JPH0657825B2 - Flame-retardant adhesive composition for flexible printed circuit board - Google Patents
Flame-retardant adhesive composition for flexible printed circuit boardInfo
- Publication number
- JPH0657825B2 JPH0657825B2 JP60292878A JP29287885A JPH0657825B2 JP H0657825 B2 JPH0657825 B2 JP H0657825B2 JP 60292878 A JP60292878 A JP 60292878A JP 29287885 A JP29287885 A JP 29287885A JP H0657825 B2 JPH0657825 B2 JP H0657825B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- printed circuit
- solid content
- adhesive composition
- 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
Links
Classifications
-
- 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】 〔産業上の利用分野〕 本発明は、フレキシブル印刷回路基板に使用される接着
剤組成物に関し、更に詳しくは、銅、アルミニウム等の
金属箔と耐熱性樹脂フィルム又は耐熱性樹脂の含浸不織
シートとを接着してなる金属箔張り積層板や耐熱性樹脂
フィルム又は、耐熱性樹脂の含浸不織シートと接着剤と
離型性を有する保護シートからなるカバーレイフィルム
などの形成に使用されるフレキシブル印刷回路基板用難
燃性接着剤組成物に関する。TECHNICAL FIELD The present invention relates to an adhesive composition used for a flexible printed circuit board, and more specifically, a metal foil such as copper or aluminum and a heat resistant resin film or a heat resistant resin film. A metal foil-clad laminate or heat-resistant resin film obtained by adhering a non-woven sheet impregnated with a heat-resistant resin, or a coverlay film including a non-woven sheet impregnated with a heat-resistant resin and an adhesive and a protective sheet having releasability. A flame-retardant adhesive composition for a flexible printed circuit board, which is used for forming a film.
近年電子機器の小型化、軽量化、高密度化の要望に伴な
い、フレキシブル印刷基板の普及はめざましいものとな
っている。かかる普及に伴い、難燃化の要求、特に輸出
用に必要な難燃化の要求が特に強くなっている。In recent years, with the demand for smaller, lighter, and higher density electronic devices, the spread of flexible printed boards has become remarkable. With such widespread use, the demand for flame retardancy, particularly the demand for flame retardance necessary for export, has become particularly strong.
フレキシブル印刷回路基板の基本的な加工は、以下のご
とくである。すなわち基材としてのポリイミド樹脂、ポ
リアミドイミド樹脂、ポリパラバン酸樹脂などの耐熱性
樹脂のフィルム又はこれら樹脂の繊維からなる不織シー
トを用い、その基材上に接着剤を介して、銅やアルミニ
ウムなどの導電性金属箔を積層して金属箔張り積層板と
して提供され、ひきつづいて所定のパターンにエッチン
グ法を用いて回路形成される。形成された金属導体配線
パターンは、酸化などによる劣化を防止する目的として
カバーレイフィルムを積層され、フレキシブル印刷回路
基板となる。このカバーレイシートは、金属箔張り積層
板の基材として用いたものと同様の耐熱性樹脂フィルム
や不織シトに接着剤を塗布し、半硬化した後、ポリオレ
フィンフィルムや離型性付与処理をした紙などの保護シ
ートを貼合せて提供される。The basic processing of the flexible printed circuit board is as follows. That is, a polyimide resin, a polyamideimide resin, a film of a heat-resistant resin such as polyparabanic acid resin or a non-woven sheet made of fibers of these resins is used as a base material, and copper, aluminum, etc. are provided on the base material via an adhesive. It is provided as a metal foil-clad laminate by laminating conductive metal foils, and subsequently a circuit is formed into a predetermined pattern by using an etching method. The formed metal conductor wiring pattern is laminated with a coverlay film for the purpose of preventing deterioration due to oxidation or the like, and becomes a flexible printed circuit board. This cover lay sheet is applied with an adhesive agent on the same heat-resistant resin film or non-woven sheet as that used as the base material of the metal foil-clad laminate, and after being semi-cured, is subjected to a polyolefin film or a release property imparting treatment. It is provided by pasting a protective sheet such as paper.
このフレキシブル金属箔張り積層板やカバーレイシート
（以下、特に区別が必要な時以外は単にフレキシブル基
板と総称する）用の接着剤には、従来通りの接着強さ、
耐熱性、可撓性、電気絶縁性などの特性が要求され、更
にカバーレイシートではこれに加えて積層加工時の接着
剤の流れ、半硬化状態での保存寿命の特性をも要求され
ており、これら特性を満足しつつ難燃性を付与するとい
う困難な要求を充足することが要求される。The adhesive for this flexible metal foil-clad laminate or coverlay sheet (hereinafter, simply referred to as a flexible substrate unless otherwise particularly required) has a conventional adhesive strength,
Properties such as heat resistance, flexibility, and electrical insulation are required. In addition to this, coverlay sheets are also required to have adhesive flow during lamination processing and storage life in the semi-cured state. However, it is required to satisfy the difficult requirement of imparting flame retardancy while satisfying these characteristics.
