JP2001019930A - Flame-retardant adhesive composition, flexible copper- clad laminate, cover lay and adhesive film - Google Patents
Flame-retardant adhesive composition, flexible copper- clad laminate, cover lay and adhesive filmInfo
- Publication number
- JP2001019930A JP2001019930A JP11197220A JP19722099A JP2001019930A JP 2001019930 A JP2001019930 A JP 2001019930A JP 11197220 A JP11197220 A JP 11197220A JP 19722099 A JP19722099 A JP 19722099A JP 2001019930 A JP2001019930 A JP 2001019930A
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- Prior art keywords
- adhesive composition
- halogen
- epoxy
- rubber
- composition according
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ハロゲンフリーの
難燃性接着剤組成物ならびにそれを用いたフレキシブル
銅張積層板、カバーレイおよび接着剤フィルムに関し、
またこれらを用いて製造されたプリント配線板に関す
る。The present invention relates to a halogen-free flame-retardant adhesive composition and a flexible copper-clad laminate, a coverlay and an adhesive film using the same.
Also, the present invention relates to a printed wiring board manufactured using the same.
【０００２】[0002]
【従来の技術】近年、世界的な環境問題、人体に対する
安全性についての関心の高まりに伴なって、電気・電子
機器については、従来からの難燃性に加えて、より少な
い有害性、より高い安全性という要求が増大している。
すなわち、電気・電子機器は、単に燃えにくいだけでな
く、有害ガスや発煙などの発生が少ないことが要望され
ている。従来、電気・電子機器の配線に使用するフレキ
シブルプリント配線板は、フレキシブル銅張積層板、カ
バーレイ及び接着剤フィルムにより構成されるが、そこ
に使用されている接着剤には、難燃剤として作用する臭
素が含まれる臭素化エポキシ樹脂、特にテトラブロモビ
スフェノールＡ型エポキシ樹脂が一般に使用されてい
る。2. Description of the Related Art In recent years, as environmental concerns around the world and concerns about safety for the human body have increased, electric and electronic devices have become less hazardous in addition to the conventional flame retardancy. The demand for high security is increasing.
That is, it is demanded that electric / electronic devices not only hardly burn, but also generate less harmful gas and smoke. Conventionally, flexible printed wiring boards used for wiring of electric and electronic devices are composed of flexible copper-clad laminates, coverlays and adhesive films, but the adhesive used there acts as a flame retardant. A brominated epoxy resin containing bromine, particularly a tetrabromobisphenol A type epoxy resin, is generally used.
【０００３】このような臭素化エポキシ樹脂は、良好な
難燃性を有するものの、燃焼時に有害なハロゲン化水素
（臭化水素）ガスを発生することや、ブロモ化ダイオキ
シン、フラン類を発生する可能性があるため、その使用
が抑制されつつある。[0003] Such brominated epoxy resins have good flame retardancy, but can generate harmful hydrogen halide (hydrogen bromide) gas upon combustion, and can also generate brominated dioxins and furans. Therefore, its use is being suppressed.
【０００４】そこで、例えば、窒素化合物、リン化合
物、有機化合物等を配合した種々のエポキシ樹脂組成物
が開発されている（英国特許第１，１１２，１３９号明
細書、日本国特開平２−２６９７３０号公報参照）。Therefore, for example, various epoxy resin compositions containing a nitrogen compound, a phosphorus compound, an organic compound and the like have been developed (British Patent No. 1,112,139, Japanese Patent Application Laid-Open No. 2-269730). Reference).
【０００５】しかし、これらに記載の化合物では、エポ
キシ樹脂の硬化に悪影響を及ぼしたり、硬化組成物の耐
湿性、耐熱性を低下させる等の問題点があった。[0005] However, the compounds described above have problems such as adversely affecting the curing of the epoxy resin and lowering the moisture resistance and heat resistance of the cured composition.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、ハロ
ゲンを含まずに良好な難燃性を示す（ハロゲンフリー）
とともに、上記従来技術の欠点を解消した接着剤組成物
を提供することにある。An object of the present invention is to exhibit good flame retardancy without halogen (halogen free).
Another object of the present invention is to provide an adhesive composition which has solved the above-mentioned disadvantages of the conventional technology.
【０００７】さらに、本発明は、そのような難燃性接着
剤組成物を用いたフレキシブル銅張積層板、カバーレイ
および接着剤フィルム並びにこれらを用いて製造された
フレキシブルプリント配線板を提供することをも目的と
する。Further, the present invention provides a flexible copper-clad laminate, a coverlay and an adhesive film using such a flame-retardant adhesive composition, and a flexible printed wiring board manufactured using the same. Also aim.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記の目
的を達成しようと鋭意研究を重ねた結果、接着剤組成物
に、シクロホスファゼン化合物とエポキシド化合物その
他を適当に組み合わせるという新規な配合によって、ハ
ロゲンを含まずに良好な難燃性を示すとともに、耐湿
性、耐熱性が向上し、上記目的が達成されることを見い
だし、本発明を完成させたものである。Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, have found that a novel compound in which a cyclophosphazene compound and an epoxide compound are appropriately combined with an adhesive composition. Thus, the present invention has been found to exhibit good flame retardancy without containing halogen, to improve moisture resistance and heat resistance, and to achieve the above object, thereby completing the present invention.
【０００９】即ち、本発明は、（Ａ）少なくとも一種の
シクロホスファゼン化合物、（Ｂ）少なくとも一種のポ
リエポキシド化合物、（Ｃ）エポキシ用硬化剤および
（Ｄ）合成ゴム（Ｅ）無機充填剤を必須成分とすること
を特徴とするハロゲンフリーの難燃性接着剤組成物であ
る。また、上記難燃性接着剤組成物を用いたフレキシブ
ル銅張積層板、カバーレイおよび接着剤フィルム並びに
これらを用いて製造されたフレキシブルプリント配線板
である。That is, the present invention comprises (A) at least one cyclophosphazene compound, (B) at least one polyepoxide compound, (C) a curing agent for epoxy, and (D) a synthetic rubber (E) an inorganic filler. And a halogen-free flame-retardant adhesive composition. Also, a flexible copper-clad laminate, a coverlay and an adhesive film using the above flame-retardant adhesive composition, and a flexible printed wiring board manufactured using these.
