JP2625646B2 - Adhesive composition for flexible printed circuit boards - Google Patents

Adhesive composition for flexible printed circuit boards

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Publication number
JP2625646B2
JP2625646B2 JP6223515A JP22351594A JP2625646B2 JP 2625646 B2 JP2625646 B2 JP 2625646B2 JP 6223515 A JP6223515 A JP 6223515A JP 22351594 A JP22351594 A JP 22351594A JP 2625646 B2 JP2625646 B2 JP 2625646B2
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JP
Japan
Prior art keywords
weight
printed circuit
flexible printed
adhesive
epoxy resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP6223515A
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Japanese (ja)
Other versions
JPH07300577A (en
Inventor
大羽 任
丁洛 金
在垠 趙
チャン・キュンホー
Original Assignee
第一合纖株式會社
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Publication of JPH07300577A publication Critical patent/JPH07300577A/en
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Publication of JP2625646B2 publication Critical patent/JP2625646B2/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は接着性及び耐熱性に優
れ、特に難燃性に優れた柔軟性印刷回路基板用接着剤組
成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition for a flexible printed circuit board having excellent adhesiveness and heat resistance, and particularly excellent flame retardancy.

【０００２】[0002]

【従来の技術】最近、電気、電子及び半導体分野の軽薄
短小化、高密度化、高性能化の趨勢が著しく現れてお
り、多層印刷回路基板の場合も既存のリジドな単層或い
は両面中心のものから柔軟性印刷回路基板への比重が急
に大きくなっている。柔軟性印刷回路基板は柔軟性の金
属箔回路の両側にフィルムが付着されており、その厚さ
が５０〜３００μｍ程度で大変薄くてリジド印刷回路基
板が適用されにくい、軽薄短小、柔軟性、高密度化が要
求される製品に主に使用されている。軽薄短小製品に適
用された例としてはカメラ、小型録音機、カムコーダ、
ノートブックコンピューター等があり、柔軟性を要求す
る製品に適用された例としてはプリンターヘッド等があ
り、高密度化製品に適用された例としては半導体リード
フレームの代用として使われるテープ自動化ボンディン
グ等で、柔軟性印刷回路基板の用途は日毎に拡張されて
いる。2. Description of the Related Art In recent years, there has been a remarkable trend in the fields of electrical, electronic and semiconductor applications to achieve lighter, thinner, smaller, higher density, and higher performance. The specific gravity from flexible materials to flexible printed circuit boards is rapidly increasing. A flexible printed circuit board has films attached to both sides of a flexible metal foil circuit, and has a thickness of about 50 to 300 μm, which is very thin, so that a rigid printed circuit board is difficult to be applied, light and thin, small, flexible, and high. It is mainly used for products that require density. Examples applied to small and light products include cameras, small recorders, camcorders,
There is a notebook computer, etc., an example applied to products that require flexibility is a printer head, etc.An example applied to a high-density product is tape automation bonding used as a substitute for semiconductor lead frames, etc. The use of flexible printed circuit boards is being expanded daily.

【０００３】柔軟性印刷回路基板の基材は、主としてポ
リイミド、ポリエステル等のプラスチックフィルムと、
アクリル系、エポキシ系、ポリウレタン系、ポリエステ
ル系等の接着剤と、銅、アルミニウム、錫等金属箔とか
ら成っている。柔軟性印刷回路基板の製造において、フ
レキシブル銅クラッドラミネート（フィルム上に接着剤
を塗布し銅をラミネートして製造）にドライフィルムの
ようなフォトレジストをラミネートした後、マスク上で
露光して現像することにより銅箔面に回路を形成した
後、塩化第２鉄水溶液等で銅層をエッチングし、アルカ
リ水溶液でフォトレジスト層を剥き、カバーレーをラミ
ネートし、必要によって半田付け等をする一連の工程に
より柔軟性印刷回路基板を製造する。[0003] The base material of the flexible printed circuit board is mainly made of a plastic film such as polyimide or polyester,
It is made of an adhesive such as acrylic, epoxy, polyurethane, or polyester, and a metal foil such as copper, aluminum, or tin. In manufacturing a flexible printed circuit board, a photoresist such as a dry film is laminated on a flexible copper clad laminate (prepared by applying an adhesive on a film and laminating copper), and then exposed and developed on a mask. After forming a circuit on the copper foil surface, the copper layer is etched with a ferric chloride aqueous solution or the like, the photoresist layer is stripped with an alkaline aqueous solution, a coverlay is laminated, and soldering is performed as necessary. Manufacture flexible printed circuit boards.