従来、これらの要求を満たすべき接着剤として種種の試
みがなされたが、最近前記特性の全般にわたり比較的バ
ランスのとれた接着剤としてアクリルゴム／ブロム化エ
ポキシ系の接着剤が注目されるようになった。Although various attempts have been made in the past as adhesives that should meet these requirements, recently, acrylic rubber / brominated epoxy adhesives have attracted attention as adhesives that are relatively balanced over the above properties. became.
しかしながら、これらの接着剤は、いづれもメチルエチ
ルケトン、トルエン、アセトンなどの引火性有機溶剤の
溶液として供給されるために、フレキシブル基板製造に
於ける耐熱性基板と金属箔との接着や耐熱性基材への接
着剤の塗工および半硬化などの工程に際して、これら有
機溶媒の揮発除去の作業が必然的に要求される。この作
業は危険性が高く、また作業にあたっては安全性や労働
衛生上の格別の配慮が必要であることが指摘されてい
た。However, since all of these adhesives are supplied as a solution of a flammable organic solvent such as methyl ethyl ketone, toluene, or acetone, the adhesion between the heat-resistant substrate and the metal foil in the production of flexible substrates and the heat-resistant base material. In the steps of applying an adhesive agent to the substrate and semi-curing, the work of volatilizing and removing these organic solvents is inevitably required. It was pointed out that this work is highly dangerous and that special consideration must be given to safety and occupational hygiene in the work.
このような観点より有機溶媒を使用しない乳化重合型の
水系の接着剤の開発が行なわれており、これに難燃性を
付与する方法の検討が種々行なわれている。通常一般的
に、難燃性を与える手法として、ハロゲン元素を導入す
る方法；ハロゲン元素とリン化合物を導入する方法；ハ
ロゲン元素と三酸化アンチモンを導入する方法；無機フ
ィラーを添加する方法などがあげられる。From such a viewpoint, an emulsion polymerization type water-based adhesive which does not use an organic solvent has been developed, and various studies have been conducted on a method for imparting flame retardancy to the emulsion-based adhesive. Generally, as a method of imparting flame retardance, a method of introducing a halogen element; a method of introducing a halogen element and a phosphorus compound; a method of introducing a halogen element and antimony trioxide; a method of adding an inorganic filler, etc. To be
しかしながら、水系の場合かかる公知の方式を適用して
ハロゲン化合物、三酸化アンチモン等の粉状の無機フィ
ラーを接着剤系に添加する事は容易にこれらの凝集、分
離、沈降を生じ均一な接着剤層を形成する事が困難とな
るという問題があった。又、リン化合物の添加は、接着
強度や絶縁抵抗の大巾な低下を生じたこと水系接着剤に
おいては前記特性を満足するものは皆無であった。However, in the case of an aqueous system, it is easy to add a powdery inorganic filler such as a halogen compound or antimony trioxide to the adhesive system by applying such a known method, and easily cause aggregation, separation, or sedimentation of these to form a uniform adhesive. There is a problem that it is difficult to form a layer. In addition, none of the water-based adhesives satisfied the above-mentioned characteristics because the addition of the phosphorus compound caused a large decrease in the adhesive strength and the insulation resistance.
我々は、上記問題点を解決すべく鋭意検討の結果、接着
強さ、耐熱性、可撓性、電気特性、難燃性に優れたフレ
キシブル回路基板用難燃性接着剤組成物を発明するに至
った。As a result of intensive studies to solve the above-mentioned problems, we have invented a flame-retardant adhesive composition for flexible circuit boards, which is excellent in adhesive strength, heat resistance, flexibility, electrical characteristics, and flame retardancy. I arrived.
本発明は、水性アクリル共重合物および水溶性エポキシ
および／または乳化エポキシよりなる臭素を固型分の４
〜３０重量％含有する水性ポリマーの固型分１００重量
部に対し五酸化アンチモンゾルの固型分として４〜３０
重量部を配合してなるフレキシブル印刷回路基板用難燃
性接着剤組成物に関するものである。The present invention comprises a bromine solid content of 4 which is composed of an aqueous acrylic copolymer and a water-soluble epoxy and / or an emulsified epoxy.
-30% by weight, based on 100 parts by weight of the solid content of the aqueous polymer, 4 to 30 as the solid content of the antimony pentoxide sol.
The present invention relates to a flame-retardant adhesive composition for flexible printed circuit boards, which is mixed with parts by weight.
本発明における水性アクリル共重合物としては、以下の
モノマーの共重合物である。The aqueous acrylic copolymer in the present invention is a copolymer of the following monomers.
