201209124 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及電路板技術領域，尤其涉及一種應用於電路 板生產並具有電磁遮罩作用之膠片及其製作方法。 【先前技術】 [0002] [0003] [0004] 隨著科學技術之進步，印刷電路板於電子領域得到之廣 泛之應用。關於電路板之應用請參見文獻Takahashi A. Ooki, N. Nagai, A. Akahoshi, H. Muk〇h ^201209124 VI. Description of the Invention: [Technical Field] The present invention relates to the field of circuit board technology, and more particularly to a film applied to a circuit board and having an electromagnetic shielding effect and a manufacturing method thereof. [Prior Art] [0002] [0004] With the advancement of science and technology, printed circuit boards have been widely used in the field of electronics. For the application of the circuit board, please refer to the literature Takahashi A. Ooki, N. Nagai, A. Akahoshi, H. Muk〇h ^
Wajima, M. Res. Lab, High density multii〇 iaYer printed circuit board for HITAC M-880 ， iEeeWajima, M. Res. Lab, High density multii〇 iaYer printed circuit board for HITAC M-880 , iEee
Trans, on Components, Packaging, and Manu facturing Technology， i992， 14(4): 418〜425 隨著電路板產品層數增加’電路板產品於實際工作時 往往會產生電磁干擾現象，影響電路板訊號傳送。這樣 ，於電路板產品中需要設置電磁遮罩層。目前，採用 電磁遮罩層通採用厚度較小之不錢鋼片制你，妝 衣rF將不鱗 鋼片設置於電路板產品之表面之覆簟骐上，從而起到 磁遮罩之作用。然而，不銹鋼片之重量較大從 電 了電路板產品之重量。並且不_片之撓折性較差^ 用不錢㈣製作之電磁遮罩層影響㈣電路板撓折^ 。由於不錄鋼片之價格較高，增加了電路板之生產成本 【發明内容】 板以起到電磁遮罩 0992049513-0 有鑑於此，提供一種能夠應用於電路 作用之膠片及其製造方法實屬必要。 099128158 表單編號A0101 第4頁/共20頁 201209124 [0005] [0006] Ο [0007] Ο 以下將以實施例說明一種具有電磁遮罩作用之膠片及其 製作方法。 一種膠片’其包括離型基材層及環氧樹脂複合材料^ 所述離型基材層具有第一離型表面，所述環氧樹妒複人 材料層形成於所述第一離型表面上。所述環氧樹於複人 材料廣由壤氧樹脂複合材料組成。所述環氧樹脂複0 料包括端羧基聚合物改性之環氧樹脂、奈米碳管及無機 分散材料，所述奈米碳管於所述環氧樹脂複合材料中所 佔之重量百分比為4. 6 %至16 V。所述環氧樹脂複合材料之 黏度為60000厘泊矣*7 5 0 0 0盧泊。 π '縣蠢..蠢零心;; 一種膠片之製作方法，包括步騍：採用端羧基聚合物對 環氧樹脂進行改性以得到端羧基聚备物改性之環氧樹脂 ;將奈米碳管均勻分散於無機分散材料中，以得到奈米 碳管分散體；將所述端羧基聚合物改性之環氧樹脂與奈 米礙官分散體進行混合並研磨分散’以得到環氧樹脂複 合材料’所述奈米碳管於所述環氣樹脂複合材料所佔之 重量百分比為4. 6%至16% ;提供基材層，所述離型基 材層具有第一離型表面；將所述環氧樹脂複合材料塗佈 於絕緣基材層之第一離型表面形成環氧樹脂複合材料層 ;以及將所述環氧樹脂複合材料層半固化。 [0008] 相較於先前技術’本技術方案提供之膠片，其包括環氧 樹脂複合材料層，所述環氧樹脂複合材料層中具有分散 均勻之奈米碳官而具有電磁遮罩作用，所述璆片可直接 將其貼合於電路板之表面或者設置於多層電路板之内層 中，所述膠片具有電磁遮罩之作用。相較於不銹鋼片， 099128158 表單編號Α0101 第5頁/共20頁 0992049513-0 201209124 能夠增加柔性電路板之撓折性能，並且可降低電路板之 生產成本。本技術方案提供之膠片之製作方法，能夠簡 單之製作出具有電磁遮罩作用之膠片。 【實施方式】 [0009] 下面結合實施例對本技術方案提供之具有電磁遮罩作用 之膠片及其製作方法進一步之詳細說明。 [0010] 請參閱圖1，本技術方案提供一種膠片100，其包括依次 堆疊之離型基材層110、環氧樹脂複合材料層120及離型 隔離層130。 [0011] 離型基材層110用於承載環氧樹脂複合材料層120。離型 基材層110可為PET離型膜，即其基材為PET，於基材之 一個或者兩個相對之表面上塗佈有矽油等材料而形成離 型表面。所述離型表面能夠能黏住形成於其上之環氧樹 脂複合材料層120，但又易於使離型基材層110與環氧樹 脂複合材料層120分離。本實施例中，離型基材層110採 用單面PET離型膜，其具有第一離型表面111。離型基材 層110之材料不限於本實施例中提供之PET離型膜，其亦 可為其他具有離型表面之材料，如離型紙等。所述離型 紙可為矽油紙或淋膜紙。 [0012] 離型隔離層130用於將保護環氧樹脂複合材料層120。當 生產之膠片100不需要運輸或長時間保存時，膠片100亦 可不包括離型隔離層130。離型隔離層130之材料可與離 型基材層110之材料形同，即其可為PET離型膜，其亦可 為其他具有離型表面之材料，如各種離型紙等。離型隔 離層130具有第二離型表面131，第二離型表面131與環 099128158 表單編號 A0101 第 6 頁/共 20 頁 0992049513-0 201209124 氧樹脂複合材料層120相互接觸，從而於進行 存過程中，當多層膠片100相互堆疊時，離韶 速輸成著儲 隔離層 可隔離相互接觸之膠片100以避免相互黏連。並且離型基 材層110及離型隔離層130於運輸及儲存過程中，亦可使 得環氧樹脂複合材料層120與外界隔離，防止環氛樹脂複 合材料層120被污染或者吸潮。 [0013] Ο 環氧樹脂複合材料層120用於起到電磁遮罩作用。環氧樹 脂複合材料層120之厚度可根據實際需要遮罩之電磁干擾 之強弱進行設定。環氧樹脂複合材料層120設置於離型基 材層110之第一離型表面lu及離型隔離層13〇之第二離 型表面131之間，其厚度約為8微米至微米。環氧樹脂 複合材料層120為半固化狀態。環氧樹脂複备材料層12〇 内之環氧樹脂複合材料包括端羧基聚合物改性之環氧樹 脂、奈米碳管、無機分散材料、硬化劑、催化劑溶劑 及消泡劑。Trans, on Components, Packaging, and Manu facturing Technology, i992, 14(4): 418~425 With the increase in the number of circuit board products, 'circuit board products often produce electromagnetic interference when they actually work, affecting board signal transmission. . Thus, an electromagnetic mask layer needs to be provided in the circuit board product. At present, the electromagnetic mask layer is made of a small thickness of steel, and the makeup rF is placed on the surface of the surface of the circuit board product to act as a magnetic mask. However, the weight of the stainless steel sheet is greater than the weight of the board product. And not _ piece of the flexibility is poor ^ with no money (four) made of electromagnetic shielding layer impact (four) circuit board deflection ^. Since the price of the unrecorded steel sheet is relatively high, the production cost of the circuit board is increased. [Invention] The board is used as an electromagnetic mask 0992049513-0. In view of this, a film which can be applied to a circuit and a manufacturing method thereof are provided. necessary. 