【０００４】前述したように、柔軟性回路基板の製造工
程には、酸、塩基等の化学処理、加熱ラミネーション、
半田付け等の熱処理工程があるため、これらの工程で接
着剤の特性低下がないことが要求される。接着剤は工程
中のどの環境でも所定値以上の接着特性を維持しなけら
ばならず、銅箔エッチング時に露出された接着剤表面の
耐溶剤性及び半田付け時の耐熱性が要求され、電気、電
子製品に主に用いられるため原板又は回路基板部品状態
において難燃性が要求される場合が多い。[0004] As described above, the manufacturing process of the flexible circuit board includes chemical treatment of an acid and a base, heat lamination, and the like.
Since there are heat treatment steps such as soldering, it is required that the properties of the adhesive do not deteriorate in these steps. Adhesives must maintain adhesive properties at or above a specified value in any environment during the process, require solvent resistance of the exposed adhesive surface during copper foil etching and heat resistance during soldering, and Since it is mainly used for electronic products, it is often required to have flame retardancy in the original plate or circuit board component state.

【０００５】しかしながら、柔軟性印刷回路基板の材質
のうち、銅箔及びポリイミドフィルムはそれ自体難燃性
を有するので、接着剤に難燃性を付与することが製品の
難燃性に直結する。従来の柔軟性印刷回路基板用接着剤
としてはエポキシ系、アクリル系、ポリウレタン系、ポ
リエステル系接着剤等が一般的に広く使用されている。
特に、この接着剤のうち、ポリイミドフィルムと銅箔を
接着して柔軟性基板を製造することにあって、特開昭６
３―２９７４８３号公報及び特開昭６３―１２０７８３
号公報に記載されたもののように、エポキシ系及びアク
リルゴム／エポキシ接着剤が多く使われていた。However, among the materials of the flexible printed circuit board, the copper foil and the polyimide film themselves have flame retardancy, so that imparting flame retardancy to the adhesive directly relates to the flame retardancy of the product. As adhesives for conventional flexible printed circuit boards, epoxy-based, acrylic-based, polyurethane-based, polyester-based adhesives and the like are generally and widely used.
In particular, of this adhesive, in manufacturing a flexible substrate by bonding a polyimide film and a copper foil, Japanese Patent Laid-Open No.
JP-A-3-297483 and JP-A-63-120783
As described in Japanese Patent Application Publication, epoxy-based and acrylic rubber / epoxy adhesives have been frequently used.

【０００６】又、特開昭５６―８１３８２号公報にはブ
ロム化エポキシ樹脂、ブロム化ビニールフェノール樹脂
及びアクリル共重合樹脂を混合して難燃性を付与する接
着剤が記載されている。JP-A-56-81382 describes an adhesive which imparts flame retardancy by mixing a brominated epoxy resin, a brominated vinylphenol resin and an acrylic copolymer resin.

【０００７】[0007]

【発明が解決しようとする課題】しかしながら、前二者
の特許において、エポキシ系接着剤の場合は耐熱性、耐
化学性、寸法安定性は優れているが接着力と柔軟性が足
りないという問題点があり、アクリルゴム／エポキシ系
接着剤は難燃性が足りないという問題点があった。However, in the former two patents, the epoxy adhesive has the problem that heat resistance, chemical resistance and dimensional stability are excellent, but the adhesive strength and flexibility are insufficient. There is a problem that the acrylic rubber / epoxy adhesive has insufficient flame retardancy.

【０００８】又、後者の特許に記載された接着剤は難燃
性に優れているが接着力と柔軟性の問題点があることが
知られている。従って、本発明の目的は柔軟性印刷基板
用難燃性接着剤で、難燃性（UL 94-Vo）の他、耐熱性、
接着剤及び柔軟性等の諸特性が大変優れた柔軟性印刷回
路基板用接着剤組成物を提供することである。[0008] The adhesive described in the latter patent is known to have excellent flame retardancy, but has problems of adhesive strength and flexibility. Therefore, an object of the present invention is a flame-retardant adhesive for flexible printed circuit boards, in addition to flame retardancy (UL 94-Vo), heat resistance,
An object of the present invention is to provide an adhesive composition for a flexible printed circuit board, which has very excellent properties such as an adhesive and flexibility.

