JP3927516B2 - Resin sheet - Google Patents

Description

【００４５】
上記式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４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。
【００４６】
上記ポリフェニレンエーテル単独重合体としては特に限定されず、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。
【００４７】
上記ポリフェニレンエーテル共重合体としては特に限定されず、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系樹脂は、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。
【００４８】
上記官能基変性されたポリフェニレンエーテル系樹脂としては特に限定されず、例えば、上記ポリフェニレンエーテル系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系樹脂は、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系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ワニス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。
【００４９】
上記ポリフェニレンエーテル系樹脂又は官能基変性されたポリフェニレンエーテル系樹脂とポリスチレン系樹脂との混合物としてば特に限定されず、例えば、上記ポリフェニレンエーテル系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系樹脂と、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、ビニルトルニ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系樹脂との混合物等が挙げられる。上記ポリスチレン系樹脂は、単独で用いられてもよく、２種以上が併用されてもよい。又、これらのポリフェニレンエーテル系樹脂又は官能基変性されたポリフェニレンエーテル系樹脂とポリスチレン系樹脂との混合物は、単独で用いられてもよく、２種以上が併用されてもよい。
【００５０】
上記脂環式炭化水素系樹脂としては、高分子鎖中に環状の炭化水素基を有する炭化水素系樹脂であれば特に限定されず、例えば、環状オレフイン、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系樹脂は、単独で用いられてもよく、２種以上が併用されてもよい。
【００５１】
上記環状オレフィンとしては特に限定されず、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。
【００５２】
上記ノルボルネン等の置換体における置換基としては特に限定されず、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。
【００５３】
上記ノルボルネン等の置換体としては特に限定されず、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。
【００５４】
上記脂環式炭化水素系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。
【００５５】
上記熱可塑性ポリイミド系樹脂としては特に限定されず、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。これらの熱可塑性ポリイミド系樹脂は、単独で用いられてもよく、２種以上が併用されてもよい。
【００５６】
上記ポリエーテルエーテルケトン樹脂としては特に限定されず、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。
【００５７】
本発明の樹脂シートは、層状珪酸塩を含有する。本明細書において、上記層状珪酸塩とは、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。上記層状珪酸塩としては特に限定されず、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。なかでも、膨潤性フッ素マイカがより好適である。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。
【００５８】
上記層状珪酸塩としては、下記式（２）で定義される形状異方性効果の大きいスメクタイト系粘土鉱物や膨潤性マイカを用いることが好ましい。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、本発明の樹脂シートはより優れた力学的物性を有するものとなる。
形状異方性効果＝結晶表面（Ａ）の面積／結晶表面（Ｂ）の面積 （２）
式中、結晶表面（Ａ）は層表面を意味し、結晶表面（Ｂ）は層側面を意味する。
【００５９】
上記層状珪酸塩の形状としては特に限定されるものではないが、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。
【００６０】
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、層状珪酸塩の結晶表面上に存在するナトリウムやカルシウム等の金属イオンのことであり、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。
【００６１】
上記層状珪酸塩のカチオン交換容量は、特に限定されるものではないが、好ましい下限が５０ミリ等量／１００ｇ、上限が２００ミリ等量／１００ｇである。層状珪酸塩のカチオン交換容量が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）されないことがあり、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。
【００６２】
本発明において、熱可塑性樹脂、光硬化性樹脂又は熱硬化性樹脂として例えばポリフェニレンエーテル系樹脂等の低極性樹脂を用いる場合には、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て、疎水化しておくことが好ましい。予め層状珪酸塩の層間を疎水化しておくことにより、樹脂との親和性が高まり、層状珪酸塩を低極性の樹脂中により均一に微分散させることができる。
【００６３】
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非極性化（疎水化）し得ることから、炭素数６以上のアルキル鎖を有する４級アンモニウム塩（炭素数６以上のアルキルアンモニウム塩）が好適に用いられる。
【００６４】
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、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、ポリエチレングリコール鎖を二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二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一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一つ有するトリアルキル４級アンモニウム塩が挙げられる。この中でも特に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良いし、２種類以上が併用されても良い。
【００６５】
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良いし、２種類以上が併用されても良い。
【００６６】
本発明で用いられる層状珪酸塩は、上述のような化学処理によって樹脂中への分散性を向上させることができる。
上記化学処理は、カチオン性界面活性剤によるカチオン交換法（以下、化学修飾（１）法ともいう）に限定されるものではなく、例えば、以下に示す化学修飾
（２）〜化学修飾（６）法の各種化学処理法によっても実施することができる。
これらの化学修飾法は、単独で用いられても良いし、２種類以上が併用されても良い。なお、化学修飾（１）法を含め、以下に示す各種化学処理法によって樹脂中への分散性を向上させた層状珪酸塩を、以下、「有機化層状珪酸塩」ともいう。
【００６７】
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、これと化学結合し得る官能基、又は、化学結合はしなくとも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。
【００６８】
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、これと化学結合し得る官能基、又は、化学結合はしなくとも化学的親和性の大きい官能基及び反応性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。
【００６９】
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。
【００７０】
化学修飾（５）法は、化学修飾（４）法において、アニオン性界面活性を有する化合物の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。
【００７１】
化学修飾（６）法は、上記化学修飾（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系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添加した組成物を用いる方法である。
【００７２】
上記化学修飾（２）法における、水酸基と化学結合し得る官能基、又は、化学結合はしなくとも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、アルデヒド基等の官能基や、水酸基との化学的親和性が高いその他の官能基等が挙げられる。また、上記水酸基と化学結合し得る官能基、又は、化学結合はしなくとも化学的親和性の大きい官能基を有する化合物としては、特に限定されるものではないが、例えば、上記に例示した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良いし、２種類以上が併用されても良い。
【００７３】
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良いし、２種類以上が併用されても良い。
【００７４】
化学修飾（４）法及び化学修飾（５）法における、アニオン性界面活性を有する化合物、アニオン性界面活性を有し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良いし、２種類以上が併用されても良い。
【００７５】
上記層状珪酸塩は、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、一部又は全部が５層以下に分散していることが好ましい。上記層状珪酸塩が平均層間距離が３ｎｍ以上であり、かつ、一部又は全部が５層以下にて分散することにより、熱硬化性樹脂、光硬化性樹脂及び熱可塑性樹脂からなる群より選択される少なくとも１種の樹脂と、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、層状珪酸塩の分散による充分な効果が得られ、樹脂材料において、通常の無機充填材を用いたときよりも大きな力学物性、難燃性の改善効果が得られる。
【００７６】
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、燃焼時の被膜形成が遅くなり、難燃性の向上が充分に得られないことがある。なお、本明細書において層状珪酸塩の平均層間距離とは、層状珪酸塩の微細薄片状結晶を層とした場合の平均の層間距離を意味し、Ｘ線回折ピーク及び透過型電子顕微鏡撮影、即ち、広角Ｘ線回折測定法により算出することができる。
【００７７】
上記層状珪酸塩の一部又は全部が５層以下に分散するとは、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１０％以上が５層以下の積層体として分散しており、層状珪酸塩の２０％以上が５層以下の積層体として分散していることがより好ましい。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、本発明の樹脂シート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（３）から算出することができる。
５層以下に分散している層状珪酸塩の割合（％）＝（Ｙ／Ｘ）×１００ （３）
【００７８】
層状珪酸塩の積層数は、５層以下に分層していることが好ましく、そのことにより、上記効果を得ることができるが、より好ましくは３層以下に分層していることであり、特に好ましくは単層状に薄片化していることである。
【００７９】
上記樹脂材料は、樹脂と層状珪酸塩との界面面積が充分に大きいことにより、樹脂と層状珪酸塩の表面との相互作用が大きくなるので、溶融粘度、溶液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、樹脂のガラス転移点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、ガラス転移点又は融点以上の領域においても、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が適度なものとなると、上記樹脂材料は、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り得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、樹脂材料は優れた難燃性を発現する。従って、本発明の樹脂シートは、燃焼時の形状保持効果による優れた難燃性を有する。
【００８０】
更に、上記樹脂材料は、樹脂中を拡散する際に気体分子は無機物を迂回しながら拡散するので、ガスバリア性が向上する。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、吸水性等が向上する。これにより、例えば、本発明の樹脂シートを用いてなる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を抑制することもできる。
【００８１】
本発明の樹脂シートにおいて、上記熱可塑性樹脂及び／又は熱硬化性樹脂との混合物１００重量部に対する上記層状珪酸塩の配合量の下限は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、難燃性や力学物性の改善効果が小さくなり、１００重量部を超えると、樹脂シートの密度（比重）が高くなり、また、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５０重量部である。１重量部未満であると、樹脂シートを薄く成形する際に充分な難燃効果が得られないことがあり、５０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５重量部、上限は２０重量部である。この範囲内であると、機械物性、工程適性に問題となる領域はなく、充分な難燃効果が得られる。
【００８２】
上記樹脂中に上記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、上記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。
【００８３】
上記樹脂と層状珪酸塩とを常法により混合した後に発泡させる方法は、発泡剤を用いて樹脂を発泡させ、その発泡エネルギーを層状珪酸塩の分散エネルギーに転換する方法である。
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良いし、２種類以上が併用されても良い。
【００８４】
層状珪酸塩の存在下で樹脂を発泡させることにより層状珪酸塩を樹脂中に分散せしめる具体的な方法としては特に限定されず、例えば、樹脂１００重量部及び層状珪酸塩０．１〜１００重量部とからなる樹脂組成物に対し、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ることにより、発泡体を形成せしめることによる方法；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、発泡体を形成せしめることによる方法等が挙げられる。
【００８５】
本発明の樹脂シートは、実質的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、実質的にハロゲン系組成物を含有しないとは、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ということを意味する。
【００８６】
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；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が施されたもののようなメラミン誘導体等の窒素系化合物、ハイドロタルサイト等の層状複水和物等が挙げられる。なかでも金属水酸化物及びメラミン誘導体が好適に用いられる。
【００８７】
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ている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良いし、２種類以上が併用されても良い。