【００１０】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１１】本発明に用いる（Ａ）シクロホスファゼン
化合物としては、耐熱性、耐湿性、難燃性、耐薬品性の
観点から、シクロホスファゼンオリゴマーが好適であ
る。シクロホスファゼンオリゴマーは、下記一般式に示
されるものであり、さらにその融点は、８０℃以上であ
ることが好ましい。The cyclophosphazene compound (A) used in the present invention is preferably a cyclophosphazene oligomer from the viewpoint of heat resistance, moisture resistance, flame retardancy and chemical resistance. The cyclophosphazene oligomer is represented by the following general formula, and its melting point is preferably 80 ° C. or higher.
【００１２】[0012]
【化２】 （但し、式中、Ｘは水素原子であるかハロゲンを含まな
い有機基であって、それらが互いに同じでも異なっても
よい。また、式中のｎは３〜１０の整数を表す。） シクロホスファゼンオリゴマーにおけるハロゲンを含ま
ない有機基Ｘとしては、アルコキシ基、フェノキシ基、
アミノ基、アリル基などが挙げられる。Embedded image (In the formula, X is a hydrogen atom or an organic group containing no halogen, and they may be the same or different from each other. In the formula, n represents an integer of 3 to 10.) Examples of the halogen-free organic group X in the phosphazene oligomer include an alkoxy group, a phenoxy group,
Examples include an amino group and an allyl group.
【００１３】本発明に用いる（Ｂ）ポリエポキシド化合
物としては、グリシジルエーテル系エポキシ樹脂が好適
である。これには、ビスフェノールＡ型エポキシ樹脂、
ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキ
シ樹脂等が挙げられ、これらは単独又は２種以上混合し
て使用することができる。また、このエポキシ樹脂に
は、グリシジルエーテル系の変性エポキシ樹脂も含む。
変性エポキシ樹脂として例えば、ＢＴ樹脂などを使用す
ることができる。As the polyepoxide compound (B) used in the present invention, a glycidyl ether epoxy resin is preferred. This includes bisphenol A type epoxy resin,
Bisphenol F type epoxy resin, novolak type epoxy resin and the like can be mentioned, and these can be used alone or in combination of two or more. The epoxy resin also includes a glycidyl ether-based modified epoxy resin.
As the modified epoxy resin, for example, a BT resin or the like can be used.
【００１４】本発明に用いる（Ｃ）エポキシ用硬化剤と
しては、ジシアンジアミド（ＤＩＣＹ）とその誘導体、
ノボラック型フェノール樹脂、アミノ変性ノボラック型
フェノール樹脂、ポリビニルフェノール樹脂、有機酸ヒ
ドラジッド、ジアミノマレオニトリルとその誘導体、メ
ラミンとその誘導体、アミンイミド、ポリアミン塩、モ
レキュラーシーブ、アミン、酸無水物、ポリアミド、イ
ミダゾールのうちの少なくとも一種を用いることができ
る。As the epoxy curing agent (C) used in the present invention, dicyandiamide (DICY) and its derivatives,
Novolak-type phenolic resin, amino-modified novolak-type phenolic resin, polyvinylphenol resin, organic acid hydrazide, diaminomaleonitrile and its derivatives, melamine and its derivatives, amine imide, polyamine salt, molecular sieve, amine, acid anhydride, polyamide, imidazole At least one of them can be used.
【００１５】本発明においては、必要に応じて、（Ｄ）
硬化促進剤を用いる。硬化促進剤としては、必要な場
合、通常のエポキシ樹脂用硬化促進剤として用いられる
第三アミン、イミダゾール、芳香族アミンのうちの少な
くとも一種を用いることができる。In the present invention, if necessary, (D)
Use a curing accelerator. If necessary, at least one of tertiary amines, imidazoles, and aromatic amines used as ordinary curing accelerators for epoxy resins can be used as the curing accelerator.
【００１６】（Ｂ）成分のビスフェノールＡ型エポキシ
樹脂などは、ビスフェノールＡとエピクロルヒドリンと
をアルカリの存在下で反応させるために、その反応残
渣、反応副生成物としての不純物ハロゲンが残存する。
ハロゲンフリーの本発明において使用される（Ａ）〜
（Ｅ）成分は、それぞれについて不純物ハロゲンの含有
量が０．１重量％以下のものとすることが好ましい。The bisphenol A epoxy resin or the like as the component (B) reacts bisphenol A with epichlorohydrin in the presence of an alkali, so that a reaction residue and impurity halogen as a reaction by-product remain.
(A) used in the present invention which is halogen-free
It is preferable that each component (E) has an impurity halogen content of 0.1% by weight or less.
【００１７】本発明に用いる（Ｅ）合成ゴムとしては、
アクリルゴム、アクリロニトリルブタジエンゴム、スチ
レンブタジエンゴム、ブタジエンメチルアクリレートア
クリロニトリルゴム、ブタジエンゴム、カルボキシル含
有アクリロニトリルブタジエンゴム、ビニル含有アクリ
ロニトリルブタジエンゴム、シリコーンゴム、ウレタン
ゴム、ポリビニルブチラール等のハロゲンを含まないゴ
ムのうち少なくとも１種を用いることができる。The (E) synthetic rubber used in the present invention includes:
Acrylic rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, butadiene methyl acrylate acrylonitrile rubber, butadiene rubber, carboxyl-containing acrylonitrile-butadiene rubber, vinyl-containing acrylonitrile-butadiene rubber, silicone rubber, urethane rubber, and polyvinyl-butyral rubber-free rubber at least. One type can be used.