【０００９】[0009]

【課題を解決するための手段】前記目的だけでなく容易
に表出される他の目的を達成するために、本発明は、ア
クリル共重合樹脂１００重量％（固形分基準）に対し
て、多官能基のエポキシ樹脂約１０〜３０重量％と、ブ
ロム化エポキシ樹脂２０〜９０重量％とをブレンドした
ものであって、アクリル共重合樹脂は、アクリロニトリ
ル１０〜４５重量％と、炭素数８以下のアルキルアクリ
レート４０〜７０重量％と、エポキシと反応し得る官能
基１種以上を有するオレフィン化合物３〜１５重量％と
により重合されたものであることにより、接着性、耐熱
性及び難燃性が優れた柔軟性印刷回路基板用接着剤を提
供する。SUMMARY OF THE INVENTION In order to achieve not only the above object but also other objects which are easily expressed, the present invention relates to an acrylic copolymer resin having a polyfunctionality of 100% by weight (based on solid content). About 10-30% by weight of the base epoxy resin and 20-90% by weight of the brominated epoxy resin were blended .
Wherein the acrylic copolymer resin is acrylonitrile
10 to 45% by weight of an alkyl acrylate having 8 or less carbon atoms.
A rate of 40 to 70% by weight and an epoxy-reactive functional group
3 to 15% by weight of an olefin compound having at least one group
The present invention provides an adhesive for a flexible printed circuit board having excellent adhesiveness, heat resistance, and flame retardancy by being polymerized by the method described above.

【００１０】本発明をより具体的に説明すると次のよう
である。本発明で使用されるアクリル共重合樹脂は、ア
クリロニトリルと、エチルアクリレート、メチルメタク
リレート、メタクリレート、ブチルアクリレート等のよ
うに炭素数が８以下であるアルキルアクリレートと、エ
ポキシと反応し得る官能基（カルボキシル基、ヒドロキ
シル基、アマイド基等）の一種以上を有するオレフィン
化合物とからなる溶液重合物である。The present invention is described below more specifically. The acrylic copolymer resin used in the present invention includes acrylonitrile, an alkyl acrylate having 8 or less carbon atoms such as ethyl acrylate, methyl methacrylate, methacrylate, and butyl acrylate, and a functional group (carboxyl group) capable of reacting with epoxy. , A hydroxyl group, an amide group, etc.).

【００１１】アクリル共重合体は各成分の含量に応じて
耐熱性、柔軟性、安定性等に影響を及ぼす。アクリロニ
トリルの含有量は、アクリル共重合体の全重量に対し１
０〜４５重量％であることが好ましい。アクリロニトリ
ル含量が１０重量％未満であると半田耐熱性の低下の原
因となり、４５重量％を超えると柔軟性及び接着剤の安
定性が落ち高温で変色する可能性がある。The acrylic copolymer affects heat resistance, flexibility, stability and the like depending on the content of each component. The content of acrylonitrile was 1 to the total weight of the acrylic copolymer.
It is preferably 0 to 45% by weight. When the acrylonitrile content is less than 10% by weight, the solder heat resistance is reduced. When the acrylonitrile content exceeds 45% by weight, the flexibility and the stability of the adhesive are reduced, and the color may be changed at high temperatures.

【００１２】炭素数が８以下であるアルキルアクリレー
トは、アクリル共重合体の全重量に対し４０〜７０重量
％であることが好ましい。少なくとも１の官能基を有す
るオレフィン化合物はアクリル共重合体の全重量に対し
３〜１５重量％であることが好ましい。官能基を有する
オレフィン化合物の含量が３％未満であるとエポキシと
の架橋密度が低く、最終的に得られる接着剤組成物の耐
熱性が落ち、１５重量％を超えると未反応官能基が柔軟
性印刷回路基板の電気的特性を低下させ得る。 Alkyl acrylate having 8 or less carbon atoms
DOO is preferably 40 to 70 wt% relative to the total weight of the acrylic copolymer. The amount of the olefin compound having at least one functional group is preferably 3 to 15% by weight based on the total weight of the acrylic copolymer. When the content of the olefin compound having a functional group is less than 3%, the crosslinking density with epoxy is low, and the heat resistance of the finally obtained adhesive composition is lowered. When the content exceeds 15% by weight, the unreacted functional group is flexible. The electrical characteristics of the flexible printed circuit board.

