JP2005023118A - Flame retardant resin composition and prepreg, laminate, printed wiring board, and electronic component using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a method for producing a resin composition having sufficient flame retardance with the use of a resin endowed with a flame-retardant effect in the skeleton while having sufficient physical and chemical properties without containing a halogen flame-retardant. <P>SOLUTION: The flame-retardant resin composition comprises (A) a compound having a dihydrobenzoxadine ring, (B) an organic phosphorus compound represented by formula (1) (wherein R1 is hydrogen or a halogen element-free organic group) or its derivative, and (C) an organic compound represented by formula (2) (wherein R2-R6 are each any halogen element-free organic group). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（但し，Ｒ１は水素もしくはハロゲン元素を含まない任意の有機基を示す）
【化６】

（但し，Ｒ２〜Ｒ６はハロゲン元素を含まない任意の有機基を示す。）
（２）また、本発明は、（１）（Ｂ）記載の有機リン化合物が，１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド ［式３］である樹脂組成物に関する。
【化７】

（３）また、本発明は、（１）（Ｃ）記載の有機リン化合物が，式４に示す縮合リン酸エステルである（１）〜（２）に記載の樹脂組成物に関する。
【化８】

（４）また、本発明は、（１）〜（３）記載の樹脂組成物にエポキシ樹脂，硬化剤，またはフィラーを単数もしくは複数添加して得られる樹脂組成物に関する。
（５）また、本発明は、（１）〜（４）記載の樹脂組成物を用いて作られるプリプレグに関する。
（６）また、本発明は（５）記載のプリプレグを用いて作られる銅張積層板に関する。
（７）また、本発明は、（１）〜（４）記載の樹脂組成物を用いて作られる樹脂付き銅はくに関する。
（８）また、本発明は、（１）〜（４）記載の樹脂組成物を用いて作られる接着フィルムに関する。
（９）また、本発明は、（５）記載のプリプレグ，（６）記載の銅張り積層板，（７）記載の樹脂付き銅はく，（８）記載の接着フィルムのいずれかを用いて、または組み合わせて用いて作られるプリント配線板に関する。
（１０）また、本発明は、（９）記載のプリント配線板を用いて作られる電子部品に関する。
【０００４】
【発明の実施の形態】
ジヒドロベンゾオキサジン環を有する化合物は，その骨格中に窒素成分を含有することから難燃化効果が得られる。一方，９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドもしくはその誘導体は，その骨格中にリンを含有することから難燃化効果を付与している。さらに，縮合型リン酸エステルも骨格中にリンを含有するため，難燃化効果を得られるが。これらの，異なる機構を有する材料を組合せることにより，相乗効果が生じ，それぞれを単独で用いた場合では得られない飛躍的な特性の向上が期待できる。事実，本手法においても，これら三つの成分をある一定の比率で配合することにより，高い難燃性を獲得することに成功した。
【０００５】
従来のジヒドロベンゾオキサジンと縮合型リン酸エステルを組合せた配合では，ある量を越えると，縮合型リン酸エステルの添加量の増加に対して難燃化効果が伴なわなくなってしまう。しかし，ここに９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドもしくはその誘導体を併用するとで，高い難燃化効果を得ることに成功した。縮合型リン酸エステルは，単なる添加材であるが，９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドもしくはその誘導体は，反応性を有する場合があり，その場合，硬化反応においてジヒドロベンゾオキサジン環を有する化合物骨格中に取り込まれる場合もある。無論，微視的にはジヒドロベンゾオキサジン環を有する化合物から独立して存在する可能性も予想される。しかし，本発明の範囲内で用いることにより，従来の添加型の難燃剤に見られるような顕著な物理的，化学的特性の低下を非常に低い範囲に抑えることに成功した。特に，代表的なリン系難燃剤の１つであるジヒドロベンゾオキサジン環を有する化合物に。縮合型リン酸エステルを添加した場合と比べると，その差は非常に顕著に現れ，樹脂中のリン含有率が同じ場合より高い難燃化効果を得られた。このように良好な特性が発現した原因は，９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドの主骨格中に含まれる酸素成分量がリン酸エステルに比べて圧倒的に少ないために，燃焼中に外部から供給される酸素を固定化してしまう効果がある為に，縮合型リン酸エステルとは異なる難燃化システムを有することも推定されるが，その原因は解明するに至っていない。
本発明は，ジヒドロベンゾオキサジン環を有する化合物もしくは，９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドおよびその誘導体，縮合型リン酸エステルを配合することをよって得られる樹脂組成物であり，高い難燃化効果を得ると同時に，樹脂組成物，積層板，プリプレグ，接着フィルム及びプリント配線板として良好な特性を獲得する。
【０００６】
ジヒドロベンゾオキサジン環を有する化合物は，メチルエチルケトン（ＭＥＫ）等の適当な溶媒中で，フェノール類、アミン類、アルデヒド類を，加熱反応させ，溶剤および水を除去することでから容易に合成できる。例えば，用いるフェノール１モルに対して，アニリンを１モル，ホルムアルデヒドを２モルの割合で配合し，還流させ任意の反応率の点で冷却。その後に，溶剤および水分，場合によっては未反応物質を除去することにより樹脂を得ることができる。フェノール類としてはフェノール，クレゾール，ビスフェノールＡ，ビスフェノールＦ，ビスフェノールＳ等を用いることができ，アミン類としてはアニリン，ジアミノベンゼン等を用いることができ，アルデヒド類では，ホルムアルデヒド，パラホルム等を用いることができる。
【０００７】
また，ジヒドロベンゾオキサジン環を有する化合物に９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドをもしくはその誘導体と縮合型リン酸エステルを配合する場合，その添加量は溶剤を除く樹脂組成物を１００とした場合，リン分の含有量が０．２〜６の範囲で添加する場合が良好であり，好ましくは０．５〜５．５であり，より好ましくは０．８〜５の範囲で配合し，この範囲における，９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドもしくはその誘導体の添加量および，縮合型リン酸エステルのそれぞれの占める割合は，一方がゼロにならない任意の場合に本特性を得ることができるが，好ましくは，添加した９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドもしくはその誘導体の含むリン量１０に対して，添加した縮合型リン酸エステルの含むリン量が０．１〜１０００，より好ましくは，１〜１００，さらに好ましくは３〜５０の範囲で添加する場合に，良好な成形性を有し，かつ十分な耐熱性と難燃性を有する樹脂組成物およびプリプレグ，積層板，プリント配線板、電子部品を得ることができる。
【０００８】
この配合範囲において，良好な難燃性，耐熱性を付与せしめるに至った理由に関しては，現在のところ判明していない。しかし従来多用されてきたリン系難燃材は，その骨格中に多量の酸素成分を含むことから，難燃化効果の低下，極性上昇による水分子との親和性の向上による吸水に由来する耐熱性の低下，さらにはリン酸部と硬化促進剤の相互作用による硬化阻害の発生等の理由により著しく低下していたと推定され，式７で示される有機化合物を一部に用いることによりこれらの問題が，緩和されたものと推定される。
【化９】