【００８８】
上記難燃剤の熱硬化性樹脂、光硬化性樹脂及び熱可塑性樹脂からなる群より選択される少なくとも１種の樹脂１００重量部に対する好ましい含有量の下限は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、これらを含有することによる難燃化効果が充分には得られず、１００重量部を超えると、樹脂シートの密度（比重）が高くなりすぎて、実用性が乏しくなり、柔軟性や伸度が極端に低下してしまう。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、樹脂シートを薄くすると充分な難燃化効果が得られないことがあり、８０重量部を超えると、高温での工程中に膨れ等による不良率が高くなることがある。より好ましい下限は１０重量部、上限は７０重量部である。この範囲であると、機械物性、電気物性、工程適性に問題となる領域がなく、充分な難燃性を発現するので好適である。
【００８９】
本発明の樹脂シートには、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、無機フィラー、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、着色剤等の添加物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。
【００９０】
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。
【００９１】
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。樹脂との相容性を高めるために、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。
【００９２】
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。
【００９３】
本発明の樹脂シートは、表面に無電解メッキ、電気メッキ、スパッタリング又は真空蒸着により金属層を形成したときの金属層のはく離接着強度が３．９Ｎ／ｃｍ以上である。３．９Ｎ／ｃｍ未満であると、本発明の樹脂シートを用いて多層プリント基板を作製した場合に、ビルドアップ加工時や製品を過酷な環境下で使用したときに金属配線が樹脂からはずれてしまいショートや断線を起こすことがある。好ましくは４．９Ｎ／ｃｍ以上、より好ましくは６．９Ｎ／ｃｍ以上である。
なお、上記はく離接着強度は、例えば、表面に形成した厚さ２２μｍ、電極幅１ｃｍ程度の銅電極を剥離速度５０ｍｍ／分の条件で９０度剥離測定を行うことにより測定することができる。
【００９４】
このような性能を達成するためには、シートの表面に粗化処理を施すことが好ましい。粗化処理を施し表面に凹凸を形成することにより、表面に無電解メッキ、電気メッキ、スパッタリング又は真空蒸着により形成した金属配線との密着力を飛躍的に向上させることができる。
【００９５】
上記粗化処理の方法としては特に限定されないが、過マンガン酸ナトリウムや過マンガン酸カリウム等の過マンガン酸塩等の酸化剤により粗化する方法が好適である。本発明の樹脂シートは、表面のエポキシ樹脂硬化物からなる樹脂部分を過マンガン酸塩等の酸化剤により溶解することにより表面に凹凸が発生する、即ち粗化されるが、それに加えて、本発明のエポキシ樹脂シートは層状珪酸塩や難燃剤、必要に応じて無機フィラーを含有することから、表面樹脂が酸化溶解された際に、層状珪酸塩、難燃剤、無機フィラーが表出し、表面凹凸を更に大きくすることができる。
具体的には、例えば、まず樹脂シート表面を膨潤させ、過マンガン酸ナトリウム等の酸化剤により樹脂を酸化させて樹脂シートの表面を粗化するが、６０〜７０ｇ／Ｌ過マンガン酸溶液、４０〜８０ｇ／Ｌ水酸化ナトリウム溶液を用いて、処理温度７０〜８５℃で１又は２回処理する方法が好ましい。処理の回数が多い方が粗化効果も大きいが、処理を繰り返すと層状珪酸塩や難燃剤も削られていくため、３回以上行っても実質的な効果は変わらないか、又は、明確な凹凸が得られにくくなることがある。
【００９６】
しかしながら、熱硬化性樹脂、光硬化性樹脂、樹脂硬化物及び熱可塑性樹脂からなる群より選択される少なくとも１種の樹脂中に層状珪酸塩がナノスケールで分散しているシートは、吸水率が極めて低く、かつ、耐薬品性が極めて高いため、上述のように過マンガン酸ナトリウム又は酸化剤を用いて粗化処理を行おうとしても充分に粗化されないことがある。
このような場合には、層状珪酸塩としてアスペクト比の大きなものを用いる、又は、シートの表面の層状珪酸塩の割合だけを減らし樹脂の割合を多くすることが好ましい。すなわち、上述の吸水率や耐薬品性は層状珪酸塩が樹脂中に微分散していることに起因するものであることから、少なくとも表面における層状珪酸塩の含有量が小さくなれば、相対的に過マンガン酸ナトリウム等の酸化剤による粗化処理効果も大きなものとなる。
【００９７】
層状珪酸塩としてアスペクト比の大きなものを用いる場合には、より少量の添加でも充分な微分散の効果を得ることができることから、層状珪酸塩の配合量を減らすことができ、過マンガン酸ナトリウム等の酸化剤による粗化処理効果も大きくなる。このような層状珪酸塩としては、例えば、膨潤性フッ素マイカ等が挙げられる。この場合、樹脂１００重量部に対する膨潤性フッ素マイカの配合量の下限は０．１重量部、好ましい上限は１０重量部である。０．１重量部未満であると、層状珪酸塩を配合する効果が得られず、１０重量部を超えると、過マンガン酸ナトリウム又は酸化剤による粗化処理では充分に表面を粗化できないことがある。より好ましい上限は５重量部である。
また、シートの表面にのみ、上記アスペクト比の大きい層状珪酸塩が含有されるようにすることによっても同様の効果が得られる。
【００９８】
また、このような効果は、層状珪酸塩以外の添加成分を少なくし、シートの表面の樹脂の割合を多くすることによっても達成できる。すなわち、金属層を形成する表面部分を、有機成分比率が全体の平均の有機成分比率以上であるようにすれば、表面部分における層状珪酸塩の含有割合が相対的に小さくなり、過マンガン酸ナトリウム等の酸化剤による粗化処理効果も大きくなる。
上記表面部分とは、表面から２μｍ以上、２０μｍ以下の深さであることが好ましい。２μｍであると、上述の効果が得られないことがあり、２０μｍを超えると、樹脂シート全体の物性が劣ることがある。
また、表面部分の有機成分比率は、全体平均の１．０２倍以上であることが好ましい。１．０２倍未満であると、上述の効果が得られないことがある。より好ましくは１．０５倍以上である。
なお、上記有機成分比率は、有機成分／（有機成分＋無機成分）で表される値である。
【００９９】
シートの表面の樹脂の割合を多くする方法としては、樹脂シートを多層構造にする方法の他に、塗工後、ゆっくりと乾燥させることで、無機フィラー等を沈降させる方法や、塗布するフィルムに接している面に静電的相互作用により樹脂を偏在させる方法等が挙げられる。具体的には、表面処理がなされ、表面エネルギーの低いＰＥＴフィルム上に塗布すると、樹脂が塗布フィルム面に偏在したシートを得ることができる。
【０１００】
また、シートの表面又は全体に、過マンガン酸ナトリウムや過マンガン酸カリウム等の過マンガン酸塩等の酸化剤により比較的酸化されやすい樹脂を用いると、シートの表面に粗化による凹凸を容易に付与することができる。上記酸化剤により比較的酸化されやすい樹脂としては、例えば、ポリブタジエン骨格等のように分子内に二重結合を有するエポキシ樹脂、ゴム等が挙げられる。
従って、酸化剤により比較的酸化されやすい樹脂を用いる場合は、上記熱可塑性樹脂及び／又は熱硬化性樹脂との混合物１００重量部に対する上記層状珪酸塩の配合量が多いものであっても、充分にシートの表面を粗化することができる。
このような場合、上記層状珪酸塩の割合は高くなってもよく、上記熱可塑性樹脂及び／又は熱硬化性樹脂との混合物１００重量部に対する上記層状珪酸塩の配合量の好ましい上限は９０重量部、より好ましい上限は５０重量部である。
なお、上記層状珪酸塩を２０重量部以上配合しても、充分にシートの表面を粗化することができる。
【０１０１】
後述するような樹脂ワニス組成物を乾燥させて樹脂シートを作製する場合、乾燥条件を制御することで、シートの表面に凹凸を付与することができる。
この場合、過マンガン酸ナトリウムや過マンガン酸カリウム等の過マンガン酸塩等の酸化剤により粗化する方法を用いなくても、電気メッキにより形成した銅配線との間で優れた密着強度を実現することができる。このように、乾燥条件を制御して、表面に凹凸を付与した後、酸化剤により粗化する方法を実施すると、表面に凹凸がなかった場合と比較して、密着強度を更に向上させることができる。
【０１０２】
また、予め層状珪酸塩、又は、難燃剤として金属水酸化物が粒子径０．５μｍ以上になるように分散した熱硬化性樹脂及び／又は熱可塑性樹脂からなる樹脂からなる層を樹脂シート上に形成しておき、その表面に上記粗化処理を施すことも好ましい。粒子径の大きな層状珪酸塩や難燃剤を表出させることにより、より大きな凹凸を形成することができ、樹脂シートと金属配線との密着力をより向上することができる。
なお、上記層状珪酸塩又は難燃剤が粒子径０．５μｍ以上で分散した層の厚さは、５μｍ以下であることが好ましい。５μｍを超えると、本発明の樹脂シート全体に占める該層の割合が大きくなり、本発明の樹脂シートの力学的強度、難燃性等が充分に発揮できないことがある。
【０１０３】
過マンガン酸ナトリウムや過マンガン酸カリウム等の過マンガン酸塩等の酸化剤により粗化する方法では、シートの表面を極性化することで、電気メッキによる銅配線との密着強度を向上させることができる。
シートの表面を極性化する方法としては、そのほかに、コロナ処理、プラズマ処理等も有効である。
【０１０４】
酸化剤による粗化、コロナ処理又はプラズマ処理を行った場合、シートの表面を極性化する効果以外にも、シートの表層の不純物や未反応物を取り除く効果を有することがある。このような場合、処理時間が短くなり、スパッタリングや電気メッキにより形成した銅配線との密着強度を向上させることができる。
【０１０５】
本発明の樹脂シートは、ＡＳＴＭ Ｅ １３５４に準拠した燃焼試験において、５０ｋＷ／ｍ^２の輻射加熱条件下で３０分間加熱することにより燃焼させた燃焼残渣を速度０．１ｃｍ／ｓで圧縮した際の降伏点応力が４．９ｋＰａ以上であることが好ましい。４．９ｋＰａ未満であると、微小な力で燃焼残渣の崩壊が起こり易くなって、難燃性が不充分となることがある。即ち、本発明の樹脂シートにおいて、焼結体が難燃被膜としての機能を充分に発現するためには、燃焼終了時まで焼結体がその形状を保持していることが好ましい。より好ましくは１５．０ｋＰａ以上である。
【０１０６】
本発明の樹脂シートを作製する方法としては特に限定されないが、例えば、樹脂、層状珪酸塩及び有機溶媒を混合した樹脂ワニス組成物を作製し、この樹脂ワニス組成物から有機溶媒を留去して樹脂シートを作製し、更にこの樹脂シートの表面を粗化処理する方法等が挙げられる。
本発明の樹脂シートを製造する方法であって、熱硬化性樹脂、光硬化性樹脂、樹脂硬化物及び熱可塑性樹脂からなる群より選択される少なくとも１種の樹脂１００重量部に対して層状珪酸塩０．１〜１００重量部及び有機溶媒３０〜１０００重量部を混合して樹脂ワニス組成物を作製する工程と、樹脂ワニス組成物から有機溶媒を留去する工程とを有する樹脂シートの製造方法もまた、本発明の１つである。
【０１０７】
上記有機溶媒としては特に限定されず、例えば、ヘキサン、シクロヘキサン、四塩化炭素、クロロホルム、ジクロロメタン、ジエチルエーテル、１，２−ジメトキシエタン、テトラヒドロフラン、１，４−ジオキサン、酢酸エチル、Ｎ，Ｎ−ジメチルホルムアミド、ヘキサメチルホスホルアミド、酢酸、アセトン、メチルエチルケトン、メタノール、エタノール、ニトロメタン、ジメチルスルホキシド、スルホラン、ベンゼン、トルエン、キシレン、ナフタレン、クロロベンゼン、アニソール、ジフェニルエーテル、ピリジン、ニトロベンゼン等が挙げられる。なかでも、層状珪酸塩を分散するには極性有機溶媒が好ましく、より好ましくは非プロトン性の極性有機溶媒である。非プロトン性の極性有機溶媒とは、強い水素結合の形成に適した水素を持たない極性有機溶媒を意味し、具体的には、アセトン、メチルエチルケトン、アセトニトリル、ジメチルスルホキシド、ｎ，ｎ−ジメチルホルムアミド、ヘキサメチルホスホルアミド等が挙げられる。これら有機溶媒は、単独で用いられてもよく、２種以上が併用されてもよい。
【０１０８】
上記有機溶媒の配合量としては、上記樹脂、層状珪酸塩の配合量及び有機溶媒の種類により最適量は異なるが、一般に樹脂濃度、層状珪酸塩濃度共に低い方が好ましく、樹脂１００重量部及び層状珪酸塩０．０１〜１００重量部に対して３０〜１０００重量部が混合される。３０重量部未満であると、樹脂組成物の溶液粘度が高すぎて、キャストが困難である。１０００重量部を超えると、溶液キャスト時の塗工不良が生じたり、厚膜化が困難となったりすることがある。上記有機溶媒の配合量の好ましい下限は１００重量部、より好ましい下限は１５０重量部以上であり、層状珪酸塩よりも多く配合されることが好ましい。
【０１０９】
上記樹脂ワニス組成物を作製する方法としては、層状珪酸塩と有機溶媒とをあらかじめ混合しておき、得られた混合物と樹脂又は樹脂溶液とを混合する方法が好ましい。上記混合には、流星式撹拌装置、ホモジナイザー、メカノケミカル撹拌機等を用いることが好ましい。
【０１１０】
次いで、上記樹脂ワニス組成物から上記有機溶媒を留去することにより樹脂シートが得られる。上記留去の方法としては特に限定されず、樹脂ワニス組成物の組成に応じて選択される。
【０１１１】
また、片面のみが相対的に樹脂の割合が多い樹脂シートを作製する方法としては特に限定されず、例えば、比重の重い層状珪酸塩を用いたり、溶液キャスト速度を遅くしたりして、層状珪酸塩を沈降させてシート厚み方向での有機成分比率の異なるシートを作製する方法；有機成分比率の異なるシートを積層する方法等が挙げられる。
【０１１２】
本発明の樹脂シートは、熱硬化性樹脂、光硬化性樹脂、樹脂硬化物及び熱可塑性樹脂からなる群より選択される少なくとも１種の樹脂中に層状珪酸塩がナノスケールで分散していることにより、優れた力学物性や透明性、耐湿性等を有し、分子鎖の拘束によるガラス転移点温度や耐熱変形温度の上昇に基づく耐熱性の向上や熱線膨張率の低減、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等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。また、燃焼時には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、延焼を防止することができ、優れた難燃性を発現する。更に、金属水酸化物等のノンハロゲン難燃剤と組み合わせることで、環境にも配慮しつつ、高い力学的物性等と高い難燃性とを両立することができる。上記樹脂シートにおいては、層状珪酸塩が通常の無機充填剤のように多量に配合しなくとも優れた力学的物性等を付与することから薄い成形体に加工でき、多層プリント基板の高密度化、薄型化に対応して厚さの薄い本発明の樹脂シートが得られる。本発明の樹脂シートからなる絶縁基板用材料は、優れた難燃性、力学的物性、高温物性、耐熱性、寸法安定性等の諸性能を発現できる。
【０１１３】
更に、本発明の樹脂シートは、表面に粗化加工を施すことにより、表面に無電解メッキ、電気メッキ、スパッタリング又は真空蒸着により形成した金属配線との密着力が飛躍的に向上している。これにより、ビルドアップ加工時や製品を過酷な環境下で使用したときでも金属配線が樹脂からはずれることがなく、高い信頼性を確保できる。
本発明の樹脂シートは、プリント多層基板、ビルドアップ基板、樹脂基板等に好適に用いることができる。
【０１１４】
【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。
【０１１５】
（実施例１）
ビスフェノールＦ型エポキシ樹脂（大日本インキ化学工業社製、エビクロン８３０ＬＶＰ）５７．７重量部、ＢＴレジン（三菱瓦斯化学社製、ＢＴ２１００Ｂ）１５．７重量部及びネオペンチルグリコールジグリシジルエーテル１５．７重量部からなるエポキシ樹脂組成物８９．１重量部、カップリング剤としてγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー社製、Ａ−１８７）２．１重量部、硬化触媒としてアセチルアセトン鉄（日本化学産業社製）１．１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）７．７重量部、難燃剤として水酸化マグネシウム（協和化学工業社製、キスマ５Ｊ）７０重量部、及び、有機溶媒としてメチルエチルケトン（和光純薬社製、特級）２００重量部をビーカーに加え、攪拌機にて１時間攪拌した後、脱泡し、樹脂ワニスを得た。
【０１１６】
得られた樹脂ワニスを鋳型に入れた状態で６０℃で３時間加熱して溶媒を留去した後、１１０℃で３時間加熱し、更に１６０℃で３時間加熱して硬化させ、厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１１７】
別に、得られた樹脂ワニスをドクターブレード法により、ポリエチレンテレフタレートフィルム上に塗工し、乾燥させて厚さ２４μｍのシー卜を得た。なお、ドクターブレード条件は、乾燥温度＝７０℃、スピード＝０．３ｍ／ｍｉｎとした。
得られたシートをコア材（厚さ０．６ｍｍ：利昌工業社製）の両面に、９０℃、１０ｓｅｃ、圧力１ｋｇ／ｃｍ^２の条件で真空ラミネートした。ラミネート後、ポリエチレンテレフタレートフィルムを取り除き、１７０℃、６０ｍｉｎで熱硬化して、基板を得た。
【０１１８】
得られた基板に、以下のそれぞれの条件により粗化処理を施した。
条件１：基板を８０℃に設定した膨潤液（アドテック社製、スウェリングディップ セキュリ ガントＰ）にて５分間膨潤させた後、８０℃に設定した粗化液（５０ｇ／Ｌ過マンガン酸ナトリウム、３０ｇ／Ｌ水酸化ナトリウムを含有する溶液）に１５分浸漬した（処理回数１回）。