すなわち、メチルアクリレート、エチルアクリレート、
ブチルアクリレート、イソブチルアクリレート、２−エ
チルヘキシルアクリレートなどのアクリル酸エステル
類；メチルメタクリレート、エチルメタクリレート、ブ
チルメタクリレート、イソブチルメタクリレート、２−
エチルヘキシルメタクリレートなどのメタクリル酸エス
テル類；メタクリル酸、アクリル酸などの不飽和酸類；
ヒドロキシエチルメタクリレート、ヒドロキシプロピル
メタクリレートなどのヒドロキシアルキルメタクリル酸
エステル類；アクリルアマイド、Ｎ−メチロールアクリ
ルアマイドなどのアクリルアマイド類；スチレン、アク
リロニトリル、グリシジルメタクリレート；さらに臭素
を含有するモノマーとしてポリブロモフェノキシアクリ
レート、ポリブロモフェノキシヒドロプロピルアクリレ
ート、ポリブロモフェノキシメタクリレート、ポリブロ
モフェノキシヒドロキシプロピルメタクリレートなどの
モノマーがあり、これらのモノマー群の共重合物が使用
出来るが、このうち上記不飽和酸類および／またはヒド
ロキシアルキルメタクリル酸エステル類および／または
アクリルアマイド類および／またはグリシジルメタクリ
レートの配合量は、水性アクリル共重合物の固型分の中
の0.5〜１５重量％である事が望ましい。0.5重量部未満
では、水性アクリル共重合物の安定性に乏しくなり、１
５重量％を越えると耐熱性が低下する。又、水性アクリ
ル共重合物のガラス転移温度は、−５０℃〜５℃が好ま
しく、この範囲を越えても未満でも耐熱性、接着強度が
低下する。That is, methyl acrylate, ethyl acrylate,
Acrylic esters such as butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-
Methacrylic acid esters such as ethylhexyl methacrylate; unsaturated acids such as methacrylic acid and acrylic acid;
Hydroxyalkyl methacrylic acid esters such as hydroxyethyl methacrylate and hydroxypropyl methacrylate; acrylic amides such as acrylic amide and N-methylol acrylic amide; styrene, acrylonitrile, glycidyl methacrylate; and polybromophenoxy acrylate and polybromine as monomers containing bromine. There are monomers such as bromophenoxyhydropropyl acrylate, polybromophenoxy methacrylate, and polybromophenoxy hydroxypropyl methacrylate, and copolymers of these monomer groups can be used. Among them, the unsaturated acids and / or hydroxyalkyl methacrylates And / or acrylic amides and / or glycidyl methacrylate It is desirable that 0.5 to 15 wt% in the solid content of the aqueous acrylic copolymer. If it is less than 0.5 parts by weight, the stability of the aqueous acrylic copolymer becomes poor, and 1
If it exceeds 5% by weight, the heat resistance decreases. Further, the glass transition temperature of the aqueous acrylic copolymer is preferably -50 ° C to 5 ° C, and if it exceeds or falls below this range, heat resistance and adhesive strength are deteriorated.
以上の如きモノマー群よりなる水性アクリル共重合物
は、たとえば以下のような方法により製造される。即
ち、重合開始剤として例えば過硫酸カリウムの所定量を
例えば７０℃の蒸留水に溶解した液に、別の調合した上
記モノマー群と蒸留水との混合液を約３〜４時間攪拌し
つつ滴下重合し、更に３〜４時間かけて重合を終了させ
たのち、常温迄冷却後、粗大粒子を過し、アンモニア
水などによりpH７〜９程度に調製する。この際、当水性
アクリル共重合物は、反応系全体の４０〜７０重量％程
度、すなわち共重合反応が良好に行なわれる範囲内に調
整し、この反応液に直接水溶性エポキシおよび／または
乳化エポキシを加えて本発明の水性ポリマーを得ること
が出来る。The aqueous acrylic copolymer comprising the above monomer group is produced, for example, by the following method. That is, as a polymerization initiator, for example, a predetermined amount of potassium persulfate is dissolved in distilled water at 70 ° C., and a mixed liquid of the above-prepared monomer group and distilled water is added dropwise with stirring for about 3 to 4 hours. After the polymerization is completed and the polymerization is further completed over 3 to 4 hours, the mixture is cooled to room temperature, filtered with coarse particles, and adjusted to pH 7 to 9 with aqueous ammonia. At this time, the aqueous acrylic copolymer is adjusted to about 40 to 70% by weight of the whole reaction system, that is, within the range where the copolymerization reaction is favorably carried out, and the reaction solution is directly added with a water-soluble epoxy and / or an emulsified epoxy. Can be added to obtain the aqueous polymer of the present invention.
本発明に用いられる水溶性エポキシとしては、１分子中
にエーテル基および／またはアルコール性水酸基を有
し、２個以上のエポキシ基を有する化合物があげられ、
例えばポリエチレングリコールジグリシジルエーテル、
グリセリンポリグリシジルエーテル、ソルビトールポリ
グリシジルエーテル、トリメチロールプロパンポリグリ
シジルエーテルさらに臭素を有するものとして、テトラ
ブロモビスフェノールＡポリアルキレンオキサイド付加
物のジグリシジルエーテル、ジブロモネオベンチルグリ
コールジグリシジルエーテルなどがあげられる。Examples of the water-soluble epoxy used in the present invention include compounds having an ether group and / or an alcoholic hydroxyl group in one molecule and having two or more epoxy groups,
For example polyethylene glycol diglycidyl ether,
Examples of glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether and those having bromine include diglycidyl ether of tetrabromobisphenol A polyalkylene oxide adduct and dibromoneopentyl glycol diglycidyl ether.