（但し，Ｒ１は水素もしくはハロゲン元素を含まない任意の有機基を示す）
【０００９】
式７に示した化合物とは，９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドもしくは，その誘導体，例えば１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド［式３］や１０−（２，５−ジヒドロキシ−６−メチルフェニル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド，１０−（１，４−ジヒドロキシ−２−ナフチル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドが使用できる。
【化１０】

【００１０】
これら化合物は，直接ジヒドロベンゾオキサジン環を有する化合物と配合しても良いが，事前に，ジヒドロベンゾオキサジン環を有する化合物やエポキシ樹脂，フェノール系硬化等と反応させた後に使用する事もできる。
一方，式６に示す構造の有機リン化合物としては，種々の化合物が使用でき，Ｒ２〜Ｒ６はハロゲン元素を含まない任意の有機基を示す。
【化１１】

（但し，Ｒ２〜Ｒ６はハロゲン元素を含まない任意の有機基を示す。）
これは即ちＲ２を介して複数のホスフォリル基が結合した所謂縮合リン酸エステルである。これらの具体例としては，１，３−ビス（ジフェニルホスフォリル）ベンゼン ［レゾルシノールビス（ジフェニルホスフェート）と慣用名で表記する。以下同］，レゾルシノールビス（ジキシレニルホスフェート），ビスフェノールＡビス（ジフェニルホスフェート），ビスフェノールＡビス（ジキシレニルホスフェート）等が使用でき，特に［式８］に示すレゾルシノールビス（ジキシレニルホスフェート）が溶剤溶解性や価格の点でより好ましい。
【化１２】

