九、發明說明：Nine, invention description:
【發明所屬之技術領域J 發明領域 本發明係關於一種用於表面覆膜薄犋之 i勒者劑組成 物，並且’更特別的是，滿足表面覆膜薄骐 两之所有物 理性質，如黏性強度、可流動性、抗熱性、絕緣性等之 表面覆膜薄膜之黏著劑組成物。TECHNICAL FIELD OF THE INVENTION The present invention relates to a composition for a surface coating, and more particularly, it satisfies all physical properties of the surface coating, such as sticking. Adhesive composition of a surface coating film such as strength, flowability, heat resistance, and insulation.
【先前J 發明背景 近年來’隨著消費者偏好小型、薄且高度整合的消費 者電子產品’可彎曲之電路板的需求因此而增加。於是，' 更多的表面覆膜薄膜被用在保護電路板上。改善黏性強 度、可流動性、抗熱性、與防燃性的能力係高度的被薄犋 所需要。 ' 通常’該表面覆膜薄膜由覆蓋在抗熱性薄膜和為保護 黏著劑之離形薄膜橫切面之半固態黏著劑層所組成。因為 這些表面覆膜薄膜被接附在具彈性的印刷電路板上係為了 保護印刷電路，它必須具備所有重要的物理性質，如點性 強度、可流動性、抗熱性、防燃性等。 傳統用於表面覆膜薄媒之黏著劑已經典型的用N邱/學 氧樹脂、丙稀樹脂齡树月曰、或聚S旨樹脂製造，但前述物質 有自己個別的優點和缺點且不能滿達到表面覆膜薄祺所需 要的所有物理性質。 1335931 【發明内容】 發明概要 本發明係被提議以解決這些問題。本發明的一目的為 提供一種用於發明的表面覆膜薄膜之黏著劑組成物，能在 5 所有必須的物理性質如抗熱性、黏性強度、防燃性、可流 動性等具有絕佳性。 該上述和其他的目的及本發明的優點，從閱讀以下本 發明之較佳實體例的敘述將可更明瞭。 圖式簡單說明 10 C實施方式3 較佳實施例之詳細說明 為達到前述之目的，用於表面覆膜薄膜之該黏著劑組 成物，根據本發明，係被用來製造一具有層狀構造之絕緣 15 薄膜、黏著劑和離形薄膜的表面覆膜薄膜。根據本發明， 該黏著劑組成物其特徵在於包含：（a)含有羧基基團之 NBR，（b)每分子具有兩個或更多環氧化物之多官能環氧樹 脂，（c)每分子具有兩個或更多環氧化物之漠化環氧樹脂， (d)胺或酐硬化劑，和（e)無機粒子。 20 較佳的，根據本發明黏著劑組成物之特徵在於其包 含，（a)100份重量計之含有羧基基團之NBR(於計算組成物 之相對量時，用來當成一基數），（b) 20到100份重量計之 每分子具有兩個或更多環氧化物之多官能環氧樹脂，（c) 50 到170份重量計之每分子具有兩個或更多環氧化物之溴化 6 1335931 環氧樹脂，（d) 20到60份重量計之無機粒子，及（e)對 於該環氧樹脂之總量而言，5至15重量％之胺或酐硬化劑。 更佳的，本發明之特徵亦在於含有叛基基團之NBR(a) 具有2, 000至200, 000之重量平均分子量；其中丙烯腈的含 5量為10至60重量且其中該羧基基團的含量為1至20重 量％ 〇 以下，本發明之實體例將被詳細敘述。熟習此藝者應 明瞭這些實體例僅意圖去更詳細的闡述本發明，且本發明 的範圍非僅止於此些實體例。 10 根據本發明之用於表面覆膜薄膜的黏著劑組成物，是 用在製造具層狀結構的絕緣薄膜、黏著劑和離形薄膜之表 面覆膜薄膜’且該表面覆膜薄膜有絕佳的所有需要之物理 性質，如黏性強度、抗熱性、防燃性、可流動性等。 根據本發明之用於表面覆膜薄膜的黏著劑組成物中， 15含有羧基基團之NBR具有2, 000至200, 000之重量平均分 子量較佳的為3，000至200,000分子量。且，丙稀猜的 含量為10至60重量％和該羧基基團的含量為1至20重量 %。此例中’若重量平均分子量沒有高於2, 〇〇〇會造成該合 成薄膜有較差的熱穩定性。若重量平均分子量高於2〇〇, 〇〇〇 20會造成該合成薄膜對溶劑有較差的溶解力，且當製造溶液 時亦會造成黏性增加並因此產生較差的可用性和低的黏性 強度。 當丙烯腈的含量低於10重量％，該合成薄膜表現出低 的溶劑溶解力且當它高於6〇重量％，它表現出較差的電絕 7 緣丨生备幾基基團的含量為1至20重量％，介於NBR和其 他樹月曰之❹接合被達成，且該接合導姉性強度增加。 至於根據本發明用於表面覆膜薄膜之黏著劑組成物中 的¥氧樹脂’使用的為具有兩個或更多環氧之多官能環氧 5及每分子具有兩個或更多環氧之溴化環氧樹脂。該多 b此衣氡如旨和賴化環氧樹脂必須u合織使用。如 果僅使用夕官能環氧樹脂，該薄膜缺乏防燃性，且如果僅 使用肩化％氧樹脂，該薄膜缺乏基本的物理性質如黏性 強度、彈性等’如此—來’該薄膜不能使用在表面覆膜薄 膜。 该多官能環氧樹脂和該溴化環氧樹脂之總合能介於按 重里计算70份與270份之間，此係以1〇〇份重量計算之 NBR為基礎而言。當總合沒有多於按重量計算7〇份，該合 成的表面覆膜薄膜具有太高之可流動性，會導致很明顯的 低可用性。當它為按重量計算27〇份或更高，該合成的薄 膜具有較低的黏性強度和較低的可流動性且因此變成易脆 的，如此一來它本身將困難去形成表面覆膜薄膜。 就100份重量計之NBR為基礎而言，20至100份重量計 之多g能環氧樹脂可被加入且該環氧樹脂可為雙紛A型、 雙盼F型或鄰型且具有200至1〇〇〇之結合重量（g/eq)。 當多官能環氧樹脂含量低於按重量計算2〇份，黏性強 度係較低且黏著劑層因此變的易脆，如此一來該薄膜不能 用做表面覆膜薄膜。當含量高於按重量計算1〇〇份，該溴 化環氧樹脂的數量變的相對性較少’如此一來防燃性降低 且因此困難去成為UL94標準的V0級。 該環氧樹脂需有每分子二或更多的環氧及溴原子，且 該>臭化環氧樹脂之溴化比需為19至51重量％。示範的溴化 環氧樹脂可為雙酚型、或鄰型之環氧樹脂。如果需要，二 或多型不同溴化比之樹脂可被混合然後使用。該溴化環氧 樹脂之使用量為按重量計算5〇至170份就按重量計算1〇〇 份之NBR為基礎而言。如果按重量計算該量為5〇份或更 少，該薄膜缺乏防燃性且如果該量高於按重量計算17〇份， 該薄膜可能缺乏黏性強度且該黏著劑層可能缺乏彈性等 等。 至於根據本發明用於表面覆膜薄膜之黏著劑組成物的 硬化劑，胺硬化劑或酐硬化劑可被使用，個別的或一起被 使用。該硬化劑的量可為5至15重量％就環氧樹脂的總量 而&。而且’有機或無機過氧化物可被用來當成橡膠交叉 連結劑’量可為1至5份就按重量計算1〇〇份之NBR為基 礎而言。 根據本發明用於表面覆膜薄膜之黏著劑組成物中的無 機粒子係主要用來達成在黏著劑中抗熱性和防燃性且改善 穿孔能力當成一額外的功能。可應用的無機粒子範例可為 氫氧化鋁、氫氧化鎂、氧化鋅、氧化鎂、三氧化銻等。較 佳的該無機粒子含量為按重量計算20至60份就按重量計 算100份之NBR為基礎而言。如果含量沒有高於按重量計 算之20份，該黏著劑有較低的抗熱性和穿孔能力。如果它 1335931 尚於按重量計算之60份，該黏著劑有較低之物理性質，如 減少可流動性和黏性強度。 