adhesive film comprising the adhesive composition can be used to form a double-sided metal-clad laminate having a substrate, a hardened adhesive layer, a first metal foil, and a second metal foil. . The two hardened adhesive layers are respectively located on opposite sides of the substrate, and the hardened adhesive layer is formed by hardening the adhesive composition of the foregoing or the adhesive film comprising the adhesive composition. The first metal foil and the second metal foil are respectively covered on the surface of the hardened adhesive layer facing away from the substrate, and are hot pressed to adhere to the double hardened adhesive layer. In a specific embodiment, the glass fiber substrate in the foregoing film may directly replace the supporting substrate of the substrate as a double-sided metal-clad laminate to form a double-sided metal-clad laminate comprising the first metal foil and hardening. The layer is then followed by a second metal foil. The hardened adhesive layer is on the first metal foil and is formed by hardening the aforementioned adhesive composition or a film comprising the adhesive composition. The second metal box is located on the surface of the hardened back layer facing away from the first metal foil. Fig. 1 is a schematic cross-sectional view showing a metal-clad laminate 1 according to an embodiment of the present invention. In a specific embodiment, the fiberglass substrate in the film can be directly used as a support substrate of the double-sided metal-clad laminate 1 to replace the substrate to form a double-sided metal-clad laminate 100, which includes the first The metal foil 140, a hardened back layer 120 and a second metal foil 16 are. The hardened adhesive layer 12 is placed on the first metal foil 14A and is cured by the aforementioned adhesive composition or an adhesive film comprising the adhesive composition. The second metal foil 160 is on the surface of the hardened back layer 120 facing away from the first metal foil 14A. Fig. 2 is a cross-sectional view showing a liquid crystal laminate 200 according to an embodiment of the present invention. In a specific embodiment, the foregoing adhesive composition can form the adhesive layer 21 of the liquid crystal laminate 200, and the intermediate layer is sequentially a polyimide (Pi) layer 23, a liquid crystal polymer layer 24 (Liquid Crystal 9 201041994
Polymer, LCP)、聚對苯二甲酸乙二醇酯層 25〇(p〇lyethylene Terephthalate, PET)、聚萘二曱酸乙二酯層 260 (Polyethylene-2,6-naphthalate, PEN)及聚四氟乙烯層 270 (Polytetrafluoroethylene，PTFE)，由前述接著劑組成物所形 成的接著層210, 220則分別位於此液晶積層板2〇〇之上下 層。 以下具體的例子是’應被視為僅僅是說明性的，無論 在任何情況皆不是用以限定本揭露之其他部分。如果沒有 〇 進一步闡述，咸信在本技藝中具有通常技藝者可基於在此 之敘述而充分利用本發明。 接著劑之配製 表一係列出本發明實施例1、2及3以及比較實施例1 及2之接著劑組成物配方。 實施例1 先將增韌劑5克KS-1、5克NBR與80克的一 丁二烯-苯乙浠_二乙燁苯共聚物溶解於150克的丁酮（methyl ethyl 〇 ketone，ΜΕΚ)，並進行一預聚合反應，其溫度範圍介於約 60〜約150°C以及時間範圍介於約0.5小時至約4小時之 間，以製備KS1-NBR MEK增韌劑溶液，其中KS_i係為 Sekisui公司所生產的一種聚乙婦縮丁酸（p〇iyVinyi butyral ; PVB)產品。