【００１８】本発明に用いる（Ｆ）無機充填剤として
は、難燃性などの補助添加剤として使用する無機充填剤
であり、接着剤としての諸特性を阻害しない範囲で可能
である。これらの充填剤には、タルク、シリカ、アルミ
ナ、水酸化アルミニウム、水酸化マグネシウム等が挙げ
られ、これらは単独又は２種以上混合して使用すること
ができる。The (F) inorganic filler used in the present invention is an inorganic filler used as an auxiliary additive such as flame retardancy, and can be used as long as various properties as an adhesive are not impaired. These fillers include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide and the like, and these can be used alone or in combination of two or more.
【００１９】本発明の接着剤組成物において、化合物な
どの配合割合は、（Ａ）シクロホスファゼン化合物が２
〜５０重量％、（Ｆ）の無機充填剤は、０〜５０重量％
の割合である。また、（Ａ）成分＋（Ｆ）成分が、樹脂
組成物において、２０〜７０重量％配合することが好ま
しい。In the adhesive composition of the present invention, the compounding ratio of the compound and the like is such that (A) the cyclophosphazene compound is 2%.
0 to 50% by weight, the inorganic filler of (F) is 0 to 50% by weight
Is the ratio of Further, it is preferable that the component (A) + the component (F) be blended in the resin composition in an amount of 20 to 70% by weight.
【００２０】本発明の接着剤組成物は上述した（Ａ）〜
（Ｆ）成分を必須成分とするが、本発明の目的に反しな
い限度において、また必要に応じて、顔料、劣化防止剤
等を添加配合することができる。The adhesive composition of the present invention has the above-mentioned (A) to (A).
Although the component (F) is an essential component, a pigment, a deterioration inhibitor and the like can be added and blended as long as the object of the present invention is not adversely affected, and if necessary.
【００２１】以上述べた本発明の接着剤組成物は、これ
をプロピレングリコールモノメチルエーテル等の好適な
有機溶剤で希釈してワニスとなし、これをポリイミドフ
ィルム上に塗布し、熱ロールで銅箔を片面または両面に
貼り合わせた後、加熱硬化するという通常の方法により
フレキシブル銅張積層板を製造することができる。The adhesive composition of the present invention described above is diluted with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish, which is coated on a polyimide film, and a copper foil is coated with a hot roll. A flexible copper-clad laminate can be manufactured by the usual method of bonding by heating to one side or both sides, followed by curing.
【００２２】また、本発明の接着剤組成物は、これをプ
ロピレングリコールモノメチルエーテル等の好適な有機
溶剤で希釈してワニスとなし、これをポリイミドフィル
ム上に塗布し、加熱乾燥するという通常の方法によりカ
バーレイを製造することができる。The adhesive composition of the present invention is prepared by diluting the adhesive composition with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish, applying the varnish on a polyimide film, and drying by heating. Can produce a coverlay.
【００２３】また、本発明の接着剤組成物は、これをプ
ロピレングリコールモノメチルエーテル等の好適な有機
溶剤で希釈してワニスとなし、キャリアフィルム上に塗
布し、加熱乾燥して剥離するという通常の方法により接
着剤フィルムを製造することができる。The adhesive composition of the present invention is usually diluted with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish, applied on a carrier film, and dried by heating to be peeled off. The method can produce an adhesive film.
【００２４】また、該フレキシブル銅張積層板に回路を
形成し、必要であれば穴明けスルーホールメッキを施
し、ついで所定箇所に穴を明けた該カバーレイを重ねて
加熱加圧成形するという通常の方法でフレキシブルプリ
ント配線板を製造することができる。更にこのフレキシ
ブルプリント配線板に該フィルム接着剤を介して補強板
を重ね合わせ、加熱加圧成形するという通常の方法で補
強板付きフレキシブルプリント配線板を製造することが
できる。Also, a circuit is formed on the flexible copper-clad laminate, if necessary, a through-hole plating is performed, and then the coverlay having a hole formed in a predetermined place is overlapped and heated and pressed. The flexible printed wiring board can be manufactured by the method described above. Further, a flexible printed wiring board with a reinforcing plate can be manufactured by a usual method of laminating a reinforcing plate on the flexible printed wiring board via the film adhesive and performing heating and press molding.
【００２５】また、多層プリント配線板は、該フレキシ
ブルプリント配線板に該フィルム接着剤を介して該フレ
キシブル銅張積層板またはハロゲンを含まないガラスエ
ポキシ銅張積層板などを重ね合わせ、加熱加圧成形し、
スルーホールを形成し、スルーホールメッキを行った
後、所定の回路を形成するという通常の方法により製造
することができる。The multilayer printed wiring board may be formed by laminating the flexible copper-clad laminate or the halogen-free glass epoxy copper-clad laminate or the like via the film adhesive on the flexible printed wiring board, followed by heat and pressure molding. And
It can be manufactured by a usual method of forming a through hole, plating the through hole, and then forming a predetermined circuit.
【００２６】[0026]
【発明の実施の形態】以下、本発明を実施例により説明
するが、本発明はこれらの実施例によって限定されるも
のではない。以下の実施例および比較例において「部」
とは「重量部」を意味する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. "Part" in the following Examples and Comparative Examples
Means "parts by weight".
