JP3854931B2 - Resin composition - Google Patents

Description

【００８５】
上記層状珪酸塩の層間に存在する交換性金属カチオンとは、層状珪酸塩の薄片状結晶表面に存在するナトリウムやカルシウム等の金属イオンを意味し、これらの金属イオンは、カチオン性物質とのカチオン交換性を有するため、カチオン性を有する種々の物質を上記層状珪酸塩の結晶層間に挿入（インターカレート）することができる。
【００８６】
上記層状珪酸塩のカチオン交換容量としては特に限定されないが、好ましい下限は５０ミリ等量／１００ｇ、上限は２００ミリ等量／１００ｇである。５０ミリ等量／１００ｇ未満であると、カチオン交換により層状珪酸塩の結晶層間にインターカレートされるカチオン性物質の量が少なくなるために、結晶層間が充分に非極性化（疎水化）されないことがある。２００ミリ等量／１００ｇを超えると、層状珪酸塩の結晶層間の結合力が強固になりすぎて、結晶薄片が剥離し難くなることがある。
【００８７】
上記無機化合物として層状珪酸塩を用いて本発明の樹脂組成物を製造する場合、層状珪酸塩を化学修飾して樹脂との親和性を高めることにより樹脂中への分散性を向上されたものが好ましく、このような化学処理により樹脂中に層状珪酸塩を大量に分散することができる。本発明に用いられる樹脂、あるいは本発明の樹脂組成物を製造する際に用いられる溶媒に適した化学修飾を層状珪酸塩に施さない場合、層状珪酸塩は凝集しやすくなるので大量に分散させることができないが、樹脂あるいは溶媒に適した化学修飾を施すことにより、層状珪酸塩は１０重量部以上添加した場合においても、樹脂中に凝集することなく分散させることができる。上記化学修飾としては、例えば、以下に示す化学修飾（１）法〜化学修飾（６）法によって実施することができる。これらの化学修飾方法は、単独で用いられてもよく、２種以上が併用されてもよい。
【００８８】
上記化学修飾（１）法は、カチオン性界面活性剤によるカチオン交換法ともいい、具体的には、低極性樹脂を用いて本発明の樹脂組成物を得る際に予め層状珪酸塩の層間をカチオン性界面活性剤でカチオン交換し、疎水化しておく方法である。予め層状珪酸塩の層間を疎水化しておくことにより、層状珪酸塩と低極性樹脂との親和性が高まり、層状珪酸塩を低極性樹脂中により均一に微分散させることができる。
【００８９】
上記カチオン性界面活性剤としては特に限定されず、例えば、４級アンモニウム塩、４級ホスホニウム塩等が挙げられる。なかでも、層状珪酸塩の結晶層間を充分に疎水化できることから、炭素数６以上のアルキルアンモニウムイオン、芳香族４級アンモニウムイオン又は複素環４級アンモニウムイオンが好適に用いられる。
【００９０】
上記４級アンモニウム塩としては特に限定されず、例えば、トリメチルアルキルアンモニウム塩、トリエチルアルキルアンモニウム塩、トリブチルアルキルアンモニウム塩、ジメチルジアルキルアンモニウム塩、ジブチルジアルキルアンモニウム塩、メチルベンジルジアルキルアンモニウム塩、ジベンジルジアルキルアンモニウム塩、トリアルキルメチルアンモニウム塩、トリアルキルエチルアンモニウム塩、トリアルキルブチルアンモニウム塩；ベンジルメチル｛２−［２−（ｐ−１，１，３，３−テトラメチルブチルフェノオキシ）エトキシ］エチル｝アンモニウムクロライド等の芳香環を有する４級アンモニウム塩；トリメチルフェニルアンモニウム等の芳香族アミン由来の４級アンモニウム塩；アルキルピリジニウム塩、イミダゾリウム塩等の複素環を有する４級アンモニウム塩；ポリエチレングリコール鎖を２つ有するジアルキル４級アンモニウム塩、ポリプロピレングリコール鎖を２つ有するジアルキル４級アンモニウム塩、ポリエチレングリコール鎖を１つ有するトリアルキル４級アンモニウム塩、ポリプロピレングリコール鎖を１つ有するトリアルキル４級アンモニウム塩等が挙げられる。なかでも、ラウリルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、トリオクチルメチルアンモニウム塩、ジステアリルジメチルアンモニウム塩、ジ硬化牛脂ジメチルアンモニウム塩、ジステアリルジベンジルアンモニウム塩、Ｎ−ポリオキシエチレン−Ｎ−ラウリル−Ｎ，Ｎ−ジメチルアンモニウム塩等が好適である。これらの４級アンモニウム塩は、単独で用いられてもよく、２種以上が併用されてもよい。
【００９１】
上記４級ホスホニウム塩としては特に限定されず、例えば、ドデシルトリフェニルホスホニウム塩、メチルトリフェニルホスホニウム塩、ラウリルトリメチルホスホニウム塩、ステアリルトリメチルホスホニウム塩、トリオクチルメチルホスホニウム塩、ジステアリルジメチルホスホニウム塩、ジステアリルジベンジルホスホニウム塩等が挙げられる。これらの４級ホスホニウム塩は、単独で用いられてもよく、２種以上が併用されてもよい。
【００９２】
上記化学修飾（２）法は、化学修飾（１）法で化学処理された有機化層状珪酸塩の結晶表面に存在する水酸基を、水酸基と化学結合し得る官能基又は水酸基との化学的親和性の大きい官能基を分子末端に１個以上有する化合物で化学処理する方法である。
【００９３】
上記水酸基と化学結合し得る官能基又は水酸基との化学的親和性の大きい官能基としては特に限定されず、例えば、アルコキシ基、グリシジル基、カルボキシル基（二塩基性酸無水物も包含する）、水酸基、イソシアネート基、アルデヒド基等が挙げられる。
【００９４】
上記水酸基と化学結合し得る官能基を有する化合物又は水酸基との化学的親和性の大きい官能基を有する化合物としては特に限定されず、例えば、上記官能基を有する、シラン化合物、チタネート化合物、グリシジル化合物、カルボン酸類、アルコール類等が挙げられる。これらの化合物は、単独で用いられてもよく、２種以上が併用されてもよい。
【００９５】
上記シラン化合物としては特に限定されず、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルジメチルメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルジメチルエトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、Ｎ−β−（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）γ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、オクタデシルトリメトキシシラン、オクタデシルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン等が挙げられる。これらのシラン化合物は、単独で用いられてもよく、２種以上が併用されてもよい。
【００９６】
上記化学修飾（３）法は、化学修飾（１）法で化学処理された有機化層状珪酸塩の結晶表面に存在する水酸基を、水酸基と化学結合し得る官能基又は水酸基と化学的親和性の大きい官能基と、反応性官能基を分子末端に１個以上有する化合物とで化学処理する方法である。
【００９７】
上記化学修飾（４）法は、化学修飾（１）法で化学処理された有機化層状珪酸塩の結晶表面を、アニオン性界面活性を有する化合物で化学処理する方法である。
【００９８】
上記アニオン性界面活性を有する化合物としては、イオン相互作用により層状珪酸塩を化学処理できるものであれば特に限定されず、例えば、ラウリル酸ナトリウム、ステアリン酸ナトリウム、オレイン酸ナトリウム、高級アルコール硫酸エステル塩、第２級高級アルコール硫酸エステル塩、不飽和アルコール硫酸エステル塩等が挙げられる。これらの化合物は、単独で用いられてもよく、２種以上が併用されてもよい。
【００９９】
上記化学修飾（５）法は、上記アニオン性界面活性を有する化合物のうち、分子鎖中のアニオン部位以外に反応性官能基を１個以上有する化合物で化学処理する方法である。
【０１００】
上記化学修飾（６）法は、化学修飾（１）法〜化学修飾（５）法のいずれかの方法で化学処理された有機化層状珪酸塩に、更に、例えば、無水マレイン酸変性ポリフェニレンエーテル樹脂のような層状珪酸塩と反応可能な官能基を有する樹脂を用いる方法である。
【０１０１】
上記層状珪酸塩は、本発明の樹脂組成物中に、広角Ｘ線回折測定法により測定した（００１）面の平均層間距離が３ｎｍ以上であるように、かつ、一部又は全部が５層以下の層数で分散されていることが好ましい。上記平均層間距離が３ｎｍ以上であるように、かつ、一部又は全部が５層以下の層数で分散されていることにより、樹脂と層状珪酸塩との界面面積は充分に大きく、かつ、層状珪酸塩の薄片状結晶間の距離は適度なものとなり、高温物性、力学的物性、耐熱性、寸法安定性等において分散による改善効果を充分に得ることができる。
【０１０２】
上記平均層間距離の好ましい上限は５ｎｍである。５ｎｍを超えると、層状珪酸塩の結晶薄片が層毎に分離して相互作用が無視できるほど弱まるので、高温での束縛強度が弱くなり、充分な寸法安定性が得られないことがある。
【０１０３】
なお、本明細書において、層状珪酸塩の平均層間距離とは、層状珪酸塩の薄片状結晶を層とみなした場合における層間の距離の平均を意味し、Ｘ線回折ピーク及び透過型電子顕微鏡撮影、すなわち、広角Ｘ線回折測定法により算出することができるものである。
【０１０４】
上記一部又は全部が５層以下の層数で分散されているとは、具体的には、層状珪酸塩の薄片状結晶間の相互作用が弱められて薄片状結晶の積層体の一部又は全部が分散していることを意味する。好ましくは、層状珪酸塩の積層体の１０％以上が５層以下の層数で分散されており、層状珪酸塩の積層体の２０％以上が５層以下の層数で分散されていることがより好ましい。
なお、５層以下の積層体として分散している層状珪酸塩の割合は、樹脂組成物を透過型電子顕微鏡により５万〜１０万倍に拡大して観察し、一定面積中において観察できる層状珪酸塩の積層体の全層数Ｘ及び５層以下の積層体として分散している積層体の層数Ｙを計測することにより、下記式（４）から算出することができる。
【０１０５】
【数４】

【０１０６】
また、層状珪酸塩の積層体における積層数としては、層状珪酸塩の分散による効果を得るためには５層以下であることが好ましく、より好ましくは３層以下であり、更に好ましくは１層である。
【０１０７】
本発明の樹脂組成物は、上記無機化合物として層状珪酸塩を用い、層状珪酸塩が、広角Ｘ線回折測定法により測定した（００１）面の平均層間距離が３ｎｍ以上であるように、かつ、一部又は全部が５層以下の層数で分散されているものとすることにより、樹脂と層状珪酸塩との界面面積が充分に大きくなって、樹脂と層状珪酸塩の表面との相互作用が大きくなり、溶融粘度が高まり熱プレスなどの熱成形性が向上することに加え、シボ、エンボスなど賦形した形状も保持しやすく、また、常温から高温までの広い温度領域で弾性率等の力学的物性が向上し、樹脂のＴｇ又は融点以上の高温でも力学的物性を保持することができ、高温時の線膨張率も低く抑えることができる。かかる理由は明らかではないが、Ｔｇ又は融点以上の温度領域においても、微分散状態の層状珪酸塩が一種の疑似架橋点として作用しているためにこれら物性が発現すると考えられる。一方、層状珪酸塩の薄片状結晶間の距離も適度なものとなるので、燃焼時に、層状珪酸塩の薄片状結晶が移動して難燃被膜となる焼結体を形成しやすくなる。この焼結体は、燃焼時の早い段階で形成されるので、外界からの酸素の供給を遮断するのみならず、燃焼により発生する可燃性ガスをも遮断することができ、本発明の樹脂組成物は優れた難燃性を発現する。
【０１０８】
更に、本発明の樹脂組成物では、ナノメートルサイズで層状珪酸塩が微分散していることから、本発明の樹脂組成物からなる基板等に炭酸ガスレーザ等のレーザにより穿孔加工を施した場合、樹脂成分と層状珪酸塩成分とが同時に分解蒸発し、部分的に残存する層状珪酸塩の残渣も数μｍ以下の小さなもののみでありデスミア加工により容易に除去できる。これにより、穿孔加工により発生する残渣によってメッキ不良等が発生するのを防止することができる。
【０１０９】
樹脂中に層状珪酸塩を分散させる方法としては特に限定されず、例えば、有機化層状珪酸塩を用いる方法、樹脂と層状珪酸塩とを常法により混合した後に樹脂を発泡剤により発泡させる方法、分散剤を用いる方法等が挙げられる。これらの分散方法を用いることにより、樹脂中に層状珪酸塩をより均一かつ微細に分散させることができる。
【０１１０】
上記樹脂と層状珪酸塩とを常法により混合した後に樹脂を発泡剤により発泡させる方法は、発泡によるエネルギーを層状珪酸塩の分散に用いるものである。上記発泡剤としては特に限定されず、例えば、気体状発泡剤、易揮発性液状発泡剤、加熱分解型固体状発泡剤等が挙げられる。これらの発泡剤は、単独で用いられてもよいし、２種以上が併用されてもよい。
【０１１１】
上記樹脂と層状珪酸塩とを常法により混合した後に樹脂を発泡剤により発泡させる方法としては特に限定されず、例えば、樹脂と層状珪酸塩とからなる樹脂組成物に気体状発泡剤を高圧下で含浸させた後、この気体状発泡剤を上記樹脂組成物内で気化させて発泡体を形成する方法；層状珪酸塩の層間に予め加熱分解型発泡剤を含有させ、その加熱分解型発泡剤を加熱により分解させて発泡体を形成する方法等が挙げられる。
【０１１２】
上記無機化合物の上記熱硬化性樹脂１００重量部に対する配合量の下限は０．１重量部、上限は６５重量部である。０．１重量部未満であると、高温物性や吸湿性の改善効果が小さくなる。６５重量部を超えると、本発明の樹脂組成物の密度（比重）が高くなり、機械的強度も低下することから実用性に乏しくなる。好ましい下限は１重量部、上限は４５重量部である。１重量部未満であると、本発明の樹脂組成物を薄く成形した際に充分な高温物性の改善効果が得られないことがある。４５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３０重量部である。５〜３０重量部であると、力学的物性、工程適性において問題となる領域はなく、充分な難燃性が得られる。
【０１１３】
本発明の樹脂組成物のうち、無機化合物として層状珪酸塩を用いる場合、上記層状珪酸塩の配合量の下限は１重量部、上限は５０重量部が好ましい。１重量部未満であると高温物性や吸湿性の改善効果が小さくなることがある。５０重量部を超えると、本発明の樹脂組成物の密度（比重）が高くなり、機械的強度も低下することから実用性に乏しくなることがある。より好ましい下限は５重量部、上限は４５重量部である。５重量未満であると本発明の樹脂組成物を薄く成形した際に充分な高温物性の改善効果が得られないことがある。４５重量部を超えると、層状珪酸塩の分散性が悪くなることがある。さらに好ましい下限は８重量部であり、上限は４０重量部である。８〜４０重量部であると工程適性において問題となる領域はなく、充分な低吸水性が得られ、かつ、平均線膨張率の低減効果がα１およびα２の両方の領域でも充分に得られる。