【００１３】アクリル共重合樹脂は、好適にはガラス転
移温度（Tg）が５〜３５℃のものを用いる。これは各成
分の組成を適宜にコントロールすることにより製造され
る。本発明の接着剤組成物に用いられるアクリル共重合
体樹脂は、α，α′―アゾビスイソブチロニトリル（以
下、ＡＩＢＮと略記する）、ベゾイルペルオキシド（以
下、ＢＰＯと略記する）等の開始剤を使用して溶液重合
し、溶媒としてはメチルエチルケトン、エチルアセテー
ト、トルエン等の溶媒又は混合溶媒を用いて重合する。
製造された共重合体の分子量はゲル透過クロマトグラフ
ィーを用いて測定することができ、本発明では数平均分
子量が１０万〜８０万であるものを使用する。An acrylic copolymer resin having a glass transition temperature (Tg) of 5 to 35 ° C. is preferably used. This is produced by appropriately controlling the composition of each component. The acrylic copolymer resin used in the adhesive composition of the present invention includes α, α′-azobisisobutyronitrile (hereinafter abbreviated as AIBN), bezoyl peroxide (hereinafter abbreviated as BPO) and the like. Solution polymerization is carried out using an initiator, and polymerization is carried out using a solvent such as methyl ethyl ketone, ethyl acetate, toluene or a mixed solvent as a solvent.
The molecular weight of the produced copolymer can be measured using gel permeation chromatography. In the present invention, a copolymer having a number average molecular weight of 100,000 to 800,000 is used.

【００１４】本発明の接着剤組成物に用いられる多官能
基エポキシ樹脂としては、ソルビトールポリグリシジル
エーテル、ポリグリセロールポリグリシジルエーテル、
トリグリシジルトリス（２―ヒドキシエチル）イソシア
ンウレート、エポキシクレゾールノボラック樹脂のよう
な１００〜３００のエポキシ当量を有する樹脂が挙げら
れる。これらは耐熱性及び接着力を向上させる役割をす
る。[0014] polyfunctional used in the adhesive composition of the present invention
As the group epoxy resin, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether,
Resins having an epoxy equivalent of 100 to 300, such as triglycidyl tris (2-hydroxyethyl) isocyanurate, epoxy cresol novolak resin. These serve to improve heat resistance and adhesive strength.

【００１５】ブロム化エポキシ樹脂としては、下記構造
式（I）で表現されるジブロムネオペンチルグリコール
ジグリシジルエーテル、下記式（II）で表現されるジブ
ロムフェニルグリシジルエーテル又は下記構造式（II
I）で表現されるビスフェノールブロム化エポキシ樹脂
により構成される群から選択された難燃性樹脂又は樹脂
混合物が選択される。As the brominated epoxy resin, dibromoneopentylglycol diglycidyl ether represented by the following structural formula (I), dibromophenylglycidyl ether represented by the following formula (II) or the following structural formula (II)
A flame-retardant resin or resin mixture selected from the group consisting of bisphenol-brominated epoxy resins represented by I) is selected.

【００１６】[0016]

【化１】 Embedded image

【００１７】[0017]

【化２】 Embedded image

【００１８】[0018]

【化３】 Embedded image

【００１９】本発明の接着剤組成物において、アクリル
共重合樹脂、多官能性エポキシ樹脂、ブロム化エポキシ
樹脂の三種の混合比率は、アクリル共重合樹脂１００重
量％（固形分基準）に対して、多官能基のエポキシ樹脂
１０〜３０重量％、そしてブロム化エポキシ樹脂２０〜
９０重量％とする時によい特性を期待し得る。多官能性
エポキシ樹脂の含量が１０％未満である場合は接着性が
不十分で、３０％以上を超える場合は難燃性を低下させ
る原因となる。ブロム化エポキシの含量が２０％未満で
あると難燃性が不十分で、９０％を超えると耐熱性及び
接着力が低下する。In the adhesive composition of the present invention, the mixing ratio of the three types of the acrylic copolymer resin, the polyfunctional epoxy resin, and the brominated epoxy resin is based on 100% by weight (based on solid content) of the acrylic copolymer resin. 10 to 30% by weight of a polyfunctional epoxy resin and 20 to 20% of a brominated epoxy resin
Good characteristics can be expected when the content is 90% by weight. When the content of the polyfunctional epoxy resin is less than 10%, the adhesiveness is insufficient, and when the content is more than 30%, it causes a decrease in flame retardancy. If the content of the brominated epoxy is less than 20%, the flame retardancy is insufficient, and if it exceeds 90%, the heat resistance and the adhesive strength decrease.