これら水溶性エポキシはもちろん１種類以上用いてもか
まわない。Of course, one or more of these water-soluble epoxies may be used.
また、本発明に用いられる乳化エポキシとしては、ノボ
ラック形エポキシ、クレゾール形エポキシ、ビスフェノ
ールＡ形エポキシ、ビスフェノールＦ型エポキシ、さら
に臭素を含有するものとしてポリブロモビスフェノール
Ａ形エポキシ、ポリブロモノボラック形エポキシ、ポリ
ブロモビスフェノールＦ形エポキシなどの固形エポキシ
の乳化物があげられる。これら乳化エポキシは１種類以
上用いてもかまわない。The emulsified epoxy used in the present invention includes novolac type epoxy, cresol type epoxy, bisphenol A type epoxy, bisphenol F type epoxy, and polybromobisphenol A type epoxy and polybromo novolac type epoxy as those containing bromine. Examples thereof include solid epoxy emulsions such as polybromobisphenol F type epoxy. One or more kinds of these emulsified epoxies may be used.
水性ポリマー組成物としての配合量は、水性アクリル共
重合物固型分１００重量部に対して水溶性エポキシおよ
び／または乳化エポキシの固型分として３〜１５０重量
部が望ましい。この範囲を越えても未満でも耐熱性、接
着強度が低下する。又、水性ポリマーに含まれる臭素の
量としては、水性ポリマーの固型分の内４〜２０重量％
である事が望ましく、４重量％未満では、難燃効果が得
られず、２０重量％を越えると接着強度、可撓性が著し
く低下する。The content of the aqueous polymer composition is preferably 3 to 150 parts by weight as the solid content of the water-soluble epoxy and / or the emulsified epoxy based on 100 parts by weight of the solid content of the aqueous acrylic copolymer. If it exceeds or is less than this range, the heat resistance and the adhesive strength are lowered. The amount of bromine contained in the aqueous polymer is 4 to 20% by weight of the solid content of the aqueous polymer.
If it is less than 4% by weight, the flame retardant effect cannot be obtained, and if it exceeds 20% by weight, the adhesive strength and flexibility are significantly lowered.
本発明に用いられる五酸化アンチモンゾルとしては、公
知の製造法で得られたものでよく、粒径少くとも１μ以
下程度、好ましくは0.1μ以下程度の五酸化アンチモン
の水ゾルであり、アンモニウム、アミン、水酸化ナトリ
ウム、水酸化カリウム等によりpHを５〜１０に調製した
ものが望ましく市販品が入手できる。五酸化アンチモン
ゾルの配合量は、水性ポリマーの固型分１００重量部に
対して五酸化アンチモンゾルの固型分３〜３０重量部が
好ましく、更に好ましくは５〜２０重量部が好ましい。
五酸化アンチモンゾルの固型分が３重量部になると難燃
効果が得られなくなり、３０重量部を越えると接着強度
及び耐折性が著しく低下する。The antimony pentoxide sol used in the present invention may be obtained by a known production method, and is a water sol of antimony pentoxide having a particle size of at least about 1 μm or less, preferably about 0.1 μm or less, ammonium, A product having a pH adjusted to 5 to 10 with amine, sodium hydroxide, potassium hydroxide or the like is desirable and a commercially available product can be obtained. The compounding amount of the antimony pentoxide sol is preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the solid content of the aqueous polymer.
If the solid content of the antimony pentoxide sol is 3 parts by weight, the flame retardant effect cannot be obtained, and if it exceeds 30 parts by weight, the adhesive strength and the folding endurance are significantly lowered.
以上の如くして得られる本発明の接着剤組成物は、通常
pH７−９、粘度が１００〜５０００センチポイズの水性
接着剤である。この接着剤は、耐熱性フィルム又は不織
シート基材上に通常１０ないし８０μの膜厚（ドライベ
ース）となる様に塗工したのち乾燥と樹脂の硬化を行な
って所望のフレキシブル基材を得る。この塗工、乾燥の
工程において溶剤型接着剤の場合のごとく有機溶剤が揮
散することもなく、製造作業者は揮散溶剤の吸引や火災
の危険性から解放される。又、本発明の接着剤を用いた
印刷回路基板は、接着強さ、耐熱性、可撓性、電気絶縁
性、難燃性に優れるなど工業的に極めて有用な硬化を奏
するものである。The adhesive composition of the present invention obtained as described above is usually
It is an aqueous adhesive having a pH of 7-9 and a viscosity of 100 to 5000 centipoise. This adhesive is usually applied to a heat-resistant film or a non-woven sheet base material so as to have a film thickness (dry base) of 10 to 80 μm, and then dried and cured to obtain a desired flexible base material. . In the coating and drying process, the organic solvent does not evaporate as in the case of the solvent-type adhesive, and the manufacturing operator is free from the risk of inhaling the evaporating solvent and the risk of fire. Further, the printed circuit board using the adhesive of the present invention exhibits an industrially extremely useful cure such as excellent adhesive strength, heat resistance, flexibility, electrical insulation and flame retardancy.