【００２７】実施例１ カルボキシル含有アクリロニトリルブタジエンゴムのニ
ポール１０７２（日本ゼオン社製商品名、ニトリル含量
２７）３００部、ビスフェノールＡ型エポキシ樹脂のエ
ピコート１００１（油化シェル社製商品名、エポキシ当
量４７０）３２０部、クレゾールノボラックエポキシ樹
脂のＹＤＣＮ−７０３Ｐ（東都化成社製商品名、エポキ
シ当量２１０）１４７部、フェノールノボラック樹脂
（昭和高分子社製商品名、水酸基価１０６）１４６部、
フェノキシシクロホスファゼンオリゴマー（融点１００
℃）３００部、劣化防止剤として２，６−ジ−ｔｅｒｔ
−ブチル−４−メチルフェノール（川口化学社製、商品
名）１．５部、水酸化アルミニウム３００部および２−
エチル−４−メチルイミダゾール０．５部からなる混合
物に溶媒としてプロピレングリコールモノメチルエーテ
ル（ＰＧＭ）及びメチルエチルケトンを加えて固形分４
０重量％の接着剤を調製した。Example 1 300 parts of Nipol 1072, a carboxyl-containing acrylonitrile butadiene rubber (trade name, manufactured by Nippon Zeon Co., Ltd., nitrile content: 27), Epicoat 1001, a bisphenol A type epoxy resin (trade name, manufactured by Yuka Shell Co., epoxy equivalent: 470) 320 parts, 147 parts of cresol novolak epoxy resin YDCN-703P (trade name, manufactured by Toto Kasei Co., epoxy equivalent 210), 146 parts of phenol novolak resin (trade name, manufactured by Showa Polymer Co., hydroxyl value 106),
Phenoxycyclophosphazene oligomer (melting point 100
° C) 300 parts, 2,6-di-tert as a deterioration inhibitor
1.5 parts of -butyl-4-methylphenol (trade name, manufactured by Kawaguchi Chemical Co., Ltd.), 300 parts of aluminum hydroxide and 2-part
Propylene glycol monomethyl ether (PGM) and methyl ethyl ketone as a solvent were added to a mixture consisting of 0.5 parts of ethyl-4-methylimidazole to give a solid content of 4 parts.
A 0% by weight adhesive was prepared.
【００２８】この接着剤組成物を厚さ２５μｍのポリイ
ミドフィルムのカプトン（東レデュポン社製、商品名）
にロールコーターで乾燥後の厚さが１５μｍになるよう
に塗布乾燥し、その接着剤面と銅箔（３５μｍ）の処理
面とを重ね合わせて１２０℃のラミネートロールで圧着
した後、オーブンで１００℃，３時間、１３０℃，３時
間、１６０℃，３時間処理し、接着剤を硬化させてフレ
キシブル銅張積層板を得た。This adhesive composition was coated on a 25 μm-thick polyimide film Kapton (trade name, manufactured by Dupont Toray).
And dried by a roll coater so that the thickness after drying becomes 15 μm. The adhesive surface and the treated surface of copper foil (35 μm) are overlapped and pressed by a laminating roll at 120 ° C. C., 3 hours, 130.degree. C., 3 hours, 160.degree. C., 3 hours, and the adhesive was cured to obtain a flexible copper-clad laminate.
【００２９】実施例２ カルボキシル含有アクリロニトリルブタジエンゴムのニ
ポール１０７２（日本ゼオン社製商品名、ニトリル含量
２７）４００部、ビスフェノールＡ型エポキシ樹脂のエ
ピコート１００１（油化シェル社製商品名、エポキシ当
量４７０）２７４部、クレゾールノボラックエポキシ樹
脂のＹＤＣＮ−７０３Ｐ（東都化成社製商品名、エポキ
シ当量２１０）１２６部、フェノールノボラック樹脂
（昭和高分子社製商品名、水酸基価１０６）１２５部、
フェノキシシクロホスファゼンオリゴマー（融点１００
℃）３００部、劣化防止剤として２，６−ジ−ｔｅｒｔ
−ブチル−４−メチルフェノール（川口化学社製、商品
名）４部、水酸化アルミニウム３００部および２−エチ
ル−４−メチルイミダゾール２部からなる混合物に溶媒
としてプロピレングリコールモノメチルエーテル（ＰＧ
Ｍ）及びメチルエチルケトンを加えて固形分３４重量％
の接着剤を調製した。Example 2 Carboxy-containing acrylonitrile butadiene rubber Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd., nitrile content: 27) 400 parts, bisphenol A type epoxy resin epicoat 1001 (trade name, manufactured by Yuka Shell Co., epoxy equivalent 470) 274 parts, 126 parts of cresol novolak epoxy resin YDCN-703P (trade name, manufactured by Toto Kasei Co., epoxy equivalent 210), 125 parts of phenol novolak resin (trade name, manufactured by Showa Polymer Co., hydroxyl value 106),
Phenoxycyclophosphazene oligomer (melting point 100
° C) 300 parts, 2,6-di-tert as a deterioration inhibitor
A mixture of 4 parts of -butyl-4-methylphenol (trade name, manufactured by Kawaguchi Chemical Co., Ltd.), 300 parts of aluminum hydroxide and 2 parts of 2-ethyl-4-methylimidazole was used as a solvent in propylene glycol monomethyl ether (PG
M) and methyl ethyl ketone to add 34% by weight solids
Was prepared.
【００３０】この接着剤組成物を厚さ２５μｍのポリイ
ミドフィルムのカプトン（東レデュポン社製、商品名）
にロールコーターで乾燥後の厚さが２５μｍになるよう
に塗布乾燥し、カバーレイを得た。このカバーレイを実
施例１で得られたフレキシブル銅張積層板に重ね合わ
せ、熱プレスで１６０℃，４ＭＰａ，１時間加熱加圧接
着し、評価用のカバーレイ付きフレキシブル基板を作成
した。This adhesive composition was coated on a 25 μm-thick polyimide film Kapton (trade name, manufactured by Toray DuPont).
The coating was dried by a roll coater so that the thickness after drying was 25 μm, and a coverlay was obtained. This coverlay was superimposed on the flexible copper-clad laminate obtained in Example 1, and heated and pressed at 160 ° C. and 4 MPa for 1 hour with a hot press to prepare a flexible substrate with a coverlay for evaluation.