条件２：基板を８０℃に設定した膨潤液（アドテック社製、スウェリングディップ セキュリガントＰ）にて５分間膨潤させた後、８０℃に設定した粗化液（７５ｇ／Ｌ過マンガン酸ナトリウム、５０ｇ／Ｌ水酸化ナトリウムを含有する溶液）に１５分浸漬した（処理回数１回）。
条件３：基板を８０℃に設定した膨潤液（アドテック社製、スウェリングディップ セキュリガントＰ）にて５分間膨潤させた後、８０℃に設定した粗化液（７５ｇ／Ｌ過マンガン酸ナトリウム、５０ｇ／Ｌ水酸化ナトリウムを含有する溶液）に１５分浸漬した（処理回数２回）。
条件４：基板を８０℃に設定した膨潤液（アドテック社製、スウェリングディップ セキュリガントＰ）にて５分間膨潤させた後、８０℃に設定した粗化液（７５ｇ／Ｌ過マンガン酸ナトリウム、５０ｇ／Ｌ水酸化ナトリウムを含有する溶液）に１５分浸漬した（処理回数３回）。
【０１１９】
粗化処理を行った基板上に、パラジウム触媒、無電解銅メッキ液を用いて３５℃、１０分の条件で無電解メッキを行い、厚さ０．８μｍの無電解メッキ銅層を形成した。
更に、この上に、２Ａ／ｄｍ^２、７０分の条件で電気メッキを行い、厚さ２４μｍの電気メッキ銅層を形成した。
【０１２０】
（実施例２）
ビスフェノールＦ型エポキシ樹脂（大日本インキ化学工業社製、エピクロン８３０ＬＶＰ）５７．７重量部、ＢＴレジン（三菱瓦斯化学社製、ＢＴ２１００Ｂ）１５．７重量部及びネオペンチルグリコールジグリシジルエーテル１５．７重量部からなるエポキシ樹脂組成物８９．１重量部、カップリング剤としてγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー社製、Ａ−１８７）２．１重量部、硬化触媒としてアセチルアセトン鉄（日本化学産業社製）１．１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天然モンモリロナイト（粒子径＝１μｍ）７．７重量部、難燃剤として水酸化マグネシウム（粒子径＝１μｍ）７０重量部、及び、有機溶媒としてメチルエチルケトン（和光純薬社製、特級）２００重量部をビーカーに加え、攪拌機にて１時間攪拌した後、脱泡し、樹脂ワニス１を得た。
【０１２１】
一方、ビスフェノールＦ型エポキシ樹脂（大日本インキ化学工業社製、エピクロン８３０ＬＶＰ）５７．７重量部、ＢＴレジン（三菱瓦斯化学社製、ＢＴ２１００Ｂ）１５．７重量部及びネオペンチルグリコールジグリシジルエーテル１５．７重量部からなるエポキシ樹脂組成物８９．１重量部、カップリング剤としてγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー社製、Ａ−１８７）２．１重量部、硬化触媒としてアセチルアセトン鉄（日本化学産業社製）１．１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（粒子径＝０．１μｍ）７．７重量部、難燃剤として水酸化マグネシウム（粒子径＝０．１μｍ）７０重量部、及び、有機溶媒としてメチルエチルケトン（和光純薬社製、特級）２００重量部をビーカーに加え、攪拌機にて１時間攪拌した後、脱泡し、樹脂ワニス２を得た。
【０１２２】
得られた樹脂ワニス２を鋳型に入れた状態で６０℃で３時間加熱して溶媒を留去した後、１１０℃で３時間加熱し、更に１６０℃で３時間加熱して硬化させ、厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１２３】
別に、得られた樹脂ワニス１をドクターブレード法により、ポリエチレンテレフタレートフィルム上に塗工し、乾燥させて厚さ４μｍのシー卜を得た。なお、ドクターブレード条件は、乾燥温度＝７０℃、スピード＝０．３ｍ／ｍｉｎとした。
次に、樹脂ワニス２を同様の条件のドクターブレード法により、樹脂ワニス１からなるシート上に塗工し、乾燥させて厚さ２０μｍのシー卜を得た。
得られたシートをコア材（厚さ０．６ｍｍ：利昌工業社製）の両面に、９０℃、１０ｓｅｃ、圧力１ｋｇ／ｃｍ^２の条件で真空ラミネートした。ラミネート後、ポリエチレンテレフタレートフィルムを取り除き、１７０℃、６０ｍｉｎで熱硬化して、基板を得た。
【０１２４】
得られた基板に、実施例１の条件２により粗化処理を施した。
粗化処理を行った基板上に、パラジウム触媒、無電メッキ液３５℃、１０分の条件で無電解メッキを行い、厚さ０．８μｍの無電解メッキ銅層を形成した。
更に、この上に、２Ａ／ｄｍ^２、７０分の条件で電気メッキを行い、厚さ２４μｍの電気メッキ銅層を形成した。
【０１２５】
（実施例３）
膨潤性フッ素マイカ（コープケミカル社製、ソマシフＭＡＥ−１００）７．７重量部を０．５重量部とした以外は実施例１と同様にして、樹脂ワニスを調製し、これを用いて厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１２６】
別に、得られた樹脂ワニス１をドクターブレード法により、ポリエチレンテレフタレートフィルム上に塗工し、乾燥させて厚さ４μｍのシー卜を得た。なお、ドクターブレード条件は、乾燥温度＝７０℃、スピード＝０．３ｍ／ｍｉｎとした。
次に、樹脂ワニス２を同様の条件のドクターブレード法により、樹脂ワニス１からなるシート上に塗工し、乾燥させて厚さ２０μｍのシー卜を得た。
得られたシートをコア材（厚さ０．６ｍｍ：利昌工業社製）の両面に、９０℃、１０ｓｅｃ、圧力１ｋｇ／ｃｍ^２の条件で真空ラミネートした。ラミネート後、ポリエチレンテレフタレートフィルムを取り除き、１７０℃、６０ｍｉｎで熱硬化して、基板を得た。
【０１２７】
得られた基板に、以下の条件により粗化処理を施した。
基板を８０℃に設定した膨潤液（アドテック社製、スウェリングディップ セキュリガントＰ）にて５分間膨潤させた後、８０℃に設定した粗化液（５０ｇ／Ｌ過マンガン酸ナトリウム、３０ｇ／Ｌ水酸化ナトリウムを含有する溶液）に浸漬した。
【０１２８】
粗化処理を行った基板上に、パラジウム触媒、無電解銅メッキ液を用いて３５℃、１０分の条件で無電解メッキを行い、厚さ０．８μｍの無電解メッキ銅層を形成した。
更に、この上に、２Ａ／ｄｍ^２、７０分の条件で電気メッキを行い、厚さ２４μｍの電気メッキ銅層を形成した。
【０１２９】
（実施例４）
メチルエチルケトン（和光純薬社製、特級）２００重量部を１００重量部とした以外は実施例１と同様にして、樹脂ワニスを調製し、これを用いて厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１３０】
別に、得られた樹脂ワニス１をドクターブレード法により、ポリエチレンテレフタレートフィルム上に塗工し、乾燥させて厚さ４μｍのシー卜を得た。なお、ドクターブレード条件は、乾燥温度＝７０℃、スピード＝０．３ｍ／ｍｉｎとした。
次に、樹脂ワニス２を同様の条件のドクターブレード法により、樹脂ワニス１からなるシート上に塗工し、乾燥させて厚さ２０μｍのシー卜を得た。
得られたシートをコア材（厚さ０．６ｍｍ：利昌工業社製）の両面に、９０℃、１０ｓｅｃ、圧力１ｋｇ／ｃｍ^２の条件で真空ラミネートした。ラミネート後、ポリエチレンテレフタレートフィルムを取り除き、１７０℃、６０ｍｉｎで熱硬化して、基板を得た。
【０１３１】
得られた基板に、実施例３と同様の条件により粗化処理を施した。
粗化処理を行った基板上に、パラジウム触媒、無電解銅メッキ液を用いて３５℃、１０分の条件で無電解メッキを行い、厚さ０．８μｍの無電解メッキ銅層を形成した。
更に、この上に、２Ａ／ｄｍ^２、７０分の条件で電気メッキを行い、厚さ２４μｍの電気メッキ銅層を形成した。
【０１３２】
（実施例５）
難燃剤として水酸化マグネシウム（協和化学工業社製、キスマ５Ｊ）７０重量部を用いなかった以外は実施例１と同様にして、樹脂ワニスを調製し、これを用いて厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１３３】
別に、得られた樹脂ワニスをドクターブレード法により、ポリエチレンテレフタレートフィルム上に塗工し、乾燥させて厚さ２４μｍのシー卜を得た。なお、ドクターブレード条件は、乾燥温度＝７０℃、スピード＝０．３ｍ／ｍｉｎとした。
得られたシートをコア材（厚さ０．６ｍｍ：利昌工業社製）の両面に、９０℃、１０ｓｅｃ、圧力１ｋｇ／ｃｍ^２の条件で真空ラミネートした。ラミネート後、ポリエチレンテレフタレートフィルムを取り除き、１７０℃、６０ｍｉｎで熱硬化して、基板を得た。
【０１３４】
得られた基板に、実施例１の条件２により粗化処理を施した。
粗化処理を行った基板上に、パラジウム触媒、無電解銅メッキ液を用いて３５℃、１０分の条件で無電解メッキを行い、厚さ０．８μｍの無電解メッキ銅層を形成した。
更に、この上に、２Ａ／ｄｍ^２、７０分の条件で電気メッキを行い、厚さ２４μｍの電気メッキ銅層を形成した。
【０１３５】
（実施例６）
Ｎ，Ｎ−ジメチルホルムアミド（和光純薬社製）２４３．９重量部に、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−Ａ）２０重量部、ビスフェノールＡ型エポキシ樹脂（東都化成社製エポトートＹＤ−８１２５）４０重量部、フェノキシ樹脂（東都化成社製フェノトートＹＰ−５５）４０重量部、ジシアンジアミド（旭電化工業社製アデカハードナーＥＨ−３６３６）２．８重量部及び変性イミダゾール（旭電化工業社製アデカハードナーＥＨ−３３６６）１．２重量部を添加し、撹拌機にて２時間撹拌混合した後、脱泡し、樹脂溶液を得た。
【０１３６】
別に、得られた樹脂ワニスをドクターブレード法により、ポリエチレンテレフタレートフィルム上に塗工し、乾燥させて厚さ４０μｍのシー卜を得た。なお、ドクターブレード条件は、乾燥温度＝１００℃、スピード＝０．３ｍ／ｍｉｎとした。
得られたシートをコア材（厚さ０．６ｍｍ：利昌工業社製）の両面に、９０℃、１０ｓｅｃ、圧力１ｋｇ／ｃｍ^２の条件で真空ラミネートした。ラミネート後、ポリエチレンテレフタレートフィルムを取り除き、１７０℃、６０ｍｉｎで熱硬化して、基板を得た。
また、得られた基板にコロナ放電処理機（サイリスター・インバーター方式、 ＨＦＳ４０２、春日電機社製）を用い、空気中でコロナ放電処理（処理条件：印加エネルギー６０００Ｊ／ｍ^２、処理速度２０ｍ／分、温度２０℃）を行った。
【０１３７】
このようにして得られた基板に、以下の条件により粗化処理を施した。
基板を８０℃に設定した膨潤液（アドテック社製、スウェリングディップ セキュリガントＰ）にて５分間膨潤させた後、８０℃に設定した粗化液（５０ｇ／Ｌ過マンガン酸ナトリウム、３０ｇ／Ｌ水酸化ナトリウムを含有する溶液）に浸漬した。
【０１３８】
粗化処理を行った基板上に、パラジウム触媒、無電解銅メッキ液を用いて３５℃、１０分の条件で無電解メッキを行い、厚さ０．８μｍの無電解メッキ銅層を形成した。
更に、この上に、２Ａ／ｄｍ^２、７０分の条件で電気メッキを行い、厚さ２４μｍの電気メッキ銅層を形成した。
【０１３９】
（実施例７）
Ｎ，Ｎ−ジメチルホルムアミド（和光純薬社製）１１１０．９重量部に、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−Ａ）８４．３１重量部、エポキシ変性ブタジエンゴム（日本曹達社製ＥＰＢ−１３）３８４重量部、フェノールノボラック樹脂（大日本インキ社製、フェノライトＬＡ−１３５６）９３．７５重量部および合成シリカ（アドマテックス社製アドマファインＳＯ−Ｅ２）５５．８８重量部を添加し、撹拌機にて２時間撹拌混合した後、脱泡し樹脂溶液を得た。
【０１４０】
別に、得られた樹脂ワニスをドクターブレード法により、ポリエチレンテレフタレートフィルム上に塗工し、乾燥させて厚さ４０μｍのシー卜を得た。なお、ドクターブレード条件は、乾燥温度＝１００℃、スピード＝０．３ｍ／ｍｉｎとした。
得られたシートをコア材（厚さ０．６ｍｍ：利昌工業社製）の両面に、９０℃、１０ｓｅｃ、圧力１ｋｇ／ｃｍ^２の条件で真空ラミネートした。ラミネート後、ポリエチレンテレフタレートフィルムを取り除き、１７０℃、６０ｍｉｎで熱硬化して、基板を得た。
【０１４１】
次に、得られた基板に、以下の条件により粗化処理を施した。
基板を８０℃に設定した膨潤液（アドテック社製、スウェリングディップ セキュリガントＰ）にて５分間膨潤させた後、８０℃に設定した粗化液（５０ｇ／Ｌ過マンガン酸ナトリウム、３０ｇ／Ｌ水酸化ナトリウムを含有する溶液）に浸漬した。
【０１４２】
粗化処理を行った基板上に、パラジウム触媒、無電解銅メッキ液を用いて３５℃、１０分の条件で無電解メッキを行い、厚さ０．８μｍの無電解メッキ銅層を形成した。
更に、この上に、２Ａ／ｄｍ^２、７０分の条件で電気メッキを行い、厚さ２４μｍの電気メッキ銅層を形成した。
【０１４３】
（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）７．７重量部の代わりに平均粒子径５０μｍの炭酸カルシウム７．７重量部を用いたこと以外は実施例１と同様にして、樹脂ワニスを調製し、これを用いて厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４４】
別に、得られた樹脂ワニスをドクターブレード法により、ポリエチレンテレフタレートフィルム上に塗工し、乾燥させて厚さ２４μｍのシー卜を得た。なお、ドクターブレード条件は、乾燥温度＝７０℃、スピード＝０．３ｍ／ｍｉｎとした。
得られたシートをコア材（厚さ０．６ｍｍ：利昌工業社製）の両面に、９０℃、１０ｓｅｃ、圧力１ｋｇ／ｃｍ^２の条件で真空ラミネートした。ラミネート後、ポリエチレンテレフタレートフィルムを取り除き、１７０℃、６０ｍｉｎで熱硬化して、基板を得た。
【０１４５】
得られた基板に、実施例１の条件２により粗化処理を施した。
粗化処理を行った基板上に、パラジウム触媒、無電解銅メッキ液を用いて３５℃、１０分の条件で無電解メッキを行い、厚さ０．８μｍの無電解メッキ銅層を形成した。
更に、この上に、２Ａ／ｄｍ^２、７０分の条件で電気メッキを行い、厚さ２４μｍの電気メッキ銅層を形成した。
【０１４６】
実施例１〜７及び比較例１で作製した板状成形体について下記の方法により、層状珪酸塩の平均層間距離、５層以下に分散している層状珪酸塩の割合、燃焼時形状保持性、最大発熱速度、燃焼残渣の被膜強度を評価した。また、得られた銅層形成前の基板の表面の粗化状態、銅層を形成した基板の銅層のはく離接着強度を下記の方法により評価した。
結果を表１に示した。
【０１４７】
（１）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（４）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 （４）
式中、λは０．１５４であり、ｄは層状珪酸塩の面間隔を表し、θは回折角を表す。
【０１４８】
（２）５層以下に分散している層状珪酸塩の割合
透過型電子顕微鏡を用いて５万〜１０万倍で観察して、一定面積中において観察できる層状珪酸塩の積層集合体の全層数（Ｘ）のうち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（３）により５層以下に分散している層状珪酸塩の割合（％）を算出した。
５層以下に分散している層状珪酸塩の割合（％）＝（Ｙ／Ｘ）×１００ （３）
【０１４９】
（３）燃焼時形状保持性
ＡＳＴＭ Ｅ １３５４「建築材料の燃焼性試験方法」に準拠して、１００ｍｍ×１００ｍｍに裁断した厚さ２ｍｍの板状成形体にコーンカロリーメーターによって５０ｋＷ／ｍ^２の熱線を照射して燃焼させた。このとき燃焼前後の板状成形体の形状の変化を目視で観察し、下記判定基準により燃焼時形状保持性を評価した。
○：形状変化は微少であった。
×：形状変化が激しかった。
【０１５０】
（４）最大発熱速度及び燃焼残渣の被膜強度
ＡＳＴＭ Ｅ １３５４「建築材料の燃焼性試験方法」に準拠して、１００ｍｍ×１００ｍｍに裁断した厚さ２ｍｍの板状成形体にコーンカロリーメーターによって５０ｋＷ／ｍ^２の熱線を照射して燃焼させた。このときの最大発熱速度（ｋＷ／ｍ^２）を測定した。また、強度測定装置を用いて、燃焼残渣を速度０．１ｃｍ／ｓで圧縮し、燃焼残渣の被膜強度（ｋＰａ）を測定した。
【０１５１】
（５）粗化状態
断面を走査形電子顕微鏡（ＳＥＭ）を用いて観察することにより、表面の凹凸を測定し、凸部の高さの平均値を求めた。
【０１５２】
（６）はく離接着強度
カッターを用いて基板表面に形成された銅層を１ｃｍ幅でカットし、引張速度５０ｍ／ｍｉｎの条件ではく離接着強度を測定した。
【０１５３】
【表１】

【０１５４】
表１より、実施例１〜７で作製した板状成形体は、いずれも含有する層状珪酸塩の平均層間距離が３ｍｍ以上であり、かつ、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が１０％以上であり、燃焼時の形状保持性に優れていた。また、難燃被膜となる焼結体を形成しやすかったことから、最大発熱速度が遅く、燃焼残渣の被膜強度も４．９ｋＰａ以上であった。これに対し、層状珪酸塩の代わりに炭酸カルシウムを用いて作製した比較例１の板状成形体は、炭酸カルシウムが層状に分散しておらず、燃焼時の形状保持性が悪く、最大発熱速度がかなり速く、燃焼残渣の被膜強度が極端に低かった。
更に、表面に粗化処理を施した場合、実施例１〜７で作製した基板の粗化状態は、いずれも１μｍ以上の凹凸があり、はく離接着強度も３．９Ｎ／ｃｍ以上と優れていた。これに対して、比較例１で作製した基板では、形成された凹凸も小さく、はく離接着強度も低かった。
【０１５５】
【発明の効果】
本発明によれば、力学的物性、寸法安定性、耐熱性等に優れ、特に燃焼時の形状保持効果による優れた難燃性を有し、更に表面に金属配線を形成したときに金属配線の密着性に優れている樹脂シートを提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin sheet that is excellent in mechanical properties, dimensional stability, heat resistance, and the like, and further excellent in adhesion of a metal layer when a metal layer is formed on the surface.