実施例及び補足 以下に実施例を示しつつ補足説明を加える。Examples and Supplements Supplementary explanations are given below with reference to examples.
なお、実施例及び比較例中で示す。印刷回路基板の特性
評価は下記の如き方法に従って行なった。In addition, it shows in an Example and a comparative example. The characteristics of the printed circuit board were evaluated according to the following methods.
ａ．接着強さ ＩＰＣ−ＴＭ６５０ ２．４．９に基づき銅箔とベース
耐熱フィルム間の接着強さを測定した。a. Adhesive strength The adhesive strength between the copper foil and the base heat-resistant film was measured based on IPC-TM650 2.4.9.
ｂ．耐熱性 ＩＰＣ−ＴＭ６５０ ２．４．１３に基づき外観変化を
調べた。b. Heat resistance The appearance change was examined based on IPC-TM650 2.4.13.
ｃ．耐折性 ＭＩＴ型繰返し折り曲げ試験器を用い、試験片に５００
ｇの加重をかけた状態で導体の導通が停止するまでの折
り曲げ回数を測定した。c. Folding resistance Using a MIT type repeated bending tester, 500
The number of times of bending until the conduction of the conductor was stopped was measured under the condition that the weight g was applied.
ｄ．絶縁抵抗 ＩＰＣ−ＴＭ６５０ ２．５．２７に基づき常態（温度
２０℃、相対湿度６５％ＲＨ）における表面絶縁抵抗を
測定した。d. Insulation resistance Based on IPC-TM650 2.5.27, the surface insulation resistance in a normal state (temperature 20 ° C, relative humidity 65% RH) was measured.
ｅ．難燃性 ＵＬ−９４に基づき自己消火性を測定した。e. Flame retardance The self-extinguishing property was measured based on UL-94.
実施例１ アクリロニトリル２０重量部、ブチルアクリレート４０
重量部、２エチルヘキシルアクリレート２０重量部、メ
チルメタクリレート１０重量部、２ヒドロキシエチルメ
タクリレート５重量部、メタクリル酸５重量部を蒸留水
と混合しモノマー混合液を調製した。Example 1 Acrylonitrile 20 parts by weight, butyl acrylate 40
20 parts by weight of 2 ethylhexyl acrylate, 10 parts by weight of methyl methacrylate, 5 parts by weight of 2 hydroxyethyl methacrylate and 5 parts by weight of methacrylic acid were mixed with distilled water to prepare a monomer mixture solution.
次に重合開始剤として過硫酸カリウムの所定量を７０℃
の蒸留水に溶解した水溶液を調製し、この水溶液にこれ
を攪拌しながら４時間かけて滴下し、滴下終了後更に４
時間重合を進め反応を完了した。Next, a predetermined amount of potassium persulfate as a polymerization initiator is added at 70 ° C.
An aqueous solution dissolved in distilled water was prepared and added dropwise to this aqueous solution with stirring for 4 hours.
Polymerization proceeded for a period of time to complete the reaction.
反応液を常温まで冷却後、アンモニア水によりpHを7.5
に調製し、粗大粒子を過により除去して樹脂固型分が
５０重量％の水性アクリル共重合物を得た。得られた水
性アクリル共重合物は、粘度が８０センチポイズ、ＤＳ
Ｃ法により測定したガラス転移温度は−１６℃であっ
た。この水性アクリル共重合物１００部に対し、ソルビ
トールポリグリシジルエーテル１０重量部を混合溶解し
た後ポリブロモビスフェノールＡ型エポキシ乳化物（商
品名：アクアトート４５２０東都化成株式会社製）の６
７重量部（固型分４０重量部）を加え水性ポリマー１７
７部を得た（固型分１００部）。更に五酸化アンチモン
ゾル（商品名：Ａ−１５３０、日産化学株式会社製）を
４０重量部（固型分１２重量部）を加え本発明の接着剤
組成物１を得た。この接着剤組成物１を厚さ２５μのポ
リイミドフィルム（商品名：カプトン、イー・アイ・デ
ュポン社製）にリバースロールコーターにより約２５μ
（ドライベース）の厚さで塗布し、乾燥半硬化（温度１
００℃、時間６分間）させた後、厚さ３５μの電解銅箔
（商品名Ｔ−７、福田金属社製）を積層し、線圧５kg/c
m、温度１７０℃の条件にてプレスし、その後１５０
℃、５時間アフターキュアしてフレキシブル銅張積層板
を得た。After cooling the reaction solution to room temperature, adjust the pH to 7.5 with aqueous ammonia.
And the coarse particles were excessively removed to obtain an aqueous acrylic copolymer having a resin solid content of 50% by weight. The obtained aqueous acrylic copolymer has a viscosity of 80 centipoise and DS.
