JP2004176032A - Resin composition - Google Patents

Abstract

A resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil, a copper-clad laminate, which is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and particularly excellent in high-temperature properties. Provide a TAB tape, a printed board, a prepreg, and an adhesive sheet.
The resin composition contains 100 parts by weight of a thermoplastic resin and 0.1 to 65 parts by weight of an inorganic compound. A resin composition having an average linear expansion coefficient (α2) of 1.0 × 10 ⁻³ [° C. ⁻¹ ] or less up to a temperature higher by 50 ° C. than the glass transition temperature.
[Selection diagram] None

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、上記樹脂のガラス転移温度よりも１０℃高い温度から、上記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；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；ポリエーテルサルフォン樹脂；ポリアミドイミド樹脂；ポリエステルイミド樹脂；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；ポリエーテルイミド樹脂；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、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、ポリエステルイミド樹脂、ポリエーテルイミド樹脂、及び、熱可塑性ポリベンゾイミダゾール樹脂等が好適に用いられる。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。
【００６６】
上記熱可塑性ポリイミド樹脂としては、例えば、分子主鎖中にイミド結合とエーテル結合とを有するポリエーテルイミド樹脂、分子主鎖中にイミド結合とアミド結合とを有するポリアミドイミド樹脂、分子主鎖中にイミド結合とエステル結合とを有するポリエステルイミド樹脂等が挙げられる。また、用いる原料としては特に限定されず、例えば、無水ピロメリット酸、３，３’，４，４’−ベンゾフェノンテトラカルボン酸ニ無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸ニ無水物、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物、エチレングリコールビス（アンヒドロトリメテート）、（５−ジオキソテトラヒドロ−３−フラニル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸無水物、１，３，３ａ，４，５，９ｂ−ヘキサヒドロ−５−（テトラヒドロ−２，５−ジオキソ−３−フラニル）ナフト［１，２−ｃ］フラン−１，３−ジオン等からなるテトラカルボン酸無水物と４，４’−ビス（３−アミノフェノキシ）ビフェニル、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、１，３−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ジアミノジフェニルエーテル等のジアミンが挙げられる。
【００６７】
これらの熱可塑性ポリイミド樹脂は、単独で用いられてもよく、２種以上が併用されてもよい。上記熱可塑性ポリイミド樹脂のうち市販されているものとしては、例えば、三井化学社製の商品名「オーラム」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、ポリアミドイミド樹脂、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、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、ポリエーテルイミド樹脂、ポリアミドイミド樹脂、熱可塑性ポリイミド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以上であり、かつ、一部又は全部の積層体が５層以下であるように分散していることが好ましい。上記平均層間距離が３ｎｍ以上であり、かつ、一部又は全部の積層体が５層以下であるように層状珪酸塩が分散していることにより、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】
上記一部又は全部の積層体が５層以下であるように層状珪酸塩が分散しているとは、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層以下にして分散されており、層状珪酸塩の積層体の２０％以上が５層以下にして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、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以上であり、かつ、一部又は全部の積層体が５層以下である層状珪酸塩が分散し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。
【０１３３】
（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、２９０℃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イミド樹脂（三井化学社製、オーラムＰＤ−４５０）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、４２０℃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４２０℃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。
【０１３４】
（実施例２）
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。
【０１３５】
（実施例３）
ビス［４−（３−アミノフェノキシ）フェニル］スルホン６６．１２重量部を５００ｍｌセパラブルフラスコに秤取り、脱水したＮ−メチルピロリドン３７０重量部を添加し、窒素置換後、１５０ｒｐｍで約３０分攪拌した。次いで、無水ピロメリット酸３３．７２重量部と脱水したＮ−メチルピロリドン４０重量部を添加し、１５０ｒｐｍで１時間攪拌した。続いて、７．９％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）含有Ｎ−メチルピロリドン溶液２５３．２重量部、アニリン０．００１重量部、脱水Ｎ−メチルピロリドン４０重量部を６００ｒｐｍで４時間攪拌を行い、クレイ含有ポリアミック酸溶液を得た。
【０１３６】
得られたポリアミック酸溶液を高温に加熱し、大半の溶剤を稀薄させてフィルムにしたあと、さらに高温に加熱して反応を進行させ、イミド化を行った。クレイ含有ポリイミドのマスターバッチを得た。次いで小型押出機（日本製鋼所社製、ＴＥＸ３０）中に、熱可塑性樹脂（商品名「オーラムＰＤ−４５０」（三共化学社製）１００重量部、得たマスターバッチ４３重量部を投入し、窒素気流下、４２０℃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、樹脂組成物のペレットを得た。次いで、得られた樹脂組成物の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し圧延して、厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１３７】
（実施例４）
１，３−ビス（４−アミノフェノキシ）ベンゼン（和光純薬社製）４７．２４重量部を５００ｍｌセパラブルフラスコに秤取り、脱水したＮ−メチルピロリドン（和光純薬社製）３７０重量部を添加し、窒素置換後、１５０ｒｐｍで約３０分攪拌した。次いで、３，３‘４，４’−ベンゾフェノンテトラカルボン酸２無水物（ダイセル化学社製、ＢＴＤＡ−ＢＦＳ−０６）５２．６０重量部と脱水したＮ−メチルピロリドン４０重量部を添加し、１５０ｒｐｍで１時間攪拌した。続いて、３．９％合成マイカ（１，２−ジメチル−３−Ｎ−デシル−イミダゾリウム処理合成マイカ）含有Ｎ−メチルピロリドン溶液２５３．２重量部、アニリン（和光純薬社製）０．００２重量部、脱水Ｎ−メチルピロリドン４０重量部を６００ｒｐｍで４時間攪拌を行い、クレイ含有ポリアミック酸溶液を得た。得たポリアミック酸溶液の溶剤乾燥、イミド化を行い、クレイ含有ポリイミドのマスターバッチを得た。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オーラム（三井化学社製、ＰＤ−４５０）１００重量部、得たマスターバッチ２５重量部を投入し、窒素気流下、４２０℃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のペレットを得た。次いで、得られた樹脂組成物の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し圧延して、厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１３８】
（実施例５）
ビス［４−（３−アミノフェノキシ）フェニル］スルホン６６．１２重量部を５００ｍＬセパラブルフラスコに秤取り、脱水ジメチルホルムアミド（ＤＭＦ）３７０重量部を添加し、窒素置換後、１５０ｒｐｍで約３０分間撹拌した。次いで、無水ピロメリット酸３３．７２重量部と脱水したジメチルホルムアミド（ＤＭＦ）４０重量部を添加し、１５０ｒｐｍで１時間撹拌した。続いて、７．９％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）含有ＤＭＦ溶液２５３．２重量部、アニリン０．００１重量部、脱水ＤＭＦ４０重量部を６００ｒｐｍで４時間撹拌を行い、クレイ含有ポリアミック酸溶液を得た。
【０１３９】
得られたポリアミック酸溶液の溶剤乾燥、イミド化を行い、クレイ含有ポリイミドのマスターバッチを得た。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オーラム（三井化学社製、ＰＤ−４５０）１００重量部、得られたマスターバッチ１７.６重量部、ホウ酸アルミニウムウィスカー（四国化成工業株式会社製）１０重量部を投入し、窒素気流下、４２０℃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のペレットを得た。次いで、得られた樹脂組成物の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し圧延して、厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４０】
（実施例６）
１，３−ビス（４−アミノフェノキシ）ベンゼン４７．２４重量部を５００ｍＬセパラブルフラスコに秤取り、脱水したＮ−メチルピロリドン（ＮＭＰ）３７０重量部を添加し、窒素置換後、１５０ｒｐｍで約３０分間撹拌した。次いで、３，３’４，４’−ベンゾフェノンテトラカルボン酸２無水物５２．６０重量部と脱水したＮＭＰ４０重量部を添加し、１５０ｒｐｍで１時間撹拌した。続いて、３．９％合成マイカ（コープケミカル社製、ソマシフＭＰＥ）含有ＮＭＰ溶液２５３．２重量部、アニリン０．００２重量部、脱水したＮＭＰ４０重量部を６００ｒｐｍで４時間撹拌を行い、クレイ含有ポリアミック酸溶液を得た。
【０１４１】
得られたポリアミック酸溶液の溶剤乾燥、イミド化を行い、クレイ含有ポリイミドのマスターバッチを得た。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オーラム（三井化学社製、ＰＤ−４５０）１００重量部、得たマスターバッチ２５重量部、炭化ケイ素ウィスカー（東洋カーボン社製）８重量部を投入し、窒素気流下、４２０℃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のペレットを得た。次いで、得られた樹脂組成物の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し圧延して、厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４２】
（実施例７）
小型押出機（日本製鋼所社製、ＴＥＸ３０）中に、熱可塑性樹脂としてオーラム(三井化学社製、PD-450Ｍ)１００重量部、合成マイカ（コープケミカル社製、ソマシフＭＰＥ）３重量部、窒素気流下、３３０℃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のペレットを得た。次いで、得られた樹脂組成物のペレットを窒素気流下、上下各３４０℃に温調した熱プレスでプレスし圧延して、厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４３】
（実施例８）
小型押出機（日本製鋼所社製、ＴＥＸ３０）中に、熱可塑性樹脂としてオーラム(三井化学社製、PD-450)１００重量部、合成マイカ（１，２−ジメチル−３−Ｎ−デシル−イミダゾリウム処理合成マイカ）３重量部、シリカ（アドマテックス社製、ＳＯ−Ｅ５）１５重量部を投入し、窒素気流下、４２０℃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のペレットを得た。次いで、得られた樹脂組成物の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し圧延して、厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４４】
（実施例９）
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１０）
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。
【０１４６】
（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。
【０１４７】
（比較例２）
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２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。
【０１４８】
（比較例３）
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）を配合しなかったこと以外は実施例３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。
【０１４９】
（比較例４）
合成マイカ（１，２−ジメチル−３−Ｎ−デシル−イミダゾリウム処理合成マイカ）を配合しなかったこと以外は実施例４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。
【０１５０】
（比較例５）
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）を配合しなかったこと以外は実施例５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。
【０１５１】
（比較例６）
合成マイカ（コープケミカル社製、ソマシフＭＰＥ）を配合しなかったこと以外は実施例６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。
【０１５２】
（比較例７）
合成マイカ（コープケミカル社製、ソマシフＭＰＥ）を配合しなかったこと以外は実施例７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。
【０１５３】
（比較例８）
合成マイカ（１，２−ジメチル−３−Ｎ−デシル−イミダゾリウム処理合成マイカ）を配合しなかったこと以外は実施例８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。
【０１５４】
（比較例９）
シリカ（アドマテックス社製、ＳＯ−Ｅ５）の配合量を６０重量部に変更し、合成マイカ（１，２−ジメチル−３−Ｎ−デシル−イミダゾリウム処理合成マイカ）を配合しなかったこと以外は実施例８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１０）
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１〜１０及び比較例１〜１０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。なお、実施例５、６及び比較例５、６で作製した板状成形体については弾性率も評価した。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。
【０１６５】
（７）弾性率の測定
ＪＩＳ Ｋ ６３０１に準ずる方法により測定を行った。
【０１６６】
（８）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】
（９）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]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil, and a copper-clad laminate, which are excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and particularly 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, high performance, high functionality, and miniaturization of electronic devices have been rapidly progressing, and there has been an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. Along with this, further improvements in various physical properties such as heat resistance, mechanical strength, and electrical properties of materials for electronic components have been demanded.For example, for a packaging method of a semiconductor element and a wiring board for mounting the semiconductor element. In addition, higher density, higher performance and higher performance are required.