用於具有前述成份和根據本發明之表面覆膜薄膜的黏 著劑組成物，係一致的與有機溶劑如甲基乙基_、曱醇、 5本曱基醇、甲苯、四氫11夫。南（tetrahydrofuran)、氣苯等混 合°在此例中，該組成物之黏度為100至2, 000CPS，較佳的 為400至l，〇〇〇cps。該組成物被應用在抗熱薄膜上，如此一 來在乾燥後其之厚度可為10〜35/im。該最終的表面覆膜薄膜 在硬化該組成物於50到170°C、1至10分鐘後，經由壓板一 10離形紙或離形薄膜的過程中所獲得。 [資施例] 用於該實體例和比較例之組成物成份係選自下列所 述： (a) NBR:重量平均分子重量8〇,〇〇q含有27%之丙烯 腈和8%之羧基基團； (b) ，（c)環氧樹脂： ①：雙酚A型，等重量之環氧樹脂19〇，Epik〇te828 (商標），曰本氧樹脂股份有限公司。 ② ：雙酚Α型，等重量之環氧樹脂62〇，Epik〇te 1〇〇3 (商標），日本環氧樹脂股份有限公司。 ③ .雙紛A型’ /臭化環氧樹脂，51 %之漠化比，Ep i kote 5050，日本環氧樹脂股份有限公司。 10 1335931 ④：雙酚A型，溴化環氧樹脂，19%之溴化比，Epikote 5046，日本環氧樹脂股份有限公司； (d)硬化劑：4, 4-二胺基苯化硬（diaminodiphenyl sulfone);及 5 (e)無機粒子：氫氧化鋁（平均粒子直徑：1/μ) [實施例1] 加入100重量之NBR(含有27%之丙烯腈和8%之羧基基 團）之中的為70重量之環氧樹脂（①）、1〇〇重量之溴化環氧 10樹脂（③）樹脂、15重量之該硬化劑和60重量之該無機粒 子。伴隨著甲基乙基酮為溶劑，該溶液黏度被製造成400 至1，200CPS。在用銳床（mi 11丨叩machine)充分的混合該黏 著劑溶液後’該溶液被應用在聚亞酿胺（p〇lyimide)薄膜 上’其厚度為25卿，如此一來在乾燥後它的厚度為30卿， 15且之後繼續乾燥（在160°C，3分鐘）。接下來一離形薄膜被 壓板在其上去製造一表面覆膜薄膜。 [實施例2] 加入100重量之NBR(含有27%之丙烯腈和8%之羧基基 20團）之中的為40重量之環氧樹脂（①）、60重量之環氧樹脂 (②）、170重量之溴化環氧樹脂（④）、24重量之該硬化劑 和40重量之該無機粒子。使用如實施例1之相同方法，去 製造一表面覆膜薄膜。 11 1335931 [實施例3] 加入100重量之NBR(含有27%之丙烯腈和8%之羧基基 團）之中的為40重量之環氧樹脂（①）' 6〇重量之環氧樹脂 (②）、60重量之溴化環氧樹脂（③）、1〇〇重量之溴化環氧 5樹脂（④）、21重量之該硬化劑和4〇重量之該無機粒子。 使用如實施例1之相同方法，去製造一表面覆膜薄膜。 [實施例4] 加入100重量之NBR(含有27%之丙烯腈和8%之羧基基 10團）之中的為70重量之環氧樹脂（①）、1〇〇重量之溴化環氧 樹脂（③）、15重量之該硬化劑和2〇重量之該無機粒子。 使用如實施例1之相同方法’去製造一表面覆膜薄膜。 [比較例1] 15 加入重量之NBR(含有27%之丙烯腈和8%之羧基基 團）之中的為70重量之環氧樹脂（①）、1()〇重量之環氧樹脂 (②）、15重量之該硬化劑和60重量之該無機粒子。使用如 實施例1之相同方法，去製造一表面覆膜薄膜。 [比較例2] 加入100重量之NBR(含有27%之丙烯腈和8%之叛基基 團）之中的為70重量之溴化環氧樹脂（③）、1〇0重量之溴化 環氧樹脂（④）、15重量之該硬化劑和60重量之該無機粒 子。使用如實施例1之相同方法，去製造一表面覆膜薄膜。 12 1335931 [比較例3] 加入100重量之NBR(含有27%之丙烯腈和8%之羧基基 團）之中的為150重量之環氧樹脂（①）、1〇〇重量之溴化環 5氧樹脂（③）、20重量之溴化環氧樹脂（④）、22重量之該硬 化劑和60重量之該無機粒子。使用如實施例丨之相同方 法，去製造一表面覆膜薄膜。 [比較例4] 10 加入100重量之NBR(含有27%之丙烯腈和8%之羧基基 團）之中的為80重量之環氧樹脂（①）、1〇〇重量之溴化環氧 樹脂（③）、100重量之溴化環氧樹脂（④）、25重量之該硬 化劑和60重量之該無機粒子。使用如實施例丨之相同方 法，去製造一表面覆膜薄膜。 15 [比較例5] 加入100重量之NBR(含有27%之丙烯腈和8%之羧基基 團）之中的為70重量之壤氧樹脂（①）、1〇〇重量之演化環氧 樹脂（③）、15重量之該硬化劑和70重量之該無機粒子。使 20用如實施例1之相同方法，去製造一表面覆膜薄膜。 [比較例6] 加入100重篁之NBR(含有27%之丙烯腈和8%之羧基基 團）之中的為70重量之環氧樹脂（①）、1〇〇重量之溴化環氧 13 1335931 樹脂（③）、15重量之該硬化劑和1〇重量之該無機粒子。使 用如實施例1之相同方法，去製造一表面覆膜薄膜。 [比較例7] 加入100重量之NBR(含有27%之丙烯腈和8%之羧基基 團）之中的為70重量之環氧樹脂（①）、100重量之溴化環氧 樹脂（③）、5重量之該硬化劑和重量之該無機粒子。使 用如實施例1之相同方法，去製造一表面覆膜薄膜。 10 [比較例8] 加入100重量之NBR(含有27%之丙埽腈和8%之羧基基 團）之中的為70重量之環氧樹脂（①）、ι〇〇重量之溴化環氧 樹脂（③）、30重量之該硬化劑和60重量之該無機粒子。使 用如實施例1之相同方法，去製造一表面覆膜薄膜。 15 接下來表格1展示了在前述實施例中之成份和含量且 表格2和3展示了在比較例中之成份和含量（份按重量計 算）。 [表格1] 實施例1 實施例2 實施例3 實施例4 NBR Γοό 100 100 100 環氧樹脂 ① 70 40 40 70 ② - 60 60 - ③ 100 一 60 100 ④ — 170 100 一 硬化劑 15 24 21 15 無機粒子 60 40 40 20 14 1335931 [表格2] 比較例1 比較例2 比較例3 比較例4 NBR 100 100 100 100 環氧樹脂 ① 70 - 150 80 ② 100 — - — ③ — 70 100 100 ④ 一 100 20 100 硬化劑 15 15 22 25 無機粒子 60 60 60 60 [表格3] 比較例5 比較例6 比較例7 比較例8 NBR 100 100 100 100 環氧樹脂 ① 70 70 70 70 ② - — - — ③ 100 100 100 100 ④ — — — — 硬化劑 15 15 5 30 無機粒子 70 10 60 60 藉由評估在前述實施例和比較例中，以前述之組成物 和方法所產生之表面覆膜薄膜的物理性質所得之結果揭示 在以下表格4至6中。 10 [表格4] 實施例 1 實施例 2 實施例 3 實施例 4 條件 黏性強度 (N/cm) 11.8 10.2 10. 1 13.4 JIS C6471 (1995)8. 1 可流動性 (/M) 150 180 170 200 氺 15 1335931 抗熱性 (°C) 360 360 360 350 JIS C6471 (1995)9.3 80% RH/30min 防燃性 V-0 V-0 V-0 V-0 UL94 [表格5] 比較例 1 比較例 2 比較例 3 比較例 4 條件 黏性強度 (N/cm) 12. 