099128158 Form No. A0101 Page 4 of 20 201209124 [0005] [0007] A film having an electromagnetic mask effect and a method of fabricating the same will be described below by way of embodiments. A film comprising a release substrate layer and an epoxy resin composite material, wherein the release substrate layer has a first release surface, and the epoxy resin layer is formed on the first release surface on. The epoxy tree is composed of a lytic resin composite material. The epoxy resin composite comprises a carboxyl group-modified epoxy resin, a carbon nanotube and an inorganic dispersion material, and the weight percentage of the carbon nanotube in the epoxy resin composite material is 4. 6 % to 16 V. The epoxy resin composite has a viscosity of 60,000 cps 矣*7,500 lux. π 'County stupid.. stupid zero heart;; a film manufacturing method, including the step: using a carboxyl terminated polymer to modify the epoxy resin to obtain a terminal carboxyl group modified epoxy resin; The carbon tube is uniformly dispersed in the inorganic dispersion material to obtain a carbon nanotube dispersion; the epoxy resin modified with the terminal carboxyl group is mixed with the nanoparticle dispersion and ground and dispersed to obtain an epoxy resin a 6% by weight of the carbon nanotubes of the composite material, wherein the weight of the carbon nanotubes is 4.6% to 16%; providing a substrate layer, the release substrate layer having a first release surface; Applying the epoxy resin composite material to the first release surface of the insulating substrate layer to form an epoxy resin composite layer; and semi-curing the epoxy resin composite material layer. [0008] Compared with the film provided by the prior art 'the present technical solution, which includes an epoxy resin composite layer having a uniformly dispersed nano carbon official layer and having an electromagnetic shielding effect, The ruthenium can be directly attached to the surface of the circuit board or disposed in the inner layer of the multilayer circuit board, and the film has the function of an electromagnetic mask. Compared with stainless steel sheets, 099128158 Form No. Α0101 Page 5 of 20 0992049513-0 201209124 It can increase the flexural performance of flexible boards and reduce the production cost of the board. The film produced by the technical solution can be simply fabricated into a film having an electromagnetic mask. [Embodiment] [0009] Hereinafter, a film having an electromagnetic mask function and a manufacturing method thereof provided by the present technical solution will be further described in detail with reference to the embodiments. Referring to FIG. 1, the present technical solution provides a film 100 comprising a release substrate layer 110, an epoxy resin composite layer 120, and a release spacer 130 which are sequentially stacked. [0011] The release substrate layer 110 is used to carry the epoxy resin composite layer 120. The release substrate layer 110 may be a PET release film, i.e., the substrate is PET, and a release surface is formed by coating a material such as eucalyptus oil on one or both of the opposite surfaces of the substrate. The release surface is capable of adhering to the epoxy resin composite layer 120 formed thereon, but is also susceptible to separating the release substrate layer 110 from the epoxy resin composite layer 120. In the present embodiment, the