之後，在一個1000毫升(ml)的反應瓶 中依序加入10克的異氰酸脂樹脂、3克的甲基醚化樹脂、 0.5克的過氧化二異丙苯(Dicumyl peroxide, DCP)、5克的 酚醛硬化劑GPH78、50克球型氧化鋁及15克的奈米矽化 物。最後將100克前述10%的增韌劑溶液加入前述1〇〇〇 毫反應瓶中以完成製備實施例1之接著劑組成物。 201041994 實施例2 先將增韌劑10克KS-1、5克NBR與80克的一丁二 稀-本乙烯-一乙稀苯共聚物溶解於160克的丁酮（methyl • 池丫1 ket〇ne，MEK)，並進行一預聚合反應，其溫度範圍 介於約60〜約150°C以及時間範圍介於約〇.5小時至約4小 時之間，以製備KS1-NBR MEK增韌劑溶液。之後，在一 個1000毫升(ml)的反應瓶中依序加入1〇克的環氧化聚丁 二烯樹脂、10克的甲基醚化樹脂、1克的過氧化二異丙苯 〇 (Dicumy1 peroxide，DCP) ' 8 克的酚醛硬化劑 GPH78、150 克球型氧化鋁及25克的奈米矽化物。最後將1〇〇克前述增 韌劑溶液加入前述1000毫升反應瓶中以完成製備實施例2 之接著劑組成物。 實施例3 先將增韌劑10克KS-1、10克NBR與90克的一丁二 烯-苯乙烯-二乙烯苯共聚物溶解於17〇克的丁酮（methyi ethyl ketone，MEK)，並進行一預聚合反應，其溫度範圍 ❹ 介於約60〜約150°C以及時間範圍介於約〇.5小時至約4小 時之間，以製備KS1-NBR MEK增韌劑溶液。之後，在一 個1000毫升(ml)的反應瓶中依序加入5克的異氰酸脂樹 脂、5克的酚醛樹脂、2克的過氧化二異丙笨（Dicumyl peroxide, DCP)、100克球型氧化鋁及2克的奈米矽化物。 最後將100克前述10%的增韌劑溶液加入前述1〇〇〇毫升 反應瓶中以完成製備實施例3之接著劑組成物。 比較實施例1 . 先將20克增動劑KS-1溶解於180克的丁 _(methyl ethyl ketone，MEK)’以製備 10%的 KS1-MEK 增動劑溶液。 11 201041994 之後’在一個1000毫升(ml)的反應瓶中依序加入100克雙 盼A型環氧樹脂(Bisphenol A，BPA)、140克氧化銘、〇 1 克2苯基-1氰乙基咪唑(2PI-CN)、18克的4,4-二胺基-二笨 基砜(4,4DDS)。最後將200克前述10%的增韌劑溶液加人 前述1000毫升反應瓶中以完成製備比較實施例1之接著劑 組成物。 比較實施例2 先將60克增韌劑KS-1溶解於240克的丁酮(methyl 〇 ethyl ketone，MEK)，以製備 10% 的 KS1-MEK 增韌劑溶液。 之後，在一個1000毫升(ml)的反應瓶中依序加入1〇〇克雙 酚A型環氧樹脂(Bisphenol A，BPA)、240克氧化紹、〇.ι 克2苯基-1氰乙基咪唑(2PI-CN)、18克的4,4-二胺基-二苯 基砜(4,4DDS)。最後將200克前述10%的增韌劑溶液加入 前述1000毫升反應瓶中以完成製備比較實施例2之接著劑 組成物。 表一各接著劑之成份 X. 組別 \ 組成物 實 施 例 1 實 施 例 2 實 施 例 3 比較 實施例1 比較 實施例2 異氰酸脂樹脂 10 0 5 0 0 丁二烯-苯乙烯-二 乙稀苯樹脂 100 80 90 0 0 環氧化聚丁二烯樹 脂 0 10 0 0 0 12 201041994 酚醛樹脂 0 0 5 0 0 甲基醚化樹脂 3 10 0 0 0 雙酚A型環氧樹脂 (BPA) 0 0 0 100 100 雙酚F型環氧樹脂 (BPF) 0 0 0 0 100 羧基化丁腈橡膠 (CTBN) 0 0 0 20 60 聚乙烯縮甲醛 (KS-1) 5 10 10 20 60 丁腈橡膠(NBR) 5 5 10 0 0 丁酮溶劑 150 160 170 180 240 2苯基-1氰乙基咪 唑(2PI-CN) 0 0 0 0.1 0.1 過氧化二異丙苯 (DCP) 0.5 1 2 0 0 盼醒·硬化劑 (GPH78) 5 8 0 0 0 4,4-二胺基-二苯基 砜(4,4DDS) 0 0 0 18 18 氧化鋁 50 150 100 140 240 奈米矽化物 15 25 2 0 0 接著劑的性質測試 為了測試接著劑組成物所形成接著劑層之特性，將上 13 201041994 述實施例卜2、3及比較實施例卜2所製成之接著劑組成 物塗佈於厚度15μιη的聚醯亞胺薄膜上壓於銅箔表面以185 。(：的溫度進行烘烤一小時之後，所製得試片供測試其物性。 接著，對上述接著劑層試片進行玻璃轉移溫度Polymer, LCP), polyethylene terephthalate (PET), polyethylene phthalate 260 (Polyethylene-2, 6-naphthalate, PEN) and polytetraethylene The fluoroethylene layer 270 (Polytetrafluoroethylene, PTFE), and the subsequent layers 210 and 220 formed of the foregoing adhesive composition are respectively located on the lower layer of the liquid crystal laminate 2 〇〇. The following specific examples are intended to be merely illustrative, and are not intended to limit the scope of the disclosure. In the absence of further elaboration, it is common for those skilled in the art to make the best use of the present invention based on the description herein. The formulation of the subsequent agent is a series of formulations of the adhesive compositions of Examples 1, 2 and 3 of the present invention and Comparative Examples 1 and 2. Example 1 First, a toughening agent of 5 g of KS-1, 5 g of NBR and 80 g of a copolymer of monobutadiene-phenethyl hydrazine-diethyl benzene was dissolved in 150 g of methyl