[0003]
A multilayer printed board used for an electronic device is constituted by a plurality of layers of insulating substrates.Conventionally, as this interlayer insulating substrate, for example, a thermosetting resin prepreg in which a thermosetting resin is impregnated into a glass cloth, A film made of a thermosetting resin or a photocurable resin has been used. Also in the above-mentioned multilayer printed circuit board, it is desired that the interlayer is extremely thin for high density and thinning, and an interlayer insulating substrate using a thin glass cloth or an interlayer insulating substrate not using a glass cloth is required. ing. As such an interlayer insulating substrate, for example, a substrate made of a rubber (elastomer), a thermosetting resin material modified with an acrylic resin, a thermoplastic resin material containing a large amount of an inorganic filler, and the like are known. Patent Document 1 discloses a varnish containing a high-molecular-weight epoxy polymer and a polyfunctional epoxy resin as a main component, an inorganic filler having a predetermined particle diameter, and coating the support to form an insulating layer. A method for manufacturing a multilayer insulating substrate is disclosed.
[0004]
However, in the multilayer insulating substrate manufactured by the above manufacturing 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 the polyfunctional epoxy resin. In addition, it is necessary to mix a large amount of an inorganic filler, which causes problems in processing such as an increase in the number of manufacturing steps, and there is a problem that it is difficult to reduce the thickness of the interlayer.
[0005]
In addition, the interlayer insulating substrate using a thin glass cloth or the interlayer insulating substrate not using a glass cloth has problems such as insufficient heat resistance, dimensional stability, and the like. There is a problem that often occurs.
[0006]
The multilayer printed circuit board is manufactured by a build-up method of obtaining a multilayer laminate by repeating circuit formation and lamination on layers, or a batch lamination method of collectively laminating layers on which circuits are formed. In any of the manufacturing methods, the quality of the material greatly affects the yield due to the large number of processes, and the process includes a plating process, a hardening 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; little moisture absorption affecting electrical characteristics; dimensional stability at high temperatures and after heating affecting high-precision circuit connection between upper and lower layers; Heat resistance up to 260 ° C. required for mounting with lead-free solder; copper migration which affects connection reliability is required to be unlikely to occur.
[0007]
For example, build-up boards and printed multi-layer boards used for IC packages may be subjected to high temperature conditions due to heat generation, and it is required that high reliability can be maintained even in such an environment. When it is large, there is a problem that a metal wiring such as copper forming a circuit is peeled off, and a short circuit or disconnection is caused. In addition, even in a flexible multi-layer board, which has recently attracted attention as a thin board, the thermal dimensional change between an adhesive layer for bonding single-layer flexible boards to each other and a polyimide film for forming the flexible board and metal wiring such as copper for forming a circuit. If the difference is large, a similar problem occurs.
[0008]
Patent Document 1 listed 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. However, at temperatures higher than the glass transition temperature, the effect of improving physical properties is not improved. Almost no improvement is seen, and the improvement effect is small even at a temperature lower than the glass transition temperature. Further, the effect of improving hygroscopicity and solvent resistance cannot be expected.
[0009]
Conventionally, as a method for lowering the linear expansion coefficient at a temperature lower than the glass transition temperature, a method using an inorganic filler has been known, but it has not been adapted to a 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 been further increased. There is a problem that the coefficient of expansion is large and a problem occurs during high-temperature treatment.
[0010]
In recent years, progress in semiconductor mounting technology has been remarkable. Among them, TAB (Tape Automated Bonding) can easily cope with the increase in the number of pins because a conductor pattern can be formed at an extremely high density. Since the entire lead can be connected to the semiconductor element at one time without using it, the development of high-density mounting technology has been actively promoted.
[0011]
There are two types of TAB tapes, a two-layer structure and a three-layer structure. A three-layer structure (hereinafter abbreviated as a three-layer TAB) generally bonds a conductive foil such as a copper foil to a heat-resistant resin film. Even if a resin film having excellent properties such as heat resistance and chemical resistance was used, it had an adhesive layer with poor heat resistance, so that the properties could not be fully utilized.
[0012]
On the other hand, a two-layered TAB (hereinafter, abbreviated as a two-layered TAB) generally has excellent heat resistance as a TAB because it does not have an adhesive layer on a base film, but is practically used due to the difficulty of its production method. There were few things.
[0013]
Polyimide film is one of various organic polymers, because of its excellent heat resistance, low temperature properties, chemical resistance, electrical properties, etc., as a material for electric and electronic equipment, and further from space, aviation to electronic communications. Widely used.
[0014]
However, even this polyimide does not sufficiently satisfy the required performance, and is required to have various performances depending on the application. In particular, for electronic materials, polyimides having a low water absorption are desired for higher functionality and smaller size. By lowering the water absorption, 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 moisture expansion. Considering the example of manufacturing TAB tapes other than water absorption, the process involves many steps of receiving stress and temperature changes, and the organic insulating film of the base material has a small dimensional change due to stress and temperature changes. Is desired.
[0015]
As described above, with high performance, high functionality, and miniaturization, TAB tapes, base films for flexible printed circuit boards, and resins for laminated boards have little dimensional change due to heat and water absorption in addition to heat resistance. It is desired that the elastic modulus is high. However, a polyimide film that sufficiently satisfies these properties has not been obtained at present.
[0016]
On the other hand, speaking of polyimide film, "Kapton" (trade name, manufactured by Dupont Toray Co., Ltd.), "Upilex" (trade name, manufactured by Ube Industries, Ltd.) and "Apical" (trade name, manufactured by Kanegabuchi Chemical Co., Ltd.) And the like are used. Although these films have high heat resistance, they decompose before reaching the softening temperature. Therefore, the films are formed by a solution casting method. In addition, there is a problem that the equipment cost and the manufacturing cost are increased, and furthermore, it is difficult to perform molding by heat.
[0017]
On the other hand, in recent years, with the development of optical communication technology, there is a demand for inexpensive connection of optical communication devices. Therefore, an optical communication material made of a polymer material has been attracting attention. However, when a conventional polymer material was used as a material for optical communication, there were various problems.
[0018]
The polymer material for optical communication is required to have low loss, excellent heat resistance, low coefficient of linear thermal expansion, low moisture permeability, easy control of the refractive index, and the like.
[0019]
Note that the low loss means that a polymer material has almost no absorption band in a wavelength band used for optical communication, and thus a small propagation loss.
In Patent Document 2 below, a conventional polymer material has a coefficient of linear thermal expansion that is nearly 10 times the coefficient of thermal expansion of a semiconductor or metal material, and is formed on a substrate having a small coefficient of thermal expansion such as silicon. In this case, stress may be applied, causing the polarization dependency of the optical communication material, causing warpage between the optical communication material and the substrate, and causing the polymer optical communication material edge to peel off from the substrate. Has been described.
[0020]
Patent Literature 3 describes a problem that a fiber strand protrudes from a jacket due to a difference in thermal expansion coefficient between a fiber strand (quartz glass) and a resin case, and cracks occur in the fiber strand due to stress concentration. ing.
[0021]
Further, in Patent Document 4, when connecting the optical waveguide substrate and the optical fiber using an adhesive, if the difference in thermal expansion between the optical waveguide substrate and the connecting component is large, a displacement occurs due to thermal expansion, and a stable optical waveguide is generated. It is described that connection with a wave path cannot be realized.
[0022]
Regarding moisture permeability, in Patent Document 3, when water vapor penetrates into a hollow case, it condenses on the surface of an optical element or a fiber strand, causing corrosion of the optical element or promoting the growth of cracks and the fiber element. There is a problem that the wire is broken, and it is described that these factors, together with the thermal expansion, totally reduce the reliability of the optical communication component using the polymer material. In addition, when the hygroscopicity is high, light absorption due to the O—H bond of water is likely to occur, which requires a material having low hygroscopicity.
[0023]
Regarding heat resistance, if optical communication is introduced to terminal equipment, it is necessary to convert optical signals to electrical signals or electrical signals to optical signals. A polymeric material will be used. Therefore, the polymer material for optical communication needs to have heat resistance to the process temperature at the time of manufacturing the printed circuit board and heat resistance to the heat generated from the electric circuit during 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 coefficient of linear expansion, and low moisture absorption are desired as optical communication materials.
On the other hand, Patent Document 5 below discloses that a fluorinated polyimide having a rigid skeleton achieves a low coefficient of linear thermal expansion.
[0025]
Patent Document 6 below discloses a polymer optical waveguide comprising a core layer and a cladding layer surrounding the core layer, wherein the polymer optical waveguide includes a second cladding layer having a smaller thermal expansion coefficient than the cladding layer outside the cladding layer. Is disclosed. Here, by making the polymers constituting the cladding layer and the second cladding layer different from each other, the thermal expansion coefficient of the second cladding layer can be made relatively low, and the difference in thermal expansion coefficient from the electro-optical device can be reduced. It is shown.
[0026]
Further, in Patent Document 7 below, by sealing an end face of an optical communication material with a resin, the resin adheres an insulating film forming an optical communication material to a substrate and peels off at an end where stress is concentrated. Is described as being able to be prevented.
[0027]
Patent Document 7 below discloses that the coefficient of thermal expansion can be reduced by using a polyimide film having a specific structure as a resin for an optical waveguide.
[0028]
The fluorinated polyimide described in Patent Document 5 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 cladding layer of an optical communication material. Was not appropriate.
[0029]
On the other hand, in a resin for an optical waveguide containing particles described in Patent Document 6, it is suggested that there is a possibility that both a low linear expansion coefficient and transparency can be achieved. Must add a large amount of particles. Therefore, when a large amount of particles are added, it is difficult to realize sufficient transparency. There is also a problem that when a large amount of particles is contained, the resin composition becomes brittle. In addition, when particles are added in a large amount, the hydrophilicity may be increased and the hygroscopicity may be increased.