1 6. 7 11. 9 7. 3 JIS C6471 (1995)8.1 可流動性 (坪1) 130 180 140 190 氺 抗熱性 (°C) 350 350 340 360 JIS C6471 (1995)9. 3 80% RH/30min 防燃性 V-1 V-0 V-1 V-0 UL94 [表格6] 比較例 5 比較例 6 比較例 7 比較例 8 條件 黏性強度 (N/cm) 9. 1 13. 7 7. 1 3. 8 JIS C6471 (1995)8.1 可流動性 (现1) 110 250 310 80 氺 抗熱性 (°C) 370 290 260 300 JIS C6471 (1995)9. 3 80% RH/30min 防燃性 V-0 V-1 V-1 V-0 UL94 5 *在完成的表面覆膜薄膜上鑽直徑5mm的孔和以30Kg/cm2力 量壓該薄膜3分鐘後，測量流出孔外之該黏著劑長度。 實際上為了使表面覆膜薄膜之物理性質合適，該黏性 強度必須10 N/cm或更大。該薄膜之可流動性必須150至 16 1335931 200卿。抗熱性必須300°C或更高。防燃性必須為V-Ο。如 表格4所見，該表面覆膜薄膜由用於表面覆膜薄膜之黏著 劑組成物所組成，如同根據如本發明實體例1至4,其中之 表面覆膜薄膜滿足所有前述所有所需之物理性質。 5 從先前所述，需被注意到的是，熟習此藝者可根據本 發明做出各種不同修改和改變，但須無違反本發明之真實 精神和範圍。需被知道的是，前述僅意圖去闡明本發明而 非限定本發明的範圍，本發明的範圍如申請專利範圍中所 請求。 10 【圖式簡單說明3 <無> 【主要元件符號說明】 <無> 17[Previous J Background] In recent years, the demand for flexible circuit boards has become increasing as consumers prefer small, thin and highly integrated consumer electronics. Thus, 'more surface film is used to protect the board. The ability to improve viscous strength, flowability, heat resistance, and flame resistance is highly desirable. The 'normal' surface film consists of a semi-solid adhesive layer covering the heat-resistant film and the cross-section of the release film which is a protective adhesive. Because these surface film films are attached to flexible printed circuit boards to protect printed circuits, they must possess all important physical properties such as point strength, flowability, heat resistance, and flame resistance. The adhesives conventionally used for the surface coating thin film have been typically made of N Qiu/School Oxygen Resin, Acrylic Resin Age, or Poly S resin, but the aforementioned substances have their own individual advantages and disadvantages and cannot be filled. All physical properties required to achieve a thin film of surface coating. 1335931 SUMMARY OF THE INVENTION The present invention has been proposed to solve these problems. An object of the present invention is to provide an adhesive composition for a surface coating film of the invention which is excellent in all necessary physical properties such as heat resistance, viscous strength, flame resistance, flowability and the like. . The above and other objects and advantages of the present invention will become apparent from the following description of the preferred embodiments of the invention. BRIEF DESCRIPTION OF THE DRAWINGS 10 C Embodiment 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT In order to achieve the foregoing object, the adhesive composition for a surface coating film is used according to the present invention to produce a layered structure. Insulating 15 film, adhesive and surface film of the release film. According to the present invention, the adhesive composition is characterized by comprising: (a) a NBR having a carboxyl group, (b) a polyfunctional epoxy resin having two or more epoxides per molecule, and (c) per molecule a desertified epoxy resin having two or more epoxides, (d) an amine or anhydride hardener, and (e) inorganic particles. Preferably, the