ethyl ketone (ΜΕΚ). And performing a prepolymerization at a temperature ranging from about 60 to about 150 ° C and a time ranging from about 0.5 hours to about 4 hours to prepare a KS1-NBR MEK toughening agent solution, wherein the KS_i system A product of p〇iyVinyi butyral (PVB) produced by Sekisui. Thereafter, 10 g of isocyanate resin, 3 g of methyl etherified resin, and 0.5 g of Dicumyl peroxide (DCP) were sequentially added to a 1000 ml (ml) reaction flask. 5 g of phenolic hardener GPH78, 50 g of spherical alumina and 15 g of nano-telluride. Finally, 100 g of the aforementioned 10% toughening agent solution was added to the aforementioned 1 毫 reaction flask to complete the adhesive composition of Preparation Example 1. 201041994 Example 2 First, a toughening agent 10 g KS-1, 5 g NBR and 80 g of a monobutylene-ethylene-ethylene benzene copolymer were dissolved in 160 g of methyl ethyl ketone (methyl • pool 1 ket 〇ne, MEK), and a prepolymerization reaction, the temperature range is from about 60 to about 150 ° C and the time range is between about 0.5 hours to about 4 hours to prepare the KS1-NBR MEK toughening Solution solution. Thereafter, 1 gram of epoxidized polybutadiene resin, 10 grams of methyl etherified resin, and 1 gram of dicumyl peroxide were added to a 1000 ml (ml) reaction flask. , DCP) '8 grams of phenolic hardener GPH78, 150 grams of spherical alumina and 25 grams of nano-telluride. Finally, 1 g of the aforementioned toughening agent solution was added to the aforementioned 1000 ml reaction bottle to complete the adhesive composition of Preparation Example 2. Example 3 First, a toughening agent 10 g of KS-1, 10 g of NBR and 90 g of a butadiene-styrene-divinylbenzene copolymer were dissolved in 17 g of methyi ethyl ketone (MEK). A prepolymerization is carried out having a temperature in the range of from about 60 to about 150 ° C and a time ranging from about 0.5 hours to about 4 hours to prepare a KS1-NBR MEK toughening agent solution. Thereafter, 5 g of isocyanate resin, 5 g of phenolic resin, 2 g of Dicumyl peroxide (DCP), 100 g of ball were sequentially added to a 1000 ml (ml) reaction flask. Type alumina and 2 grams of nano-halide. Finally, 100 g of the aforementioned 10% toughening agent solution was added to the aforementioned 1 ml-ml reaction bottle to complete the adhesive composition of Preparation Example 3. Comparative Example 1. 20 g of the extender KS-1 was first dissolved in 180 g of methyl ethyl ketone (MEK) to prepare a 10% KS1-MEK extender solution. 