【０１１４】
本発明の樹脂組成物は、更に、ハロゲン系組成物を含有しない難燃剤を含有することが好ましい。なお、難燃剤の製造工程上の都合等により微量のハロゲンが混入することはかまわない。
【０１１５】
上記難燃剤としては特に限定されず、例えば、水酸化アルミニウム、水酸化マグネシウム、ドーソナイト、アルミン酸化カルシウム、２水和石こう、水酸化カルシウム等の金属水酸化物；金属酸化物；赤リンやポリリン酸アンモニウム等のリン系化合物；メラミン、メラミンシアヌレート、メラミンイソシアヌレート、リン酸メラミン及びこれらに表面処理を施したメラミン誘導体等の窒素系化合物；フッ素樹脂；シリコーンオイル；ハイドロタルサイト等の層状複水和物；シリコーン−アクリル複合ゴム等が挙げられる。なかでも、金属水酸化物及びメラミン誘導体が好適である。上記金属水酸化物のなかでも、特に水酸化マグネシウム、水酸化アルミニウムが好ましく、これらは各種の表面処理剤により表面処理が施されたものであってもよい。上記表面処理剤としては特に限定されず、例えば、シランカップリング剤、チタネート系カップリング剤、ＰＶＡ系表面処理剤、エポキシ系表面処理剤等が挙げられる。これらの難燃剤は、単独で用いられてもよいし、２種以上が併用されてもよい。
【０１１６】
上記難燃剤として金属水酸化物を用いた場合、金属水酸化物の熱硬化性樹脂１００重量部に対する好ましい配合量の下限は０．１重量部、上限は１００重量部である。０．１重量部未満であると、難燃化効果が充分に得られないことがある。１００重量部を超えると、本発明の樹脂組成物の密度（比重）が高くなりすぎて、実用性が乏しくなったり、柔軟性や伸度が極端に低下することがある。より好ましい下限は５重量部、上限は８０重量部である。５重量部未満であると、本発明の樹脂組成物を薄く成形した際に充分な難燃化効果が得られないことがある。８０重量部を超えると、高温処理を行う工程において膨れ等による不良率が高くなることがある。更に好ましい下限は１０重量部、上限は７０重量部である。１０〜７０重量部の範囲であると、力学的物性、電気物性、工程適性等で問題となる領域がなく、充分な難燃性を発現する。
【０１１７】
上記難燃剤としてメラミン誘導体を用いた場合、メラミン誘導体の熱硬化性樹脂１００重量部に対する好ましい配合量の下限は０．１重量部、上限は１００重量部である。０．１重量部未満であると、難燃化効果が充分に得られないことがある。１００重量部を超えると、柔軟性や伸度等の力学的物性が極端に低下することがある。より好ましい下限は５重量部、上限は７０重量部である。５重量部未満であると、絶縁基板を薄くしたときに充分な難燃化効果が得られないことがある。７０重量部を超えると、柔軟性や伸度等の力学的物性が極端に低下することがある。更に好ましい下限は１０重量部、上限は５０重量部である。１０〜５０重量部の範囲であると、力学的物性、電気物性、工程適性等で問題となる領域がなく、充分な難燃性を発現する。
【０１１８】
本発明の樹脂組成物には、本発明の課題達成を阻害しない範囲で特性を改質することを目的に、必要に応じて、熱可塑性エラストマー類、架橋ゴム、オリゴマー類、造核剤、酸化防止剤（老化防止剤）、熱安定剤、光安定剤、紫外線吸収剤、滑剤、難燃助剤、帯電防止剤、防曇剤、充填剤、軟化剤、可塑剤、着色剤等の添加剤が配合されてもよい。これらはそれぞれ単独で用いられてもよく、２種以上が併用されてもよい。
【０１１９】
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。
【０１２０】
上記架橋ゴムとしては特に限定されず、例えば、イソプレンゴム、ブタジエンゴム、１，２−ポリブタジエン、スチレン−ブタジエンゴム、ニトリルゴム、ブチルゴム、エチレン−プロピレンゴム、シリコーンゴム、ウレタンゴム等が挙げられる。樹脂との相溶性を高めるために、これらの架橋ゴムを官能基変性したものであることが好ましい。上記官能基変性した架橋ゴムとしては特に限定されず、例えば、エポキシ変性ブタジエンゴムやエポキシ変性ニトリルゴム等が挙げられる。これらの架橋ゴム類は単独で用いられてもよく、２種以上が併用されてもよい。
【０１２１】
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。
【０１２２】
本発明の樹脂組成物を製造する方法としては特に限定されず、例えば、樹脂と無機化合物の各所定量と、必要に応じて配合される１種又は２種以上の添加剤の各所定量とを、常温下又は加熱下で、直接配合して混練する直接混練法、及び、溶媒中で混合した後、溶媒を除去する方法；予め上記樹脂又は上記樹脂以外の樹脂に所定量以上の無機化合物を配合して混練したマスターバッチを作製しておき、このマスターバッチ、樹脂の所定量の残部、及び、必要に応じて配合される１種又は２種以上の添加剤の各所定量を、常温下又は加熱下で、混練又は溶媒中で混合するマスターバッチ法等が挙げられる。
【０１２３】
上記マスターバッチ法において、上記樹脂又は上記樹脂以外の樹脂に無機化合物を配合したマスターバッチと、マスターバッチを希釈して所定の無機化合物濃度とする際に用いる上記樹脂を含有するマスターバッチ希釈用樹脂組成物は同一の組成であっても、異なる組成であってもよい。
【０１２４】
上記マスターバッチとしては特に限定されないが、例えば、無機化合物の分散が容易であるポリアミド樹脂、ポリフェニレンエーテル樹脂、ポリエーテルサルフォン樹脂、及び、ポリエステル樹脂からなる群より選択される少なくとも１種の樹脂を含有することが好ましい。上記マスターバッチ希釈用樹脂組成物としては特に限定されないが、例えば、高温物性に優れた熱硬化性ポリイミド樹脂、エポキシ樹脂からなる群より選択される少なくとも１種の樹脂を含有することが好ましい。
【０１２５】
上記マスターバッチにおける無機化合物の配合量は特に限定されないが、樹脂１００重量部に対する好ましい下限は１重量部、上限は５００重量部である。１重量部未満であると、任意の濃度に希釈可能なマスターバッチとしての利便性が薄れる。５００重量部を超えると、マスターバッチ自体における分散性や、特にマスターバッチ希釈用樹脂組成物によって所定の配合量に希釈する際の無機化合物の分散性が悪くなることがある。より好ましい下限は５重量部、上限は３００重量部である。
【０１２６】
また、例えば、遷移金属錯体類のような重合触媒（重合開始剤）を含有する無機化合物を用い、熱可塑性樹脂のモノマーと無機化合物とを混練し、上記モノマーを重合させることにより、熱可塑性樹脂の重合と樹脂組成物の製造とを同時に一括して行う方法を用いてもよい。
【０１２７】
本発明の樹脂組成物の製造方法における混合物を混練する方法としては特に限定されず、例えば、押出機、２本ロール、バンバリーミキサー等の混練機を用いて混練する方法等が挙げられる。
【０１２８】
本発明の樹脂組成物は、樹脂と無機化合物とが組み合わせられ、分子鎖の拘束によるＴｇや耐熱変形温度の上昇が図られていることにより、高温での低い線膨張率を有し、耐熱性、力学的物性、透明性等に優れている。
【０１２９】
更に、樹脂中では無機化合物に比べて気体分子の方がはるかに拡散しやすく、樹脂中を拡散する際に気体分子は無機化合物を迂回しながら拡散するので、ガスバリア性も向上している。同様にして気体分子以外に対するバリア性も向上し、耐溶剤性、吸湿性、吸水性等が向上している。これにより、例えば、多層プリント配線板での銅回路からの銅のマイグレーションを抑制することができる。更に、樹脂中の微量添加物が表面にブリードアウトしてメッキ不良等の不具合が発生することも抑制できる。
【０１３０】
本発明の樹脂組成物において、上記無機化合物として層状珪酸塩を用いれば、多量に配合しなくとも優れた力学的物性が得られることから、薄い絶縁基板とすることができ、多層プリント基板の高密度化、薄型化が可能となる。また、結晶形成における層状珪酸塩の造核効果や耐湿性の向上に伴う膨潤抑制効果等に基づく寸法安定性の向上等が図られている。更に、燃焼時に層状珪酸塩による焼結体が形成されるので燃焼残渣の形状が保持され、燃焼後も形状崩壊が起こらず、延焼を防止することができ、優れた難燃性を発現する。
【０１３１】
また、本発明の樹脂組成物において、ノンハロゲン難燃剤を用いれば、環境にも配慮しつつ、高い力学的物性と高い難燃性とを両立することができる。
本発明の樹脂組成物の用途としては特に限定されないが、適当な溶媒に溶解したり、フィルム状に成形したりして加工することにより、例えば、多層基板のコア層やビルドアップ層等を形成する基板用材料、シート、積層板、樹脂付き銅箔、銅張積層板、ＴＡＢ用テープ、プリント基板、プリプレグ、ワニス等に好適に用いられる。かかる本発明の樹脂組成物を用いてなる基板用材料、シート、積層板、樹脂付き銅箔、銅張積層板、ＴＡＢ用テープ、プリント基板、プリプレグ、接着シートもまた本発明の１つである。
【０１３２】
上記成形の方法としては特に限定されず、例えば、押出機にて、溶融混練した後に押出し、Ｔダイやサーキュラーダイ等を用いてフィルム状に成形する押出成形法；有機溶剤等の溶媒に溶解又は分散させた後、キャスティングしてフィルム状に成形するキャスティング成形法；有機溶剤等の溶媒に溶解又は分散して得たワニス中に、ガラス等の無機材料や有機ポリマーからなるクロス状又は不織布状の基材をディッピングしてフィルム状に成形するディッピング成形法等が挙げられる。なかでも、多層基板の薄型化を図るためには、押出成形法やキャスティング成形法が好適である。なお、上記ディッピング成形法において用いる基材としては特に限定されず、例えば、ガラスクロス、アラミド繊維、ポリパラフェニレンベンゾオキサゾール繊維等が挙げられる。
【０１３３】
本発明の基板用材料、シート、積層板、樹脂付き銅箔、銅張積層板、ＴＡＢ用テープ、プリント基板、プリプレグ、接着シート及び光回路形成材料は、本発明の樹脂組成物からなることにより、高温物性、寸法安定性、耐溶剤性、耐湿性及びバリア性に優れ、多工程を通じて製造される場合でも高い歩留りで得ることができる。
【０１３４】
また、本発明の基板用材料は、熱硬化性樹脂中に層状珪酸塩がナノメートルサイズで微分散していることから低線膨張率、耐熱性、低吸水率であることに加え、高い透明性をも実現できる。従って、本発明の基板用材料は、光パッケージの形成材料、光導波路材料、接続材料、封止材料等の光回路形成材料、光通信用材料としても好適に使用することができる。
【０１３５】
本発明の樹脂組成物は熱硬化性樹脂中に層状珪酸塩がナノメートルサイズで微分散していることから低線膨張率、耐熱性、低吸水率であることに加え、高い透明性をも実現できる。従って、本発明の樹脂組成物は、光パッケージの形成材料、光導波路材料、接続材料、封止材料等の光回路形成材料として好適に用いることができる。
【０１３６】
【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。
【０１３７】
（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、エピクロン８３０ＬＶＰ）５４重量部、ＢＴレジン（三菱瓦斯化学社製、ＢＴ２１００Ｂ）１４．７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１４．７重量部からなるエポキシ樹脂組成物８３．４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）１．９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）１．０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）１３．７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重量部を加え、撹拌機にて１時間撹拌した後、更に流星式撹拌機にて混合した。その後、脱泡し、樹脂／層状珪酸塩溶液を得た。次いで、得られた樹脂／層状珪酸塩溶液を鋳型に入れた状態で溶媒を除去した後、１１０℃で３．５時間加熱し、更に１６０℃で３時間加熱して硬化させ、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１３８】
（実施例２）
ビスフェノールＡ型エポキシ樹脂（ダウケミカル日本社製、Ｄ．Ｅ．Ｒ３３１Ｌ）４０重量部、及び、固形エポキシ樹脂（東都化成社製、ＹＰ５５）４０重量部からなるエポキシ樹脂組成物８０重量部、ジシアンアジド（アデカ社製、アデカハードナーＥＨ−３６３６）２．８重量部、変性イミダゾール（アデカ社製、アデカハードナーＥＨ−３３６６）１．２重量部、層状珪酸塩としてトリオクチルメチルアンモニウム塩で有機化処理が施された合成ヘクトライト（コープケミカル社製、ルーセンタイトＳＴＮ）１６重量部、及び、有機溶媒としてジメチルホルムアミド（和光純薬社製、特級）４００重量部をビーカーに加え、撹拌機にて１時間撹拌した後、脱泡し、樹脂／層状珪酸塩溶液を得た。次いで、得られた樹脂／層状珪酸塩溶液をポリエチレンテレフタレートのシート上に塗布した状態で溶媒を除去した後、１１０℃で３時間加熱し、更に１７０℃で３０分間加熱して硬化させ、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１３９】
（実施例３）
ビスフェノールＡ型エポキシ樹脂（ダウケミカル日本社製、Ｄ．Ｅ．Ｒ３３１Ｌ）５６重量部、及び、固形エポキシ樹脂（東都化成社製、ＹＰ５５）２４重量部からなるエポキシ樹脂組成物８０重量部、ジシアンアジド（アデカ社製、アデカハードナーＥＨ−３６３６）３．９重量部、変性イミダゾール（アデカ社製、アデカハードナーＥＨ−３３６６）１．７重量部、層状珪酸塩としてトリオクチルメチルアンモニウム塩で有機化処理が施された合成ヘクトライト（コープケミカル社製、ルーセンタイトＳＴＮ）３０重量部、及び、有機溶媒としてジメチルホルムアミド（和光純薬社製、特級）２５０重量部、合成シリカ（アドマテックス社製、アドマファインＳＯ−Ｅ２）２２重量部をビーカーに加え、撹拌機にて１時間撹拌した後、脱泡し、樹脂／層状珪酸塩溶液を得た。次いで、得られた樹脂／層状珪酸塩溶液をポリエチレンテレフタレートのシート上に塗布した状態で溶媒を除去した後、１１０℃で３時間加熱し、更に１７０℃で３０分間加熱して硬化させ、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４０】
（実施例４）