release substrate layer 110 employs a single-sided PET release film having a first release surface 111. The material of the release substrate layer 110 is not limited to the PET release film provided in this embodiment, and may be other materials having a release surface such as a release paper or the like. The release paper may be slick paper or coated paper. [0012] The release spacer 130 is used to protect the epoxy resin composite layer 120. The film 100 may also not include the release barrier 130 when the produced film 100 does not need to be transported or stored for long periods of time. The material of the release spacer 130 may be the same as the material of the release substrate layer 110, that is, it may be a PET release film, and may be other materials having a release surface such as various release papers and the like. The release liner 130 has a second release surface 131, and the second release surface 131 and the ring 099128158 Form No. A0101 Page 6 of 20 0992049513-0 201209124 The oxy-resin composite layer 120 is in contact with each other, thereby performing the deposit process. In the case where the multilayer film 100 is stacked on each other, the film is separated from the idle contact film by the idle speed to avoid mutual adhesion. Moreover, during the transportation and storage process, the release substrate layer 110 and the release spacer layer 130 can also isolate the epoxy resin composite material layer 120 from the outside to prevent the epoxy resin composite material layer 120 from being contaminated or moisture absorbing. [0013] The epoxy resin composite layer 120 is used to function as an electromagnetic mask. The thickness of the epoxy resin composite layer 120 can be set according to the actual electromagnetic interference of the mask. The epoxy resin composite layer 120 is disposed between the first release surface lu of the release substrate layer 110 and the second release surface 131 of the release spacer 13 and has a thickness of about 8 micrometers to micrometers. The epoxy resin composite layer 120 is in a semi-cured state. The epoxy resin composite material in the epoxy resin composite material layer 12 包括 includes a carboxyl group-modified epoxy resin, a carbon nanotube, an inorganic dispersion material, a hardener, a catalyst solvent, and an antifoaming agent.
[0014] G 所述端幾«合物改性之環氧娜騎氧樹脂與端幾基 聚合物發生絲合反錢之產物，即環氧樹脂末端之環 氧基與端It絲合物之末狀絲發生反應而生成一個 醋基，從而得到有包括交替之環氧樹脂重複單元及端叛 基聚合物之重複單元之聚合物。其中，環氧樹脂可為雙 紛A型環縫脂’料絲合物可為《聚丁二歸丙稀腈 (CTBN) °本實施例中’採用之環氧樹脂於未改性前之環 氧當量為則至195，優選為188，絲聚合物改性後之 環氧樹脂之環氧當量為323至脱，優選為如。端幾基 聚合物改性之環氣樹脂於縣職複合材料巾之重量百 099128158 表單編號A0101 第7頁/共20頁 0992049513-0 201209124 分比約為55%至65%，優選約為6〇%。 [0015] [0016] [0017] [0018] ，输繼罐聚合物改 合材料中所起到電磁遮罩作用。奈米礙管於複 米碳管之含ρ, I百分比為4.6%至16%。複合材料中奈 性能進行可根據實際需要得龍合材料之導電 多，環〜中奈米碳管之含量越 管之含量越少：電阻越小’複合材料中奈米碳 v 環氧樹脂複合材料之電阻越大。 無機分散持料限 句分佈於環氧樹^散奈米碳管，峨得奈米碳管可均 米黏土或者太米中。所述無機分散材料為奈 _，直罝f二粉。所述奈米黏土為2:1之頁石夕酸 > -可為蒙脫石（Montmo,illonite，分子式為 Χ 4~χΜδχ) Sl8O20(OH)4)、鐘蒙脫石（Hectorite ’分子式為MxUuuw。⑽v或者息石（ Saponue，分子式為^%⑶卜扎)九⑽)4)等 。其中，奈米碳管與無機分散材料之重量比為8至12比1 。所述無機分散材轉優選為奈米雲母粉。 所述硬化劑用於對複合材料起到硬化作用◊本實施例中 ，採用之硬化劑為雙氰胺（DiCyandiamine)，所述硬 化劑於環氧樹脂複合材料所佔之重量百分比約為5%。硬 化劑之用量應與端羧基聚合物改性之環氧樹脂相對應， 其中端幾基聚合物改性之環氧樹腊與硬化劑之重量比約 為13至14比1。 所述催化劑為2-十一烷基咪唑（2-Undecyl imidazole) 099128158 表單編珑A0101 第8頁/共20頁 0992049513-0 201209124 ’催化劑之含量與端縣聚合物改性之環氧樹脂之含量 相互對應。催化劑於環氧樹脂複合材射所佔 百 分含量約為〇.跑1%，優選級65%。所述溶劑為二匕 二醇單乙醚 W0)lethylenegiyeQii^ethyi ether 一⑻，所述溶劑於環氡樹脂複合材料中之含 量約為20%至25%，優選為24%。該溶劑用於溶解上述其 他組分，以形成均勻之液態分散料'。所述;肖泡劑用於 消除上述環氧樹脂複合材料中之泡沐，所述消泡劑於環 Ο [0019] 氧樹脂複合材料中之重量百^為2%m包劑可 為市售之台灣淳政公司生產之218311消泡劑。 優選地’帛氧樹脂複合材射，端缓基聚合物改性之環 yKy V ：! ... ,· 氧樹脂之重量百分含量約為6 〇:. 3 %，奈米碳管之重量百分 含量約為7· 8%，無機分散材料之重量百分含量約為〇. 6% ，硬化劑之重量百分含量約為4. 5%、催化劑之重量百分 含量約為0· 65%，溶劑之重量百分含量約_24. 3%，消泡 劑之重量百分含量約為1 85%。無機分散材料選用雲母粉 ❹ [0020] [0021] [0022] 。本實施例中環氧樹脂複合卞^料之黏度可達到6〇〇〇〇至 75000厘泊’其可方便地與電路板中覆蓋膜或者其他膠層 相互黏合。