JP4167909B2 - Resin composition - Google Patents

Description

【００４３】
平均線膨張率比（３）が１．５以下であると、本発明の樹脂組成物からなる樹脂材料は、寸法安定性がよく、他の材料と積層して、又は、張り合わせた場合にも、製造時及び使用時に反りや剥がれを生じることがない。より好ましくは１．４以下であり、更に好ましくは１．３以下である。
【００４４】
本発明の樹脂組成物は、樹脂組成物のガラス転移温度よりも１０℃高い温度から、樹脂組成物のガラス転移温度よりも５０℃高い温度までの樹脂組成物の平均線膨張率（α２）を、上記樹脂組成物に含まれる熱可塑性樹脂のガラス転移温度よりも１０℃高い温度から、上記樹脂組成物に含まれる熱可塑性樹脂のガラス転移温度よりも５０℃高い温度までの上記樹脂組成物に含まれる熱可塑性樹脂の平均線膨張率で除して求めた改善率が０．５０以下であることが好ましい。０．５０以下であると、本発明の樹脂組成物からなる樹脂材料は、無機化合物による高温物性の充分な改善が得られており、高温処理を行う製造工程や高温での使用において不具合を生じることがない。より好ましくは０．３５以下であり、更に好ましくは０．２５以下である。
【００４５】
本発明の樹脂組成物は、上述のようにガラス転移温度以上の高温における平均線膨張率が低いことから、高温での寸法安定性等の高温物性を向上させて、メッキ工程、硬化工程、鉛フリーハンダのリフロー工程等の高温処理工程においても反りや剥がれを生じることがない樹脂材料に用いることができる。
【００４６】
本発明の樹脂組成物は、引張弾性率が６ＧＰａ以上、１ＭＨｚでの誘電率が３．３以下であることが好ましい。本発明の樹脂組成物をＴＡＢ用テープとして用いる場合、引張弾性率が６ＧＰａ未満であると、必要な強度を確保するためには厚みを増す必要があり小型のＴＡＢを作製することができなくなることがあり、また、１ＭＨｚでの誘電率が３．３より大きいと、充分な信頼性を確保するためには厚みを増す必要があり小型のＴＡＢを作製することができなくなることがある。
【００４７】
本発明の樹脂組成物は、吸水率が１．０％以下、湿度線膨張率が１．５×１０^-5［％ＲＨ^-1］以下であることが好ましい。吸水率が１．０％を超えると、本発明の樹脂組成物を用いて基板を作製する場合、絶乾時と吸水時で寸法変化が起こることから微細配線が困難となり、小型化し得ないことがある。より好ましくは０．７％以下、更に好ましくは０．３％以下である。湿度線膨張率が１．５×１０^-5［％ＲＨ^-1］を超えると、得られる基板に反りが発生し、銅箔の変化率の違いから銅箔が剥がれてしまうことがある。より好ましくは１．２×１０^-5［％ＲＨ^-1］以下であり、更に好ましくは１．０×１０^-5［％ＲＨ^-1］以下である。
【００４８】
また、本発明の樹脂組成物は、吸水率が１．０％以下、１ＭＨｚでの誘電率が３．３以下かつ前記樹脂組成物を水に浸漬させて水を吸収させた場合の吸水処理後の誘電率が３．４以下であることが好ましい。吸水することにより電気特性が大きく変化すると信頼性が保てなくなることがあり、また、ハンダリフロー等の製造工程において材料が爆ぜてしまい歩留りが低下することがある。
【００４９】
なお、上記吸水率は、厚さ５０〜１００μｍのフィルムを３×５ｃｍの短冊状にした試験片について、８０℃で５時間乾燥させたときの重さＷ１と、水に浸漬し２５℃で２４時間放置した後に表面をよく拭き取ってときの重さＷ２とを測定し、下記式により求めた値である。
【００５０】
吸水率（％）＝（Ｗ２−Ｗ１）／Ｗ１×１００
本発明の樹脂組成物は、ガラス転移温度が１００℃以上であることが好ましい。ガラス転移温度が１００℃以上であると、本発明の樹脂組成物を基板等に用いた場合、高温物性、特に鉛フリーハンダ耐熱性や加熱に対する寸法安定性が向上する。より好ましくは１４０℃以上、更に好ましくは２００℃以上である。
【００５１】
本発明の樹脂組成物は、ガラス転移温度が１００℃以上であり、かつ、１ＭＨｚでの誘電率が３．３以下であることが好ましい。ガラス転移温度が１００℃以上であり、かつ、１ＭＨｚでの誘電率が３．３以下であることにより、本発明の樹脂組成物からなる樹脂材料は、高温物性、特に、鉛フリーハンダ耐熱性や加熱に対する寸法安定性が改善され、電子材料として必要な高い信頼性を得ることができ、かつ、高周波領域における信号の伝達速度においても、電子材料として必要な伝達速度が得られる。ガラス転移温度は、より好ましくは１４０℃以上であり、更に好ましくは２００℃以上である。１ＭＨｚの誘電率は、より好ましくは３．２以下であり、更に好ましくは３．０以下である。
【００５２】
本発明の樹脂組成物は、上述の優れた高温物性を有するものであって、熱可塑性樹脂と無機化合物とを含有するものである。
上記熱可塑性樹脂としては、例えば、ポリフェニレンエーテル樹脂；官能基変性されたポリフェニレンエーテル樹脂；ポリフェニレンエーテル樹脂又は官能基変性されたポリフェニレンエーテル樹脂と、ポリスチレン樹脂等のポリフェニレンエーテル樹脂又は官能基変性されたポリフェニレンエーテル樹脂と相溶し得る熱可塑性樹脂との混合物；脂環式炭化水素樹脂；ポリエーテルエーテルケトン樹脂；ポリエーテルサルフォン樹脂；ポリエステル樹脂；ポリオレフィン樹脂；ポリスチレン樹脂；ポリアミド樹脂；ポリビニルアセタール樹脂；ポリビニルアルコール樹脂；ポリ酢酸ビニル樹脂；ポリ（メタ）アクリル酸エステル樹脂；ポリオキシメチレン樹脂；熱可塑性ポリベンゾイミダゾール樹脂等が挙げられる。なかでも、ポリフェニレンエーテル樹脂、官能基変性されたポリフェニレンエーテル樹脂、ポリフェニレンエーテル樹脂又は官能基変性されたポリフェニレンエーテル樹脂とポリスチレン樹脂との混合物、脂環式炭化水素樹脂、ポリエーテルエーテルケトン樹脂、及び、熱可塑性ポリベンゾイミダゾール樹脂等が挙げられる。本発明では、熱可塑性樹脂は、官能基変性されたポリフェニレンエーテル樹脂とポリエーテルエーテルケトン樹脂との組合せ、ポリイソボルニルアクリレート、及びポリメチルメタクリレートの内のいずれかである。これらの熱可塑性樹脂は、単独で用いられてもよく、２種以上が併用されてもよい。なお、本明細書において、（メタ）アクリルとは、アクリル又はメタクリルを意味する。
【００５３】
上記ポリフェニレンエーテル樹脂とは、下記式（２）に示した繰り返し単位からなるポリフェニレンエーテル単独重合体又はポリフェニレンエーテル共重合体である。
【００５４】
【化１】

【００５５】
上記式（２）中、Ｒ１、Ｒ２、Ｒ３及びＲ４は、水素原子、アルキル基、アラルキル基、アリール基又はアルコキシル基を表す。これらのアルキル基、アラルキル基、アリール基及びアルコキシル基は、それぞれ官能基で置換されていてもよい。
【００５６】
上記ポリフェニレンエーテル単独重合体としては、例えば、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル−１，４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６− イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル等が挙げられる。
【００５７】
上記ポリフェニレンエーテル共重合体としては、例えば、上記ポリフェニレンエーテル単独重合体の繰り返し単位中に２，３，６−トリメチルフェノール等のアルキル三置換フェノール等を一部含有する共重合体や、これらのポリフェニレンエーテル共重合体に更にスチレン、α−メチルスチレン、ビニルトルエン等のスチレン系モノマーの１種又は２種以上がグラフト共重合された共重合体等が挙げられる。これらのポリフェニレンエーテル樹脂は、それぞれ単独で用いられてもよく、組成、成分、分子量等の異なるものが２種以上併用されてもよい。
【００５８】
上記官能基変性されたポリフェニレンエーテル樹脂としては、例えば、上記ポリフェニレンエーテル樹脂が無水マレイン酸基、グリシジル基、アミノ基、アリル基等の官能基の１種又は２種以上で変性されたもの等が挙げられる。これらの官能基変性されたポリフェニレンエーテル樹脂は、単独で用いられてもよく、２種以上が併用されてもよい。上記官能基変性されたポリフェニレンエーテル樹脂を熱可塑性樹脂として用いると、架橋反応することにより本発明の樹脂組成物の力学的物性、耐熱性、寸法安定性等をより向上させることができる。
【００５９】
上記ポリフェニレンエーテル樹脂又は官能基変性されたポリフェニレンエーテル樹脂とポリスチレン樹脂との混合物としては、例えば、上記ポリフェニレンエーテル樹脂又は上記官能基変性されたポリフェニレンエーテル樹脂と、スチレン単独重合体；スチレンと、α−メチルスチレン、エチルスチレン、ｔ−ブチルスチレン及びビニルトルエン等のスチレン系モノマーの１種又は２種以上との共重合体；スチレン系エラストマー等のポリスチレン樹脂との混合物等が挙げられる。
【００６０】
上記ポリスチレン樹脂は、単独で用いられてもよく、２種以上が併用されてもよい。また、これらのポリフェニレンエーテル樹脂又は官能基変性されたポリフェニレンエーテル樹脂とポリスチレン樹脂との混合物は、単独で用いられてもよく、２種以上が併用されてもよい。
【００６１】
上記脂環式炭化水素樹脂としては、高分子鎖中に環状の炭化水素基を有する炭化水素樹脂であり、例えば、環状オレフィン、すなわちノルボルネン系モノマーの単独重合体又は共重合体等が挙げられる。これらの脂環式炭化水素樹脂は、単独で用いられてもよく、２種以上が併用されてもよい。
【００６２】
上記環状オレフィンとしては、例えば、ノルボルネン、メタノオクタヒドロナフタレン、ジメタノオクタヒドロナフタレン、ジメタノドデカヒドロアントラセン、ジメタノデカヒドロアントラセン、トリメタノドデカヒドロアントラセン、ジシクロペンタジエン、２，３−ジヒドロシクロペンタジエン、メタノオクタヒドロベンゾインデン、ジメタノオクタヒドロベンゾインデン、メタノデカヒドロベンゾインデン、ジメタノデカヒドロベンゾインデン、メタノオクタヒドロフルオレン、ジメタノオクタヒドロフルオレンやこれらの置換体等が挙げられる。これらの環状オレフィンは、単独で用いられてもよく、２種以上が併用されてもよい。
【００６３】
上記ノルボルネン等の置換体における置換基としては、例えば、アルキル基、アルキリデン基、アリール基、シアノ基、アルコキシカルボニル基、ピリジル基、ハロゲン原子等の公知の炭化水素基や極性基が挙げられる。これらの置換基は、単独で用いられてもよく、２種以上が併用されてもよい。
【００６４】
上記ノルボルネン等の置換体としては、例えば、５−メチル−２−ノルボルネン、５，５−ジメチル−２−ノルボルネン、５−エチル−２−ノルボルネン、５−ブチル−２−ノルボルネン、５−エチリデン−２−ノルボルネン、５−メトキシカルボニル−２−ノルボルネン、５−シアノ−２−ノルボルネン、５−メチル−５−メトキシカルボニル−２−ノルボルネン、５−フェニル−２−ノルボルネン、５−フェニル−５−メチル−２−ノルボルネン等が挙げられる。これらのノルボルネン等の置換体は、単独で用いられてもよく、２種以上が併用されてもよい。
【００６５】
上記脂環式炭化水素樹脂のうち市販されているものとしては、例えば、ジェイエスアール（ＪＳＲ）社製の商品名「アートン」シリーズや日本ゼオン社製の商品名「ゼオノア」シリーズ等が挙げられる。
【００６８】
上記ポリエーテルエーテルケトン樹脂としては、例えば、ジハロゲノベンゾフェノンとヒドロキノンとを重縮合して得られるもの等が挙げられる。上記ポリエーテルエーテルケトン樹脂のうち市販されているものとしては、例えば、ＩＣＩ社製の商品名「Ｖｉｃｔｒｅｘ ＰＥＥＫ」等が挙げられる。
【００６９】
上記熱可塑性ポリベンゾイミダゾール樹脂としては、例えば、ジオクタデシルテレフタルアルドイミンと３，３’−ジアミノベンジジンとを重縮合して得られるもの等が挙げられる。市販されているものとしては、例えば、クラリアントジャパン社製の商品名「セラゾール」シリーズ等が挙げられる。
【００７０】
上記熱可塑性樹脂は、Ｆｅｄｏｒｓの計算式を用いて求めた溶解度パラメーター（ＳＰ値）が４２［Ｊ／ｃｍ³］^1/2以上であることが好ましい。なお、上記Ｆｅｄｏｒｓの計算式によれば、ＳＰ値は、各原子団のモル凝集エネルギーの和を体積で割ったものの平方根とされ、単位体積あたりの極性を示す。ＳＰ値が４２［Ｊ／ｃｍ³］^1/2以上であることにより、大きな極性を持つので、化学処理された層状珪酸塩等の無機化合物との相溶性がよく、無機化合物として層状珪酸塩を用いた場合であっても、層状珪酸塩の層間を広げ、一層ずつ分散させることができる。より好ましくは４６．２［Ｊ／ｃｍ³］^1/2以上であり、更に好ましくは５２．５［Ｊ／ｃｍ³］^1/2以上である。
【００７１】
上記ＳＰ値が４２［Ｊ／ｍ³］^1/2以上である樹脂としては、例えば、ポリブチレンテレフタレート、ポリブチレンナフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル樹脂、ポリアミド６、ポリアミド６６、ポリアミド１２等のポリアミド樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンエーテル樹脂、変性ポリフェニレンエーテル樹脂、ポリベンゾイミダゾール樹脂等が挙げられる。
【００７２】
上記熱可塑性樹脂は、窒素雰囲気中での熱重量測定を行った場合に、１０％重量減少温度が４００℃以上であることが好ましい。４００℃以上であることにより、本発明の樹脂組成物からなる樹脂材料は、鉛フリーハンダのリフロー工程等の高温処理工程において、アウトガスを発生することがなく、電子材料として好適なものとなる。より好ましくは４５０℃以上であり、更に好ましくは５００℃以上である。上記窒素雰囲気中での熱重量測定における１０％重量減少温度が４００℃以上である樹脂としては、例えば、ポリエーテルエーテルケトン樹脂等が挙げられる。
【００７３】
本発明の樹脂組成物は、無機化合物を含有するものである。
上記無機化合物としては、例えば、層状珪酸塩、タルク、シリカ、アルミナ、ガラスビーズ等が挙げられるが、なかでも、高温物性を向上させるためには層状珪酸塩が好適に用いられる。なお、本明細書において、層状珪酸塩とは、層間に交換性金属カチオンを有する層状の珪酸塩鉱物を意味し、天然物であってもよく、合成物であってもよい。
【００７４】
また、特に高い引張弾性率が必要な場合には、無機化合物として層状珪酸塩及びウィスカを含有することが好ましい。樹脂にウィスカを配合すると弾性率が向上することは知られているが、高い引張弾性率を達成できるほどにウィスカを配合した樹脂組成物は成形性が悪くなるという問題があった。本発明の樹脂組成物では、無機化合物として層状珪酸塩とウィスカとを併用することにより、少量のウィスカの配合でも充分な弾性率の向上が得られる。
【００７５】
ウィスカを層状珪酸塩と共に無機化合物として配合する場合、無機化合物１００重量％中、ウィスカを２５〜９５重量％の割合とすることが望ましい。２５重量％未満では、ウィスカを配合したことによる効果が十分でなく、９５重量％を超えた場合には、層状珪酸塩の添加による効果が十分でないことがある。
【００７６】
また、特に低吸水率が必要となる場合は、無機化合物として層状珪酸塩及びシリカを含有することが好ましい。上記シリカとしては、特に限定されないが、例えば日本アエロジル社製のアエロジルなどが挙げられる。層状珪酸塩とシリカとを無機化合物として併用することにより、本発明の樹脂組成物から得られる高分子材料の吸湿性を効果的に低めることができる。樹脂にシリカを配合すると吸水率が向上することは知られているが、低吸水率を達成するほどにシリカを配合した樹脂組成物は、引張強度等の物性が低下するという問題点があった。本発明の樹脂組成物では、無機化合物として層状珪酸塩とシリカとを併用することにより、少量のシリカ配合でも充分な吸水率の低減効果が得られる。シリカの無機化合物中に占める割合は、２５〜９５重量％の範囲とすることが好ましい。２５重量％未満では、シリカを層状珪酸塩と配合した効果が十分でなく、９５重量％を超えると、層状珪酸塩の添加による効果が損なわれることがある。
【００７７】
上記層状珪酸塩としては、例えば、モンモリロナイト、ヘクトライト、サポナイト、バイデライト、スティブンサイト及びノントロナイト等のスメクタイト系粘土鉱物、膨潤性マイカ、バーミキュライト、ハロイサイト等が挙げられる。なかでも、モンモリロナイト、ヘクトライト、膨潤性マイカ、及び、バーミキュライトからなる群より選択される少なくとも１種が好適に用いられる。これらの層状珪酸塩は、単独で用いられてもよく、２種以上が併用されてもよい。
【００７８】
上記層状珪酸塩の結晶形状としては特に限定されないが、平均長さの好ましい下限は０．０１μｍ、上限は３μｍ、厚さの好ましい下限は０．００１μｍ、上限は１μｍ、アスペクト比の好ましい下限は２０、上限は５００であり、平均長さのより好ましい下限は０．０５μｍ、上限は２μｍ、厚さのより好ましい下限は０．０１μｍ、上限は０．５μｍ、アスペクト比のより好ましい下限は５０、上限は２００である。
【００７９】
上記層状珪酸塩は、下記式（３Ａ）で定義される形状異方性効果が大きいことが好ましい。形状異方性効果の大きい層状珪酸塩を用いることにより、本発明の樹脂組成物から得られる樹脂は優れた力学的物性を有するものとなる。
【００８０】
【数３】