【００１１】
また，樹脂組成物にピール強度向上等の目的で，エポキシ樹脂を配合することができ，含有されるエポキシ樹脂としては，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，ビスフェノールＳ型エポキシ樹脂，ビフェニル型エポキシ樹脂，ナフタレンジオール型エポキシ樹脂，フェノールノボラック型エポキシ樹脂，クレゾールノボラック型エポキシ樹脂，ビスフェノールＡノボラック型エポキシ樹脂，環状脂肪族エポキシ樹脂，グリシジルエステル樹脂，グリシジルアミン樹脂，複素環式エポキシ樹脂（トリグリシジルイソシアヌレート，ジグリシジルヒンダトイン等），およびこれらを種々の反応性モノマで変性した変性エポキシ樹脂等が使用でき，これらのエポキシ樹脂を２種類以上適宜組合せて使用することもできる。特に，電気電子材料用途に適用できる高い耐熱性や信頼性が必要であることから，フェノールノボラック型エポキシ樹脂またはクレゾールノボラック型エポキシ樹脂またはビスフェノールＡノボラック型エポキシ樹脂を用いることが望ましく，その添加量は特に規定されないが，十分な硬化物を得るためには，全樹脂組成物中０〜５０重量％の範囲が好ましい。
【００１２】
また，加工性改良，添加したエポキシの硬化促進等の目的で，硬化剤を添加することができる。硬化剤には，フェノール系，アミン系，酸無水物系等あるが，フェノール系硬化剤を用いることが好ましい。なぜなら，フェノール系硬化剤は，積層板の耐湿性の低減，およびエポキシ樹脂の硬化促進と共に，ジヒドロベンゾオキサジン環を有する化合物はフェノール系水酸基を有する化合物と反応することができるため，ジヒドロベンゾオキサジン環を有する化合物の硬化反応も促進することができるためである。さらに，その添加量は，樹脂組成物の硬化反応を著しく阻害しない範囲であれば，任意の量を添加することができ，特に樹脂組成物の０〜５０重量％の範囲で用いることが好ましい。具体的には，例えばフェノールノボラック，クレゾールノボラック，ビスフェノールＡ，ビスフェノールＦ，ビスフェノールＳ，等のフェノール性水酸基を有する硬化剤を用いることができ，これらを複数組み合わせ用いても良い。
また本発明で用いるエポキシ樹脂および硬化剤を，事前に適宜反応させてから用いることもできる。
【００１３】
本発明の樹脂組成物は，このほかに，可燃成分を減少させる目的で，フィラーを添加することも可能である。シリカ，タルク，マイカ，ケイ酸カルシウム，ケイ酸カリウム，焼成クレー，酸化チタン，硫酸バリウム，酸化アルミニウム，炭酸マグネシウム，炭酸カルシウム，炭酸バリウムなど，酸化モリブデン，酸化亜鉛，珪酸マグネシウム，等の金属酸化物が良く，このほかにも，モリブデン，亜鉛，カルシウム，リン，アルミニウム，カリウム等の複数の元素からなる酸化物等の化合物であっても良い。また，モリブデン，珪素，マグネシウム，亜鉛からなる酸化物の複数の組み合わせからなる化合物であっても良い。
【００１４】
また，本発明の樹脂組成物には，これら以外に高剛性化，低熱膨張化の目的で無機質充填剤を添加することもでき，その他にも顔料，接着助剤，酸化防止剤，硬化促進剤および有機溶剤などを添加することができるが，それぞれ公知の物質を使用することができ，非ハロゲン化合物で積層板，プリント配線板特性を低下させない物質であれば特に制限はない。
【００１５】
有機溶剤の種類と量については，樹脂組成物を構成するエポキシ樹脂と硬化剤を均一に溶解もしくは分散し，プリプレグを作製するのに適正な粘度と揮発性を有していれば特に限定されるものではないが，これらの要件を満たし，かつ価格や取扱い性，安全性の観点から，メチルエチルケトン，２−メトキシエタノール，２−メトキシプロパノール，１−メトキシ−２−プロパノール等の溶剤を含む樹脂組成物全重量の５〜４０重量％程度使用することが好ましい。
【００１６】
また，本発明の樹脂組成物は，ガラスもしくはアラミド樹脂等を原料とする不織布，もしくはガラスクロス等の基材に含浸・乾燥することによってプリプレグを作製することができる。またさらに，このプリプレグに金属箔を重ね，加熱・加圧して積層一体化することにより積層板を製造することができる。
さらに，本発明の樹脂組成物を，銅はくに塗布，乾燥することによって樹脂付き銅はくを，ＰＥＴフィルム等樹脂フィルムに塗布，乾燥することによって接着フィルムを作製することができる。
【００１７】