ビスフェノールＡ型エポキシ樹脂（ダウケミカル日本社製、Ｄ．Ｅ．Ｒ３３１Ｌ）５６重量部、及び、固形エポキシ樹脂（東都化成社製、ＹＰ５５）２４重量部からなるエポキシ樹脂組成物８０重量部、ジシアンアジド（アデカ社製、アデカハードナーＥＨ−３６３６）１．７重量部、変性イミダゾール（アデカ社製、アデカハードナーＥＨ−３３６６）０．７重量部、層状珪酸塩としてトリオクチルメチルアンモニウム塩で有機化処理が施された合成ヘクトライト（コープケミカル社製、ルーセンタイトＳＴＮ）１６重量部、ホウ酸アルミニウムウィスカ（四国化成工業社製、アルボレックスＹＳ３Ａ）１０重量部、水酸化マグネシウム（協和化学工業社製、キスマ５Ｊ）２２重量部、及び、有機溶媒としてジメチルホルムアミド（和光純薬社製、特級）２５０重量部をビーカーに加え、撹拌機にて１時間撹拌した後、脱泡し、樹脂／層状珪酸塩溶液を得た。次いで、得られた樹脂／層状珪酸塩溶液をポリエチレンテレフタレートのシート上に塗布した状態で溶媒を除去した後、１１０℃で３時間加熱し、更に１７０℃で３０分間加熱して硬化させ、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４１】
（比較例１）
膨潤性フッ素マイカ（コープケミカル社製、ソマシフＭＡＥ−１００）を配合しなかったこと以外は実施例１と同様にして樹脂組成物、及び、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４２】
（比較例２）
合成ヘクトライト（コープケミカル社製、ルーセンタイトＳＴＮ）を配合しなかったこと以外は実施例２と同様にして樹脂組成物、及び、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４３】
（比較例３）
合成ヘクトライト（コープケミカル社製、ルーセンタイトＳＴＮ）を配合せず、合成シリカの添加量を５２重量部としたこと以外は実施例３と同様にして樹脂組成物、及び、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４４】
（比較例４）
合成ヘクトライト（コープケミカル社製、ルーセンタイトＳＴＮ）を配合せず、水酸化マグネシウムの添加量を４２重量部とした以外は実施例４と同様にして樹脂組成物、及び、樹脂組成物からなる厚さ２ｍｍ及び１００μｍの板状成形体を作製した。
【０１４５】
＜評価＞
実施例１〜４及び比較例１〜４で作製した板状成形体の性能を以下の項目について評価した。結果は表１及び表２に示した。
【０１４６】
（１）熱膨張係数の測定
板状成形体を裁断して３ｍｍ×２５ｍｍにした試験片を、ＴＭＡ（ｔｈｅｒｍｏｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｙｓ）装置（セイコー電子社製、ＴＭＡ／ＳＳ１２０Ｃ）を用いて、昇温速度５℃／分で昇温し、平均線膨張率の測定を行い、以下の項目について評価を行った。
【０１４７】
・樹脂組成物のガラス転移温度よりも１０℃〜５０℃高い温度での平均線膨張率（α２）［℃^-1］。
・樹脂組成物のガラス転移温度よりも１０℃〜５０℃高い温度での平均線膨張率（α２）を、樹脂組成物のガラス転移温度よりも５０℃〜１０℃低い温度での平均線膨張率（α１）で除して求めた平均線膨張率比（α２／α１）。
・５０〜１００℃での平均線膨張率［℃^-1］及び２００〜２４０℃での平均線膨張率［℃^-1］。
・１５０〜２００℃での平均線膨張率を、５０〜１００℃での平均線膨張率で除して求めた平均線膨張率比（１）、及び、２５０〜３００℃での平均線膨張率を、５０〜１００℃での平均線膨張率で除して求めた平均線膨張率比（２）。
・板状成形体を２５℃から３００℃まで昇温したときの長さの変化量を、板状成形体の２５℃での長さで除して求めた変化率（％）。
・前述した式（１）で表される平均線膨張率比（３）。
・樹脂組成物のＴｇよりも１０℃〜５０℃高い温度での平均線膨張率を、各実施例に対応する比較例１、２、３、４、５で作製した樹脂組成物のＴｇよりも１０℃〜５０℃高い温度での平均線膨張率でそれぞれ除して求めた改善率。
【０１４８】
（２）層状珪酸塩の平均層間距離
Ｘ線回折測定装置（リガク社製、ＲＩＮＴ１１００）を用いて、厚さ２ｍｍの板状成形体中の層状珪酸塩の積層面の回折より得られる回折ピークの２θを測定し、下記式（５）のブラックの回折式により、層状珪酸塩の（００１）面間隔ｄを算出し、得られたｄを平均層間距離（ｎｍ）とした。
λ＝２ｄｓｉｎθ ・・・（５）
上記式（５）中、λは０．１５４であり、θは回折角を表す。
【０１４９】
（３）５層以下の積層体として分散している層状珪酸塩の割合
厚さ１００μｍの板状成形体を透過型電子顕微鏡により１０万倍で観察し、一定面積中において観察できる層状珪酸塩の積層体の全層数Ｘ及び５層以下で分散している層状珪酸塩の層数Ｙを計測し、下記式（４）により５層以下の積層体として分散している層状珪酸塩の割合（％）を算出した。
【０１５０】
【数５】

【０１５１】
（４）吸水率の測定
厚さ１００μｍの板状成形体を３×５ｃｍの短冊状にした試験片を作製し、１５０℃で５時間乾燥させた後の重さ（Ｗ１）を測定した。次いで、試験片を水に浸漬し、１００℃の沸騰水中に１時間放置した後取り出し、ウエスで丁寧に拭き取った後の重さ（Ｗ２）を測定した。下記式により吸水率を求めた。
吸水率（％）＝（Ｗ２−Ｗ１）／Ｗ１×１００
【０１５２】
（５）誘電率の測定
インピーダンス測定器（ヒューレットパッカード社製、ＨＰ４２９１Ｂ）を用いて、周波数１ＭＨｚ付近の誘電率を測定した。
【０１５３】
（６）引張弾性率の測定
ＪＩＳ Ｋ６３０１に準ずる方法により測定を行った。
【０１５４】
（７）溶解度パラメーターの測定
Ｆｅｄｏｒｓの計算式により算出した。
【０１５５】
（８）１０％重量減少温度の測定
サンプル５〜１０ｍｇを１５０℃で５時間乾燥させた後、ＴＧ／ＤＴＡ装置（セイコー電子社製、ＴＧ／ＤＴＡ３２０）を用いて、以下の測定条件により測定した。
【０１５６】
測定温度：２５〜６００℃
昇温速度：１０℃／ｍｉｎ
窒素ガス：２００ｍｌ／ｍｉｎ
【０１５７】
【表１】

【０１５８】
【表２】

【０１５９】
【発明の効果】
本発明によれば、力学的物性、寸法安定性、耐熱性、難燃性等に優れ、特に高温物性に優れた樹脂組成物、基板用材料、シート、積層板、樹脂付き銅箔、銅張積層板、ＴＡＢ用テープ、プリント基板、プリプレグ及び接着シートを提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and in particular, a resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil, a copper-clad laminate excellent in high-temperature properties TAB tape, printed circuit board, prepreg, and adhesive sheet.
[0002]
[Prior art]
2. Description of the Related Art In recent years, electronic devices with high performance, high functionality, and miniaturization are rapidly progressing, and there is an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. As a result, further improvements in physical properties such as heat resistance, mechanical strength, and electrical characteristics have been demanded for the materials of electronic components. For example, for semiconductor device packaging methods and wiring boards for mounting semiconductor devices. However, there is a demand for higher density, higher functionality, and higher performance.
[0003]
Multilayer printed circuit boards used in electronic devices are composed of a plurality of insulating substrates, and conventionally, as this interlayer insulating substrate, for example, a thermosetting resin prepreg in which a glass cloth is impregnated with a thermosetting resin, Films made of thermosetting resins or photocurable resins have been used. Even in the multilayer printed circuit board, it is desired to make the interlayer extremely thin for high density and thinning, and an interlayer insulating board using a thin glass cloth or an interlayer insulating board not using a glass cloth is required. ing. As such an interlayer insulating substrate, for example, those made of rubber (elastomer), thermosetting resin material modified with acrylic resin, thermoplastic resin material containing a large amount of inorganic filler, etc. are known. In Patent Document 1 below, an varnish mainly composed of a high molecular weight epoxy polymer and a polyfunctional epoxy resin is blended with an inorganic filler having a predetermined particle diameter, and applied to a support to form an insulating layer. A method for manufacturing a multilayer insulating substrate is disclosed.
[0004]
However, in the multilayer insulating substrate produced by the above production method, in order to sufficiently improve the mechanical properties such as mechanical strength by securing the interface area between the inorganic filler and the high molecular weight epoxy polymer or polyfunctional epoxy resin. In addition, it is necessary to add a large amount of an inorganic filler, which causes problems in processing such as an increase in the manufacturing process, and it is difficult to make the interlayer thin.
[0005]
In addition, interlayer insulation substrates that use thin glass cloth and interlayer insulation substrates that do not use glass cloth have problems such as insufficient heat resistance and dimensional stability. There was a problem that often occurred.
[0006]
The multilayer printed circuit board is manufactured by a build-up method for obtaining a multilayer laminate by repeating circuit formation and lamination on a layer, a batch lamination method for laminating layers on which circuits are formed, or the like. In any manufacturing method, since the number of processes is large, the quality of the material greatly affects the yield, and the process includes a plating process, a curing process, a solder reflow process, and the like. , Heat resistance and dimensional stability at high temperatures are required. Specifically, for example, resistance to acids, alkalis, and organic solvents; low moisture absorption that affects electrical characteristics; dimensional stability at high temperatures and after heating that affects high-precision circuit connections between upper and lower layers; Heat resistance up to 260 ° C required for mounting with lead-free solder; copper migration that affects connection reliability is unlikely to occur.
[0007]
For example, build-up boards and printed multilayer boards used in IC packages may be subject to high-temperature conditions due to heat generation, and it is required to maintain high reliability even in such an environment. If it is large, there is a problem that peeling occurs from a metal wiring such as copper forming a circuit, causing a short circuit or disconnection. In addition, even in a flexible multilayer substrate that has recently attracted attention as a thin substrate, the thermal dimensional change between the adhesive layer that bonds single-layer flexible substrates to each other, the polyimide film that forms the flexible substrate, and the metal wiring such as copper that forms the circuit If the difference is large, the same problem occurs.
[0008]
Patent Document 1 discloses a technique for improving high-temperature physical properties by using an epoxy resin having excellent heat resistance and an inorganic compound in combination, but almost no improvement effect on physical properties at temperatures above the glass transition temperature. The improvement effect is small even at temperatures below the glass transition temperature. In addition, no improvement in hygroscopicity or solvent resistance can be expected.
[0009]
Conventionally, a method using an inorganic filler has been known as a method for reducing the linear expansion coefficient at a temperature lower than the glass transition temperature, but it has not been compatible with high-temperature treatment such as solder reflow. In recent years, lead-free solder has been used in consideration of the environment, and the temperature of the solder reflow process has further increased. Therefore, even if a resin with high heat resistance is used, the wire above the glass transition temperature is used. There was a problem that the expansion rate was large and problems occurred during high temperature treatment.
[0010]
On the other hand, in recent years, with the progress of optical communication technology, it has been demanded that optical communication devices be connected at low cost. Therefore, attention has been paid to optical communication materials made of polymer materials. However, when a conventional polymer material is used as an optical communication material, there are various problems.
[0011]
The polymer material for optical communication is required to have low loss, excellent heat resistance, a low coefficient of thermal linear expansion, low moisture permeability, and easy control of the refractive index.
[0012]
Note that low loss means that the propagation loss is small because the polymer material has almost no absorption band in the wavelength band used for optical communication.
In the following Patent Document 2, a polymer optical communication material formed on a substrate such as silicon having a coefficient of thermal expansion close to 10 times the coefficient of thermal expansion of a semiconductor or metal material and having a low coefficient of thermal expansion. However, stress may be applied to cause polarization dependency of the optical communication material, warpage of the optical communication material and the substrate, or the edge of the polymer optical communication material may peel off from the substrate. Are listed.
[0013]
Patent Document 3 describes a problem that a fiber strand protrudes from a jacket due to a difference in thermal expansion coefficient between the fiber strand (quartz glass) and a resin case, or a crack occurs in the fiber strand due to stress concentration. ing.
[0014]
Further, in Patent Document 4, when the optical waveguide substrate and the optical fiber are connected using an adhesive, if the difference in thermal expansion between the optical waveguide substrate and the connection component is large, a positional shift due to thermal expansion occurs, and a stable optical It is described that connection with a waveguide cannot be realized.
[0015]
With respect to moisture permeability, in Patent Document 3, when water vapor penetrates into the hollow case, condensation occurs on the surface of the optical element or the fiber strand, causing corrosion of the optical element or causing crack growth to proceed. There is a problem that the wire is broken, and it is described that these factors, together with thermal expansion, comprehensively reduce the reliability of optical communication parts using polymer materials. Further, if the hygroscopic property is high, light absorption due to the O—H bond of moisture is likely to occur, and thus a material having low hygroscopic property is required.
[0016]
With regard to heat resistance, when optical communication is introduced to terminal equipment, conversion from optical signals to electrical signals or conversion from electrical signals to optical signals is required. A polymeric material will be used. Therefore, the polymer material for optical communication is required to have heat resistance against the process temperature at the time of manufacturing the printed circuit board and heat resistance from the electric circuit during use. Non-Patent Document 1 describes solder heat resistance as a required characteristic.
[0017]
As described above, materials that satisfy physical properties such as transparency, heat resistance, low linear expansion coefficient, and low hygroscopicity are desired as optical communication materials.
On the other hand, Patent Document 5 below describes that a fluorinated polyimide having a rigid skeleton achieves a low coefficient of thermal expansion.
[0018]
Patent Document 6 below discloses a polymer optical waveguide comprising a core layer and a clad layer surrounding the core layer, the polymer optical waveguide having a second clad layer having a thermal expansion coefficient smaller than that of the clad layer outside the clad layer. Is disclosed. Here, it is said that by making the polymers constituting the cladding layer and the second cladding layer different, the thermal expansion coefficient of the second cladding layer can be made relatively low, and the difference in thermal expansion coefficient from the electric / optical element can be reduced. It is shown.
[0019]
Further, in Patent Document 7 below, the end face of the optical communication material is sealed with a resin so that the resin adheres the insulating film forming the optical communication material and the substrate, and the peeling at the end where stress concentrates. It is stated that it can be prevented.
[0020]
Patent Document 7 below describes that the thermal expansion coefficient can be lowered by using a polyimide film having a specific structure as the resin for the optical waveguide.
[0021]
The fluorinated polyimide described in Patent Document 5 below is inferior in transparency to other types of fluorinated polyimide, has a high refractive index of 1.647, and is used as a material constituting a clad layer of an optical communication material. It was not appropriate.
[0022]
On the other hand, in the optical waveguide resin containing the particles described in Patent Document 6 below, it has been suggested that the low linear expansion coefficient and the transparency may be compatible. A large amount of particles must be added. Therefore, when a large amount of particles are added, it is difficult to achieve sufficient transparency. Further, when a large amount of particles are contained, there is a problem that the resin composition becomes brittle. In addition, when a large amount of particles are added, the hydrophilicity increases and the hygroscopicity may increase.
[0023]
Further, in the configuration described in Patent Document 2 below, the number of manufacturing processes increases, and an increase in cost cannot be avoided.
On the other hand, when a polyimide-based film having a specific structure described in Patent Document 7 is used as an optical waveguide resin, it is difficult to achieve low hygroscopicity, although the thermal expansion coefficient can be lowered, and the cost is still high. I had to stay high.
[0024]
Therefore, the optical circuit forming material is also excellent in transparency, heat resistance, low linear expansion coefficient and low hygroscopicity, and it has been difficult to realize a material capable of realizing particularly high transparency.
Patent Document 8 listed below describes a resin sheet in which a glass cloth is impregnated with a resin containing an inorganic filler. The obtained resin sheet is said to have a low linear expansion coefficient. However, it was about the linear expansion coefficient expected by actually using glass cloth. Further, in the examples, only about 7% by weight or less of the inorganic filler is contained, and there is little description about the dispersion method in the specification, so it cannot be considered highly dispersed.
[0025]
[Patent Document 1]
JP 2000-183539 A
[Patent Document 2]
JP 2001-183539 A
[Patent Document 3]
WO98 / 45741
[Patent Document 4]
JP-A-9-152522
[Patent Document 5]
Japanese Patent No. 2843314
[Patent Document 6]
JP 2001-108854 A
[Patent Document 7]
JP 2001-4850 A
[Patent Document 8]
JP 2002-220513 A
[Non-Patent Document 1]
Hitachi Technical Report No. 37 (July 2001), pp. 7-16
[0026]
[Problems to be solved by the invention]
In view of the above situation, the present invention is excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and in particular, a resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil excellent in high temperature properties An object of the present invention is to provide a copper-clad laminate, a TAB tape, a printed circuit board, a prepreg, and an adhesive sheet.
[0027]
Another object of the present invention is to provide a resin composition that is excellent in transparency and heat resistance, has a low coefficient of linear expansion and moisture absorption, and can provide an optical circuit forming material that can achieve particularly high transparency. There is.
[0028]
[Means for Solving the Problems]
The present invention relates to 100 parts by weight of a thermosetting resin and / or a photocurable resin. Layered silicate A resin composition containing 0.1 to 65 parts by weight, the resin composition Cured products From a temperature 10 ° C. higher than the glass transition temperature of the resin composition Cured products Up to 50 ° C higher than the glass transition temperature of Of the cured resin composition Average linear expansion coefficient (α2) is 17 × 10 ^-Five [℃ ^-1 The resin composition is as follows.
[0029]
The present invention is described in detail below.
The resin composition of the present invention is a resin composition. Cured products From a temperature 10 ° C. higher than the glass transition temperature (hereinafter also referred to as Tg) of the resin composition Cured products Up to 50 ° C higher than the glass transition temperature of Of the cured resin composition Average linear expansion coefficient (hereinafter also referred to as α2) is 17 × 10 ^-Five [℃ ^-1 It is the following. 17 × 10 ^-Five [℃ ^-1 ] By the following, the resin material comprising the resin composition of the present invention has a small dimensional change when heat-treated at a high temperature, and warpage occurs due to a difference in shrinkage when laminated with a copper foil, It will not peel off. Preferably, 15x10 ^-Five [℃ ^-1 ], More preferably 12 × 10 ^-Five [℃ ^-1 It is the following. The average linear expansion coefficient can be measured by a method according to JIS K7197. For example, a test of about 3 mm × 15 mm using a TMA (Thermal Mechanical Analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C). It can be determined by heating the piece at a heating rate of 5 ° C./min.
[0030]
In the resin composition of the present invention, the α2 is changed to the resin composition. Cured products From a temperature lower by 50 ° C. than the Tg of the resin composition Cured products Up to 10 ° C lower than the glass transition temperature of Of the cured resin composition The average linear expansion coefficient ratio (α2 / α1) obtained by dividing by the average linear expansion coefficient (hereinafter also referred to as α1) is preferably 2 or less. When it is 2 or less, the resin material comprising the resin composition of the present invention has a small dimensional change near Tg, and does not generate wrinkles or warpage near Tg when used as a laminated material or a laminated material. More preferably, it is 1.85 or less, More preferably, it is 1.75 or less.
[0031]
The resin composition of the present invention is at 50 to 100 ° C. Of the cured resin composition Average linear expansion coefficient is 10 × 10 ^-Five [℃ ^-1 ] And at 200 to 240 ° C. Of the cured resin composition Average linear expansion coefficient is 25 × 10 ^-Five [℃ ^-1 It is preferable that At 50-100 ° C Of the cured resin composition Average linear expansion coefficient is 10 × 10 ^-Five [℃ ^-1 ] And at 200 to 240 ° C. Of the cured resin composition Average linear expansion coefficient is 25 × 10 ^-Five [℃ ^-1 The resin material comprising the resin composition of the present invention is suitable for electronic materials and the like that require a small amount of dimensional change under normal use conditions and require high precision, such as solder reflow. No warpage or peeling occurs in the manufacturing process or the like in which high temperature treatment is performed. At 50-100 ° C Of the cured resin composition The average linear expansion coefficient is more preferably 8 × 10 ^-Five [℃ ^-1 ], More preferably 6 × 10 ^-Five [℃ ^-1 It is the following. At 200-240 ° C Of the cured resin composition The average linear expansion coefficient is more preferably 20 × 10 ^-Five [℃ ^-1 ], More preferably 15 × 10 ^-Five [℃ ^-1 It is the following.
[0032]
The resin composition of the present invention is at 150 to 200 ° C. Of the cured resin composition Average linear expansion coefficient at 50 to 100 ° C. Of the cured resin composition The average linear expansion coefficient ratio (1) obtained by dividing by the average linear expansion coefficient is 2.5 or less, and at 250 to 300 ° C. Of the cured resin composition Average linear expansion coefficient at 50 to 100 ° C. Of the cured resin composition The average linear expansion coefficient ratio (2) obtained by dividing by the average linear expansion coefficient is preferably 4.5 or less. When the average linear expansion coefficient ratio (1) is 2.5 or less and the average linear expansion coefficient ratio (2) is 4.5 or less, the resin material comprising the resin composition of the present invention has dimensions for heating. It has good stability and is suitable for applications that are used at high temperatures without warping or peeling even in manufacturing processes that perform high-temperature processing such as reflow of lead-free solder. The average linear expansion coefficient ratio (1) is more preferably 2.2 or less, still more preferably 2.0 or less. The average linear expansion coefficient (2) is more preferably 4.0 or less, and still more preferably 3.5 or less.
[0033]
In the resin composition of the present invention, the amount of change in length when a resin piece made of the resin composition is heated from 25 ° C. to 300 ° C. is divided by the length of the resin piece made of the resin composition at 25 ° C. It is preferable that the change rate obtained in this way is 5% or less. When it is 5% or less, the resin material comprising the resin composition of the present invention has good dimensional stability with respect to temperature, and even when laminated with other materials or pasted together, at the time of manufacture and use There is no warping or peeling. More preferably, it is 4.5% or less, More preferably, it is 4% or less.
[0034]
The resin composition of the present invention preferably has an average linear expansion coefficient ratio (3) represented by the following formula (1) of 1.05 or less.
[0035]
[Expression 2]
Average linear expansion coefficient ratio (3) = ( T +40) to ( T +60) at ° C Of the cured resin composition Average coefficient of linear expansion / T ~ ( T +20) at ° C Of the cured resin composition Average linear expansion coefficient (1)
However, T (° C.) is 50 ° C. or higher and 400 ° C. or lower, and is excluded when the average linear expansion coefficient ratio (3) is calculated across Tg.