adhesive composition according to the present invention is characterized in that it comprises (a) 100 parts by weight of a NBR having a carboxyl group (used as a base when calculating the relative amount of the composition), b) 20 to 100 parts by weight of a polyfunctional epoxy resin having two or more epoxides per molecule, (c) 50 to 170 parts by weight of bromine having two or more epoxides per molecule 6 1335931 epoxy resin, (d) 20 to 60 parts by weight of inorganic particles, and (e) 5 to 15% by weight of the amine or anhydride hardener for the total amount of the epoxy resin. More preferably, the present invention is characterized in that the NBR (a) having a thiol group has a weight average molecular weight of from 2,000 to 2,000,000; wherein the acrylonitrile contains 5 in an amount of 10 to 60% by weight and wherein the carboxyl group The content of the group is 1 to 20% by weight or less, and the physical examples of the present invention will be described in detail. It will be apparent to those skilled in the art that these examples are only intended to illustrate the invention in more detail, and that the scope of the invention is not limited to such embodiments. 10 The adhesive composition for a surface coating film according to the present invention is used for producing a surface film of an insulating film, an adhesive, and a release film having a layered structure, and the surface film is excellent. All the physical properties required, such as viscous strength, heat resistance, flame resistance, flowability, etc. In the adhesive composition for a surface film of the present invention, 15 the NBR having a carboxyl group has a weight average molecular weight of from 2,000 to 2,000,000, preferably from 3,000 to 200,000. Further, the content of propylene is 10 to 60% by weight and the content of the carboxyl group is 1 to 20% by weight. In this case, if the weight average molecular weight is not higher than 2, the resultant film may have poor thermal stability. If the weight average molecular weight is higher than 2 〇〇, 〇〇〇20 will cause the synthetic film to have poor solubility to the solvent, and also cause an increase in viscosity when the solution is produced and thus result in poor usability and low viscous strength. . When the content of acrylonitrile is less than 10% by weight, the synthetic film exhibits low solvent solubility and when it is higher than 6% by weight, it exhibits a poor electrical content of the base group. From 1 to 20% by weight, the bonding between NBR and other tree stalks is achieved, and the joint guiding strength is increased. As for the oxy-resin used in the adhesive composition for a surface-coated film according to the present invention, a polyfunctional epoxy 5 having two or more epoxies and two or more epoxides per molecule are used. Brominated epoxy resin. The multi-b, the clothing and the Laihua epoxy resin must be used together. If only a oxime-functional epoxy resin is used, the film lacks flame retardancy, and if only a shoulder-based oxy-resin is used, the film lacks basic physical properties such as viscous strength, elasticity, etc. 