また，この積層板の金属箔の不要な部分をエッチング除去することによってプリント配線板を製造することもでき，必要に応じて，これらプリント配線板と，プリプレグ，樹脂付き銅はく，もしくは接着フィルム，および銅はくを単独もしくは複数組合わせて適宜積層し，加熱，加圧することにより，多層化したプリント配線板を製造することもできる。これらプリプレグ，積層板，樹脂付き銅はく，接着フィルム，プリント配線板の製造においては，当該業界における通常の塗工，積層，回路加工工程を適用することができ，これにより高耐熱性，高難燃性，高信頼性でかつハロゲン系難燃剤を含有しない積層板およびプリント配線板が得られる。かかる配線板を用いて、電子部品を製造することが出来る。
【００１８】
【実施例】
以下、本発明の実施例およびその比較例によって本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００１９】
実施例および比較例において，ジヒドロベンゾオキサジン化合物，エポキシ樹脂，硬化剤，有機リン化合物およびその他の特殊材料には下記のものを用いた。その他の有機溶剤，添加剤，汎用無機質充填剤および積層板・プリプレグを構成するガラス布，銅箔などについては，特に記載したものを除き化学工業および電子工業分野において一般的に用いられる原材料類を用いた。
ジヒドロベンゾオキサジン化合物：メチルエチルケトン（ＭＥＫ）中ビスフェノールＡ、アニリン、ホルマリンを１／２／４のモル比で混合し、４時間還流させた後、水分とＭＥＫを蒸留除去して残った樹脂状物を取り出し粉砕したもの
エポキシ樹脂：大日本インキ化学工業製、クレゾールノボラック型エポキシ樹脂、商品名：Ｎ−６７３（エポキシ当量２１０）
フェノール系硬化材：大日本インキ製、フェノールノボラック樹脂、商品名：フェノライトＴＤ−２１６０
有機リン化合物Ａ：三光製、１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、商品名：ＨＣＡ−ＨＱ
有機リン化合物Ｂ：大八化学工業製、縮合型リン酸エステル、商品名：ＰＸ−２００
無機難燃剤：住友化学製、水酸化アルミ 商品名：ＣＬ−３１０
【００２０】
積層板およびプリント配線板の特性評価は，難燃性についてはＵＬ−９４垂直法による燃焼時間により評価し，平均燃焼時間５秒以下かつ最大燃焼時間１０秒以下をＶ−０，平均燃焼時間１０秒以下かつ最大燃焼時間３０秒以下をＶ−１，それ以上燃焼した場合をＨＢで分類した。その他の積層板特性（銅箔引き剥がし強さ，吸湿はんだ耐熱性，耐薬品性）についてはＪＩＳ Ｃ６４８１に基づき評価した。吸湿はんだ耐熱性の評価は，
○：変化なし
△：ミーズリングまたは目浮き発生
×：ふくれ発生
で判定し，ワニスの硬化性は１６０℃のホットプレート上に０．５ｃｃのワニスを滴下し，直径１ｍｍの棒で攪拌しゲル化するまでの時間（ゲル化時間）で評価した。
【００２１】
実施例１〜３
表１に示す配合により積層板用樹脂組成物を作製した。この樹脂組成物をガラスクロス（厚さ０．０６ｍｍ）に含浸させ，１６０〜１７５℃で４分間乾燥してプリプレグを得た。このプリプレグを７枚重ね，その両面に１８μｍの銅箔を重ね，１８５℃，圧力４ＭＰａにて８０分間加熱加圧成形して厚さ０．５ｍｍの両面銅張積層板を作製した。積層板の特性を表１に示した。
【００２２】
実施例１から３で作製した両面銅張積層板の表面にサブトラクティブ法により回路形成（テストパターン）を行った。さらに，作製した２枚の回路付き両面銅張積層板表面を接着性向上のため酸化粗化処理し，実施例１から３で作製したプリプレグ各２枚を挟んで重ね合せ，さらに外側にプリプレグ２枚と１８μｍ銅箔を重ねて積層プレスして内層回路付き６層プリント配線板を作製した。同時に，前述同様，表面酸化粗化処理を施した回路付き両面倒張り積層板に，樹脂付き銅はくを重ねて積層プレスして内層回路付き４層プリント配線板を作製した。さらに，表面酸化粗化処理を施した回路付き両面倒張り積層板に接着フィルムおよび１８μｍ銅箔を重ねてプレスし，内層回路付き４層プリント配線板を作製した。これらプリント配線板に定法により外層回路加工，スルーホール形成，レジストインク印刷，部品実装を行ったが，通常のプリント配線板製造工程において問題無く製造できることを確認した。
【００２３】
比較例１〜２
実施例１〜３と同様にして，表１に示す配合および実施例に示す方法で樹脂組成物を作製した。この樹脂組成物を用いて実施例と同様にプリプレグを作製し，銅張積層板の作製を行った。しかし，比較例１においては，リン系難燃剤を添加しなかったために，十分な難燃性が得られなかった。よって，他の評価は中止した。また，比較例２においては，リン系難燃剤を添加したが，用いた難燃剤が縮合型リン酸エステルのみであったために，十分な難燃性が確保できなかった。
【表１】