[0002]
[Prior art]
In general, a multilayer printed circuit board used for an electronic device is composed of a plurality of insulating substrates. Examples of the interlayer insulating substrate include transparent resin sheets made of alicyclic hydrocarbon resin and acrylic resin, optical Thermosetting resin sheet, thermosetting resin sheet made of phenol resin, epoxy resin and unsaturated polyester resin, thermosetting resin prepreg, thermosetting resin impregnated with glass cloth A prepreg or the like is used.
[0003]
In recent years, downsizing of resin sheets has also been demanded. Especially in the field of multilayer printed circuit boards, with higher density and thinner substrates, performance such as strength, heat resistance and flame retardancy has been improved and high reliability has been achieved. There is a demand for a thin resin sheet that secures properties.
On the other hand, methods for improving physical properties by adding inorganic fillers to resins have been widely performed. For example, a resin sheet made of a thermoplastic resin containing a large amount of an inorganic filler, a resin sheet made of a thermosetting resin modified with rubber (elastomer) or acrylic resin, and the like have been proposed.
In Patent Document 1, an inorganic filler having a predetermined particle size is blended in a varnish mainly composed of a high molecular weight epoxy polymer and a polyfunctional epoxy resin, and applied to a support to form an insulating layer. A method for manufacturing a multilayer insulating substrate is disclosed. However, in the multilayer insulating substrate by this manufacturing method, since the interface area between the inorganic filler and the high molecular weight epoxy polymer or polyfunctional epoxy resin is limited, in order to improve mechanical properties such as mechanical strength There is a problem that it is necessary to blend a large amount of an inorganic filler, and it is difficult to make the interlayer thin, or problems such as an increase in processing steps occur.
[0004]
On the other hand, polymer materials used for industrial use have recently been demanded to be environmentally friendly materials due to the problems of waste plastic treatment and environmental hormones, and the conversion to environmentally adaptable materials is desired. . Specifically, for example, conversion from a halogen-containing flame retardant to a non-halogen flame retardant has been studied in order to cope with problems such as dioxin generation during combustion. In addition, halogen-containing flame retardants have a high flame-retardant effect and relatively little deterioration in moldability and mechanical properties of molded products. Halogen-containing gas may be generated, and the generated halogen-based gas may corrode equipment and have an unfavorable effect on the human body. Therefore, from the viewpoint of safety, halogen-free flame retardants are not used. The establishment of flame retardant treatment technology and treatment methods is strongly desired.
[0005]
For this reason, in recent years, with respect to insulating substrate materials, materials using non-halogen flame retardants have been developed in order to switch to environment-friendly materials. However, in the case of non-halogen type flame retardants, it is necessary to add a large amount of flame retardants in order to develop the necessary flame retardant, so halogen-containing type flame retardants are used in terms of heat resistance and dimensional stability. There is a problem that it does not reach the conventional insulating substrate material.
[0006]
Furthermore, build-up boards and printed multilayer boards used for general communications and in-vehicle use are usually used in harsh environments, and high reliability is required even in such harsh environments. ing. However, when metal wiring is formed on a resin sheet by electroless plating, electroplating, sputtering, or vacuum deposition, the metal wiring is detached from the resin during build-up processing due to low adhesion between the metal wiring and the resin. There was a problem that sometimes caused disconnection.
[0007]
[Patent Document 1]
JP 2000-183539 A
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation, and an object thereof is to provide a resin sheet that is excellent in mechanical properties, dimensional stability, heat resistance, etc., and further has excellent adhesion of metal wiring when the metal wiring is formed on the surface. And
[0009]
[Means for Solving the Problems]
The present invention contains 100 parts by weight of at least one resin selected from the group consisting of a thermosetting resin, a photocurable resin, a cured resin, and a thermoplastic resin, and 0.1 to 100 parts by weight of a layered silicate. Resin sheet that has a metal layer on the surface by electroless plating, electroplating, sputtering or vacuum deposition But Formation Has been The metal sheet is a resin sheet having a peel adhesion strength of 3.9 N / cm or more.
The present invention is described in detail below.
[0010]
The resin sheet of the present invention contains at least one resin selected from the group consisting of a thermosetting resin, a photocurable resin, a cured resin, and a thermoplastic resin, and a layered silicate. In the present specification, the sheet means a planar material and includes a film.
The thermosetting resin and the photocurable resin are liquid, semi-solid or solid at room temperature, and a relatively low molecular weight substance exhibiting fluidity at room temperature or under heating is a curing agent, a catalyst, It means a resin that can be an insoluble and infusible resin that forms a network-like three-dimensional structure while increasing the molecular weight by causing a curing reaction or a crosslinking reaction by the action of heat or light.
Moreover, the said resin cured material means resin which the said thermosetting resin or photocurable resin hardens | cures.
In addition, it is preferable that it is a resin sheet which formed into a sheet | seat the resin which consists of a resin composition which thermosetting resin or photocurable resin semi-hardened or hardened | cured. That is, although it is a cured resin at the time of roughening, since the dissolution of the resin by the roughening tends to proceed gently, it is easy to adjust the roughening conditions.
[0011]
The thermosetting resin is not particularly limited. For example, epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, urea resin, allyl resin, silicon resin, benzoxazine resin, phenol Resin, unsaturated polyester resin, bismaleimide triazine resin, alkyd resin, furan resin, melamine resin, polyurethane resin, aniline resin, and the like. Among them, epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, urea resins, allyl resins, silicon resins, benzoxazine resins, phenol resins, unsaturated polyester resins, bismaleimide triazines Resins and the like are preferred.
Moreover, as said photocurable resin, the epoxy resin containing a latent photocationic polymerization initiator etc. are mentioned, for example.
These thermosetting resins or photocurable resins may be used alone or in combination of two or more.
In addition, when hardening the said photocurable resin, it is preferable to apply heat simultaneously with light irradiation.
[0012]
The epoxy resin refers to an organic compound having at least one epoxy group. The number of epoxy groups in the epoxy resin is preferably 1 or more per molecule, and more preferably 2 or more per molecule. Here, the number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy resin by the total number of molecules in the epoxy resin.
[0013]
It does not specifically limit as said epoxy resin, A conventionally well-known epoxy resin can be used, For example, the epoxy resin (1)-epoxy resin (11) shown below etc. are mentioned. These epoxy resins may be used independently and 2 or more types may be used together.
[0014]
Examples of the epoxy resin (1) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolak type Examples thereof include novolak-type epoxy resins such as epoxy resins; aromatic epoxy resins such as trisphenolmethane triglycidyl ether, and their water additives and bromides.
[0015]
Examples of the epoxy resin (2) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methyl. Cyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxy Examples thereof include alicyclic epoxy resins such as cyclohexyl-5,5-spiro-3,4-epoxycyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, etc. Commercially available epoxy resin (2). For example, quotient Name "EHPE-3150" (softening temperature 71 ° C., manufactured by Daicel Chemical Industries Ltd.).
[0016]
Examples of the epoxy resin (3) include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol. Polyglycidyl ether of polypropylene glycol, polyglycidyl ether of long-chain polyol containing polyoxyalkylene glycol or polytetramethylene ether glycol containing an alkylene group having 2 to 9 carbon atoms (preferably 2 to 4 carbon atoms) And aliphatic epoxy resins.
[0017]
Examples of the epoxy resin (4) include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, salicylic acid glycidyl ether-glycidyl ester, and dimer. Examples thereof include glycidyl ester type epoxy resins such as acid glycidyl esters and hydrogenated products thereof.
[0018]
Examples of the epoxy resin (5) include triglycidyl isocyanurate, N, N′-diglycidyl derivative of cyclic alkylene urea, N, N, O-triglycidyl derivative of p-aminophenol, N of m-aminophenol, Examples thereof include glycidylamine type epoxy resins such as N, O-triglycidyl derivatives and hydrogenated products thereof.
[0019]
Examples of the epoxy resin (6) include a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer such as ethylene, vinyl acetate, and (meth) acrylic acid ester. In addition, in this specification, (meth) acryl means acryl or methacryl.
[0020]
Examples of the epoxy resin (7) include those obtained by epoxidizing unsaturated carbon double bonds in polymers mainly composed of conjugated diene compounds such as epoxidized polybutadiene or partially hydrogenated polymers thereof. It is done.
[0021]
Examples of the epoxy resin (8) include a polymer block mainly composed of a vinyl aromatic compound such as epoxidized SBS, a polymer block mainly composed of a conjugated diene compound, or a partially hydrogenated product thereof. Examples thereof include those obtained by epoxidizing an unsaturated carbon double bond of a conjugated diene compound in a block copolymer having a combined block in the same molecule.
[0022]
Examples of the epoxy resin (9) include a polyester resin having one or more, preferably two or more epoxy groups per molecule.
[0023]
Examples of the epoxy resin (10) include urethane-modified epoxy resins and polycaprolactone-modified epoxy resins in which urethane bonds and polycaprolactone bonds are introduced into the structures of the epoxy resins (1) to (9).
[0024]
Examples of the epoxy resin (11) include rubber-modified epoxy resins in which the epoxy resins (1) to (10) contain a rubber component such as NBR, CTBN, polybutadiene, or acrylic rubber.
In addition to the epoxy resin, a resin or oligomer having at least one oxirane ring may be added.
[0025]
The curing agent used for the curing reaction of the epoxy resin is not particularly limited, and conventionally known curing agents for epoxy resins can be used. For example, amine compounds, compounds such as polyaminoamide compounds synthesized from amine compounds, A tertiary amine compound, an imidazole compound, a hydrazide compound, a melamine compound, an acid anhydride, a phenol compound, a thermal latent cationic polymerization catalyst, a photolatent cationic polymerization initiator, dicyanamide, and derivatives thereof may be mentioned. These hardening | curing agents may be used independently and 2 or more types may be used together.
[0026]
The amine compound is not particularly limited, and examples thereof include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, and derivatives thereof; Foronediamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethylcyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8 , 10-tetraoxaspiro (5,5) undecane and other cyclic aliphatic amines and derivatives thereof; m-xylenediamine, α- (m / paminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diami Diphenyl sulfone, alpha, alpha-bis (4-aromatic amines and derivatives thereof aminophenyl -p- diisopropylbenzene and the like.
[0027]
The compound synthesized from the amine compound is not particularly limited. For example, the amine compound and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid, tetrahydroisophthalic acid. Polyaminoamide compounds synthesized from carboxylic acid compounds such as acid and hexahydroisophthalic acid and derivatives thereof; Polyaminoimide compounds synthesized from maleimide compounds such as the above amine compounds and diaminodiphenylmethane bismaleimide; and derivatives thereof Ketimine compounds synthesized from compounds and ketone compounds and derivatives thereof; polyamines synthesized from the above amine compounds and compounds such as epoxy compounds, urea, thiourea, aldehyde compounds, phenol compounds, acrylic compounds, etc. Compounds and derivatives thereof.
[0028]
The tertiary amine compound is not particularly limited. For example, N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) Examples thereof include phenol, 1,8-diazabiscyclo (5,4,0) undecene-1 and derivatives thereof.
[0029]
The imidazole compound is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and derivatives thereof.
[0030]
The hydrazide compound is not particularly limited. For example, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosane diacid dihydrazide, Examples include adipic acid dihydrazide and its derivatives.
[0031]
The melamine compound is not particularly limited, and examples thereof include 2,4-diamino-6-vinyl-1,3,5-triazine and derivatives thereof.
[0032]
The acid anhydride is not particularly limited. For example, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol trisanhydro Trimellitate, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- (2 , 5-Dioxotetrahydrofuryl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazeline acid anhydride , Polydodecanedioic anhydride, Rend anhydride and derivatives thereof.
[0033]
The phenol compound is not particularly limited, and examples thereof include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, and derivatives thereof.
[0034]
The thermal latent cationic polymerization catalyst is not particularly limited. For example, benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt, benzyl having antimony hexafluoride, phosphorous hexafluoride, boron tetrafluoride and the like as a counter anion. Examples include ionic thermal latent cationic polymerization catalysts such as phosphonium salts; nonionic thermal latent cationic polymerization catalysts such as N-benzylphthalimide and aromatic sulfonic acid esters.
[0035]
The photolatent cationic polymerization initiator is not particularly limited. For example, aromatic diazonium salts, aromatic halonium salts, and aromatics having antimony hexafluoride, phosphorous hexafluoride, boron tetrafluoride and the like as counter anions. Ionic photolatent cationic polymerization initiators such as onium salts such as sulfonium salts, and organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes; nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid Nonionic photolatent cationic polymerization initiators such as esters, phenol sulfonates, diazonaphthoquinones, N-hydroxyimide sulfonates, etc. may be mentioned.
[0036]
The thermosetting modified polyphenylene ether resin is not particularly limited, and examples thereof include a resin obtained by modifying the polyphenylene ether resin with a functional group having thermosetting properties such as a glycidyl group, an isocyanate group, and an amino group. These thermosetting modified polyphenylene ether resins may be used alone or in combination of two or more.
[0037]
The thermosetting polyimide resin is not particularly limited as long as the resin has an imide bond in the molecular main chain. Specifically, for example, a condensation polymer of aromatic diamine and aromatic tetracarboxylic acid, Bismaleimide resin, which is an addition polymer of aromatic diamine and bismaleimide, polyamino bismaleimide resin, which is an addition polymer of aminobenzoic acid hydrazide and bismaleimide, bismaleimide triazine resin consisting of dicyanate compound and bismaleimide resin, etc. Is mentioned. Of these, bismaleimide triazine resin is preferably used. These thermosetting polyimide resins may be used alone or in combination of two or more.
[0038]
The urea resin is not particularly limited as long as it is a thermosetting resin obtained by addition condensation reaction of urea and formaldehyde. The curing agent used for the curing reaction of the urea resin is not particularly limited. For example, an apparent curing agent composed of an acidic salt such as an inorganic acid, an organic acid, or acidic sodium sulfate; a carboxylic acid ester, an acid anhydride, or a chloride. Examples include latent curing agents such as salts of ammonium and ammonium phosphate. Among these, a latent curing agent is preferable from the viewpoint of shelf life.
[0039]
The allyl resin is not particularly limited as long as it is obtained by polymerization and curing reaction of diallyl phthalate monomer. Examples of the diallyl phthalate monomer include an ortho isomer, an iso isomer, and a tele isomer. Although it does not specifically limit as a catalyst of hardening reaction, For example, combined use of t-butyl perbenzoate and di-t-butyl peroxide is suitable.