[0030]
Further, with the configuration described in Patent Literature 2 below, the number of manufacturing steps increases, and an increase in cost cannot be avoided.
On the other hand, when a polyimide film having a specific structure described in Patent Document 7 is used as an optical waveguide resin, it is possible to reduce the coefficient of thermal expansion, but it is difficult to realize low moisture absorption, and the cost is also high. I had to stay high.
[0031]
Therefore, even the optical circuit forming material is excellent in transparency, heat resistance, low coefficient of linear expansion and low hygroscopicity, and it is still difficult to realize a material capable of realizing particularly high transparency.
[0032]
[Patent Document 1]
JP-A-2000-183538
[Patent Document 2]
JP 2001-183439 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 is particularly excellent in high temperature properties, a resin composition, a substrate material, a sheet, a laminate, and a copper foil with resin. It is an object of the present invention to provide a copper-clad laminate, a TAB tape, a printed circuit board, a prepreg, an adhesive sheet, and an optical circuit forming material.
[0034]
[Means for Solving the Problems]
The present invention relates to a resin composition containing 100 parts by weight of a thermoplastic resin and 0.1 to 65 parts by weight of an inorganic compound, and from a temperature 10 ° C. higher than a glass transition temperature of the resin composition, The average linear expansion coefficient (α2) up to a temperature 50 ° C. higher than the glass transition temperature is 3.0 × 10 ^-3 [℃ ^-1 ] The following resin composition.
[0035]
Hereinafter, the present invention will be described in detail.
The resin composition of the present invention has an average linear expansion coefficient from a temperature 10 ° C. higher than the glass transition temperature (hereinafter also referred to as Tg) of the resin composition to a temperature 50 ° C. higher than the glass transition temperature of the resin composition ( Hereinafter, also referred to as α2) is 3.0 × 10 ^-3 [℃ ^-1 ] Is as follows. 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 ratio when bonded to a copper foil or the like, There is no peeling. Preferably, 1.0 × 10 ^-3 [℃ ^-1 And more preferably 8.0 × 10 ^-Four [℃ ^-1 ], More preferably 5.0 × 10 ^-Four [℃ ^-1 ] Is as follows.
[0036]
The average coefficient of linear expansion can be measured by a method according to JIS K7197. For example, a test of about 3 mm × 15 mm using a TMA (Thermomechanical Analysis) device (manufactured by Seiko Electronics Co., Ltd., TMA / SS120C). It can be determined by heating the piece at a rate of 5 ° C./min.
[0037]
In the resin composition of the present invention, the above 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. ), The average linear expansion coefficient ratio (α2 / α1) is preferably 70 or less. When it is 70 or less, the resin material made of the resin composition of the present invention has a small dimensional change near Tg, and does not generate wrinkles or warpage near Tg when used as a laminated material or a laminated material. More preferably, it is 15 or less, further preferably, 10 or less, and most preferably, 5 or less.
[0038]
The resin composition of the present invention has an average coefficient of linear expansion at 50 to 100 ° C. of 4.5 × 10 4. ^-Five [℃ ^-1 And an average linear expansion coefficient at 200 to 240 ° C. of 7 × 10 ^-Five [℃ ^-1 ] It is preferable that it is the following. The average linear expansion coefficient at 50 to 100 ° C. is 4.5 × 10 ^-Five [℃ ^-1 And an average linear expansion coefficient at 200 to 240 ° C. of 7 × 10 ^-Five [℃ ^-1 In the following, the resin material comprising the resin composition of the present invention has a small dimensional change under ordinary use conditions, is suitable for an electronic material or the like that requires precise precision, and has a solder reflow. Even in a manufacturing process in which high-temperature treatment is performed, warping or peeling does not occur. The average linear expansion coefficient at 50 to 100 ° C. is more preferably 4.0 × 10 4 ^-Five [℃ ^-1 ], More preferably 3.5 × 10 ^-Five [℃ ^-1 ] Is as follows. The average linear expansion coefficient at 200 to 240 ° C. is more preferably 6.5 × 10 ^-Five [℃ ^-1 ], And more preferably 5.5 × 10 ^-Five [℃ ^-1 ] Is as follows.
[0039]
The resin composition of the present invention has an 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. of 2.0 or less. In addition, it is preferable that 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 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 to heating. Also, even in a manufacturing process or the like in which high-temperature treatment such as reflow of lead-free solder is performed, warpage or peeling does not occur, which is suitable for applications used at high temperatures. The average linear expansion coefficient ratio (1) is more preferably 1.5 or less, and further preferably 1.2 or less. The average linear expansion coefficient (2) is more preferably 15 or less, and further preferably 10 or less.
[0040]
In the resin composition of the present invention, the amount of change in length when the temperature of the resin piece made of the resin composition is raised from 25 ° C. to 300 ° C. is divided by the length of the resin piece made of the resin composition at 25 ° C. Is preferably 7% or less. When the content is 7% or less, the resin material comprising the resin composition of the present invention has good dimensional stability with respect to temperature, and can be used when laminated or bonded with other materials during production or use. There is no warping or peeling. It is more preferably at most 6%, further preferably at most 5%.
[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]
(Equation 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 can be laminated with another material or even when laminated. No warping or peeling occurs during manufacturing and use. It is more preferably 1.4 or less, and still more preferably 1.3 or less.
[0044]
The resin composition of the present invention has an average linear expansion coefficient (α2) of the resin composition from 10 ° C. higher than the glass transition temperature of the resin composition to 50 ° C. higher than the glass transition temperature of the resin composition. The improvement rate obtained by dividing by an average linear expansion coefficient of the resin from a temperature 10 ° C. higher than the glass transition temperature of the resin to a temperature 50 ° C. higher than the glass transition temperature of the resin is 0.50 or less. Preferably, there is. When it is 0.50 or less, the resin material comprising the resin composition of the present invention has sufficiently improved high-temperature physical properties by an inorganic compound, and causes a problem in a manufacturing process for performing a high-temperature treatment or use at a high temperature. Nothing. It is more preferably at most 0.35, even more preferably at most 0.25.
[0045]
Since the resin composition of the present invention has a low average linear expansion coefficient at a high temperature equal to or higher than the glass transition temperature as described above, it improves high-temperature physical properties such as dimensional stability at a high temperature, and performs a plating step, a curing step, and a lead step. It can be used for a resin material that does not warp or peel even in a high-temperature processing 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 secure necessary strength, and it becomes impossible to produce a small TAB. If the dielectric constant at 1 MHz is greater than 3.3, the thickness must be increased in order to secure sufficient reliability, and a small TAB may not be manufactured.
[0047]
The resin composition of the present invention has a water absorption of 1.0% or less and a humidity linear expansion coefficient of 1.5 × 10 ^-Five [% RH ^-1 ] It is preferable that it is the following. When the water absorption exceeds 1.0%, when a substrate is produced using the resin composition of the present invention, dimensional changes occur between absolute drying and water absorption, so that fine wiring becomes difficult and miniaturization cannot be achieved. There is. More preferably, it is 0.7% or less, still more preferably 0.3% or less. Humidity linear expansion coefficient is 1.5 × 10 ^-Five [% RH ^-1 ], The obtained substrate may be warped, and the copper foil may be peeled off due to the difference in the rate of change of the copper foil. More preferably 1.2 × 10 ^-Five [% RH ^-1 ], More preferably 1.0 × 10 ^-Five [% RH ^-1 ] Is as follows.
[0048]
Further, the resin composition of the present invention preferably has a water absorption of 1.0% or less, a dielectric constant at 1 MHz of 3.3 or less, and a dielectric constant after water absorption treatment of 3.4 or less. If the electrical characteristics change significantly due to water absorption, the reliability may not be maintained, and the material may explode in a manufacturing process such as solder reflow to lower the yield.
[0049]
The water absorption was determined based on the weight W1 when a test piece in which a film having a thickness of 50 to 100 μm was formed into a 3 × 5 cm strip was dried at 80 ° C. for 5 hours, and immersed in water and immersed in water at 25 ° C. It is a value obtained by measuring the weight W2 when the surface is thoroughly wiped off after being left for a long time, and obtained by the following equation.
[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 physical properties, particularly heat resistance to lead-free solder and dimensional stability to heating are improved. The temperature is more preferably 140 ° C or higher, and further preferably 200 ° C or higher.
[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 physical properties, particularly, lead-free solder heat resistance, The dimensional stability against heating is improved, the high reliability required for an electronic material can be obtained, and the transmission speed required for an electronic material can be obtained even in the signal transmission speed in a high frequency range. The glass transition temperature is more preferably 140 ° C. or higher, even more preferably 200 ° C. or higher. The dielectric constant at 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; and a polyphenylene ether resin such as a polystyrene resin or a functional group-modified polyphenylene. Mixture of a thermoplastic resin compatible with an ether resin; an alicyclic hydrocarbon resin; a thermoplastic polyimide resin; a polyether ether ketone resin; a polyether sulfone resin; a polyamideimide resin; a polyesterimide resin; Resin; polystyrene resin; polyamide resin; polyvinyl acetal resin; polyvinyl alcohol resin; polyvinyl acetate resin; poly (meth) acrylate resin resin; Polyetherimide resins; thermoplastic polybenzimidazole resins. Among them, polyphenylene ether resin, functional group-modified polyphenylene ether resin, a mixture of polyphenylene ether resin or functional group-modified polyphenylene ether resin and polystyrene resin, alicyclic hydrocarbon resin, thermoplastic polyimide resin, polyether ether Ketone resins, polyesterimide resins, polyetherimide resins, thermoplastic polybenzimidazole resins, and the like are preferably used. These thermoplastic resins may be used alone or in combination of two or more. In this specification, (meth) acryl means acryl or methacryl.
[0053]
The polyphenylene ether resin is a polyphenylene ether homopolymer or a polyphenylene ether copolymer comprising a repeating unit represented by the following formula (2).
[0054]
Embedded image

[0055]
In the above 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, for example, a copolymer partially containing an alkyl trisubstituted phenol such as 2,3,6-trimethylphenol or the like in a repeating unit of the polyphenylene ether homopolymer, or a polyphenylene such as these. Examples of the ether copolymer further include a copolymer in which one or more styrene monomers such as styrene, α-methylstyrene, and vinyltoluene are graft-copolymerized. Each of these polyphenylene ether resins may be used alone, or two or more of them having different compositions, components, molecular weights and the like may be used in combination.