'So--the film cannot be used in Surface film. The total energy of the polyfunctional epoxy resin and the brominated epoxy resin is between 70 parts and 270 parts by weight, based on 1 part by weight of the NBR. When the total amount is not more than 7 parts by weight, the resultant surface film has too high flowability, resulting in markedly low usability. When it is 27 parts by weight or more by weight, the synthetic film has a lower viscosity strength and a lower flowability and thus becomes brittle, so that it itself will be difficult to form a surface film. film. Based on 100 parts by weight of NBR, 20 to 100 parts by weight of multi-g epoxy can be added and the epoxy can be double-type A, double-f-type or adjacent and have 200 Binding weight to 1〇〇〇 (g/eq). When the content of the polyfunctional epoxy resin is less than 2 parts by weight, the viscosity is low and the adhesive layer becomes brittle, so that the film cannot be used as a surface film. When the content is more than 1 part by weight, the amount of the brominated epoxy resin becomes less relative'. As a result, the flame retardancy is lowered and thus it is difficult to become the V0 grade of the UL94 standard. The epoxy resin needs to have two or more epoxy and bromine atoms per molecule, and the brominated epoxy resin has a bromination ratio of 19 to 51% by weight. Exemplary brominated epoxy resins can be bisphenol or o-type epoxy resins. If desired, two or more different bromination ratio resins may be mixed and then used. The brominated epoxy resin is used in an amount of from 5 to 170 parts by weight based on 1 part by weight of NBR. If the amount is 5 parts by weight or less, the film lacks flame retardancy and if the amount is higher than 17 parts by weight, the film may lack adhesive strength and the adhesive layer may lack elasticity, etc. . As the hardener for the adhesive composition of the surface film according to the present invention, an amine hardener or an anhydride hardener may be used, either individually or together. The amount of the hardener may be from 5 to 15% by weight based on the total amount of the epoxy resin. Further, the 'organic or inorganic peroxide can be used as a rubber cross-linking agent' in an amount of from 1 to 5 parts by weight based on 1 part by weight of NBR. The inorganic particle system used in the adhesive composition for a surface film according to the present invention is mainly used for achieving heat resistance and flame resistance in an adhesive and improving the piercing ability as an additional function. Examples of applicable inorganic particles may be aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, antimony trioxide or the like. Preferably, the inorganic particle content is from 20 to 60 parts by weight based on 100 parts by weight of NBR. If the content is not higher than 20 parts by weight, the adhesive has lower heat resistance and perforation ability. If it is 1335931 still 60 parts by weight, the adhesive has lower physical properties such as reduced flowability and viscous strength. The adhesive composition for the surface film having the foregoing composition and the film according to the present invention is identical to an organic solvent such as methylethyl, decyl alcohol, 5 decyl alcohol, toluene, tetrahydro-11. Mixture of tetrahydrofuran, benzene, etc. In this example, the viscosity of the composition is from 100 to 2,000 CPS, preferably from 400 to 1, 〇〇〇cps. The composition is applied to a heat-resistant film so that it can have a thickness of 10 to 35 / im after drying. The final surface film is obtained by hardening the composition at 50 to 170 ° C for 1 to 10 minutes, via a press plate - 10 release paper or release film. [Means] The composition components used in the solid examples and the comparative examples are selected from the following: (a) NBR: weight average molecular weight 8 〇, 〇〇q contains 27% acrylonitrile and 8% carboxyl group (b), (c) Epoxy resin: 1: bisphenol A type, equal weight epoxy resin 19 〇, Epik〇te 828 (trademark), 曰 氧 Oxygen Resin Co., Ltd. 2: bisphenol hydrazine type, equal weight epoxy resin 62 〇, Epik〇te 1 〇〇 3 (trademark), Japan Epoxy Resin Co., Ltd. 3. Double-type A/smoke epoxy resin, 51% desertification ratio, Ep i kote 5050, Japan Epoxy Resin Co., Ltd. 10 1335931 4: bisphenol A type, brominated epoxy resin, 19% bromination ratio, Epikote 5046, Japan Epoxy Resin Co., Ltd.; (d) Hardener: 4, 4-diaminobenzene hard ( Diaminodiphenyl sulfone); and 5 (e) Inorganic particles: aluminum hydroxide (average particle diameter: 1/μ) [Example 1] 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group) was added. The resin was 70 parts by weight of epoxy resin (1), 1 part by weight of brominated epoxy 10 resin (3) resin, 15 parts by weight of the hardener, and 60 parts by weight of the inorganic particles. The viscosity of the solution was made to be 400 to 1,200 CPS with methyl ethyl ketone as a solvent. After thoroughly mixing the adhesive solution with a sharp bed (mi 11丨叩machine), the solution was applied to a polypyramine film with a thickness of 25 qing, so that after drying it The thickness was 30 qing, 15 and then continued to dry (at 160 ° C, 3 minutes). Next, a release film is pressed onto the film to form a surface film. [Example 2] 40 parts by weight of epoxy resin (1), 60 parts by weight of epoxy resin (2), among 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group 20 group), 170 parts by weight of brominated epoxy resin (4), 24 parts by weight of the hardener and 40 parts by weight of the inorganic particles. A surface film film was produced in the same manner as in Example 1. 11 1335931 [Example 3] 40 parts by weight of epoxy resin (1) '6〇 by weight of epoxy resin (2) added to 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group) And 60 parts by weight of a brominated epoxy resin (3), 1 part by weight of a brominated epoxy 5 resin (4), 21 parts by weight of the hardener, and 4 parts by weight of the inorganic particles. A surface film was produced by the same method as in Example 1. [Example 4] 70 parts by weight of epoxy resin (1), 