【００２０】望ましくは多官能性エポキシ樹脂及びブロ
ム化エポキシ樹脂の含有量の合計は、アクリル共重合樹
脂１００重量％を基準として４０〜１００重量％の範囲
とする。このような範囲としたときに難燃性、耐熱性、
接着性が全て優秀な結果を得ることができる。ブロム化
エポキシ樹脂は２００〜９００のエポキシ当量を有し、
ブロムの含量が３０〜７０重量％であることが望まし
い。Preferably, the total content of the polyfunctional epoxy resin and the brominated epoxy resin is in the range of 40 to 100% by weight based on 100% by weight of the acrylic copolymer resin. Flame resistance, heat resistance,
Excellent results can be obtained with all adhesive properties. The brominated epoxy resin has an epoxy equivalent of 200-900,
It is desirable that the bromine content be 30 to 70% by weight.

【００２１】これらを造液して本発明の接着剤組成物を
製造する際に、硬化反応触媒として３級アミン又はイミ
ダゾール類を使用し、必要によってジアミン又はジアン
ヒドライド等のエポキシ硬化剤を使用し得る。柔軟性柔
軟性印刷回路原板は以下のように製造することができ
る。前記組成の接着剤を厚さ２０〜１００μｍのポリイ
ミド又はポリエステルフィルム上にロール、リバースロ
ール、カンマコーター等を用いて乾燥後の接着剤塗布厚
さが２０〜５０μｍとなるように塗布した後、８０〜１
００℃の乾燥機（滞留時間１〜５分）を通過させて溶剤
等の揮発分を除去した後、加熱、加圧ロールで銅、アル
ミニウム等の金属箔を８０〜１４０℃、５〜２０ｋｇ／
ｃｍ2 の温度／圧力で接合する。カバーレーの場合、前
記条件と同じ条件で接着剤を塗布、乾燥した後、常温
（２０℃）〜１００℃で接着層保護フィルム又は離型紙
を接合する。In preparing the adhesive composition of the present invention by preparing these liquids, a tertiary amine or imidazole is used as a curing reaction catalyst, and an epoxy curing agent such as a diamine or dianhydride is used if necessary. I can do it. Flexibility A flexible printed circuit board can be manufactured as follows. After applying the adhesive having the above composition on a polyimide or polyester film having a thickness of 20 to 100 μm using a roll, a reverse roll, a comma coater or the like so that the adhesive applied thickness after drying becomes 20 to 50 μm, 80 ~ 1
After removing volatiles such as a solvent by passing through a dryer at 00 ° C (residence time of 1 to 5 minutes), a metal foil such as copper or aluminum is heated at 80 to 140 ° C with a pressure roll at 5 to 20 kg /
Join at a temperature / pressure of cm 2 . In the case of a coverlay, an adhesive is applied and dried under the same conditions as described above, and then the adhesive layer protective film or release paper is bonded at room temperature (20 ° C) to 100 ° C.

【００２２】このように製造した柔軟性印刷回路原板は
１２０℃で１２時間熱処理した後、カバーレーの場合１
００℃で２０分間乾燥した後、または１７８℃、３０ｋ
ｇ／ｃｍ2 、６０分間処理した後の物性を評価した。次
の実施例及び比較実施例は本発明をより具体的に説明す
るのであるが、本発明の範囲を限定するのではない。The thus-prepared flexible printed circuit board was heat-treated at 120 ° C. for 12 hours.
After drying at 00 ° C for 20 minutes or at 178 ° C, 30k
The physical properties after the treatment at g / cm 2 for 60 minutes were evaluated. The following examples and comparative examples illustrate the invention more specifically, but do not limit the scope of the invention.