表１より，例示した実施例においては，必要なリン系難燃剤量を含み且つ樹脂組成物の組成が適正であるため，生産性・成形性に問題がなく十分な難燃性を保持した積層板が得られた。ここで，ジヒドロベンゾオキサジン環を有する化合物は，熱硬化性樹脂としては硬化が遅く，生産性の点では用途が限定される傾向がある，本発明においても，実施例１で，ワニス硬化時間が２０００秒台と他の実施例と比べて長くなる傾向として現れているが，プリプレグおよび銅張り積層板，樹脂付き銅はく，接着フィルムを製造するに当り，特に制約になるものではない。一方，実施例２，３に示したように，硬化剤を併用することにより，このジヒドロベンゾオキサジン環を有する化合物の硬化速度を向上する効果が得られ，ワニスの硬化時間を短縮し，生産性を大幅に向上する結果となった。また，エポキシ樹脂を添加することにより，ピール強度が向上し，微細回路形成時の回路加工性を向上することになった。さらに，水酸化アルミニウムを添加した実施例３では，難燃性がさらに向上する結果となり，基材の信頼性をより向上する結果となり，よりバランスの取れた特性を獲得することができた。
一方，比較例１においては，リン系難燃剤を添加しなかったために難燃性を確保できず，比較例２においては，９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドもしくはその誘導体を用いなかったために，十分難燃性を確保しつつ耐熱性を得ることができなかった。また，比較例２においては，リン系難燃剤を添加したが，用いた難燃剤がリン酸エステルであったために，難燃性は確保できたものの，十分な耐熱性が得られなかった。
よって，十分な難燃性を確保しつつ適正な硬化性を保てる適正な難燃剤の配合比，配合量という点において，本発明の優位性は明確である。
【００２４】
【発明の効果】
本発明により，非ハロゲン系難燃剤を用いた難燃化手法において，十分な難燃性を確保しつつ適正な硬化性を保てる樹脂配合が確立され，これら樹脂を用いた製品についても，機械的，電気的，化学的に適正な特性を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a laminated board for electrical insulation, a prepreg, a copper foil with resin, an adhesive film, a printed wiring board, an electronic component, and a resin composition.
[0002]
[Prior art]
In recent years, laminates for electrical insulation (in the present invention, laminates include laminates with one or both sides covered with metal foil, that is, metal-clad laminates), prepregs, printed wiring boards, and electronic components are environmental problems. Due to the growing trend, it is required that hazardous substances are not released into the environment during disposal or incineration. Therefore, products characterized by not containing a halogen-based flame retardant for the purpose of avoiding so-called dioxin generation during combustion are increasing. At present, inorganic materials, phosphorus compounds, nitrogen compounds, etc. are widely used as alternative flame retardants for halogen flame retardants. (Example: Patent Document 1)
[Patent Document 1]
JP-A-2-69567
[Problems to be solved by the invention]
Industrially, flame retardancy is often secured by combining these alternative flame retardants. However, if these alternative flame retardants are added in an amount sufficient to ensure flame retardancy, the varnish characteristics, prepreg characteristics, or laminate and printed wiring board characteristics may be greatly varied unexpectedly. is there. One reason for this is that current non-halogen flame retardant methods depend greatly on the method of adding a material that imparts a flame retardant effect to the basic resin. This is because most of the materials used in conventional halogen-based flame retardant methods, as typified by tetrabubromobisphenol A, incorporate a material imparting flame retardance into a part of the resin skeleton by a chemical reaction. As a result, the resin properties after the curing reaction were determined by the properties of the resin that forms the basic skeleton, whereas flame retardants using non-halogen flame retardants were used. This is because the method often becomes a composite system of a resin and a low molecule or an inorganic material, resulting in a physically and chemically weak part. Of course, studies have been made to develop non-halogen flame retardant resins that impart flame retardancy to the resin skeleton, but no sufficient method has yet been found.
Therefore, in the present invention, attention has been paid to compounds having a dihydrobenzoxazine ring. A compound having a dihydrobenzoxazine ring has a nitrogen component in the skeleton, so that it can have a flame-retarding effect, and compared with other nitrogen-containing epoxies or resin systems using nitrogen-containing curing agents. However, it is a promising non-halogen flame retardant resin because it has high characteristics in terms of heat resistance and the like. However, this resin has not yet achieved sufficient flame retardancy alone, satisfactory moldability as a product, and various electrical, mechanical and chemical properties. However, inorganic flame retardants typified by aluminum hydroxide and phosphorus flame retardants typified by phosphoric acid esters have been used in combination. However, until now, when these inorganic and organic low-molecular-weight flame retardants are added to such an extent that they exhibit sufficient flame retardancy, the resin often becomes physically and chemically fragile. In particular, when a phosphate ester-type flame retardant is added, depending on the amount added, the heat resistance may decrease due to moisture absorption, or the characteristics may be deteriorated such as curing inhibition. Therefore, it was difficult to add a large amount, and it was difficult to add a sufficient amount to ensure flame retardancy.
[0003]
[Means for Solving the Problems]
The inventors of the present invention use a resin that has sufficient physical and chemical properties, does not contain a halogen-based flame retardant, and imparts a flame retarding effect in the skeleton, and has sufficient flame retardancy. As a result of various investigations on the method for producing the resin composition, the following inventions have been found.
(1) The present invention provides a flame retardant resin comprising (A) a compound having a dihydrobenzooscisazine ring, (B) an organophosphorus compound represented by Formula 1 or a derivative thereof, and (C) an organic compound represented by Formula 2. Relates to the composition.
[Chemical formula 5]