[0058]
Examples of the functional group-modified polyphenylene ether resin include, for example, those in which the polyphenylene ether resin is modified with one or more functional groups such as a maleic anhydride group, a glycidyl group, an amino group, and an allyl group. No. These functional group-modified polyphenylene ether resins may be used alone or in combination of two or more. When the above functional group-modified polyphenylene ether resin is used as a thermoplastic resin, the mechanical properties, heat resistance, dimensional stability and the like 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, for example, the polyphenylene ether resin or the functional group-modified polyphenylene ether resin, a styrene homopolymer; styrene; Copolymers with one or more styrene monomers such as methylstyrene, ethylstyrene, t-butylstyrene and vinyltoluene; and mixtures with polystyrene resins such as styrene elastomers.
[0060]
The polystyrene resin may be used alone, or two or more kinds may be used in combination. Further, these polyphenylene ether resins or a mixture of a polyphenylene ether resin modified with a functional group and a 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 includes, for example, a cyclic olefin, that is, a homopolymer or a copolymer of a norbornene-based monomer. These alicyclic hydrocarbon resins may be used alone or in combination of two or more.
[0062]
Examples of the cyclic olefin include, for example, norbornene, methanooctahydronaphthalene, dimethanooctahydronaphthalene, dimethanodecahydroanthracene, dimethanodecahydroanthracene, trimethanododecahydroanthracene, dicyclopentadiene, and 2,3-dihydrocyclopentadiene. Methanooctahydrobenzoindene, dimethanooctahydrobenzoindene, methanodecahydrobenzoindene, dimethanodecahydrobenzoindene, methanooctahydrofluorene, dimethanooctahydrofluorene, and substituted products thereof. These cyclic olefins may be used alone or in combination of two or more.
[0063]
Examples of the substituent in the substituent such as norbornene or the like 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 substituents such as the above 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 substituted products such as norbornene may be used alone or in combination of two or more.
[0065]
Among the alicyclic hydrocarbon resins, commercially available ones include, for example, the "ARTON" series manufactured by JSR Corporation and the "Zeonor" series manufactured by Zeon Corporation.
[0066]
Examples of the thermoplastic polyimide resin include, for example, a polyetherimide resin having an imide bond and an ether bond in a molecular main chain, a polyamideimide resin having an imide bond and an amide bond in a molecular main chain, A polyester imide resin having an imide bond and an ester bond is exemplified. The raw materials used are not particularly restricted but include, for example, pyromellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimethate) , (5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2 , 5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione and other tetracarboxylic anhydrides and 4,4'-bis (3-aminophenoxy) biph Cycloalkenyl, bis [4- (3-aminophenoxy) phenyl] sulfone, 1,3-bis (4-aminophenoxy) benzene and diamine and 4,4'-diaminodiphenyl ether.
[0067]
These thermoplastic polyimide resins may be used alone or in combination of two or more. Commercially available thermoplastic polyimide resins include, for example, "Aurum" series manufactured by Mitsui Chemicals, Inc.
[0068]
Examples of the polyether ether ketone resin include those obtained by polycondensation of dihalogenobenzophenone and hydroquinone. Commercially available polyether ether ketone resins include, for example, "Victrex PEEK" (trade name, manufactured by ICI).
[0069]
Examples of the thermoplastic polybenzimidazole resin include those obtained by polycondensation of dioctadecyl terephthalaldimine with 3,3′-diaminobenzidine. Examples of commercially available products include “Cerazole” series manufactured by Clariant Japan.
[0070]
The thermoplastic resin has a solubility parameter (SP value) of 42 [J / cm] determined using the Fedors equation. ^Three ] ^1/2 It is preferable that it is above. According to the above Fedors calculation formula, the SP value is defined as the square root of the sum of the molar aggregation energies of the respective atomic groups divided by the volume, and indicates the polarity per unit volume. SP value is 42 [J / cm ^Three ] ^1/2 By having the above, since it has a large polarity, it has good compatibility with inorganic compounds such as chemically treated layered silicate, and even when layered silicate is used as the inorganic compound, the interlayer of the layered silicate is used. And can be dispersed one by one. More preferably, 46.2 [J / cm ^Three ] ^1/2 And more preferably 52.5 [J / cm ^Three ] ^1/2 That is all.
[0071]
The SP value is 42 [J / m ^Three ] ^1/2 Examples of the above resin include, for example, polyester resins such as polybutylene terephthalate, polybutylene naphthalate, polyethylene terephthalate, and polyethylene naphthalate; polyamide resins such as polyamide 6, polyamide 66, and polyamide 12, polyamide imide resins, polyimide resins, and polyester resins. Examples include imide resin, polyetherimide resin, polyetheretherketone resin, polyphenyleneether resin, modified polyphenyleneether resin, and polybenzimidazole resin.
[0072]
The thermoplastic resin preferably has a 10% weight loss temperature of 400 ° C. or higher when subjected to thermogravimetry in a nitrogen atmosphere. When the temperature is 400 ° C. or higher, the resin material comprising the resin composition of the present invention does not generate outgas in a high-temperature treatment step such as a reflow step of lead-free solder, and is suitable as an electronic material. The temperature is more preferably 450 ° C. or higher, and still more preferably 500 ° C. or higher. Examples of the resin having a 10% weight loss temperature of 400 ° C. or higher in the thermogravimetric measurement in the nitrogen atmosphere include, for example, a polyetheretherketone resin, a polyetherimide resin, a polyamideimide resin, and a thermoplastic polyimide resin. .
[0073]
The resin composition of the present invention contains an inorganic compound.
Examples of the inorganic compound include layered silicate, talc, silica, alumina, glass beads, and the like. Among them, layered silicate is preferably used to improve high-temperature physical properties. In the present specification, the layered silicate means a layered silicate mineral having exchangeable metal cations between layers, and may be a natural product or a synthetic product.
[0074]
When a particularly high tensile modulus is required, it is preferable to contain a layered silicate and a whisker as the inorganic compound. It is known that mixing a whisker with a resin improves the elastic modulus, but there has been a problem that the resin composition containing the whisker has a poor moldability such that a high tensile elastic modulus can be achieved. In the resin composition of the present invention, by using a layered silicate and a whisker together as an inorganic compound, a sufficient improvement in elastic modulus can be obtained even with a small amount of a whisker.
[0075]
When the whisker is blended with the layered silicate as an inorganic compound, it is preferable that the whisker is contained in a proportion of 25 to 95% by weight based on 100% by weight of the inorganic compound. If the amount is less than 25% by weight, the effect obtained by blending the whisker is not sufficient. If the amount exceeds 95% by weight, the effect obtained by adding the layered silicate may not be sufficient.
[0076]
When a particularly low water absorption is required, it is preferable to contain a layered silicate and silica as inorganic compounds. The silica is not particularly limited, and includes, for example, Aerosil manufactured by Nippon Aerosil Co., Ltd. By using a 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 the water absorption is improved when silica is added to the resin.However, a resin composition containing silica to achieve a low water absorption has a problem that physical properties such as tensile strength are reduced. . In the resin composition of the present invention, by using a layered silicate and silica as the inorganic compound, a sufficient effect of reducing the water absorption 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 the layered silicate is not sufficient, and if it exceeds 95% by weight, the effect of the addition of the layered silicate may be impaired.
[0077]
Examples of the layered silicate include smectite-based clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite, and nontronite, swellable mica, vermiculite, halloysite, and the like. Among them, 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 lower limit of the average length is preferably 0.01 μm, the upper limit is 3 μm, the lower limit of the thickness is preferably 0.001 μm, the upper limit is 1 μm, and the lower limit of the aspect ratio is 20. The upper limit is 500, the more preferable lower limit of the average length is 0.05 μm, the upper limit is 2 μm, the more preferable lower limit of the thickness is 0.01 μm, the upper limit is 0.5 μm, the more preferable lower limit of the aspect ratio is 50, and 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 present between the layers of the layered silicate means metal ions such as sodium and calcium present on the surface of the flaky crystal of the layered silicate, and these metal ions are cations with a cationic substance. Because of the exchangeability, various cationic substances can be inserted (intercalated) between the crystal layers of the layered silicate.
[0082]
The cation exchange capacity of the layered silicate is not particularly limited, but the preferred lower limit is 50 milliequivalents / 100 g, and the upper limit is 200 milliequivalents / 100 g. If the amount is less than 50 milliequivalents / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate by cation exchange decreases, so that the crystal layers are not sufficiently depolarized (hydrophobicized). Sometimes. If it exceeds 200 milliequivalents / 100 g, the bonding strength between the crystal layers of the layered silicate may be too strong, and the crystal flakes may not be easily separated.
[0083]
When the resin composition of the present invention is produced using a layered silicate as the inorganic compound, one in which dispersibility in the resin is improved by chemically modifying the layered silicate to increase affinity with the resin. Preferably, such a chemical treatment makes it possible to disperse the layered silicate in the resin in a large amount. If the layered silicate is not subjected to chemical modification suitable for the resin used in the present invention or the solvent used in producing the resin composition of the present invention, the layered silicate is likely to be agglomerated, so that it should be dispersed in a large amount. However, by applying chemical modification suitable for the resin or the solvent, the layered silicate can be dispersed in the resin without agglomeration even when 10 parts by weight or more are added. The chemical modification can be carried out, for example, by the following chemical modification (1) to chemical modification (6) methods. 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 a resin composition of the present invention is obtained using a low-polar resin such as a polyphenylene ether resin, the layered silica is used in advance. This is a method in which cation exchange is performed between the layers of the salt with a cationic surfactant to make the layer hydrophobic. By making the interlayer 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 more uniformly in the low-polarity resin.
[0085]
The cationic surfactant is not particularly limited, and includes, for example, quaternary ammonium salts and quaternary phosphonium salts. Among them, an alkylammonium ion having 6 or more carbon atoms, an aromatic quaternary ammonium ion or a heterocyclic quaternary ammonium ion is preferably used since the crystal layer of the layered silicate can be sufficiently hydrophobicized. In particular, when a thermoplastic polyimide resin, polyesterimide resin, or polyetherimide resin is used as the thermoplastic resin, an aromatic quaternary ammonium ion or a heterocyclic quaternary ammonium ion is preferable.
[0086]
The quaternary ammonium salt is not particularly limited and includes, for example, trimethylalkylammonium salt, triethylalkylammonium salt, tributylalkylammonium salt, dimethyldialkylammonium salt, dibutyldialkylammonium salt, methylbenzyldialkylammonium salt, dibenzyldialkylammonium 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; a quaternary ammonium salt derived from an aromatic amine such as trimethylphenylammonium; an alkylpyridinium salt, imidazoly Quaternary ammonium salts having a heterocyclic ring, such as dimethyl salts; dialkyl quaternary ammonium salts having two polyethylene glycol chains, dialkyl quaternary ammonium salts having two polypropylene glycol chains, and trialkyl quaternary quaternary ammonium salts having one polyethylene glycol chain. 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-hardened tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N , N-dimethylammonium salts 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, the hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method is converted into a functional group capable of chemically bonding to the hydroxyl group or a chemical affinity with the hydroxyl group. Is a chemical treatment with a compound having at least one functional group having a large molecular weight at the molecular terminal.