The glass transition temperature measured by the C method was -16 ° C. To 100 parts of this aqueous acrylic copolymer, 10 parts by weight of sorbitol polyglycidyl ether were mixed and dissolved, and then 6 of polybromobisphenol A type epoxy emulsion (trade name: Aquatote 4520 manufactured by Toto Kasei Co., Ltd.)
Aqueous polymer 17 with addition of 7 parts by weight (solid content 40 parts by weight)
7 parts were obtained (100 parts of solid content). Furthermore, 40 parts by weight (solid content: 12 parts by weight) of antimony pentoxide sol (trade name: A-1530, manufactured by Nissan Chemical Industries, Ltd.) was added to obtain an adhesive composition 1 of the present invention. About 25 μm of this adhesive composition 1 on a 25 μm-thick polyimide film (trade name: Kapton, manufactured by EI DuPont) using a reverse roll coater.
(Dry base) applied and dried and semi-cured (Temperature 1
After the temperature is set to 00 ° C. for 6 minutes, an electrolytic copper foil having a thickness of 35 μm (trade name: T-7, manufactured by Fukuda Metals Co., Ltd.) is laminated and the linear pressure is 5 kg / c.
Press at m, temperature 170 ℃, then 150
After curing at 5 ° C. for 5 hours, a flexible copper-clad laminate was obtained.
更に本発明の接着剤組成物１を厚さ２５μのポリイミド
フィルムにリバースロールコーターにより約３８μ（ド
ライベース）の厚さで塗布し、乾燥半硬化（温度１００
℃、時間６分間）させ、これに厚さ２５μのポリエステ
ルフィルムを積層してカバーレイシートを作製した。Further, the adhesive composition 1 of the present invention was applied to a polyimide film having a thickness of 25 μm by a reverse roll coater so as to have a thickness of about 38 μm (dry base), and dried and semi-cured (temperature 100).
C., time 6 minutes), and a 25 μm-thick polyester film was laminated thereon to prepare a coverlay sheet.
先に作製したフレキシブル銅張り積層板を用いサブトラ
クト法によりテストパターンの印刷回路加工を実施し、
テスト用印刷回路基板を得た。この基板上に上記カバー
レイシートを熱プレスにより貼合せフレキシブル印刷回
路基板を得た。本基板の特性を各項目について評価し
た。その結果を表１に示す。なお、カバーレイシートの
プレス条件は、プレス圧力３０kg/cm2、温度１６０℃、
プレス時間３０分であった。Printed circuit processing of the test pattern is carried out by the subtract method using the flexible copper-clad laminate prepared earlier,
A test printed circuit board was obtained. The cover lay sheet was laminated on this substrate by hot pressing to obtain a flexible printed circuit board. The characteristics of this substrate were evaluated for each item. The results are shown in Table 1. The pressing conditions for the coverlay sheet are as follows: press pressure 30 kg / cm 2 , temperature 160 ° C.
The pressing time was 30 minutes.
実施例２ アクリロニトリル２０重量部、ブチルアクリレート５２
重量部、スチレン２５重量部、Ｎ−メチロールアクリル
アマイド１重量部、メタクリル酸２重量部を蒸留水中に
混合し、実施例１の方法に従い重合させ、樹脂成分が６
０重量％の水性アクリル共重合物を得た。pHが7.9、粘
度が１５０センチポイズであり、ＤＳＣ法によるガラス
転移温度は０℃であった。この水性アクリル共重合物１
００重量部に対し水溶性エポキシとしてテトラブロモビ
スフェノールＡ ジテトラエチレングリコールジグリシ
ジルエーテルを３０重量部、ノボラックエポキシ乳化物
６重量部（固型分1.5重量部）及び五酸化アンチモンゾ
ル２０重量部（固型分６重量部）を加え、接着剤組成物
２を得た。Example 2 20 parts by weight of acrylonitrile, 52 butyl acrylate
Parts by weight, 25 parts by weight of styrene, 1 part by weight of N-methylol acrylate, and 2 parts by weight of methacrylic acid were mixed in distilled water and polymerized according to the method of Example 1 to obtain a resin component of 6 parts.
A 0% by weight aqueous acrylic copolymer was obtained. The pH was 7.9, the viscosity was 150 centipoise, and the glass transition temperature by the DSC method was 0 ° C. This aqueous acrylic copolymer 1
30 parts by weight of tetrabromobisphenol A ditetraethylene glycol diglycidyl ether as a water-soluble epoxy, 6 parts by weight of novolac epoxy emulsion (1.5 parts by weight of solid content) and 20 parts by weight of antimony pentoxide sol (solid content) with respect to 00 parts by weight. A mold component (6 parts by weight) was added to obtain an adhesive composition 2.
実施例１と同様にしてフレキシブル印刷回路基板を作製
し、評価結果を表−１に示す。A flexible printed circuit board was prepared in the same manner as in Example 1, and the evaluation results are shown in Table-1.