1 〇〇 by weight of brominated epoxy resin among 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group 10 group) (3) 15 parts by weight of the hardener and 2 parts by weight of the inorganic particles. A surface film film was produced using the same method as in Example 1. [Comparative Example 1] 15 70 parts by weight of epoxy resin (1), 1 () by weight of epoxy resin (2% by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group)) And 15 parts by weight of the hardener and 60 parts by weight of the inorganic particles. A surface film was produced by the same method as in Example 1. [Comparative Example 2] 70 parts by weight of a brominated epoxy resin (3), 1 〇 0 by weight of a brominated ring, among 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of a thiol group) An oxygen resin (4), 15 parts by weight of the hardener, and 60 parts by weight of the inorganic particles. A surface film was produced by the same method as in Example 1. 12 1335931 [Comparative Example 3] 150 parts by weight of epoxy resin (1), 1 〇〇 weight of brominated ring 5 among 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group) An oxygen resin (3), 20 parts by weight of a brominated epoxy resin (4), 22 parts by weight of the hardener, and 60 parts by weight of the inorganic particles. A surface film film was produced in the same manner as in Example 。. [Comparative Example 4] 10 80 parts by weight of epoxy resin (1), 1 〇〇 by weight of brominated epoxy resin among 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group) (3) 100 parts by weight of a brominated epoxy resin (4), 25 parts by weight of the hardener, and 60 parts by weight of the inorganic particles. A surface film film was produced in the same manner as in Example 。. 15 [Comparative Example 5] 70 parts by weight of a oxy-resin (1), 1 〇〇 weight of an evolved epoxy resin among 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl groups) 3) 15 parts by weight of the hardener and 70 parts by weight of the inorganic particles. A surface film was produced in the same manner as in Example 1 except that the surface film was formed. [Comparative Example 6] 70 parts by weight of epoxy resin (1), 1 〇〇 by weight of brominated epoxy 13 among 100 parts of NBR (containing 27% of acrylonitrile and 8% of carboxyl group) 1335931 Resin (3), 15 parts by weight of the hardener and 1 part by weight of the inorganic particles. A surface film film was produced in the same manner as in Example 1. [Comparative Example 7] 70 parts by weight of epoxy resin (1), 100 parts by weight of brominated epoxy resin (3) among 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group) And 5 parts by weight of the hardener and the weight of the inorganic particles. A surface film film was produced in the same manner as in Example 1. 10 [Comparative Example 8] 70 parts by weight of epoxy resin (1), iodine weight of brominated epoxy among 100 parts by weight of NBR (containing 27% of acrylonitrile and 8% of carboxyl group) Resin (3), 30 parts by weight of the hardener and 60 parts by weight of the inorganic particles. A surface film film was produced in the same manner as in Example 1. 