[0089]
The functional group capable of chemically bonding to the hydroxyl group or the functional group having high chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, a carboxyl group (including a dibasic acid anhydride), Examples include a hydroxyl group, an isocyanate group, and an aldehyde group.
[0090]
The compound having a functional group capable of chemically bonding to the hydroxyl group or the compound having a functional group having a high chemical affinity with the hydroxyl group is not particularly limited. For example, a silane compound, a titanate compound, or a glycidyl compound having the functional group Carboxylic acids, alcohols and the like. These compounds may be used alone or in combination of two or more.
[0091]
The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, 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 Ethoxysilane and the like can be mentioned. These silane compounds may be used alone or in combination of two or more.
[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 is converted into a functional group capable of chemically bonding to a hydroxyl group or a hydroxyl group. This is a method in which a large functional group and a compound having one or more reactive functional groups at the molecular terminals are chemically treated.
The chemical modification (4) method is a method of chemically treating the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method with a compound having an anionic surfactant.
[0093]
The compound having an anionic surface activity is not particularly limited as long as it can chemically treat the layered silicate by ionic interaction. Examples thereof include sodium laurate, sodium stearate, sodium oleate, and higher alcohol sulfate. And secondary higher alcohol sulfates and unsaturated alcohol sulfates. These compounds may be used alone or in combination of two or more.
[0094]
The chemical modification (5) method is a method of chemically treating a compound having one or more reactive functional groups other than the anionic site in the molecular chain among the compounds having the anionic surface activity.
[0095]
In the chemical modification (6) method, the organically modified layered silicate chemically treated by any of the chemical modification (1) method to the chemical modification (5) method is further added to, for example, a maleic anhydride-modified polyphenylene ether resin. And a method using a resin having a functional group capable of reacting with the layered silicate.
[0096]
In the resin composition of the present invention, the layered silicate has an average interlayer distance of the (001) plane measured by a wide-angle X-ray diffraction measurement method of 3 nm or more, and has a five-layer laminate of a part or all of the laminate. Preferably, they are dispersed as follows. By dispersing the layered silicate so that the average interlayer distance is 3 nm or more and part or all of the laminates are 5 layers or less, the interface area between the resin and the layered silicate is sufficiently large. The distance between the flaky crystals of the layered silicate is large, and the distance between the flaky crystals of the layered silicate becomes appropriate, so that the effects of dispersion can be sufficiently improved in high-temperature physical properties, mechanical physical properties, heat resistance, dimensional stability and the like.
[0097]
A preferred upper limit of the average interlayer distance is 5 nm. If it exceeds 5 nm, the crystal flakes of the layered silicate are separated for each layer and the interaction is weakened to a negligible level, so that the binding strength at high temperatures is weakened and sufficient dimensional stability may not be obtained.
[0098]
In the present specification, the average interlayer distance of the layered silicate means the average of the distance between the layers when the flaky crystal of the layered silicate is regarded as a layer, and is obtained by X-ray diffraction peak and transmission electron microscopy. That is, it can be calculated by the wide-angle X-ray diffraction measurement method.
[0099]
The fact that the layered silicate is dispersed so that the above-mentioned part or all of the laminated body has five layers or less specifically means that the interaction between the layered silicate flaky crystals is weakened and the flaky silicates are weakened. Means that some or all of the laminates are dispersed. Preferably, 10% or more of the layered silicate laminate is dispersed in 5 layers or less, and more preferably 20% or more of the layered silicate laminate is dispersed in 5 layers or less.
[0100]
The proportion of the layered silicate dispersed as a laminate of 5 layers or less is determined by observing the resin composition at a magnification of 50,000 to 100,000 times with a transmission electron microscope and observing the layered silicate in a fixed area. By calculating 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 or less layers, the total can be calculated from the following equation (4).
[0101]
(Equation 4)

[0102]
In addition, the number of layers in the layered silicate laminate is preferably 5 layers or less, more preferably 3 layers or less, and still 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, has an average interlayer distance of the (001) plane measured by a wide-angle X-ray diffraction measurement method of 3 nm or more, and has a part or all of a laminate. Is less than 5 layers, the interface area between the resin and the layered silicate becomes sufficiently large, and the interaction between the resin and the surface of the layered silicate becomes large. In addition to improving the melt viscosity and moldability, the mechanical properties such as the elastic modulus are improved over a wide temperature range from room temperature to high temperature, and the mechanical properties are maintained even at high temperatures higher than the Tg or melting point of the resin. And the coefficient of linear expansion at high temperatures can also be kept low. Although the reason for this is not clear, it is considered that these physical properties are exhibited even in the temperature range above Tg or the melting point because the finely dispersed layered silicate acts as a kind of pseudo-crosslinking point. On the other hand, the distance between the flaky crystals of the lamellar silicate is also appropriate, so that the flaky crystals of the lamellar silicate move during combustion to easily form a sintered body that becomes a flame-retardant film. Since this sintered body is formed at an early stage of combustion, it can not only shut off the supply of oxygen from the outside world but also cut off the flammable gas generated by combustion. The material 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 substrate such as the resin composition of the present invention is subjected to perforation by a laser such as a carbon dioxide gas laser, The resin component and the layered silicate component decompose and evaporate at the same time, and the only partially remaining layered silicate residue of several μm or less can be easily removed by desmearing. Thereby, it is possible to prevent the occurrence of plating failure or the like due to the residue generated by the perforation processing.
[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 mixing the resin and the layered silicate by a conventional method, and then foaming the resin with a blowing agent, Examples 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]
The method of mixing the resin and the layered silicate by a conventional method and then foaming the resin with a foaming agent uses energy generated by foaming to disperse the layered silicate.
The foaming agent is not particularly limited, and examples thereof include a gaseous foaming agent, a volatile liquid foaming agent, and a heat-decomposable solid foaming agent. These foaming agents may be used alone or in combination of two or more.
[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. And then vaporizing the gaseous foaming agent in the resin composition to form a foam; containing a pyrolytic foaming agent in advance between the layers of the layered silicate, To form a foam by decomposing the polymer by heating.
[0108]
The lower limit of the amount of the inorganic compound to be added to 100 parts by weight of the thermoplastic resin is 0.1 part by weight, and the upper limit is 65 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving high-temperature physical properties and hygroscopicity is reduced. If the amount exceeds 65 parts by weight, the density (specific gravity) of the resin composition of the present invention becomes high, and the mechanical strength is lowered, so that the practicality becomes poor. The preferred lower limit is 1 part by weight and the upper limit is 60 parts by weight. If the amount is less than 1 part by weight, a sufficient effect of improving the high-temperature properties may not be obtained when the resin composition of the present invention is thinly formed. If the amount exceeds 60 parts by weight, the moldability may decrease. 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 problematic region in mechanical properties and process suitability, and sufficient flame retardancy can be obtained.
[0109]
When a layered silicate is used as the inorganic compound in the resin composition of the present invention, the lower limit of the amount of the layered silicate is preferably 0.5 part by weight, and the upper limit is preferably 50 parts by weight. If the amount is less than 0.5 part by weight, the effect of improving high-temperature physical properties and hygroscopicity may be reduced. If the amount exceeds 50 parts by weight, the density (specific gravity) of the resin composition of the present invention becomes high, and the mechanical strength is also lowered. A more preferred lower limit is 1 part by weight and an upper limit is 45 parts by weight. When the amount is less than 1% by weight, when the resin composition of the present invention is thinly formed, a sufficient effect of improving high-temperature physical properties may not be obtained. If the amount 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 problematic area in the process suitability, sufficient low water absorption is obtained, and the effect of reducing the average linear expansion coefficient is sufficiently obtained in both the α1 and α2 regions. Can be
[0110]
It is preferable that the resin composition of the present invention further contains a flame retardant that does not contain a halogen-based composition. It is to be noted that a small amount of halogen may be mixed due to the production process of the flame retardant or the like.
[0111]
The flame retardant is not particularly limited, and examples thereof include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, gypsum gypsum, and calcium hydroxide; metal oxides; red phosphorus and polyphosphoric acid Phosphorus compounds such as ammonium; Nitrogen compounds such as melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate and melamine derivatives obtained by subjecting these to surface treatment; fluorine resins; silicone oils; layered double water such as hydrotalcite Japanese products: silicone-acrylic composite rubber and the like. Among them, metal hydroxides and melamine derivatives are preferred. Among the above-mentioned 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 preferred amount of the metal hydroxide relative 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 the amount is less than 0.1 part by weight, a sufficient flame retarding effect may not be obtained. If the amount exceeds 100 parts by weight, the density (specific gravity) of the resin composition of the present invention may be too high, and the practicality may be poor, or the flexibility and elongation may be extremely reduced. A more preferred lower limit is 5 parts by weight and an upper limit is 80 parts by weight. If the amount 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 molded thin. If the amount exceeds 80 parts by weight, the defect rate due to swelling and the like in the step of performing the high-temperature treatment may increase. 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 which is problematic 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 amount of the melamine derivative per 100 parts by weight of the thermoplastic resin is 0.1 part by weight, and the upper limit is 100 parts by weight. If the amount is less than 0.1 part by weight, a sufficient flame retarding effect may not be obtained. If it exceeds 100 parts by weight, mechanical properties such as flexibility and elongation may be extremely reduced. A more preferred lower limit is 5 parts by weight and an upper limit is 70 parts by weight. If the amount is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained when the insulating substrate is made thin. If it exceeds 70 parts by weight, mechanical properties such as flexibility and elongation may be extremely reduced. More preferably, the lower limit is 10 parts by weight and the upper limit is 50 parts by weight. When the amount is in the range of 10 to 50 parts by weight, there is no problematic region in mechanical properties, electrical properties, process suitability, etc., and sufficient flame retardancy is exhibited.
[0114]
In the resin composition of the present invention, thermoplastic elastomers, cross-linked rubbers, oligomers, nucleating agents, oxidizing agents, if necessary, for the purpose of modifying properties within a range that does not hinder achievement of the object of the present invention. Additives such as antioxidants (antiaging agents), heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, flame retardant aids, antistatic agents, antifoggants, 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 include, for example, styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, and the like. These thermoplastic elastomers may be modified with a functional group in order to enhance compatibility with the resin. These thermoplastic elastomers may be used alone or in combination of two or more.