[0040]
The silicon resin is not particularly limited as long as it contains a silicon-silicon bond, a silicon-carbon bond, a siloxane bond, or a silicon-nitrogen bond in the molecular chain. Specifically, for example, polysiloxane, polycarbo Examples thereof include silane and polysilazane.
[0041]
The benzoxazine resin is not particularly limited as long as it is obtained by ring-opening polymerization of an oxazine ring of a benzoxazine monomer. The benzoxazine monomer is not particularly limited, and examples thereof include those in which a functional group such as a phenyl group, a methyl group, or a cyclohexyl group is bonded to nitrogen of the oxazine ring.
[0042]
The thermoplastic resin is not particularly limited. For example, polyphenylene ether resins, functional group-modified polyphenylene ether resins; polyphenylene ether resins or functional group-modified polyphenylene ether resins, and polyphenylenes such as polystyrene resins. Mixtures of ether resins or functional group-modified polyphenylene ether resins and compatible thermoplastic resins; alicyclic hydrocarbon resins, thermoplastic polyimide resins, polyether ether ketone (PEEK) resins, poly Ether sulfone resin, polyamideimide resin, polyesterimide resin, polyester resin, polyolefin resin, polystyrene resin, polyamide resin, polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl acetate resin Poly (meth) acrylate resin, polyoxymethylene resins. Among them, polyphenylene ether resins, functional group-modified polyphenylene ether resins, polyphenylene ether resins or mixtures of functional group-modified polyphenylene ether resins and polystyrene resins, alicyclic hydrocarbon resins, thermoplastics Polyimide resins, polyether ether ketone resins, polyether sulfone resins, polyamide imide resins, polyester imide resins, and the like are preferably used. These thermoplastic resins may be used independently and 2 or more types may be used together.
[0043]
The polyphenylene ether-based resin is a polyphenylene ether homopolymer or polyphenylene ether copolymer composed of repeating units represented by the following formula (1).
[0044]
[Chemical 1]

[0045]
In the above formula (1), R ¹ , R ² , R ³ And R ⁴ Represents 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.
[0046]
The polyphenylene ether homopolymer is not particularly limited, and examples thereof 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.
[0047]
The polyphenylene ether copolymer is not particularly limited. For example, a copolymer partially containing an alkyl trisubstituted phenol such as 2,3,6-trimethylphenol in the repeating unit of the polyphenylene ether homopolymer, These polyphenylene ether copolymers further include copolymers obtained by graft copolymerization of one or more styrene monomers such as styrene, α-methylstyrene, vinyltoluene and the like. These polyphenylene ether resins may be used alone or in combination of two or more of those having different compositions, components, molecular weights and the like.
[0048]
The functional group-modified polyphenylene ether-based resin is not particularly limited. For example, the polyphenylene ether-based resin includes one or more functional groups such as a maleic anhydride group, a glycidyl group, an amino group, and an allyl group. Examples thereof include modified ones. These functional group-modified polyphenylene ether resins may be used alone or in combination of two or more. When the polyphenylene ether resin modified with the functional group is used as a thermoplastic resin, the mechanical properties, heat resistance, dimensional stability, etc. of the resin varnish composition of the present invention can be further improved by a crosslinking reaction.
[0049]
The polyphenylene ether resin or a mixture of functional group-modified polyphenylene ether resin and polystyrene resin is not particularly limited. For example, the polyphenylene ether resin or the functional group-modified polyphenylene ether resin and styrene Homopolymer; Copolymer of styrene and one or more styrenic monomers such as α-methyl styrene, ethyl styrene, t-butyl styrene, vinyl tonin, etc .; Mixture of polystyrene resin such as styrene elastomer, etc. Is mentioned. The said polystyrene resin may be used independently and 2 or more types may be used together. These polyphenylene ether resins or a mixture of functional group-modified polyphenylene ether resins and polystyrene resins may be used alone or in combination of two or more.
[0050]
The alicyclic hydrocarbon-based resin is not particularly limited as long as it is a hydrocarbon-based resin having a cyclic hydrocarbon group in a polymer chain. For example, cyclic olefin, that is, a norbornene monomer homopolymer or copolymer. A polymer etc. are mentioned. These alicyclic hydrocarbon resins may be used alone or in combination of two or more.
[0051]
The cyclic olefin is not particularly limited. For example, norbornene, methanooctahydronaphthalene, dimethanooctahydronaphthalene, dimethanododecahydroanthracene, dimethanodecahydroanthracene, trimethanododecahydroanthracene, dicyclopentadiene, 2,3 -Dihydrocyclopentadiene, methanooctahydrobenzoindene, dimethanooctahydrobenzoindene, methanodecahydrobenzoindene, dimethanodecahydrobenzoindene, methanooctahydrofluorene, dimethanooctahydrofluorene, and substituted products thereof . These cyclic olefins may be used independently and 2 or more types may be used together.
[0052]
The substituent in the substituted product such as norbornene is not particularly limited, and examples thereof include known hydrocarbon groups and polar groups such as alkyl groups, alkylidene groups, aryl groups, cyano groups, alkoxycarbonyl groups, pyridyl groups, and halogen atoms. Can be mentioned. These substituents may be used alone or in combination of two or more.
[0053]
The substituent such as norbornene is not particularly limited, and examples thereof include 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5 -Ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5 -Methyl-2-norbornene and the like. These substituents such as norbornene may be used alone or in combination of two or more.
[0054]
Examples of the commercially available alicyclic hydrocarbon-based resins include a trade name “Arton” series manufactured by JSR Corporation and a product name “ZEONOR” series manufactured by Nippon Zeon Co., Ltd. .
[0055]
The thermoplastic polyimide resin is not particularly limited, for example, a polyetherimide resin having an imide bond and an ether bond in the molecular main chain, a polyamideimide resin having an imide bond and an amide bond in the molecular main chain, Examples thereof include a polyesterimide resin having an imide bond and an ester bond in the molecular main chain. These thermoplastic polyimide resins may be used alone or in combination of two or more.
[0056]
The polyether ether ketone resin is not particularly limited, and examples thereof include those obtained by polycondensation of dihalogenobenzophenone and hydroquinone.
[0057]
The resin sheet of the present invention contains a layered silicate. In the present specification, the layered silicate means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product. The layered silicate is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite, and nontronite, swelling mica, vermiculite, and halloysite. Among these, at least one selected from the group consisting of montmorillonite, hectorite, and swellable mica is preferably used. Of these, swellable fluorine mica is more preferable. These layered silicates may be used alone or in combination of two or more.
[0058]
As the layered silicate, it is preferable to use a smectite clay mineral or swellable mica having a large shape anisotropy effect defined by the following formula (2). By using a layered silicate having a large shape anisotropy effect, the resin sheet of the present invention has more excellent mechanical properties.
Shape anisotropy effect = area of crystal surface (A) / area of crystal surface (B) (2)
In the formula, the crystal surface (A) means the layer surface, and the crystal surface (B) means the layer side surface.
[0059]
The shape of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.01 μm, the upper limit is 3 μm, the preferable lower limit of the thickness is 0.001 μm, the upper limit is 1 μm, and the aspect ratio is preferable. The lower limit 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, and the more preferable lower limit of the aspect ratio is 50, the upper limit is 200.
[0060]
The exchangeable metal cation existing between the layers of the layered silicate is a metal ion such as sodium or calcium existing on the crystal surface of the layered silicate, and these metal ions are cations with a cationic substance. Since it has exchangeability, various substances having cationic properties can be inserted (intercalated) between the crystal layers of the layered silicate.
[0061]
The cation exchange capacity of the layered silicate is not particularly limited, but a preferred lower limit is 50 milliequivalent / 100 g and an upper limit is 200 milliequivalent / 100 g. If the cation exchange capacity of the layered silicate is less than 50 milliequivalent / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate due to cation exchange is reduced, so that there is sufficient space between the crystal layers. In some cases, it is not depolarized (hydrophobized), and when it exceeds 200 milliequivalents / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.
[0062]
In the present invention, when a low-polarity resin such as a polyphenylene ether resin is used as a thermoplastic resin, a photocurable resin or a thermosetting resin, the layers of the layered silicate are previously exchanged with a cationic surfactant. Thus, it is preferable to make it hydrophobic. By making the interlayer of the layered silicate hydrophobic beforehand, the affinity with the resin is increased, and the layered silicate can be finely dispersed more uniformly in the low-polarity resin.
[0063]
The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Among them, a quaternary ammonium salt having an alkyl chain having 6 or more carbon atoms (alkyl ammonium salt having 6 or more carbon atoms) is suitably used because the crystal layer of the layered silicate can be sufficiently nonpolarized (hydrophobized). Used.
[0064]
The quaternary ammonium salt is not particularly limited, and examples thereof include trimethyl alkyl ammonium salt, triethyl alkyl ammonium salt, tributyl alkyl ammonium salt, dimethyl dialkyl ammonium salt, dibutyl dialkyl ammonium salt, methyl benzyl dialkyl ammonium salt, and dibenzyl dialkyl ammonium salt. , Trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt, quaternary ammonium salt having an aromatic ring, quaternary ammonium salt derived from an aromatic amine such as trimethylphenylammonium, having two polyethylene glycol chains Dialkyl quaternary ammonium salt, dialkyl quaternary ammonium salt having two polypropylene glycol chains, polyethylene glycol chain One having trialkyl quaternary ammonium salts, trialkyl quaternary ammonium salt having one polypropylene glycol chain. Among these, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N N-dimethylammonium salt and the like are preferred. These quaternary ammonium salts may be used alone or in combination of two or more.
[0065]
The quaternary phosphonium salt is not particularly limited. For example, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethyl Examples thereof include phosphonium salts and distearyl dibenzylphosphonium salts. These quaternary phosphonium salts may be used alone or in combination of two or more.
[0066]
The layered silicate used in the present invention can improve the dispersibility in the resin by the chemical treatment as described above.
The chemical treatment is not limited to the cation exchange method using a cationic surfactant (hereinafter also referred to as the chemical modification (1) method).
It can also be carried out by various chemical treatment methods (2) to chemical modification (6).
These chemical modification methods may be used alone or in combination of two or more. In addition, the layered silicate whose dispersibility in the resin is improved by various chemical treatment methods shown below including the chemical modification (1) method is also referred to as “organized layered silicate”.
[0067]
In the chemical modification (2) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method can be combined with a functional group or a chemical bond. In this method, chemical treatment is performed with a compound having at least one functional group having high chemical affinity at the molecular end.
[0068]
In the chemical modification (3) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method can be chemically bonded to a functional group or a chemical bond. In this method, chemical treatment is performed with a compound having one or more functional groups and reactive functional groups having high chemical affinity at the molecular ends.
[0069]
The chemical modification (4) method is a method in which the crystallized surface of the organically modified layered silicate chemically treated by the chemical modification (1) method is chemically treated with a compound having an anionic surface activity.
[0070]
The chemical modification (5) method is a chemical treatment (4) method in which a chemical treatment is performed with a compound having one or more reactive functional groups in addition to the anion site in the molecular chain of the compound having anionic surface activity.
[0071]
In the chemical modification (6) method, the organically modified layered silicate chemically treated by any one of the chemical modification (1) method to the chemical modification (5) method is further used, for example, maleic anhydride-modified polyphenylene ether type. This is a method using a composition to which a resin having a functional group capable of reacting with a layered silicate such as a resin is added.
[0072]
In the chemical modification (2) method, the functional group that can be chemically bonded to the hydroxyl group or the functional group having a large chemical affinity without chemical bonding is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, and a carboxyl group. Groups (including dibasic acid anhydrides), hydroxyl groups, isocyanate groups, aldehyde groups and other functional groups, and other functional groups having high chemical affinity with hydroxyl groups. In addition, the functional group that can be chemically bonded to the hydroxyl group, or a compound having a functional group with high chemical affinity without chemical bonding is not particularly limited. Examples thereof include silane compounds having a group, titanate compounds, glycidyl compounds, carboxylic acids, alcohols and the like. These compounds may be used independently and 2 or more types may be used together.
[0073]
The silane compound is not particularly limited. For example, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyl Methyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxy Silane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, octadecyltrimethoxysilane, oct Decyl triethoxysilane, .gamma.-methacryloxypropyl methyl dimethoxy silane, .gamma.-methacryloxypropyl methyl diethoxy silane, .gamma.-methacryloxypropyl trimethoxysilane, .gamma.-methacryloxypropyl triethoxysilane, and the like. These silane compounds may be used alone or in combination of two or more.
[0074]
In the chemical modification (4) method and the chemical modification (5) method, as a compound having an anionic surface activity, a compound having an anionic surface activity and having one or more reactive functional groups in addition to the anion site in the molecular chain The layer silicate is not particularly limited as long as it can be chemically treated by ionic interaction, for example, sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfate, secondary higher alcohol sulfate, Examples thereof include unsaturated alcohol sulfate salts. These compounds may be used independently and 2 or more types may be used together.
[0075]
The layered silicate preferably has an average interlayer distance of (001) plane measured by wide angle X-ray diffraction measurement method of 3 nm or more, and part or all of them are dispersed in 5 layers or less. The layered silicate is selected from the group consisting of a thermosetting resin, a photocurable resin, and a thermoplastic resin by dispersing an average interlayer distance of 3 nm or more and a part or all of the layered silicate being dispersed in 5 layers or less. The interface area between at least one kind of resin and the layered silicate is sufficiently large, and the distance between the flaky crystals of the layered silicate becomes appropriate, and a sufficient effect is obtained by the dispersion of the layered silicate. In the resin material, a greater effect of improving mechanical properties and flame retardancy can be obtained than when a normal inorganic filler is used.
[0076]
A preferable upper limit of the average interlayer distance is 5 nm. If it exceeds 5 nm, the lamellar silicate crystal flakes are separated into layers and the interaction is negligibly weak, so the formation of the coating during combustion becomes slow, and the flame retardancy may not be sufficiently improved. . In the present specification, the average interlayer distance of the layered silicate means an average interlayer distance when the layered silicate fine flaky crystal is used as a layer, and X-ray diffraction peak and transmission electron microscope photography, It can be calculated by a wide-angle X-ray diffraction measurement method.
[0077]
Specifically, when part or all of the layered silicate is dispersed in 5 layers or less, the interaction between the layered silicate flake crystals is weakened, and part or all of the laminate of flake crystals is Means distributed. Preferably, 10% or more of the layered silicate is dispersed as a laminate of 5 layers or less, and 20% or more of the layered silicate is dispersed as a laminate of 5 layers or less. In addition, the ratio of the layered silicate dispersed as a laminate of 5 layers or less can be observed in a certain area by observing the resin sheet of the present invention with a transmission electron microscope at a magnification of 50,000 to 100,000 times. It can be calculated from the following formula (3) by measuring the total number of layers X of the layered silicate laminate and the number of layers Y of the laminate dispersed as five or less layers.
Ratio of layered silicate dispersed in 5 layers or less (%) = (Y / X) × 100 (3)
[0078]
The number of layered silicate layers is preferably divided into 5 layers or less, whereby the above effect can be obtained, but more preferably 3 layers or less. Particularly preferably, it is thinned into a single layer.
[0079]
Since the resin material has a sufficiently large interface area between the resin and the layered silicate, the interaction between the resin and the surface of the layered silicate is increased, so that the melt viscosity and the solution viscosity are increased and the moldability is improved. In addition, mechanical properties such as elastic modulus are improved over a wide temperature range from room temperature to high temperature, and the mechanical properties can be maintained even at high temperatures above the glass transition point or melting point of the resin. Can be kept low. The reason for this is not clear, but it is considered that even in the region of the glass transition point or the melting point or higher, the finely dispersed layered silicate acts as a kind of pseudo-crosslinking point, so that these physical properties are expressed.