【００８１】
上記層状珪酸塩の層間に存在する交換性金属カチオンとは、層状珪酸塩の薄片状結晶表面に存在するナトリウムやカルシウム等の金属イオンを意味し、これらの金属イオンは、カチオン性物質とのカチオン交換性を有するため、カチオン性を有する種々の物質を上記層状珪酸塩の結晶層間に挿入（インターカレート）することができる。
【００８２】
上記層状珪酸塩のカチオン交換容量としては特に限定されないが、好ましい下限は５０ミリ等量／１００ｇ、上限は２００ミリ等量／１００ｇである。５０ミリ等量／１００ｇ未満であると、カチオン交換により層状珪酸塩の結晶層間にインターカレートされるカチオン性物質の量が少なくなるために、結晶層間が充分に非極性化（疎水化）されないことがある。２００ミリ等量／１００ｇを超えると、層状珪酸塩の結晶層間の結合力が強固になりすぎて、結晶薄片が剥離し難くなることがある。
【００８３】
上記無機化合物として層状珪酸塩を用いて本発明の樹脂組成物を製造する場合、層状珪酸塩を化学修飾して樹脂との親和性を高めることにより樹脂中への分散性を向上されたものが好ましく、このような化学処理により樹脂中に層状珪酸塩を大量に分散することができる。本発明に用いられる樹脂、あるいは本発明の樹脂組成物を製造する際に用いられる溶媒に適した化学修飾を層状珪酸塩に施さない場合、層状珪酸塩は凝集しやすくなるので大量に分散させることができないが、樹脂あるいは溶媒に適した化学修飾を施すことにより、層状珪酸塩は１０重量部以上添加した場合においても、樹脂中に凝集することなく分散させることができる。上記化学修飾としては、例えば、以下に示す化学修飾（１）法〜化学修飾（６）法によって実施することができる。これらの化学修飾方法は、単独で用いられてもよく、２種以上が併用されてもよい。
【００８４】
上記化学修飾（１）法は、カチオン性界面活性剤によるカチオン交換法ともいい、具体的には、ポリフェニレンエーテル樹脂等の低極性樹脂を用いて本発明の樹脂組成物を得る際に予め層状珪酸塩の層間をカチオン性界面活性剤でカチオン交換し、疎水化しておく方法である。予め層状珪酸塩の層間を疎水化しておくことにより、層状珪酸塩と低極性樹脂との親和性が高まり、層状珪酸塩を低極性樹脂中により均一に微分散させることができる。
【００８５】
上記カチオン性界面活性剤としては特に限定されず、例えば、４級アンモニウム塩、４級ホスホニウム塩等が挙げられる。なかでも、層状珪酸塩の結晶層間を充分に疎水化できることから、炭素数６以上のアルキルアンモニウムイオン、芳香族４級アンモニウムイオン又は複素環４級アンモニウムイオンが好適に用いられる。特に熱可塑性樹脂として熱可塑性ポリイミド樹脂、ポリエステルイミド樹脂、ポリエーテルイミド樹脂を用いる場合には、芳香族４級アンモニウムイオン又は複素環４級アンモニウムイオンが好適である。
【００８６】
上記４級アンモニウム塩としては特に限定されず、例えば、トリメチルアルキルアンモニウム塩、トリエチルアルキルアンモニウム塩、トリブチルアルキルアンモニウム塩、ジメチルジアルキルアンモニウム塩、ジブチルジアルキルアンモニウム塩、メチルベンジルジアルキルアンモニウム塩、ジベンジルジアルキルアンモニウム塩、トリアルキルメチルアンモニウム塩、トリアルキルエチルアンモニウム塩、トリアルキルブチルアンモニウム塩；ベンジルメチル｛２−［２−（ｐ−１，１，３，３−テトラメチルブチルフェノオキシ）エトキシ］エチル｝アンモニウムクロライド等の芳香環を有する４級アンモニウム塩；トリメチルフェニルアンモニウム等の芳香族アミン由来の４級アンモニウム塩；アルキルピリジニウム塩、イミダゾリウム塩等の複素環を有する４級アンモニウム塩；ポリエチレングリコール鎖を２つ有するジアルキル４級アンモニウム塩、ポリプロピレングリコール鎖を２つ有するジアルキル４級アンモニウム塩、ポリエチレングリコール鎖を１つ有するトリアルキル４級アンモニウム塩、ポリプロピレングリコール鎖を１つ有するトリアルキル４級アンモニウム塩等が挙げられる。なかでも、ラウリルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、トリオクチルメチルアンモニウム塩、ジステアリルジメチルアンモニウム塩、ジ硬化牛脂ジメチルアンモニウム塩、ジステアリルジベンジルアンモニウム塩、Ｎ−ポリオキシエチレン−Ｎ−ラウリル−Ｎ，Ｎ−ジメチルアンモニウム塩等が好適である。これらの４級アンモニウム塩は、単独で用いられてもよく、２種以上が併用されてもよい。
【００８７】
上記４級ホスホニウム塩としては特に限定されず、例えば、ドデシルトリフェニルホスホニウム塩、メチルトリフェニルホスホニウム塩、ラウリルトリメチルホスホニウム塩、ステアリルトリメチルホスホニウム塩、トリオクチルメチルホスホニウム塩、ジステアリルジメチルホスホニウム塩、ジステアリルジベンジルホスホニウム塩等が挙げられる。これらの４級ホスホニウム塩は、単独で用いられてもよく、２種以上が併用されてもよい。
【００８８】
上記化学修飾（２）法は、化学修飾（１）法で化学処理された有機化層状珪酸塩の結晶表面に存在する水酸基を、水酸基と化学結合し得る官能基又は水酸基との化学的親和性の大きい官能基を分子末端に１個以上有する化合物で化学処理する方法である。
【００８９】
上記水酸基と化学結合し得る官能基又は水酸基との化学的親和性の大きい官能基としては特に限定されず、例えば、アルコキシ基、グリシジル基、カルボキシル基（二塩基性酸無水物も包含する）、水酸基、イソシアネート基、アルデヒド基等が挙げられる。
【００９０】
上記水酸基と化学結合し得る官能基を有する化合物又は水酸基との化学的親和性の大きい官能基を有する化合物としては特に限定されず、例えば、上記官能基を有する、シラン化合物、チタネート化合物、グリシジル化合物、カルボン酸類、アルコール類等が挙げられる。これらの化合物は、単独で用いられてもよく、２種以上が併用されてもよい。
【００９１】
上記シラン化合物としては特に限定されず、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルジメチルメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルジメチルエトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、Ｎ−β−（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）γ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、オクタデシルトリメトキシシラン、オクタデシルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン等が挙げられる。これらのシラン化合物は、単独で用いられてもよく、２種以上が併用されてもよい。
【００９２】
上記化学修飾（３）法は、化学修飾（１）法で化学処理された有機化層状珪酸塩の結晶表面に存在する水酸基を、水酸基と化学結合し得る官能基又は水酸基と化学的親和性の大きい官能基と、反応性官能基を分子末端に１個以上有する化合物とで化学処理する方法である。
上記化学修飾（４）法は、化学修飾（１）法で化学処理された有機化層状珪酸塩の結晶表面を、アニオン性界面活性を有する化合物で化学処理する方法である。
【００９３】
上記アニオン性界面活性を有する化合物としては、イオン相互作用により層状珪酸塩を化学処理できるものであれば特に限定されず、例えば、ラウリル酸ナトリウム、ステアリン酸ナトリウム、オレイン酸ナトリウム、高級アルコール硫酸エステル塩、第２級高級アルコール硫酸エステル塩、不飽和アルコール硫酸エステル塩等が挙げられる。これらの化合物は、単独で用いられてもよく、２種以上が併用されてもよい。
【００９４】
上記化学修飾（５）法は、上記アニオン性界面活性を有する化合物のうち、分子鎖中のアニオン部位以外に反応性官能基を１個以上有する化合物で化学処理する方法である。
【００９５】
上記化学修飾（６）法は、化学修飾（１）法〜化学修飾（５）法のいずれかの方法で化学処理された有機化層状珪酸塩に、更に、例えば、無水マレイン酸変性ポリフェニレンエーテル樹脂のような層状珪酸塩と反応可能な官能基を有する樹脂を用いる方法である。
【００９６】
上記層状珪酸塩は、本発明の樹脂組成物中に、広角Ｘ線回折測定法により測定した（００１）面の平均層間距離が３ｎｍ以上であるように、かつ、一部又は全部が５層以下の層数で分散されていることが好ましい。上記平均層間距離が３ｎｍ以上であるように、かつ、一部又は全部が５層以下の層数で分散されていることにより、樹脂と層状珪酸塩との界面面積は充分に大きく、かつ、層状珪酸塩の薄片状結晶間の距離は適度なものとなり、高温物性、力学的物性、耐熱性、寸法安定性等において分散による改善効果を充分に得ることができる。
【００９７】
上記平均層間距離の好ましい上限は５ｎｍである。５ｎｍを超えると、層状珪酸塩の結晶薄片が層毎に分離して相互作用が無視できるほど弱まるので、高温での束縛強度が弱くなり、充分な寸法安定性が得られないことがある。
【００９８】
なお、本明細書において、層状珪酸塩の平均層間距離とは、層状珪酸塩の薄片状結晶を層とみなした場合における層間の距離の平均を意味し、Ｘ線回折ピーク及び透過型電子顕微鏡撮影、すなわち、広角Ｘ線回折測定法により算出することができるものである。
【００９９】
上記一部又は全部が５層以下の層数で分散されているとは、具体的には、層状珪酸塩の薄片状結晶間の相互作用が弱められて薄片状結晶の積層体の一部又は全部が分散していることを意味する。好ましくは、層状珪酸塩の積層体の１０％以上が５層以下の層数で分散されており、層状珪酸塩の積層体の２０％以上が５層以下の層数で分散されていることがより好ましい。
【０１００】
なお、５層以下の積層体として分散している層状珪酸塩の割合は、樹脂組成物を透過型電子顕微鏡により５万〜１０万倍に拡大して観察し、一定面積中において観察できる層状珪酸塩の積層体の全層数Ｘ及び５層以下の積層体として分散している積層体の層数Ｙを計測することにより、下記式（４）から算出することができる。
【０１０１】
【数４】