優選地’環氧樹脂複合材料之黏度約為7〇〇〇〇 厘泊。 本技術方案還提供一種所述具有電磁遮罩作用之膠片1〇〇 之製作方法，所述製作方法包括如下步驟： 第一步，製作所述環氧樹脂複合材料。 本實施例中述環氧樹脂複合材料可採用如下方法製作： 099128158 表單編號Α0101 第9頁/共20頁 0992049513-0 201209124 [0023] 首先’採用端羧基聚合物改性環氧樹月旨 合物改性之環氧樹脂。 以得到端羧基聚 [0024] [0025] [0026] 將端羧基聚合物及環氡樹脂放置於乒 丄、 置於反應宠哭 中’並維持反應溫度為12 0攝氏度，於許扯 、視拌之條件下及雍 約3小時，從而得到端錄聚合物改性後環氛樹脂: 施例中，採狀環氧樹脂為雙嶋型環氧樹脂，其環氧當 量為188 »採用之端緩基聚合物可為液態聚丁 _ (CTBN)，反應後得到之改性後之還氧樹脂= 337。經過上述反應，環氧樹脂柄之—個環氧基=叛 基聚合物末端之一個羧基相互結合’產脫除一個分子之 水’從而得到-個醋基。從雨相比於未進行改性^環氧 樹脂，改性後之環氧樹脂具有良好之柔軟性。當然^採 用之環氧樹脂不限於本實_提供之雙㈣型環氣樹脂， 其亦可為其他類型之環氧樹脂。採用之賴基聚合物日亦 不限於本實施例中提供之液態聚丁二烯丙烯腈，其亦可 為端羧基聚酯等聚合物。 然後’將奈米碳管均句分散於無機分散材料中以形成分 散均勻之奈米碳管分散體。 採用物理方式將奈米碳管分散於無機分散材料中。所述 無機分散材料可為層狀奈米黏土或者雲母粉。本實施例 中，選用之無機分散材料為層狀奈米黏土。配置重量比8 比1至12比1之奈米碳官與層狀奈米黏土，並藉由搜拌或 者震盡之方式合，使得奈米碳管均勻分散於所述層狀 奈米黏土中。採用之層狀奈米黏土可為2 : 1之頁矽酸鹽 ，其具體可為蒙脫石、鋰蒙脫石或者皂石等。採用之奈 099128158 表單編號A0101 第10頁/共20頁 0992049513-0 201209124 [0027] [0028] Ό Ο [0029] 米碳管可為單壁奈米碳管，亦可為多壁奈米碳管。 最後，將端羧基聚合物改性之環氧樹脂、奈米碳管分散 體、溶劑、硬化劑、催化劑及消泡劑進行混合並研磨分 散，從而得到環氧樹脂複合材料。 本實施例中，採用三滾筒式研磨分散機對所述之端羧基 聚合物改性環氧樹脂、奈米碳管分散體、溶劑、硬化劑 、催化劑及消泡劑進行研磨分散。將上述端羧基聚合物 改性環氧樹脂、奈米碳管分散體、溶劑、硬化劑、催化 劑及消泡劑按照上述各自之含量投入於三滾筒式研磨分 散機中，啟動三滾筒式研磨分散機以進行研磨分散，從 而使得上述各組成中固體成份均勻分散於液體成分中， 從而形成分散均勻之環氧樹脂複合材料。本實施例中， 於上述各成分中，端羧基聚合物改性之環氧樹脂之重量 百分含量約為60. 3%，奈米碳管之重量百分含量約為 7.8%，無機分散材料之重量百分含量約為0.6%，硬化劑 之重量百分含量約為4. 5%、催化劑之重量百分含量約為 0. 6 5 %，溶劑之重量百分含量約為2 4. 3 %，消泡劑之重量 百分含量約為1. 85°/〇。 為得到不同表面電阻率之環氧樹脂複合材料，可藉由改 變投料時奈米碳管分散體之用量進行控制。當奈米碳管 佔複合材料之重量百分比為4. 6%至16%之間，環氧樹脂複 合材料表面電阻率變化區間約為十萬歐姆至十歐姆之間 。其中，環氧樹脂複合材料中奈米碳管之含量越大，環 氧樹脂複合材料之表面電阻率越小。 099128158 表單編號Α0101 第11頁/共20頁 0992049513-0 201209124 [0030] 藉由所述方法製作之環氧樹脂複合材料，其黏度可達到 70000厘泊，外觀呈現黑色，微弱反光。於顯微鏡放大 100倍觀測下，無孔洞。並具有良好之附著特性及焊錫特 性，並且能夠耐酸、域及溶劑之腐蝕。溫度為25攝氏度 時，於重量百分含量為10%之鹽酸或重量百分含量為10% 之氫氧化納溶液中浸泡0. 5小時，均無剝落現象。於丙酮 中浸泡1 7小時後進行百格附著測試，亦無剝落現象。 [0031] 請參閱圖2，第二步，提供離型基材層110。 [0032] 本實施例中，離型基材層110為PET離型膜，其具有第一 離型表面111。 [0033] 請參閱圖3，第三步，將所述環氧樹脂複合材料塗佈於第 一離型表面111以形成環氧樹脂複合材料屬12 0。 [0034] 本實施例中，採用狹縫式塗佈機將液態之環氧樹脂複合 材料塗佈於離型基材層110之第一離型表面111，以形成 環氧樹脂複合材料層120。本實施例中由於採用狹縫式塗 佈機進行塗佈，可控制形成之環氧樹脂複合材料層120之 厚度滿足要求並且塗層均勻。本實施例中，形成之環氧 樹脂複合材料層120之厚度為8微米至25微米，優選為10 至20微米。環氧樹脂複合材料層120具有遠離離型基材層 110之第一表面121。 [0035] 第四步，對離型基材層110之第一離型表面111上塗佈形 成之環氧樹脂複合材料層120進行處理，以使得環氧樹脂 複合材料層120半固化。 [0036] 本實施例中，環氧樹脂複合材料層120半固化採用之方法 099128158 表單編號A0101 第12頁/共20頁 0992049513-0 201209124 [0037] 為預烘烤處理。 於野環氧樹純合㈣層12〇進行舰烤之持續之時間約 為15分鐘’預烘烤時保持之溫度約為8()攝氏度至9〇攝氏 度。藉由進彳了預烘烤處理’使得環氧樹脂複合材料層120 中之部分溶劑揮發，使得環氧樹脂複合材料層120處於半 固化狀態。 [0038] Ο °理解進行預洪烤持續時間及供烤之溫度可根據實際 之環氧樹脂複合材料層12Q之厚度進行較，當環氧樹脂 複。材料層120厚度較大時，可將處理之時間適當延長或 溫度適當㈣’而當魏樹脂複合材料層120厚度較小時 :可將處理之時間適t縮短秦溫度適當降低，以保證環 氧樹脂複合材料層12G能夠形成相化膜狀結構。 [0039] [0040]Ο 請-併參閱圖3及圖卜第五步，於環·脂複合材料層 12。之第一表面121上貼合離型隔離層— 貼〇之離5L隔離層13Q用於儲存及運輪過程中對環氧 複合材料唐120進行保護。離型隔離層㈣可為離型Μ? 膜’其可為各種離型紙。離ί隔離層13。具有第二離型表 n型表面131與環氧樹脂複合材料層12〇之 第一表面121相互貼合。當製作形成之膠片100直接用於 電路板裝作時’於環氧樹脂複合材料層120之第-表面； 121上亦可不貼合離型隔離層130。 [0041] 於此梦驟之俊，還可進 099128158 支對膠片100進行裁切，將朦 1_作《要句狀，以方便使I製作形成之膠7 100不直接進行應用時，可將w 1GG放置於低溫環境下 表單編號A0101 第13頁/共20頁 0992049513-0 201209124 存儲’存儲之溫度可大約為5攝氏度。移片 路板製作時，可將膠片100之離型隔離層應用於電 將環氧樹脂複合材料層120直接壓合於來 除去，然後 & '/成有導電绦敗々[0014] G the end of the compound modified epoxy naxygenated resin and the terminal polymer to produce the product of the anti-money, that is, the epoxy resin terminal epoxy and the terminal It complex The terminal filaments react to form a vine group, thereby obtaining a polymer having repeating units including alternating epoxy repeating units and terminal ruthenium polymers. Wherein, the epoxy resin may be a double-type A-type ring-stitching agent's filament compound, which may be "polybutylene dimethyl nitrile (CTBN) ° in the present embodiment, the epoxy resin used in the unmodified ring The oxygen equivalent weight is then 195, preferably 188, and the epoxy resin of the silk polymer modified epoxy compound has an epoxy equivalent of from 323 to detach, preferably as defined. The weight of the end-group polymer modified ring gas resin in the county composite towel is 10099128158 Form No. A0101 Page 7 / Total 20 pages 0992049513-0 201209124 The ratio is about 55% to 65%, preferably about 6〇 %. [0018] [0018] [0018] The transmission can be used as an electromagnetic mask in the polymer conversion material. Nano has a ρ, I percentage of 4.6% to 16% in the carbon nanotubes. The performance of the composite material can be made according to the actual needs of the long material. The content of the ring ~ medium carbon nanotubes is less than the content of the tube: the smaller the resistance, the nano carbon v epoxy resin composite material in the composite material. The greater the resistance. The inorganic dispersion holding limit is distributed in the epoxy tree and the carbon nanotubes can be in the average clay or the rice. The inorganic dispersion material is a nano-powder. The nano-clay is a 2:1 page of sulphuric acid> - may be montmorillonite (Montmo, lentite, molecular formula Χ 4~χΜδχ) Sl8O20(OH)4), and montmorillonite (Hectorite' molecular formula is MxUuuw. (10)v or Sashiue (Saponue, formula is ^% (3) Buza) Nine (10)) 4) and so on. Wherein, the weight ratio of the carbon nanotubes to the inorganic dispersion material is 8 to 12 to 1. The inorganic dispersion material is preferably a nanometer mica powder. The hardener is used for hardening the composite material. In the present embodiment, the hardener used is dicyandiamide, and the hardener is about 5% by weight of the epoxy resin composite. . The amount of the hardener should correspond to the epoxy resin modified with the terminal carboxyl group polymer, wherein the weight ratio of the end group polymer modified epoxy wax to the hardener is about 13 to 14 to 1. The catalyst is 2-undecyl imidazole 099128158 Form compilation A0101 Page 8 / Total 20 pages 0992049513-0 201209124 'The content of the catalyst and the content of the polymer modified epoxy resin of Duan County Correspond to each other. The catalyst accounts for about 100% of the epoxy resin composite shot. It runs 1%, preferably 65%. The solvent is dioxol monoethyl ether W0)lethylenegiyeQii^ethyi ether-(8), and the solvent is contained in the cyclic ruthenium resin composite in an amount of about 20% to 25%, preferably 24%. This solvent is used to dissolve the other components described above to form a uniform liquid dispersion. The foaming agent is used for eliminating the foam in the epoxy resin composite material, and the defoaming agent is in the ring Ο [0019] The weight of the oxygen resin composite material is 2% m. The 218311 defoamer produced by Taiwan's Yuzheng Company. Preferably, the 'oxygenated resin composite material is shot, the end retarded polymer modified ring yKy V :! ..., the weight percentage of the oxygen resin is about 6 〇: 3. 3 %, the weight of the carbon nanotube The percentage by weight of the inorganic dispersing material is about 〇. 6%, the weight percentage of the hardener is about 4.5%, and the weight percentage of the catalyst is about 0·65. %, the weight percentage of the solvent is about _24. 3%, and the weight percentage of the antifoaming agent is about 185%. The inorganic dispersion material is selected from mica powder [0020] [0022]. In the present embodiment, the epoxy resin composite material has a viscosity of 6 〇〇〇〇 to 75,000 cp., which can be easily bonded to the cover film or other adhesive layer in the circuit board. Preferably, the epoxy resin composite has a viscosity of about 7 厘 centipoise. The technical solution also provides a manufacturing method of the film 1 具有 having an electromagnetic shielding effect, and the manufacturing method comprises the following steps: In the first step, the epoxy resin composite material is prepared. The epoxy resin composite material described in this embodiment can be produced by the following method: 099128158 Form No. 1010101 Page 