【００２３】[0023]

【実施例】実施例１ （１）アクリル共重合樹脂の重合 窒素雰囲気下で、還流冷却機と撹拌機が備えられた１ｌ
の３口フラスコに表２に記載された組成の単量体１００
ｇを入れ、エチルアセテート５０ｇにＡＩＢＮ（アゾビ
スイソブチロニトリル）０．１ｇを溶かした溶液を添加
した後、温度を７０℃に上げて重合開始反応を進行し
た。EXAMPLES Example 1 (1) Polymerization of Acrylic Copolymer Resin Under nitrogen atmosphere, 1 l equipped with a reflux condenser and a stirrer
Of a monomer 100 having the composition shown in Table 2 in a three-necked flask
g, and a solution prepared by dissolving 0.1 g of AIBN (azobisisobutyronitrile) in 50 g of ethyl acetate was added. Then, the temperature was increased to 70 ° C., and the polymerization initiation reaction proceeded.

【００２４】再び、５重量％ＡＩＢＮのエチルアセテー
ト溶液０．５ｇを２時間毎に４回に分けて分割投入し、
１０時間撹拌し、再び５重量％ＡＩＢＮのエチルアセテ
ート溶液５ｇとエチルアセテート溶媒３４５ｇを添加し
た後、重合反応をさらに４時間進行して、Tgが２８℃、
数平均分子量（Ｍｎ）が２５万、固形分が２０重量％で
あるアクリル共重合樹脂を製造した。Again, 0.5 g of a 5% by weight AIBN solution in ethyl acetate was divided and charged in four portions every two hours.
After stirring for 10 hours, 5 g of AIBN solution of 5 wt% AIBN and 345 g of ethyl acetate solvent were added again, and the polymerization reaction was further proceeded for 4 hours, and Tg was 28 ° C.
An acrylic copolymer resin having a number average molecular weight (Mn) of 250,000 and a solid content of 20% by weight was produced.

【００２５】（２）接着剤の造液と銅クラッドラミネー
ト（ＣＣＬ）の製造 上記のように製造した固形分が２０重量％であるアクリ
ル共重合樹脂５００ｇにソルビトールポリグリシジルエ
ーテル系エポキシ樹脂（分子量：１０万）２０ｇとジブ
ロムネオペンチルグリコールグリシジルエーテル１５ｇ
とビスフェノール型ブロム化エポキシ樹脂（数平均分子
量：１２万）１５ｇを入れ、硬化促進剤０．０１ｇを入
れた後、１５分間撹拌し、１０００メッシュフィルター
でろ過した。ろ過後、マイヤバーを用いてポリイミドフ
ィルム（２５μｍ）にコーティングし、１００℃で３分
間乾燥し、１３０℃／１５ｋｇ／ｃｍ2 のラミネター
（Laminator）で３５μｍの銅箔をラミネートし、再び
１２０℃の乾燥機で１２時間熱処理した。得られた銅ク
ラッドラミネートの特性を評価した。(2) Preparation of adhesive and production of copper clad laminate (CCL) 500 g of the acrylic copolymer resin having a solid content of 20% by weight produced as described above was added to a sorbitol polyglycidyl ether-based epoxy resin (molecular weight: 100,000) 20 g and dibromoneopentyl glycol glycidyl ether 15 g
And 15 g of a bisphenol-type brominated epoxy resin (number average molecular weight: 120,000), 0.01 g of a curing accelerator was added, followed by stirring for 15 minutes and filtration with a 1000 mesh filter. After filtration, a polyimide film (25 μm) was coated with a Myr bar, dried at 100 ° C. for 3 minutes, and a 35 μm copper foil was laminated with a 130 ° C./15 kg / cm 2 laminator, and dried at 120 ° C. again. Heat treatment was performed for 12 hours in a machine. The properties of the obtained copper clad laminate were evaluated.

【００２６】（３）接着剤の造液及びカバーレーの製造 アクリル共重合樹脂５００ｇ（固形分２０重量％）にソ
ルビトールポリグリシジルエーテル系エポキシ樹脂（分
子量：１０万）１５ｇとジブロムネオペンチルグリコー
ルジグリシジルエーテル系エポキシ樹脂３０ｇとビスフ
ェノール型ブロム化エポキシ樹脂（数平均分子量：１２
万）３５ｇを入れ、硬化促進剤０．０１ｇを入れてから
１５分間撹拌し、１０００メッシュフィルターでろ過
し、マイヤバーを用いてポリイミドフィルム（２５μ
ｍ）にコーティングし、１００℃で４分間乾燥して接着
剤層が３０μｍであるフィルムを得た。このポリイミド
フィルムに、３５μｍのポリエステルフィルムを常温で
ラミネートしてカバーレーフィルムを製造した。(3) Preparation of adhesive liquid and production of coverlay In 500 g of acrylic copolymer resin (solid content: 20% by weight), 15 g of sorbitol polyglycidyl ether epoxy resin (molecular weight: 100,000) and dibromoneopentyl glycol diglycidyl 30 g of ether type epoxy resin and bisphenol type brominated epoxy resin (number average molecular weight: 12
35 g, and 0.01 g of a curing accelerator, and then stirred for 15 minutes. The mixture was filtered through a 1000 mesh filter.
m) and dried at 100 ° C. for 4 minutes to obtain a film having an adhesive layer of 30 μm. A 35 μm polyester film was laminated on this polyimide film at room temperature to produce a coverlay film.