[0036]
When the average linear expansion coefficient ratio (3) is 1.05 or less, the resin material composed of the resin composition of the present invention has good dimensional stability, and even when laminated or pasted with other materials. No warping or peeling during manufacturing and use. More preferably, it is 1.04 or less, More preferably, it is 1.03 or less.
[0037]
The resin composition of the present invention is a resin composition. Cured products From a temperature 10 ° C. higher than the glass transition temperature of the resin composition Cured products Resin composition up to 50 ° C. higher than glass transition temperature of Cured products The average linear expansion coefficient (α2) of the above Hardened product of resin comprising thermosetting resin and / or photocurable resin contained in resin composition From a temperature 10 ° C. higher than the glass transition temperature of Hardened product of resin comprising thermosetting resin and / or photocurable resin contained in resin composition Up to 50 ° C above the glass transition temperature of Hardened product of resin comprising thermosetting resin and / or photocurable resin contained in resin composition It is preferable that the improvement rate obtained by dividing by the average linear expansion coefficient is 0.98 or less. When it is 0.98 or less, the resin material comprising the resin composition of the present invention has sufficiently improved high-temperature properties due to the inorganic compound, and causes problems in the manufacturing process for high-temperature treatment and use at high temperatures. There is nothing. More preferably, it is 0.90 or less, More preferably, it is 0.75 or less.
[0038]
Since the resin composition of the present invention has a low average linear expansion coefficient at a high temperature above the glass transition temperature as described above, the high temperature physical properties such as dimensional stability at a high temperature are improved, and the plating process, curing process, lead It can be used for a resin material that does not warp or peel off even in a high-temperature treatment step such as a free solder reflow step.
[0039]
The resin composition of the present invention is Of the cured resin composition Tensile modulus at 140 ° C. is 10 MPa or more, Of the cured resin composition The dielectric constant at 1 MHz is preferably 4.5 or less. When the resin composition of the present invention is used as a TAB tape, if the tensile elastic modulus at 140 ° C. is less than 10 MPa, it is necessary to increase the thickness in order to ensure the required strength, and a small TAB can be produced. If the dielectric constant at 1 MHz exceeds 4.5, it may be necessary to increase the thickness to ensure sufficient reliability, and it may not be possible to produce a small TAB. .
[0040]
The resin composition of the present invention is Of the cured resin composition The water absorption is preferably 2.0% or less. When the water absorption rate exceeds 2.0%, when a substrate is produced using the resin composition of the present invention, the dimensional change occurs during absolutely dry and water absorption, so that fine wiring becomes difficult and the size cannot be reduced. There is.
[0041]
Moreover, the resin composition of the present invention comprises: Of the cured resin composition Water absorption is 2.0% or less, Of the cured resin composition The dielectric constant at 1 MHz is 4.5 or less and When the cured product of the resin composition is immersed in water to absorb water The dielectric constant after the water absorption treatment is preferably 5.0 or less. If the electrical characteristics change greatly due to water absorption, the reliability may not be maintained, and the material may explode in the manufacturing process such as solder reflow and the yield may decrease. In addition, the said water absorption is the weight W1 when drying at 150 degreeC for 5 hours about the test piece which made the film of 50-100 micrometers thickness into a 3x5 cm strip shape, and 1 hour in boiling water of 100 degreeC It is a value obtained by measuring the weight W2 when the surface is thoroughly wiped off after being left to stand and by the following equation (2).
Water absorption (%) = (W2−W1) / W1 × 100 (2)
[0042]
The resin composition of the present invention has an insulation resistance of 10 when molded into a resin sheet having a thickness of 25 μm. ⁸ It is preferable that it is Ω or more. When a substrate or the like is produced using the resin composition of the present invention, a thickness of at least 25 μm is necessary to ensure sufficient insulation performance, but the insulation resistance at this thickness is 10 ⁸ When it is Ω or more, high insulation reliability can be secured.
[0043]
Resin composition of the present invention Cured products The glass transition temperature is preferably 100 ° C. or higher. When the glass transition temperature is 100 ° C. or higher, when the resin composition of the present invention is used for a substrate or the like, high-temperature properties, particularly lead-free soldering heat resistance and dimensional stability against heating are improved. More preferably, it is 140 degreeC or more, More preferably, it is 200 degreeC or more.
[0044]
The resin composition of the present invention is Of the cured resin composition The elongation at break at 260 ° C. is preferably 10% or more. When the elongation at break at 260 ° C. is 10% or more, when the resin composition of the present invention is used for a substrate or the like, it is excellent in following to other base materials in the solder reflow process.
[0045]
The resin composition of the present invention has the above-described excellent high-temperature properties and contains a thermosetting resin and an inorganic compound. The thermosetting resin or photocurable resin is a liquid, semi-solid or solid at room temperature, and a relatively low molecular weight substance exhibiting fluidity at room temperature or under heating, 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 causing a chemical reaction such as a curing reaction or a crosslinking reaction by the action of heat or light to increase the molecular weight.
[0046]
Examples of the thermosetting resin include epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, silicon resin, benzoxazine resin, melamine resin, urea resin, allyl resin, phenol resin, unsaturated polyester resin. , Bismaleimide triazine resin, alkyd resin, furan resin, polyurethane resin, aniline resin and the like. Among these, epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, benzoxazine resins, melamine resins, and the like are preferable. These thermosetting resins may be used alone or in combination of two or more.
[0047]
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.
[0048]
A conventionally well-known epoxy resin can be used as said epoxy resin, 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.
[0049]
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 hydrogenated products and brominated products thereof.
[0050]
Examples of the epoxy resin (2) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane. Carboxylate, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxy And cycloaliphatic epoxy resins such as cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane and bis (2,3-epoxycyclopentyl) ether. As what is marketed among this epoxy resin (2), the brand name "EHPE-3150" (softening temperature 71 degreeC) by Daicel Chemical Industries, etc. are mentioned, for example.
[0051]
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. Diglycidyl ether, diglycidyl 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 (preferably 2 to 4) carbon atoms, etc. Aliphatic epoxy resins and the like.
[0052]
Examples of the epoxy resin (4) include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, glycidyl ether-glycidyl ester of salicylic acid, and dimer acid. Examples thereof include glycidyl ester type epoxy resins such as glycidyl ester and hydrogenated products thereof.
[0053]
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.
[0054]
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.
[0055]
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.
[0056]
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.
[0057]
Examples of the epoxy resin (9) include a polyester resin having one or more, preferably two or more epoxy groups per molecule.
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).
[0058]
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.
[0059]
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.
[0060]
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 (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8, Cycloaliphatic amines such as 10-tetraoxaspiro (5,5) undecane and derivatives thereof; m-xylenediamine, α- (m / paminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, dia Roh diphenyl sulfone, alpha, alpha-bis (4-aminophenyl)-p-like aromatic amines and derivatives thereof diisopropylbenzene and the like.
[0061]
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 acids 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.
[0062]
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.
[0063]
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.
[0064]
The hydrazide compound is not particularly limited, and examples thereof include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosanedioic acid dihydrazide, Examples include adipic acid dihydrazide and its derivatives.
[0065]
The melamine compound is not particularly limited, and examples thereof include 2,4-diamino-6-vinyl-1,3,5-triazine and derivatives thereof.
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, polydodecane Dianhydride, Rorendo anhydride and derivatives thereof.
[0066]
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.
[0067]
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.
[0068]
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.
[0069]
Examples of the thermosetting modified polyphenylene ether resin include resins 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.
[0070]
The thermosetting polyimide resin is a resin having an imide bond in the molecular main chain. Specifically, for example, a condensation polymer of aromatic diamine and aromatic tetracarboxylic acid, aromatic diamine and bismaleimide And bismaleimide resin which is an addition polymer of aminobenzoic acid hydrazide and bismaleimide, and bismaleimide triazine resin composed of a dicyanate compound and a bismaleimide resin. Of these, bismaleimide triazine resin is preferably used. These thermosetting polyimide resins may be used alone or in combination of two or more.
[0071]
Examples of the silicon resin include those containing a silicon-silicon bond, a silicon-carbon bond, a siloxane bond, or a silicon-nitrogen bond in the molecular chain. Specific examples include polysiloxane, polycarbosilane, and polysilazane. Can be mentioned.
[0072]
The benzoxazine resin 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.
[0073]
The urea resin 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.
[0074]
The allyl resin 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.
[0075]
The above thermosetting resin Cured products The glass transition temperature is preferably 100 ° C. or higher, and the dielectric constant at 1 MHz is preferably 4.5 or lower. Since the glass transition temperature is 100 ° C. or higher and the dielectric constant at 1 MHz is 4.5 or lower, the resin material comprising the resin composition of the present invention has high-temperature properties, particularly lead-free solder heat resistance and The dimensional stability against heating is improved, high reliability required for an electronic material can be obtained, and the transmission speed necessary for an electronic material can be obtained even in the transmission speed of a signal in a high frequency region. The glass transition temperature is more preferably 140 ° C. or higher, and further preferably 200 ° C. or higher. The dielectric constant of 1 MHz is more preferably 4.0 or less, and still more preferably 3.6 or less.
[0076]
Before curing The thermosetting resin has a solubility parameter (SP value) of 42 [J / cm] determined using the Fedors equation. ^Three ] ^1/2 The above is preferable. According to the Fedors calculation formula, the SP value is the square root of the sum of the molar aggregation energy of each atomic group divided by the volume, and indicates the polarity per unit volume. SP value is 42 [J / cm ^Three ] ^1/2 Because of the above, since it has a large polarity, it has good compatibility with inorganic compounds such as chemically treated layered silicates, and even when layered silicates are used as inorganic compounds, the interlayer of layered silicates Can be spread and dispersed one by one. More preferably 46.2 [J / cm ^Three ] ^1/2 Or more, more preferably 52.5 [J / cm ^Three ] ^1/2 That's it.
[0077]
The SP value is 42 [J / m ^Three ] ^1/2 Examples of the above resins include epoxy resins, phenol resins, urea resins, unsaturated polyester resins, allyl resins, thermosetting polyimide resins, bismaleimide triazine resins, thermosetting modified polyphenylene ether resins, silicon resins, benzoates. An oxazine resin etc. are mentioned.
[0078]
The above thermosetting resin Cured products When thermogravimetry is performed in a nitrogen atmosphere, the 10% weight loss temperature is preferably 400 ° C. or higher. By being 400 degreeC or more, the resin material which consists of a resin composition of this invention does not generate | occur | produce outgas in high temperature processing processes, such as a reflow process of lead-free solder, and becomes a suitable electronic material. More preferably, it is 450 degreeC or more, More preferably, it is 500 degreeC or more. Examples of the resin having a 10% weight loss temperature of 400 ° C. or higher in thermogravimetry in a nitrogen atmosphere include, for example, thermosetting polyimide resin, liquid crystal resin, polysulfone resin, polyethersulfone resin, polyoxadiazole resin, Examples thereof include polycarbonate resin.
[0079]
The resin composition of the present invention contains an inorganic compound.
Examples of the inorganic compound include layered silicates, talc, silica, alumina, glass beads and the like, and among them, layered silicates are preferably used in order to improve high temperature physical properties. In the present specification, the layered silicate means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product.
[0080]
When a particularly high tensile elastic modulus is required, it is preferable to contain a layered silicate and a whisker as the inorganic compound. Although it is known that when a whisker is added to a resin, the elastic modulus is improved, the resin composition containing the whisker so that a high tensile elastic modulus can be achieved has a problem that the moldability deteriorates. In the resin composition of the present invention, by using a layered silicate and whisker as an inorganic compound, a sufficient improvement in elastic modulus can be obtained even with a small amount of whisker.
[0081]
Examples of the layered silicate include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite and nontronite, swelling mica, vermiculite, and halloysite. Among these, at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite is preferably used. These layered silicates may be used alone or in combination of two or more.
[0082]
The crystal shape of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.01 μm, the upper limit is 3 μm, the preferable lower limit of the thickness is 0.001 μm, the upper limit is 1 μm, and the preferable lower limit of the aspect ratio is 20 μm. The upper limit is 500, the more preferred lower limit of the average length is 0.05 μm, the upper limit is 2 μm, the more preferred lower limit of the thickness is 0.01 μm, the upper limit is 0.5 μm, the more preferred lower limit of the aspect ratio is 50, the upper limit Is 200.
[0083]
The layered silicate preferably has a large shape anisotropy effect defined by the following formula (3). By using a layered silicate having a large shape anisotropy effect, the resin obtained from the resin composition of the present invention has excellent mechanical properties.
[0084]
[Equation 3]

[0085]
The exchangeable metal cation existing between the layers of the layered silicate means a metal ion such as sodium or calcium existing on the surface of the lamellar crystal of the layered silicate, and these metal ions are cations with the cationic substance. Since it has exchangeability, various substances having cationic properties can be inserted (intercalated) between the crystal layers of the layered silicate.