9 / Total 20 Page 0992049513-0 201209124 [0023] Firstly, the end-carboxyl polymer modified epoxy tree month composition Modified epoxy resin. To obtain the terminal carboxyl group [0024] [0025] [0026] Place the terminal carboxyl polymer and the cyclic resin in the tablecloth, placed in the reaction pet crying 'and maintain the reaction temperature of 120 degrees Celsius, in the pull, mix Under the conditions of about 3 hours, the end-capped polymer modified epoxy resin is obtained. In the example, the epoxy resin is a double-twisted epoxy resin, and the epoxy equivalent is 188. The base polymer may be liquid polybutylene (CTBN), and the modified oxygenated resin obtained after the reaction = 337. After the above reaction, an epoxy group of an epoxy resin handle = a carboxyl group at the end of the ribopolymer is bonded to each other to produce water of one molecule to obtain a vine group. The modified epoxy resin has good flexibility from the rain compared to the unmodified epoxy resin. Of course, the epoxy resin used is not limited to the double (four) type ring gas resin provided by the present invention, and it may be other types of epoxy resin. The base polymer used herein is not limited to the liquid polybutadiene acrylonitrile provided in the present embodiment, and may be a polymer such as a terminal carboxyl group. The carbon nanotubes are then uniformly dispersed in the inorganic dispersion to form a dispersed homogeneous carbon nanotube dispersion. The carbon nanotubes are physically dispersed in the inorganic dispersion material. The inorganic dispersion material may be a layered nano clay or a mica powder. In this embodiment, the inorganic dispersion material selected is a layered nano clay. Configuring carbon nanostructures with a weight ratio of 8 to 1 to 12 to 1 and layered nano-clay, and mixing them by means of mixing or shocking, so that the carbon nanotubes are uniformly dispersed in the layered nano-clay . The layered nano-clay used may be a 2:1 page citrate, which may specifically be smectite, hectorite or saponite. Adopted No. 099128158 Form No. A0101 Page 10 / Total 20 Page 0992049513-0 201209124 [0027] [0028] 00 Ο [0029] The carbon nanotube can be a single-walled carbon nanotube or a multi-walled carbon nanotube . Finally, the epoxy group-modified epoxy resin, the carbon nanotube dispersion, the solvent, the hardener, the catalyst, and the antifoaming agent are mixed and ground to obtain an epoxy resin composite material. In this embodiment, the terminal carboxyl polymer-modified epoxy resin, the carbon nanotube dispersion, the solvent, the hardener, the catalyst, and the antifoaming agent are ground and dispersed by a three-roll type grinding and dispersing machine. The above-mentioned terminal carboxyl polymer-modified epoxy resin, carbon nanotube dispersion, solvent, hardener, catalyst, and antifoaming agent are put into a three-roll type grinding and dispersing machine according to the respective contents described above, and three-roller type grinding and dispersing is started. The machine is subjected to grinding and dispersion so that the solid components in the above respective compositions are uniformly dispersed in the liquid component, thereby forming a uniformly dispersed epoxy resin composite material. In this embodiment, the weight percent of the epoxy resin modified by the terminal carboxyl group is about 60.3%, and the weight percentage of the carbon nanotubes is about 7.8%. The inorganic dispersion material The weight percentage of the hardener is about 4.5%, the weight percentage of the catalyst is about 0.65%, and the weight percentage of the solvent is about 2 4. 3. %。 The weight percentage of the antifoaming agent is about 1. 