On the other hand, when the distance between the lamellar crystals of the layered silicate becomes appropriate, the resin material can easily form a sintered body that can be converted into a flame retardant film by burning the lamellar crystals of the lamellar silicate during combustion. Become. Since this sintered body is formed at an early stage during combustion, not only the supply of oxygen from the outside world but also the flammable gas generated by the combustion can be blocked, and the resin material is excellent. Expresses flame retardancy. Therefore, the resin sheet of the present invention has excellent flame retardancy due to the shape retention effect during combustion.
[0080]
Furthermore, when the above resin material diffuses in the resin, gas molecules diffuse while bypassing the inorganic substance, so that the gas barrier property is improved. Similarly, the barrier property against other than gas molecules is improved, and solvent resistance, hygroscopicity, water absorption and the like are improved. Thereby, for example, copper migration from a copper circuit in a multilayer printed wiring board using the resin sheet of the present invention can be suppressed. Furthermore, it is possible to suppress the occurrence of defects such as poor plating due to bleed-out of trace additives in the resin on the surface.
[0081]
In the resin sheet of the present invention, the lower limit of the amount of the layered silicate with respect to 100 parts by weight of the mixture with the thermoplastic resin and / or the thermosetting resin is 0.1 parts by weight, and the upper limit is 100 parts by weight. When the amount is less than 0.1 parts by weight, the effect of improving the flame retardancy and mechanical properties is reduced. When the amount exceeds 100 parts by weight, the density (specific gravity) of the resin sheet is increased and the mechanical strength is also decreased. Therefore, it becomes poor in practicality. The preferred lower limit is 1 part by weight and the upper limit is 50 parts by weight. When the amount is less than 1 part by weight, a sufficient flame retardant effect may not be obtained when the resin sheet is thinly formed. When the amount exceeds 50 parts by weight, moldability may be deteriorated. A more preferred lower limit is 5 parts by weight and an upper limit is 20 parts by weight. Within this range, there is no region that causes problems in mechanical properties and process suitability, and a sufficient flame retardant effect can be obtained.
[0082]
The method for dispersing the layered silicate in the resin is not particularly limited. For example, the method using the organically modified layered silicate; the method of foaming after mixing the resin and the layered silicate by a conventional method; And the like. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed in the resin.
[0083]
The method of foaming after mixing the resin and the layered silicate by a conventional method is a method of foaming the resin using a foaming agent and converting the foaming energy into the dispersion energy of the layered silicate.
It does not specifically limit as said foaming agent, For example, a gaseous foaming agent, an easily volatile liquid foaming agent, a heat decomposable solid foaming agent etc. are mentioned. These foaming agents may be used independently and 2 or more types may be used together.
[0084]
A specific method for dispersing the layered silicate in the resin by foaming the resin in the presence of the layered silicate is not particularly limited. For example, the resin is 100 parts by weight and the layered silicate is 0.1 to 100 parts by weight. A method of forming a foam by impregnating a gaseous foaming agent under high pressure with respect to the resin composition comprising: and then vaporizing the gaseous foaming agent in the resin composition; Examples thereof include a method in which a thermally decomposable foaming agent is previously contained between the salt layers and the thermally decomposable foaming agent is decomposed by heating to form a foam.
[0085]
It is preferable that the resin sheet of this invention contains the flame retardant which does not contain a halogen-type composition substantially. The phrase “substantially containing no halogen-based composition” means that a trace amount of halogen may be mixed due to the manufacturing process of the flame retardant.
[0086]
The flame retardant is not particularly limited, and examples thereof include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum and calcium hydroxide; phosphorus such as red phosphorus and ammonium polyphosphate. Compounds such as melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate and melamine derivatives such as those subjected to surface treatment, layered double hydrates such as hydrotalcite, etc. . Of these, metal hydroxides and melamine derivatives are preferably used.
[0087]
Among the metal hydroxides, magnesium hydroxide and aluminum hydroxide are particularly preferable, and these may be surface-treated 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.
[0088]
The lower limit of the preferable content with respect to 100 parts by weight of at least one resin selected from the group consisting of the thermosetting resin, the photocurable resin and the thermoplastic resin of the flame retardant is 0.1 part by weight, and the upper limit is 100 parts by weight. It is. If it is less than 0.1 part by weight, the flame retarding effect due to the inclusion of these cannot be sufficiently obtained, and if it exceeds 100 parts by weight, the density (specific gravity) of the resin sheet becomes too high and is practical. And the flexibility and elongation are extremely reduced. The preferred lower limit is 5 parts by weight and the upper limit is 80 parts by weight. If it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained if the resin sheet is thinned. If it exceeds 80 parts by weight, the defect rate due to swelling or the like may increase during high-temperature processes. is there. A more preferred lower limit is 10 parts by weight and an upper limit is 70 parts by weight. Within this range, there is no region that causes problems in mechanical properties, electrical properties, and process suitability, and it is preferable because sufficient flame retardancy is exhibited.
[0089]
The resin sheet of the present invention has an inorganic filler, a thermoplastic elastomer, a cross-linked rubber, an oligomer, a nucleating agent as necessary for the purpose of modifying the properties within the range not inhibiting the achievement of the object of the present invention. , Antioxidants (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, lubricants, flame retardant aids, antistatic agents, antifogging agents, fillers, softeners, plasticizers, colorants, etc. Additives may be blended. These may be used alone or in combination of two or more.
[0090]
The thermoplastic elastomers are not particularly limited, and examples thereof include styrene elastomers, olefin elastomers, urethane elastomers, and polyester elastomers. In order to enhance the compatibility with the resin, these thermoplastic elastomers may be functional group-modified. These thermoplastic elastomers may be used alone or in combination of two or more.
[0091]
The crosslinked rubber is not particularly limited, and examples thereof include isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, and urethane rubber. In order to enhance compatibility with the resin, it is preferable that these crosslinked rubbers are functional group-modified. The functional group-modified crosslinked rubber is not particularly limited, and examples thereof include epoxy-modified butadiene rubber and epoxy-modified nitrile rubber. These crosslinked rubbers may be used alone or in combination of two or more.
[0092]
The oligomers are not particularly limited, and examples thereof include maleic anhydride-modified polyethylene oligomers. These oligomers may be used independently and 2 or more types may be used together.
[0093]
The resin sheet of the present invention has a peel adhesion strength of 3.9 N / cm or more when the metal layer is formed on the surface by electroless plating, electroplating, sputtering or vacuum deposition. When it is less than 3.9 N / cm, when a multilayer printed board is produced using the resin sheet of the present invention, the metal wiring is detached from the resin during build-up processing or when the product is used in a harsh environment. It may cause short circuit and disconnection. Preferably it is 4.9 N / cm or more, more preferably 6.9 N / cm or more.
The peel adhesion strength can be measured, for example, by performing 90 ° peel measurement on a copper electrode having a thickness of 22 μm and an electrode width of about 1 cm formed on the surface at a peel rate of 50 mm / min.
[0094]
In order to achieve such performance, it is preferable to roughen the surface of the sheet. By performing roughening treatment and forming irregularities on the surface, it is possible to dramatically improve the adhesion with a metal wiring formed on the surface by electroless plating, electroplating, sputtering or vacuum deposition.
[0095]
The roughening treatment method is not particularly limited, but a roughening method using an oxidizing agent such as permanganate such as sodium permanganate or potassium permanganate is preferred. In the resin sheet of the present invention, the resin portion formed of the cured epoxy resin on the surface is dissolved by an oxidizing agent such as permanganate, so that unevenness is generated on the surface, that is, roughened. Since the epoxy resin sheet of the invention contains a layered silicate, a flame retardant, and if necessary, an inorganic filler, when the surface resin is oxidized and dissolved, the layered silicate, the flame retardant, and the inorganic filler appear, and the surface irregularities Can be further increased.
Specifically, for example, first, the surface of the resin sheet is swollen, and the surface of the resin sheet is roughened by oxidizing the resin with an oxidizing agent such as sodium permanganate, but a 60 to 70 g / L permanganate solution, 40 A method of treating once or twice at a treatment temperature of 70 to 85 ° C. using a ~ 80 g / L sodium hydroxide solution is preferred. The larger the number of treatments, the greater the roughening effect, but if the treatment is repeated, the layered silicate and flame retardant will also be scraped, so the actual effect will not change even if it is performed 3 times or more, or clear Unevenness may be difficult to obtain.
[0096]
However, a sheet in which layered silicate is dispersed in nanoscale in at least one resin selected from the group consisting of a thermosetting resin, a photocurable resin, a resin cured product, and a thermoplastic resin has a water absorption rate. Since it is extremely low and has extremely high chemical resistance, it may not be sufficiently roughened even if a roughening treatment is performed using sodium permanganate or an oxidizing agent as described above.
In such a case, it is preferable to use a layered silicate having a large aspect ratio or to reduce only the proportion of the layered silicate on the surface of the sheet and increase the proportion of the resin. That is, since the water absorption rate and chemical resistance described above are caused by the fine dispersion of the layered silicate in the resin, if the content of the layered silicate at least on the surface is reduced, The effect of the roughening treatment with an oxidizing agent such as sodium permanganate is also great.
[0097]
When a layered silicate having a large aspect ratio is used, a sufficient fine dispersion effect can be obtained even with a smaller amount of addition, so the amount of layered silicate can be reduced, such as sodium permanganate. The effect of the roughening treatment by the oxidizing agent is also increased. Examples of such layered silicates include swellable fluorine mica. In this case, the lower limit of the amount of the swellable fluorine mica based on 100 parts by weight of the resin is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight. If it is less than 0.1 part by weight, the effect of blending the layered silicate cannot be obtained, and if it exceeds 10 parts by weight, the surface cannot be sufficiently roughened by the roughening treatment with sodium permanganate or an oxidizing agent. is there. A more preferred upper limit is 5 parts by weight.
Moreover, the same effect can be obtained by allowing the layered silicate having a large aspect ratio to be contained only on the surface of the sheet.
[0098]
Such an effect can also be achieved by reducing the amount of additive components other than the layered silicate and increasing the proportion of the resin on the surface of the sheet. That is, if the surface portion forming the metal layer is such that the organic component ratio is equal to or greater than the overall average organic component ratio, the content of layered silicate in the surface portion becomes relatively small, and sodium permanganate The effect of the roughening treatment by the oxidizing agent such as is also increased.
The surface portion preferably has a depth of 2 μm or more and 20 μm or less from the surface. When the thickness is 2 μm, the above effects may not be obtained. When the thickness exceeds 20 μm, the physical properties of the entire resin sheet may be inferior.
Moreover, it is preferable that the organic component ratio of a surface part is 1.02 times or more of a whole average. If it is less than 1.02, the above-mentioned effect may not be obtained. More preferably, it is 1.05 times or more.
The organic component ratio is a value represented by organic component / (organic component + inorganic component).
[0099]
As a method of increasing the ratio of the resin on the surface of the sheet, in addition to the method of making the resin sheet a multi-layer structure, after coating, the method of slowly drying the inorganic filler, etc. by coating, or the film to be applied Examples thereof include a method in which a resin is unevenly distributed on the contact surface by electrostatic interaction. Specifically, when a surface treatment is performed and coating is performed on a PET film having a low surface energy, a sheet in which the resin is unevenly distributed on the coated film surface can be obtained.
[0100]
In addition, when a resin that is relatively easily oxidized by an oxidizing agent such as permanganate such as sodium permanganate or potassium permanganate is used on the surface or the entire surface of the sheet, unevenness due to roughening can be easily formed on the surface of the sheet. Can be granted. Examples of the resin that is relatively easily oxidized by the oxidizing agent include an epoxy resin having a double bond in the molecule, such as a polybutadiene skeleton, and a rubber.
Therefore, when using a resin that is relatively easily oxidized by an oxidizing agent, even if the amount of the layered silicate is large relative to 100 parts by weight of the mixture of the thermoplastic resin and / or thermosetting resin, it is sufficient. The surface of the sheet can be roughened.
In such a case, the ratio of the layered silicate may be high, and the preferable upper limit of the amount of the layered silicate with respect to 100 parts by weight of the mixture with the thermoplastic resin and / or thermosetting resin is 90 parts by weight. A more preferred upper limit is 50 parts by weight.
In addition, even if it mixes 20 parts by weight or more of the layered silicate, the surface of the sheet can be sufficiently roughened.
[0101]
When a resin varnish composition as will be described later is dried to produce a resin sheet, irregularities can be imparted to the surface of the sheet by controlling the drying conditions.
In this case, excellent adhesion strength is achieved with copper wiring formed by electroplating without using a method of roughening with an oxidizing agent such as permanganate such as sodium permanganate or potassium permanganate. can do. As described above, controlling the drying conditions to give unevenness to the surface and then roughening with an oxidizing agent can further improve the adhesion strength compared to the case where the surface has no unevenness. it can.
[0102]
Further, a layer made of a layered silicate or a resin made of a thermosetting resin and / or a thermoplastic resin in which a metal hydroxide as a flame retardant is dispersed so as to have a particle diameter of 0.5 μm or more is formed on the resin sheet. It is also preferable that the surface is formed and the surface is subjected to the roughening treatment. By exposing a layered silicate or flame retardant having a large particle size, larger irregularities can be formed, and the adhesion between the resin sheet and the metal wiring can be further improved.
In addition, it is preferable that the thickness of the layer which the said layered silicate or the flame retardant disperse | distributed with the particle diameter of 0.5 micrometer or more is 5 micrometers or less. If it exceeds 5 μm, the proportion of the layer in the entire resin sheet of the present invention will increase, and the mechanical strength, flame retardancy, etc. of the resin sheet of the present invention may not be fully exhibited.
[0103]
In the method of roughening with an oxidizing agent such as permanganate such as sodium permanganate or potassium permanganate, the adhesion strength with copper wiring by electroplating can be improved by polarizing the surface of the sheet. it can.
In addition to this, corona treatment, plasma treatment, etc. are also effective as methods for polarizing the surface of the sheet.
[0104]
When roughening with an oxidizing agent, corona treatment or plasma treatment is performed, in addition to the effect of polarizing the surface of the sheet, it may have the effect of removing impurities and unreacted substances on the surface layer of the sheet. In such a case, the processing time is shortened, and the adhesion strength with the copper wiring formed by sputtering or electroplating can be improved.
[0105]
The resin sheet of the present invention is 50 kW / m in a combustion test in accordance with ASTM E 1354. ² It is preferable that the yield point stress is 4.9 kPa or more when the combustion residue burned by heating for 30 minutes under the radiant heating condition is compressed at a speed of 0.1 cm / s. If it is less than 4.9 kPa, the combustion residue tends to collapse with a minute force, and the flame retardancy may be insufficient. That is, in the resin sheet of the present invention, in order for the sintered body to sufficiently exhibit the function as a flame retardant coating, it is preferable that the sintered body keeps its shape until the end of combustion. More preferably, it is 15.0 kPa or more.
[0106]
Although it does not specifically limit as a method of producing the resin sheet of this invention, For example, the resin varnish composition which mixed resin, layered silicate, and the organic solvent is produced, and the organic solvent is distilled off from this resin varnish composition. Examples include a method of preparing a resin sheet and further roughening the surface of the resin sheet.