(However, R1 represents any organic group containing no hydrogen or halogen element)
[Chemical 6]

(However, R2 to R6 represent any organic group not containing a halogen element.)
(2) The present invention also relates to (1) the organophosphorus compound described in (B), wherein 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide It is related with the resin composition which is [Formula 3].
[Chemical 7]

(3) Moreover, this invention relates to the resin composition as described in (1)-(2) whose organophosphorus compound as described in (1) (C) is condensed phosphoric ester shown in Formula 4.
[Chemical 8]

(4) The present invention also relates to a resin composition obtained by adding one or more epoxy resins, curing agents, or fillers to the resin compositions described in (1) to (3).
(5) Moreover, this invention relates to the prepreg made using the resin composition of (1)-(4) description.
(6) Moreover, this invention relates to the copper clad laminated board made using the prepreg of (5) description.
(7) Moreover, this invention relates to the copper foil with resin made using the resin composition of (1)-(4) description.
(8) Moreover, this invention relates to the adhesive film made using the resin composition of (1)-(4) description.
(9) Moreover, this invention uses any one of the prepreg of (5) description, the copper clad laminated board of (6) description, the copper foil with resin of (7) description, and the adhesive film of (8) description. Or a printed wiring board made by using a combination thereof.
(10) Moreover, this invention relates to the electronic component made using the printed wiring board as described in (9).
[0004]
DETAILED DESCRIPTION OF THE INVENTION
Since the compound having a dihydrobenzoxazine ring contains a nitrogen component in its skeleton, a flame retarding effect can be obtained. On the other hand, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof has a flame retarding effect because it contains phosphorus in its skeleton. In addition, the condensed phosphate ester also contains phosphorus in the skeleton, so it has a flame retardant effect. By combining these materials with different mechanisms, a synergistic effect is produced, and a dramatic improvement in characteristics that cannot be obtained when each of them is used alone can be expected. In fact, even in this method, high flame retardancy was successfully achieved by blending these three components at a certain ratio.
[0005]
In the combination of the conventional dihydrobenzoxazine and the condensed phosphate ester, if it exceeds a certain amount, the flame retarding effect is not accompanied with the increase of the addition amount of the condensed phosphate ester. However, when 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof was used in combination, a high flame retarding effect was successfully obtained. Condensed phosphates are merely additives, but 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its derivatives may be reactive, in which case In some cases, the compound is incorporated into a compound skeleton having a dihydrobenzoxazine ring. Of course, microscopically, the possibility of existing independently from a compound having a dihydrobenzoxazine ring is also expected. However, by using it within the scope of the present invention, it has succeeded in suppressing the remarkable decrease in physical and chemical properties found in conventional additive-type flame retardants to a very low range. Especially for compounds with dihydrobenzoxazine ring, which is one of the typical phosphorus flame retardants. Compared with the case where condensed phosphate ester was added, the difference was very remarkable, and a higher flame retarding effect was obtained than when the phosphorus content in the resin was the same. The reason why such good characteristics are manifested is that the amount of oxygen component contained in the main skeleton of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is overwhelming compared to phosphate esters. It is estimated that it has a flame retardant system different from the condensed phosphate ester because it has the effect of fixing oxygen supplied from the outside during combustion. It hasn't been done yet.
The present invention relates to a resin obtained by blending a compound having a dihydrobenzoxazine ring, or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a derivative thereof, and a condensed phosphate ester. It is a composition and obtains good properties as a resin composition, a laminate, a prepreg, an adhesive film, and a printed wiring board while obtaining a high flame retardancy effect.
[0006]
A compound having a dihydrobenzoxazine ring can be easily synthesized by heating and reacting phenols, amines and aldehydes in an appropriate solvent such as methyl ethyl ketone (MEK) and removing the solvent and water. For example, 1 mole of phenol and 1 mole of aniline and 2 moles of formaldehyde are added to 1 mole of phenol to be refluxed and cooled at any reaction rate. Thereafter, the resin can be obtained by removing the solvent, moisture, and possibly unreacted substances. Phenols can be phenol, cresol, bisphenol A, bisphenol F, bisphenol S, etc., amines can be aniline, diaminobenzene, etc., and aldehydes can be formaldehyde, paraform, etc. it can.
[0007]
When a compound having a dihydrobenzoxazine ring is blended with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof and a condensed phosphate, When the resin composition to be removed is 100, it is preferable that the phosphorus content is added in the range of 0.2 to 6, preferably 0.5 to 5.5, more preferably 0.8. In this range, the amount of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its derivative added and the proportion of each condensed phosphate ester This property can be obtained in any case where one does not reach zero, but preferably the added 9,10-dihydro-9-oxa-10-phosphatase is added. The amount of phosphorus contained in the added condensed phosphate ester is 0.1 to 1000, more preferably 1 to 100, more preferably 3 to 50 with respect to the amount of phosphorus contained in the enanthrene-10-oxide or derivative thereof. When added in a range, resin compositions and prepregs, laminates, printed wiring boards, and electronic components having good moldability and sufficient heat resistance and flame retardancy can be obtained.
[0008]
At present, the reason why the flame retardancy and heat resistance have been imparted in this blending range has not been clarified. However, phosphorus-based flame retardants that have been widely used in the past contain a large amount of oxygen components in their skeletons. Therefore, the heat resistance derived from water absorption due to reduced flame retardancy and improved affinity with water molecules due to increased polarity. It is presumed that it was remarkably lowered due to the deterioration of the property, and also the occurrence of curing inhibition due to the interaction between the phosphoric acid part and the curing accelerator. Is presumed to be relaxed.
[Chemical 9]

(However, R1 represents any organic group containing no hydrogen or halogen element)
[0009]
The compound shown in Formula 7 is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof such as 10- (2,5-dihydroxyphenyl) -9,10-dihydro. -9-oxa-10-phosphaphenanthrene-10-oxide [Formula 3] and 10- (2,5-dihydroxy-6-methylphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 10- (1,4-dihydroxy-2-naphthyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide can be used.
Embedded image

[0010]
These compounds may be blended directly with a compound having a dihydrobenzoxazine ring, but can also be used after reacting with a compound having a dihydrobenzoxazine ring, an epoxy resin, phenolic curing or the like in advance.
On the other hand, various compounds can be used as the organophosphorus compound having the structure shown in Formula 6, and R2 to R6 each represent an arbitrary organic group not containing a halogen element.
Embedded image

(However, R2 to R6 represent any organic group not containing a halogen element.)
This is a so-called condensed phosphate ester in which a plurality of phosphoryl groups are bonded via R2. Specific examples thereof include 1,3-bis (diphenylphosphoryl) benzene [resorcinol bis (diphenyl phosphate) and a common name. The same applies to the following: resorcinol bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dixylenyl phosphate), etc. Is more preferable in terms of solvent solubility and cost.
Embedded image