11 After 201041994 'In a 1000 ml (ml) reaction flask, sequentially add 100 g of Bisphenol A (BPA), 140 g of Oxide, 〇1 g of 2 phenyl-1 cyanoethyl Imidazole (2PI-CN), 18 g of 4,4-diamino-diphenylsulfone (4,4 DDS). Finally, 200 g of the aforementioned 10% toughening agent solution was added to the above 1000 ml reaction bottle to complete the preparation of the adhesive composition of Comparative Example 1. Comparative Example 2 60 g of the toughening agent KS-1 was first dissolved in 240 g of methyl ketone ethyl ketone (MEK) to prepare a 10% KS1-MEK toughening agent solution. Then, in a 1000 ml (ml) reaction bottle, 1 g of bisphenol A epoxy resin (Bisphenol A, BPA), 240 g of oxidized Shao, 〇. Imidazole (2PI-CN), 18 grams of 4,4-diamino-diphenyl sulfone (4,4 DDS). Finally, 200 g of the aforementioned 10% toughening agent solution was added to the aforementioned 1000 ml reaction flask to complete the preparation of the adhesive composition of Comparative Example 2. Table 1. Composition of each adhesive X. Group\Composition Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Isocyanate resin 10 0 0 0 0 Butadiene-styrene-II Dilute benzene resin 100 80 90 0 0 Epoxidized polybutadiene resin 0 10 0 0 0 12 201041994 Phenolic resin 0 0 5 0 0 Methyl etherification resin 3 10 0 0 0 Bisphenol A type epoxy resin (BPA) 0 0 0 100 100 Bisphenol F-type epoxy resin (BPF) 0 0 0 0 100 Carboxylated nitrile rubber (CTBN) 0 0 0 20 60 Polyvinyl formal (KS-1) 5 10 10 20 60 Nitrile rubber ( NBR) 5 5 10 0 0 Butanone Solvent 150 160 170 180 240 2Phenyl-1 cyanoethylimidazole (2PI-CN) 0 0 0 0.1 0.1 Dicumyl peroxide (DCP) 0.5 1 2 0 0 · Hardener (GPH78) 5 8 0 0 0 4,4-Diamino-diphenylsulfone (4,4DDS) 0 0 0 18 18 Alumina 50 150 100 140 240 Nano Telluride 15 25 2 0 0 Next Property test of the agent In order to test the characteristics of the adhesive layer formed by the adhesive composition, the adhesive composition prepared in the above Examples 2, 3 and 3 of Comparative Example 2, 2010 and Comparative Example 2 was applied to a polymer having a thickness of 15 μm. The ruthenium imide film was pressed against the surface of the copper foil by 185 Å. After the temperature was baked for one hour, the test piece was prepared for testing the physical properties. Next, the glass transition temperature of the above-mentioned adhesive layer test piece was carried out.
transition temperature ’ Tg)、剝離強度、介電常數(d=lectric C〇nStant，Dk)及介電損失(dielectric loss，Df)測試。介電常 數為材料可儲存電能的特性，介電損失則為材料損失電能 的性質，高介電常數及低介電損失之接著劑則有助於運= 於電子元件上。玻璃轉移溫度可利用熱示差掃瞄卡量計 (Differential Scanning Calorimeter)來量測’而剝離強度的 測試方式為測試銅箔與聚醯亞胺薄膜間的剝離情形。而介 電常數與介電損失的測試則是將前述試片以頻率為i Mhz 的條件進行測試。其結果係詳列於表二。Transition temperature 'Tg), peel strength, dielectric constant (d = lectric C〇n Stant, Dk) and dielectric loss (Df) test. The dielectric constant is the property of the material to store electrical energy, the dielectric loss is the nature of the material's loss of electrical energy, and the high dielectric constant and low dielectric loss of the adhesive helps to transport the electronic component. The glass transition temperature can be measured using a Differential Scanning Calorimeter, and the peel strength is measured by testing the peeling between the copper foil and the polyimide film. The dielectric constant and dielectric loss were tested by testing the test piece at a frequency of i Mhz. The results are detailed in Table 2.