【０１０２】
また、層状珪酸塩の積層体における積層数としては、層状珪酸塩の分散による効果を得るためには５層以下であることが好ましく、より好ましくは３層以下であり、更に好ましくは１層である。
【０１０３】
本発明の樹脂組成物は、上記無機化合物として層状珪酸塩を用い、層状珪酸塩が、広角Ｘ線回折測定法により測定した（００１）面の平均層間距離が３ｎｍ以上であるように、かつ、一部又は全部が５層以下の層数で分散されているものとすることにより、樹脂と層状珪酸塩との界面面積が充分に大きくなって、樹脂と層状珪酸塩の表面との相互作用が大きくなり、溶融粘度が高まり成形性が向上することに加え、常温から高温までの広い温度領域で弾性率等の力学的物性が向上し、樹脂のＴｇ又は融点以上の高温でも力学的物性を保持することができ、高温時の線膨張率も低く抑えることができる。かかる理由は明らかではないが、Ｔｇ又は融点以上の温度領域においても、微分散状態の層状珪酸塩が一種の疑似架橋点として作用しているためにこれら物性が発現すると考えられる。一方、層状珪酸塩の薄片状結晶間の距離も適度なものとなるので、燃焼時に、層状珪酸塩の薄片状結晶が移動して難燃被膜となる焼結体を形成しやすくなる。この焼結体は、燃焼時の早い段階で形成されるので、外界からの酸素の供給を遮断するのみならず、燃焼により発生する可燃性ガスをも遮断することができ、本発明の樹脂組成物は優れた難燃性を発現する。
【０１０４】
更に、本発明の樹脂組成物では、ナノメートルサイズで層状珪酸塩が微分散していることから、本発明の樹脂組成物からなる基板等に炭酸ガスレーザ等のレーザにより穿孔加工を施した場合、樹脂成分と層状珪酸塩成分とが同時に分解蒸発し、部分的に残存する層状珪酸塩の残渣も数μｍ以下の小さなもののみでありデスミア加工により容易に除去できる。これにより、穿孔加工により発生する残渣によってメッキ不良等が発生するのを防止することができる。
【０１０５】
樹脂中に層状珪酸塩を分散させる方法としては特に限定されず、例えば、有機化層状珪酸塩を用いる方法、樹脂と層状珪酸塩とを常法により混合した後に樹脂を発泡剤により発泡させる方法、分散剤を用いる方法等が挙げられる。これらの分散方法を用いることにより、樹脂中に層状珪酸塩をより均一かつ微細に分散させることができる。
【０１０６】
上記樹脂と層状珪酸塩とを常法により混合した後に樹脂を発泡剤により発泡させる方法は、発泡によるエネルギーを層状珪酸塩の分散に用いるものである。
上記発泡剤としては特に限定されず、例えば、気体状発泡剤、易揮発性液状発泡剤、加熱分解型固体状発泡剤等が挙げられる。これらの発泡剤は、単独で用いられてもよいし、２種以上が併用されてもよい。
【０１０７】
上記樹脂と層状珪酸塩とを常法により混合した後に樹脂を発泡剤により発泡させる方法としては特に限定されず、例えば、樹脂と層状珪酸塩とからなる樹脂組成物に気体状発泡剤を高圧下で含浸させた後、この気体状発泡剤を上記樹脂組成物内で気化させて発泡体を形成する方法；層状珪酸塩の層間に予め加熱分解型発泡剤を含有させ、その加熱分解型発泡剤を加熱により分解させて発泡体を形成する方法等が挙げられる。
【０１０８】
上記無機化合物の上記熱可塑性樹脂１００重量部に対する配合量の下限は０．１重量部、上限は６５重量部である。０．１重量部未満であると、高温物性や吸湿性の改善効果が小さくなる。６５重量部を超えると、本発明の樹脂組成物の密度（比重）が高くなり、機械的強度も低下することから実用性に乏しくなる。好ましい下限は１重量部、上限は６０重量部である。１重量部未満であると、本発明の樹脂組成物を薄く成形した際に充分な高温物性の改善効果が得られないことがある。６０重量部を超えると、成形性が低下することがある。より好ましい下限は１．５重量部、上限は５０重量部である。１．５〜５０重量部であると、力学的物性、工程適性において問題となる領域はなく、充分な難燃性が得られる。
【０１０９】
本発明の樹脂組成物のうち、無機化合物として層状珪酸塩を用いる場合、上記層状珪酸塩の配合量の下限は０．５重量部、上限は５０重量部が好ましい。０．５重量部未満であると高温物性や吸湿性の改善効果が小さくなることがある。５０重量部を超えると、本発明の樹脂組成物の密度（比重）が高くなり、機械的強度も低下することから実用性に乏しくなることがある。より好ましい下限は１重量部、上限は４５重量部である。１重量未満であると本発明の樹脂組成物を薄く成形した際に充分な高温物性の改善効果が得られないことがある。４５重量部を超えると、層状珪酸塩の分散性が悪くなることがある。さらに好ましい下限は１．５重量部であり、上限は４０重量部である。１．５〜４０重量部であると工程適性において問題となる領域はなく、充分な低吸水性が得られ、かつ、平均線膨張率の低減効果がα１およびα２の両方の領域でも充分に得られる。
【０１１０】
本発明の樹脂組成物は、更に、ハロゲン系組成物を含有しない難燃剤を含有することが好ましい。なお、難燃剤の製造工程上の都合等により微量のハロゲンが混入することはかまわない。
【０１１１】
上記難燃剤としては特に限定されず、例えば、水酸化アルミニウム、水酸化マグネシウム、ドーソナイト、アルミン酸化カルシウム、２水和石こう、水酸化カルシウム等の金属水酸化物；金属酸化物；赤リンやポリリン酸アンモニウム等のリン系化合物；メラミン、メラミンシアヌレート、メラミンイソシアヌレート、リン酸メラミン及びこれらに表面処理を施したメラミン誘導体等の窒素系化合物；フッ素樹脂；シリコーンオイル；ハイドロタルサイト等の層状複水和物；シリコーン−アクリル複合ゴム等が挙げられる。なかでも、金属水酸化物及びメラミン誘導体が好適である。上記金属水酸化物のなかでも、特に水酸化マグネシウム、水酸化アルミニウムが好ましく、これらは各種の表面処理剤により表面処理が施されたものであってもよい。上記表面処理剤としては特に限定されず、例えば、シランカップリング剤、チタネート系カップリング剤、ＰＶＡ系表面処理剤、エポキシ系表面処理剤等が挙げられる。これらの難燃剤は、単独で用いられてもよいし、２種以上が併用されてもよい。
【０１１２】
上記難燃剤として金属水酸化物を用いた場合、金属水酸化物の熱可塑性樹脂１００重量部に対する好ましい配合量の下限は０．１重量部、上限は１００重量部である。０．１重量部未満であると、難燃化効果が充分に得られないことがある。１００重量部を超えると、本発明の樹脂組成物の密度（比重）が高くなりすぎて、実用性が乏しくなったり、柔軟性や伸度が極端に低下することがある。より好ましい下限は５重量部、上限は８０重量部である。５重量部未満であると、本発明の樹脂組成物を薄く成形した際に充分な難燃化効果が得られないことがある。８０重量部を超えると、高温処理を行う工程において膨れ等による不良率が高くなることがある。更に好ましい下限は１０重量部、上限は７０重量部である。１０〜７０重量部の範囲であると、力学的物性、電気物性、工程適性等で問題となる領域がなく、充分な難燃性を発現する。
【０１１３】
上記難燃剤としてメラミン誘導体を用いた場合、メラミン誘導体の熱可塑性樹脂１００重量部に対する好ましい配合量の下限は０．１重量部、上限は１００重量部である。０．１重量部未満であると、難燃化効果が充分に得られないことがある。１００重量部を超えると、柔軟性や伸度等の力学的物性が極端に低下することがある。より好ましい下限は５重量部、上限は７０重量部である。５重量部未満であると、絶縁基板を薄くしたときに充分な難燃化効果が得られないことがある。７０重量部を超えると、柔軟性や伸度等の力学的物性が極端に低下することがある。更に好ましい下限は１０重量部、上限は５０重量部である。１０〜５０重量部の範囲であると、力学的物性、電気物性、工程適性等で問題となる領域がなく、充分な難燃性を発現する。
【０１１４】
本発明の樹脂組成物には、本発明の課題達成を阻害しない範囲で特性を改質することを目的に、必要に応じて、熱可塑性エラストマー類、架橋ゴム、オリゴマー類、造核剤、酸化防止剤（老化防止剤）、熱安定剤、光安定剤、紫外線吸収剤、滑剤、難燃助剤、帯電防止剤、防曇剤、充填剤、軟化剤、可塑剤、着色剤等の添加剤が配合されてもよい。これらはそれぞれ単独で用いられてもよく、２種以上が併用されてもよい。
【０１１５】
上記熱可塑性エラストマー類としては特に限定されず、例えば、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー等が挙げられる。樹脂との相容性を高めるために、これらの熱可塑性エラストマーを官能基変性したものであってもよい。これらの熱可塑性エラストマー類は、単独で用いられてもよく、２種以上が併用されてもよい。
【０１１６】
上記架橋ゴムとしては特に限定されず、例えば、イソプレンゴム、ブタジエンゴム、１，２−ポリブタジエン、スチレン−ブタジエンゴム、ニトリルゴム、ブチルゴム、エチレン−プロピレンゴム、シリコーンゴム、ウレタンゴム等が挙げられる。樹脂との相溶性を高めるために、これらの架橋ゴムを官能基変性したものであることが好ましい。上記官能基変性した架橋ゴムとしては特に限定されず、例えば、エポキシ変性ブタジエンゴムやエポキシ変性ニトリルゴム等が挙げられる。これらの架橋ゴム類は単独で用いられてもよく、２種以上が併用されてもよい。
【０１１７】
上記オリゴマー類としては特に限定されず、例えば、無水マレイン酸変性ポリエチレンオリゴマー等が挙げられる。これらのオリゴマー類は、単独で用いられてもよく、２種以上が併用されてもよい。
【０１１８】
本発明の樹脂組成物を製造する方法としては特に限定されず、例えば、樹脂と無機化合物の各所定量と、必要に応じて配合される１種又は２種以上の添加剤の各所定量とを、常温下又は加熱下で、直接配合して混練する直接混練法、及び、溶媒中で混合した後、溶媒を除去する方法；予め上記樹脂又は上記樹脂以外の樹脂に所定量以上の無機化合物を配合して混練したマスターバッチを作製しておき、このマスターバッチ、樹脂の所定量の残部、及び、必要に応じて配合される１種又は２種以上の添加剤の各所定量を、常温下又は加熱下で、混練又は溶媒中で混合するマスターバッチ法等が挙げられる。
【０１１９】
上記マスターバッチ法において、上記樹脂又は上記樹脂以外の樹脂に無機化合物を配合したマスターバッチと、マスターバッチを希釈して所定の無機化合物濃度とする際に用いる上記樹脂を含有するマスターバッチ希釈用樹脂組成物は同一の組成であっても、異なる組成であってもよい。
【０１２０】
上記マスターバッチとしては特に限定されないが、例えば、無機化合物の分散が容易であるポリアミド樹脂、ポリフェニレンエーテル樹脂、ポリエーテルサルフォン樹脂、及び、ポリエステル樹脂からなる群より選択される少なくとも１種の樹脂を含有することが好ましい。上記マスターバッチ希釈用樹脂組成物としては特に限定されないが、例えば、高温物性に優れた熱可塑性ポリイミド樹脂、ポリエーテルエーテルケトン樹脂、熱可塑性ポリペンゾイミダゾール樹脂からなる群より選択される少なくとも１種の樹脂を含有することが好ましい。
【０１２１】
上記マスターバッチにおける無機化合物の配合量は特に限定されないが、樹脂１００重量部に対する好ましい下限は１重量部、上限は５００重量部である。１重量部未満であると、任意の濃度に希釈可能なマスターバッチとしての利便性が薄れる。５００重量部を超えると、マスターバッチ自体における分散性や、特にマスターバッチ希釈用樹脂組成物によって所定の配合量に希釈する際の無機化合物の分散性が悪くなることがある。より好ましい下限は５重量部、上限は３００重量部である。
【０１２２】
また、例えば、遷移金属錯体類のような重合触媒（重合開始剤）を含有する無機化合物を用い、熱可塑性樹脂のモノマーと無機化合物とを混練し、上記モノマーを重合させることにより、熱可塑性樹脂の重合と樹脂組成物の製造とを同時に一括して行う方法を用いてもよい。
【０１２３】
本発明の樹脂組成物の製造方法における混合物を混練する方法としては特に限定されず、例えば、押出機、２本ロール、バンバリーミキサー等の混練機を用いて混練する方法等が挙げられる。
【０１２４】
本発明の樹脂組成物は、樹脂と無機化合物とが組み合わせられ、分子鎖の拘束によるＴｇや耐熱変形温度の上昇が図られていることにより、高温での低い線膨張率を有し、耐熱性、力学的物性、透明性等に優れている。
【０１２５】
更に、樹脂中では無機化合物に比べて気体分子の方がはるかに拡散しやすく、樹脂中を拡散する際に気体分子は無機化合物を迂回しながら拡散するので、ガスバリア性も向上している。同様にして気体分子以外に対するバリア性も向上し、耐溶剤性、吸湿性、吸水性等が向上している。これにより、例えば、多層プリント配線板での銅回路からの銅のマイグレーションを抑制することができる。更に、樹脂中の微量添加物が表面にブリードアウトしてメッキ不良等の不具合が発生することも抑制できる。
【０１２６】
本発明の樹脂組成物において、上記無機化合物として層状珪酸塩を用いれば、多量に配合しなくとも優れた力学的物性が得られることから、薄い絶縁基板とすることができ、多層プリント基板の高密度化、薄型化が可能となる。また、結晶形成における層状珪酸塩の造核効果や耐湿性の向上に伴う膨潤抑制効果等に基づく寸法安定性の向上等が図られている。更に、燃焼時に層状珪酸塩による焼結体が形成されるので燃焼残渣の形状が保持され、燃焼後も形状崩壊が起こらず、延焼を防止することができ、優れた難燃性を発現する。
また、本発明の樹脂組成物において、ノンハロゲン難燃剤を用いれば、環境にも配慮しつつ、高い力学的物性と高い難燃性とを両立することができる。
【０１２７】
本発明の樹脂組成物の用途としては特に限定されないが、適当な溶媒に溶解したり、フィルム状に成形したりして加工することにより、例えば、多層基板のコア層やビルドアップ層等を形成する基板用材料、シート、積層板、樹脂付き銅箔、銅張積層板、ＴＡＢ用テープ、プリント基板、プリプレグ、ワニス等に好適に用いられる。かかる本発明の樹脂組成物を用いてなる基板用材料、シート、積層板、樹脂付き銅箔、銅張積層板、ＴＡＢ用テープ、プリント基板、プリプレグ、接着シートもまた本発明の１つである。
【０１２８】
上記成形の方法としては特に限定されず、例えば、押出機にて、溶融混練した後に押出し、Ｔダイやサーキュラーダイ等を用いてフィルム状に成形する押出成形法；有機溶剤等の溶媒に溶解又は分散させた後、キャスティングしてフィルム状に成形するキャスティング成形法；有機溶剤等の溶媒に溶解又は分散して得たワニス中に、ガラス等の無機材料や有機ポリマーからなるクロス状又は不織布状の基材をディッピングしてフィルム状に成形するディッピング成形法等が挙げられる。なかでも、多層基板の薄型化を図るためには、押出成形法が好適である。なお、上記ディッピング成形法において用いる基材としては特に限定されず、例えば、ガラスクロス、アラミド繊維、ポリパラフェニレンベンゾオキサゾール繊維等が挙げられる。
【０１２９】
本発明の基板用材料、シート、積層板、樹脂付き銅箔、銅張積層板、ＴＡＢ用テープ、プリント基板、プリプレグ、接着性シート及び光回路形成材料は、本発明の樹脂組成物からなることにより、高温物性、寸法安定性、耐溶剤性、耐湿性及びバリア性に優れ、多工程を通じて製造される場合でも高い歩留りで得ることができる。なお、本明細書において、シートには自立性のないフィルム状のシートも含む。なお、これらのシートのすべりを良くするために表面にエンボス加工が施されていてもよい。
【０１３０】
熱可塑性樹脂の場合、設備及び製造コストが安くすむだけでなく、上述の加工がシート成形時に同時に出来たり、簡易な方法で後加工できたりして賦形性に優れている。また、溶融することにより再利用可能であり、環境負荷低減といった利点もある。
【０１３１】
また、本発明の樹脂組成物は、熱可塑性樹脂中に層状珪酸塩がナノメートルサイズで微分散していることから低線膨張率、耐熱性、低吸水率であることに加え、高い透明性をも実現できる。従って、本発明の樹脂組成物は、光パッケージの形成材料、光導波路材料、接続材料、封止材料等の光回路形成材料として好適に用いることができる。
【０１３２】
【実施例】
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。
【０１３４】
（実施例１）
小型押出機（日本製鋼所社製、ＴＥＸ３０）中に、熱可塑性樹脂として変性ポリフェニレンエーテル系樹脂（旭化成工業社製、ザイロン（ＰＫＬ）Ｘ９１０２）１００重量部、層状珪酸塩としてジステアリルジメチル４級アンモニウム塩で有機化処理が施された膨潤性フッ素マイカ（コープケミカル社製、ソマシフＭＡＥ−１００）３０重量部をフイードし、２８０℃で溶融混練してストランド状に押出し、押出されたストランドをペレタイザーによりペレット化することによりマスターバッチを作製した。次いで小型押出機（日本製鋼所社製、ＴＥＸ３０）中に、熱可塑性樹脂としてポリエーテルエーテルケトン１００重量部、得られたマスターバッチ９．５重量部をフイードし、窒素気流下、４００℃で溶融混練して押出し、押出されたストランドをペレタイザーによりペレット化することにより樹脂組成物からなるペレットを得た。次いで、得られた樹脂組成物からなるペレットを窒素気流下、上下各４００℃に温調した熱プレスでプレスすることにより圧延して、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４４】
（実施例２）
イソボルニルアクリレート９２．３ｇを５００ｍｌフラスコに秤取し、このフラスコに合成ヘクトライト（コープケミカル社製、ルーセンタイトＳＴＮ）を１０重量％含有するジメチルホルムアミド（ＤＭＦ）溶液７７．０ｇを加えた後、１時間撹拌を行い、クレイ含有イソボルニルアクリレート溶液を得た。次いで、８０℃のオーブン気流下で得られたクレイ含有イソボルニルアクリレート溶液からＤＭＦを留去し、クレイ含有イソボルニルアクリレートを得た。得られたクレイ含有イソボルニルアクリレートに光重合開始剤（チバスペシャリティケミカル社製、イルガキュア６５１）０．９ｇを添加し、均一状態とした後、３６５ｎｍの紫外線を１ｍＷ／ｃｍ²の照度にて１０分間照射し、更に１６０℃の熱プレスを行い、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４５】
（実施例３）
メチルメタクリレート９２．３ｇを１０００ｍｌフラスコに秤取し、このフラスコに合成ヘクトライト（コープケミカル社製、ルーセンタイトＳＴＮ）を１０重量％含有するメチルエチルケトン（ＭＥＫ）溶液７７．０ｇ及びＭＥＫ２００ｇを加え、湯浴により８０℃にした状態で撹拌を行った。次いで、湯浴により８０℃にした状態で撹拌を行っているフラスコにアゾイソブチロニトリル（ＡＩＢＮ）２．５gとＭＥＫ１００ｍｌとからなるＡＩＢＮ溶液を２０ｍｌずつ５回に分けて１時間おきに添加し、最後の添加後、更に２時間８０℃に保持した。得られた反応混合物から減圧加熱乾燥によりＭＥＫを留去した後、１６０℃の熱プレスを行い、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４７】
（比較例１）
膨潤性フッ素マイカ（コープケミカル社製、ソマシフＭＡＥ−１００）を配合しなかったこと以外は実施例１と同様にして樹脂組成物、及び、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１５５】
（比較例２）
イソボルニルアクリレート９２．３ｇに光重合開始剤（チバスペシャリティケミカル社製、イルガキュア６５１）０．９ｇを添加し、均一状態とした後、３６５ｎｍの紫外線を１ｍＷ／ｃｍ²の照度にて１０分間照射し、更に１６０℃で熱プレスを行い、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１５６】
＜評価＞
実施例１〜３及び比較例１、２で作製した板状成形体の性能を以下の項目について評価した。結果は表１，表２に示した。
【０１５７】
（１）熱膨張係数の測定
板状成形体を裁断して３ｍｍ×２５ｍｍにした試験片を、ＴＭＡ（Ｔｈｅｒｍｏｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｙｓ）装置（セイコー電子社製、ＴＭＡ／ＳＳ１２０Ｃ）を用いて、昇温速度５℃／分で昇温し、平均線膨張率（以下、「ＣＴＥ」と記載することがある）の測定を行い、以下の項目について評価を行った。
【０１５８】
・樹脂組成物のガラス転移温度よりも１０℃〜５０℃高い温度での平均線膨張率（α２）［℃^-1］。
・樹脂組成物のガラス転移温度よりも１０℃〜５０℃高い温度での平均線膨張率（α２）を、樹脂組成物のガラス転移温度よりも５０℃〜１０℃低い温度での平均線膨張率（α１）で除して求めた平均線膨張率比（α２／α１）。
・５０〜１００℃での平均線膨張率［℃^-1］及び２００〜２４０℃での平均線膨張率［℃^-1］。
・１５０〜２００℃での平均線膨張率を、５０〜１００℃での平均線膨張率で除して求めた平均線膨張率比（１）、及び、２５０〜３００℃での平均線膨張率を、５０〜１００℃での平均線膨張率で除して求めた平均線膨張率比（２）。
・板状成形体を２５℃から３００℃まで昇温したときの長さの変化量を、板状成形体の２５℃での長さで除して求めた変化率（％）。
・上記式（１）で表される平均線膨張率比（３）。
・樹脂組成物のＴｇよりも１０℃〜５０℃高い温度での平均線膨張率を、各実施例に対応する比較例で作製した樹脂組成物のＴｇよりも１０℃〜５０℃高い温度での平均線膨張率でそれぞれ除して求めた改善率。
【０１５９】
（２）層状珪酸塩の平均層間距離
Ｘ線回折測定装置（リガク社製、ＲＩＮＴ１１００）を用いて、厚さ２ｍｍの板状成形体中の層状珪酸塩の積層面の回折より得られる回折ピークの２θを測定し、下記式（５）のブラックの回折式により、層状珪酸塩の（００１）面間隔ｄを算出し、得られたｄを平均層間距離（ｎｍ）とした。
λ＝２ｄｓｉｎθ ・・・式（５）
上記式（５）中、λは０．１５４であり、θは回折角を表す。
【０１６０】
（３）５層以下の積層体として分散している層状珪酸塩の割合厚さ１００μｍの板状成形体を透過型電子顕微鏡により１０万倍で観察し、一定面積中において観察できる層状珪酸塩の積層体の全層数Ｘ及び５層以下で分散している層状珪酸塩の層数Ｙを計測し、下記式（４）により５層以下の積層体として分散している層状珪酸塩の割合（％）を算出した。
【０１６１】
【数５】