85 ° / 〇. In order to obtain an epoxy resin composite material having different surface resistivities, it can be controlled by changing the amount of the carbon nanotube dispersion at the time of feeding. When the carbon nanotubes account for between 6% and 16% by weight of the composite material, the surface resistivity of the epoxy resin composite varies between about 100,000 ohms and ten ohms. Among them, the larger the content of the carbon nanotubes in the epoxy resin composite material, the smaller the surface resistivity of the epoxy resin composite material. 099128158 Form No. Α0101 Page 11 of 20 0992049513-0 201209124 [0030] The epoxy resin composite material produced by the method has a viscosity of 70,000 cps, and the appearance is black and slightly reflective. Under the microscope magnification of 100 times, there is no hole. It has good adhesion properties and solder properties, and is resistant to acid, domain and solvent corrosion. 5小时,不脱落。 When the temperature is 25 degrees Celsius, in a 10% by weight of hydrochloric acid or 10% by weight of sodium hydroxide solution soaked for 0.5 hours, no peeling phenomenon. After immersing in acetone for 17 hours, the adhesion test was performed without peeling. [0031] Referring to FIG. 2, the second step, a release substrate layer 110 is provided. [0032] In the present embodiment, the release substrate layer 110 is a PET release film having a first release surface 111. Referring to FIG. 3, in the third step, the epoxy resin composite material is coated on the first release surface 111 to form an epoxy resin composite material genre 120. In the present embodiment, a liquid epoxy resin composite material is applied to the first release surface 111 of the release substrate layer 110 by a slit coater to form an epoxy resin composite material layer 120. In the present embodiment, since the coating by the slit coater is applied, the thickness of the formed epoxy resin composite material layer 120 can be controlled to be satisfactory and the coating layer is uniform. In the present embodiment, the epoxy resin composite material layer 120 is formed to have a thickness of 8 μm to 25 μm, preferably 10 to 20 μm. The epoxy composite layer 120 has a first surface 121 that is remote from the release substrate layer 110. [0035] In the fourth step, the epoxy resin composite layer 120 coated on the first release surface 111 of the release substrate layer 110 is treated to semi-cure the epoxy resin composite layer 120. [0036] In the present embodiment, the epoxy resin composite material layer 120 is semi-cured by a method. 099128158 Form No. A0101 Page 12 of 20 0992049513-0 201209124 [0037] It is a prebaking treatment. The duration of the ship's roasting in the homogenous (four) layer of Yuye Epoxy is about 15 minutes. The temperature maintained during pre-baking is about 8 () degrees Celsius to 9 degrees Celsius. The epoxy resin composite material layer 120 is in a semi-cured state by volatilizing a part of the solvent in the epoxy resin composite layer 120 by the prebaking treatment. [0038] 理解 ° It is understood that the duration of the pre-baked roasting and the temperature for bake can be compared according to the thickness of the actual epoxy resin composite layer 12Q, when the epoxy resin is recovered. When the thickness of the material layer 120 is large, the treatment time may be appropriately extended or the temperature is appropriate (4)'. When the thickness of the Wei resin composite material layer 120 is small: the treatment time may be shortened to appropriately shorten the Qin temperature to ensure the epoxy. The resin composite material layer 12G is capable of forming a phased film structure. [0040] Ο Please - and refer to Figure 3 and Figure 5, step 5, in the ring-and-fat composite layer 12. The first surface 121 is attached to the release barrier layer - the 5L isolation layer 13Q is used to protect the epoxy