[0086]
Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, A preferable minimum is 50 milliequivalent / 100g, and an upper limit is 200 milliequivalent / 100g. When the amount is less than 50 milliequivalents / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate is reduced by cation exchange, so that the crystal layers are not sufficiently depolarized (hydrophobized). Sometimes. If it exceeds 200 milliequivalents / 100 g, the bonding strength between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.
[0087]
When the resin composition of the present invention is produced using a layered silicate as the inorganic compound, the dispersibility in the resin is improved by chemically modifying the layered silicate to increase the affinity with the resin. Preferably, a large amount of layered silicate can be dispersed in the resin by such chemical treatment. If the layered silicate is not subjected to chemical modification suitable for the resin used in the present invention or the solvent used in the production of the resin composition of the present invention, the layered silicate tends to aggregate and be dispersed in large quantities. However, by applying a chemical modification suitable for the resin or solvent, the layered silicate can be dispersed in the resin without agglomeration even when added in an amount of 10 parts by weight or more. As said chemical modification, it can implement by the chemical modification (1) method-chemical modification (6) method shown below, for example. These chemical modification methods may be used alone or in combination of two or more.
[0088]
The chemical modification (1) method is also referred to as a cation exchange method using a cationic surfactant. Specifically, when the resin composition of the present invention is obtained using a low-polar resin, the layer of the layered silicate is previously cationized. In this method, the cation is exchanged with a hydrophobic surfactant to make it hydrophobic. By making the layers of the layered silicate hydrophobic in advance, the affinity between the layered silicate and the low polarity resin is increased, and the layered silicate can be finely dispersed in the low polarity resin more uniformly.
[0089]
The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Of these, alkyl ammonium ions, aromatic quaternary ammonium ions, or heterocyclic quaternary ammonium ions having 6 or more carbon atoms are preferably used because the crystal layers of the layered silicate can be sufficiently hydrophobized.
[0090]
The quaternary ammonium salt is not particularly limited, and examples thereof include trimethyl alkyl ammonium salt, triethyl alkyl ammonium salt, tributyl alkyl ammonium salt, dimethyl dialkyl ammonium salt, dibutyl dialkyl ammonium salt, methyl benzyl dialkyl ammonium salt, and dibenzyl dialkyl ammonium salt. , Trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt; benzylmethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride A quaternary ammonium salt having an aromatic ring such as trimethylphenylammonium; a quaternary ammonium salt derived from an aromatic amine such as trimethylphenylammonium; an alkylpyridinium salt, an imidazoli A quaternary ammonium salt having a heterocyclic ring such as a dimethyl salt; a dialkyl quaternary ammonium salt having two polyethylene glycol chains, a dialkyl quaternary ammonium salt having two polypropylene glycol chains, and a trialkyl quaternary having one polyethylene glycol chain Examples thereof include ammonium salts and trialkyl quaternary ammonium salts having one polypropylene glycol chain. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N N-dimethylammonium salt and the like are preferred. These quaternary ammonium salts may be used independently and 2 or more types may be used together.
[0091]
The quaternary phosphonium salt is not particularly limited. For example, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethylphosphonium salt, distearyl And dibenzylphosphonium salts. These quaternary phosphonium salts may be used alone or in combination of two or more.
[0092]
In the chemical modification (2) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method has a chemical affinity with a functional group or a hydroxyl group capable of chemically bonding to the hydroxyl group. This is a method of chemical treatment with a compound having at least one functional group having a large molecular weight at the molecular end.
[0093]
The functional group capable of chemically bonding to the hydroxyl group or the functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, a carboxyl group (including dibasic acid anhydrides), A hydroxyl group, an isocyanate group, an aldehyde group, etc. are mentioned.
[0094]
The compound having a functional group capable of chemically bonding to the hydroxyl group or the compound having a functional group having a large chemical affinity with the hydroxyl group is not particularly limited. For example, a silane compound, titanate compound, or glycidyl compound having the functional group. , Carboxylic acids, alcohols and the like. These compounds may be used independently and 2 or more types may be used together.
[0095]
The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-amino. Propyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltri Ethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ- Minopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri An ethoxysilane etc. are mentioned. These silane compounds may be used independently and 2 or more types may be used together.
[0096]
In the chemical modification (3) method, the hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method has a functional group capable of chemically bonding to the hydroxyl group or a chemical affinity with the hydroxyl group. This is a chemical treatment method using a large functional group and a compound having at least one reactive functional group at the molecular end.
[0097]
The chemical modification (4) method is a method in which the crystal 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.
[0098]
The compound having an anionic surface activity is not particularly limited as long as the layered silicate can be chemically treated by ionic interaction. For example, sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfate ester salt , Secondary higher alcohol sulfates, unsaturated alcohol sulfates and the like. These compounds may be used independently and 2 or more types may be used together.
[0099]
The chemical modification (5) method is a method of chemically treating a compound having one or more reactive functional groups in addition to the anion site in the molecular chain among the compounds having anionic surface activity.
[0100]
In the chemical modification (6) method, an organically modified layered silicate chemically treated by any one of the chemical modification (1) method to the chemical modification (5) method is further used, for example, maleic anhydride-modified polyphenylene ether resin. This is a method using a resin having a functional group capable of reacting with the layered silicate.
[0101]
The layered silicate has an average interlayer distance of 3 nm or more on the (001) plane measured by the wide angle X-ray diffraction measurement method in the resin composition of the present invention. As And some or all Part 5 layers or less In the number of layers dispersion Is It is preferable. The average interlayer distance is 3 nm or more As And some or all Part 5 layers or less In the number of layers dispersion Is As a result, the interface area between the resin and the layered silicate is sufficiently large, and the distance between the flaky crystals of the layered silicate becomes moderate, and high-temperature properties, mechanical properties, heat resistance, dimensional stability The improvement effect by dispersion can be sufficiently obtained.
[0102]
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 becomes so weak that the interaction is negligible. Therefore, the binding strength at high temperatures becomes weak, and sufficient dimensional stability may not be obtained.
[0103]
In the present specification, the average interlayer distance of the layered silicate means the average distance between layers when the flaky crystal of the layered silicate is regarded as a layer, and X-ray diffraction peak and transmission electron microscope photography That is, it can be calculated by a wide-angle X-ray diffraction measurement method.
[0104]
Some or all of the above Part 5 layers or less In the number of layers dispersion Is Specifically, it means that the interaction between the flaky crystals of the layered silicate is weakened and a part or all of the laminate of flaky crystals is dispersed. Preferably, 10% or more of the layered silicate laminate is 5 layers or less In the number of layers 20% or more of the layered silicate laminate is 5 layers or less In the number of layers More preferably, it is dispersed.
In addition, the ratio of the layered silicate dispersed as a laminate of 5 layers or less is a layered silicic acid that can be observed in a fixed area by observing the resin composition at a magnification of 50,000 to 100,000 times with a transmission electron microscope. It can be calculated from the following formula (4) by measuring the total number of layers X of the salt laminate and the number of layers Y of the laminate dispersed as a laminate of 5 layers or less.
[0105]
[Expression 4]

[0106]
The number of layers in the layered silicate laminate is preferably 5 layers or less, more preferably 3 layers or less, and even more preferably 1 layer in order to obtain the effect of dispersion of the layered silicate. is there.
[0107]
The resin composition of the present invention uses a layered silicate as the inorganic compound, Layered silicate (001) plane average interlayer distance measured by wide angle X-ray diffraction measurement method is 3 nm or more As And some or all Part 5 layers or less In the number of layers dispersion Is As a result, the interface area between the resin and the layered silicate becomes sufficiently large, the interaction between the resin and the surface of the layered silicate increases, the melt viscosity increases, and thermoformability such as hot press In addition to improving the shape, it is easy to retain shaped shapes such as embossing and embossing, and mechanical properties such as elastic modulus are improved in a wide temperature range from room temperature to high temperature. However, the mechanical properties can be maintained and the linear expansion coefficient at high temperatures can be kept low. The reason for this is not clear, but it is considered that even in the temperature range above Tg or the melting point, these physical properties are manifested because the finely dispersed layered silicate acts as a kind of pseudo-crosslinking point. On the other hand, since the distance between the lamellar crystals of the layered silicate is also appropriate, the lamellar crystals of the lamellar silicate move during combustion, and it becomes easy to form a sintered body that becomes a flame retardant coating. Since this sintered body is formed at an early stage during combustion, not only the supply of oxygen from the outside world but also the flammable gas generated by the combustion can be blocked, and the resin composition of the present invention The product exhibits excellent flame retardancy.
[0108]
Furthermore, in the resin composition of the present invention, since the layered silicate is finely dispersed in a nanometer size, when a perforation process is performed on the substrate or the like made of the resin composition of the present invention by a laser such as a carbon dioxide laser, The resin component and the layered silicate component are simultaneously decomposed and evaporated, and the partially remaining layered silicate residue is only a small one of several μm or less and can be easily removed by desmearing. Thereby, it is possible to prevent the occurrence of defective plating due to the residue generated by the drilling process.
[0109]
The method for dispersing the layered silicate in the resin is not particularly limited, for example, a method using an organically modified layered silicate, a method of foaming the resin with a foaming agent after mixing the resin and the layered silicate by a conventional method, Examples thereof include a method using a dispersant. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed in the resin.
[0110]
In the method in which the resin and the layered silicate are mixed by a conventional method and the resin is foamed with a foaming agent, the energy of foaming is used for the dispersion of the layered silicate. It does not specifically limit as said foaming agent, For example, a gaseous foaming agent, an easily volatile liquid foaming agent, a heat decomposable solid foaming agent etc. are mentioned. These foaming agents may be used independently and 2 or more types may be used together.
[0111]
The method of foaming the resin with a foaming agent after mixing the resin and the layered silicate by a conventional method is not particularly limited. For example, a gaseous foaming agent is added to a resin composition comprising the resin and the layered silicate under high pressure. A method in which the gaseous foaming agent is vaporized in the resin composition to form a foam after impregnation with the above-mentioned method; a thermally decomposable foaming agent is previously contained between the layers of the layered silicate, and the thermally decomposable foaming agent And a method of decomposing the foam by heating to form a foam.
[0112]
The minimum of the compounding quantity with respect to 100 weight part of said thermosetting resins of the said inorganic compound is 0.1 weight part, and an upper limit is 65 weight part. If it is less than 0.1 parts by weight, the effect of improving high-temperature properties and hygroscopicity is reduced. If it exceeds 65 parts by weight, the density (specific gravity) of the resin composition of the present invention will increase, and the mechanical strength will also decrease, making it impractical. The preferred lower limit is 1 part by weight and the upper limit is 45 parts by weight. When the amount is less than 1 part by weight, a sufficient effect of improving high-temperature physical properties may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 45 parts by weight, the moldability may deteriorate. A more preferred lower limit is 5 parts by weight and an upper limit is 30 parts by weight. When the amount is 5 to 30 parts by weight, there is no region causing problems in mechanical properties and process suitability, and sufficient flame retardancy is obtained.
[0113]
Among the resin compositions of the present invention, when a layered silicate is used as the inorganic compound, the lower limit of the amount of the layered silicate is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight. If it is less than 1 part by weight, the effect of improving high-temperature properties and hygroscopicity may be reduced. If it exceeds 50 parts by weight, the density (specific gravity) of the resin composition of the present invention is increased, and the mechanical strength is also decreased, so that it may be impractical. A more preferred lower limit is 5 parts by weight and an upper limit is 45 parts by weight. If it is less than 5 weights, a sufficient effect of improving high-temperature properties may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 45 parts by weight, the dispersibility of the layered silicate may deteriorate. A more preferred lower limit is 8 parts by weight, and an upper limit is 40 parts by weight. When the amount is 8 to 40 parts by weight, there is no region causing a problem in process suitability, sufficient low water absorption is obtained, and the effect of reducing the average linear expansion coefficient is sufficiently obtained even in both the α1 and α2 regions.
[0114]
The resin composition of the present invention preferably further contains a flame retardant that does not contain a halogen-based composition. It should be noted that a trace amount of halogen may be mixed due to the manufacturing process of the flame retardant.
[0115]
The flame retardant is not particularly limited. For example, metal hydroxide such as aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum, calcium hydroxide; metal oxide; red phosphorus or polyphosphoric acid Phosphorus compounds such as ammonium; Nitrogen compounds such as melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate and melamine derivatives obtained by surface treatment thereof; Fluororesin; Silicone oil; Layered double water such as hydrotalcite Japanese products: silicone-acrylic composite rubber and the like. Of these, metal hydroxides and melamine derivatives are preferred. Among the metal hydroxides, magnesium hydroxide and aluminum hydroxide are particularly preferable, and these may be subjected to surface treatment with various surface treatment agents. The surface treatment agent is not particularly limited, and examples thereof include a silane coupling agent, a titanate coupling agent, a PVA surface treatment agent, and an epoxy surface treatment agent. These flame retardants may be used alone or in combination of two or more.