実施例３ アクリロニトリル３３重量部、ブチルアクリレート５２
重量部、２−ヒドロキシエチルメタクリレート３重量
部、メタクリル酸１重量部、アクリルアマイド１重量
部、ジブロモフエノキシヒドロキシプロピルアクリレー
ト１０重量部を蒸留水中に混合し実施例１の方法に従い
重合させ樹脂成分が４０重量％の水性アクリル共重合物
を得た。pHが8.5、粘度が２００センチポイズであり、
ＤＳＣ法によるガラス転移温度は０℃であった。Example 3 33 parts by weight of acrylonitrile, 52 butyl acrylate
Parts by weight, 3 parts by weight of 2-hydroxyethyl methacrylate, 1 part by weight of methacrylic acid, 1 part by weight of acrylate, 10 parts by weight of dibromophenoxyhydroxypropyl acrylate are mixed in distilled water and polymerized according to the method of Example 1 to obtain a resin component. To obtain 40% by weight of an aqueous acrylic copolymer. pH 8.5, viscosity 200 centipoise,
The glass transition temperature by the DSC method was 0 ° C.
この水性アクリル共重合物１００重量部に対し、乳化エ
ポキシとしてポリブロモビスフェノールＡ型エポキシ乳
化物を６７重量部（固型分４０重量部）加え、更に五酸
化アンチモンゾル５３重量部を加え、接着剤組成物３を
得た。実施例１と同様にしてフレキシブル印刷回路基板
を作製し、評価結果を表−１に示す。To 100 parts by weight of this water-based acrylic copolymer, 67 parts by weight of polybromobisphenol A type epoxy emulsion as an emulsified epoxy (40 parts by weight of solid content) and 53 parts by weight of antimony pentoxide sol were further added to form an adhesive. Composition 3 was obtained. A flexible printed circuit board was prepared in the same manner as in Example 1, and the evaluation results are shown in Table-1.
実施例４ アクリロニトリル１０重量部、ブチルアクリレート４重
量部、２エチルヘキシルアクリレート７２重量部、２−
ヒドロキシエチルメタクリレート６重量部、メタクリル
酸５重量部、アクリルアマイド３重量部を蒸留水中に混
合し、実施例１の方法に従い重合させ樹脂成分が５０重
量％の水性アクリル共重合物を得た。pHが7.2、粘度が
２８０センチポイズであり、ＤＳＣ法によるガラス転移
温度は−４５℃であった。Example 4 Acrylonitrile 10 parts by weight, butyl acrylate 4 parts by weight, 2 ethylhexyl acrylate 72 parts by weight, 2-
6 parts by weight of hydroxyethyl methacrylate, 5 parts by weight of methacrylic acid and 3 parts by weight of acrylic amide were mixed in distilled water and polymerized according to the method of Example 1 to obtain an aqueous acrylic copolymer having a resin component of 50% by weight. The pH was 7.2, the viscosity was 280 centipoise, and the glass transition temperature by the DSC method was -45 ° C.
この水性アクリル共重合物１００重量部に対し、水溶性
エポキシとしてジブロモネオペンチルグリコールジグリ
シジルエーテル４０重量部、乳化エポキシとしてポリブ
ロモビスフェノールＡ型エポキシ乳化物５０重量部（固
型分３０重量部）を加え、更に五酸化アンチモンゾル２
０重量部（固型分６重量部）を加え、接着剤組成物５を
得た。To 100 parts by weight of this aqueous acrylic copolymer, 40 parts by weight of dibromoneopentyl glycol diglycidyl ether as a water-soluble epoxy and 50 parts by weight of polybromobisphenol A type epoxy emulsion as an emulsified epoxy (solid content 30 parts by weight) In addition, antimony pentoxide sol 2
An adhesive composition 5 was obtained by adding 0 parts by weight (solid content: 6 parts by weight).
実施例１と同様にしてフレキシブル印刷回路基板を作製
し、評価結果を表−１に示す。A flexible printed circuit board was prepared in the same manner as in Example 1, and the evaluation results are shown in Table-1.
比較例−１ 実施例１にて得られた水性ポリマー１００重量部（固型
分５６部）に対し、五酸化アンチモンゾル６０重量部
（固型分１８重量部）を加えて接着剤組成物５を得た。
実施例１と同様にしてフレキシブル印刷回路基板を作製
し、評価結果を表−１に示す。あまり五酸化アンチモン
ゾルの添加量が多すぎると接着強さや耐折性が大巾に低
下する。Comparative Example-1 To 100 parts by weight of the aqueous polymer obtained in Example 1 (56 parts by weight of solid content), 60 parts by weight of antimony pentoxide sol (18 parts by weight of solid content) was added to obtain an adhesive composition 5. Got
A flexible printed circuit board was prepared in the same manner as in Example 1, and the evaluation results are shown in Table-1. If the amount of the antimony pentoxide sol added is too large, the adhesive strength and the folding endurance will be significantly reduced.
