1378981 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，高分子保護臈層用 • 於提供保護的功能’而接著劑膜層則用於黏合在電路板 上奇膠膜在商化時，通常會再貼合一層離型紙於接著 劑膜層上。 ^1378981 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] 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 layer for providing a protective function'. The film layer is used to bond to the circuit board. When the gelatin film is commercialized, a layer of release paper is usually attached to the adhesive film layer. ^
，背膠膜位於電路板層與層之間 用以作為電路板的保護膜。在印刷電路 及高温製程，因此背膠膜需要有相 由於背膠膜的高分子保護膜一般多選用 亞胺，因此在熱穩定性例如玻璃轉 數的改良上，就需由接著劑的改良方向The adhesive film is located between the circuit board layer and the layer to serve as a protective film for the circuit board. In the printed circuit and high-temperature process, the adhesive film needs to have a phase. Because of the polymer protective film of the adhesive film, the imide is generally used. Therefore, in the improvement of thermal stability such as glass rotation, it is necessary to improve the adhesive.
環氣樹脂接著劑為 目前所需 係位於多層電路板中的層與層之 #膠膜需具有較低的介電係數與介 ι-^ι> 具有良好的熱穩定性 傳遞的延遲與能量的損失。因此， 十生以及較低介電係數與介電損失的 【發明内容】 目的係提供一種接著劑之組成物， 因此，本發明之 1378981 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35phr〜230phr重量之具有半互穿型網狀結構之聚合物、 lOphr〜55phr重量份之聚酯樹脂以及lphr〜35phl·重量份之 橡膠彈性體’本發明之phr係指重量份(parts per hundred)， 其中該具有半互穿型網狀結構之聚合物係由3〇phr〜150phr 重里之丁二烯_苯乙烯-二乙婦苯共聚物、5phr〜80phr重量份 增勤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_二乙烯苯共聚 物 增初劑及一觸媒。接著進行一預聚合反應以得一具 有半互牙型網狀結構之聚合物。最後加入聚酯樹脂以及橡 膝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 酿，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 1378981 板，至少包含一基板、二硬化接著層以及一第一金屬箔與 一第二金屬箱。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破 Φ 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、 _ lOphr〜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-苯乙稀-二 乙稀苯共聚物、5phr~80phr增勃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。 前述之增勃劑（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 1378981 丁腈橡膠(NitrileButadiene Rubber)。如果前述增勒劑之含 .量未滿^p則會使得接著劑組成物之㈣不足，如果增 '韋刃劑^置局於7〇% ’則會使得接著劑組成物对熱性下降。 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3〇phr，則介電常數無法小於 3.7，且介電損失無法小於〇 〇〇8，如果前述之具有半互穿 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-二苯基研(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 機填充劑。藉由無機填充物的加入，可提昇接著劑的尺寸 女疋性與影響接著劑組成物的熱傳係數。無機填充劑可為 愈1氧化銘、氧化紹或其組合。 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 媒過氣化二異丙苯(Dicumyl Peroxide, DCP)或一級胺或二 1378981 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，先將増韌劑以及一丁二烯_苯乙烯_二乙烯笨共聚物溶 於丁酮（Methyl_Ethyl Ketone ; MEK)溶劑中，並進行一預聚 合反應，配製成增韌劑溶液。之後，在另一反應瓶中加入 聚酯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 航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 型層可由聚對笨二曱酸乙二脂（p〇lyethylene 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 對苯一曱酸乙二酯，再將溶劑去除，同時將pET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，膜具有一半互穿形網狀結構。在使用上，可直接將此 接^劑薄膜夾在欲固著的固體間，再以185。〇的温度進行 熱壓1小時，即可形成位於兩固體間的接著劑層。除了以 塗佈的方式形成接著劑薄膜外，亦可將玻纖基材浸泡於前 述接著劑組成物中，使接著劑組成物包覆玻纖基材。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 1378981 成具有玻纖基材之接著膠片。 純定實施射’上述之接著劑組成物或包含接著劑 •.組成物的接著膠月可用以製作雙面覆金屬積層板，其具有 ' —基板、二硬化接著層、第—金屬荡以及第二金屬羯。二 硬^接著層分別位於基板相對之兩側面上，硬化接著層係 由刖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。第一金屬箱與第二金屬羯分別覆蓋於硬化接著層 月對基板之表面，並進行熱壓，以黏著於二硬化接著層上。 • 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组成物的接著膠片硬化而成。第二金 屬箔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 # 基材亦可直接作為雙面覆金屬積層板100取代基板的支撐 基材’以製作雙面覆金屬積層板100，其包含第一金屬箱 140、一硬化接著層丨2〇與第二金屬箔16〇。硬化接著層12〇 位於第一金屬箔140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16〇位於 硬化接著層120背對第一金屬箔140之表面上。 第2圖所示為本發明之一實施例之液晶積層板2〇〇之 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210，220，中間層依序為聚亞醯 fe：(Polyimide，PI)層 230、液晶兩分子層 240(Liquid Crystal 1378981The epoxy resin adhesive is the layer and layer currently required to be in the multilayer circuit board. The film has a lower dielectric constant and dielectric properties. It has a good thermal stability transfer delay and energy. loss. Therefore, the tenth and the lower dielectric constant and the dielectric loss are aimed at providing a composition of an adhesive. Therefore, the 1378981 of the present invention meets the requirements of the process, and has both thermal stability and lower dielectric properties. The electrical coefficient and dielectric loss' can overcome or ameliorate the problems of the prior art described above. According to the above object of the present