【０１６２】
（４）吸水率の測定
厚さ１００μｍの板状成形体を３×５ｃｍの短冊状にした試験片を作製し、８０℃で５時間乾燥させた後の重さ（Ｗ１）を測定した。次いで、試験片を水に浸漬し、２５℃の雰囲気下で２４時間放置した後取り出し、ウエスで丁寧に拭き取った後の重さ（Ｗ２）を測定した。下記式により吸水率を求めた。
吸水率（％）＝（Ｗ２−Ｗ１）／Ｗ１×１００
【０１６３】
（５）湿度線膨張率の測定
厚さ１００μｍの板状成形体を５０℃３０％Ｒｈの恒温恒湿器に２４時間放置後の寸法（Ｌ１）を測定した。次いで、板状成形体を５０℃８０％Ｒｈの恒温恒湿器に２４時間放置後の寸法（Ｌ２）を測定した。下記式により湿度線膨張率を求めた。
湿度線膨張率［％ＲＨ-1］＝（Ｌ２−Ｌ１）／Ｌ１／（８０−３０）
【０１６４】
（６）誘電率の測定
インピーダンス測定器（ＨＰ社製、ＨＰ４２９１Ｂ）を用いて、周波数１ＭＨｚ付近の誘電率を測定した。
【０１６６】
（７）溶解度パラメーターの測定
Ｆｅｄｏｒｓの計算式により算出した。
【０１６７】
（８）加熱１０％重量減少温度の測定
サンプル５〜１０ｍｇを１５０℃で5時間乾燥させた後、ＴＧ／ＤＴＡ装置（セイコー電子社製、ＴＧ／ＤＴＡ３２０）を用いて、以下の測定条件により測定した。
【０１６８】
測定温度：２５〜６００℃
昇温速度：１０℃／ｍｉｎ
窒素ガス：２００ｍｌ／ｍｉｎ
【０１６９】
【表１】