[0011]
In addition, an epoxy resin can be blended in the resin composition for the purpose of improving peel strength, etc. The epoxy resin contained is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl. Type epoxy resin, naphthalene diol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester resin, glycidyl amine resin, heterocyclic epoxy resin (tri Glycidyl isocyanurate, diglycidyl hindatoin, etc.), and modified epoxy resins modified with various reactive monomers, etc., and two or more of these epoxy resins can be used in appropriate combination. That. In particular, it is desirable to use phenol novolac type epoxy resin, cresol novolac type epoxy resin or bisphenol A novolac type epoxy resin, because high heat resistance and reliability applicable to electrical and electronic materials are required. Although not particularly defined, a range of 0 to 50% by weight in the total resin composition is preferable in order to obtain a sufficient cured product.
[0012]
In addition, a curing agent can be added for the purpose of improving workability and accelerating the curing of the added epoxy. Curing agents include phenol-based, amine-based and acid anhydride-based ones, but it is preferable to use phenol-based curing agents. This is because the phenolic curing agent reduces the moisture resistance of the laminate and accelerates the curing of the epoxy resin, and the compound having a dihydrobenzoxazine ring can react with a compound having a phenolic hydroxyl group. This is because the curing reaction of the compound having the can also be accelerated. Furthermore, the addition amount can be added as long as it does not significantly inhibit the curing reaction of the resin composition, and it is preferably used in the range of 0 to 50% by weight of the resin composition. Specifically, for example, a curing agent having a phenolic hydroxyl group such as phenol novolak, cresol novolak, bisphenol A, bisphenol F, bisphenol S, or the like may be used in combination.
Further, the epoxy resin and the curing agent used in the present invention can be used after appropriately reacting in advance.
[0013]
In addition to the above, the resin composition of the present invention can also contain a filler for the purpose of reducing combustible components. Metal oxides such as silica, talc, mica, calcium silicate, potassium silicate, calcined clay, titanium oxide, barium sulfate, aluminum oxide, magnesium carbonate, calcium carbonate, barium carbonate, molybdenum oxide, zinc oxide, magnesium silicate, etc. In addition, a compound such as an oxide composed of a plurality of elements such as molybdenum, zinc, calcium, phosphorus, aluminum, and potassium may be used. Moreover, the compound which consists of a some combination of the oxide which consists of molybdenum, silicon, magnesium, and zinc may be sufficient.
[0014]
In addition to these, an inorganic filler can be added to the resin composition of the present invention for the purpose of achieving high rigidity and low thermal expansion, and in addition, pigments, adhesion assistants, antioxidants, curing accelerators. In addition, there are no particular limitations as long as a known material can be used, and a non-halogen compound does not deteriorate the characteristics of the laminated board and the printed wiring board.
[0015]
The type and amount of the organic solvent are particularly limited as long as the epoxy resin and the curing agent constituting the resin composition are uniformly dissolved or dispersed and have appropriate viscosity and volatility to produce a prepreg. Although not intended, a resin composition that satisfies these requirements and contains a solvent such as methyl ethyl ketone, 2-methoxyethanol, 2-methoxypropanol, 1-methoxy-2-propanol from the viewpoints of price, handleability, and safety It is preferable to use about 5 to 40% by weight of the total weight.
[0016]
In addition, the resin composition of the present invention can produce a prepreg by impregnating and drying a non-woven fabric made of glass or aramid resin, or a substrate such as glass cloth. Furthermore, a laminated sheet can be manufactured by stacking a metal foil on the prepreg and stacking and integrating by heating and pressing.
Furthermore, an adhesive film can be produced by applying and drying the resin-coated copper foil on a resin film such as a PET film by applying and drying the resin composition of the present invention to a copper foil.
[0017]
It is also possible to manufacture printed wiring boards by etching away unnecessary portions of the metal foil of this laminated board. If necessary, these printed wiring boards and prepreg, copper foil with resin, or adhesive film A multilayered printed wiring board can also be manufactured by appropriately laminating copper foils alone or in combination, and heating and pressing them. In the manufacture of these prepregs, laminates, resin-coated copper foils, adhesive films, and printed wiring boards, the usual coating, lamination, and circuit processing processes in the industry can be applied. A laminated board and printed wiring board that are flame retardant and highly reliable and do not contain a halogen flame retardant can be obtained. An electronic component can be manufactured using such a wiring board.
[0018]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.
[0019]
In the examples and comparative examples, the following were used as dihydrobenzoxazine compounds, epoxy resins, curing agents, organophosphorus compounds and other special materials. For other organic solvents, additives, general-purpose inorganic fillers, glass cloths and copper foils that make up laminates and prepregs, the raw materials generally used in the chemical and electronics industries are used except for those specifically mentioned. Using.
Dihydrobenzoxazine compound: Bisphenol A, aniline, and formalin in methyl ethyl ketone (MEK) were mixed at a molar ratio of 1/2/4, and refluxed for 4 hours. Taken out and pulverized epoxy resin: manufactured by Dainippon Ink and Chemicals, cresol novolac type epoxy resin, trade name: N-673 (epoxy equivalent 210)
Phenolic hardener: Made by Dainippon Ink, phenol novolac resin, trade name: Phenolite TD-2160
Organophosphorus compound A: manufactured by Sanko, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, trade name: HCA-HQ
Organophosphorus compound B: manufactured by Daihachi Chemical Industry, condensed phosphate ester, trade name: PX-200
Inorganic flame retardant: Sumitomo Chemical, aluminum hydroxide Product name: CL-310
[0020]
The characteristics of the laminated board and the printed wiring board are evaluated by the combustion time according to the UL-94 vertical method for flame retardancy. The average combustion time is 5 seconds or less and the maximum combustion time is 10 seconds or less. When the combustion time was less than 1 second and the maximum combustion time was 30 seconds or less, it was classified as V-1, and the combustion time was classified as HB. Other laminate characteristics (copper foil peel strength, hygroscopic solder heat resistance, chemical resistance) were evaluated based on JIS C6481. Evaluation of heat resistance of hygroscopic solder
○: No change △: Miesling or bulge occurrence x: Judged by blistering. The varnish curability was dropped on a hot plate at 160 ° C with 0.5 cc of varnish and stirred with a 1 mm diameter rod to gel. Evaluation was made based on the time until gelation (gelation time).
[0021]
Examples 1-3
A resin composition for laminates was prepared according to the formulation shown in Table 1. A glass cloth (thickness: 0.06 mm) was impregnated with this resin composition and dried at 160 to 175 ° C. for 4 minutes to obtain a prepreg. Seven prepregs were stacked, 18 μm copper foils were stacked on both sides thereof, and heated and pressed at 185 ° C. and a pressure of 4 MPa for 80 minutes to prepare a double-sided copper-clad laminate having a thickness of 0.5 mm. The properties of the laminate are shown in Table 1.
[0022]
Circuit formation (test pattern) was performed on the surface of the double-sided copper-clad laminate produced in Examples 1 to 3 by a subtractive method. Furthermore, the surface of the two produced double-sided copper-clad laminates with circuits was oxidized and roughened to improve adhesion, and the two prepregs produced in Examples 1 to 3 were sandwiched and overlapped. A 6-layer printed wiring board with an inner layer circuit was manufactured by laminating and pressing the sheet and 18 μm copper foil. At the same time, a four-layer printed wiring board with an inner layer circuit was produced by laminating and pressing a copper foil with a resin on a double-sided tension laminated board with a circuit subjected to surface oxidation roughening as described above. Further, an adhesive film and 18 μm copper foil were stacked and pressed on a double-sided laminated laminate with circuit subjected to surface oxidation roughening treatment to produce a four-layer printed wiring board with an inner layer circuit. Outer layer circuit processing, through-hole formation, resist ink printing, and component mounting were performed on these printed wiring boards by conventional methods, and it was confirmed that they could be manufactured without problems in the normal printed wiring board manufacturing process.
[0023]
Comparative Examples 1-2
Resin compositions were prepared in the same manner as in Examples 1 to 3, using the formulations shown in Table 1 and the methods shown in Examples. Using this resin composition, a prepreg was produced in the same manner as in the example, and a copper-clad laminate was produced. However, in Comparative Example 1, since no phosphorus flame retardant was added, sufficient flame retardancy was not obtained. Therefore, other evaluations were stopped. In Comparative Example 2, a phosphorus-based flame retardant was added. However, since the flame retardant used was only a condensed phosphate ester, sufficient flame retardance could not be ensured.
[Table 1]

