TW572983B

TW572983B - Method for producing substrate for flexible circuit board, and adhesive used by the method

Info

Publication number: TW572983B
Application number: TW90117685A
Authority: TW
Inventors: Tang-Jie Huang; Jau-Chin Juang
Original assignee: Microcosm Technology Co Ltd
Priority date: 2001-07-19
Filing date: 2001-07-19
Publication date: 2004-01-21

Abstract

The present invention provides a method for producing a substrate for a flexible circuit board, and an adhesive used by the method. The adhesive comprises: a main agent, a hardener, and a hardening catalyst, in which the main agent consists of: an epoxy resin, a toughening agent, a main catalyst, a filling agent, an ion exchange agent, a dispersing agent, and a solvent. In order for the substrate for a circuit board having a better flame retardancy and environmental tolerance, the present invention adopts a method of increasing the content of a brominated epoxy resin, while adopting a phosphorous compound as a main catalyst. A production process comprises grinding a filling agent, an ion exchange agent, a dispersing agent, and a portion of the solvent; adding other components of the main agent to prepare the main agent; mixing the main agent, the hardener, the hardening catalyst according to a specified ratio into an adhesive; and coating the adhesive between a plastic mold and a copper foil and thermally pressing the composite. Thus, a substrate for a flexible printed circuit board according to the present invention can be produced.

Description

572983 Α7 Β7 經濟部智慧財產局員工消費合作社印製五、發明說明（1 ) 【發明領域】本發明是關於一種軟性印刷電路板用基板之製法，以及使用於該製法之接著劑與該接著劑之主劑，特別是指一種製得之軟性印刷電路板用基板具有良好的銅線遷移抑制性，同時兼具有較佳難燃性及耐環境性之製法與使用於該製法之接著劑。【習知技藝說明】軟性印刷電路板用基板在製造上，為了將銅箔固定在一例如聚醯亞胺的塑膠膜上，通常是在該塑膠膜上塗佈一層接著劑，由於接著劑是銅箔和塑膠膜間黏結的一個介質’因此，接著劑在電流負載及溼氣下是否銅線仍可穩定不遷移，乃直接影響製作之軟性印刷電路板用基板的品質。在已知的技藝中，使用於軟性印刷電路板用基板之接著劑大都以丙烯腈-丁二烯橡膠 (Nitrile-butadiene rubble，以下簡稱 NBR)來增加高溫熟化時之撓曲性，儘管NBr可增進軟性印刷電路板用基板之撓曲性，惟當電路板上銅線間的寬度在O.i mm ’且在電流負載與溼氣的侵蝕下，銅線會開始產生解離形成樹枝狀，此種銅線離開原本被設置位置的現象 ’ 一般稱為遷移（migration)。為了改善銅線遷移的現象，曰本特開平2-269788 案係在軟性印刷電路板用基板的接著劑中，添加可捕捉銅離子並減低銅離子移動速度之酼基三吖嗉(mercaptotriazine)，而曰本特開平 3·294349 案，則是第3頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注裝—— 寫本頁) .. ί -線· 572983 A7 經濟部智慧財產局員工消費合作社印製五、發明說明（2 ) 在接著悧中加入苯酚還原劑，以接以v nbr藉以有效的抑制軟性印刷電路板用A # 上的銅線遷移，卜诚允链P A t 用基板上达各種已知的技藝雖可抑制銅線遷私…、、而，、白必需額外添加化合物，戋者以1 ^ & 來取伙工豐勿扃耆以其他橡膠末取代工業上容易取得< NBR，因此，本上較高。 1 a考成為了仍M NBR來增加軟性印刷電路板用基板之曲：’並提高接著劑之抑制遷移性及抗吸溼性，公： :第342410唬發明專利案提供一種軟性印刷電路板用基板之製法，以及用於該製法之接著劑及主劑，主州係由· 1 〇〇重量份環氧樹脂、30〜100重量份之^ 膠〇.01〜1,0重量份之三級胺主觸媒、1〇〇〜4〇〇重 ^ 及2〜3〇重置份之填料所構成，其中，環氧樹脂之每一分子至少含有兩個以上之環氧官能基， :橡膠中含有]基（·⑺叫氰基（_c明❹基（·0Η) 能基：儘管前述專利案所製造之軟性印刷電路板 =土板’係Μ容易取得之NBR為材料，並具有良好的 ^移抑制性及抗吸溼性，然而前述專利案為了達到較佳之遷移抑制性，其環氧樹脂中不可含有過量的溴元 '、、、丨玄電路板在加工形成電路時，銅線仍然會產生遷移之現象，此外，當含溴之環氧樹脂添加過量時 :然難::性愈佳，但銅線遷移現象會更為嚴重，亦會成接著切黏度增加，導致接著劑塗佈在塑膠膜後，第4頁卜紙張尺度適財關tl?HiS)A4規格⑽x297公爱） ------------ 裝 (請先閱讀背面之注意事項寫本頁> _ 線： 572983 A7572983 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (1) [Field of the Invention] The present invention relates to a method for manufacturing a substrate for a flexible printed circuit board, and an adhesive and the adhesive used in the method The main agent refers to a manufacturing method of a substrate for a flexible printed circuit board which has good copper wire migration resistance, and also has a good flame retardancy and environmental resistance, and an adhesive used in the manufacturing method. [Know-how] In the manufacture of substrates for flexible printed circuit boards, in order to fix the copper foil on a plastic film such as polyimide, a layer of adhesive is usually coated on the plastic film. Since the adhesive is A medium that is bonded between the copper foil and the plastic film. Therefore, whether the copper wire can still be stable and does not migrate under the current load and moisture, which directly affects the quality of the substrate for the flexible printed circuit board produced. In known techniques, most of the adhesives used for flexible printed circuit board substrates are acrylonitrile-butadiene rubble (hereinafter referred to as NBR) to increase the flexibility at high temperature curing, although NBr can Improve the flexibility of the substrate for flexible printed circuit boards, but when the width between the copper wires on the circuit board is Oi mm 'and under the erosion of the current load and moisture, the copper wires will begin to dissociate and form dendritic shapes. The phenomenon that a line leaves its original position is generally called migration. In order to improve the migration of copper wires, Japanese Patent Application Laid-Open No. 2-269788 is based on the addition of mercaptotriazine, which can trap copper ions and reduce the speed of copper ions, in the adhesive for substrates for flexible printed circuit boards. On the other hand, the case of Japanese Patent Application No. 3,294,349 is on page 3. The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back-write this page) .. ί-line · 572983 A7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Add phenol reducing agent to the following 悧 to use v nbr to effectively suppress the use of A # on flexible printed circuit boards Copper wire migration, Bu Chengyun chain PA t using a variety of known techniques on the substrate can inhibit the migration of copper wires ... ,,, and white compounds must be added, the person with 1 ^ & Do not replace the industrially available < NBR with other rubber powders, so the cost is higher. 1 a test has become a M NBR to increase the flexibility of the substrate for flexible printed circuit boards: 'and improve the migration resistance and moisture absorption resistance of the adhesive, public:: Patent No. 342410 provides a flexible printed circuit board The substrate manufacturing method, as well as the adhesive and main agent used in the manufacturing method, the main state is three grades: · 100 parts by weight of epoxy resin, 30 ~ 100 parts by weight of ^ glue, 0.01 ~ 1,0 parts by weight It is composed of amine main catalyst, 100 ~ 400 weight ^ and 2 ~ 30 reset parts of filler, wherein each molecule of epoxy resin contains at least two epoxy functional groups, in rubber Contains] group (· ⑺ called cyano (_c 明 ❹ 基 (· 0Η)) energy base: Although the flexible printed circuit board = soil board manufactured in the aforementioned patent case is NBR easily obtained as a material, and has a good ^ Migration inhibition and moisture absorption resistance, however, in order to achieve better migration inhibition in the aforementioned patents, the epoxy resin must not contain excessive bromine, and copper wires will still be formed when the circuit board is processed to form a circuit. Migration occurs, and when bromine-containing epoxy resin is added in excess: Difficulties: The better the performance, but the copper wire migration phenomenon will be more serious, and it will also increase the viscosity of the cut, resulting in the adhesive is coated on the plastic film. 297x297 public love) ------------ outfit (please read the precautions on the back first to write this page) _ line: 572983 A7