[0116]
When a metal hydroxide is used as the flame retardant, the lower limit of the preferable blending amount of the metal hydroxide with respect to 100 parts by weight of the thermosetting resin is 0.1 part by weight, and the upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the flame retarding effect may not be sufficiently obtained. If it exceeds 100 parts by weight, the density (specific gravity) of the resin composition of the present invention may become too high, resulting in poor practicality and extremely low flexibility and elongation. A more preferred lower limit is 5 parts by weight and an upper limit is 80 parts by weight. When it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained when the resin composition of the present invention is thinly molded. If it exceeds 80 parts by weight, the defect rate due to blistering or the like may increase in the step of performing high temperature treatment. A more preferred lower limit is 10 parts by weight and an upper limit is 70 parts by weight. When the amount is in the range of 10 to 70 parts by weight, there is no region causing problems in mechanical properties, electrical properties, process suitability, etc., and sufficient flame retardancy is exhibited.
[0117]
When a melamine derivative is used as the flame retardant, the lower limit of the preferable amount of the melamine derivative with respect to 100 parts by weight of the thermosetting resin is 0.1 part by weight, and the upper limit is 100 parts by weight. If it is less than 0.1 part by weight, the flame retarding effect may not be sufficiently obtained. If it exceeds 100 parts by weight, mechanical properties such as flexibility and elongation may be extremely lowered. A more preferred lower limit is 5 parts by weight and an upper limit is 70 parts by weight. If it is less than 5 parts by weight, a sufficient flame retarding effect may not be obtained when the insulating substrate is thinned. If it exceeds 70 parts by weight, mechanical properties such as flexibility and elongation may be extremely lowered. A more preferred lower limit is 10 parts by weight and an upper limit is 50 parts by weight. When the amount is in the range of 10 to 50 parts by weight, there is no region causing problems in mechanical properties, electrical properties, process suitability, etc., and sufficient flame retardancy is exhibited.
[0118]
The resin composition of the present invention includes, as necessary, thermoplastic elastomers, crosslinked rubber, oligomers, nucleating agents, oxidizers, and the like for the purpose of modifying the properties within a range that does not hinder achievement of the present invention. Additives such as inhibitors (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, lubricants, flame retardant aids, antistatic agents, antifogging agents, fillers, softeners, plasticizers, colorants, etc. May be blended. These may be used alone or in combination of two or more.
[0119]
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.
[0120]
The crosslinked rubber is not particularly limited, and examples thereof include isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, and urethane rubber. In order to enhance the compatibility with the resin, it is preferable that these crosslinked rubbers are functional group-modified. The functional group-modified crosslinked rubber is not particularly limited, and examples thereof include epoxy-modified butadiene rubber and epoxy-modified nitrile rubber. These crosslinked rubbers may be used alone or in combination of two or more.
[0121]
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.
[0122]
The method for producing the resin composition of the present invention is not particularly limited. For example, each predetermined amount of a resin and an inorganic compound, and each predetermined amount of one or more additives blended as necessary, Direct kneading method of directly blending and kneading at normal temperature or under heating, and a method of removing the solvent after mixing in a solvent; previously blending a predetermined amount or more of an inorganic compound in the resin or a resin other than the resin Then, a master batch kneaded is prepared, and this master batch, the remainder of the predetermined amount of the resin, and each predetermined amount of one or more additives to be blended as necessary are at room temperature or heated. Below, the masterbatch method etc. which knead | mix or mix in a solvent are mentioned.
[0123]
In the master batch method, a master batch in which an inorganic compound is blended with the resin or a resin other than the resin, and a master batch dilution resin containing the resin used when the master batch is diluted to a predetermined inorganic compound concentration The compositions may be the same composition or different compositions.
[0124]
The masterbatch is not particularly limited. For example, at least one resin selected from the group consisting of a polyamide resin, a polyphenylene ether resin, a polyether sulfone resin, and a polyester resin, in which an inorganic compound can be easily dispersed, is used. It is preferable to contain. Although it does not specifically limit as said resin composition for masterbatch dilution, For example, it is preferable to contain the at least 1 sort (s) of resin selected from the group which consists of a thermosetting polyimide resin excellent in the high temperature physical property, and an epoxy resin.
[0125]
Although the compounding quantity of the inorganic compound in the said masterbatch is not specifically limited, The preferable minimum with respect to 100 weight part of resin is 1 weight part, and an upper limit is 500 weight part. When the amount is less than 1 part by weight, the convenience as a master batch that can be diluted to an arbitrary concentration is reduced. If it exceeds 500 parts by weight, the dispersibility in the master batch itself, and particularly the dispersibility of the inorganic compound when diluted to a predetermined blending amount by the master batch dilution resin composition may deteriorate. A more preferred lower limit is 5 parts by weight and an upper limit is 300 parts by weight.
[0126]
Further, for example, by using an inorganic compound containing a polymerization catalyst (polymerization initiator) such as a transition metal complex, a thermoplastic resin monomer and an inorganic compound are kneaded, and the above monomer is polymerized, thereby thermoplastic resin. You may use the method of performing simultaneously superposition | polymerization and manufacture of a resin composition collectively.
[0127]
The method for kneading the mixture in the method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method for kneading using a kneader such as an extruder, two rolls, and a Banbury mixer.
[0128]
The resin composition of the present invention is a combination of a resin and an inorganic compound, and has a low linear expansion coefficient at a high temperature due to an increase in Tg and heat-resistant deformation temperature due to molecular chain restraint. Excellent mechanical properties and transparency.
[0129]
Furthermore, gas molecules are much easier to diffuse in the resin than inorganic compounds, and when diffusing in the resin, the gas molecules diffuse while bypassing the inorganic compound, so the gas barrier properties are also improved. Similarly, barrier properties against other than gas molecules are improved, and solvent resistance, hygroscopicity, water absorption and the like are improved. Thereby, for example, copper migration from a copper circuit in a multilayer printed wiring board can be suppressed. Furthermore, it is possible to suppress the occurrence of defects such as defective plating due to bleed-out of trace additives in the resin on the surface.
[0130]
In the resin composition of the present invention, if layered silicate is used as the inorganic compound, excellent mechanical properties can be obtained without adding a large amount, and thus a thin insulating substrate can be obtained. Density and thickness can be reduced. In addition, improvement in dimensional stability based on a nucleation effect of layered silicate in crystal formation and a swelling suppression effect accompanying improvement in moisture resistance, and the like have been attempted. Furthermore, since a sintered body made of layered silicate is formed at the time of combustion, the shape of the combustion residue is maintained, the shape does not collapse after the combustion, the spread of fire can be prevented, and excellent flame retardancy is exhibited.
[0131]
Moreover, in the resin composition of this invention, if a non-halogen flame retardant is used, it is possible to achieve both high mechanical properties and high flame retardancy while considering the environment.
The use of the resin composition of the present invention is not particularly limited. For example, a core layer or a build-up layer of a multilayer substrate is formed by processing in a suitable solvent or by forming into a film. It is suitably used for substrate materials, sheets, laminates, copper foils with resin, copper-clad laminates, TAB tapes, printed boards, prepregs, varnishes and the like. Substrate materials, sheets, laminates, resin-coated copper foils, copper-clad laminates, TAB tapes, printed boards, prepregs, and adhesive sheets using the resin composition of the present invention are also one aspect of the present invention. .
[0132]
The molding method is not particularly limited. For example, an extrusion molding method in which an extruder is melted and kneaded and then extruded and formed into a film using a T die or a circular die; dissolved in a solvent such as an organic solvent or Casting molding method in which the material is dispersed and then cast into a film shape; in a varnish obtained by dissolving or dispersing in a solvent such as an organic solvent, a cloth-like or non-woven fabric made of an inorganic material such as glass or an organic polymer Examples include a dipping molding method in which a substrate is dipped to form a film. Of these, the extrusion molding method and the casting molding method are suitable for reducing the thickness of the multilayer substrate. In addition, it does not specifically limit as a base material used in the said dipping molding method, For example, a glass cloth, an aramid fiber, a polyparaphenylene benzoxazole fiber etc. are mentioned.
[0133]
The substrate material, sheet, laminate, resin-coated copper foil, copper-clad laminate, TAB tape, printed circuit board, prepreg, adhesive sheet, and optical circuit forming material of the present invention are composed of the resin composition of the present invention. It is excellent in high-temperature physical properties, dimensional stability, solvent resistance, moisture resistance and barrier properties, and can be obtained with a high yield even when it is manufactured through multiple processes.
[0134]
In addition, the substrate material of the present invention has a low linear expansion coefficient, heat resistance, low water absorption, and high transparency because the layered silicate is finely dispersed in a nanometer size in the thermosetting resin. Can also be realized. Therefore, the substrate material of the present invention can be suitably used as an optical package forming material, an optical waveguide material, a connecting material, an optical circuit forming material such as a sealing material, and an optical communication material.
[0135]
The resin composition of the present invention has a low linear expansion coefficient, heat resistance, and low water absorption as well as high transparency because the layered silicate is finely dispersed in a nanometer size in the thermosetting resin. realizable. Therefore, the resin composition of the present invention can be suitably used as an optical circuit forming material such as an optical package forming material, an optical waveguide material, a connecting material, and a sealing material.
[0136]
【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.
[0137]
Example 1
From 54 parts by weight of bisphenol F type epoxy resin (Dainippon Ink Chemical Co., Ltd., Epicron 830 LVP), 14.7 parts by weight of BT resin (BT2100B, manufactured by Mitsubishi Gas Chemical Co., Inc.) and 14.7 parts by weight of neopentyl glycol diglycidyl ether 83.4 parts by weight of the epoxy resin composition, 1.9 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.) as a curing catalyst 1.0 part by weight, 13.7 parts by weight of swellable fluorine mica treated with distearyldimethyl quaternary ammonium salt as a layered silicate (manufactured by Co-op Chemical Co., Ltd., Somasif MAE-100), and As an organic solvent, 200 parts by weight of methyl ethyl ketone (made by Wako Pure Chemical Industries, special grade) is added, After stirring for 1 hour at agitator and mixed with further meteor stirrer. Thereafter, defoaming was performed to obtain a resin / layered silicate solution. Next, after removing the solvent in a state where the obtained resin / layered silicate solution was put in a mold, it was heated at 110 ° C. for 3.5 hours, and further heated at 160 ° C. for 3 hours to be cured. A plate-like molded body having a thickness of 2 mm and 100 μm was produced.
[0138]
(Example 2)
80 parts by weight of an epoxy resin composition comprising 40 parts by weight of a bisphenol A type epoxy resin (D.R. 331L, manufactured by Dow Chemical Japan Co., Ltd.) and 40 parts by weight of a solid epoxy resin (manufactured by Toto Kasei Co., Ltd., YP55), dicyan azide ( Adeka hardener EH-3636 (2.8 parts by weight), modified imidazole (adeca hardener EH-3366) 1.2 parts by weight, organically treated with trioctylmethylammonium salt as a layered silicate 16 parts by weight of synthetic hectorite (manufactured by Corp Chemical Co., Lucentite STN) and 400 parts by weight of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) as an organic solvent are added to a beaker and stirred for 1 hour with a stirrer. After degassing, a resin / layered silicate solution was obtained. Next, after removing the solvent in a state where the obtained resin / layered silicate solution was coated on a polyethylene terephthalate sheet, it was heated at 110 ° C. for 3 hours, and further heated at 170 ° C. for 30 minutes to be cured. A plate-like molded body having a thickness of 2 mm and a thickness of 100 μm was prepared.
[0139]
Example 3
80 parts by weight of an epoxy resin composition comprising 56 parts by weight of a bisphenol A type epoxy resin (D.R. 331L manufactured by Dow Chemical Japan Co., Ltd.) and 24 parts by weight of a solid epoxy resin (manufactured by Toto Kasei Co., Ltd., YP55), dicyan azide ( Adeka Hardener EH-3636) 3.9 parts by weight, modified imidazole (Adeka Hardener EH-3366) 1.7 parts by weight, organically treated with trioctylmethylammonium salt as a layered silicate 30 parts by weight of synthetic hectorite (manufactured by Corp Chemical Co., Lucentite STN), 250 parts by weight of dimethylformamide (manufactured by Wako Pure Chemicals, special grade) as an organic solvent, synthetic silica (manufactured by Admatechs, Admafine SO) -E2) Add 22 parts by weight to a beaker, stir with a stirrer for 1 hour, To obtain a resin / layered silicate solution. Next, after removing the solvent in a state where the obtained resin / layered silicate solution was coated on a polyethylene terephthalate sheet, it was heated at 110 ° C. for 3 hours, and further heated at 170 ° C. for 30 minutes to be cured. A plate-like molded body having a thickness of 2 mm and a thickness of 100 μm was prepared.