A method for producing a resin sheet according to the present invention, wherein the layered silicic acid is used with respect to 100 parts by weight of at least one resin selected from the group consisting of a thermosetting resin, a photocurable resin, a resin cured product, and a thermoplastic resin. The manufacturing method of the resin sheet which has the process of mixing 0.1-100 weight part of salt and 30-1000 weight part of organic solvents, and producing the resin varnish composition, and distilling off the organic solvent from the resin varnish composition Is also one aspect of the present invention.
[0107]
The organic solvent is not particularly limited, and for example, hexane, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, ethyl acetate, N, N-dimethyl. Examples include formamide, hexamethylphosphoramide, acetic acid, acetone, methyl ethyl ketone, methanol, ethanol, nitromethane, dimethyl sulfoxide, sulfolane, benzene, toluene, xylene, naphthalene, chlorobenzene, anisole, diphenyl ether, pyridine, nitrobenzene and the like. Among these, a polar organic solvent is preferable for dispersing the layered silicate, and an aprotic polar organic solvent is more preferable. The aprotic polar organic solvent means a polar organic solvent having no hydrogen suitable for forming a strong hydrogen bond, specifically, acetone, methyl ethyl ketone, acetonitrile, dimethyl sulfoxide, n, n-dimethylformamide, Examples include hexamethylphosphoramide. These organic solvents may be used independently and 2 or more types may be used together.
[0108]
As the blending amount of the organic solvent, the optimum amount varies depending on the blending amount of the resin and the layered silicate and the type of the organic solvent, but generally, the lower the resin concentration and the lamellar silicate concentration are preferable, the resin is 100 parts by weight and the layered layer. 30 to 1000 parts by weight are mixed with 0.01 to 100 parts by weight of silicate. If it is less than 30 parts by weight, the solution viscosity of the resin composition is too high and casting is difficult. If it exceeds 1000 parts by weight, coating failure may occur during solution casting, or thickening may be difficult. A preferable lower limit of the amount of the organic solvent is 100 parts by weight, and a more preferable lower limit is 150 parts by weight or more, and it is preferable to add more than the layered silicate.
[0109]
As a method for producing the resin varnish composition, a method of mixing a layered silicate and an organic solvent in advance and mixing the obtained mixture with a resin or a resin solution is preferable. It is preferable to use a meteor stirrer, a homogenizer, a mechanochemical stirrer, or the like for the mixing.
[0110]
Subsequently, the resin sheet is obtained by distilling off the organic solvent from the resin varnish composition. The distillation method is not particularly limited, and is selected according to the composition of the resin varnish composition.
[0111]
In addition, the method for producing a resin sheet having a relatively high resin ratio on only one side is not particularly limited. For example, a layered silicate may be used by using a layered silicate having a heavy specific gravity or by slowing a solution casting speed. Examples thereof include a method of preparing a sheet having different organic component ratios in the sheet thickness direction by precipitating salt; a method of laminating sheets having different organic component ratios, and the like.
[0112]
In the resin sheet of the present invention, the layered silicate is dispersed on a nanoscale in at least one resin selected from the group consisting of a thermosetting resin, a photocurable resin, a resin cured product, and a thermoplastic resin. It has excellent mechanical properties, transparency, moisture resistance, etc., improved heat resistance based on increase in glass transition temperature and heat distortion temperature due to molecular chain restraint, reduced thermal expansion coefficient, layered silicic acid in crystal formation Improvements in dimensional stability, etc. based on the swelling-inhibiting effect associated with the nucleation effect of salt and the improvement in moisture resistance, etc., have been attempted. Further, since a sintered body made of layered silicate is formed at the time of combustion, the shape of the combustion residue is maintained, the spread of fire can be prevented, and excellent flame retardancy is exhibited. Furthermore, by combining with a non-halogen flame retardant such as a metal hydroxide, it is possible to achieve both high mechanical properties and high flame retardancy while considering the environment. In the above-mentioned resin sheet, the layered silicate can be processed into a thin molded body without imparting a large amount of mechanical properties such as a normal inorganic filler, so that it can be processed into a thin molded body. The resin sheet of the present invention having a small thickness can be obtained corresponding to the reduction in thickness. The insulating substrate material comprising the resin sheet of the present invention can exhibit various performances such as excellent flame retardancy, mechanical properties, high temperature properties, heat resistance, and dimensional stability.
[0113]
Furthermore, the surface of the resin sheet of the present invention is roughened, so that the adhesion with the metal wiring formed on the surface by electroless plating, electroplating, sputtering, or vacuum deposition is dramatically improved. Thereby, even when the build-up process is performed or when the product is used in a harsh environment, the metal wiring does not come off from the resin, and high reliability can be secured.
The resin sheet of the present invention can be suitably used for printed multilayer boards, build-up boards, resin boards and the like.
[0114]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
[0115]
Example 1
Bisphenol F type epoxy resin (Dainippon Ink & Chemicals, Ebicron 830LVP) 57.7 parts by weight, BT resin (Mitsubishi Gas Chemicals, BT2100B) 15.7 parts by weight and neopentyl glycol diglycidyl ether 15.7 parts by weight 89.1 parts by weight of an epoxy resin composition comprising 2.1 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Nihon Unicar Company, A-187) as a coupling agent, and acetylacetone iron (Nippon Chemical Co., Ltd.) as a curing catalyst 1.1 parts by weight, swellable fluorine mica treated with distearyldimethyl quaternary ammonium salt as a layered silicate (Scorpif MAE-100, 7.7 parts by weight), 70 parts by weight of magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) as a flame retardant, and Methyl ethyl ketone as an organic solvent (manufactured by Wako Pure Chemical Industries, Ltd., special grade) 200 parts by weight was added to the beaker, and the mixture was stirred for 1 hour at a stirrer, was deaerated to obtain a resin varnish.
[0116]
The obtained resin varnish was put in a mold and heated at 60 ° C. for 3 hours to distill off the solvent, then heated at 110 ° C. for 3 hours, and further heated at 160 ° C. for 3 hours to be cured to a thickness of 2 mm. And the 100-micrometer plate-shaped molded object was produced.
[0117]
Separately, the obtained resin varnish was coated on a polyethylene terephthalate film by a doctor blade method and dried to obtain a sheet having a thickness of 24 μm. The doctor blade conditions were drying temperature = 70 ° C. and speed = 0.3 m / min.
The obtained sheet was placed on both sides of a core material (thickness 0.6 mm: manufactured by Risho Kogyo Co., Ltd.) at 90 ° C., 10 sec, pressure 1 kg / cm. ² Vacuum lamination was performed under the following conditions. After laminating, the polyethylene terephthalate film was removed and thermosetting was performed at 170 ° C. for 60 minutes to obtain a substrate.
[0118]
The obtained substrate was subjected to a roughening treatment under the following conditions.
Condition 1: The substrate was swollen for 5 minutes with a swelling liquid set at 80 ° C. (manufactured by Adtech, Swelling Dip Securigant P), and then a roughening liquid set at 80 ° C. (50 g / L sodium permanganate, (Solution containing 30 g / L sodium hydroxide) was immersed for 15 minutes (1 treatment).
Condition 2: The substrate was swollen for 5 minutes with a swelling liquid set to 80 ° C. (manufactured by Adtech, Swelling Dip Securigant P), and then a roughening liquid set to 80 ° C. (75 g / L sodium permanganate, (Solution containing 50 g / L sodium hydroxide) was immersed for 15 minutes (one treatment).
Condition 3: The substrate was swollen for 5 minutes with a swelling liquid set to 80 ° C. (manufactured by Adtech, Swelling Dip Securigant P), and then a roughening liquid set to 80 ° C. (75 g / L sodium permanganate, A solution containing 50 g / L sodium hydroxide) was immersed for 15 minutes (twice the number of treatments).
Condition 4: After the substrate was swollen for 5 minutes with a swelling liquid set to 80 ° C. (manufactured by Adtech Corp., Swelling Dip Securigant P), a roughening liquid set to 80 ° C. (75 g / L sodium permanganate, (Solution containing 50 g / L sodium hydroxide) was immersed for 15 minutes (3 times of treatment).
[0119]
On the roughened substrate, electroless plating was performed at 35 ° C. for 10 minutes using a palladium catalyst and an electroless copper plating solution to form an electroless plated copper layer having a thickness of 0.8 μm.
Furthermore, on this, 2 A / dm ² Electroplating was performed for 70 minutes to form an electroplated copper layer having a thickness of 24 μm.
[0120]
(Example 2)
Bisphenol F type epoxy resin (Dainippon Ink and Chemicals, Epicron 830LVP) 57.7 parts by weight, BT resin (Mitsubishi Gas Chemicals, BT2100B) 15.7 parts by weight and neopentyl glycol diglycidyl ether 15.7 parts by weight 89.1 parts by weight of an epoxy resin composition comprising 2.1 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Nihon Unicar Company, A-187) as a coupling agent, and acetylacetone iron (Nippon Chemical Co., Ltd.) as a curing catalyst Sangyo Co., Ltd.) 1.1 parts by weight, 7.7 parts by weight of natural montmorillonite treated with distearyldimethyl quaternary ammonium salt as a layered silicate (particle size = 1 μm), magnesium hydroxide (flame retardant) 70 parts by weight of particle diameter = 1 μm and methyl ethyl ketone (Wako Pure) as an organic solvent Company Ltd., special grade) 200 parts by weight was added to the beaker, and the mixture was stirred for 1 hour at a stirrer, was deaerated to obtain a resin varnish 1.
[0121]
On the other hand, 57.7 parts by weight of bisphenol F-type epoxy resin (Dainippon Ink & Chemicals, Epicron 830LVP), 15.7 parts by weight of BT resin (BT2100B, manufactured by Mitsubishi Gas Chemical Co., Inc.) and 15.5 parts of neopentyl glycol diglycidyl ether. 89.1 parts by weight of an epoxy resin composition comprising 7 parts by weight, 2.1 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Nihon Unicar Co., Ltd., A-187) as a coupling agent, and acetylacetone iron ( Nippon Chemical Industry Co., Ltd.) 1.1 parts by weight, swellable fluorine mica treated with distearyldimethyl quaternary ammonium salt as a layered silicate (particle size = 0.1 μm) 7.7 parts by weight, difficult 70 parts by weight of magnesium hydroxide (particle size = 0.1 μm) as a flame retardant and methyl ethyl ketone as an organic solvent Down (manufactured by Wako Pure Chemical Industries, Ltd., special grade) 200 parts by weight was added to the beaker, and the mixture was stirred for 1 hour at a stirrer, was deaerated to obtain a resin varnish 2.
[0122]
The resin varnish 2 obtained was heated in a mold at 60 ° C. for 3 hours to distill off the solvent, then heated at 110 ° C. for 3 hours, and further heated at 160 ° C. for 3 hours to be cured. 2 mm and 100 μm plate-shaped compacts were prepared.
[0123]
Separately, the obtained resin varnish 1 was coated on a polyethylene terephthalate film by a doctor blade method and dried to obtain a sheet having a thickness of 4 μm. The doctor blade conditions were drying temperature = 70 ° C. and speed = 0.3 m / min.
Next, the resin varnish 2 was applied onto a sheet made of the resin varnish 1 by a doctor blade method under the same conditions, and dried to obtain a sheet having a thickness of 20 μm.
The obtained sheet was placed on both sides of a core material (thickness 0.6 mm: manufactured by Risho Kogyo Co., Ltd.) at 90 ° C., 10 sec, pressure 1 kg / cm. ² Vacuum lamination was performed under the following conditions. After laminating, the polyethylene terephthalate film was removed and thermosetting was performed at 170 ° C. for 60 minutes to obtain a substrate.
[0124]
The obtained substrate was subjected to a roughening treatment under condition 2 of Example 1.
On the roughened substrate, electroless plating was performed under the conditions of a palladium catalyst, electroless plating solution 35 ° C., and 10 minutes to form an electroless plated copper layer having a thickness of 0.8 μm.
Furthermore, on this, 2 A / dm ² Electroplating was performed for 70 minutes to form an electroplated copper layer having a thickness of 24 μm.
[0125]
(Example 3)
A resin varnish was prepared in the same manner as in Example 1 except that 7.7 parts by weight of swellable fluorine mica (manufactured by Co-op Chemical Co., Ltd., Somasif MAE-100) was changed to 0.5 part by weight. 2 mm and 100 μm plate-shaped compacts were prepared.
[0126]
Separately, the obtained resin varnish 1 was coated on a polyethylene terephthalate film by a doctor blade method and dried to obtain a sheet having a thickness of 4 μm. The doctor blade conditions were drying temperature = 70 ° C. and speed = 0.3 m / min.
Next, the resin varnish 2 was applied onto a sheet made of the resin varnish 1 by a doctor blade method under the same conditions, and dried to obtain a sheet having a thickness of 20 μm.
The obtained sheet was placed on both sides of a core material (thickness 0.6 mm: manufactured by Risho Kogyo Co., Ltd.) at 90 ° C., 10 sec, pressure 1 kg / cm. ² Vacuum lamination was performed under the following conditions. After laminating, the polyethylene terephthalate film was removed and thermosetting was performed at 170 ° C. for 60 minutes to obtain a substrate.
[0127]
The obtained substrate was subjected to a roughening treatment under the following conditions.
The substrate was swelled for 5 minutes with a swelling liquid set to 80 ° C. (manufactured by Adtech, Swelling Dip Securigant P), and then the roughening liquid set to 80 ° C. (50 g / L sodium permanganate, 30 g / L (Solution containing sodium hydroxide).
[0128]
On the roughened substrate, electroless plating was performed at 35 ° C. for 10 minutes using a palladium catalyst and an electroless copper plating solution to form an electroless plated copper layer having a thickness of 0.8 μm.
Furthermore, on this, 2 A / dm ² Electroplating was performed for 70 minutes to form an electroplated copper layer having a thickness of 24 μm.
[0129]
Example 4
A resin varnish was prepared in the same manner as in Example 1 except that 200 parts by weight of methyl ethyl ketone (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 100 parts by weight. A plate-like molded product having a thickness of 2 mm and 100 μm was prepared using the resin varnish. Produced.
[0130]
Separately, the obtained resin varnish 1 was coated on a polyethylene terephthalate film by a doctor blade method and dried to obtain a sheet having a thickness of 4 μm. The doctor blade conditions were drying temperature = 70 ° C. and speed = 0.3 m / min.
Next, the resin varnish 2 was applied onto a sheet made of the resin varnish 1 by a doctor blade method under the same conditions, and dried to obtain a sheet having a thickness of 20 μm.
The obtained sheet was placed on both sides of a core material (thickness 0.6 mm: manufactured by Risho Kogyo Co., Ltd.) at 90 ° C., 10 sec, pressure 1 kg / cm. ² Vacuum lamination was performed under the following conditions. After laminating, the polyethylene terephthalate film was removed and thermosetting was performed at 170 ° C. for 60 minutes to obtain a substrate.
[0131]
The obtained substrate was subjected to a roughening treatment under the same conditions as in Example 3.
On the roughened substrate, electroless plating was performed at 35 ° C. for 10 minutes using a palladium catalyst and an electroless copper plating solution to form an electroless plated copper layer having a thickness of 0.8 μm.
Furthermore, on this, 2 A / dm ² Electroplating was performed for 70 minutes to form an electroplated copper layer having a thickness of 24 μm.
[0132]
(Example 5)
A resin varnish was prepared in the same manner as in Example 1 except that 70 parts by weight of magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5J) was not used as a flame retardant, and a plate having a thickness of 2 mm and 100 μm was used. A shaped compact was produced.