銅、七會有不易調整及加工不便等缺失，此外前述專利案之耐候性亦較不理想。五、發明說明（3 ) 【發明概要】因此’本發明之目的是在提供一種製得之成品具有較佳難燃性及耐環境性之軟性印刷電路板用基板的製法。本發明之另一目的在於提供一種用於製造軟性印席J電路板用基板之接著劑以及該接著劑之主劑，特別疋^曰種可提而軟性印刷電路板用基板之難燃性及而才環境性之接著劑及其主劑。於是，本發明之接著劑的主劑係可被運用在軟性印刷電路板用基板的製造上，該主劑包含： (a) 1 〇〇重量份之環氧樹脂，該環氧樹脂之每一分子中至少含有兩個以上之環氧官能基，且樹脂中具有8 0重量份以上的溴化型環氧樹脂，該溴化型環氧樹脂之溴含量在10〜50重量％ ; (b) 20〜50重量份的增韋刃劑，該增勃劑是選自至少一種：含有魏基（carboxy)及氰基（-CeN，cyano)之橡膠、含有二級胺基（-NH-，ami no)及氰基之橡膠、含有環氧基，epoxy)及氰基之橡膠及/ 或雙環氧化物； (c) 0.1〜2.0重量份之磷化合物； (d) 2〜12重量份之填充劑； (e) 1〜10重量份之離子交換劑；第5頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項^寫本頁) · •線· 經濟部智慧財產局員工消費合作社印製 572983 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（4 ) (f) 0.1~1·0重量份之分散劑；及 (g) 125〜170重量份之溶劑。本發明之接著劑乃使用上述主劑，並進一步填加 1〜20重量份的硬化劑，以及0.1〜2重量份的硬化觸媒〇本發明軟性印刷電路板用基板之製法包含以下步驟： (a) 預先研磨：將2〜12重量份之填充劑、1〜10重量份之離子交換劑、0.1〜1.0重量份之分散劑及少量的溶劑預先進行研磨； (b) 製備主劑：將（a)步驟研磨混合物與100重量份之環氧樹脂、20〜50重量份之增韌劑、0.1〜2.0重量份之磷化合物，以及與（a)步驟中使用之溶劑合計 125〜170重量份的溶劑混合均勻，其中環氧樹脂中含有 8 0重量份以上之溴化型環氧樹脂，且溴化型環氧樹脂中溴含量在 10〜50重量％以上，然後以 5 0〜120 °C之反應溫度進行預聚合反應，待黏度提高至3OOcps以上，即可製得預聚合反應之主劑； (c) 製備接著劑：取（b)步驟製得之主劑100重量份，再與1〜20重量份之硬化劑，以及0.1〜2重量份的硬化觸媒混合均句，以製得接著劑；及 (d) 製備電路板用基板：在一塑膠膜上塗佈一層（c)步驟製成之接著劑，再於該接著劑上貼附一層銅箔，三者間藉由高溫熟化，即可製得軟性印刷電路板用第6頁 (請先閱讀背面之注意事項寫本頁) 1霞 . 線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） Α7The copper and the Seventh Congress are not easy to adjust and inconvenient to process. In addition, the weather resistance of the aforementioned patent case is also less than ideal. V. Description of the invention (3) [Summary of the invention] Therefore, the object of the present invention is to provide a method for manufacturing a substrate for a flexible printed circuit board having better flame retardancy and environmental resistance. Another object of the present invention is to provide an adhesive for manufacturing a substrate for a flexible printed circuit board and a main agent for the adhesive, in particular, it can improve the flame retardancy of the substrate for a flexible printed circuit board and And environmentally friendly adhesive and its main agent. Therefore, the main agent of the adhesive of the present invention can be applied to the manufacture of substrates for flexible printed circuit boards. The main agent includes: (a) 100 parts by weight of epoxy resin, each of which The molecule contains at least two epoxy functional groups, and the resin has more than 80 parts by weight of a brominated epoxy resin, and the bromine content of the brominated epoxy resin is 10 to 50% by weight; (b) 20 to 50 parts by weight of Zengwei blade agent, the swelling agent is selected from at least one: rubber containing carboxy and cyano (-CeN, cyano), and secondary amine (-NH-, ami) no) and cyano-based rubber, rubber and / or biepoxide containing epoxy) and cyano-based rubber; (c) 0.1 to 2.0 parts by weight of a phosphorus compound; (d) 2 to 12 parts by weight of a filler ; (E) 1 ~ 10 parts by weight of ion exchanger; page 5 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first ^ write this page) · • Line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 572983 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) (f) 0.1 to 1.0 parts by weight of a dispersant; and (g) 125 to 170 parts by weight of a solvent. The adhesive of the present invention uses the above-mentioned main agent, and further adds 1 to 20 parts by weight of a hardener and 0.1 to 2 parts by weight of a hardening catalyst. The method for manufacturing a substrate for a flexible printed circuit board of the present invention includes the following steps: ( a) Pre-grinding: pre-mill 2 to 12 parts by weight of filler, 1 to 10 parts by weight of ion exchanger, 0.1 to 1.0 part by weight of dispersant, and a small amount of solvent; (b) Preparation of the main agent: ( a) Step grinding mixture with 100 parts by weight of epoxy resin, 20 ~ 50 parts by weight of toughening agent, 0.1 ~ 2.0 parts by weight of phosphorus compound, and 125 ~ 170 parts by weight with the solvent used in step (a) The solvent is mixed uniformly, wherein the epoxy resin contains more than 80 parts by weight of brominated epoxy resin, and the bromine content of the brominated epoxy resin is more than 10 to 50% by weight, and then the temperature is 50 to 120 ° C. The prepolymerization reaction is carried out at the reaction temperature, and the main agent of the prepolymerization reaction can be obtained when the viscosity is increased to more than 3OOcps; (c) Preparation of the adhesive: Take 100 parts by weight of the main agent obtained in step (b), and then 20 parts by weight of hardener, and 0.1 ~ 2 weight Parts of the hardening catalyst are mixed to make an adhesive; and (d) preparing a substrate for a circuit board: coating a layer of the adhesive made in step (c) on a plastic film, and then pasting on the adhesive With a layer of copper foil, the three can be cured by high temperature to produce a flexible printed circuit board. Page 6 (Please read the precautions on the back first to write this page) 1 Xia. Line · This paper size applies to Chinese national standards ( CNS) A4 size (210 X 297 mm) Α7

572983 五、發明說明（5 ) 基板。本發明所使用之環氧樹脂乃選自··酚醛清漆樹脂、苯酚Α型環氧樹脂、芳香族環氧樹脂、脂肪族環氧樹脂，以及鹵化環氧樹脂等，所使用之環氧樹脂中每一分子至少含有兩個或兩個以上之環氧官能基。基= 難燃性之要求，本發明之環氧樹脂中含有8〇重量份以上的溴化型環氧樹脂，當溴化型環氧樹脂之組成比例低於8 0重量份時，無法通過難燃性試驗。本發明所使用之增韋刃劑可提供接著劑在高溫熟化後所需的咼撓曲性，即增加接著劑之韌性，適合於本發明之增韌劑可分為橡膠及雙環氧化物兩類，其中，適合於本發明之橡膠包括： ①叛基封端之丁腈共聚物（carb〇xy_terminated butadiene-acrylonitrile，以下簡稱 CTBN)，該共聚物為同時含有羧基及氰基之橡膠，其結構式為： 0 0572983 5. Description of the invention (5) Substrate. The epoxy resin used in the present invention is selected from the group of novolac resins, phenol A epoxy resins, aromatic epoxy resins, aliphatic epoxy resins, and halogenated epoxy resins. Each molecule contains at least two or more epoxy functional groups. Base = flame retardant requirements. The epoxy resin of the present invention contains more than 80 parts by weight of a brominated epoxy resin. When the composition ratio of the brominated epoxy resin is less than 80 parts by weight, it is difficult to pass through. Flammability test. The Zengwei blade used in the present invention can provide the required flexibility of the adhesive after curing at high temperature, that is, to increase the toughness of the adhesive. The toughener suitable for the present invention can be divided into two types: rubber and double epoxy. Among them, rubbers suitable for the present invention include: ① Carboxyterminated butadiene-acrylonitrile (hereinafter referred to as CTBN), the copolymer is a rubber containing both carboxyl and cyano groups, and its structural formula For: 0 0

II π IIII π II

HO-C— Ρ —C-OH 其中，結構式中之p 代表（以下亦同）： -4CH2-CH=CH-CH2)5n~(CH2-CH)^~CCH2-CH)y——HO-C— Ρ —C-OH where p represents in the structural formula (the same applies hereinafter): -4CH2-CH = CH-CH2) 5n ~ (CH2-CH) ^ ~ CCH2-CH) y——

CH C-NCH C-N

II CH2 以上結構式中R、Xi、X2、y、η皆為1以上之第7頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）裝--- (請先閱讀背面之注咅？事項^^^寫本頁) 訂· 線. 經濟部智慧財產局員工消費合作社印製 572983 A7 B7 五、發明說明（6 ) 整數。 ②胺基封端之丁腈共聚物（amine-terminated butadiene-acrylonitrile ，以下簡稱 ATBN) ，該共聚物為同時含有胺基及氰基之橡膠，其結構式為： Η Η ΗΝ Ν Ν 〇 ρ CII ο Ν /\Α kN ΝΗ ③環氧基封端之丁腈共聚物（epoxide-terminated butadiene-acrylonitrile，以下簡稱 ETBN)，該共聚物為同時含有環氧基及氰基之橡膠，其結構式為·· 0II CH2 In the above structural formula, R, Xi, X2, y, η are all 1 or more. Page 7 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Packing --- (Please read first Note on the back? Matters ^^^ Write this page) Order. Thread. Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 572983 A7 B7 V. Description of the invention (6) Integer. ② Amine-terminated butadiene-acrylonitrile (hereinafter referred to as ATBN), which is a rubber containing both amine and cyano groups, and its structural formula is: Η Η ΗΝ Ν Ν Ν 〇ρ CII ο Ν / \ Α kN ΝΗ ③ Epoxy-terminated butadiene-acrylonitrile (ETBN), an epoxy-terminated butadiene-acrylonitrile copolymer. The copolymer is a rubber containing both epoxy and cyano groups. Its structural formula is ·· 0

R CII 〇R CII 〇

〇H 0H〇H 0H

〇請先閱讀背面之注意事項〇 Please read the notes on the back first

f 經濟部智慧財產局員工消費合作社印製適合於本發明之雙環氧化物的具體例子有： ① 二甘醇二縮水甘油醚（diethylene glycol diglycidoyl ether)，其結構式為： Α Λ ch2-chch2o(ch2)2o(ch2)2och2ch-ch2 ② 丁二醇二縮水甘油 _ (butanediol diglycidoyl ether) ，其結構式為：八 Λ ch2-chch2o(ch2)4och2ch-ch2 第8頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 572983 A7 ----- B7 經濟部智慧財產局員工消費合作社印製五、發明說明（7 ) ③間本二紛一縮水甘油鱗（res〇rcin glycol diglycidoyl ether)，其結構式為：f Specific examples of biepoxides suitable for the invention printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics are: ① Diethylene glycol diglycidoyl ether, whose structural formula is: Α Λ ch2-chch2o ( ch2) 2o (ch2) 2och2ch-ch2 ② Butanediol diglycidoyl ether, whose structural formula is: Λ ch2-chch2o (ch2) 4och2ch-ch2 Page 8 This paper is in accordance with Chinese national standards ( CNS) A4 specifications (210 X 297 mm) 572983 A7 ----- B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) ③ Refining glycerol scales diglycidoyl ether), its structural formula is:

八 och2ch-ch OCH2qH^CH2 ο 本發明之增韌劑可選擇其中一種或者兩種以上併用，其使用量乃相對於100重量份之環氧樹脂的20〜50 重量份。本發明所使用之主觸媒為一種磷化合物，其具體之例子有：三苯基填（Triphenyl phosphite，以下簡稱 TPP)、溴化乙院三苯基膦（ethyl triphenyl phosphine bromide，簡稱 ETPPB)、碘化乙烷三苯基膦（ethyl triphenyl phosphine iodide，簡稱 ETPPI)等，其中三苯基磷之結構式為：© 上述TPP是一種可促進反應之催化劑，由於其立體障礙較大，因此，在催化項次二環氧樹脂進行醚化反應時，會因為官能基位在分子鏈中間，而導製反應不易進行，基於上述原因，本發明使用 TPP可非常有效地促進反應官能基位在分子鏈末端的環氧樹脂與增第頁 (請先閱讀背面之注音3事項δ寫本頁) 1襄 :線_ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 572983 A7 B7 五、發明說明（8 ) 韌劑間進行聚合反應。上述主觸媒之使用量為〇1~2() 重量份。 (請先閱讀背面之注意事項再填寫本頁) 本發明所使用的填充劑乃相對於1 〇〇重量份之環氧樹脂的2〜1 2重量份，添加填充劑之目的在於提高接著劑之高溫熟化後的尺寸安定性、耐熱性及機械打孔性。適合於本發明之填充劑乃例如：二氧化矽（Si〇^ 、三氧化二鋁（Al2〇3)、氫氧化鋁[A1(〇h)3]、氫氧化鎂 [Mg(OH)2]、三氧化二銻（Sb2〇3)、矽酸鈣（CaSi〇3)、碳酸鈣（CaC03)、碳酸鎂（MgC03)、氧化鎂（MgO)、氧化鋅（ZnO)及氮化硼（BN)。上述填充劑可視需要單獨使用一種或者兩種以上併用，使用時可利用球磨機將原本 1〜1 0 # m的填充劑研磨成〇 · 〇 1〜1 # ^大小的細微粒子〇經濟部智慧財產局員工消費合作社印製本發明所使用之溴化型環氧樹脂以及填充劑皆會產生陰、陽離子，為了避免陰、陽離子遷移導致導電短路’本發明乃加入1〜1 0重量份之離子交換劑，適合於本發明之離子交換劑乃例如：Sb205 · 2H20、 Bi(OH)0 7(NO3)0.3、Bi〇(〇H) 0 74 (NO3)0.15(HsiO3)0 n、 BiO(OH)等，其中，Sb205 · 2H2〇為陽離子交換劑，其餘皆為陰離子交換劑。本發明所使用之分散劑可降低填充劑表面能量，避免被研磨成細微粒子之填充劑因凡得瓦力作用再度凝結。本發明使用溶劑對填充劑有潤溼的效果，其係選第10頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 572983 A7Eight och2ch-ch OCH2qH ^ CH2 ο One or two or more of the toughening agents of the present invention may be used in combination, and the amount used is 20 to 50 parts by weight relative to 100 parts by weight of the epoxy resin. The main catalyst used in the present invention is a phosphorus compound, and specific examples thereof include: Triphenyl phosphite (hereinafter referred to as TPP), ethyl triphenyl phosphine bromide (ETPPB), Ethyl triphenyl phosphine iodide (ETPPI), etc., where the structural formula of triphenyl phosphorus is: © The above TPP is a catalyst that can promote the reaction. Because of its large steric hindrance, When the secondary epoxy resin is catalyzed in the etherification reaction, the guiding reaction is not easy because the functional group is in the middle of the molecular chain. Based on the above reasons, the use of TPP in the present invention can very effectively promote the reaction of the functional group in the molecular chain. Epoxy resin at the end and the first page (please read the note on the back 3 items δ write this page) 1 Xiang: Line_ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 572983 A7 B7 V. Description of the invention (8) Polymerization between the toughening agents. The amount of the main catalyst used is 0 to 2 () parts by weight. (Please read the precautions on the back before filling this page.) The filler used in the present invention is 2 to 12 parts by weight relative to 1000 parts by weight of epoxy resin. The purpose of adding a filler is to improve the adhesive. Dimensional stability, heat resistance and mechanical perforation after high temperature curing. Suitable fillers for the present invention are, for example: silicon dioxide (Si〇 ^, aluminum oxide (Al203), aluminum hydroxide [A1 (〇h) 3], magnesium hydroxide [Mg (OH) 2] , Antimony trioxide (Sb203), calcium silicate (CaSi03), calcium carbonate (CaC03), magnesium carbonate (MgC03), magnesium oxide (MgO), zinc oxide (ZnO), and boron nitride (BN) The above-mentioned fillers can be used alone or in combination of two or more. If necessary, the original filler can be ground to a size of 〇 · 〇1 ~ 1 # ^ by using a ball mill. 〇 The intellectual property of the Ministry of Economic Affairs Bureau employee consumer cooperatives print the brominated epoxy resins and fillers used in the present invention to produce anions and cations. In order to avoid conductive short circuits caused by the migration of cations and cations, the present invention adds 1 to 10 parts by weight of ion exchange. Agents suitable for the ion exchanger of the present invention are, for example, Sb205 · 2H20, Bi (OH) 0 7 (NO3) 0.3, Bi〇 (〇H) 0 74 (NO3) 0.15 (HsiO3) 0 n, BiO (OH) Among them, Sb205 · 2H2O is a cation exchanger, and the rest are anion exchangers. The dispersant used in the present invention can reduce The surface energy of the filler prevents the filler which has been ground into fine particles from re-condensing due to the effect of van der Waals. The solvent used in the present invention has a wetting effect on the filler. It is selected on page 10. This paper size applies Chinese national standards ( CNS) A4 size (210 X 297 public love) 572983 A7

五、發明說明（9 ) 目：甲乙酮、丙酮、甲醇、乙醇、異丙醇、正丙醇、曱笨以及二甲苯。本發明接著劑使用硬化劑之目的在於：當接著劑經塗佈機塗佈在塑膠膜上後，在烘箱乾燥及高溫熟化寺’月b與主劑中的壞氧樹脂產生交聯作用（c r 〇 s s _ hnking)。本發明之硬化劑可選自：氰基胍 (Cyanoguanidine)、二乙撐基三胺（Diethylene triamine) 、二乙樓基四胺（!>iethylene tetraamine)、二氨基二苯基甲烧（Diamino diphenyl methane)、二氨基二苯基讽 (Diamino diphenyl sulfone)、欧肝（phthalic anhydride) 、四氫酜酐（Tetrahydro phthalic anhydride)、三氟化棚胺錯化物（Boron trifluoride amine complex compounds) 、多官能基環氧樹脂（Multi-functional epoxy)，以及紛醛樹脂（phenolic resin)等，上述硬化劑可視需要選用一種，或者混合兩種以上使用，其使用量為1〜20重量份。本發明接著劑使用硬化觸媒之目的在於：提高接著劑組成中的環氧樹脂和硬化劑的交聯速率，上述硬化觸媒乃選自：2·苯基口米唾（2-phenyl imidazole)、1-苯基-2-甲基味口坐（1-0]161171-2-11161:117111111(1&2〇16)、2-乙基-4-曱基口米唾（2-ethyl-4-methyl imidazole)、BF3 單乙基胺（BF3 monoethylamine)、氟蝴化鋅（Zinc borofluoride)、氟棚化錫（Tin borofluoride)、氟棚化鎳 (Zickel boro fluoride)、六氫吼 °定（Piperidine，以下簡第11頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項寫本頁) I!裝訂—-—U—線- 經濟部智慧財產局員工消費合作社印製 572983 A7 五、發明說明（10) 稱間等，上述硬化觸媒可視需要單獨選用—種或混合兩種以上使用，其添加量在01~2重量份間。本發明電路板用&板在製造時L進行㈣製備’即先將主劑中的填充劑、離子交換劑、分散劑、以及部份的溶劑預先以球磨機研磨，然後將主劑中的環氧樹脂、增動劑、主觸媒等完全的溶解在其餘的溶劑中，待反應完成後即形成主劑。將預定比例之主劑、硬化劑、硬化觸媒混合均句後，即可製得本發明之接著劑。然後以塗佈機將接著劑塗佈在一塑膠膜上，上述塑膠膜可為：聚醯亞胺、聚乙烯（PE)、聚酯（PET) 、聚笨撐颯、聚氯乙烯（PVC)、聚丙烯（pp)等，上述塗佈有本發明接著劑之塑膠膜再經過烘箱乾燥卜3分鐘，乾燥的溫度從100~15(rc，最後再和銅箱熱滚壓貼合，經高溫熟化後即可製得一性能優異之軟性印刷電路板用基板。【評價方式】 1) 難燃性測試：依UL94認證之VTM-O試驗。 2) 耐熱性測試：依IPC TM650 2,4,23方式測試，將 δ式驗片置於而溫錫錯浴中浸泡1 〇秒鐘後，觀察是否起泡。 3) 剝離強度測試··依IPC ΤΜ650 2,4,9方法測試，切割寬約1公分的試驗片，再以拉力機測試其剝離時之強度。 4) 線間絕緣阻抗：依jis C5016方法測試。第12頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意 I I I I I - I I 意事項寫本頁) 經濟部智慧財產局員工消費合作社印製 572983 A7 五、發明說明（11 > 5) 表面阻抗：依IpCTM65〇2,5，i7方法測試。 6) 體積阻抗：依IpcTM65〇2,5,i7方法測試。 7) 撓曲性須丨J試· /六Λ/ΤΤΤ女 •依 MIT 方法及 IPC TM650 2,4,3 方法測試。 8) 耐環境性測雙·胳崎鉍Η里八·將δ式驗片置於 8〇。〇、l〇〇%RH之怪溫恆濕機中1 ηηη I 士 ^ /、】式試驗片之而才熱性及剝離強度。 9) 耐溶劑性：將叫緣Η久兄丨1班將忒驗片各別置於氫氧化鈉、氯化氫及曱乙酉同專溶劑中1 5分鐘，々 J中1 5刀麵各別觀察溶劑滲入聚醯亞細與銅箔間的距離。 10) 銅線遷移抑制糾、、目彳叫·力叫，一制14測5式·在我驗片蝕刻出0.1mm線平行、久路，然後將該试驗片置於80°C、100%rh 之怪溫悝濕機巾，孟# 7彳Πην 甲再施以1 00ν的直流電路，並記錄銅線析出物長出的時間。 1 1)尺寸女及性（蝕刻收縮率％)測試：依IPC ΤΜ650 2,2,4方法測試。【較佳實施例及比較例之詳細說明】貫施例一將表一所示5重量份之Sb2〇3、2 5重量份之Al2〇3 、1·5重量份之Sb205 · 2Η2〇、 15重量份之V. Description of the Invention (9) Title: Methyl ethyl ketone, acetone, methanol, ethanol, isopropanol, n-propanol, benzene and xylene. The purpose of the hardener used in the adhesive of the present invention is: after the adhesive is coated on the plastic film by a coater, it is dried in an oven and cured at a high temperature to produce a cross-linking effect (cr 〇ss hnking). The hardening agent of the present invention may be selected from the group consisting of: Cyanoguanidine, Diethylene triamine, Diethylene tetraamine (! &Gt; iethylene tetraamine), Diamino diphenyl methane (Diamino diphenyl methane, diamino diphenyl sulfone, phthalic anhydride, tetrahydro phthalic anhydride, boron trifluoride amine complex compounds, polyfunctional Multi-functional epoxy, phenolic resin, etc., the above-mentioned hardener can be selected according to need, or a mixture of two or more, the amount of which is 1 to 20 parts by weight. The purpose of using a hardening catalyst in the adhesive of the present invention is to increase the cross-linking rate of the epoxy resin and the hardener in the composition of the adhesive. The hardening catalyst is selected from the group consisting of 2-phenylimidazole , 1-phenyl-2-methyl taste mouth (1-0) 161171-2-11161: 117111111 (1 & 2〇16), 2-ethyl-4-fluorenyl mouth rice saliva (2-ethyl- 4-methyl imidazole), BF3 monoethylamine, BF3 monoethylamine, Zinc borofluoride, Tin borofluoride, Zickel boro fluoride, Hexahydrogen Piperidine, page 11 below This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back first to write this page) I! Binding —-— U—Line-Ministry of Economy Printed by the Consumer Property Cooperative of the Intellectual Property Bureau 572983 A7 V. Description of the invention (10) Weighing room, etc. The above hardening catalyst can be selected individually or in combination of two or more types, and the added amount is between 01 and 2 parts by weight. Invented the circuit board & board at the time of manufacture. It was 'prepared', that is, the filler and ion exchange in the main agent , Dispersant, and some solvents are ground in advance with a ball mill, and then the epoxy resin, accelerator, and catalyst in the main agent are completely dissolved in the remaining solvents, and the main agent is formed after the reaction is completed. After the predetermined proportion of the main agent, the hardening agent, and the hardening catalyst are mixed, the adhesive of the present invention can be prepared. Then, the adhesive is coated on a plastic film by a coating machine, and the plastic film can be: Polyimide, polyethylene (PE), polyester (PET), polystyrene, polyvinyl chloride (PVC), polypropylene (pp), etc. The plastic film coated with the adhesive of the present invention is then passed through an oven. Dry for 3 minutes, and the drying temperature is from 100 to 15 (rc, and finally hot-rolled and bonded to the copper box. After high-temperature curing, a substrate for flexible printed circuit boards with excellent performance can be obtained. [Evaluation method] 1) Flame resistance test: VTM-O test according to UL94 certification 2) Heat resistance test: Test according to IPC TM650 2,4,23 method, δ-type test piece is placed in a warm tin bath for 10 seconds 3) Peel strength test · Test according to IPC TM650 2,4,9 method Cutting a test piece 1 cm wide, and then to tensile test machine when the peel strength. 4) Insulation resistance between wires: tested according to jis C5016 method. Page 12 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the notes on the back IIIII-II) and write this page) Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative 572983 A7 V. Description of the invention (11 > 5) Surface impedance: tested according to IpCTM650, 2, 5 and i7 methods. 6) Volume impedance: tested in accordance with IpcTM650,5, i7 method. 7) Flexibility must be tested by J / Six Λ / ΤΤΤ Female • Tested according to MIT method and IPC TM650 2,4,3 method. 8) Environmental resistance test double kisaki bismuth VIII. Place the δ-type test piece at 80. 〇, 100% RH in the strange temperature and humidity machine 1 ηηη I ± ^ /,] type test piece of the thermal properties and peel strength. 9) Solvent resistance: will be called Yuan Jiu brother 丨 class 1 will be placed in the sodium hydroxide, hydrogen chloride and ethyl acetate in the same special solvent for 15 minutes, 15 in the JJ knife surface observation solvent Infiltrate the distance between polyfluorene and copper foil. 10) Copper wire migration suppression correction, screaming, screaming, 14-type 5 test, one system. 0.1mm parallel lines and long paths were etched in my test piece, and then the test piece was placed at 80 ° C, 100 % rh's strange temperature wet wipes, Meng # 7 彳 Πην A DC circuit of 1 00 ν was applied, and the time for the copper wire precipitates to be recorded was recorded. 1 1) Size female and sexual (etching shrinkage%) test: tested according to IPC TM650 2,2,4 method. [Detailed description of the preferred embodiment and the comparative example] In the first embodiment, 5 parts by weight of Sb203, 2.5 parts by weight of Al2O3, and 1.5 parts by weight of Sb205, 2Η20, 15 are shown in Table 1. Parts by weight

BiCOH)^ /NOJo 3、〇.5重量份之無機化合物，以及12 重ΐ份之甲乙酮預先置於一球磨罐中研磨72小時，然後將上述混合物與1 〇重量份環氧樹脂、2 〇重量份之 >臭化型環氧樹脂、7 4重量份之咼填化環氧樹脂、2 4重第13頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）請先閱讀背之注項 1% I裝頁吞丁經濟部智慧財產局員工消費合作社印製 572983 A7 ----- B7 經濟部智慧財產局員工消費合作社印製五、發明說明（12 ) 量份之液態NBR、1 2重量份之固態丙烯腈-丁二烯橡膠NBR、0.2重量份之TPP、138重量份之甲乙綱，以及8重量份之正丙醇混合溶解均勻，並在8 〇下反應 15小時，即可製成本發明所需之主劑，製成之主劑的黏度為500cps，固形份約為5〇重量％。將前述主劑配合硬化劑之二氨基二苯基甲烧、二氨基二苯基颯，以及硬化觸媒之氰基胍、BF3_pIp以1〇〇 :1·〇 : 0.4 : 0.1 : 0.04的比例混合均勻後，即可製成本發明之接著劑。將前述接著劑以塗佈機塗佈在一聚醯亞胺塑膠膜表面，並使該結合體通過1〇〇〜15〇aC烘箱乾燥丨〜3分麵’然後將銅箔貼在接著劑上方，再以8 5 °C的溫度將其熱滚壓在接著劑上方，貼合後經1 9 0 °C高溫熟化，即可製得一軟性印刷電路板用基板。依上述評價方式的說明，將該印刷電路板用基板製成需要的試驗片，並進行各項試驗，試驗結果載於表二。實施例二製程及接著劑的成份組成比例皆相同於實施例一 ’貫施例二與實施例一間的差別在於主劑的成份，而主劑的種類及使用量皆載於表一，試驗結果载於表二〇比較例一製程及接著劑的成份組成比例皆相同於實施例一，比較例一與實施例一間的差別在於主劑的成份，而第14頁 ----------- 裝 (請先閱讀背面之注意事項寫本頁) · -ί 線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 572983 A7 _B7_五、發明說明（l3 ) 主劑的種類及使用量皆載於表一，試驗結果載於表二例較比例施實於同相皆例比成組份成的亦'>=1 著接及程製而二，表份於成載的果劑結主驗於試在，別一差表的於 s_ --38-1 一皆例量施用實使與及二類 TUMW 參一 | ♦ 種較的比劑，主三例較比例施實於同相皆例比成組份成的劑著接及程製而二，表份於成載的果劑結主驗於試在，別一差表的於間載一皆例量施用實使與及三類 rNJ. .ft 食種較的比劑，主四例較比例施實於同相皆例比成組份成的劑著接及程製而二，表份於成載的果劑結主驗於試在，別一差表的於間載一皆例量施用實使與及四類 ♦ 種較的比劑，主化無溴板中基脂用樹板氧路環電當，，時知份得量 ^ ί 結80 試於測低之例一比例的 m旨比樹由氧環型 (請先閱讀背面之注意事項再填寫本頁) 訂：經濟部智慧財產局員工消費合作社印製乏主缺當中，劑差主變當性，制知抑得移二遷例線較銅比之由板，路試電測，性時燃劑難換過交通子法離，試在時測了媒的為觸四明主、發為三本 ΡΓ ruj 作仓，胺較例級比施三由實用此兩採，案者性本或境閱，環參時耐再劑的。散板實分路證乏電以缺之得中得果劑製結頁 5 11 第本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 572983 A7 _B7 五、發明說明（l4 ) 不降低軟性印刷電路板用基板各物性的情況下，進一步提高電路板之難燃性及耐環境性，其係提高溴化型環氧樹脂之比例，同時改變主觸媒的種類，並增添離子交換劑及分散劑，上述組成之配合確實可達到預期之效果，故本發明確實具有產業上利用價值。惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明書内容所作之簡單的等效變化與修飾，皆應仍屬本發明專利涵蓋之範圍内。表一：本發明各實施例與比較例之主劑成份表。表二：本發明各實施例與比較例之測試結果。 (請先閱讀背面之注意事項寫本頁) I:裝訂：線· 經濟部智慧財產局員工消費合作社印製頁 6 11 第本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 572983 表一 (各實施例及比較例之主劑成份) 成份(重量份 —___實驗編號實施例交例 ) 1 2 1 2 3 4 環娜旨玉哀月旨 (註1) 10 10 34 10 10 10 溴似觀封脂（註2) 20 20 一 20 20 20 20 高溴似裒氧樹脂(註3) 74 74 ~ 50 74 74 74 液態騰 (註4) 24 24 24 24 24 增韌劑固態NBR (註5) 12 12 12 12 12 臓衍生物 (註6) 36 域媒 ΊΡΡ (註7) 0.2 0.2 0.2 0.2 0.2 ( 三乙胺 0.2 填充劑 5 Γ 5 5 5 5 5 A1A 2.5 2.5 2.5 2.5 2.5 2.5 離子交麵 _-2职 1.5 1.5 1.5 0 1.5 1.5 Bi(OH)〇7(N(^)03 1.5 1.5 1.5 0 1.5 1.5 対欠劑無機北餘 (註8) 0.5 0.5 0.5 0.5 0 0.5 溶劑甲乙酮 138 138 138 135 138 138 正丙醇 8 8 8 8 8 8 成品黏)乂 (cps) 500 500 800 480 500 850 固形物含量 (°/〇) 50 50 卜50 50 50 50 s : D環氧_旨：長春ibx製造，商品名為BE 501。 2) fbi裒城f脂.CIBA~<iEIGY製造，商品名為必〇〇8，固升擒腿。 3) 高裒氧樹脂：長春ftji製造，商品名為 35〇。 2液·液態丙稀猜—丁二_^，Goodrich Co.製造，商品名為CTBN1300>t«。 ^，歷|液，丙烯腈-丁二獅，南帝彳江製造，商品名為Hycarl〇42 〇 $液悲·液態丙烯腈-丁二;，G〇〇drich &•製造，商品名為歷13〇〇*35。 7) TPP :三苯綱，Triphenyl phosphine。 8) 無機化合物··東亞合成製造，商品名為a—6114。 572983 表二 (各實施例與比較例之測試結果) ------>>>>^^測言式结果 g觸目實施例 tb#交例 1 2 1 2 3 4 雞燃性（註1) 〇〇 X 〇〇〇耐熱l±(〇C) >340 >340 >340 >340 >340 >340 垄丨J離強度(kg〇 >1.2 >1.2 >1.2 >1.2 >1.2 >1.2 電氣待H 線間絕緣酿(Ω、0· 1腿) 2·21*1013 >洲013 >3*1013 >5*1012 >2*1013 >2*1013 表面阻抗（Ω、0. Iran) 1.9TO014 >2*1014 >2*1013 >7*1013 >2*1014 >2*1014 體積喊（Ω、0.1腿) 8.52^1015 >5*1015 >8*1013 >8*1014 >5*1015 >2*1015 繞曲性 MIT(R=2) >3000 >3000 >3000 >3000 >3000 >3000< IPC㈣ >1*106 >1*106 >1*106 >1*106 >1*106 >1*106 而燦境性耐謝生 (°〇 >320 >320 >320 >320 >310 >300 剝離強度 _ >1.0 >1.0 >1.0 >1.0 >0.8 >0.8 而办容劑性氫氧钱(10°/〇) (腿) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 氯化氫(10%) (mm) <0.1 <0.1 <0.2 <0.3 <0.4 <0.5 甲乙酮〇m〇 <0.3 <0.3 <0.3 <0.3 <0.3 <0.3 銅移：; 冲制性（hr) >1000 >1000 >1000 >200 >1000 >1000 尺寸安定性（侧收縮率%) <+0.15 <+0.15 <+0· 15 <±0·15 ±0.15 <±0.让註1 :難燃性測試中之符號「〇」代表通過UL94認證之稱-〇測試，符號「X」代表無法通過測試。BiCOH) ^ / NOJo 3, 0.5 parts by weight of inorganic compounds, and 12 parts by weight of methyl ethyl ketone were ground in a ball mill can for 72 hours, and then the above mixture was mixed with 10 parts by weight of epoxy resin and 2 parts by weight. Parts > Smelt type epoxy resin, 7 4 parts by weight of filled epoxy resin, 2 4 weight page 13 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) Please first Read the note at the back 1% I Printed page Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 572983 A7 ----- B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) Liquid NBR, 12 parts by weight of solid acrylonitrile-butadiene rubber NBR, 0.2 parts by weight of TPP, 138 parts by weight of methyl ethylate, and 8 parts by weight of n-propanol are mixed and dissolved uniformly, and reacted at 80 ° C for 15 Within hours, the main agent required by the present invention can be prepared. The viscosity of the prepared main agent is 500 cps and the solid content is about 50% by weight. The diamino diphenyl methane, diamino diphenyl sulfonium and the curing agent cyanoguanidine and BF3_pIp are mixed at a ratio of 100: 1 · 〇: 0.4: 0.1: 0.04. After homogenization, the adhesive of the present invention can be prepared. The aforementioned adhesive is coated on the surface of a polyimide plastic film with a coater, and the combined body is dried in an oven of 100 ~ 150aC, and then 3-facets, and then a copper foil is pasted on the adhesive. Then, it is hot-rolled over the adhesive at a temperature of 8 5 ° C, and after curing, it is cured at a high temperature of 190 ° C to obtain a substrate for a flexible printed circuit board. According to the description of the above evaluation method, a required test piece of this printed circuit board substrate was made, and various tests were performed. The test results are shown in Table 2. The manufacturing process of the second embodiment and the composition ratio of the components of the adhesive are the same as those of the first embodiment. The difference between the second embodiment and the first embodiment lies in the ingredients of the main agent, and the types and amounts of the main agents are shown in Table 1. The results are shown in Table 20. The process of Comparative Example 1 and the composition ratio of the components of the adhesive are the same as those of Example 1. The difference between Comparative Example 1 and Example 1 lies in the ingredients of the main agent, and page 14 ------ ----- Loading (please read the precautions on the back to write this page) ·-Thread · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 572983 A7 _B7_ V. Description of the invention (L3) The types and usage amounts of the main agents are shown in Table 1. The test results are shown in Table 2. The proportions are implemented in the same phase as the proportions of the components. Also, '> = 1 The test result is based on the test results of the loaded fruit agent. The difference is in the case of s_ --38-1, which is an example of the application of TUMW and the second type of TUMW. The main three cases are more proportionally implemented in the same phase than the case The second step is to make a test. The test results are shown in the test results, and the test results are in the test results. The difference is that the test results are compared with the test results of the three types of rNJ. .Ft. The main four cases are implemented in proportion to the same phase and all cases are compared to the component connection and process system. The second one is the test result of the fruit test. The main test is the test, and the other is the difference. All of them are compared with four kinds of specific agents, and the base fats in the main bromine-free board are used with the tree board oxygen circuit ring, and the amount is known ^ ί 80 80 Try to measure the lower Example 1: The proportion of m is compared with the oxygen ring type (please read the precautions on the back before filling this page). Order: Among the lack of printing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy, It is difficult to change the two-moving routine compared with the copper ratio. The electric test is conducted on the road. It is difficult to change the fuel when it is transported by the traffic method. When the test is performed, the tester touches the master and sends three books. ruj is used as a warehouse, the amine is more than the standard, and the three are applied. The present environmental or read by, and then resistant agent when the reference rings. Loose-leaf solid shunt permits lack of electricity and lack of gains to obtain fruit agents. 5 11 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 572983 A7 _B7 V. Description of the invention (l4 ) Without reducing the physical properties of the substrate for flexible printed circuit boards, the flame retardancy and environmental resistance of the circuit board are further improved. It is to increase the proportion of brominated epoxy resin, and to change the type of main catalyst and increase The combination of the above composition of the ion exchanger and dispersant can indeed achieve the expected effect, so the present invention does have industrial utilization value. However, the above are only the preferred embodiments of the present invention. When the scope of implementation of the present invention cannot be limited by this, that is, the simple equivalent changes and modifications made according to the scope of the patent application and the content of the invention specification, All should still fall within the scope of the invention patent. Table 1: Table of main ingredients of the examples and comparative examples of the present invention. Table 2: Test results of the examples and comparative examples of the present invention. (Please read the notes on the back first to write this page) I: Binding: Printed by the line · Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 6 11 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 572983 Table 1 (the main ingredients of each example and comparative example) Ingredients (parts by weight-___Experiment number, examples of examples) 1 2 1 2 3 4 Huan Nazhi Yuyuezhi (Note 1) 10 10 34 10 10 10 Bromine-like grease (Note 2) 20 20-20 20 20 20 20 High-bromine phosphonium-like resin (Note 3) 74 74 ~ 50 74 74 74 Liquid evaporation (Note 4) 24 24 24 24 24 Toughening agent Solid NBR (Note 5) 12 12 12 12 12 Pyrene derivatives (Note 6) 36 Domain media PP (Note 7) 0.2 0.2 0.2 0.2 0.2 (Triethylamine 0.2 Filler 5 Γ 5 5 5 5 5 A1A 2.5 2.5 2.5 2.5 2.5 2.5 Ion interface_-2 position 1.5 1.5 1.5 0 1.5 1.5 Bi (OH) 〇7 (N (^) 03 1.5 1.5 1.5 0 1.5 1.5 対 Inorganic agent inorganic Beiyu (Note 8) 0.5 0.5 0.5 0.5 0 0.5 Solvent Methyl ethyl ketone 138 138 138 135 138 138 n-propanol 8 8 8 8 8 8 finished product) (cps) 500 500 800 480 500 850 solid content (° / 〇) 50 50 bu 50 50 50 50 50 s: D epoxy_Purpose: Made by Changchun ibx, trade name BE 501. 2) fbi 裒城 f grease. CIBA ~ < iEIGY manufacture, trade name must be 08, Gusheng escape leg. 3) High oxygen resin: manufactured by Changchun ftji, trade name is 35. 2-Liquid · Liquid Acrylic—Ding Er_ ^, manufactured by Goodrich Co., trade name CTBN1300 > t «. ^, Li | Liquid, Acrylonitrile-Dingershi, made by Nandi Minjiang, trade name Hycar1042 $ Liquid · Liquid acrylonitrile-Dinger ;, Godrich & • Production, trade name Calendar 1300 * 35. 7) TPP: Triphenyl phosphine. 8) Inorganic compounds · East Asia Synthetic Manufacturing, trade name a-6114. 572983 Table 2 (test results of each example and comparative example) ------ > > > > ^^ Test result g eye-catching example tb # crossing example 1 2 1 2 3 4 (Note 1) 〇〇X 〇〇〇 heat resistance 1 ± (〇C) > 340 > 340 > 340 > 340 > 340 > 340 ridge J strength (kg〇 > 1.2 > 1.2 > 1.2 > 1.2 > 1.2 > 1.2 Electrical standby H line insulation (Ω, 0 · 1 leg) 2 · 21 * 1013 > Chau 013 > 3 * 1013 > 5 * 1012 > 2 * 1013 > 2 * 1013 surface impedance (Ω, 0. Iran) 1.9TO014 > 2 * 1014 > 2 * 1013 > 7 * 1013 > 2 * 1014 > 2 * 1014 volume shout (Ω, 0.1 leg) 8.52 ^ 1015 > 5 * 1015 > 8 * 1013 > 8 * 1014 > 5 * 1015 > 2 * 1015 flexibility MIT (R = 2) > 3000 > 3000 > 3000 > 3000 > 3000 > 3000 < IPC㈣ > 1 * 106 > 1 * 106 > 1 * 106 > 1 * 106 > 1 * 106 > 1 * 106 > 320 > 320 > 320 > 310 > 300 peel strength_ > 1.0 > 1.0 > 1.0 > 1.0 > 0.8 > 0.8 (Legs) < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 chloride (10%) (mm) < 0.1 < 0.1 < 0.2 < 0.3 < 0.4 < 0.5 methyl ethyl ketone 0m〇 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 Copper shift: ; Punchability (hr) > 1000 > 1000 > 1000 > 200 > 1000 > 1000 dimensional stability (side shrinkage%) < +0.15 < +0.15 < + 0 · 15 < ± 0 · 15 ± 0.15 < ± 0. Let Note 1: The symbol "〇" in the flame resistance test represents the test of UL94 certification -〇, and the symbol "X" represents the failure of the test.

Claims

572983__ 1 A8 公告本、申請專利範圍 1. 一種軟性印刷電路板用基板之接著劑的主劑，該主劑包含： (a) 1 00重量份之環氧樹脂，該環氧樹脂之每一分子中至少含有兩個以上之環氧官能基，且樹脂中具有80重量份以上的溴化型環氧樹脂，該溴化型環氧樹脂之溴含量在1 〇〜5 0重量％ ; (b) 20〜50重量份的增韌劑，該增韌劑是選自至少一種：含有羧基及氰基之橡膠、含有二級胺基及氰基之橡膠、含有環氧基及氰基之橡膠及/或雙環氧化物； (c) 0.1〜2.0重量份之磷化合物； (d) 2〜12重量份之填充劑； (e) 1〜10重量份之離子交換劑； (f) 0.1〜1.0重量份之分散劑；及 (g) 125〜170重量份之溶劑。 2、依據申請專利範圍第1項所述軟性印刷電路板用基板之接著劑的主劑，其中，該增韌劑是選自：羧基封端之丁腈共聚物、胺基封端之丁腈共聚物、環氧基封端之丁腈共聚物、二甘醇二縮水甘油醚、丁二醇二縮水甘油醚及/或間苯二盼二縮水甘油醚。 3、依據申請專利範圍第1項所述軟性印刷電路板用基板之接著劑的主劑，其中，該填充劑係選自：二氧化矽、三氧化二鋁、氫氧化鋁、氫氧化鎂、三氧化二銻、矽酸鈣、碳酸鈣、碳酸鎂、氧化鎂、氧化鋅第17頁本紙張尺度適用中國國家標準（CNS ) A4規格（210><297公釐） (請先閱讀背面之注意事項再ΙΡτ本頁) -裝· .—訂經濟部智慧財/$局員工消費合作社印製 572983 經濟部智慧財是局Μ工消費合作社印製六、申請專利範圍、氮化删。、依據申請專利範圍第丨項所述軟性印刷電路板用基板之接著劑的主劑，其中，該離子交換劑係選自：叫〇5 · 2H2〇、 Bi(〇H)〇.7(N〇3)〇3 、 BiO(OH)。74(N〇3)。15(Hsi〇3)。n、Bi〇(〇H)。、依據申請專利範圍第丨項所述軟性印刷電路板用基板之接著劑的主劑，其中，該溶劑42選自··甲乙酮丙g同、曱醇、乙醇、異丙醇、正丙醇、曱苯以及二甲苯。、一種軟性印刷電路板用基板之接著劑，該接著劑包含： (a) 1〇〇重量份如第1項所述之主劑； (b) 1〜20重量份之硬化劑；及 (c) 〇.1〜2重量份之硬化觸媒。、依據申請專利範圍第6項所述軟性印刷電路板用基板之接著劑，其中，該硬化劑係選自·氰基脈、二乙撐基三胺、三乙撐基四胺、二氨基二笨基甲烷、二氨基二苯基颯、酞酐、四氫酞酐、三氟化硼胺錯化物、多官能基環氧樹脂，以及酚醛樹脂。、依據申請專利範圍帛6項所述棘性印刷電路板用基板之接著劑，其中，該硬化觸媒係選自· 苯基咪 4 6 1-苯基-2 -曱基味ϋ坐、2 -乙單乙基胺、氟硼化鋅、氟硼化吼咬。基錫一4-曱基咪唾、BF3 、氟硼化鎳及六氫 (請先閱讀背面之注意事項本I) -裝· 、1T 線第18頁本紙張尺度適用中國國家標準（CNS )八4規格（210X297公釐） 572983 經濟部智慧財4局員工消費合作社印製 A8 B8 C8 D8六、申請專利範圍 9、一種軟性印刷電路板用基板之製法，其包含以下步驟： (a) 預先研磨：將2〜12重量份之填充劑、1〜10重量份之離子交換劑、0.1〜1.0重量份之分散劑及少量的溶劑預先進行研磨； (b) 製備主劑：將（a)步驟研磨混合物與100重量份之環氧樹脂、20〜50重量份之增韌劑、0.1〜2.0重量份之磷化合物，以及與（a)步驟中使用之溶劑合計125〜170重量份的溶劑混合均勻，其中環氧樹脂中含有8 0重量份以上之溴化型環氧樹脂，且溴化型環氧樹脂中溴含量在 10〜50重量％以上，然後以 50〜120°C之反應溫度進行預聚合反應，待黏度提高至300cps以上，即可製得預聚合反應之主劑； (c) 製備接著劑：取（b)步驟製得之主劑100重量份，再與1〜2 0重量份之硬化劑，以及0.1 ~ 2重量份的硬化觸媒混合均勻，以製得接著劑；及 (d) 製備電路板用基板：在一塑膠膜上塗佈一層（c) 步驟製成之接著劑，再於該接著劑上貼附一層銅箔，三者間藉由高溫熟化，即可製得軟性印刷電路板用基板。 (請先閱讀背面之注意事項本貢) -裝· 線第19頁本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐）572983__ 1 A8 Announcement and scope of patent application 1. A main agent of an adhesive for a substrate for a flexible printed circuit board, the main agent comprising: (a) 100 parts by weight of epoxy resin, each molecule of the epoxy resin Contains at least two epoxy functional groups, and the resin has more than 80 parts by weight of a brominated epoxy resin, and the bromine content of the brominated epoxy resin is 10 to 50% by weight; (b) 20 to 50 parts by weight of a toughening agent, the toughening agent is selected from at least one: rubber containing carboxyl group and cyano group, rubber containing secondary amine group and cyano group, rubber containing epoxy group and cyano group, and / Or biepoxide; (c) 0.1 to 2.0 parts by weight of a phosphorus compound; (d) 2 to 12 parts by weight of a filler; (e) 1 to 10 parts by weight of an ion exchanger; (f) 0.1 to 1.0 parts by weight A dispersant; and (g) a solvent of 125 to 170 parts by weight. 2. The main agent of the adhesive for substrates for flexible printed circuit boards according to item 1 of the scope of the patent application, wherein the toughening agent is selected from the group consisting of carboxy-terminated butyronitrile copolymer and amine-terminated butyronitrile Copolymers, epoxy-terminated butyronitrile copolymers, diethylene glycol diglycidyl ether, butanediol diglycidyl ether, and / or m-phenylene diglycidyl ether. 3. According to the main agent of the adhesive for substrates for flexible printed circuit boards described in item 1 of the scope of the patent application, wherein the filler is selected from the group consisting of silicon dioxide, aluminum trioxide, aluminum hydroxide, magnesium hydroxide, Antimony trioxide, calcium silicate, calcium carbonate, magnesium carbonate, magnesium oxide, zinc oxide page 17 This paper applies Chinese National Standard (CNS) A4 specifications (210 > < 297 mm) (Please read the back Note on this page again)-Installation ·.