【００２７】（４）柔軟性印刷回路基板用接着剤の項目
別評価規格及び方法 このように製造した銅クラッドラミネート及びカバーレ
ーを表１に示す項目、方法で評価した。(4) Evaluation Standards and Methods for Adhesives for Flexible Printed Circuit Boards The copper clad laminates and coverlays thus manufactured were evaluated according to the items and methods shown in Table 1.

【００２８】[0028]

【表１】 [Table 1]

【００２９】特性評価の結果を表２と表３に要約して表
した。The characteristics evaluation results are summarized in Tables 2 and 3.

【００３０】[0030]

【表２】 [Table 2]

【００３１】[0031]

【表３】 [Table 3]

【００３２】尚、表中、ＨＥＭＡはヒドロキシエチルメ
タクリレートを、ＳＰＧＥはソルビトールポリグリシジ
ルエーテル系エポキシを、ＥＣＮはエポキシクレゾール
・ノボラック樹脂を、ＤＮＧＤＥはジブロムネオペンチ
ルグリコールジグリシジルエーテルを、ＢＰＢＥはビス
フェノール形ブロム化エポキシを、ＤＥＭＩは１−ジシ
アノエチル−２−エチル−４−メチルイミダゾールを表
す。実施例２〜５及び比較例１〜５ アクリル共重合体の組成と接着剤の配合比率を表２及び
表３に記載したものに変更したことを除き、実施例１と
同様に銅クラッドラミネート及びカバーレーを製造し、
その特性を評価した。In the table, HEMA is hydroxyethyl methacrylate, SPGE is sorbitol polyglycidyl ether epoxy, ECN is epoxy cresol / novolak resin, DNGDE is dibromoneopentyl glycol diglycidyl ether, and BPBE is bisphenol type. Brominated epoxy, DEMI stands for 1-dicyanoethyl-2-ethyl-4-methylimidazole. Examples 2 to 5 and Comparative Examples 1 to 5 Except that the composition of the acrylic copolymer and the compounding ratio of the adhesive were changed to those described in Tables 2 and 3, a copper clad laminate was prepared in the same manner as in Example 1. Manufacture coverlay,
Its properties were evaluated.

【００３３】[0033]

【発明の効果】上述の実施例及び比較実施例からわかる
ように、アクリル共重合樹脂のエポキシ官能基と架橋反
応し得る適切量のカルボキシル基、ヒドロキシ基、アマ
イド基等の存在が重要であり、又アクリロニトリルもや
はり耐熱性に重要な役割をし、多官能エポキシ樹脂は接
着剤の接着力及び耐熱性を向上させる役割をし、難燃性
を付与するためには一定量以上のブロム化エポキシ樹脂
を添加させなければならない。アクリル共重合樹脂１０
０重量％に対して、多官能基エポキシ樹脂の含量を１０
〜３０重量％、ブロム化エポキシ樹脂の含量を２０〜９
０重量％とする時によい特性の柔軟性印刷回路基板用接
着剤を製造し得る。As can be seen from the above Examples and Comparative Examples, it is important that an appropriate amount of a carboxyl group, a hydroxy group, an amide group, etc., capable of undergoing a crosslinking reaction with the epoxy functional group of the acrylic copolymer resin is important. Acrylonitrile also plays an important role in heat resistance, polyfunctional epoxy resin plays a role in improving the adhesive strength and heat resistance of the adhesive, and a certain amount or more of brominated epoxy resin is used to impart flame retardancy. Must be added. Acrylic copolymer resin 10
With respect to 0% by weight, the content of the polyfunctional epoxy resin is 10%.
-30% by weight, the content of brominated epoxy resin is 20-9
An adhesive for a flexible printed circuit board having good characteristics when the content is 0% by weight can be manufactured.