【０１７０】
【表２】

【０１７１】
【発明の効果】
本発明によれば、力学的物性、寸法安定性、耐熱性、難燃性等に優れ、特に高温物性に優れた樹脂組成物、基板用材料、シート、積層板、樹脂付き銅箔、銅張積層板、ＴＡＢ用テープ、プリント基板、プリプレグ、接着シート及び光回路形成材料を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and in particular, a resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil, a copper-clad laminate excellent in high-temperature properties TAB tape, printed circuit board, prepreg, adhesive sheet and optical circuit forming material.
[0002]
[Prior art]
2. Description of the Related Art In recent years, electronic devices with high performance, high functionality, and miniaturization are rapidly progressing, and there is an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. As a result, further improvements in physical properties such as heat resistance, mechanical strength, and electrical characteristics are required for electronic component materials. For example, a packaging method for semiconductor elements and a wiring board for mounting semiconductor elements. However, higher density, higher functionality, and higher performance are required.
[0003]
Multilayer printed circuit boards used in electronic devices are composed of a plurality of insulating substrates, and conventionally, as this interlayer insulating substrate, for example, a thermosetting resin prepreg in which a glass cloth is impregnated with a thermosetting resin, Films made of thermosetting resins or photocurable resins have been used. Even in the multilayer printed circuit board, it is desired to make the interlayer extremely thin for high density and thinning, and an interlayer insulating board using a thin glass cloth or an interlayer insulating board not using a glass cloth is required. ing. As such an interlayer insulating substrate, for example, those made of rubber (elastomer), thermosetting resin material modified with acrylic resin, thermoplastic resin material containing a large amount of inorganic filler, etc. are known. In Patent Document 1 below, an inorganic filler having a predetermined particle size is blended in a varnish mainly composed of a high molecular weight epoxy polymer and a polyfunctional epoxy resin, and applied to a support to form an insulating layer. A method for manufacturing a multilayer insulating substrate is disclosed.
[0004]
However, in the multilayer insulating substrate produced by the above production method, in order to sufficiently improve the mechanical properties such as mechanical strength by securing the interface area between the inorganic filler and the high molecular weight epoxy polymer or polyfunctional epoxy resin. In addition, it is necessary to add a large amount of an inorganic filler, which causes problems in processing such as an increase in the manufacturing process and difficulty in thinning the interlayer.
[0005]
In addition, interlayer insulation substrates that use thin glass cloth and interlayer insulation substrates that do not use glass cloth have problems such as insufficient heat resistance and dimensional stability. There was a problem that often occurred.
[0006]
The multilayer printed circuit board is manufactured by a build-up method for obtaining a multilayer laminate by repeating circuit formation and lamination on a layer, a batch lamination method for laminating layers on which circuits are formed, or the like. In any manufacturing method, since the number of processes is large, the quality of the material greatly affects the yield, and the process includes a plating process, a curing process, a solder reflow process, and the like. , Heat resistance and dimensional stability at high temperatures are required. Specifically, for example, resistance to acids, alkalis, and organic solvents; low moisture absorption that affects electrical characteristics; dimensional stability at high temperatures and after heating that affects high-precision circuit connections between upper and lower layers; Heat resistance up to 260 ° C required for mounting with lead-free solder; copper migration that affects connection reliability is unlikely to occur.
[0007]
For example, build-up boards and printed multilayer boards used in IC packages may be subject to high-temperature conditions due to heat generation, and it is required to maintain high reliability even in such an environment. If it is large, there is a problem that peeling occurs from a metal wiring such as copper forming a circuit, causing a short circuit or disconnection. In addition, even in a flexible multilayer substrate that has recently attracted attention as a thin substrate, the thermal dimensional change between the adhesive layer that bonds single-layer flexible substrates to each other, the polyimide film that forms the flexible substrate, and the metal wiring such as copper that forms the circuit If the difference is large, the same problem occurs.
[0008]
Patent Document 1 below discloses a technique for improving high-temperature physical properties by using an epoxy resin having excellent heat resistance and an inorganic compound in combination, but the effect of improving physical properties at a temperature higher than the glass transition temperature is disclosed. Almost no effect is seen, and the effect of improvement is small even at temperatures below the glass transition temperature. In addition, no improvement in hygroscopicity or solvent resistance can be expected.
[0009]
Conventionally, a method using an inorganic filler has been known as a method for reducing the linear expansion coefficient at a temperature lower than the glass transition temperature, but it has not been compatible with high-temperature treatment such as solder reflow. In recent years, lead-free solder has been used in consideration of the environment, and the temperature of the solder reflow process has further increased. Therefore, even if a resin with high heat resistance is used, the wire above the glass transition temperature is used. There was a problem that the expansion rate was large and problems occurred during high temperature treatment.
[0010]
In recent years, the progress of semiconductor packaging technology has been remarkable. Among them, TAB (Tape Automated Bonding) can easily form multi-pins because conductor patterns can be formed at an extremely high density, and wires can be used for bonding. Since it is possible to wire-connect the entire lead to a semiconductor element at one time without using it, development of a high-density mounting technology is being actively promoted.
[0011]
There are two types of TAB tapes, a two-layer structure and a three-layer structure, but a three-layer structure (hereinafter abbreviated as three-layer TAB) generally bonds a conductive foil such as copper foil and a heat-resistant resin film. Even if a resin film having excellent characteristics such as heat resistance and chemical resistance is used, it has an adhesive layer that is inferior in heat resistance, so that the characteristics could not be fully utilized.
[0012]
On the other hand, in general, a two-layer structure TAB (hereinafter abbreviated as two-layer TAB) is excellent in heat resistance as a TAB because it does not have an adhesive layer in the base film, but is practically used because of its difficulty in production. There were few things.
[0013]
Polyimide film, among various organic polymers, has excellent heat resistance, low temperature characteristics, chemical resistance, electrical characteristics, etc., and is used as a material for electrical and electronic equipment. Widely used.
[0014]
However, even this polyimide does not sufficiently satisfy the required performance, and it is required to have various performances depending on the application. In particular, as an electronic material application, a polyimide having a low water absorption rate is desired for high functionality and miniaturization. By reducing the water absorption rate, it is possible to suppress problems such as a decrease in electrical characteristics such as a dielectric constant due to water absorption and a dimensional change due to hygroscopic expansion. In addition to water absorption, taking TAB tape as an example, there are many processes that receive stress and temperature changes, and the base material organic insulation film has little dimensional change due to stress or temperature changes. Is desired.
[0015]
As described above, with high performance, high functionality, and downsizing, TAB tapes, flexible printed circuit board base films, and laminated board resins have less dimensional change due to heat and water absorption besides heat resistance. It is desired that the elastic modulus is high. However, a polyimide film that sufficiently satisfies these performances has not been obtained at present.
[0016]
Speaking of polyimide film, the product name “Kapton” manufactured by Toray DuPont Co., Ltd., the product name “Upilex” manufactured by Ube Industries, Ltd., and the product name “Apical” manufactured by Kaneka Chemical Co., Ltd. A polyimide film such as is used. Although these films have high heat resistance, they are decomposed before reaching the softening temperature, so that the films are formed by a solution casting method. In addition, the equipment cost and the manufacturing cost are increased, and further, there is a problem that it is difficult to perform molding by heat.
[0017]
On the other hand, in recent years, with the progress of optical communication technology, it has been demanded that optical communication devices be connected at low cost. Therefore, attention has been paid to optical communication materials made of polymer materials. However, when a conventional polymer material is used as an optical communication material, there are various problems.
[0018]
The polymer material for optical communication is required to have low loss, excellent heat resistance, a low coefficient of thermal linear expansion, low moisture permeability, and easy control of the refractive index.
[0019]
Note that low loss means that the propagation loss is small because the polymer material has almost no absorption band in the wavelength band used for optical communication.
In the following Patent Document 2, a polymer optical communication material formed on a substrate such as silicon having a coefficient of thermal expansion close to 10 times the coefficient of thermal expansion of a semiconductor or metal material and having a low coefficient of thermal expansion. However, stress may be applied to cause polarization dependency of the optical communication material, warpage of the optical communication material and the substrate, or the edge of the polymer optical communication material may peel off from the substrate. Are listed.
[0020]
Patent Document 3 describes a problem that a fiber strand protrudes from a jacket due to a difference in thermal expansion coefficient between the fiber strand (quartz glass) and a resin case, or a crack occurs in the fiber strand due to stress concentration. ing.
[0021]
Further, in Patent Document 4, when the optical waveguide substrate and the optical fiber are connected using an adhesive, if the difference in thermal expansion between the optical waveguide substrate and the connection component is large, a positional shift due to thermal expansion occurs, and a stable optical It is described that connection with a waveguide cannot be realized.
[0022]
With respect to moisture permeability, in Patent Document 3, when water vapor penetrates into the hollow case, condensation occurs on the surface of the optical element or the fiber strand, causing corrosion of the optical element or causing crack growth to proceed. There is a problem that the wire is broken, and it is described that these factors, together with thermal expansion, comprehensively reduce the reliability of optical communication parts using polymer materials. In addition, if the hygroscopic property is high, light absorption due to the O—H bond of moisture is likely to occur, and from this reason, a material having low hygroscopic property is required.
[0023]
With regard to heat resistance, when optical communication is introduced to terminal equipment, conversion from optical signals to electrical signals or conversion from electrical signals to optical signals is required. A polymeric material will be used. Accordingly, the polymer material for optical communication needs to have heat resistance against the process temperature at the time of manufacturing the printed circuit board and heat resistance from the electric circuit at the time of use. Non-Patent Document 1 describes solder heat resistance as a required characteristic.
[0024]
As described above, materials that satisfy physical properties such as transparency, heat resistance, low linear expansion coefficient, and low hygroscopicity are desired as optical communication materials.
On the other hand, Patent Document 5 below describes that a fluorinated polyimide having a rigid skeleton achieves a low coefficient of thermal expansion.
[0025]
Patent Document 6 below discloses a polymer optical waveguide comprising a core layer and a clad layer surrounding the core layer, the polymer optical waveguide having a second clad layer having a thermal expansion coefficient smaller than that of the clad layer outside the clad layer. Is disclosed. Here, it is said that by making the polymers constituting the cladding layer and the second cladding layer different, the thermal expansion coefficient of the second cladding layer can be made relatively low, and the difference in thermal expansion coefficient from the electric / optical element can be reduced. It is shown.
[0026]
Further, in Patent Document 7 below, the end face of the optical communication material is sealed with a resin so that the resin adheres the insulating film forming the optical communication material and the substrate, and the peeling at the end where stress concentrates. It is stated that it can be prevented.
[0027]
Patent Document 7 below describes that the thermal expansion coefficient can be lowered by using a polyimide film having a specific structure as the resin for the optical waveguide.
[0028]
The fluorinated polyimide described in Patent Document 5 below is inferior in transparency to other types of fluorinated polyimide, has a high refractive index of 1.647, and is used as a material constituting a clad layer of an optical communication material. It was not appropriate.
[0029]
On the other hand, in the optical waveguide resin containing the particles described in Patent Document 6 below, it has been suggested that both low linear expansion coefficient and transparency may be achieved, but in order to actually realize the low linear expansion coefficient. A large amount of particles must be added. Therefore, when a large amount of particles are added, it is difficult to achieve sufficient transparency. Further, when a large amount of particles are contained, there is a problem that the resin composition becomes brittle. In addition, when a large amount of particles are added, hydrophilicity is increased and hygroscopicity may be increased.
[0030]
Further, in the configuration described in Patent Document 2 below, the number of manufacturing processes increases, and an increase in cost is inevitable.
On the other hand, when a polyimide-based film having a specific structure described in Patent Document 7 is used as an optical waveguide resin, it is difficult to achieve low hygroscopicity, although the thermal expansion coefficient can be lowered, and the cost is still high. I had to stay high.
[0031]
Therefore, the optical circuit forming material is also excellent in transparency, heat resistance, low linear expansion coefficient and low hygroscopicity, and it has been difficult to realize a material capable of realizing particularly high transparency.
[0032]
[Patent Document 1]
JP 2000-183539 A
[Patent Document 2]
JP 2001-183539 A
[Patent Document 3]
WO98 / 45741
[Patent Document 4]
JP-A-9-152522
[Patent Document 5]
Japanese Patent No. 2843314
[Patent Document 6]
JP 2001-108854 A
[Patent Document 7]
JP 2001-4850 A
[Non-Patent Document 1]
Hitachi Technical Report No. 37 (July 2001), pp. 7-16
[0033]
[Problems to be solved by the invention]
In view of the above situation, the present invention is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and in particular, a resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil excellent in high temperature properties An object of the present invention is to provide a copper-clad laminate, a TAB tape, a printed board, a prepreg, an adhesive sheet, and an optical circuit forming material.
[0034]
[Means for Solving the Problems]
The present invention is a resin composition for an electronic material or optical circuit containing 100 parts by weight of a thermoplastic resin and 0.5 to 50 parts by weight of a layered silicate, wherein the thermoplastic resin is Functional group modified A combination of a polyphenylene ether resin and a polyether ether ketone resin, Poly Isovo Le Nyl acrylate, and Poly The average linear expansion coefficient (α2) from any one of methyl methacrylate to a temperature that is 10 ° C. higher than the glass transition temperature of the resin composition and 50 ° C. higher than the glass transition temperature of the resin composition is 1. 0x10 ^-3 [℃ ^-1 And the average linear expansion coefficient (α2) from a temperature lower by 50 ° C. than the glass transition temperature of the resin composition to a temperature lower by 10 ° C. than the glass transition temperature of the resin composition. The resin composition has an average coefficient of linear expansion ratio (α2 / α1) obtained by dividing by (α1) of 70 or less.
Further, the present invention is a resin composition for electronic materials or optical circuit forming containing 100 parts by weight of a thermoplastic resin and 0.5 to 50 parts by weight of a layered silicate, wherein the thermoplastic resin is Functional group modified A combination of a polyphenylene ether resin and a polyether ether ketone resin, Poly Isovo Le Nyl acrylate, and Poly Any of methyl methacrylate, and the thermoplastic resin is Functional group modified In the case of a combination of a polyphenylene ether resin and a polyether ether ketone resin, the layered silicate is swellable mica, and the thermoplastic resin is Poly Isovo Le Nyl acrylate or Poly In the case of methyl methacrylate, the layered silicate is hectorite, and is an average line from a temperature 10 ° C. higher than the glass transition temperature of the resin composition to a temperature 50 ° C. higher than the glass transition temperature of the resin composition. Expansion coefficient (α2) is 1.0 × 10 ^-3 [℃ ^-1 And the average linear expansion coefficient (α2) from a temperature lower by 50 ° C. than the glass transition temperature of the resin composition to a temperature lower by 10 ° C. than the glass transition temperature of the resin composition. The resin composition has an average coefficient of linear expansion ratio (α2 / α1) obtained by dividing by (α1) of 70 or less.
[0035]
The present invention is described in detail below.
The resin composition of the present invention has an average coefficient of linear expansion (from 10 ° C. higher than the glass transition temperature of the resin composition (hereinafter also referred to as Tg) to 50 ° C. higher than the glass transition temperature of the resin composition ( (Hereinafter also referred to as α2) is 3.0 × 10 ^-3 [℃ ^-1 It is the following. 3.0 × 10 ^-3 [℃ ^-1 ] By the following, the resin material comprising the resin composition of the present invention has a small dimensional change when heat-treated at a high temperature, and warpage occurs due to a difference in shrinkage when laminated with a copper foil or the like, It will not peel off. Preferably, 1.0 × 10 ^-3 [℃ ^-1 ], More preferably 8.0 × 10 ^-Four [℃ ^-1 ], More preferably 5.0 × 10 ^-Four [℃ ^-1 It is the following.
[0036]
The average linear expansion coefficient can be measured by a method according to JIS K7197. For example, a test of about 3 mm × 15 mm using a TMA (Thermal Mechanical Analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C). It can be determined by heating the piece at a heating rate of 5 ° C./min.
[0037]
In the resin composition of the present invention, α2 is an average linear expansion coefficient (hereinafter also referred to as α1) from a temperature 50 ° C. lower than the Tg of the resin composition to a temperature 10 ° C. lower than the glass transition temperature of the resin composition. It is preferable that the average coefficient of linear expansion ratio (α2 / α1) obtained by dividing by () is 70 or less. When it is 70 or less, the resin material comprising the resin composition of the present invention has a small dimensional change in the vicinity of Tg and does not cause wrinkles or warpage in the vicinity of Tg when used as a laminated material or a laminated material. More preferably, it is 15 or less, More preferably, it is 10 or less, Most preferably, it is 5 or less.
[0038]
The resin composition of the present invention has an average linear expansion coefficient of 4.5 × 10 5 at 50 to 100 ° C. ^-Five [℃ ^-1 The average linear expansion coefficient at 200 to 240 ° C. is 7 × 10 ^-Five [℃ ^-1 It is preferable that Average linear expansion coefficient at 50-100 ° C. is 4.5 × 10 ^-Five [℃ ^-1 The average linear expansion coefficient at 200 to 240 ° C. is 7 × 10 ^-Five [℃ ^-1 The resin material comprising the resin composition of the present invention is suitable for electronic materials and the like that require a small amount of dimensional change under normal use conditions and require high precision, and solder reflow. Even in a manufacturing process or the like in which a high temperature treatment such as the above is performed, warpage and peeling do not occur. The average linear expansion coefficient at 50 to 100 ° C. is more preferably 4.0 × 10 ^-Five [℃ ^-1 ], More preferably 3.5 × 10 ^-Five [℃ ^-1 It is the following. The average linear expansion coefficient at 200 to 240 ° C. is more preferably 6.5 × 10. ^-Five [℃ ^-1 ], More preferably 5.5 × 10 ^-Five [℃ ^-1 It is the following.
[0039]
In the resin composition of the present invention, the average linear expansion coefficient ratio (1) obtained by dividing the average linear expansion coefficient at 150 to 200 ° C. by the average linear expansion coefficient at 50 to 100 ° C. is 2.0 or less. In addition, the average linear expansion coefficient ratio (2) obtained by dividing the average linear expansion coefficient at 250 to 300 ° C. by the average linear expansion coefficient at 50 to 100 ° C. is preferably 20 or less. When the average linear expansion coefficient ratio (1) is 2.0 or less and the average linear expansion coefficient ratio (2) is 20 or less, the resin material comprising the resin composition of the present invention has dimensional stability against heating. Therefore, even in a manufacturing process or the like in which high-temperature processing such as reflow of lead-free solder is performed, warping or peeling does not occur, and it is suitable for applications that are used at high temperatures. The average linear expansion coefficient ratio (1) is more preferably 1.5 or less, and still more preferably 1.2 or less. The average linear expansion coefficient (2) is more preferably 15 or less, still more preferably 10 or less.
[0040]
In the resin composition of the present invention, the amount of change in length when a resin piece made of the resin composition is heated from 25 ° C. to 300 ° C. is divided by the length of the resin piece made of the resin composition at 25 ° C. It is preferable that the change rate obtained in this way is 7% or less. When it is 7% or less, the resin material comprising the resin composition of the present invention has good dimensional stability with respect to temperature, and even when laminated with other materials or laminated, There is no warping or peeling. More preferably, it is 6% or less, More preferably, it is 5% or less.
[0041]
The resin composition of the present invention preferably has an average linear expansion coefficient ratio (3) represented by the following formula (1) of 1.5 or less.
[0042]
[Expression 2]

[0043]
When the average linear expansion coefficient ratio (3) is 1.5 or less, the resin material comprising the resin composition of the present invention has good dimensional stability, and even when laminated with other materials or pasted together. No warping or peeling during manufacturing and use. More preferably, it is 1.4 or less, More preferably, it is 1.3 or less.
[0044]
The resin composition of the present invention has an average linear expansion coefficient (α2) of a resin composition from a temperature 10 ° C. higher than the glass transition temperature of the resin composition to a temperature 50 ° C. higher than the glass transition temperature of the resin composition. ,the above Thermoplastic resin contained in resin composition From a temperature 10 ° C. higher than the glass transition temperature of Thermoplastic resin contained in resin composition Up to 50 ° C above the glass transition temperature of Thermoplastic resin contained in resin composition It is preferable that the improvement rate obtained by dividing by the average linear expansion coefficient is 0.50 or less. If it is 0.50 or less, the resin material comprising the resin composition of the present invention has sufficiently improved high-temperature properties due to the inorganic compound, and causes problems in the manufacturing process for high-temperature treatment and use at high temperatures. There is nothing. More preferably, it is 0.35 or less, More preferably, it is 0.25 or less.
[0045]
Since the resin composition of the present invention has a low average linear expansion coefficient at a high temperature above the glass transition temperature as described above, the high temperature physical properties such as dimensional stability at a high temperature are improved, and the plating process, curing process, lead It can be used for a resin material that does not warp or peel off even in a high-temperature treatment step such as a free solder reflow step.
[0046]
The resin composition of the present invention preferably has a tensile modulus of 6 GPa or more and a dielectric constant at 1 MHz of 3.3 or less. When the resin composition of the present invention is used as a TAB tape, if the tensile elastic modulus is less than 6 GPa, it is necessary to increase the thickness in order to ensure the required strength, and it becomes impossible to produce a small TAB. If the dielectric constant at 1 MHz is larger than 3.3, it is necessary to increase the thickness in order to ensure sufficient reliability, and it may be impossible to manufacture a small TAB.
[0047]
The resin composition of the present invention has a water absorption of 1.0% or less and a coefficient of linear expansion of 1.5 × 10. ^-Five [% RH ^-1 It is preferable that If the water absorption rate exceeds 1.0%, when a substrate is produced using the resin composition of the present invention, dimensional changes occur during absolutely dry and water absorption, which makes fine wiring difficult and cannot be miniaturized. There is. More preferably, it is 0.7% or less, More preferably, it is 0.3% or less. Humidity linear expansion coefficient is 1.5 × 10 ^-Five [% RH ^-1 ], Warpage occurs in the obtained substrate, and the copper foil may be peeled off due to the difference in the change rate of the copper foil. More preferably 1.2 × 10 ^-Five [% RH ^-1 ], More preferably 1.0 × 10 ^-Five [% RH ^-1 It is the following.
[0048]
The resin composition of the present invention has a water absorption of 1.0% or less, a dielectric constant at 1 MHz of 3.3 or less, and When the resin composition is immersed in water to absorb water The dielectric constant after water absorption treatment is preferably 3.4 or less. If the electrical characteristics change greatly due to water absorption, the reliability may not be maintained, and the material may explode in the manufacturing process such as solder reflow and the yield may decrease.
[0049]
In addition, the said water absorption is the weight W1 when it dries at 80 degreeC for 5 hours about the test piece which made the film of thickness 50-100 micrometers into a 3x5 cm strip shape, and is immersed in water, and is 24 at 25 degreeC. It is a value obtained by measuring the weight W2 when the surface is thoroughly wiped off after standing for a period of time and calculated by the following formula.
[0050]
Water absorption (%) = (W2−W1) / W1 × 100
The resin composition of the present invention preferably has a glass transition temperature of 100 ° C. or higher. When the glass transition temperature is 100 ° C. or higher, when the resin composition of the present invention is used for a substrate or the like, high-temperature properties, particularly lead-free soldering heat resistance and dimensional stability against heating are improved. More preferably, it is 140 degreeC or more, More preferably, it is 200 degreeC or more.
[0051]
The resin composition of the present invention preferably has a glass transition temperature of 100 ° C. or higher and a dielectric constant at 1 MHz of 3.3 or lower. Since the glass transition temperature is 100 ° C. or higher and the dielectric constant at 1 MHz is 3.3 or lower, the resin material comprising the resin composition of the present invention has high-temperature properties, particularly lead-free solder heat resistance and The dimensional stability against heating is improved, high reliability required for an electronic material can be obtained, and the transmission speed necessary for an electronic material can be obtained even in the transmission speed of a signal in a high frequency region. The glass transition temperature is more preferably 140 ° C. or higher, and further preferably 200 ° C. or higher. The dielectric constant of 1 MHz is more preferably 3.2 or less, and still more preferably 3.0 or less.
[0052]
The resin composition of the present invention has the above-described excellent high-temperature physical properties, and contains a thermoplastic resin and an inorganic compound.
Examples of the thermoplastic resin include a polyphenylene ether resin; a functional group-modified polyphenylene ether resin; a polyphenylene ether resin or a functional group-modified polyphenylene ether resin; a polyphenylene ether resin such as a polystyrene resin; or a functional group-modified polyphenylene. Mixtures of thermoplastic resins compatible with ether resins; alicyclic hydrocarbon resins; polyether ether ketone resins; polyether sulfone resins; polyester resins; polyolefin resins; polystyrene resins; Alcohol resin; polyvinyl acetate resin; poly (meth) acrylic ester resin; polyoxymethylene resin; thermoplastic polybenzimidazole resin. Among them, polyphenylene ether resin, functional group-modified polyphenylene ether resin, polyphenylene ether resin or a mixture of functional group-modified polyphenylene ether resin and polystyrene resin, alicyclic hydrocarbon resin, polyether ether ketone resin, and Examples thereof include thermoplastic polybenzimidazole resins. In the present invention, the thermoplastic resin is Functional group modified A combination of a polyphenylene ether resin and a polyether ether ketone resin, Poly Isovo Le Nyl acrylate, and Poly One of methyl methacrylate. These thermoplastic resins may be used independently and 2 or more types may be used together. In addition, in this specification, (meth) acryl means acryl or methacryl.
[0053]
The polyphenylene ether resin is a polyphenylene ether homopolymer or polyphenylene ether copolymer composed of repeating units represented by the following formula (2).
[0054]
[Chemical 1]