[0140]
Example 4
80 parts by weight of an epoxy resin composition comprising 56 parts by weight of a bisphenol A type epoxy resin (D.R. 331L manufactured by Dow Chemical Japan Co., Ltd.) and 24 parts by weight of a solid epoxy resin (manufactured by Toto Kasei Co., Ltd., YP55), dicyan azide ( Adeka Hardener EH-3636 1.7 parts by weight, modified imidazole (Adeca Hardener EH-3366) 0.7 parts by weight, organically treated with trioctylmethylammonium salt as a layered silicate 16 parts by weight of synthetic hectorite (manufactured by Corp Chemical Co., Lucentite STN), aluminum borate whisker (manufactured by Shikoku Kasei Kogyo Co., Ltd., Arbolex YS3A), magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., Kisuma 5J) ) 22 parts by weight and dimethylformamide (Wako Pure) as an organic solvent Company Ltd., special grade) 250 parts by weight was added to the beaker and stirred for 1 hour at a stirrer, was deaerated to obtain a resin / layered silicate solution. Next, after removing the solvent in a state where the obtained resin / layered silicate solution was coated on a polyethylene terephthalate sheet, it was heated at 110 ° C. for 3 hours, and further heated at 170 ° C. for 30 minutes to be cured. A plate-like molded body having a thickness of 2 mm and a thickness of 100 μm was prepared.
[0141]
(Comparative Example 1)
Except that no swellable fluorine mica (manufactured by Co-op Chemical Co., Ltd., Somasif MAE-100) was blended, a resin composition and a plate-shaped molding having a thickness of 2 mm and 100 μm comprising the resin composition were carried out in the same manner as in Example 1. The body was made.
[0142]
(Comparative Example 2)
Except that synthetic hectorite (manufactured by Co-op Chemical Co., Ltd., Lucentite STN) was not blended, a resin composition and a plate-like molded product having a thickness of 2 mm and 100 μm comprising the resin composition were obtained in the same manner as in Example 2. Produced.
[0143]
(Comparative Example 3)
It consists of a resin composition and a resin composition in the same manner as in Example 3 except that synthetic hectorite (manufactured by Co-op Chemical Co., Ltd., Lucentite STN) was not blended and the amount of synthetic silica added was 52 parts by weight. Plate-shaped molded bodies having a thickness of 2 mm and 100 μm were produced.
[0144]
(Comparative Example 4)
A resin composition and a resin composition were prepared in the same manner as in Example 4 except that synthetic hectorite (manufactured by Co-op Chemical Co., Ltd., Lucentite STN) was not blended and the amount of magnesium hydroxide added was 42 parts by weight. Plate-shaped molded bodies having a thickness of 2 mm and 100 μm were produced.
[0145]
<Evaluation>
The performance of the plate-shaped molded bodies produced in Examples 1 to 4 and Comparative Examples 1 to 4 was evaluated for the following items. The results are shown in Tables 1 and 2.
[0146]
(1) Measurement of thermal expansion coefficient
A test piece cut to 3 mm × 25 mm by cutting the plate-shaped molded body was heated at a temperature rising rate of 5 ° C./min using a TMA (thermomechanical analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C), and averaged. The linear expansion coefficient was measured and the following items were evaluated.
[0147]
-Average linear expansion coefficient (α2) [° C. at a temperature 10 to 50 ° C. higher than the glass transition temperature of the resin composition ^-1 ].
The average linear expansion coefficient (α2) at a temperature 10 ° C. to 50 ° C. higher than the glass transition temperature of the resin composition is 50 ° C. to 10 ° C. lower than the glass transition temperature of the resin composition. Average linear expansion coefficient ratio (α2 / α1) obtained by dividing by (α1).
・ Average linear expansion coefficient at 50 to 100 ° C. [° C. ^-1 ] And average linear expansion coefficient at 200 to 240 ° C. [° C. ^-1 ].
-Average linear expansion coefficient ratio (1) obtained by dividing the average linear expansion coefficient at 150 to 200 ° C by the average linear expansion coefficient at 50 to 100 ° C, and the average linear expansion coefficient at 250 to 300 ° C Is an average linear expansion coefficient ratio (2) obtained by dividing by the average linear expansion coefficient at 50 to 100 ° C.
A rate of change (%) obtained by dividing the amount of change in length when the plate-shaped molded body was heated from 25 ° C. to 300 ° C. by the length of the plate-shaped molded body at 25 ° C.
-Average linear expansion coefficient ratio (3) represented by Formula (1) mentioned above.
The average linear expansion coefficient at a temperature 10 ° C. to 50 ° C. higher than the Tg of the resin composition is higher than the Tg of the resin compositions prepared in Comparative Examples 1, 2, 3, 4, and 5 corresponding to the respective examples. The improvement rate obtained by dividing by the average linear expansion coefficient at a temperature higher by 10 ° C to 50 ° C.
[0148]
(2) Average interlayer distance of layered silicate
Using an X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), 2θ of a diffraction peak obtained from diffraction of the laminated surface of the layered silicate in the 2 mm-thick plate-like molded product is measured, and the following formula (5) The (001) plane spacing d of the layered silicate was calculated from the black diffraction formula, and the obtained d was defined as the average interlayer distance (nm).
λ = 2 dsin θ (5)
In the above formula (5), λ is 0.154, and θ represents the diffraction angle.
[0149]
(3) Ratio of layered silicate dispersed as a laminate of 5 layers or less
A layered silicate dispersed in a total number of layers X and 5 layers or less of a layered silicate that can be observed in a fixed area by observing a plate-shaped molded body having a thickness of 100 μm with a transmission electron microscope at a magnification of 100,000 times The number Y of layers was measured, and the ratio (%) of the layered silicate dispersed as a laminate of 5 layers or less was calculated by the following formula (4).
[0150]
[Equation 5]

[0151]
(4) Measurement of water absorption
A test piece in which a plate-like molded body having a thickness of 100 μm was formed into a 3 × 5 cm strip was prepared, and the weight (W1) after drying at 150 ° C. for 5 hours was measured. Next, the test piece was immersed in water, left in 100 ° C. boiling water for 1 hour, then taken out, and the weight (W2) after carefully wiping with a waste was measured. The water absorption was determined by the following formula.
Water absorption (%) = (W2−W1) / W1 × 100
[0152]
(5) Measurement of dielectric constant
A dielectric constant in the vicinity of a frequency of 1 MHz was measured using an impedance measuring instrument (HP 4291B, manufactured by Hewlett-Packard Company).
[0153]
(6) Measurement of tensile modulus
Measurement was performed by a method according to JIS K6301.
[0154]
(7) Measurement of solubility parameter
It was calculated by the formula of Fedors.
[0155]
(8) Measurement of 10% weight loss temperature
After 5 to 10 mg of sample was dried at 150 ° C. for 5 hours, measurement was performed using a TG / DTA apparatus (TG / DTA320, manufactured by Seiko Denshi) under the following measurement conditions.
[0156]
Measurement temperature: 25-600 ° C
Temperature increase rate: 10 ° C / min
Nitrogen gas: 200 ml / min
[0157]
[Table 1]

[0158]
[Table 2]

[0159]
【The invention's effect】
According to the present invention, a resin composition, a substrate material, a sheet, a laminate, a resin-coated copper foil, a copper-clad, excellent in mechanical properties, dimensional stability, heat resistance, flame retardancy, etc., and particularly excellent in high-temperature properties. A laminate, a TAB tape, a printed board, a prepreg, and an adhesive sheet can be provided.

Claims (31)

And 100 parts by weight of the thermosetting resin and / or photo-curable resin and the layered silicate from 0.1 to 65 parts by weight a resin composition that Yusuke containing, than the glass transition temperature of the cured product of the resin composition The average linear expansion coefficient (α2) of the cured product of the resin composition from a temperature higher by 10 ° C. to a temperature higher by 50 ° C. than the glass transition temperature of the cured product of the resin composition is 17 × 10 ⁻⁵ [° C. ⁻¹ ] or less. A resin composition characterized by the above. From 10 ° C. higher than the glass transition temperature of the cured product of the resin composition, the average linear expansion coefficient of the cured product of the resin composition to a temperature 50 ° C. than the glass transition temperature of the cured product of the resin composition ([alpha] 2) and from 50 ° C. lower than the glass transition temperature of the cured product of the resin composition, the average linear expansion coefficient of the cured product of the resin composition up to 10 ° C. lower than the glass transition temperature of the cured product of the resin composition ( 2. The resin composition according to claim 1, wherein an average linear expansion coefficient ratio (α2 / α1) obtained by dividing by α1) is 2 or less. The average linear expansion coefficient of the cured product of the resin composition at 50 to 100 ° C. is 10 × 10 ⁻⁵ [° C. ⁻¹ ] or less, and the average linear expansion of the cured product of the resin composition at 200 to 240 ° C. The resin composition according to claim 1, wherein the rate is 25 × 10 ⁻⁵ [° C. ⁻¹ ] or less. Average linear expansion coefficient ratio (1) obtained by dividing the average linear expansion coefficient of the cured product of the resin composition at 150 to 200 ° C. by the average linear expansion coefficient of the cured product of the resin composition at 50 to 100 ° C. The average linear expansion coefficient of the cured product of the resin composition at 250 to 300 ° C is divided by the average linear expansion coefficient of the cured product of the resin composition at 50 to 100 ° C. The obtained average linear expansion coefficient ratio (2) is 4.5 or less, The resin composition according to any one of claims 1 to 3.   The rate of change obtained by dividing the amount of change in the length of the resin piece made of the resin composition from 25 ° C. to 300 ° C. by the length of the resin piece made of the resin composition at 25 ° C. is 5 % Or less, The resin composition according to any one of claims 1 to 4. The average linear expansion coefficient ratio (3) represented by the following formula (1) is 1.05 or less, The resin composition according to any one of claims 1 to 5.

However, T (° C.) is 50 ° C. or more and 400 ° C. or less, and is excluded when the average linear expansion coefficient ratio (3) is obtained across Tg. From 10 ° C. higher than the glass transition temperature of the cured product of the resin composition, the average linear expansion coefficient of the cured product of the resin composition to a temperature 50 ° C. than the glass transition temperature of the cured product of the resin composition, wherein The thermosetting resin and / or light contained in the resin composition from a temperature 10 ° C. higher than the glass transition temperature of the cured product of the resin comprising the thermosetting resin and / or photocurable resin contained in the resin composition mean linear expansion coefficient of the cured product of the resin made of a thermosetting resin and / or photo-curable resin contained in the resin composition up to 50 ° C. higher than the glass transition temperature of the cured product of the resin comprising the cured resin The resin composition according to claim 1, wherein the improvement rate obtained by dividing by is 0.98 or less. The tensile modulus at 140 ° C. of the cured product of the resin composition is 10 MPa or more, and the dielectric constant at 1 MHz of the cured product of the resin composition is 4.5 or less. The resin composition as described. The resin composition according to any one of claims 1 to 8, wherein the water absorption of the cured product of the resin composition is 2.0% or less. The water absorption rate of the cured product of the resin composition is 2.0% or less, the dielectric constant at 1 MHz of the cured product of the resin composition is 4.5 or less, and the cured product of the resin composition is immersed in water to absorb water. the resin composition according to any one of claims 1 to 9 having a dielectric constant after water absorption treatment is equal to or more than 5.0 when allowed to. The resin composition according to any one of claims 1 to 10, wherein when formed into a resin sheet having a thickness of 25 µm, the insulation resistance is 10 ⁸ Ω or more. The resin composition according to any one of claims 1 to 11, wherein the glass transition temperature of the cured product of the resin composition is 100 ° C or higher. The resin composition according to any one of claims 1 to 12, wherein the elongation at break at 260 ° C of the cured product of the resin composition is 10% or more. The cured product of the thermosetting resin has a glass transition temperature of 100 ° C or higher and a dielectric constant at 1 MHz of 4.5 or lower. Composition.   The thermosetting resin is at least one selected from the group consisting of epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, benzoxazine resins, and melamine resins. The resin composition according to any one of claims 1 to 14.   The resin composition according to claim 15, wherein the thermosetting resin is an epoxy resin. The thermosetting resin before curing has a solubility parameter of 42 [J / cm ³ ] ^1/2 or more determined using a Fedors calculation formula, according to any one of claims 1 to 16. Resin composition. The cured product of thermosetting resin has a 10% weight reduction temperature of 400 ° C or higher with respect to the weight at 25 ° C when thermogravimetric measurement is performed in a nitrogen atmosphere. The resin composition in any one of. The resinous composition according to any one of claims 1 to 18, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite. The layered silicate contains an alkylammonium ion having 6 or more carbon atoms, an aromatic quaternary ammonium ion or a heterocyclic quaternary ammonium ion, according to any one of claims 1 to 19 . The layered silicate has an average interlayer distance were measured by wide angle X-ray diffractometry (001) plane to be a 3nm or more, and has a part or all parts are dispersed in the layer number of 5 or less layers The resin composition according to any one of claims 1 to 20 , wherein A substrate material comprising the resin composition according to any one of claims 1 to 21 . Sheet characterized by using a resin composition according to any one of claims 1 to 21. A laminate comprising the resin composition according to any one of claims 1 to 21 . A resin-coated copper foil comprising the resin composition according to any one of claims 1 to 21 . A copper-clad laminate comprising the resin composition according to any one of claims 1 to 21 . A TAB tape comprising the resin composition according to any one of claims 1 to 21 . A printed circuit board comprising the resin composition according to any one of claims 1 to 21 . A prepreg comprising the resin composition according to any one of claims 1 to 21 . An adhesive sheet comprising the resin composition according to any one of claims 1 to 21 . An optical circuit forming material comprising the resin composition according to any one of claims 1 to 21 .