【００３１】実施例３ カルボキシル含有アクリロニトリルブタジエンゴムのニ
ポール１０７２（日本ゼオン社製商品名、ニトリル含量
２７）４００部、ビスフェノールＡ型エポキシ樹脂のエ
ピコート１００４（油化シェル社製商品名、エポキシ当
量９２５）２７４部、クレゾールノボラックエポキシ樹
脂のＹＤＣＮ−７０３Ｐ（東都化成社製商品名、エポキ
シ当量２１０）１２６部、ビスフェノールＡ型ノボラッ
ク樹脂（大日本インキ化学社製商品名、水酸基価１１
８）１０６部、フェノキシシクロホスファゼンオリゴマ
ー（融点１００℃）３００部、劣化防止剤として２，６
−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（川口
化学社製、商品名）４部、水酸化アルミニウム３００部
および２−エチル−４−メチルイミダゾール２部からな
る混合物に溶媒としてプロピレングリコールモノメチル
エーテル（ＰＧＭ）及びメチルエチルケトンを加えて固
形分３４重量％の接着剤を調製した。Example 3 400 parts of carboxyl-containing acrylonitrile-butadiene rubber Nipol 1072 (trade name, manufactured by Zeon Corporation, nitrile content: 27), Bisphenol A type epoxy resin epicoat 1004 (trade name, manufactured by Yuka Shell Co., epoxy equivalent: 925) 274 parts, 126 parts of cresol novolak epoxy resin YDCN-703P (trade name, manufactured by Toto Kasei Co., epoxy equivalent 210), bisphenol A type novolak resin (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 11)
8) 106 parts, 300 parts of phenoxycyclophosphazene oligomer (melting point 100 ° C.), 2,6 as a deterioration inhibitor
A mixture of 4 parts of di-tert-butyl-4-methylphenol (trade name, manufactured by Kawaguchi Chemical Co., Ltd.), 300 parts of aluminum hydroxide and 2 parts of 2-ethyl-4-methylimidazole was used as a solvent to prepare propylene glycol monomethyl ether ( PGM) and methyl ethyl ketone were added to prepare an adhesive having a solid content of 34% by weight.
【００３２】この接着剤組成物を厚さ４０μｍのポリプ
ロピレンフィルムにロールコーターで乾燥後の厚さが５
０μｍになるように塗布乾燥し、接着剤フィルムを得
た。この接着剤フィルムを厚さ１２５μｍのポリイミド
補強板に１２０℃のラミネートロールで圧着した後、キ
ャリアフィルムのポリプロピレンフィルムを剥がし、実
施例１で得られたフレキシブル銅張積層板のフィルム面
を重ね合わせ、１６０℃，０．５ＭＰａで１５分間加熱
加圧接着し、評価用の補強板付きフレキシブル基板を作
成した。The adhesive composition was dried on a 40 μm-thick polypropylene film with a roll coater to a thickness of 5 μm.
It was applied to a thickness of 0 μm and dried to obtain an adhesive film. After this adhesive film was pressure-bonded to a polyimide reinforcing plate having a thickness of 125 μm with a lamination roll at 120 ° C., the polypropylene film of the carrier film was peeled off, and the film surfaces of the flexible copper-clad laminate obtained in Example 1 were overlaid, Heat and pressure bonding was performed at 160 ° C. and 0.5 MPa for 15 minutes to prepare a flexible substrate with a reinforcing plate for evaluation.
【００３３】比較例１ カルボキシル含有アクリロニトリルブタジエンゴムのニ
ポール１０７２（日本ゼオン社製商品名、ニトリル含量
２７）３００部、臭素化エポキシ樹脂のＹＤＢ−４００
（東都化成社製商品名、エポキシ当量４００）３３０
部、臭素化ノボラックエポキシ樹脂のＢＲＥＮ Ｓ（日
本化薬製商品名、エポキシ当量２８５）１５４部、フェ
ノールノボラック樹脂（昭和高分子社製商品名、水酸基
価１０６）１４５部、劣化防止剤として２，６−ジ−ｔ
ｅｒｔ−ブチル−４−メチルフェノール（川口化学社
製、商品名）１．５部および２−エチル−４−メチルイ
ミダゾール０．５部からなる混合物に溶媒としてプロピ
レングリコールモノメチルエーテル（ＰＧＭ）及びメチ
ルエチルケトンを加えて固形分４０重量％の接着剤を調
製した。COMPARATIVE EXAMPLE 1 300 parts of carboxyl-containing acrylonitrile butadiene rubber Nipol 1072 (trade name, manufactured by Zeon Corporation, nitrile content: 27), brominated epoxy resin YDB-400
(Toto Kasei Co., Ltd., epoxy equivalent 400) 330
Parts, 154 parts of BREN S (trade name, manufactured by Nippon Kayaku, epoxy equivalent: 285) of a brominated novolak epoxy resin, 145 parts of a phenol novolak resin (trade name, manufactured by Showa Polymer Co., hydroxyl value 106), 2 as a deterioration inhibitor 6-di-t
Propylene glycol monomethyl ether (PGM) and methyl ethyl ketone were used as solvents in a mixture of 1.5 parts of ert-butyl-4-methylphenol (trade name, manufactured by Kawaguchi Chemical Co., Ltd.) and 0.5 parts of 2-ethyl-4-methylimidazole. In addition, an adhesive having a solid content of 40% by weight was prepared.
【００３４】この接着剤組成物を用いて実施例１と同様
にしてフレキシブル銅張積層板を得た。Using this adhesive composition, a flexible copper-clad laminate was obtained in the same manner as in Example 1.