比較例−２ 実施例１にて得られた水性ポリマー１００重量部に対
し、三酸化アンチモン微粉末１２重量部加え十分混合攪
拌し、接着剤組成物６を得た。Comparative Example-2 To 100 parts by weight of the aqueous polymer obtained in Example 1, 12 parts by weight of antimony trioxide fine powder was added and sufficiently mixed and stirred to obtain an adhesive composition 6.
実施例１と同様にフィルム上に塗布したが多くの凝集物
を生じ、均一な塗膜が得られなかった。It was coated on a film in the same manner as in Example 1, but many agglomerates were formed and a uniform coating film could not be obtained.
比較例−３ 実施例−１にて得られた水性ポリマー１００重量部に対
し、五酸化アンチモンゾル５重量部（固型分１．５重量
部）を加えて、接着剤組成物７を得た。実施例−１と同
様にして、フレキシブル印刷回路基板を作製し、評価し
た結果、五酸化アンチモンゾルの添加量が少ないと難燃
効果が殆どないことが明らかになった。Comparative Example-3 Adhesive composition 7 was obtained by adding 5 parts by weight of antimony pentoxide sol (1.5 parts by weight of solid content) to 100 parts by weight of the aqueous polymer obtained in Example-1. . A flexible printed circuit board was prepared and evaluated in the same manner as in Example-1. As a result, it was revealed that the flame retardant effect was almost nonexistent when the added amount of antimony pentoxide sol was small.
Claims (1)
シおよび／または乳化エポキシよりなる臭素を固型分の
４〜２０重量％含有する水性ポリマー接着剤組成物に、
該水性ポリマーの固形分１００重量部に対し、五酸化ア
ンチモンゾルの固形分として３〜３０重量部を配合して
なる凝集、分離、沈降を生じることなく均一な接着層を
形成しうるフレキシブル印刷回路基板用難燃性接着剤組
成物。1. An aqueous polymer adhesive composition containing 4 to 20% by weight of a solid content of bromine, which comprises an aqueous acrylic copolymer and a water-soluble epoxy and / or an emulsified epoxy,
A flexible printed circuit capable of forming a uniform adhesive layer without aggregation, separation, or sedimentation, which is obtained by mixing 3 to 30 parts by weight as a solid content of antimony pentoxide sol with respect to 100 parts by weight of a solid content of the aqueous polymer. Flame-retardant adhesive composition for substrates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60292878A JPH0657825B2 (en) | 1985-12-27 | 1985-12-27 | Flame-retardant adhesive composition for flexible printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60292878A JPH0657825B2 (en) | 1985-12-27 | 1985-12-27 | Flame-retardant adhesive composition for flexible printed circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62153373A JPS62153373A (en) | 1987-07-08 |
| JPH0657825B2 true JPH0657825B2 (en) | 1994-08-03 |
Family
ID=17787545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60292878A Expired - Lifetime JPH0657825B2 (en) | 1985-12-27 | 1985-12-27 | Flame-retardant adhesive composition for flexible printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0657825B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2644233B2 (en) * | 1987-08-03 | 1997-08-25 | 三井東圧化学株式会社 | Flame retardant adhesive composition for flexible printed circuit boards |
| US4904365A (en) * | 1988-02-29 | 1990-02-27 | Trinity Industrial Corporation | Electrodeposition coating facility |
| JPH0343238Y2 (en) * | 1988-02-29 | 1991-09-10 | ||
| CA2030145A1 (en) * | 1989-11-20 | 1991-05-21 | Thomas E. Dueber | Flame retardant adhesive composition and laminates |
| DE69415046T2 (en) * | 1993-11-03 | 1999-08-19 | H B Fuller Automotive Products | HEAT-CURABLE TOE EPOXY RESIN COMPOSITIONS |
| US6114426A (en) * | 1997-11-20 | 2000-09-05 | Lucent Technologies, Inc. | Pressure-sensitive flame retardant adhesive |
| KR100380309B1 (en) * | 2001-02-07 | 2003-04-18 | 주식회사 새 한 | Adhesive composition for electronic parts |
| KR20030029426A (en) * | 2001-10-08 | 2003-04-14 | 삼신써키트 주식회사 | Method of manufacturing hard panel for FPC |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59136319A (en) * | 1983-01-25 | 1984-08-04 | Nissan Chem Ind Ltd | Epoxy resin composition for flame retardant board |
| JPS605532A (en) * | 1983-06-23 | 1985-01-12 | Toshiba Corp | Controlling method of semiconductor resin sealing device |
| JPS605531A (en) * | 1983-06-23 | 1985-01-12 | Nec Corp | Formation of insulating film |
| JPS6020978A (en) * | 1983-07-14 | 1985-02-02 | Mitsui Toatsu Chem Inc | Adhesive composition for flexible printed circuit board substrate |
| JPS60118781A (en) * | 1983-12-01 | 1985-06-26 | Mitsui Toatsu Chem Inc | Adhesive composition for flexible printed circuit board |
-
1985
- 1985-12-27 JP JP60292878A patent/JPH0657825B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62153373A (en) | 1987-07-08 |
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