[0133]
Separately, the obtained resin varnish was coated on a polyethylene terephthalate film by a doctor blade method and dried to obtain a sheet having a thickness of 24 μm. The doctor blade conditions were drying temperature = 70 ° C. and speed = 0.3 m / min.
The obtained sheet was placed on both sides of a core material (thickness 0.6 mm: manufactured by Risho Kogyo Co., Ltd.) at 90 ° C., 10 sec, pressure 1 kg / cm. ² Vacuum lamination was performed under the following conditions. After laminating, the polyethylene terephthalate film was removed and thermosetting was performed at 170 ° C. for 60 minutes to obtain a substrate.
[0134]
The obtained substrate was subjected to a roughening treatment under condition 2 of Example 1.
On the roughened substrate, electroless plating was performed at 35 ° C. for 10 minutes using a palladium catalyst and an electroless copper plating solution to form an electroless plated copper layer having a thickness of 0.8 μm.
Furthermore, on this, 2 A / dm ² Electroplating was performed for 70 minutes to form an electroplated copper layer having a thickness of 24 μm.
[0135]
(Example 6)
24,9 parts by weight of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.), 20 parts by weight of synthetic hectorite (Lucentite STN-A, manufactured by Corp Chemical Co., Ltd.) -8125) 40 parts by weight, phenoxy resin (Toto Kasei Co., Ltd. phenototo YP-55) 40 parts by weight, dicyandiamide (Adeka Hardener EH-3636 manufactured by Asahi Denka Kogyo Co., Ltd.) 2.8 parts by weight and modified imidazole (Asahi Denka Kogyo Co., Ltd.) (Adeka Hardener EH-3366) 1.2 parts by weight was added, stirred and mixed with a stirrer for 2 hours, and then defoamed to obtain a resin solution.
[0136]
Separately, the obtained resin varnish was coated on a polyethylene terephthalate film by the doctor blade method and dried to obtain a 40 μm thick sheet. The doctor blade conditions were drying temperature = 100 ° C. and speed = 0.3 m / min.
The obtained sheet was placed on both sides of a core material (thickness 0.6 mm: manufactured by Risho Kogyo Co., Ltd.) at 90 ° C., 10 sec, pressure 1 kg / cm. ² Vacuum lamination was performed under the following conditions. After laminating, the polyethylene terephthalate film was removed and thermosetting was performed at 170 ° C. for 60 minutes to obtain a substrate.
Further, a corona discharge treatment machine (thyristor inverter method, HFS402, manufactured by Kasuga Denki Co., Ltd.) was used for the obtained substrate, and corona discharge treatment (treatment conditions: applied energy 6000 J / m) in the air. ² , Treatment speed 20 m / min, temperature 20 ° C.).
[0137]
The substrate thus obtained was subjected to a roughening treatment under the following conditions.
The substrate was swelled for 5 minutes with a swelling liquid set to 80 ° C. (manufactured by Adtech, Swelling Dip Securigant P), and then the roughening liquid set to 80 ° C. (50 g / L sodium permanganate, 30 g / L (Solution containing sodium hydroxide).
[0138]
On the roughened substrate, electroless plating was performed at 35 ° C. for 10 minutes using a palladium catalyst and an electroless copper plating solution to form an electroless plated copper layer having a thickness of 0.8 μm.
Furthermore, on this, 2 A / dm ² Electroplating was performed for 70 minutes to form an electroplated copper layer having a thickness of 24 μm.
[0139]
(Example 7)
111,9 parts by weight of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.), 84.31 parts by weight of synthetic hectorite (Lucentite STN-A, manufactured by Corp Chemical Co.), epoxy-modified butadiene rubber (EPB, manufactured by Nippon Soda Co., Ltd.) -13) 384 parts by weight, phenol novolac resin (Dainippon Ink Co., Phenolite LA-1356) 93.75 parts by weight and synthetic silica (Admafine SO-E2 by Admatechs) 55.88 parts by weight were added. After stirring and mixing with a stirrer for 2 hours, defoaming was performed to obtain a resin solution.
[0140]
Separately, the obtained resin varnish was coated on a polyethylene terephthalate film by the doctor blade method and dried to obtain a 40 μm thick sheet. The doctor blade conditions were drying temperature = 100 ° C. and speed = 0.3 m / min.
The obtained sheet was placed on both sides of a core material (thickness 0.6 mm: manufactured by Risho Kogyo Co., Ltd.) at 90 ° C., 10 sec, pressure 1 kg / cm. ² Vacuum lamination was performed under the following conditions. After laminating, the polyethylene terephthalate film was removed and thermosetting was performed at 170 ° C. for 60 minutes to obtain a substrate.
[0141]
Next, the obtained substrate was subjected to a roughening treatment under the following conditions.
The substrate was swelled for 5 minutes with a swelling liquid set to 80 ° C. (manufactured by Adtech, Swelling Dip Securigant P), and then the roughening liquid set to 80 ° C. (50 g / L sodium permanganate, 30 g / L (Solution containing sodium hydroxide).
[0142]
On the roughened substrate, electroless plating was performed at 35 ° C. for 10 minutes using a palladium catalyst and an electroless copper plating solution to form an electroless plated copper layer having a thickness of 0.8 μm.
Furthermore, on this, 2 A / dm ² Electroplating was performed for 70 minutes to form an electroplated copper layer having a thickness of 24 μm.
[0143]
(Comparative Example 1)
Resin in the same manner as in Example 1 except that 7.7 parts by weight of calcium carbonate having an average particle diameter of 50 μm was used instead of 7.7 parts by weight of swellable fluorine mica (manufactured by Corp Chemical Co., Ltd., Somasif MAE-100). A varnish was prepared, and a plate-like molded body having a thickness of 2 mm and 100 μm was produced using the varnish.
[0144]
Separately, the obtained resin varnish was coated on a polyethylene terephthalate film by a doctor blade method and dried to obtain a sheet having a thickness of 24 μm. The doctor blade conditions were drying temperature = 70 ° C. and speed = 0.3 m / min.
The obtained sheet was placed on both sides of a core material (thickness 0.6 mm: manufactured by Risho Kogyo Co., Ltd.) at 90 ° C., 10 sec, pressure 1 kg / cm. ² Vacuum lamination was performed under the following conditions. After laminating, the polyethylene terephthalate film was removed and thermosetting was performed at 170 ° C. for 60 minutes to obtain a substrate.
[0145]
The obtained substrate was subjected to a roughening treatment under condition 2 of Example 1.
On the roughened substrate, electroless plating was performed at 35 ° C. for 10 minutes using a palladium catalyst and an electroless copper plating solution to form an electroless plated copper layer having a thickness of 0.8 μm.
Furthermore, on this, 2 A / dm ² Electroplating was performed for 70 minutes to form an electroplated copper layer having a thickness of 24 μm.
[0146]
About the plate-shaped molded bodies produced in Examples 1 to 7 and Comparative Example 1, the average interlayer distance of the layered silicate, the ratio of the layered silicate dispersed in 5 layers or less, the shape retention during combustion, The maximum heat generation rate and the coating strength of the combustion residue were evaluated. Moreover, the roughening state of the surface of the board | substrate before copper layer formation obtained, and the peeling adhesive strength of the copper layer of the board | substrate which formed the copper layer were evaluated by the following method.
The results are shown in Table 1.
[0147]
(1) Average interlayer distance of layered silicate
Using an X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), 2θ of a diffraction peak obtained from diffraction of the laminated surface of the layered silicate in the 2 mm-thick plate-like molded product was measured, and the following formula (4) The (001) plane spacing (d) of the layered silicate was calculated from the black diffraction formula, and d was obtained as the average interlayer distance (nm).
λ = 2 dsin θ (4)
In the formula, λ is 0.154, d represents the interplanar spacing of the layered silicate, and θ represents the diffraction angle.
[0148]
(2) Ratio of layered silicate dispersed in 5 layers or less
Layered silicic acid dispersed in 5 layers or less out of the total number of layers (X) of the layered silicate laminate observed by a transmission electron microscope at a magnification of 50,000 to 100,000 times in a certain area The number of salt layers (Y) was measured, and the ratio (%) of the layered silicate dispersed in 5 layers or less was calculated by the following formula (3).
Ratio of layered silicate dispersed in 5 layers or less (%) = (Y / X) × 100 (3)
[0149]
(3) Shape retention during combustion
In accordance with ASTM E 1354 “Testing method for flammability of building materials”, a plate-like molded body having a thickness of 2 mm cut to 100 mm × 100 mm is subjected to 50 kW / m by a cone calorimeter. ² It was burned by irradiating the heat rays. At this time, the change in the shape of the plate-shaped molded body before and after combustion was visually observed, and the shape retention during combustion was evaluated according to the following criteria.
○: The shape change was slight.
X: The shape change was severe.
[0150]
(4) Maximum heat generation rate and coating strength of combustion residue
In accordance with ASTM E 1354 “Testing method for flammability of building materials”, a plate-like molded body having a thickness of 2 mm cut to 100 mm × 100 mm is subjected to 50 kW / m by a cone calorimeter. ² It was burned by irradiating the heat rays. Maximum heat generation rate at this time (kW / m ² ) Was measured. Moreover, the combustion residue was compressed at a speed of 0.1 cm / s using a strength measuring device, and the coating strength (kPa) of the combustion residue was measured.
[0151]
(5) Roughening state
By observing the cross section with a scanning electron microscope (SEM), the unevenness of the surface was measured, and the average value of the heights of the protrusions was obtained.
[0152]
(6) Peel adhesion strength
The copper layer formed on the substrate surface was cut with a 1 cm width using a cutter, and the peel adhesion strength was measured under the condition of a tensile speed of 50 m / min.
[0153]
[Table 1]

[0154]
From Table 1, the plate-like molded bodies produced in Examples 1 to 7 have a lamellar silicate in which the average interlayer distance of the lamellar silicate contained is 3 mm or more and is dispersed as a laminate of 5 layers or less. The proportion of salt was 10% or more, and the shape retention during combustion was excellent. Moreover, since it was easy to form the sintered compact used as a flame-resistant film, the maximum heat release rate was slow, and the film strength of the combustion residue was 4.9 kPa or more. On the other hand, the plate-like molded body of Comparative Example 1 produced using calcium carbonate instead of the layered silicate does not have calcium carbonate dispersed in layers, has poor shape retention during combustion, and has a maximum heat generation rate. However, the coating strength of the combustion residue was extremely low.
Furthermore, when the surface was roughened, the roughened state of the substrates produced in Examples 1 to 7 had an unevenness of 1 μm or more, and the peel adhesive strength was excellent at 3.9 N / cm or more. . On the other hand, in the substrate produced in Comparative Example 1, the formed irregularities were small and the peel adhesion strength was low.
[0155]
【The invention's effect】
According to the present invention, it is excellent in mechanical properties, dimensional stability, heat resistance, etc., particularly has excellent flame retardancy due to the shape retention effect during combustion, and when the metal wiring is formed on the surface, the metal wiring A resin sheet excellent in adhesion can be provided.

Claims (20)

A resin sheet containing 100 parts by weight of at least one resin selected from the group consisting of a thermosetting resin, a photocurable resin, a cured resin, and a thermoplastic resin and 0.1 to 100 parts by weight of a layered silicate. There,
A resin sheet , wherein a metal layer is formed on the surface by electroless plating, electroplating, sputtering or vacuum deposition , and the peel adhesion strength of the metal layer is 3.9 N / cm or more. A resin sheet containing 100 parts by weight of a curable resin containing a cured resin cured product or a cured resin cured product and 0.1 to 100 parts by weight of a layered silicate,
2. The resin sheet according to claim 1 , wherein a metal layer is formed on the surface by electroless plating, electroplating, sputtering or vacuum deposition , and the peel adhesion strength of the metal layer is 3.9 N / cm or more. .   Thermosetting resins include epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, urea resins, allyl resins, silicon resins, benzoxazine resins, phenol resins, unsaturated polyester resins, and bismaleimides. The resin sheet according to claim 1 or 2, wherein the resin sheet is at least one selected from the group consisting of triazine resins.   Thermoplastic resins include polyphenylene ether resins, polyphenylene ether resins modified with functional groups, polyphenylene ether resins or mixtures of polyphenylene ether resins modified with functional groups and polystyrene resins, alicyclic hydrocarbon resins The at least one selected from the group consisting of a resin, a thermoplastic polyimide resin, a polyetheretherketone resin, a polyethersulfone resin, a polyamideimide resin, and a polyesterimide resin 3. The resin sheet according to 3.   5. The resin sheet according to claim 1, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite and swellable mica.   6. The resin sheet according to claim 1, wherein the layered silicate is swellable fluorine mica.   The resin sheet according to claim 1, 2, 3, 4, 5 or 6, wherein the layered silicate contains an alkyl ammonium ion having 6 or more carbon atoms.   The layered silicate has an average interlayer distance of (001) plane measured by wide-angle X-ray diffraction measurement method of 3 nm or more, and part or all are dispersed in 5 layers or less. Item 8. A resin sheet according to item 1, 2, 3, 4, 5, 6 or 7.   Furthermore, 0.1-100 weight part of flame retardants which do not contain a halogen-type composition are contained, The resin sheet of Claim 1, 2, 3, 4, 5, 6, 7 or 8 characterized by the above-mentioned.   The resin sheet according to claim 9, wherein the flame retardant is a metal hydroxide. Claims yield stress when the combustion residues is burned and compressed at a rate 0.1 cm / s by heating in radiant heating conditions of 50 kW / m ² 30 minutes and wherein the at least 4.9kPa 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.   The surface portion of at least one surface has an organic component ratio that is equal to or higher than the average organic component ratio of the whole, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11. The resin sheet according to 11. The resin sheet according to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein a metal layer is formed on the surface by electroless plating and electroplating . Claim 1, 2, 3, 4, a 12 or 1 3 process for producing a resin sheet according,
Thermosetting resin, photocurable resin, a cured resin and at least one 0.1 weight parts layered silicate for the resin 100 parts by weight of and an organic solvent 30 is selected from the group consisting of a thermoplastic resin A step of mixing 1000 parts by weight to prepare a resin varnish composition;
And a step of distilling off the organic solvent from the resin varnish composition. Furthermore, according to claim 1 4 method for producing a resin sheet, wherein further comprising the step of roughening the surface of the resin sheet by an oxidizing agent. A method for producing a resin sheet according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13.
A method for producing a resin sheet, comprising a step of roughening a surface of the resin sheet with an oxidizing agent. The step of roughening the surface of the resin sheet with an oxidizing agent is performed at a processing temperature of 70 to 85 ° C. using a 60 to 70 g / L permanganic acid solution or a permanganate solution and a 40 to 80 g / L sodium hydroxide solution. The method for producing a resin sheet according to claim 15, wherein the method is performed by performing the treatment once or twice. From the group consisting of a thermosetting resin, a photocurable resin, a resin cured product, and a thermoplastic resin in which a metal hydroxide as a layered silicate or a flame retardant is previously dispersed on a resin sheet so as to have a particle diameter of 0.5 μm or more. at least one of claims 1 5, 16 or 1 7 method for producing a resin sheet, wherein the previously formed a layer made of resin selected. Claim 1, 2, 3, 4, printed circuit multilayer board characterized by comprising using a 12 or 1 3 resin sheet according. Claim 1, 2, 3, 4, build-up substrate, characterized by comprising using a 12 or 1 3 resin sheet according.