【００３５】比較例２ カルボキシル含有アクリロニトリルブタジエンゴムのニ
ポール１０７２（日本ゼオン社製商品名、ニトリル含量
２７）４００部、臭素化エポキシ樹脂のＹＤＢ−４００
（東都化成社製商品名、エポキシ当量４００）３００
部、臭素化ノボラックエポキシ樹脂のＢＲＥＮ Ｓ（日
本化薬社製商品名、エポキシ当量２８５）１２５部、フ
ェノールノボラック樹脂（昭和高分子社製商品名、水酸
基価１０６）１２６部、劣化防止剤として２，６−ジ−
ｔｅｒｔ−ブチル−４−メチルフェノール（川口化学社
製、商品名）４部および２−エチル−４−メチルイミダ
ゾール２部からなる混合物に溶媒としてプロピレングリ
コールモノメチルエーテル（ＰＧＭ）及びメチルエチル
ケトンを加えて固形分３４重量％の接着剤を調製した。Comparative Example 2 400 parts of Nipol 1072 of carboxyl-containing acrylonitrile butadiene rubber (trade name, manufactured by Zeon Corporation, nitrile content: 27), and YDB-400 of brominated epoxy resin
(Toto Kasei Co., Ltd., epoxy equivalent 400) 300
Part, 125 parts of BREN S (trade name, manufactured by Nippon Kayaku Co., epoxy equivalent: 285) of a brominated novolak epoxy resin, 126 parts of phenol novolak resin (trade name, manufactured by Showa Kogaku Co., hydroxyl value 106), 2 as a deterioration inhibitor , 6-di-
To a mixture consisting of 4 parts of tert-butyl-4-methylphenol (trade name, manufactured by Kawaguchi Chemical Co., Ltd.) and 2 parts of 2-ethyl-4-methylimidazole, propylene glycol monomethyl ether (PGM) and methyl ethyl ketone were added as solvents to obtain a solid content. A 34% by weight adhesive was prepared.
【００３６】こ接着剤組成物を用いて実施例２と同様に
してカバーレイを得た。このカバーレイをを比較例１で
得られたフレキシブル銅張積層板に重ね合わせ、熱プレ
スで１６０℃，４ＭＰａ，１時間加熱加圧接着し、評価
用のカバーレイ付きフレキシブル基板を作成した。Using this adhesive composition, a coverlay was obtained in the same manner as in Example 2. This coverlay was superimposed on the flexible copper-clad laminate obtained in Comparative Example 1, and heated and pressed at 160 ° C., 4 MPa for 1 hour with a hot press to prepare a flexible substrate with a coverlay for evaluation.
【００３７】比較例３ カルボキシル含有アクリロニトリルブタジエンゴムのニ
ポール１０７２（日本ゼオン社製商品名、ニトリル含量
２７）４００部、臭素化エポキシ樹脂のＡＥＲ８０１４
（旭チバ社製商品名、エポキシ当量６７０）３００部、
臭素化ノボラックエポキシ樹脂のＢＲＥＮ Ｓ（日本化
薬社製商品名、エポキシ当量２８５）１２５部、ヒスフ
ェノールＡ型ノボラック樹脂（大日本インキ化学社製商
品名、水酸基価１１８）１０５部、劣化防止剤として
２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール
（川口化学社製、商品名）４部、溶媒としてプロピレン
グリコールモノメチルエーテル（ＰＧＭ）及びメチルエ
チルケトンを加えて固形分３４重量％の接着剤を調製し
た。COMPARATIVE EXAMPLE 3 400 parts of carboxyl-containing acrylonitrile butadiene rubber Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd., nitrile content: 27), brominated epoxy resin AER8014
(Asahi Ciba product name, epoxy equivalent 670) 300 parts,
125 parts of BRENS (trade name, manufactured by Nippon Kayaku Co., epoxy equivalent: 285) of brominated novolak epoxy resin, 105 parts of hisphenol A type novolak resin (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 118), deterioration inhibitor 4 parts of 2,6-di-tert-butyl-4-methylphenol (trade name, manufactured by Kawaguchi Chemical Co., Ltd.), propylene glycol monomethyl ether (PGM) and methyl ethyl ketone as solvents, and an adhesive having a solid content of 34% by weight were added. Prepared.
【００３８】この接着剤組成物を用い、実施例３と同様
にして接着剤フィルムを得た。この接着剤フィルム接着
剤を厚さ１２５μｍのポリイミド補強板に１２０℃のラ
ミネートロールで圧着した後、キャリアフィルムのポリ
プロピレンフィルムを剥がし、比較例１で得られたフレ
キシブル銅張積層板のフィルム面を重ね合わせ、１６０
℃，０．５ＭＰａで１５分間加熱加圧接着し、評価用の
補強板付きフレキシブル基板を作成した。Using this adhesive composition, an adhesive film was obtained in the same manner as in Example 3. After this adhesive film adhesive was pressure-bonded to a polyimide reinforcing plate having a thickness of 125 μm with a 120 ° C. laminating roll, the polypropylene film of the carrier film was peeled off, and the film surfaces of the flexible copper-clad laminate obtained in Comparative Example 1 were overlaid. Together, 160
Heat and pressure bonding was performed at 0.5 ° C. for 15 minutes to form a flexible substrate with a reinforcing plate for evaluation.
【００３９】比較例４ 実施例１のフェノキシシクロホスファゼンオリゴマー
（融点１００℃）３００部、水酸化アルミニウム３００
部をそれぞれ、トリフェニレンホスフェート５４８部、
水酸化アルミニウム３６５部とした以外は全て実施例１
と同様にしてフレキシブル銅張積層板を得た。Comparative Example 4 300 parts of the phenoxycyclophosphazene oligomer of Example 1 (melting point 100 ° C.), 300 parts of aluminum hydroxide
548 parts of triphenylene phosphate,
Example 1 except that 365 parts of aluminum hydroxide were used.
In the same manner as in the above, a flexible copper-clad laminate was obtained.
【００４０】比較例５ 実施例２のフェノキシシクロホスファゼンオリゴマー
（融点１００℃）３００部、水酸化アルミニウム３００
部をそれぞれ、トリフェニレンホスフェート５５５部、
水酸化アルミニウム３７０部とした以外は全て実施例２
と同様にしてカバーレイを得て、実施例２と同様にして
評価用のカバーレイ付きフレキシブル基板を作成した。Comparative Example 5 300 parts of the phenoxycyclophosphazene oligomer of Example 2 (melting point: 100 ° C.), 300 parts of aluminum hydroxide
555 parts of triphenylene phosphate,
Example 2 except that 370 parts of aluminum hydroxide were used.
In the same manner as in Example 2, a coverlay was obtained, and a flexible substrate with a coverlay for evaluation was prepared in the same manner as in Example 2.