表一，據本發明實施例所完成之，著質測試 玻璃轉移溫 度 T“°c) 實施例 1 108 實施例2 80 實施例3 44 剝離強度 1.04 0.97 0.85 (kgf/cm2) Df(l Mhz) 0.0054 0.056 0.0061 Dk (1 Mhz) 3.43 3.45 3.63 比較實 施例 60 0.75 0.03 3.82 比較實施 ^1_2 50 0.81 0.0287 3.62 由表二可知，本發明實施例所述之接著劑組成物，相 較於比較實施例而言，具有較高的玻璃轉移溫度。如此一 來，可使其所製作之覆金屬積層板具有良好的熱穩定性。 14 201041994 此外，上述接著劑組成物所製成之覆金屬積層板，亦具有 低的介電損失（Df)，可避免通電時因過多的電流轉為熱 能，進而導致覆金屬積層板過熱的問題產生。在剝離強度 ' 的性質測試上，藉由本發明中的組成物成份的調整，相較 於比較實施例而言，也具有較佳的接著能力。在介電常數 Dk與介電損失Df的測試上，實施例1、2、3的接著劑組 成物同樣具有低於比較實施例接著劑的介電損失，且有高 於比較實施例中接著劑組成物的介電常數。由此可知在實 0 施例中所述的接著劑組成物為一高介電常數與低介電損失 的材料。 綜上所述，本發明之接著劑組成物，不但具有較高之 玻璃轉換溫度及介電常數，且熱膨脹係數亦較低，安定性 佳。本發明中的接著劑組成物具有低的介電損失(Df)，可 避免通電時因過多的電流轉為熱能，進而導致過熱的問題 產生。 雖然本發明已以一較佳實施例揭露如上，然其並非用 q 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍内，當可作各種之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 為讓本發明之上述和其他目的、特徵、優點與實施例 能更明顯易懂，所附圖式之詳細說明如下： 第1圖係繪示依照本發明之一實施例之覆金屬積層板 之剖面示意圖。 第2圖係繪示依照本發明之一實施例之液晶積層板之 15 201041994 剖面示意圖。 【主要元件符號說明】 • 100 :雙面覆金屬基積層板 120:硬化接著層 140:第一金屬箔 160:第二金屬箔 200 :液晶積層板 210、220 :接著層 230 :聚亞醯胺層 240 :液晶高分子層 250 :聚對苯二曱酸乙二醇酯層 0 260 :聚萘二曱酸乙二酯層 270:聚四氟乙烯層Table 1, according to the embodiment of the present invention, the quality test glass transition temperature T "°c) Example 1 108 Example 2 80 Example 3 44 Peel strength 1.04 0.97 0.85 (kgf/cm2) Df (l Mhz) 0.0054 0.056 0.0061 Dk (1 Mhz) 3.43 3.45 3.63 Comparative Example 60 0.75 0.03 3.82 Comparative Example ^1_2 50 0.81 0.0287 3.62 It can be seen from Table 2 that the adhesive composition described in the examples of the present invention is compared with the comparative example. In other words, the metal-clad laminate produced by the method has good thermal stability. 14 201041994 In addition, the metal-clad laminate made of the above-mentioned adhesive composition is also It has a low dielectric loss (Df), which can avoid the problem of overheating of the metal-clad laminate due to excessive current being converted into heat during energization. The composition of the composition in the present invention is tested on the properties of the peel strength. The adjustment has better adhesion ability than the comparative example. On the test of dielectric constant Dk and dielectric loss Df, the adhesive compositions of Examples 1, 2, and 3 are the same. It has a lower dielectric loss than the adhesive of the comparative example, and has a higher dielectric constant than the composition of the adhesive in the comparative example. Thus, it can be seen that the adhesive composition described in the embodiment is a high medium. The material having the electric constant and the low dielectric loss. In summary, the adhesive composition of the present invention not only has a high glass transition temperature and a dielectric constant, but also has a low thermal expansion coefficient and good stability. The adhesive composition has a low dielectric loss (Df), which can avoid the problem of overheating due to excessive current being converted into thermal energy during power-on. Although the present invention has been disclosed above in a preferred embodiment, it is not The present invention is defined by the following claims, and the scope of the present invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS [0009] The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; A schematic cross-sectional view of a metallized laminate according to an embodiment of the present invention. Fig. 2 is a cross-sectional view of a liquid crystal laminate according to an embodiment of the present invention. Metal-based laminate board 120: hardened back layer 140: first metal foil 160: second metal foil 200: liquid crystal laminates 210, 220: adhesive layer 230: polyammonium layer 240: liquid crystal polymer layer 250: polyparaphenylene Ethylene glycol dicarboxylate layer 0 260 : polyethylene naphthalate ethylene glycol layer 270: polytetrafluoroethylene layer
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