-Order printed by the Ministry of Economic Affairs ’Smart Assets / $ Bureau Employee Consumer Cooperatives 572983 Printed by the Ministry of Economic Affairs’ Smart Industry Corporation ’s Consumer Industry Cooperatives 2. The main agent of the adhesive for substrates for flexible printed circuit boards according to item 丨 in the scope of the patent application, wherein the ion exchanger is selected from the group consisting of: 〇 5 · 2H2〇, Bi (〇H) 0.7 (N 〇3) 〇3, BiO (OH). 74 (No. 3). 15 (Hsio3). n, Bi0 (OH). According to the main agent of the adhesive for substrates for flexible printed circuit boards according to item 丨 of the scope of the patent application, wherein the solvent 42 is selected from the group consisting of methyl ethyl ketone, methyl alcohol, ethanol, isopropanol, n-propanol, Xylene and xylene. An adhesive for a substrate for a flexible printed circuit board, the adhesive comprising: (a) 100 parts by weight of the main agent as described in item 1; (b) 1 to 20 parts by weight of a hardener; and (c) ) 0.1 ~ 2 parts by weight of hardened catalyst. 2. An adhesive for a substrate for a flexible printed circuit board according to item 6 of the scope of the patent application, wherein the hardener is selected from the group consisting of cyano vein, diethylenetriamine, triethylenetetramine, and diaminodiamine. Benzomethane, diaminodiphenylphosphonium, phthalic anhydride, tetrahydrophthalic anhydride, boron trifluoride complex, polyfunctional epoxy resin, and phenolic resin. 2. Adhesive for substrates for spiny printed circuit boards according to item 6 of the scope of the patent application, wherein the hardening catalyst is selected from the group consisting of · phenylimide 4 6 1-phenyl-2 -fluorenyl miso, 2 -Ethyl monoethylamine, zinc fluoboride, fluboron bite. Nitinol 4-4-methylimidazole, BF3, nickel fluoboride, and hexahydrogen (please read the precautions on the back of this book first)-Packing, 1T line, page 18 This paper applies Chinese National Standards (CNS) 4 Specifications (210X297 mm) 572983 Printed A8 B8 C8 D8 by the Consumer Cooperatives of the 4th Bureau of Wisdom and Finance of the Ministry of Economic Affairs 6. Scope of Patent Application 9. A method for manufacturing flexible printed circuit board substrates, which includes the following steps: (a) pre-grinding : Grinding 2 ~ 12 parts by weight of filler, 1 ~ 10 parts by weight of ion exchanger, 0.1 ~ 1.0 parts by weight of dispersant and a small amount of solvent in advance; (b) preparation of main agent: grinding step (a) Mix the mixture with 100 parts by weight of epoxy resin, 20 to 50 parts by weight of toughener, 0.1 to 2.0 parts by weight of phosphorus compound, and 125 to 170 parts by weight of the solvent used in step (a), The epoxy resin contains more than 80 parts by weight of a brominated epoxy resin, and the bromine content of the brominated epoxy resin is more than 10 to 50% by weight, and then prepolymerized at a reaction temperature of 50 to 120 ° C. React until viscosity increases to 30 Above 0cps, the main agent of the prepolymerization reaction can be prepared; (c) Preparation of the adhesive: 100 parts by weight of the main agent obtained in step (b), and 1 ~ 20 parts by weight of the hardener, and 0.1 ~ 2 parts by weight of the hardening catalyst are mixed uniformly to prepare an adhesive; and (d) preparing a substrate for a circuit board: coating a layer of the adhesive prepared in step (c) on a plastic film, and then applying the adhesive A layer of copper foil is affixed, and the three are aged at high temperature to prepare a substrate for a flexible printed circuit board. (Please read the precautions on the back of this article first)-Installation · Thread Page 19 This paper size applies to China National Standard (CNS) A4 (210 × 297 mm)