[0055]
In said formula (2), R1, R2, R3, and R4 represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or an alkoxyl group. These alkyl group, aralkyl group, aryl group and alkoxyl group may each be substituted with a functional group.
[0056]
Examples of the polyphenylene ether homopolymer include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and poly (2,6 -Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether Poly (2-ethyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-) 1,4-phenylene) ether and the like.
[0057]
Examples of the polyphenylene ether copolymer include a copolymer partially containing an alkyl trisubstituted phenol such as 2,3,6-trimethylphenol in the repeating unit of the polyphenylene ether homopolymer, and these polyphenylene ethers. Examples of the copolymer further include a copolymer obtained by graft copolymerization of one or more styrene monomers such as styrene, α-methylstyrene, and vinyl toluene. These polyphenylene ether resins may be used alone or in combination of two or more kinds having different compositions, components, molecular weights and the like.
[0058]
Examples of the functional group-modified polyphenylene ether resin include those obtained by modifying the polyphenylene ether resin with one or more functional groups such as a maleic anhydride group, a glycidyl group, an amino group, and an allyl group. Can be mentioned. These functional group-modified polyphenylene ether resins may be used alone or in combination of two or more. When the polyphenylene ether resin modified with the functional group is used as a thermoplastic resin, the mechanical properties, heat resistance, dimensional stability, etc. of the resin composition of the present invention can be further improved by a crosslinking reaction.
[0059]
Examples of the mixture of the polyphenylene ether resin or the functional group-modified polyphenylene ether resin and the polystyrene resin include the polyphenylene ether resin or the functional group-modified polyphenylene ether resin, a styrene homopolymer; styrene, α- Examples thereof include copolymers with one or more styrene monomers such as methyl styrene, ethyl styrene, t-butyl styrene and vinyl toluene; and mixtures with polystyrene resins such as styrene elastomers.
[0060]
The said polystyrene resin may be used independently and 2 or more types may be used together. Moreover, these polyphenylene ether resins or a mixture of functional group-modified polyphenylene ether resin and polystyrene resin may be used alone or in combination of two or more.
[0061]
The alicyclic hydrocarbon resin is a hydrocarbon resin having a cyclic hydrocarbon group in a polymer chain, and examples thereof include a cyclic olefin, that is, a norbornene monomer homopolymer or copolymer. These alicyclic hydrocarbon resins may be used alone or in combination of two or more.
[0062]
Examples of the cyclic olefin include norbornene, methanooctahydronaphthalene, dimethanooctahydronaphthalene, dimethanododecahydroanthracene, dimethanodecahydroanthracene, trimethanododecahydroanthracene, dicyclopentadiene, 2,3-dihydrocyclopentadiene. , Methanooctahydrobenzoindene, dimethanooctahydrobenzoindene, methanodecahydrobenzoindene, dimethanodecahydrobenzoindene, methanooctahydrofluorene, dimethanooctahydrofluorene, and substituted products thereof. These cyclic olefins may be used independently and 2 or more types may be used together.
[0063]
Examples of the substituent in the substituent such as norbornene include known hydrocarbon groups and polar groups such as an alkyl group, an alkylidene group, an aryl group, a cyano group, an alkoxycarbonyl group, a pyridyl group, and a halogen atom. These substituents may be used alone or in combination of two or more.
[0064]
Examples of the substituent such as norbornene include 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, and 5-ethylidene-2. -Norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl-2 -Norbornene and the like. These substituents such as norbornene may be used alone or in combination of two or more.
[0065]
Examples of commercially available alicyclic hydrocarbon resins include a trade name “Arton” series manufactured by JSR Corporation and a product name “Zeonor” series manufactured by Nippon Zeon Co., Ltd.
[0068]
Examples of the polyether ether ketone resin include those obtained by polycondensation of dihalogenobenzophenone and hydroquinone. As what is marketed among the said polyetheretherketone resin, the brand name "Victrex PEEK" by ICI, etc. are mentioned, for example.
[0069]
Examples of the thermoplastic polybenzimidazole resin include those obtained by polycondensation of dioctadecyl terephthalaldoimine and 3,3′-diaminobenzidine. As what is marketed, the brand name "cerazole" series etc. by Clariant Japan are mentioned, for example.
[0070]
The thermoplastic resin has a solubility parameter (SP value) calculated using the Fedors calculation formula of 42 [J / cm. ^Three ] ^1/2 The above is preferable. According to the Fedors calculation formula, the SP value is the square root of the sum of the molar aggregation energy of each atomic group divided by the volume, and indicates the polarity per unit volume. SP value is 42 [J / cm ^Three ] ^1/2 Because of the above, since it has a large polarity, it has good compatibility with inorganic compounds such as chemically treated layered silicates, and even when layered silicates are used as inorganic compounds, the interlayer of layered silicates Can be spread and dispersed one by one. More preferably 46.2 [J / cm ^Three ] ^1/2 Or more, more preferably 52.5 [J / cm ^Three ] ^1/2 That's it.
[0071]
The SP value is 42 [J / m ^Three ] ^1/2 Examples of the above resins include polyester resins such as polybutylene terephthalate, polybutylene naphthalate, polyethylene terephthalate, and polyethylene naphthalate, and polyamide resins such as polyamide 6, polyamide 66, and polyamide 12. The Examples of the ether ether ketone resin, polyphenylene ether resin, modified polyphenylene ether resin, and polybenzimidazole resin.
[0072]
The thermoplastic resin preferably has a 10% weight loss temperature of 400 ° C. or higher when thermogravimetric measurement is performed in a nitrogen atmosphere. By being 400 degreeC or more, the resin material which consists of a resin composition of this invention does not generate | occur | produce outgas in high temperature processing processes, such as a reflow process of lead-free solder, and becomes a suitable electronic material. More preferably, it is 450 degreeC or more, More preferably, it is 500 degreeC or more. Examples of the resin having a 10% weight loss temperature of 400 ° C. or higher in thermogravimetry in a nitrogen atmosphere include, for example, polyetheretherketone resin Fat, etc. Is mentioned.
[0073]
The resin composition of the present invention contains an inorganic compound.
Examples of the inorganic compound include layered silicates, talc, silica, alumina, glass beads and the like, and among them, layered silicates are preferably used in order to improve high temperature physical properties. In the present specification, the layered silicate means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product.
[0074]
When a particularly high tensile elastic modulus is required, it is preferable to contain a layered silicate and a whisker as the inorganic compound. Although it is known that when a whisker is added to a resin, the elastic modulus is improved, the resin composition containing the whisker so that a high tensile elastic modulus can be achieved has a problem that the moldability deteriorates. In the resin composition of the present invention, by using a layered silicate and whisker as an inorganic compound, a sufficient improvement in elastic modulus can be obtained even with a small amount of whisker.
[0075]
When the whisker is blended with the layered silicate as an inorganic compound, the whisker is preferably 25 to 95% by weight in 100% by weight of the inorganic compound. If the amount is less than 25% by weight, the effect of adding the whisker is not sufficient, and if it exceeds 95% by weight, the effect of adding the layered silicate may not be sufficient.
[0076]
In particular, when a low water absorption rate is required, it is preferable to contain a layered silicate and silica as an inorganic compound. The silica is not particularly limited, and examples thereof include Aerosil manufactured by Nippon Aerosil Co., Ltd. By using layered silicate and silica together as an inorganic compound, the hygroscopicity of the polymer material obtained from the resin composition of the present invention can be effectively reduced. It is known that when silica is added to the resin, the water absorption rate is improved. However, the resin composition containing silica so as to achieve a low water absorption rate has a problem that physical properties such as tensile strength are lowered. . In the resin composition of the present invention, by using a layered silicate and silica in combination as an inorganic compound, a sufficient water absorption reduction effect can be obtained even with a small amount of silica. The proportion of silica in the inorganic compound is preferably in the range of 25 to 95% by weight. If it is less than 25% by weight, the effect of blending silica with layered silicate is not sufficient, and if it exceeds 95% by weight, the effect of adding layered silicate may be impaired.
[0077]
Examples of the layered silicate include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite and nontronite, swelling mica, vermiculite, and halloysite. Among these, at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite is preferably used. These layered silicates may be used alone or in combination of two or more.
[0078]
The crystal shape of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.01 μm, the upper limit is 3 μm, the preferable lower limit of the thickness is 0.001 μm, the upper limit is 1 μm, and the preferable lower limit of the aspect ratio is 20 μm. The upper limit is 500, the more preferred lower limit of the average length is 0.05 μm, the upper limit is 2 μm, the more preferred lower limit of the thickness is 0.01 μm, the upper limit is 0.5 μm, the more preferred lower limit of the aspect ratio is 50, the upper limit Is 200.
[0079]
The layered silicate preferably has a large shape anisotropy effect defined by the following formula (3A). By using a layered silicate having a large shape anisotropy effect, the resin obtained from the resin composition of the present invention has excellent mechanical properties.
[0080]
[Equation 3]

[0081]
The exchangeable metal cation existing between the layers of the layered silicate means a metal ion such as sodium or calcium existing on the surface of the lamellar crystal of the layered silicate, and these metal ions are cations with the cationic substance. Since it has exchangeability, various substances having cationic properties can be inserted (intercalated) between the crystal layers of the layered silicate.
[0082]
Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, A preferable minimum is 50 milliequivalent / 100g, and an upper limit is 200 milliequivalent / 100g. When the amount is less than 50 milliequivalents / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate is reduced by cation exchange, so that the crystal layers are not sufficiently depolarized (hydrophobized). Sometimes. If it exceeds 200 milliequivalents / 100 g, the bonding strength between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.
[0083]
When the resin composition of the present invention is produced using a layered silicate as the inorganic compound, the dispersibility in the resin is improved by chemically modifying the layered silicate to increase the affinity with the resin. Preferably, a large amount of layered silicate can be dispersed in the resin by such chemical treatment. If the layered silicate is not subjected to chemical modification suitable for the resin used in the present invention or the solvent used in the production of the resin composition of the present invention, the layered silicate tends to aggregate and be dispersed in large quantities. However, by applying a chemical modification suitable for the resin or solvent, the layered silicate can be dispersed in the resin without agglomeration even when added in an amount of 10 parts by weight or more. As said chemical modification, it can implement by the chemical modification (1) method-chemical modification (6) method shown below, for example. These chemical modification methods may be used alone or in combination of two or more.
[0084]
The chemical modification (1) method is also referred to as a cation exchange method using a cationic surfactant. Specifically, when the resin composition of the present invention is obtained using a low polar resin such as a polyphenylene ether resin, a layered silicic acid is used in advance. In this method, cation exchange is performed between the salt layers with a cationic surfactant to make it hydrophobic. By making the layers of the layered silicate hydrophobic in advance, the affinity between the layered silicate and the low polarity resin is increased, and the layered silicate can be finely dispersed in the low polarity resin more uniformly.
[0085]
The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Of these, alkyl ammonium ions, aromatic quaternary ammonium ions, or heterocyclic quaternary ammonium ions having 6 or more carbon atoms are preferably used because the crystal layers of the layered silicate can be sufficiently hydrophobized. In particular, when a thermoplastic polyimide resin, polyesterimide resin, or polyetherimide resin is used as the thermoplastic resin, aromatic quaternary ammonium ions or heterocyclic quaternary ammonium ions are preferred.
[0086]
The quaternary ammonium salt is not particularly limited, and examples thereof include trimethyl alkyl ammonium salt, triethyl alkyl ammonium salt, tributyl alkyl ammonium salt, dimethyl dialkyl ammonium salt, dibutyl dialkyl ammonium salt, methyl benzyl dialkyl ammonium salt, and dibenzyl dialkyl ammonium salt. , Trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt; benzylmethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride A quaternary ammonium salt having an aromatic ring such as: a quaternary ammonium salt derived from an aromatic amine such as trimethylphenylammonium; an alkylpyridinium salt, an imidazoli A quaternary ammonium salt having a heterocyclic ring such as a dimethyl salt; a dialkyl quaternary ammonium salt having two polyethylene glycol chains, a dialkyl quaternary ammonium salt having two polypropylene glycol chains, and a trialkyl quaternary having one polyethylene glycol chain Examples include ammonium salts and trialkyl quaternary ammonium salts having one polypropylene glycol chain. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N N-dimethylammonium salt and the like are preferred. These quaternary ammonium salts may be used alone or in combination of two or more.
[0087]
The quaternary phosphonium salt is not particularly limited. For example, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethylphosphonium salt, distearyl And dibenzylphosphonium salts. These quaternary phosphonium salts may be used alone or in combination of two or more.
[0088]
In the chemical modification (2) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method has a chemical affinity with a functional group or a hydroxyl group capable of chemically bonding to the hydroxyl group. This is a method of chemical treatment with a compound having at least one functional group having a large molecular weight at the molecular end.
[0089]
The functional group capable of chemically bonding to the hydroxyl group or the functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, a carboxyl group (including dibasic acid anhydrides), A hydroxyl group, an isocyanate group, an aldehyde group, etc. are mentioned.
[0090]
The compound having a functional group capable of chemically bonding to the hydroxyl group or the compound having a functional group having a large chemical affinity with the hydroxyl group is not particularly limited. For example, a silane compound, titanate compound, or glycidyl compound having the functional group. , Carboxylic acids, alcohols and the like. These compounds may be used independently and 2 or more types may be used together.
[0091]
The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-amino. Propyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltri Ethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ- Minopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri An ethoxysilane etc. are mentioned. These silane compounds may be used independently and 2 or more types may be used together.
[0092]
In the chemical modification (3) method, the hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method has a functional group capable of chemically bonding to the hydroxyl group or a chemical affinity with the hydroxyl group. This is a chemical treatment method using a large functional group and a compound having at least one reactive functional group at the molecular end.
The chemical modification (4) method is a method in which the crystallized surface of the organically modified layered silicate chemically treated by the chemical modification (1) method is chemically treated with a compound having an anionic surface activity.
[0093]
The compound having an anionic surface activity is not particularly limited as long as the layered silicate can be chemically treated by ionic interaction. For example, sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfate ester salt , Secondary higher alcohol sulfates, unsaturated alcohol sulfates and the like. These compounds may be used independently and 2 or more types may be used together.
[0094]
The chemical modification (5) method is a method of chemically treating a compound having one or more reactive functional groups in addition to the anion site in the molecular chain among the compounds having anionic surface activity.
[0095]
In the chemical modification (6) method, an organically modified layered silicate chemically treated by any one of the chemical modification (1) method to the chemical modification (5) method is further used, for example, maleic anhydride-modified polyphenylene ether resin. This is a method using a resin having a functional group capable of reacting with the layered silicate.
[0096]
The layered silicate has an average interlayer distance of 3 nm or more on the (001) plane measured by the wide angle X-ray diffraction measurement method in the resin composition of the present invention. As And some or all Part 5 layers or less In the number of layers dispersion Is It is preferable. The average interlayer distance is 3 nm or more As And some or all Part 5 layers or less In the number of layers dispersion Is As a result, the interface area between the resin and the layered silicate is sufficiently large, and the distance between the flaky crystals of the layered silicate becomes moderate, and high-temperature properties, mechanical properties, heat resistance, dimensional stability The improvement effect by dispersion can be sufficiently obtained.
[0097]
A preferable upper limit of the average interlayer distance is 5 nm. When the thickness exceeds 5 nm, the lamellar silicate crystal flakes separate into layers and weaken so that the interaction is negligible, so that the binding strength at high temperatures becomes weak, and sufficient dimensional stability may not be obtained.
[0098]
In this specification, the average interlayer distance of the layered silicate means the average of the distance between the layers when the flaky crystals of the layered silicate are regarded as a layer, and X-ray diffraction peak and transmission electron microscope photography That is, it can be calculated by a wide-angle X-ray diffraction measurement method.
[0099]
Some or all of the above Part 5 layers or less In the number of layers dispersion Is Specifically, it means that the interaction between the flaky crystals of the layered silicate is weakened and a part or all of the laminate of flaky crystals is dispersed. Preferably, 10% or more of the layered silicate laminate is 5 layers or less In the number of layers 20% or more of the layered silicate laminate is 5 layers or less In the number of layers More preferably, it is dispersed.
[0100]
In addition, the ratio of the layered silicate dispersed as a laminate of 5 layers or less is a layered silicic acid that can be observed in a fixed area by observing the resin composition at a magnification of 50,000 to 100,000 times with a transmission electron microscope. It can be calculated from the following formula (4) by measuring the total number of layers X of the salt laminate and the number of layers Y of the laminate dispersed as a laminate of 5 layers or less.
[0101]
[Expression 4]

[0102]
The number of layers in the layered silicate laminate is preferably 5 layers or less, more preferably 3 layers or less, and even more preferably 1 layer in order to obtain the effect of dispersion of the layered silicate. is there.
[0103]
The resin composition of the present invention uses a layered silicate as the inorganic compound, Layered silicate (001) plane average interlayer distance measured by wide angle X-ray diffraction measurement method is 3 nm or more As And some or all Part 5 layers or less In the number of layers dispersion Is By ensuring that the interface area between the resin and the layered silicate is sufficiently large, the interaction between the resin and the layered silicate surface is increased, the melt viscosity is increased and the moldability is improved. In addition, the mechanical properties such as elastic modulus are improved in a wide temperature range from room temperature to high temperature, the mechanical properties can be maintained even at high temperatures above the Tg or melting point of the resin, and the linear expansion coefficient at high temperatures is kept low. be able to. The reason for this is not clear, but it is considered that even in the temperature range above Tg or the melting point, these physical properties are manifested because the finely dispersed layered silicate acts as a kind of pseudo-crosslinking point. On the other hand, since the distance between the lamellar crystals of the layered silicate is also appropriate, the lamellar crystals of the lamellar silicate move during combustion, and it becomes easy to form a sintered body that becomes a flame retardant coating. Since this sintered body is formed at an early stage during combustion, not only the supply of oxygen from the outside world but also the flammable gas generated by the combustion can be blocked, and the resin composition of the present invention The product exhibits excellent flame retardancy.
[0104]
Furthermore, in the resin composition of the present invention, since the layered silicate is finely dispersed in a nanometer size, when a perforation process is performed on the substrate or the like made of the resin composition of the present invention by a laser such as a carbon dioxide laser, The resin component and the layered silicate component are simultaneously decomposed and evaporated, and the partially remaining layered silicate residue is only a small one of several μm or less and can be easily removed by desmearing. Thereby, it is possible to prevent the occurrence of defective plating due to the residue generated by the drilling process.
[0105]
The method for dispersing the layered silicate in the resin is not particularly limited, for example, a method using an organically modified layered silicate, a method of foaming the resin with a foaming agent after mixing the resin and the layered silicate by a conventional method, Examples thereof include a method using a dispersant. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed in the resin.
[0106]
In the method in which the resin and the layered silicate are mixed by a conventional method and the resin is foamed with a foaming agent, the energy of foaming is used for the dispersion of the layered silicate.
It does not specifically limit as said foaming agent, For example, a gaseous foaming agent, an easily volatile liquid foaming agent, a heat decomposable solid foaming agent etc. are mentioned. These foaming agents may be used independently and 2 or more types may be used together.
[0107]
The method of foaming the resin with a foaming agent after mixing the resin and the layered silicate by a conventional method is not particularly limited. For example, a gaseous foaming agent is added to a resin composition comprising the resin and the layered silicate under high pressure. A method in which the gaseous foaming agent is vaporized in the resin composition to form a foam after impregnation with the above-mentioned method; a thermally decomposable foaming agent is previously contained between the layers of the layered silicate, and the thermally decomposable foaming agent And a method of decomposing the foam by heating to form a foam.
[0108]
The minimum of the compounding quantity with respect to 100 weight part of said thermoplastic resins of the said inorganic compound is 0.1 weight part, and an upper limit is 65 weight part. If it is less than 0.1 parts by weight, the effect of improving high-temperature properties and hygroscopicity is reduced. If it exceeds 65 parts by weight, the density (specific gravity) of the resin composition of the present invention will increase, and the mechanical strength will also decrease, making it impractical. The preferred lower limit is 1 part by weight and the upper limit is 60 parts by weight. When the amount is less than 1 part by weight, a sufficient effect of improving high-temperature physical properties may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 60 parts by weight, the moldability may deteriorate. A more preferred lower limit is 1.5 parts by weight and an upper limit is 50 parts by weight. When the amount is 1.5 to 50 parts by weight, there is no problem in terms of mechanical properties and process suitability, and sufficient flame retardancy is obtained.
[0109]
In the resin composition of the present invention, when a layered silicate is used as the inorganic compound, the lower limit of the amount of the layered silicate is preferably 0.5 parts by weight, and the upper limit is preferably 50 parts by weight. If it is less than 0.5 parts by weight, the effect of improving high-temperature properties and hygroscopicity may be reduced. If it exceeds 50 parts by weight, the density (specific gravity) of the resin composition of the present invention is increased, and the mechanical strength is also decreased, so that it may be impractical. A more preferred lower limit is 1 part by weight and an upper limit is 45 parts by weight. If it is less than 1 weight, sufficient improvement of the high-temperature properties may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 45 parts by weight, the dispersibility of the layered silicate may deteriorate. A more preferred lower limit is 1.5 parts by weight, and an upper limit is 40 parts by weight. When the amount is 1.5 to 40 parts by weight, there is no region causing problems in process suitability, sufficiently low water absorption is obtained, and the effect of reducing the average linear expansion coefficient is sufficiently obtained even in both the α1 and α2 regions. It is done.
[0110]
The resin composition of the present invention preferably further contains a flame retardant that does not contain a halogen-based composition. It should be noted that a trace amount of halogen may be mixed due to the manufacturing process of the flame retardant.
[0111]
The flame retardant is not particularly limited. For example, metal hydroxide such as aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum, calcium hydroxide; metal oxide; red phosphorus or polyphosphoric acid Phosphorus compounds such as ammonium; Nitrogen compounds such as melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate and melamine derivatives obtained by surface treatment thereof; fluororesins; silicone oils; layered double water such as hydrotalcite Japanese products: silicone-acrylic composite rubber and the like. Of these, metal hydroxides and melamine derivatives are preferred. Among the metal hydroxides, magnesium hydroxide and aluminum hydroxide are particularly preferable, and these may be subjected to surface treatment with various surface treatment agents. The surface treatment agent is not particularly limited, and examples thereof include a silane coupling agent, a titanate coupling agent, a PVA surface treatment agent, and an epoxy surface treatment agent. These flame retardants may be used alone or in combination of two or more.
[0112]
When a metal hydroxide is used as the flame retardant, the lower limit of the preferable blending amount of the metal hydroxide with respect to 100 parts by weight of the thermoplastic resin is 0.1 part by weight, and the upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the flame retarding effect may not be sufficiently obtained. If it exceeds 100 parts by weight, the density (specific gravity) of the resin composition of the present invention may become too high, resulting in poor practicality and extremely low flexibility and elongation. A more preferred lower limit is 5 parts by weight and an upper limit is 80 parts by weight. When it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 80 parts by weight, the defect rate due to blistering or the like may increase in the step of performing high temperature treatment. A more preferred lower limit is 10 parts by weight and an upper limit is 70 parts by weight. When the amount is in the range of 10 to 70 parts by weight, there is no region causing problems in mechanical properties, electrical properties, process suitability, etc., and sufficient flame retardancy is exhibited.
[0113]
When a melamine derivative is used as the flame retardant, the lower limit of the preferred blending amount of the melamine derivative with respect to 100 parts by weight of the thermoplastic resin is 0.1 part by weight, and the upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the flame retarding effect may not be sufficiently obtained. If it exceeds 100 parts by weight, mechanical properties such as flexibility and elongation may be extremely lowered. A more preferred lower limit is 5 parts by weight and an upper limit is 70 parts by weight. If it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained when the insulating substrate is thinned. If it exceeds 70 parts by weight, mechanical properties such as flexibility and elongation may be extremely lowered. A more preferred lower limit is 10 parts by weight and an upper limit is 50 parts by weight. When the amount is in the range of 10 to 50 parts by weight, there is no region causing problems in mechanical properties, electrical properties, process suitability, etc., and sufficient flame retardancy is exhibited.
[0114]
The resin composition of the present invention includes, as necessary, thermoplastic elastomers, crosslinked rubber, oligomers, nucleating agents, oxidizers, and the like for the purpose of modifying the properties within a range that does not hinder achievement of the present invention. Additives such as inhibitors (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, lubricants, flame retardant aids, antistatic agents, antifogging agents, fillers, softeners, plasticizers, colorants, etc. May be blended. These may be used alone or in combination of two or more.
[0115]
The thermoplastic elastomers are not particularly limited, and examples thereof include styrene elastomers, olefin elastomers, urethane elastomers, and polyester elastomers. In order to enhance the compatibility with the resin, these thermoplastic elastomers may be functional group-modified. These thermoplastic elastomers may be used alone or in combination of two or more.
[0116]
The crosslinked rubber is not particularly limited, and examples thereof include isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, and urethane rubber. In order to enhance the compatibility with the resin, it is preferable that these crosslinked rubbers are functional group-modified. The functional group-modified crosslinked rubber is not particularly limited, and examples thereof include epoxy-modified butadiene rubber and epoxy-modified nitrile rubber. These crosslinked rubbers may be used alone or in combination of two or more.
[0117]
The oligomers are not particularly limited, and examples thereof include maleic anhydride-modified polyethylene oligomers. These oligomers may be used independently and 2 or more types may be used together.
[0118]
The method for producing the resin composition of the present invention is not particularly limited. For example, each predetermined amount of a resin and an inorganic compound, and each predetermined amount of one or more additives blended as necessary, Direct kneading method of directly blending and kneading at normal temperature or under heating, and a method of removing the solvent after mixing in a solvent; previously blending a predetermined amount or more of an inorganic compound in the resin or a resin other than the resin Then, a master batch kneaded is prepared, and this master batch, the remainder of the predetermined amount of the resin, and each predetermined amount of one or more additives to be blended as necessary are at room temperature or heated. Below, the masterbatch method etc. which knead | mix or mix in a solvent are mentioned.
[0119]
In the master batch method, a master batch in which an inorganic compound is blended with the resin or a resin other than the resin, and a master batch dilution resin containing the resin used when the master batch is diluted to a predetermined inorganic compound concentration The compositions may be the same composition or different compositions.
[0120]
The masterbatch is not particularly limited. For example, at least one resin selected from the group consisting of a polyamide resin, a polyphenylene ether resin, a polyether sulfone resin, and a polyester resin, in which an inorganic compound can be easily dispersed, is used. It is preferable to contain. Although it does not specifically limit as said resin composition for masterbatch dilution, For example, at least 1 sort (s) selected from the group which consists of a thermoplastic polyimide resin excellent in the high temperature physical property, polyetheretherketone resin, thermoplastic polybenzoimidazole resin It is preferable to contain this resin.
[0121]
Although the compounding quantity of the inorganic compound in the said masterbatch is not specifically limited, The preferable minimum with respect to 100 weight part of resin is 1 weight part, and an upper limit is 500 weight part. When the amount is less than 1 part by weight, the convenience as a master batch that can be diluted to an arbitrary concentration is reduced. If it exceeds 500 parts by weight, the dispersibility in the master batch itself, and particularly the dispersibility of the inorganic compound when diluted to a predetermined blending amount by the master batch dilution resin composition may deteriorate. A more preferred lower limit is 5 parts by weight and an upper limit is 300 parts by weight.
[0122]
Further, for example, by using an inorganic compound containing a polymerization catalyst (polymerization initiator) such as a transition metal complex, a thermoplastic resin monomer and an inorganic compound are kneaded, and the above monomer is polymerized, thereby thermoplastic resin. You may use the method of performing simultaneously superposition | polymerization and manufacture of a resin composition collectively.
[0123]
The method for kneading the mixture in the method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method for kneading using a kneader such as an extruder, two rolls, and a Banbury mixer.
[0124]
The resin composition of the present invention is a combination of a resin and an inorganic compound, and has a low linear expansion coefficient at a high temperature due to an increase in Tg and heat-resistant deformation temperature due to molecular chain restraint. Excellent mechanical properties and transparency.
[0125]
Furthermore, gas molecules are much easier to diffuse in the resin than inorganic compounds, and when diffusing in the resin, the gas molecules diffuse while bypassing the inorganic compound, so the gas barrier properties are also improved. Similarly, barrier properties against other than gas molecules are improved, and solvent resistance, hygroscopicity, water absorption and the like are improved. Thereby, for example, copper migration from a copper circuit in a multilayer printed wiring board can be suppressed. Furthermore, it is possible to suppress the occurrence of defects such as defective plating due to bleed-out of trace additives in the resin on the surface.
[0126]
In the resin composition of the present invention, if layered silicate is used as the inorganic compound, excellent mechanical properties can be obtained without adding a large amount, and thus a thin insulating substrate can be obtained. Density and thickness can be reduced. In addition, improvement in dimensional stability based on a nucleation effect of layered silicate in crystal formation and a swelling suppression effect accompanying improvement in moisture resistance, and the like have been attempted. Furthermore, since a sintered body made of layered silicate is formed at the time of combustion, the shape of the combustion residue is maintained, the shape does not collapse after the combustion, the spread of fire can be prevented, and excellent flame retardancy is exhibited.
Moreover, in the resin composition of this invention, if a non-halogen flame retardant is used, it is possible to achieve both high mechanical properties and high flame retardancy while considering the environment.
[0127]
The use of the resin composition of the present invention is not particularly limited. For example, a core layer or a build-up layer of a multilayer substrate is formed by processing in a suitable solvent or by forming into a film. It is suitably used for substrate materials, sheets, laminates, copper foils with resin, copper-clad laminates, TAB tapes, printed boards, prepregs, varnishes and the like. Substrate materials, sheets, laminates, resin-coated copper foils, copper-clad laminates, TAB tapes, printed boards, prepregs, and adhesive sheets using the resin composition of the present invention are also one aspect of the present invention. .
[0128]
The molding method is not particularly limited. For example, an extrusion molding method in which an extruder is melted and kneaded and then extruded and formed into a film using a T die or a circular die; dissolved in a solvent such as an organic solvent or Casting molding method in which the material is dispersed and then cast into a film shape; in a varnish obtained by dissolving or dispersing in a solvent such as an organic solvent, a cloth-like or non-woven fabric made of an inorganic material such as glass or an organic polymer Examples include a dipping molding method in which a substrate is dipped to form a film. Among these, the extrusion molding method is suitable for reducing the thickness of the multilayer substrate. In addition, it does not specifically limit as a base material used in the said dipping molding method, For example, a glass cloth, an aramid fiber, a polyparaphenylene benzoxazole fiber etc. are mentioned.
[0129]
The substrate material, sheet, laminate, copper foil with resin, copper-clad laminate, TAB tape, printed circuit board, prepreg, adhesive sheet and optical circuit forming material of the present invention are composed of the resin composition of the present invention. Therefore, it is excellent in high temperature physical properties, dimensional stability, solvent resistance, moisture resistance and barrier properties, and can be obtained with a high yield even when manufactured through multiple processes. In the present specification, the sheet includes a film-like sheet having no self-supporting property. In addition, in order to improve the sliding of these sheets, the surface may be embossed.
[0130]
In the case of a thermoplastic resin, not only the equipment and the manufacturing cost are reduced, but also the above-mentioned processing can be performed at the same time as the sheet is formed, or it can be post-processed by a simple method and is excellent in formability. Moreover, it can be reused by melting, and has the advantage of reducing the environmental load.
[0131]
In addition, the resin composition of the present invention has a low linear expansion coefficient, heat resistance, low water absorption, and high transparency because the layered silicate is finely dispersed in a nanometer size in the thermoplastic resin. Can also be realized. Therefore, the resin composition of the present invention can be suitably used as an optical circuit forming material such as an optical package forming material, an optical waveguide material, a connecting material, and a sealing material.
[0132]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
[0134]
(Example 1 )
In a small extruder (manufactured by Nippon Steel Works, TEX30), 100 parts by weight of modified polyphenylene ether-based resin (Asahi Kasei Kogyo Co., Ltd., Zylon (PKL) X9102) as a thermoplastic resin, distearyldimethyl quaternary ammonium as a layered silicate Feeding 30 parts by weight of swellable fluorine mica (Somasif MAE-100, manufactured by Co-op Chemical Co., Ltd.) that has been organically treated with salt, melted and kneaded at 280 ° C., extruded into a strand, and extruded the strand with a pelletizer. A master batch was prepared by pelletizing. Next, 100 parts by weight of polyetheretherketone as a thermoplastic resin and 9.5 parts by weight of the obtained master batch were fed into a small extruder (manufactured by Nippon Steel Works, TEX30) and melted at 400 ° C. in a nitrogen stream. The pellets made of the resin composition were obtained by kneading and extruding, and pelletizing the extruded strand with a pelletizer. Subsequently, the pellets made of the resin composition were rolled by pressing them with a hot press adjusted to 400 ° C. in the upper and lower directions under a nitrogen stream, and a plate-like molded body having a thickness of 2 mm and 100 μm made of the resin composition. Was made.
[0144]
(Example 2 )
After weighing 92.3 g of isobornyl acrylate into a 500 ml flask and adding 77.0 g of a dimethylformamide (DMF) solution containing 10% by weight of synthetic hectorite (Corp Chemical, Lucentite STN) to this flask. Stirring was performed for 1 hour to obtain a clay-containing isobornyl acrylate solution. Subsequently, DMF was distilled off from the clay-containing isobornyl acrylate solution obtained in an oven stream at 80 ° C. to obtain clay-containing isobornyl acrylate. After adding 0.9 g of a photopolymerization initiator (Irgacure 651, manufactured by Ciba Specialty Chemicals) to the obtained clay-containing isobornyl acrylate to obtain a uniform state, ultraviolet light at 365 nm was 1 mW / cm. ² Was irradiated at an illuminance of 10 minutes and further subjected to hot pressing at 160 ° C. to produce a plate-like molded body having a thickness of 2 mm and 100 μm made of a resin composition.
[0145]
(Example 3 )
92.3 g of methyl methacrylate was weighed into a 1000 ml flask, and 77.0 g of methyl ethyl ketone (MEK) solution containing 10% by weight of synthetic hectorite (manufactured by Corp Chemical Co., Lucentite STN) and 200 g of MEK were added to the flask. The mixture was stirred at 80 ° C. Next, an AIBN solution consisting of 2.5 g of azoisobutyronitrile (AIBN) and 100 ml of MEK was added in 20 ml portions every 5 hours to a flask that had been stirred at 80 ° C. with a hot water bath. , Held at 80 ° C. for a further 2 hours after the last addition. MEK was distilled off from the resulting reaction mixture by heating and drying under reduced pressure, followed by hot pressing at 160 ° C. to produce a plate-like molded body having a thickness of 2 mm and a thickness of 100 μm made of the resin composition.
[0147]
(Comparative example 1 )
Example except that swellable fluorine mica (manufactured by Co-op Chemical Co., Ltd., Somasif MAE-100) was not blended 1 In the same manner as described above, a resin composition and a plate-like molded body having a thickness of 2 mm and 100 μm made of the resin composition were produced.
[0155]
(Comparative example 2 )
To 92.3 g of isobornyl acrylate, 0.9 g of a photopolymerization initiator (Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to obtain a uniform state, and ultraviolet light at 365 nm was 1 mW / cm. ² Was irradiated at an illuminance of 10 minutes, and further heat-pressed at 160 ° C. to produce a plate-like molded body having a thickness of 2 mm and 100 μm made of a resin composition.
[0156]
<Evaluation>
Example 1 3 And Comparative Example 1 2 We evaluated the performance of the plate-shaped compacts produced in . Result The results are shown in Tables 1 and 2.
[0157]
(1) Measurement of thermal expansion coefficient
The test piece cut to 3 mm × 25 mm by cutting the plate-like molded body was heated at a temperature rising rate of 5 ° C./min using a TMA (Thermomechanical Analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C), and the average The linear expansion coefficient (hereinafter sometimes referred to as “CTE”) was measured, and the following items were evaluated.
[0158]
-Average linear expansion coefficient (α2) [° C. at a temperature 10 to 50 ° C. higher than the glass transition temperature of the resin composition ^-1 ].
The average linear expansion coefficient (α2) at a temperature 10 ° C. to 50 ° C. higher than the glass transition temperature of the resin composition is 50 ° C. to 10 ° C. lower than the glass transition temperature of the resin composition. Average linear expansion coefficient ratio (α2 / α1) obtained by dividing by (α1).
・ Average linear expansion coefficient at 50 to 100 ° C. [° C. ^-1 ] And average linear expansion coefficient at 200 to 240 ° C. [° C. ^-1 ].
-Average linear expansion coefficient ratio (1) obtained by dividing the average linear expansion coefficient at 150 to 200 ° C by the average linear expansion coefficient at 50 to 100 ° C, and the average linear expansion coefficient at 250 to 300 ° C Is an average linear expansion coefficient ratio (2) obtained by dividing by the average linear expansion coefficient at 50 to 100 ° C.
A rate of change (%) obtained by dividing the amount of change in length when the plate-shaped molded body was heated from 25 ° C. to 300 ° C. by the length of the plate-shaped molded body at 25 ° C.
-Average linear expansion coefficient ratio (3) represented by said Formula (1).
The average linear expansion coefficient at a temperature 10 ° C. to 50 ° C. higher than the Tg of the resin composition is 10 ° C. to 50 ° C. higher than the Tg of the resin composition prepared in the comparative example corresponding to each example. The improvement rate obtained by dividing by the average linear expansion coefficient.
[0159]
(2) Average interlayer distance of layered silicate
Using an X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), 2θ of a diffraction peak obtained from diffraction of the laminated surface of the layered silicate in the 2 mm-thick plate-like molded product is measured, and the following formula (5) The (001) plane spacing d of the layered silicate was calculated from the black diffraction formula, and the obtained d was defined as the average interlayer distance (nm).
λ = 2 dsin θ (5)
In the above formula (5), λ is 0.154, and θ represents the diffraction angle.
[0160]
(3) Ratio of layered silicate dispersed as a laminate of 5 layers or less A plate-shaped molded body having a thickness of 100 μm is observed with a transmission electron microscope at a magnification of 100,000 times, and a layered silicate that can be observed in a fixed area. The total number of layers X in the laminate and the number Y of layered silicate dispersed in 5 layers or less are measured, and the ratio of the layered silicate dispersed as a laminate of 5 layers or less according to the following formula (4) ( %) Was calculated.
[0161]
[Equation 5]