【００４１】比較例６ 実施例３のフェノキシシクロホスファゼンオリゴマー
（融点１００℃）３００部、水酸化アルミニウム３００
部をそれぞれ、トリフェニレンホスフェート５５８部、
水酸化アルミニウム３７２部とした以外は全て実施例３
と同様にしてフィルム接着剤を得て、実施例３と同様に
して評価用の補強板付きフレキシブル基板を作成した。Comparative Example 6 300 parts of the phenoxycyclophosphazene oligomer of Example 3 (melting point: 100 ° C.), 300 parts of aluminum hydroxide
558 parts of triphenylene phosphate,
Example 3 except that 372 parts of aluminum hydroxide were used.
In the same manner as in Example 3, a film adhesive was obtained, and in the same manner as in Example 3, a flexible substrate with a reinforcing plate for evaluation was prepared.
【００４２】実施例１〜３および比較例１〜６で得た基
板についての特性評価結果を表１に示す。Table 1 shows the characteristic evaluation results of the substrates obtained in Examples 1 to 3 and Comparative Examples 1 to 6.
【００４３】[0043]
【表１】 ＊１：耐燃性試験に用いた試験片は、すべて銅張積層板
の銅箔を全面エッチングにより除去して作成した。[Table 1] * 1: All the test pieces used in the flame resistance test were prepared by removing the copper foil of the copper-clad laminate by etching over the entire surface.
【００４４】＊２：２６０℃、２８０℃、３００℃のは
んだ浴に１分間フロートさせてフクレの有無を調査した ＊３：各加湿処理条件で試験片を処理後、２６０℃のは
んだ浴に１分間フロートさせてフクレの有無を調査し
た。* 2: The sample was floated in a solder bath at 260 ° C., 280 ° C., and 300 ° C. for 1 minute to check for blisters. * 3: The test piece was treated under each humidification condition and then placed in a 260 ° C. solder bath. It was floated for a minute and examined for the presence of blisters.
【００４５】[0045]
【発明の効果】以上の説明および表１から明らかなよう
に、本発明によれば、ハロゲンを含有しないで優れた難
燃性を示し、しかも耐熱性、耐湿性に優れるフレキシブ
ル銅張積層板、カバーレイ、接着剤フィルムを与える接
着剤が提供される。このような材料を用いれば、良好な
環境特性を付与し、かつ種々の特性に優れたフレキシブ
ルプリント配線板を製造することができる。As is clear from the above description and Table 1, according to the present invention, a flexible copper-clad laminate showing excellent flame retardancy without containing halogen, and further having excellent heat resistance and moisture resistance, An adhesive is provided that provides a coverlay, an adhesive film. By using such a material, it is possible to provide a flexible printed wiring board having good environmental characteristics and excellent various characteristics.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０５Ｋ 3/28 Ｈ０５Ｋ 3/28 Ｃ Ｆ // Ｂ３２Ｂ 7/12 Ｂ３２Ｂ 7/12 Ｆターム(参考） 4F100 AB17B AB33B AH02H AH08H AK49A AN02H BA02 CA02H CA23H CB00 GB43 JJ07 JJ07H 4J040 CA051 CA052 CA061 CA062 CA071 CA072 CA081 CA082 DD071 DD072 DF041 DF042 EB032 EB072 EC021 EC022 EC061 EC062 EC071 EC072 EF001 EF002 EG002 EK031 EK032 GA07 HA136 HA156 HA306 HA316 HA356 HB47 HC01 HC06 HC15 HC18 HC24 HC25 HD28 JA09 KA16 KA17 KA36 KA42 LA07 LA08 MA02 MA10 NA20 5E314 AA31 AA32 AA36 AA40 CC15 FF06 GG01 GG08 GG26 5E338 AA01 AA12 AA16 BB72 BB75 CC01 EE26 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H05K 3/28 H05K 3/28 C F // B32B 7/12 B32B 7/12 F term (reference) 4F100 AB17B AB33B AH02H AH08H AK49A AN02H BA02 CA02H CA23H CB00 GB43 JJ07 JJ07H 4J040 CA051 CA052 CA061 CA062 CA071 CA072 CA081 CA082 DD071 DD072 DF041 DF042 EB032 EB072 EC021 EC02 EC07 EC02 EC07 EC03 EC03 EC03 EC03 EC03 EC031 HC25 HD28 JA09 KA16 KA17 KA36 KA42 LA07 LA08 MA02 MA10 NA20 5E314 AA31 AA32 AA36 AA40 CC15 FF06 GG01 GG08 GG26 5E338 AA01 AA12 AA16 BB72 BB75 CC01 EE26
Claims (13)
ゼン化合物、（Ｂ）少なくとも一種のポリエポキシド化
合物、（Ｃ）エポキシ用硬化剤、（Ｄ）エポキシ用硬化
促進剤、（Ｅ）合成ゴムおよび（Ｆ）無機充填剤を必須
成分とすることを特徴とするハロゲンフリーの難燃性接
着剤組成物。1. (A) at least one cyclophosphazene compound, (B) at least one polyepoxide compound, (C) a curing agent for epoxy, (D) a curing accelerator for epoxy, (E) a synthetic rubber, and (F) A halogen-free flame-retardant adhesive composition comprising an inorganic filler as an essential component.
（Ｂ）ポリエポキシド化合物、（Ｃ）エポキシ用硬化
剤、（Ｄ）エポキシ用硬化促進剤および（Ｅ）合成ゴム
が本質的にノンハロゲン化合物であって、その不純物ハ
ロゲンの含有量が、（Ａ）〜（Ｅ）化合物のそれぞれに
ついて０．１重量％以下である請求項１記載のハロゲン
フリーの難燃性接着剤組成物。2. (A) a cyclophosphazene compound,
(B) The polyepoxide compound, (C) a curing agent for epoxy, (D) a curing accelerator for epoxy, and (E) a synthetic rubber are essentially non-halogen compounds, and the content of the impurity halogen is (A) to The halogen-free flame-retardant adhesive composition according to claim 1, wherein the content of each of the compounds (E) is 0.1% by weight or less.