フロントページの続き (72)発明者 チャン・キュンホー 大韓民国ソウル特別市陽川區新井２洞統 一聨立３棟203號 (56)参考文献 特開 平３−7791（ＪＰ，Ａ) 特開 平３−221578（ＪＰ，Ａ)Continuation of the front page (72) Inventor Chang Kung Ho, No. 203, 3rd building, 2nd union, Arai 2-dong, Yangcheon-gu, Seoul, Korea (56) References JP-A-3-7791 (JP, A) JP-A-3-3 221578 (JP, A)

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】アクリル共重合樹脂１００重量％（固形分
基準）に対して、多官能基のエポキシ樹脂１０〜３０重
量％とブロム化エポキシ樹脂２０〜９０重量％とを混合
した柔軟性印刷回路基板用接着剤組成物であって、前記
アクリル共重合樹脂は、アクリロニトリル１０〜４５重
量％と、炭素数８以下のアルキルアクリレート４０〜７
０重量％と、エポキシと反応し得る官能基１種以上を有
するオレフィン化合物３〜１５重量％とにより重合され
たことを特徴とする柔軟性印刷回路基板用接着剤組成
物。1. A flexible printed circuit in which 10 to 30% by weight of a polyfunctional epoxy resin and 20 to 90% by weight of a brominated epoxy resin are mixed with respect to 100% by weight (based on solid content) of an acrylic copolymer resin. An adhesive composition for a substrate,
Acrylic copolymer resin is 10-45 acrylonitrile
% And an alkyl acrylate having 8 or less carbon atoms of 40 to 7
0% by weight and at least one functional group capable of reacting with epoxy
Polymerized with 3 to 15% by weight of the olefin compound
An adhesive composition for a flexible printed circuit board, comprising: 【請求項２】前記多官能基エポキシ樹脂は１００〜３０
０のエポキシ当量を有し、前記ブロム化エポキシ樹脂は
２００〜９００のエポキシ当量を有し、ブロムの含量が
３０〜７０重量％であることを特徴とする請求項１記載
の柔軟性印刷回路基板用接着剤組成物。2. The polyfunctional epoxy resin is 100 to 30.
The flexible printed circuit board according to claim 1, wherein the epoxy resin has an epoxy equivalent of 0, the brominated epoxy resin has an epoxy equivalent of 200 to 900, and the content of brom is 30 to 70% by weight. use adhesive composition.
JP6223515A 1993-09-20 1994-09-19 Adhesive composition for flexible printed circuit boards Expired - Lifetime JP2625646B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1019930018998A KR950008647A (en) 1993-09-20 1993-09-20 Adhesive composition for flexible printed circuit board
KR93-18998 1993-09-20

Publications (2)

Publication Number Publication Date
JPH07300577A JPH07300577A (en) 1995-11-14
JP2625646B2 true JP2625646B2 (en) 1997-07-02

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ID=19363992

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Application Number Title Priority Date Filing Date
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Country Status (2)

Country Link
JP (1) JP2625646B2 (en)
KR (1) KR950008647A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005290171A (en) * 2004-03-31 2005-10-20 Sumitomo Bakelite Co Ltd Adhesive film for semiconductor and semiconductor device
JP4947905B2 (en) * 2005-02-04 2012-06-06 株式会社日本触媒 Resin composition for optical semiconductor encapsulation
JP4977343B2 (en) * 2005-08-05 2012-07-18 アキレス株式会社 Acrylic resin composition and sheet-like molded body using the same
DE102007016950A1 (en) * 2007-04-05 2008-10-09 Tesa Ag Thermally crosslinking polyacrylates and process for their preparation
US10294341B2 (en) 2016-01-13 2019-05-21 Lg Chem, Ltd. Thermosetting resin composition for semiconductor package and prepreg using the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH037791A (en) * 1988-09-09 1991-01-14 Mitsubishi Petrochem Co Ltd Adhesive composition for sticking foil
JPH03221578A (en) * 1990-01-26 1991-09-30 Sumitomo Electric Ind Ltd Adhesive composition for flexible printed wiring board

Also Published As

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KR950008647A (en) 1995-04-19
JPH07300577A (en) 1995-11-14

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