As shown in Table 1, in the illustrated examples, the necessary amount of phosphorus flame retardant is included and the composition of the resin composition is appropriate, so that there is no problem in productivity and moldability and a sufficient flame retardancy is maintained. A plate was obtained. Here, the compound having a dihydrobenzoxazine ring is slow to cure as a thermosetting resin, and its use tends to be limited in terms of productivity. Although it appears as a tendency to be longer than the other examples in the 2000 second range, there is no particular limitation in manufacturing an adhesive film, which is a prepreg, copper-clad laminate, resin-coated copper foil. On the other hand, as shown in Examples 2 and 3, by using a curing agent in combination, the effect of improving the curing rate of the compound having a dihydrobenzoxazine ring can be obtained, the curing time of the varnish can be shortened, and the productivity can be reduced. The result was greatly improved. In addition, the addition of epoxy resin improved the peel strength and improved the circuit processability when forming fine circuits. Furthermore, in Example 3 to which aluminum hydroxide was added, the flame retardancy was further improved, the reliability of the base material was further improved, and more balanced characteristics could be obtained.
On the other hand, in Comparative Example 1, flame retardance could not be ensured because no phosphorus-based flame retardant was added. In Comparative Example 2, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Since no oxide or its derivative was used, heat resistance could not be obtained while ensuring sufficient flame retardancy. In Comparative Example 2, a phosphorus-based flame retardant was added, but since the flame retardant used was a phosphate ester, flame retardance was ensured, but sufficient heat resistance was not obtained.
Therefore, the superiority of the present invention is clear in terms of the blending ratio and blending amount of an appropriate flame retardant capable of maintaining adequate curability while ensuring sufficient flame retardancy.
[0024]
【The invention's effect】
According to the present invention, in a flame retarding method using a non-halogen flame retardant, a resin blend capable of maintaining appropriate curability while ensuring sufficient flame retardancy is established, and products using these resins are also mechanically , Electrical and chemical properties can be obtained.

Claims (10)

A flame retardant resin composition comprising (A) a compound having a dihydrobenzoosicazine ring, (B) an organic phosphorus compound represented by formula 1 or a derivative thereof, and (C) an organic compound represented by formula 2.

(However, R1 represents any organic group containing no hydrogen or halogen element)

(However, R2 to R6 represent any organic group containing no halogen element) A resin in which the organophosphorus compound according to claim 1 (B) is 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide [Formula 3] Composition.

The resin composition according to claim 1 or 2, wherein the organophosphorus compound according to claim 1 (C) is a condensed phosphate ester represented by formula 4.

A resin composition obtained by adding one or more epoxy resins, curing agents, or fillers to the resin composition according to claim 1. A prepreg made using the resin composition according to claim 1. A copper-clad laminate made using the prepreg according to claim 5. Copper foil with resin made using the resin composition according to claim 1. The adhesive film made using the resin composition of Claims 1-4 A prepreg according to claim 5, a copper-clad laminate according to claim 6, a copper foil with resin according to claim 7, a print made using any one of or in combination with the adhesive film according to claim 8. Wiring board An electronic component made using the printed wiring board according to claim 9.