composite material Tang 120 during storage and transport. The release barrier (4) can be a release liner? The film can be a variety of release papers. Separation layer 13 from ί. The first surface 121 having the second release type n-type surface 131 and the epoxy resin composite layer 12 is bonded to each other. When the formed film 100 is directly used for circuit board mounting, the first surface of the epoxy resin composite layer 120; 121 may not be attached to the release spacer 130. [0041] In this dream, you can also cut the film 100 into 099128158, and make the 朦1_ as a sentence, so that the glue 7 100 formed by I can not be directly applied. w 1GG placed in a low temperature environment Form No. A0101 Page 13 / Total 20 pages 0992049513-0 201209124 Storage 'Storage temperature can be about 5 degrees Celsius. When the transfer film is manufactured, the release spacer of the film 100 can be applied to the electric epoxy composite layer 120 directly to be pressed and removed, and then & '/ has a conductive defect.
電路板之覆蓋膜之表面’以起到電磁逾I 〜早之作用。龙 離型基材層110與環氧樹脂複合材料層丨 將 π離。本括嫩 方案提供之夥·片100亦可形成於多層電路把 Λ " 之相鄰之兩絕 緣層之間，以起到電磁遮罩作用。 [〇〇42]本技術方案提供之膠片，其包括環氧樹脂複合材料層， 所述環氧樹脂複合材料層中具有分散均勻之奈卡礙管 具有電磁遮罩作用，所述滕片可直接將其貼二於二二: 之表面或者設置於多層電路板之内層中，所述膠片具有 電磁遮罩之作用。相比於不銹鋼片，能夠增加柔性電路 板之撓折性能，並且可降低電路板之生產成本。本技術 方案提供之膠片之製作方法，能夠簡單之製作出具有電 磁遮罩作用之膠片。 [0043] 、纟示上所述’本發明確已符合發明專利|要件，遂依法提 出專利申請》惟，以上所述者僅為本發明之較佳實施方 式，自不能以此限制本案之申請專利範圍。舉凡熟悉本 案技藝之人士援依本發明之精神所作之等效修飾或變化 ，皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 [0044] 圖1係本技術方案實施方式提供之膠片之剖視圖。 [0045] 圖2係本技術方案實施例提供之離型基材層之剖視圖。 [0046] 圖3係本技術方案實施例提供之於離型基材層表面形成環 099128158 表單編號Α0101 第14頁/共20頁 0992049513-0 201209124 氧樹脂複合材料層後之剖視圖。 【主要元件符號說明】 [0047] [0048] [0049] [0050] [0051] Ο [0052] [0053] 膠片：100 離型基材層：110 第一離型表面：111 環氧樹脂複合材料層：120 第一表面：121 離型隔離層：130 第二離型表面：131The surface of the cover film of the circuit board acts to electromagnetically exceed I~ early. The detached base material layer 110 and the epoxy resin composite layer 丨 are separated by π. The package 100 provided by the present invention can also be formed between the two adjacent insulating layers of the multilayer circuit to function as an electromagnetic mask. [42] The film provided by the technical solution includes an epoxy resin composite material layer, wherein the epoxy resin composite material layer has a uniform uniformity, and the nappa film has an electromagnetic shielding effect, and the tempering piece can directly The surface is attached to the surface of the second layer or disposed in the inner layer of the multilayer circuit board, and the film has the function of an electromagnetic mask. Compared with the stainless steel sheet, the flexural performance of the flexible circuit board can be increased, and the production cost of the circuit board can be reduced. The film produced by the technical solution can be simply fabricated into a film having an electromagnetic mask. [0043] 纟 上 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本Patent scope. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS [0044] FIG. 1 is a cross-sectional view of a film provided by an embodiment of the present technical solution. 2 is a cross-sectional view of a release substrate layer provided by an embodiment of the present technical solution. 3 is a cross-sectional view of the oxyresin composite layer after forming a ring on the surface of the release substrate layer according to an embodiment of the present invention. 099128158 Form No. 1010101 Page 14 of 20 0992049513-0 201209124. [Main component symbol description] [0048] [0052] [0053] Film: 100 release substrate layer: 110 first release surface: 111 epoxy resin composite material Layer: 120 First surface: 121 Release barrier: 130 Second release surface: 131
❹ 099128158 表單編號Α0101 第15頁/共20頁 0992049513-0❹ 099128158 Form number Α0101 Page 15 of 20 0992049513-0