15 Table 1 below shows the ingredients and contents in the foregoing examples and Tables 2 and 3 show the ingredients and contents (parts by weight) in the comparative examples. [Table 1] Example 1 Example 2 Example 3 Example 4 NBR Γοό 100 100 100 Epoxy resin 1 70 40 40 70 2 - 60 60 - 3 100 A 60 100 4 — 170 100 A hardener 15 24 21 15 Inorganic particles 60 40 40 20 14 1335931 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 NBR 100 100 100 100 Epoxy Resin 1 70 - 150 80 2 100 — - 3 - 70 100 100 4 A 100 20 100 Hardener 15 15 22 25 Inorganic particles 60 60 60 60 [Table 3] Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 NBR 100 100 100 100 Epoxy Resin 1 70 70 70 70 2 - — - — 3 100 100 100 100 4 — — — — Hardener 15 15 5 30 Inorganic particles 70 10 60 60 The physical properties of the surface coating film produced by the foregoing composition and method were evaluated by evaluating the foregoing examples and comparative examples. The results are disclosed in Tables 4 to 6 below. 10 [Table 4] Example 1 Example 2 Example 3 Example 4 Conditional viscous strength (N/cm) 11.8 10.2 10. 1 13.4 JIS C6471 (1995) 8.1 Flowability (/M) 150 180 170 200 氺15 1335931 Heat resistance (°C) 360 360 360 350 JIS C6471 (1995) 9.3 80% RH/30min Flame resistance V-0 V-0 V-0 V-0 UL94 [Table 5] Comparative example 1 Comparative example 2 Comparative Example 3 Comparative Example 4 Conditional Viscosity (N/cm) 12. 1 6. 7 11. 9 7. 3 JIS C6471 (1995) 8.1 Flowability (Ping 1) 130 180 140 190 Heat resistance (° C) 350 350 340 360 JIS C6471 (1995) 9. 3 80% RH/30min Flame resistance V-1 V-0 V-1 V-0 UL94 [Table 6] Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Conditional viscous strength (N/cm) 9. 1 13. 7 7. 1 3. 8 JIS C6471 (1995) 8.1 Flowability (present 1) 110 250 310 80 氺 Heat resistance (°C) 370 290 260 300 JIS C6471 (1995) 9. 3 80% RH/30min Flame retardant V-0 V-1 V-1 V-0 UL94 5 *Drill a 5mm diameter hole and a strength of 30Kg/cm2 on the finished surface film After pressing the film for 3 minutes, the length of the adhesive outside the outflow hole was measured. In practice, in order to make the physical properties of the surface film of the film suitable, the viscosity must be 10 N/cm or more. The film has a flowability of 150 to 16 1335931 200 s. The heat resistance must be 300 ° C or higher. The flame resistance must be V-Ο. As seen in Table 4, the surface film film is composed of an adhesive composition for a surface film, as in the solid examples 1 to 4 according to the present invention, wherein the surface film satisfies all of the aforementioned physical properties. nature. 5 It is to be noted that various modifications and changes can be made thereto in accordance with the present invention without departing from the true spirit and scope of the invention. It is to be understood that the foregoing is only intended to be illustrative of the invention and not to limit the scope of the invention. 10 [Simple description of the figure 3 <None] [Description of main component symbols] <None> 17