[0116]
The crosslinked rubber is not particularly restricted but includes, for example, isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, urethane rubber and the like. In order to increase the compatibility with the resin, it is preferable that these crosslinked rubbers are modified with a functional group. The functional group-modified crosslinked rubber is not particularly limited, and examples thereof include an epoxy-modified butadiene rubber and an epoxy-modified nitrile rubber. These crosslinked rubbers may be used alone or in combination of two or more.
[0117]
The oligomers are not particularly restricted but include, for example, maleic anhydride-modified polyethylene oligomers. These oligomers may be used alone or in combination of two or more.
[0118]
The method for producing the resin composition of the present invention is not particularly limited. For example, each predetermined amount of the resin and the inorganic compound, and each predetermined amount of one or more additives added as necessary, A direct kneading method of directly mixing and kneading at room temperature or under heating, and a method of removing the solvent after mixing in a solvent; a predetermined amount or more of an inorganic compound is previously mixed with the resin or a resin other than the resin. A masterbatch is prepared by kneading the mixture, and the masterbatch, the remaining amount of the resin in a predetermined amount, and the predetermined amount of one or more additives to be blended as necessary are heated at room temperature or heated. A masterbatch method of kneading or mixing in a solvent is mentioned below.
[0119]
In the masterbatch method, a masterbatch in which an inorganic compound is blended with the resin or the resin other than the resin, and a resin for masterbatch dilution containing the resin used when the masterbatch 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, a polyamide resin, in which an inorganic compound is easily dispersed, a polyphenylene ether resin, a polyether sulfone resin, and at least one resin selected from the group consisting of polyester resins. It is preferred to contain. The resin composition for diluting the master batch is not particularly limited. For example, at least one selected from the group consisting of a thermoplastic polyimide resin, a polyetheretherketone resin, and a thermoplastic polybenzoimidazole resin having excellent high-temperature properties. It is preferable to contain the following resin.
[0121]
The blending amount of the inorganic compound in the master batch is not particularly limited, but a preferable lower limit is 1 part by weight and an upper limit is 500 parts by weight based on 100 parts by weight of the resin. When the amount is less than 1 part by weight, the convenience as a masterbatch that can be diluted to an arbitrary concentration is reduced. If the amount exceeds 500 parts by weight, dispersibility in the masterbatch itself, and in particular, dispersibility of the inorganic compound when diluted to a predetermined amount with the resin composition for diluting the masterbatch may be deteriorated. 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, kneading a monomer of the thermoplastic resin with the inorganic compound, and polymerizing the monomer, the thermoplastic resin is obtained. A method may be used in which the polymerization of the resin and the production of the resin composition are simultaneously performed simultaneously.
[0123]
The method of 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 of kneading using a kneading machine such as an extruder, a two-roll mill, or a Banbury mixer.
[0124]
The resin composition of the present invention has a low coefficient of linear expansion at a high temperature due to a combination of a resin and an inorganic compound and an increase in Tg and heat distortion temperature due to restraint of a molecular chain. Excellent mechanical properties, transparency, etc.
[0125]
Further, gas molecules are much easier to diffuse in a resin than an inorganic compound, and when diffusing in a resin, the gas molecules diffuse while bypassing the inorganic compound, so that the gas barrier properties are also improved. Similarly, the barrier properties against other than gas molecules are improved, and the solvent resistance, moisture absorption, water absorption, and the like are improved. Thereby, for example, migration of copper from a copper circuit in a multilayer printed wiring board can be suppressed. Furthermore, it is also possible to suppress the occurrence of problems such as poor plating due to bleed-out of a trace amount of additives in the resin onto the surface.
[0126]
In the resin composition of the present invention, if a layered silicate is used as the inorganic compound, excellent mechanical properties can be obtained without being compounded in a large amount. It is possible to increase the density and reduce the thickness. Further, dimensional stability is improved based on a nucleation effect of the layered silicate in crystal formation, a swelling suppression effect accompanying an improvement in moisture resistance, and the like. Further, since a sintered body of the layered silicate is formed at the time of combustion, the shape of the combustion residue is maintained, the shape does not collapse even after the combustion, and it is possible to prevent the spread of fire and to exhibit excellent flame retardancy.
Further, in the resin composition of the present invention, by using a non-halogen flame retardant, 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, but may be dissolved in an appropriate solvent, or formed into a film or processed to form, for example, a core layer or a build-up layer of a multilayer substrate. It is suitably used for substrate materials, sheets, laminates, copper foil with resin, copper-clad laminates, TAB tapes, printed boards, prepregs, varnishes, and the like. Substrate materials, sheets, laminates, copper foil with resin, copper-clad laminates, TAB tapes, printed boards, prepregs, and adhesive sheets using the resin composition of the present invention are also included in the present invention. .
[0128]
The molding method is not particularly limited, and is, for example, an extruder, which is extruded after melt-kneading and then extruded to form a film using a T-die or a circular die; dissolved in a solvent such as an organic solvent or After the dispersion, a casting molding method of casting to form a film; in a varnish obtained by dissolving or dispersing in a solvent such as an organic solvent, a cloth or nonwoven fabric made of an inorganic material such as glass or an organic polymer. A dipping molding method in which a substrate is dipped and formed into a film shape is exemplified. Among them, the extrusion molding method is suitable for reducing the thickness of the multilayer substrate. The substrate used in the dipping molding method is not particularly limited, and examples thereof include glass cloth, aramid fiber, and polyparaphenylenebenzoxazole fiber.
[0129]
The substrate material, sheet, laminate, copper foil with resin, copper-clad laminate, TAB tape, printed board, prepreg, adhesive sheet, and optical circuit forming material of the present invention comprise the resin composition of the present invention. Thereby, high-temperature properties, dimensional stability, solvent resistance, moisture resistance, and barrier properties are excellent, and a high yield can be obtained even when manufactured through multiple steps. In this specification, a sheet includes a non-self-supporting film-like sheet. The surface may be embossed to improve the slip of these sheets.
[0130]
In the case of a thermoplastic resin, not only the equipment and the production cost can be reduced, but also the above-mentioned processing can be carried out simultaneously with the sheet molding, or it can be post-processed by a simple method, so that it is excellent in formability. Further, it can be reused by melting, and has an advantage of reducing environmental load.
[0131]
In addition, the resin composition of the present invention has low linear expansion coefficient, heat resistance, low water absorption, and high transparency since the layered silicate is finely dispersed at 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, but the present invention is not limited to these Examples.
[0133]
(Example 1)
100 parts by weight of a modified polyphenylene ether-based resin (manufactured by Asahi Kasei Kogyo Co., Ltd., Zylon (PKL) X9102) as a thermoplastic resin and distearyl dimethyl quaternary ammonium as a layered silicate in a small extruder (TEX30, manufactured by Nippon Steel Works, Ltd.) 30 parts by weight of swellable fluorine mica (manufactured by Corp Chemical, Somasif MAE-100) that has been treated with a salt is fed, melt-kneaded at 290 ° C., extruded into strands, and the extruded strands are pelletized by a pelletizer. A master batch was prepared by pelletizing. Next, 100 parts by weight of a polyimide resin (manufactured by Mitsui Chemicals, Inc., Aurum PD-450) 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). In a nitrogen stream, the mixture was melt-kneaded at 420 ° C., extruded, and extruded strands were pelletized with a pelletizer to obtain pellets made of the resin composition. Subsequently, the obtained pellets made of the resin composition are rolled by being pressed by a hot press adjusted to 420 ° C. in the upper and lower directions under a nitrogen stream to thereby form a plate-shaped molded article of the resin composition having a thickness of 2 mm and 100 μm. Was prepared.
[0134]
(Example 2)
100 parts by weight of a modified polyphenylene ether-based resin (manufactured by Asahi Kasei Kogyo Co., Ltd., Zylon (PKL) X9102) as a thermoplastic resin and distearyl dimethyl quaternary ammonium as a layered silicate in a small extruder (TEX30, manufactured by Nippon Steel Works, Ltd.) 30 parts by weight of swellable fluorine mica (manufactured by Corp Chemicals, Somasif MAE-100) which has been treated with a salt is fed, melt-kneaded at 280 ° C., extruded into strands, and the extruded strands are pelletized by 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 (TEX30, manufactured by Nippon Steel Works Ltd.) and melted at 400 ° C. under a nitrogen stream. The mixture was extruded by kneading, and the extruded strand was pelletized by a pelletizer to obtain a pellet made of the resin composition. Next, the obtained pellets made of the resin composition are rolled by being pressed by a hot press adjusted to 400 ° C. in the upper and lower directions under a nitrogen stream, thereby rolling a plate-shaped molded product having a thickness of 2 mm and 100 μm made of the resin composition. Was prepared.
[0135]
(Example 3)
66.12 parts by weight of bis [4- (3-aminophenoxy) phenyl] sulfone was weighed into a 500 ml separable flask, 370 parts by weight of dehydrated N-methylpyrrolidone was added, and the mixture was purged with nitrogen and stirred at 150 rpm for about 30 minutes. did. Next, 33.72 parts by weight of pyromellitic anhydride and 40 parts by weight of dehydrated N-methylpyrrolidone were added, and the mixture was stirred at 150 rpm for 1 hour. Subsequently, 253.2 parts by weight of an N-methylpyrrolidone solution containing 7.9% synthetic hectorite (manufactured by Corp Chemical Co., Lucentite STN), 0.001 part by weight of aniline, and 40 parts by weight of dehydrated N-methylpyrrolidone at 600 rpm. The mixture was stirred for 4 hours to obtain a clay-containing polyamic acid solution.
[0136]
The resulting polyamic acid solution was heated to a high temperature to dilute most of the solvent to form a film, and then further heated to a high temperature to cause the reaction to proceed to imidization. A masterbatch of clay-containing polyimide was obtained. Next, 100 parts by weight of a thermoplastic resin (trade name “Auram PD-450” (manufactured by Sankyo Chemical Co., Ltd.)) and 43 parts by weight of the obtained master batch were charged into a small extruder (TEX30, manufactured by Nippon Steel Works), and nitrogen was added. The mixture was melt-kneaded and extruded under an air stream at 420 ° C. and extruded, and the extruded strands were pelletized by a pelletizer to obtain resin composition pellets. Each was pressed and rolled by a hot press adjusted to a temperature of 400 ° C. to produce a plate-like molded body having a thickness of 2 mm and 100 μm.