記一般式に示すシクロホスファゼンオリゴマー 【化１】 （但し、式中、Ｘは水素原子であるかハロゲン原子を含
まない有機基を、ｎは３〜１０の整数をそれぞれ表
す。）である請求項２記載のハロゲンフリーの難燃性接
着剤組成物。3. The cyclophosphazene compound (A) is a cyclophosphazene oligomer represented by the following general formula: The halogen-free flame-retardant adhesive composition according to claim 2, wherein X is a hydrogen atom or an organic group containing no halogen atom, and n represents an integer of 3 to 10. object.
ジルエーテル系エポキシ樹脂である請求項３記載のハロ
ゲンフリーの難燃性接着剤組成物。4. The halogen-free flame-retardant adhesive composition according to claim 3, wherein the polyepoxide compound (B) is a glycidyl ether epoxy resin.
アミドとその誘導体、ノボラック型フェノール樹脂、ア
ミノ変性ノボラック型フェノール樹脂、ポリビニルフェ
ノール樹脂、有機酸ヒドラジッド、ジアミノマレオニト
リルとその誘導体、メラミンとその誘導体、アミンイミ
ド、ポリアミン塩、モレキュラーシーブ、アミン、酸無
水物、ポリアミド及びイミダゾールの群のうちから選ば
れた少なくとも一種の硬化剤である請求項４記載のハロ
ゲンフリーの難燃性接着剤組成物。5. The curing agent for epoxy (C) is dicyandiamide and its derivative, novolak-type phenol resin, amino-modified novolak-type phenol resin, polyvinylphenol resin, organic acid hydrazide, diaminomaleonitrile and its derivative, and melamine and its derivative. 5. The halogen-free flame-retardant adhesive composition according to claim 4, wherein the composition is at least one curing agent selected from the group consisting of amine, amine imide, polyamine salt, molecular sieve, amine, acid anhydride, polyamide and imidazole.
ミン、イミダゾール、芳香族アミンの群のうちから選ば
れた少なくとも一種の硬化促進剤である請求項５記載の
ハロゲンフリーの難燃性接着剤組成物。6. The halogen-free flame retardant according to claim 5, wherein (D) the curing accelerator for epoxy is at least one curing accelerator selected from the group consisting of tertiary amines, imidazoles, and aromatic amines. Adhesive composition.
リロニトリルブタジエンゴム、スチレンブタジエンゴ
ム、ブタジエンメチルアクリレートアクリロニトリルゴ
ム、ブタジエンゴム、カルボキシル含有アクリロニトリ
ルブタジエンゴム、シリコーンゴム、ウレタンゴム、ポ
リビニルブチラールの群のうちから選ばれた少なくとも
一種のゴムである請求項６記載のハロゲンフリーの難燃
性接着剤組成物。7. (E) The synthetic rubber is selected from the group consisting of acrylic rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, butadiene methyl acrylate acrylonitrile rubber, butadiene rubber, carboxyl-containing acrylonitrile butadiene rubber, silicone rubber, urethane rubber, and polyvinyl butyral. The halogen-free flame-retardant adhesive composition according to claim 6, which is at least one kind of rubber selected from the group consisting of:
剤組成物でポリイミドフィルムの少なくとも片面に銅箔
を貼り合わせてなることを特徴とするフレキシブル銅張
積層板。8. A flexible copper-clad laminate obtained by bonding a copper foil to at least one surface of a polyimide film with the adhesive composition according to any one of claims 1 to 7.
剤組成物でポリイミドフィルムの表面に樹脂層を形成し
てなることを特徴とするカバーレイ。9. A coverlay comprising a resin layer formed on the surface of a polyimide film using the adhesive composition according to claim 1.
着剤組成物をフィルム状に形成してなることを特徴とす
る接着剤フィルム。10. An adhesive film formed by forming the adhesive composition according to claim 1 into a film.
着剤組成物でポリイミドフィルムの少なくとも片面に銅
箔を貼り合わせた後、回路を形成してなることを特徴と
するフレキシブルプリント配線板。11. A flexible printed circuit, wherein a circuit is formed after laminating a copper foil on at least one surface of a polyimide film with the adhesive composition according to any one of claims 1 to 7. Board.
ト配線板上に請求項９のカバーレイを貼り合わせてなる
ことを特徴とするフレキシブルプリント配線板。12. A flexible printed wiring board comprising the coverlay according to claim 9 bonded to the flexible printed wiring board according to claim 11.
キシブルプリント配線板と補強板を、請求項１０記載の
接着剤フィルムを介して貼り合わせてなることを特徴と
するプリント配線板。13. A printed wiring board comprising the flexible printed wiring board according to claim 11 and a reinforcing plate bonded together via the adhesive film according to claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19722099A JP3810954B2 (en) | 1999-07-12 | 1999-07-12 | Flame-retardant adhesive composition, flexible copper-clad laminate, coverlay and adhesive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19722099A JP3810954B2 (en) | 1999-07-12 | 1999-07-12 | Flame-retardant adhesive composition, flexible copper-clad laminate, coverlay and adhesive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001019930A true JP2001019930A (en) | 2001-01-23 |
| JP3810954B2 JP3810954B2 (en) | 2006-08-16 |
Family
ID=16370842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19722099A Expired - Lifetime JP3810954B2 (en) | 1999-07-12 | 1999-07-12 | Flame-retardant adhesive composition, flexible copper-clad laminate, coverlay and adhesive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3810954B2 (en) |
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| JP2002371263A (en) * | 2001-06-14 | 2002-12-26 | Nitto Denko Corp | Adhesive composition for multilayer flexible printed circuit board and multilayer flexible printed circuit board obtained by using the same |
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| KR101599841B1 (en) * | 2014-10-13 | 2016-03-04 | (주)테크피아 | Flexible Copper Clad Lamination with nonhalogenated flame retarding urethane resin compositions and the method of preparation it |
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