invention, there is provided a composition comprising an adhesive comprising 35 phr to 230 phr of a polymer having a semi-interpenetrating network structure, 10 phr to 55 phr parts by weight of a polyester resin, and 1 phr to 35 ph. Elastomer 'The phr of the present invention refers to parts per hundred, wherein the polymer having a semi-interpenetrating network structure is from 3 phr to 150 phr of butadiene styrene-diphenyl benzene. The copolymer, 5 phr to 80 phr parts by weight of the attendant, and a suitable amount of peroxide catalyst are obtained by a prepolymerization reaction, and the molecular weight of the polymer of the semi-interpenetrating network structure is between 350 and 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-divinylbenzene copolymer prepolymer and a catalyst. A prepolymerization is then carried out to obtain a polymer having a semi-particular network structure. Finally, a polyester resin and a rubber knee 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 binder, an amine substrate, an adhesive layer on the 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 1378981 comprising at least one substrate, two hardened back layers, and a first metal foil and a second metal tank. 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 back layers facing away from 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 understood 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, _10 phr to 55 phr of a polyester resin, and 1 phr to 35 phr. Rubber elastomer. The phr of the present invention refers to parts per hundred. The polymer having a semi-interpenetrating network structure is prepolymerized from 30 phr to 150 phr of butyl di- styrene-diethylene benzene copolymer, 5 phr to 80 phr boling agent and an appropriate amount of peroxide catalyst. The reaction is obtained, 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 modify 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 1378981 Nitrile Butadiene Rubber. If the content of the above-mentioned additive is less than (p), the (4) of the adhesive composition is insufficient, and if the addition of the "average agent" is set to 7%, the thermal conductivity of the adhesive composition is lowered. The 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 phr, the dielectric constant cannot be less than 3.7, and the dielectric loss cannot be less than 〇〇〇8, if the foregoing has a semi-interpenetrating mesh A polymer content of more than 15 phr of the structure results in an inability to process the following 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 GpH 78 or 4,4-diamino-diphenyl (4,4-DDS) or a combination thereof. In a particular embodiment, the adhesive composition of the present invention may further comprise an inorganic filler. 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 oxidized, oxidized or a combination thereof. In a particular embodiment, the adhesive composition of the present invention may further comprise a catalyst for accelerating the reaction. Catalysts suitable for use in the present invention comprise peroxidic catalyst pervaporated Dicumyl Peroxide (DCP) or a primary amine or a secondary 1378981 amine catalyst. 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-diethylene stear copolymer are first dissolved in a solvent of methyl ethyl ketone (Methyl_Ethyl Ketone; MEK), and A prepolymerization reaction is carried out to prepare a toughening agent solution. Thereafter, a polyester resin and a rubber elastomer were added to another 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 vessel to complete the preparation of the dispersed adhesive composition. In a specific embodiment, the above-mentioned adhesive composition can be applied to a polyimide substrate, and then the solvent can be removed to form a backing film. When the product is commercialized, it is only required to be an adhesive. The surface may be further coated with a release layer which may be made of p〇lyethylene Terephthalate (PET). - in a specific embodiment, the above-mentioned adhesive "can be applied to polyethylene terephthalate, and the solvent is removed, while the pET is removed, thereby forming an adhesive having the present invention. An adhesive film of the raw material, the adhesive having a half interpenetrating network structure. In use, the film can be directly sandwiched between the solids to be fixed, and then 185. The temperature of the crucible is subjected to hot pressing for 1 hour to form an adhesive layer between the two solids. In addition to forming an adhesive film by coating, the glass fiber substrate may be immersed in the above-mentioned adhesive composition to coat the glass fiber substrate with the adhesive composition. Thereafter, the glass substrate is removed and the solvent of the adhesive composition is removed to form 1378981 into a film having a glass substrate. Purely performing the above-mentioned adhesive composition or the adhesive comprising the adhesive composition can be used to make a double-sided metal-clad laminate having a 'substrate, a hardened adhesive layer, a first metal slab, and a Two metal bismuth. The two hard layers are respectively located on opposite sides of the substrate, and the hardened layer is formed by hard-pressing the composition of the adhesive or the film comprising the adhesive composition. The first metal case and the second metal bismuth are respectively covered on the surface of the hardened adhesive layer on the substrate, and are hot pressed to adhere to the second 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 the following film comprising the adhesive composition. The second metal foil is 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 glass fiber substrate in the foregoing film may directly replace the support substrate of the substrate as the double-sided metal-clad laminate 100 to form the double-sided metal-clad laminate 100, which includes the first metal case. 140, a hardening layer 2 〇 and a second metal foil 16 〇. The hardened adhesive layer 12 is placed on the first metal foil 140 and is cured by the aforementioned adhesive composition or an adhesive film comprising the adhesive composition. The second metal foil 16 is located on the surface of the hardened back layer 120 facing away from the first metal foil 140. Fig. 2 is a cross-sectional view showing a liquid crystal laminate 2 according to an embodiment of the present invention. In a specific embodiment, the foregoing adhesive composition may form an adhesive layer 210, 220 of the liquid crystal laminate 200, and the intermediate layer is sequentially a polyimide (PI) layer 230 and a liquid crystal two molecular layer 240 (Liquid Crystal). 1378981
Polymer, LCP)、聚對笨二曱酸乙二醇酯層 250(Polyethylene • Terephthalate，PET)、聚萘二曱酸乙二酯層 260 • (P〇lyethylene-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 • 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。 接著劑之配劁 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克的一丁二稀-本乙稀·一乙稀本共聚物浴解於150克的丁嗣（methyl ethyl 瞻 ketone，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_1係為 Sekisui公司所生產的一種聚乙烯縮丁醛（p〇lyvinyl 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克的曱基醚化樹脂、 〇.5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1000 毫反應瓶中以完成製備實施例1之接著劑組成物。 1378981 實施例2 先將增韌劑10克KS-1、5克NBR與80克的一丁二 烯-笨乙烯-二乙烯苯共聚物溶解於160克的丁 _(methyi ethyl ketone，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0.5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10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 # (Dicumyl peroxide，DCP)、8 克的酚醛硬化劑 gph78、150 克球型氧化紹及25克的奈米石夕化物。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-笨乙烯-二乙缔苯共聚物溶解於170克的丁鲷（methyi ethyl ketone ’ MEK) ’並進行一預聚合反應，其溫度範圍 鲁 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克的異氣酸脂樹 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克的奈米石夕化物。 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。 比鲛實施例1 . 先將20克增勃劑KS-1溶解於180克的丁嗣(methyl ethyl ketone ’ MEK) ’ 以製備 1 〇%的 KS 1-MEK 増勃劑溶液。 11 1378981 之後’在一個1000毫升(ml)的反應瓶中依序加入100克雙 酚A型環氧樹脂（Bisphenol A， BPA)、140克氧化鋁、〇」 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 ethyl ketone ’ MEK)，以製備 1 〇% 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100克雙 酚A型環氧樹脂(Bisphenol A, BPA)、240克氧化鋁' 〇] 克2苯基-1氰乙基咪唑(2?1<1^)、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 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 異乱酸脂樹脂 10 0 5 0 0 丁二烯-苯乙烯-二 乙烯苯樹脂 100 80 90 0 0 環氧化聚丁二烯樹 脂 0 10 0 0 0 12 [S] 1378981 酚醛樹脂 0 0 5 0 0 曱基醚化樹脂 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f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 酌' 酸硬化劑 (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 1378981 f施例i、2、3及比較實施例i、2所製成之接著劑組成 ,物塗佈於厚度的聚醯亞胺薄膜上壓於鋼箔表面以185 1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（giass transition temperature ’ Tg)、剝離強度、介電常數(di^ectric constant ’ 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用 • 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1 Mhz 的條件進行測試。其結果係詳列於表二。 表二依據本發明實施例所完成之接著jj的性質測試 實施例 1 實施例2 實施例3 比較實 施例1 比較實施 例2 玻璃轉移溫 度 Tg (0C) 108 80 44 60 50 剝離強度 (kgf/cm2) 1.04 0.97 0.85 0.75 0.81 Df(l Mhz) 0.0054 0.056 0.0061 0.03 0.0287 Dk (1 Mhz) 3.43 3.45 3.63 3.82 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。 1378981 . 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= 於比較實施例而言，也具有較佳的接著能力。在介電常數Polymer, LCP), Polyethylene Terephthalate (PET), Polyethylene naphthalate 260 • (P〇lyethylene-2,6-naphthalate, PEN) and Polytetrafluoroethylene (PTFE) 270 (Polytetrafluoroethylene, PTFE), the subsequent layers 210, 220 formed by the foregoing adhesive composition are respectively located on the lower layer of the liquid crystal laminate 2 〇〇. The following specific examples are to be considered as illustrative only 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 invention herein. The formulation of the subsequent compositions 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 monobutylene-ethylidene-ethylene copolymer copolymer were dissolved in 150 g of methyl ethyl ketone (methyl ethyl ketone, MEK), and a prepolymerization reaction is carried out 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 KS_1 It is a polyvinyl butyral (PVB) product produced by Sekisui. Then, in a 1000 ml (ml) reaction flask, 10 g of isocyanate resin, 3 g of mercaptoetherification resin, and 5 g of dicumyl peroxide (DCP) were sequentially added. 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 above 1000 ml reaction flask to complete the adhesive composition of Preparation Example 1. 1378981 Example 2 First, a toughening agent 10 g of KS-1, 5 g of NBR and 80 g of a butadiene-stuppyrene-divinylbenzene copolymer were dissolved in 160 g of methyi ethyl ketone (MEK). A prepolymerization is carried out 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 toughener solution. Thereafter, 10 g of epoxidized polybutadiene resin, 10 g of methyl etherified resin, and 1 g of dicumyl peroxide were sequentially added to a 1000 ml (ml) reaction flask. DCP), 8 grams of phenolic hardener gph78, 150 grams of spherical oxide and 25 grams of nano-stone. Finally, 1 gram 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-stuppyrene-diethylbenzene copolymer were dissolved in 170 g of methyi ethyl ketone 'MEK'. A prepolymerization is carried out at a temperature ranging from about 60 to about 150 ° C and a time ranging from about 5 hours to about 4 hours to prepare a KS1-NBR MEK toughening agent solution. Then, in a 1000 ml (ml) reaction bottle, 5 g of isophobic acid resin, 5 g of phenolic resin, 2 g of Dicumyl peroxide (DCP), 100 g of ball were sequentially added. Type alumina and 2 grams of nano-stone. 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 bolster KS-1 was first dissolved in 180 g of methyl ethyl ketone 'MEK' to prepare a 1% by mass solution of KS 1-MEK sputum. 11 1378981 Afterwards, '100 bis bisphenol A type epoxy resin (Bisphenol A, BPA), 140 g of alumina, 〇 gram 2 phenyl-1 cyanoethyl group were sequentially added in a 1000 ml (ml) reaction flask. 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 1. Comparative Example 2 60 g of the toughening agent KS-1 was first dissolved in 240 g of methyl ethyl ketone 'MEK' to prepare a 1% by mass solution of KS1-MEK toughening agent. Thereafter, 100 g of bisphenol A type epoxy resin (Bisphenol A, BPA), 240 g of alumina '〇' g of 2-phenyl-1 cyanoethyl imidazole were sequentially added to a 1000 ml (ml) reaction flask. 2?1 <1^), 18 g of 4,4-diamino-diphenylsulfone (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 component of the adhesive Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Isotonic acid resin 10 0 0 0 0 Butadiene-styrene-divinylbenzene resin 100 80 90 0 0 Epoxidized polybutadiene resin 0 10 0 0 0 12 [S] 1378981 Phenolic resin 0 0 5 0 0 Mercapto 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 Polyethylene acetal (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 Acid 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 composition of the adhesive, the composition of the adhesive prepared in the above examples 1 i, 2, 3 and Comparative Examples i and 2 was applied to the thickness. Polyimine film After pressure on the foil surface at a temperature of 1851 steel was baked one hour 'prepared test pieces for testing physical properties thereof. Next, the above-mentioned adhesive layer test piece was subjected to a glass transition temperature (giass transition temperature 'Tg), a peel strength, a dielectric constant (di^ectric constant ' Dk), and a dielectric loss (Df) test. The dielectric constant is the property of the material to store electrical energy, and the dielectric loss is the property of the material to lose electrical energy. The high dielectric constant and low dielectric loss of the adhesive can be applied to electronic components. 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 test of dielectric constant and dielectric loss was carried out by testing the test piece at a frequency of 1 Mhz. The results are detailed in Table 2. Table 2 Tests on the properties of subsequent jj performed in accordance with an embodiment of the present invention Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Glass transition temperature Tg (0C) 108 80 44 60 50 Peel strength (kgf/cm2) 1.04 0.97 0.85 0.75 0.81 Df (l Mhz) 0.0054 0.056 0.0061 0.03 0.0287 Dk (1 Mhz) 3.43 3.45 3.63 3.82 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. That is, it has a high glass transition temperature. In this way, the metal-clad laminate produced can have good thermal stability. 1378981. In addition, the metal-clad laminate made of the above-mentioned adhesive composition also 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 energy during energization. produce. In the peel strength/test of properties, the phase of the composition of the present invention was adjusted to have a better adhesion ability in the comparative example. Dielectric constant
Dk與介電損失Df的測試上，實施例丨、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，且有内 於比較實施例中接著劑組成物的介電常數。由此可知在^ • 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。 ' 综上所述’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。 ，然本發明已以一較佳實施例揭露如上，然其並非用 |以限定本發明’任何熟習此技藝者，在不脫離本發明 神=$巳圍内’當可作各種之更動與潤飾，因此本發明 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】 能更月之上述和其他目的、特徵、優點與實施例 月匕更明顯易Μ，所附圖式之詳細說明如下： u係繪示依照本發明之一實施例之覆金屬積 <►刮面不意圖。 第2圖係繪示依照本發明之一實施例之液晶積層板之 15 S3 1378981 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 φ 260 :聚萘二曱酸乙二酯層 270:聚四氟乙烯層 [S]In the tests of Dk and dielectric loss Df, the adhesive compositions of Examples 丨, 2, and 3 also had lower dielectric loss than the adhesive of the comparative example, and there was a composition of the adhesive composition in the comparative example. Electric constant. From this, it is understood that the adhesive composition described in the embodiment is a material having a high dielectric constant and a low dielectric loss. The above-mentioned adhesive composition of the present invention has not only a high glass transition temperature and a dielectric constant, but also a low coefficient of thermal expansion and good stability. The adhesive composition of the present invention has a low dielectric loss (Df), which avoids the problem of overheating due to excessive current being converted into heat during energization. However, the present invention has been disclosed in a preferred embodiment as above, but it is not intended to limit the present invention to anyone skilled in the art, and can make various changes and refinements without departing from the invention. Therefore, the scope of the invention is defined by the scope of the patent application. ', BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, advantages and embodiments of the present invention can be made more obvious. The detailed description of the drawings is as follows: u is an embodiment according to the present invention. The metal coating <► shaving surface is not intended. Fig. 2 is a cross-sectional view showing a liquid crystal laminate according to an embodiment of the present invention, 15 S3 1378981. [Description of main component symbols] : 100 : double-sided metal-clad laminate board 120 : hardened adhesive layer 140 : first metal foil 160 : second metal foil 200 : liquid crystal laminate 210 , 220 : adhesive layer 230 : polytheneamine Layer 240: liquid crystal polymer layer 250: polyethylene terephthalate layer φ 260: polyethylene naphthalate layer 270: polytetrafluoroethylene layer [S]
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