[0137]
(Example 4)
47.24 parts by weight of 1,3-bis (4-aminophenoxy) benzene (manufactured by Wako Pure Chemical Industries) was weighed into a 500 ml separable flask, and 370 parts by weight of dehydrated N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries) was added. After adding and purging with nitrogen, the mixture was stirred at 150 rpm for about 30 minutes. Next, 52.60 parts by weight of 3,3′4,4′-benzophenonetetracarboxylic dianhydride (BTDA-BFS-06, manufactured by Daicel Chemical Industries, Ltd.) and 40 parts by weight of dehydrated N-methylpyrrolidone were added, and 150 rpm was added. For 1 hour. Subsequently, 253.2 parts by weight of an N-methylpyrrolidone solution containing 3.9% synthetic mica (synthesized mica treated with 1,2-dimethyl-3-N-decyl-imidazolium) and aniline (manufactured by Wako Pure Chemical Industries, Ltd.) were added. 002 parts by weight and 40 parts by weight of dehydrated N-methylpyrrolidone were stirred at 600 rpm for 4 hours to obtain a clay-containing polyamic acid solution. The obtained polyamic acid solution was subjected to solvent drying and imidation to obtain a master batch of clay-containing polyimide. Then, 100 parts by weight of aurum (PD-450, manufactured by Mitsui Chemicals, Inc.) as a thermoplastic resin and 25 parts by weight of the obtained master batch were charged into a small extruder (TEX30, manufactured by Nippon Steel Works, Ltd.). The mixture was melt-kneaded at 420 ° C., extruded, and the extruded strand was pelletized with a pelletizer to obtain a resin composition pellet. Next, the pellets of the obtained resin composition were pressed and rolled under a nitrogen stream with a hot press adjusted to 400 ° C. in the upper and lower directions to produce a plate-like molded body having a thickness of 2 mm and 100 μm.
[0138]
(Example 5)
66.12 parts by weight of bis [4- (3-aminophenoxy) phenyl] sulfone is weighed into a 500 mL separable flask, 370 parts by weight of dehydrated dimethylformamide (DMF) is added, and the mixture is purged with nitrogen and stirred at 150 rpm for about 30 minutes. did. Next, 33.72 parts by weight of pyromellitic anhydride and 40 parts by weight of dehydrated dimethylformamide (DMF) were added, and the mixture was stirred at 150 rpm for 1 hour. Subsequently, 253.2 parts by weight of a DMF solution containing 7.9% synthetic hectorite (Lucentite STN, manufactured by Corp Chemical), 0.001 part by weight of aniline, and 40 parts by weight of dehydrated DMF were stirred at 600 rpm for 4 hours, and the clay was stirred for 4 hours. A polyamic acid solution was obtained.
[0139]
The resulting polyamic acid solution was dried with a solvent and imidized to obtain a master batch of clay-containing polyimide. Then, in a small extruder (manufactured by Nippon Steel Works, TEX30), 100 parts by weight of aurum (PD-450, manufactured by Mitsui Chemicals, Inc.) as a thermoplastic resin, 17.6 parts by weight of the obtained masterbatch, aluminum borate whisker 10 parts by weight (manufactured by Shikoku Chemical Industry Co., Ltd.) were charged, melt-kneaded at 420 ° C. in a nitrogen stream, extruded, and the extruded strand was pelletized with a pelletizer to obtain a resin composition pellet. Next, the pellets of the obtained resin composition were pressed and rolled under a nitrogen stream with a hot press adjusted to 400 ° C. in the upper and lower directions to produce a plate-like molded body having a thickness of 2 mm and 100 μm.
[0140]
(Example 6)
47.24 parts by weight of 1,3-bis (4-aminophenoxy) benzene was weighed into a 500 mL separable flask, 370 parts by weight of dehydrated N-methylpyrrolidone (NMP) was added, and after replacing with nitrogen, about 30 parts at 150 rpm. Stirred for minutes. Next, 52.60 parts by weight of 3,3′4,4′-benzophenonetetracarboxylic dianhydride and 40 parts by weight of dehydrated NMP were added thereto, followed by stirring at 150 rpm for 1 hour. Subsequently, 253.2 parts by weight of an NMP solution containing 3.9% synthetic mica (manufactured by Corp Chemical, Somasif MPE), 0.002 parts by weight of aniline, and 40 parts by weight of dehydrated NMP were stirred at 600 rpm for 4 hours to contain clay. A polyamic acid solution was obtained.
[0141]
The resulting polyamic acid solution was dried with a solvent and imidized to obtain a master batch of clay-containing polyimide. Then, 100 parts by weight of aurum (PD-450, manufactured by Mitsui Chemicals, Inc.) as a thermoplastic resin, 25 parts by weight of the obtained masterbatch, and silicon carbide whiskers (Toyo Carbon Co., Ltd.) in a small extruder (TEX30, manufactured by Nippon Steel Works, Ltd.) Was melt-kneaded at 420 ° C. in a nitrogen stream and extruded, and the extruded strands were pelletized by a pelletizer to obtain pellets of the resin composition. Next, the pellets of the obtained resin composition were pressed and rolled under a nitrogen stream with a hot press adjusted to 400 ° C. in the upper and lower directions to produce a plate-like molded body having a thickness of 2 mm and 100 μm.
[0142]
(Example 7)
In a small extruder (TEX30, manufactured by Japan Steel Works, Ltd.), 100 parts by weight of aurum (PD-450M, manufactured by Mitsui Chemicals, Inc.), 3 parts by weight of synthetic mica (Somasif MPE, manufactured by Corp Chemical), as a thermoplastic resin, nitrogen In a gas stream, the mixture was melt-kneaded at 330 ° C. and extruded, and the extruded strand was pelletized by a pelletizer to obtain a pellet of the resin composition. Next, the pellets of the obtained resin composition were pressed and rolled under a nitrogen stream with a hot press adjusted to 340 ° C. in the upper and lower directions to produce a plate-like molded body having a thickness of 2 mm and 100 μm.
[0143]
(Example 8)
100 parts by weight of aurum (PD-450, manufactured by Mitsui Chemicals, Inc.) as a thermoplastic resin, and synthetic mica (1,2-dimethyl-3-N-decyl-imidazo) in a small extruder (TEX30, manufactured by Japan Steel Works, Ltd.) 3 parts by weight of lium-treated synthetic mica) and 15 parts by weight of silica (manufactured by Admatechs Co., Ltd., SO-E5) are charged, melt-kneaded and extruded at 420 ° C. under a nitrogen stream, and the extruded strands are pelletized by a pelletizer. Thereby, pellets of the resin composition were obtained. Next, the pellets of the obtained resin composition were pressed and rolled under a nitrogen stream with a hot press adjusted to 400 ° C. in the upper and lower directions to produce a plate-like molded body having a thickness of 2 mm and 100 μm.
[0144]
(Example 9)
92.3 g of isobornyl acrylate was weighed into a 500 ml flask, and 77.0 g of a dimethylformamide (DMF) solution containing 10% by weight of synthetic hectorite (Lucentite STN manufactured by Corp Chemical) was added to the flask. The mixture was stirred for 1 hour to obtain a clay-containing isobornyl acrylate solution. Next, 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. To the obtained clay-containing isobornyl acrylate, 0.9 g of a photopolymerization initiator (Irgacure 651 manufactured by Ciba Specialty Chemical Co., Ltd.) was added to make a uniform state, and then ultraviolet rays of 365 nm were irradiated at 1 mW / cm. ^Two Irradiation at an illuminance of 10 minutes, followed by hot pressing at 160 ° C. to produce a 2 mm-thick and 100 μm-thick plate-like molded product made of the resin composition.
[0145]
(Example 10)
92.3 g of methyl methacrylate was weighed into a 1000 ml flask, and 77.0 g of a methyl ethyl ketone (MEK) solution containing 10 wt% of synthetic hectorite (manufactured by Corp Chemical Co., Lucentite STN) and 200 g of MEK were added to the flask. Was stirred at 80 ° C. Next, an AIBN solution consisting of 2.5 g of azoisobutyronitrile (AIBN) and 100 ml of MEK was added to the flask being stirred at a temperature of 80 ° C. in a hot water bath at an interval of 5 times in 20 ml portions, and added every hour. After the last addition, it was kept at 80 ° C. for another 2 hours. After MEK was distilled off from the obtained reaction mixture by heating under reduced pressure and drying, a hot press at 160 ° C. was performed to produce a plate-shaped molded product having a thickness of 2 mm and 100 μm made of the resin composition.
[0146]
(Comparative Example 1)
Except that swellable fluorine mica (manufactured by Corp Chemical Co., Ltd., Somasif MAE-100) was not blended, a resin composition and a 2 mm-thick and 100 μm-thick plate-shaped molding of the resin composition were performed in the same manner as in Example 1. The body was made.
[0147]
(Comparative Example 2)
Except that swellable fluorine mica (manufactured by Corp Chemicals, Somasif MAE-100) was not blended, a resin composition and a 2 mm-thick and 100 μm-thick plate-shaped molding of the resin composition were performed in the same manner as in Example 2. The body was made.
[0148]
(Comparative Example 3)
A resin composition and a 2 mm-thick and 100 μm-thick plate-like molded article made of the resin composition were prepared in the same manner as in Example 3 except that synthetic hectorite (Lupentite STN manufactured by Corp Chemical) was not blended. Produced.
[0149]
(Comparative Example 4)
Except that synthetic mica (1,2-dimethyl-3-N-decyl-imidazolium-treated synthetic mica) was not blended, a resin composition and a 2 mm thick resin composition were prepared in the same manner as in Example 4. And a plate-shaped molded product of 100 μm.
[0150]
(Comparative Example 5)
A resin composition and a 2 mm-thick and 100 μm-thick plate-like molded article made of the resin composition were prepared in the same manner as in Example 5, except that synthetic hectorite (Lupentite STN manufactured by Corp Chemical) was not blended. Produced.
[0151]
(Comparative Example 6)
A resin composition and a 2 mm-thick and 100 μm-thick plate-like molded article made of the resin composition were prepared in the same manner as in Example 6 except that synthetic mica (manufactured by Corp Chemical, Somasif MPE) was not blended. .
[0152]
(Comparative Example 7)
A resin composition and a 2 mm-thick and 100 μm-thick plate-like molded article made of the resin composition were prepared in the same manner as in Example 7 except that synthetic mica (manufactured by Corp Chemical, Somasif MPE) was not blended. .
[0153]
(Comparative Example 8)
Except that synthetic mica (1,2-dimethyl-3-N-decyl-imidazolium-treated synthetic mica) was not blended, a resin composition and a 2 mm thick resin composition were formed in the same manner as in Example 8. And a plate-shaped molded product of 100 μm.
[0154]
(Comparative Example 9)
Except that the amount of silica (Admatex, SO-E5) was changed to 60 parts by weight and synthetic mica (1,2-dimethyl-3-N-decyl-imidazolium-treated synthetic mica) was not added. In the same manner as in Example 8, a resin composition and a 2 mm-thick and 100 μm-thick plate-like molded body made of the resin composition were produced.