[0162]
(4) Measurement of water absorption
A test piece in which a plate-like molded body having a thickness of 100 μm was formed into a 3 × 5 cm strip was prepared, and the weight (W1) after drying at 80 ° C. for 5 hours was measured. Next, the test piece was immersed in water, left for 24 hours in an atmosphere at 25 ° C., then taken out, and the weight (W2) after carefully wiping with a waste was measured. The water absorption was determined by the following formula.
Water absorption (%) = (W2−W1) / W1 × 100
[0163]
(5) Measurement of humidity coefficient of linear expansion
The dimension (L1) after leaving the plate-shaped molded article having a thickness of 100 μm for 24 hours in a constant temperature and humidity chamber at 50 ° C. and 30% Rh was measured. Subsequently, the dimension (L2) after leaving a plate-shaped molded object for 24 hours in a constant temperature and humidity chamber of 50 degreeC80% Rh was measured. The coefficient of linear thermal expansion was determined by the following formula.
Humidity coefficient of linear expansion [% RH-1] = (L2-L1) / L1 / (80-30)
[0164]
(6) Measurement of dielectric constant
A dielectric constant in the vicinity of a frequency of 1 MHz was measured using an impedance measuring instrument (HP 4291B, manufactured by HP).
[0166]
( 7 ) Solubility parameter measurement
It was calculated by the formula of Fedors.
[0167]
( 8 ) Measurement of heating 10% weight loss temperature
After 5 to 10 mg of the sample was dried at 150 ° C. for 5 hours, the sample was measured using a TG / DTA apparatus (TG / DTA320, manufactured by Seiko Denshi) under the following measurement conditions.
[0168]
Measurement temperature: 25-600 ° C
Temperature increase rate: 10 ° C / min
Nitrogen gas: 200 ml / min
[0169]
[Table 1]

[0170]
[Table 2]

[0171]
【The invention's effect】
According to the present invention, a resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil, a copper-clad, excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and particularly excellent in high-temperature properties. A laminate, a TAB tape, a printed board, a prepreg, an adhesive sheet, and an optical circuit forming material can be provided.

Claims (17)

A resin composition for an electronic material or an optical circuit, comprising 100 parts by weight of a thermoplastic resin and 0.5 to 50 parts by weight of a layered silicate,
Wherein the thermoplastic resin is a combination of a functional group modified polyphenylene ether resin and polyether ether ketone resins, poly Isobo Le sulfonyl acrylate, and are either of polymethyl methacrylate,
The average linear expansion coefficient (α2) from the temperature 10 ° C. higher than the glass transition temperature of the resin composition to the temperature 50 ° C. higher than the glass transition temperature of the resin composition is 1.0 × 10 ⁻³ [° C. ⁻¹ ]. And the average linear expansion coefficient (α2) from the temperature 50 ° C. lower than the glass transition temperature of the resin composition to the temperature 10 ° C. lower than the glass transition temperature of the resin composition ( An average linear expansion coefficient ratio (α2 / α1) obtained by dividing by α1) is 70 or less. A resin composition for an electronic material or an optical circuit, comprising 100 parts by weight of a thermoplastic resin and 0.5 to 50 parts by weight of a layered silicate,
Wherein the thermoplastic resin is a combination of a functional group modified polyphenylene ether resin and polyether ether ketone resins, poly Isobo Le sulfonyl acrylate, and are either of polymethyl methacrylate,
When the thermoplastic resin is a combination of a functional group modified polyphenylene ether resin and polyether ether ketone resin, the layered silicate is a swellable mica, the thermoplastic resin is poly Isobo Le sulfonyl acrylate or poly In the case of methyl methacrylate, the layered silicate is hectorite,
The average linear expansion coefficient (α2) from the temperature 10 ° C. higher than the glass transition temperature of the resin composition to the temperature 50 ° C. higher than the glass transition temperature of the resin composition is 1.0 × 10 ⁻³ [° C. ⁻¹ ]. And the average linear expansion coefficient (α2) from the temperature 50 ° C. lower than the glass transition temperature of the resin composition to the temperature 10 ° C. lower than the glass transition temperature of the resin composition ( An average linear expansion coefficient ratio (α2 / α1) obtained by dividing by α1) is 70 or less.   The average linear expansion coefficient (α2) from a temperature 10 ° C. higher than the glass transition temperature of the resin composition to a temperature 50 ° C. higher than the glass transition temperature of the resin composition is 50 ° C. higher than the glass transition temperature of the resin composition. An average linear expansion coefficient ratio (α2 / α1) obtained by dividing by an average linear expansion coefficient (α1) from a low temperature to a temperature 10 ° C. lower than the glass transition temperature of the resin composition is 15 or less. The resin composition according to claim 1 or 2.   The average linear expansion coefficient of the resin composition from a temperature 10 ° C. higher than the glass transition temperature of the resin composition to a temperature 50 ° C. higher than the glass transition temperature of the resin composition is the thermoplastic resin contained in the resin composition. The average linear expansion coefficient of the thermoplastic resin contained in the resin composition from a temperature 10 ° C. higher than the glass transition temperature of the thermoplastic resin to a temperature 50 ° C. higher than the glass transition temperature of the thermoplastic resin contained in the resin composition. 4. The resin composition according to any one of claims 1 to 3, wherein the improvement rate obtained by dividing is 0.50 or less. Wherein the thermoplastic resin is a poly Isobo Le sulfonyl acrylate or polymethyl methacrylate, water absorption of 1.0% or less, a humidity coefficient of linear expansion is ^{1.5 × 10 -5 [% RH -1} ] or less The resin composition according to any one of claims 1 to 4.   2. The resin composition according to claim 1, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite.   The layered silicate contains an alkylammonium ion having 6 or more carbon atoms, an aromatic quaternary ammonium ion or a heterocyclic quaternary ammonium ion, according to any one of claims 1 to 6.   A substrate material comprising the resin composition according to claim 1.   A sheet comprising the resin composition according to claim 1.   A laminate comprising the resin composition according to any one of claims 1 to 7.   A resin-coated copper foil comprising the resin composition according to claim 1.   A copper-clad laminate comprising the resin composition according to claim 1.   A TAB tape comprising the resin composition according to claim 1.   A printed circuit board comprising the resin composition according to claim 1.   A prepreg comprising the resin composition according to claim 1.   An adhesive sheet comprising the resin composition according to claim 1.   An optical circuit forming material comprising the resin composition according to claim 1.