[0155]
(Comparative Example 10)
0.9 g of a photopolymerization initiator (Irgacure 651 manufactured by Ciba Specialty Chemical Co., Ltd.) was added to 92.3 g of isobornyl acrylate, and the mixture was made uniform. ^Two Irradiation at an illuminance of 10 minutes, followed by hot pressing at 160 ° C. to produce a 2 mm-thick and 100 μm-thick plate-like molded product made of the resin composition.
[0156]
<Evaluation>
The performance of the plate-like molded bodies produced in Examples 1 to 10 and Comparative Examples 1 to 10 was evaluated for the following items. The elastic modulus of the plate-like molded bodies produced in Examples 5 and 6 and Comparative Examples 5 and 6 was also evaluated. The results are shown in Tables 1 and 2.
[0157]
(1) Measurement of thermal expansion coefficient
The test piece cut into a 3 mm x 25 mm shape by cutting the plate-like molded body was heated at a heating rate of 5 ° C / min using a TMA (Thermochemical Analysis) device (TMA / SS120C, manufactured by Seiko Instruments Inc.). The linear expansion coefficient (hereinafter, sometimes referred to as “CTE”) was measured, and the following items were evaluated.
[0158]
Average coefficient of linear expansion (α2) at a temperature higher by 10 ° C. to 50 ° C. than the glass transition temperature of the resin composition [° C. ^-1 ].
The average linear expansion coefficient (α2) at a temperature higher by 10 ° C. to 50 ° C. than the glass transition temperature of the resin composition, and the average linear expansion coefficient at a temperature lower by 50 ° C. to 10 ° C. 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 an average linear expansion coefficient at 200 to 240 ° C. [° C. ^-1 ].
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., and the average linear expansion coefficient at 250 to 300 ° C. Is divided by the average linear expansion coefficient at 50 to 100 ° C. to obtain an average linear expansion coefficient ratio (2).
The rate of change (%) obtained by dividing the amount of change in length when the temperature of the plate-like molded body was raised from 25 ° C to 300 ° C by the length of the plate-like molded body at 25 ° C.
-Average linear expansion coefficient ratio (3) represented by the above formula (1).
The average linear expansion coefficient at a temperature higher by 10 ° C. to 50 ° C. than the Tg of the resin composition at a temperature higher by 10 ° C. to 50 ° C. than the Tg of the resin composition prepared in the comparative example corresponding to each example. The improvement rate obtained by dividing each by the average linear expansion coefficient.
[0159]
(2) Average interlayer distance of layered silicate
Using an X-ray diffraction measurement device (RINT1100, manufactured by Rigaku Corporation), 2θ of a diffraction peak obtained from diffraction of a lamination surface of a layered silicate in a plate-like molded body having a thickness of 2 mm was measured, and the following formula (5) was obtained. The (001) interplanar spacing d of the layered silicate was calculated by the black diffraction equation, and the obtained d was defined as the average interlayer distance (nm).
λ = 2 dsin θ Expression (5)
In the above formula (5), λ is 0.154, and θ represents a diffraction angle.
[0160]
(3) Ratio of layered silicate dispersed as a laminate of 5 layers or less: A 100 μm-thick plate-like molded product was observed at a magnification of 100,000 with a transmission electron microscope, and the layered silicate was observed in a fixed area. The total number X of layers and the number Y of layered silicate dispersed in five or less layers of the laminate were measured, and the ratio of the layered silicate dispersed in the laminate of five or less layers according to the following equation (4) ( %) Was calculated.
[0161]
(Equation 5)

[0162]
(4) Measurement of water absorption
A test piece in which a plate-shaped molded product having a thickness of 100 μm was formed into a strip having a size of 3 × 5 cm was prepared, dried at 80 ° C. for 5 hours, and the weight (W1) was measured. Next, the test piece was immersed in water, left for 24 hours in an atmosphere of 25 ° C., taken out, and carefully wiped off with a rag, and the weight (W2) was measured. The water absorption was determined by the following equation.
Water absorption (%) = (W2−W1) / W1 × 100
[0163]
(5) Measurement of humidity linear expansion coefficient
The dimensions (L1) of the 100 μm-thick plate-shaped formed body after being left in a thermo-hygrostat at 50 ° C. and 30% Rh for 24 hours were measured. Next, the dimension (L2) of the plate-shaped molded body after being left in a thermo-hygrostat at 50 ° C. and 80% Rh for 24 hours was measured. The coefficient of linear thermal expansion was determined by the following equation.
Humidity linear expansion coefficient [% RH-1] = (L2-L1) / L1 / (80-30)
[0164]
(6) Measurement of dielectric constant
The dielectric constant near a frequency of 1 MHz was measured using an impedance measuring device (HP4291B, manufactured by HP).
[0165]
(7) Measurement of elastic modulus
The measurement was performed according to a method according to JIS K6301.
[0166]
(8) Measurement of solubility parameter
It was calculated by the formula of Fedors.
[0167]
(9) Measurement of heating 10% weight loss temperature
After drying 5 to 10 mg of the sample at 150 ° C. for 5 hours, measurement was carried out using a TG / DTA device (TG / DTA320, manufactured by Seiko Instruments Inc.) under the following measurement conditions.
[0168]
Measurement temperature: 25-600 ° C
Heating 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 laminated board, a resin-coated copper foil, and a copper-clad resin having excellent mechanical properties, dimensional stability, heat resistance, flame retardancy, and the like, and particularly excellent high-temperature properties. Laminated boards, TAB tapes, printed boards, prepregs, adhesive sheets, and optical circuit forming materials can be provided.

Claims (32)

A resin composition containing 100 parts by weight of a thermoplastic resin and 0.1 to 65 parts by weight of an inorganic compound,
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 3.0 × 10 ⁻³ [° C. ⁻¹ ]. A resin composition characterized by the following. 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 1.0 × 10 ⁻³ [° C. ⁻¹ ]. The resin composition according to claim 1, wherein: The average linear thermal 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 calculated as follows: The average linear expansion coefficient ratio (α2 / α1) obtained by dividing by the 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 70 or less. The resin composition according to claim 1 or 2, wherein The average linear thermal 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 calculated as follows: 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, wherein The average linear expansion coefficient at 50 to 100 ° C. is 4.5 × 10 ⁻⁵ [° C. ⁻¹ ] or less, and the average linear expansion coefficient at 200 to 240 ° C. is 7 × 10 ⁻⁵ [° C. ⁻¹ ]. The resin composition according to claim 1, 2, 3, or 4, wherein: 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, and 250 to 300 ° C. The average linear expansion coefficient ratio (2) obtained by dividing the average linear expansion coefficient at 50 to 100 ° C by 20 is not more than 20. 6. The resin composition according to 4 or 5. The rate of change obtained by dividing the change in length when the temperature of the resin piece made of the resin composition was raised from 25 ° C. to 300 ° C. by the length of the resin piece made of the resin composition at 25 ° C. was 7 % Or less, the resin composition according to claim 1, 2, 3, 4, 5 or 6. The resin composition according to claim 1, 2, 3, 4, 5, 6, or 7, wherein an average linear expansion coefficient ratio (3) represented by the following formula (1) is 1.5 or less.

The average linear expansion coefficient of the resin composition from 10 ° C. higher than the glass transition temperature of the resin composition to 50 ° C. higher than the glass transition temperature of the resin composition is 10 ° C. higher than the glass transition temperature of the resin. The improvement rate obtained by dividing by an average linear expansion coefficient of the resin from a high temperature to a temperature 50 ° C. higher than a glass transition temperature of the resin is 0.50 or less. The resin composition according to 3, 4, 5, 6, 7, or 8. The resin composition according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, and 9, wherein the tensile modulus is 6 GPa or more and the dielectric constant at 1 MHz is 3.3 or less. The water absorption is 1.0% or less, and the humidity linear expansion coefficient is 1.5 × 10 ^-5 [% RH ^-1 ] or less. , 8, 9 or 10. The water absorption rate is 1.0% or less, the dielectric constant at 1 MHz is 3.3 or less, and the dielectric constant after water absorption processing is 3.4 or less. The resin composition according to 6, 7, 8, 9, 10, or 11. The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, having a glass transition temperature of 100 ° C or higher. The thermoplastic resin has a glass transition temperature of 100 ° C. or more and a dielectric constant at 1 MHz of 3.3 or less, wherein the thermoplastic resin has a dielectric constant of 3.3 or less. The resin composition according to 8, 9, 10, 11 or 12. The thermoplastic resin is a polyphenylene ether resin, a functional group-modified polyphenylene ether resin, a mixture of a polyphenylene ether resin or a functional group-modified polyphenylene ether resin and a polystyrene resin, an alicyclic hydrocarbon resin, a thermoplastic polyimide resin, The at least one member selected from the group consisting of an ether ether ketone resin, a polyesterimide resin, a polyetherimide resin, and a thermoplastic polybenzimidazole resin. , 6, 7, 8, 9, 10, 11, 12, 13 or 14. The thermoplastic resin has a solubility parameter of at least 42 [J / cm ³ ] ^1/2 obtained by using the Fedors calculation formula, wherein the solubility parameter is 42 [J / cm ³ ] ^1/2 or more. , 8, 9, 10, 11, 12, 13, 14 or 15. The thermoplastic resin has a 10% weight loss temperature with respect to the weight at 25 ° C of 400 ° C or more when subjected to thermogravimetry in a nitrogen atmosphere. The resin composition according to 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16. The inorganic compound is a layered silicate, and is characterized in that the inorganic compound is a layered silicate. Resin composition. The inorganic compound comprises at least one of whiskers and / or silica and a layered silicate, wherein the inorganic compound comprises a layered silicate. , 13, 14, 15, 16 or 17. 20. The resin composition according to claim 18, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite. 21. The resin composition according to claim 18, wherein the layered silicate contains an alkylammonium ion having 6 or more carbon atoms, an aromatic quaternary ammonium ion or a heterocyclic quaternary ammonium ion. A layered silicate having an average interlayer distance of (001) plane measured by a wide-angle X-ray diffraction measurement method of 3 nm or more and a partial or total laminate of 5 layers or less is dispersed. The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or 21. The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. A substrate material characterized by using: The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. A sheet characterized by using: The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. The laminated board characterized by using. The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. A copper foil with resin, characterized by using: The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. A copper-clad laminate characterized by comprising: The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. A TAB tape characterized by comprising: The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. A printed circuit board characterized by using: The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. A prepreg characterized by using: The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. An adhesive sheet characterized by using: The resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22. An optical circuit forming material characterized by using: