JP4137627B2 - Thermoplastic resin composition - Google Patents

Description

【００５６】
上記一般式（Ｉ）は次の条件を満足する。すなわち、Ｍは窒素原子またはリン原子であり、Ｒ¹およびＲ²はそれぞれ炭素原子数６〜１６のアルキル基である。Ｒ³は炭素原子数１〜１６のアルキル基であり、かつＲ⁴は炭素原子数１〜４のアルキル基である。なお、Ｒ¹とＲ²とは互いに同一の基であっても相異なる基であってもよく、また、Ｒ³とＲ⁴とは互いに同一の基であっても相異なる基であってもよい。
【００５７】
上記一般式（Ｉ）で示される有機オニウムイオンのより好適な態様は、（ｉ）前記Ｒ³が炭素原子数１〜４のアルキル基の場合である。より好しくは（ii）Ｒ³およびＲ⁴がそれぞれ炭素原子数１〜４のアルキル基であって、かつＲ¹およびＲ²がそれぞれ炭素原子数７〜１４のアルキル基の場合である。さらに好ましくは、（iii）Ｒ³およびＲ⁴がそれぞれ炭素原子数１〜４のアルキル基で、かつＲ¹およびＲ²は炭素原子数７〜１１のアルキル基の場合である。なお、これらのうちでも、Ｒ³およびＲ⁴が炭素原子数１〜３のアルキル基、より好ましくはメチル基またはエチル基、さらに好ましくはメチル基の４級アンモニウムイオンが特に好適である。
【００５８】
これら（ｉ）〜（iii）のより好適な態様（さらに好ましい態様を含む）によれば、樹脂組成物の耐加水分解性が特に優れたものとなり、本発明の熱可塑性樹脂組成物に良好な長期実用特性を与える。
【００５９】
なお、上記式（Ｉ）においてＲ¹〜Ｒ⁴はいずれも直鎖状および分岐状のいずれも選択できる。
【００６０】
かかる好適な４級アンモニウムイオンの例としては、ジメチルジオクチルアンモニウム、ジメチルジデシルアンモニウム、ジメチルジドデシルアンモニウム、ジメチルジテトラデシルアンモニウム、ジメチルジヘキサデシルアンモニウム、ジエチルジドデシルアンモニウム、ジエチルジテトラデシルアンモニウム、ジエチルジヘキサデシルアンモニウム、ジブチルジオクチルアンモニウム、ジブチルジデシルアンモニウム、ジブチルジドデシルアンモニウム等が例示される。
【００６１】
Ｂ成分の層状珪酸塩は、ＳｉＯ₂連鎖からなるＳｉＯ₄四面体シート構造とＡｌ、Ｍｇ、Ｌｉ等を含む八面体シート構造との組み合わせからなる層からなり、その層間に交換性陽イオンの配位した珪酸塩（シリケート）または粘土鉱物（クレー）である。これらの珪酸塩（シリケート）または粘土鉱物（クレー）は、スメクタイト系鉱物、バーミキュライト、ハロイサイトおよび膨潤性雲母等に代表される。具体的には、スメクタイト系鉱物としては、モンモリロナイト、ヘクトライト、フッ素ヘクトライト、サポナイト、バイデライト、スチブンサイト等が挙げられ、膨潤性雲母としては、Ｌｉ型フッ素テニオライト、Ｎａ型フッ素テニオライト、Ｎａ型四珪素フッ素雲母、Ｌｉ型四珪素フッ素雲母等の膨潤性合成雲母等が挙げられる。これら層状珪酸塩は天然品および合成品のいずれも使用可能である。合成品は、例えば、水熱合成、溶融合成、固体反応によって製造される。
【００６２】
層状珪酸塩のなかでも、陽イオン交換容量等の点から、モンモリロナイト、ヘクトライト等のスメクタイト系粘土鉱物、Ｌｉ型フッ素テニオライト、Ｎａ型フッ素テニオライト、Ｎａ型四珪素フッ素雲母等の膨潤性を持ったフッ素雲母が好適に用いられ、ベントナイトを精製して得られるモンモリロナイトや合成フッ素雲母が、純度等の点からより好適である。なかでも、良好な機械特性が得られる合成フッ素雲母が特に好ましい。
【００６３】
前記Ｂ成分である層状珪酸塩の陽イオン交換容量（陽イオン交換能ともいう）は、５０〜２００ミリ当量／１００ｇであることが必要とされ、好ましくは８０〜１５０ミリ当量／１００ｇ、さらに好ましくは１００〜１５０ミリ当量／１００ｇである。陽イオン交換容量は、土壌標準分析法として国内の公定法となっているショーレンベルガー改良法によってＣＥＣ値として測定される。すなわち、層状珪酸塩の陽イオン交換容量は、Ａ成分である非晶性熱可塑性樹脂への良好な分散性を得るために、５０ミリ当量／１００ｇ以上必要であるが、２００ミリ当量／１００ｇより大きくなると熱可塑性樹脂組成物（特に芳香族ポリカーボネート樹脂組成物）の熱劣化が大きくなり、それに伴って本発明の非晶性熱可塑性樹脂組成物の熱劣化への影響が大きくなってくる。この層状珪酸塩は、そのｐＨの値が９〜１０．５であることが好ましい。ｐＨの値が１０．５より大きくなると、本発明の熱可塑性樹脂組成物の熱安定性が低下する傾向が現れてくる。
【００６４】
層状珪酸塩への有機オニウムイオンのイオン交換は、極性溶媒中に分散させた層状珪酸塩に、有機オニウムイオン化合物（有機オニウムイオンの塩化合物）を添加し、析出してくるイオン交換化合物を収集することによって作成することができる。通常、このイオン交換反応は、有機オニウムイオン化合物を、層状珪酸塩のイオン交換容量の１当量に対し１．０〜１．５当量の割合で加えて、ほぼ全量の層間の金属イオンを有機オニウムイオンで交換させるのが一般的である。しかし、このイオン交換容量に対する交換割合を一定の範囲に制御することも、芳香族ポリカーボネート樹脂の熱劣化を抑制する上で有効である。ここで有機オニウムイオンでイオン交換される割合は、層状珪酸塩のイオン交換容量に対して４０％以上であることが好ましい。かかるイオン交換容量の割合は好ましくは４０〜９５％であり、特に好ましくは４０〜８０％である。ここで、有機オニウムイオンの交換割合は、交換後の化合物について、熱重量測定装置等を用いて、有機オニウムイオンの熱分解による重量減少を求めることにより算出することができる。
【００６５】
本発明の層状珪酸塩（Ｂ成分）のＸ線回折より求められるシリケート層の平均積層数は５〜４０（特徴Ａ）であり、好ましくは５〜３０、より好ましくは５〜２０、最も好ましくは５〜１５である。平均積層数が５未満であると熱可塑性樹脂組成物の熱安定性が低下する場合があり、４０を超えると剛性向上効果が低減する。
【００６６】
芳香族ポリカーボネート樹脂などの非晶性熱可塑性樹脂に層状珪酸塩を微分散させた熱可塑性樹脂組成物は、従来単に有機化層状珪酸塩などを層間部分で剥離させ、基体樹脂中において出来る限り微分散させることを課題としていた。しかし、分散が進みすぎると返って剛性向上効果が減少し、また熱安定性等が悪化する。そこで剛性向上や熱安定性の保持のために、本発明の適度な分散状態を必要とした。
【００６７】
本発明の層状珪酸塩（Ｂ成分）の熱可塑性樹脂組成物中の層状珪酸塩の底面間隔は、１．３〜２．３ｎｍ（特徴Ｂ）であり、より好ましくは１．５〜２．３ｎｍ、最も好ましくは１．８〜２．３ｎｍである。この底面間隔を得るためには、有機化層状珪酸塩を用いることが好ましい。底面間隔が、１．３ｎｍ未満であると剛性向上効果が不十分になることがあり、２．３ｎｍを超えると熱可塑性樹脂組成物の熱安定性が低下する場合がある。
【００６８】
上記の特徴Ｂは、Ｘ線回折測定における回折線の回折角度からＢｒａｇｇの条件により求められる。層状珪酸塩の底面間隔およびＸ線回折測定については、たとえば「粘土ハンドブック」（日本粘土学会編：技報堂出版）などに記載されている。有機化層状珪酸塩のＸ線回折測定を行うには、粉末状の試料を試料台に充填して測定することができ、また組成物中の層状珪酸塩のＸ線回折測定を行うには、組成物を例えば射出成形や押出成形などで平板に成形した後、平面部分を試料台開口部に、測定基準面と同一になるよう試料を設置し測定することができる。
【００６９】
本発明の熱可塑性樹脂組成物は、層状珪酸塩を微分散させる、すなわち上記特徴Ａ、更に特徴Ｂを兼ね備えることにより、良好な剛性を有し、良好な耐加水分解性を有し、更に良好な熱安定性を有する熱可塑性樹脂組成物を得るに至ったものである。
【００７０】
本発明における上記特徴Ａまたは特徴Ｂを達成する方法としては例えば次の方法が例示される。▲１▼特定範囲の陽イオン交換容量を有する層状珪酸塩を用いる、▲２▼多軸押出機を用いて拡散効率の高い溶融混練を行う、▲３▼特定の有機化層状珪酸塩を用いる、▲４▼非晶性樹脂と層状珪酸塩との相溶化剤（Ｃ成分等の第３成分）を配合する、▲５▼層状珪酸塩のマスターバッチを用いる等の方法があげられ、これらを組合せて用いることができ、殊に▲１▼〜▲４▼を組み合わせること、殊に好適には▲１▼〜▲５▼を組み合わせることが好ましい。
【００７１】
上記▲４▼の方法における第３成分としては、Ａ成分の非晶性熱可塑性樹脂と親和性を有し、かつ親水性成分を有する化合物が好適である。したがって本発明はより好適には、更にＡ成分１００重量部あたり、（Ｃ）Ａ成分の非晶性熱可塑性樹脂との親和性を有しかつ親水性成分を有する化合物（Ｃ成分）０．１〜５０重量部を含んでなる熱可塑性樹脂組成物を挙げることができる。
【００７２】
本発明で用いられるＢ成分の層状珪酸塩の、Ａ成分との組成割合は、Ａ成分１００重量部あたり０．１〜５０重量部、好ましくは０．５〜２０重量部、更に好ましくは０．５〜１０重量部である。この組成割合が０．１重量部より小さいときには芳香族ポリカーボネート樹脂など非晶性熱可塑性樹脂の機械特性の改良効果が見られず、また５０重量部より大きくなると、組成物の熱安定性が低下し実用的な熱可塑性樹脂組成物は得られにくい。
【００７３】
＜Ｃ成分について＞
本発明のＣ成分は、非晶性熱可塑性樹脂（Ａ成分）との親和性を有し、かつ親水性成分を有する化合物である。Ｃ成分のかかる構成は、非晶性熱可塑性樹脂および層状珪酸塩、殊に有機化層状珪酸塩の双方に対する良好な親和性を生み出す。非晶性熱可塑性樹脂および層状珪酸塩、殊に有機化層状珪酸塩双方に対する親和性は２種の成分の相溶性を向上させ、層状珪酸塩は非晶性熱可塑性樹脂中での微細かつ安定して分散するようになる。
【００７４】
有機化層状珪酸塩の分散に関するかかるＣ成分の働きは、異種ポリマー同士を相溶化させるために使用されるポリマーアロイ用相溶化剤（コンパティビライザー）と同様である。したがってＣ成分は低分子化合物よりも単量体が重合してなる重合体であることが好ましい。また重合体は混練加工時の熱安定性にも優れる。重合体の平均繰り返し単位数は２以上であることが必要であり、５以上が好ましく、１０以上がより好ましい。一方、重合体の平均分子量の上限においては数平均分子量で２，０００，０００以下であることが好ましい。かかる上限を超えない場合には良好な成形加工性が得られる。
【００７５】
本発明のＣ成分の基本的構造としては、例えば次の構造（ｉ）および（ｉｉ）を挙げることができる。
【００７６】
構造（ｉ）：非晶性熱可塑性樹脂に親和性を有する成分をα、親水性成分をβとするとき、αとβとからなるグラフト共重合体（主鎖：α、グラフト鎖：β、並びに主鎖：β、グラフト鎖：αのいずれも選択できる。）、αとβとからなるブロック共重合体（ジ−、トリ−、などブロックセグメント数は２以上を選択でき、ラジアルブロックタイプなどを含む。）、並びにαとβとからなるランダム共重合体。α、βはそれぞれ単一の重合体だけでなく共重合体であってもよい。
【００７７】
ここでαおよびβは重合体セグメント単位、および単量体単位のいずれも示す。α成分は非晶性熱可塑性樹脂との親和性の観点から重合体セグメント単位であることが好ましい。
【００７８】
構造（ｉｉ）：非晶性熱可塑性樹脂に親和性を有する成分をα、親水性成分をβとするとき、αの機能は重合体全体によって発現され、βは該α内に含まれる構造を有する重合体。
【００７９】
すなわちα単独では非晶性熱可塑性樹脂との親和性が十分ではないものの、αとβが組み合わされ一体化されることにより、非晶性熱可塑性樹脂との良好な親和性が発現する場合である。α単独の場合にも非晶性熱可塑性樹脂との親和性が良好であって、βとの組合せによって更に親和性が向上する場合もある。かかる態様は上記構造（ｉ）に含まれる。したがって構造（ｉ）および（ｉｉ）はその一部を重複する。一方、構造（ｉ）はα単独では非晶性熱可塑性樹脂との親和性が十分ではあるが、αとβが組み合わされ一体化されることにより、非晶性熱可塑性樹脂との良好な親和性が逆に低下する態様もあり得る。当然のことながらかかる態様はＣ成分に含まれる。
【００８０】
上記構造（ｉ）および（ｉｉ）は本発明においていずれも選択できる。殊に構造（ｉ）の条件および構造（ｉｉ）の条件を共に満足する態様、すなわちαのみでも非晶性熱可塑性樹脂に対する親和性が高く、βが付加したＣ成分全体において更にその親和性が高くなる態様が好適である。
【００８１】
本発明における非晶性熱可塑性樹脂に親和性を有する成分（以下、上記に従いαと称する場合がある）について説明する。上記の如くＣ成分は、ポリマーアロイにおける相溶化剤との同様の働きをすることから、αには相溶化剤と同様の重合体に対する親和性が求められる。したがってαは大きく非反応型と反応型とに分類できる。
【００８２】
非反応型では、以下の要因を有する場合に親和性が良好となる。即ち、非晶性熱可塑性樹脂とαとの間に、▲１▼化学構造の類似性、▲２▼溶解度パラメータの近似性（溶解度パラメータの差が１（ｃａｌ／ｃｍ³）^1/2以内、即ち約２．０５（ＭＰａ）^1/2以内が目安とされる）、▲３▼分子間相互作用（水素結合、イオン間相互作用など）、およびランダム重合体特有の擬引力的相互作用などの要因を有することが必要である。これらの要因は相溶化剤とポリマーアロイのベースになる重合体との親和性を判断する指標として知られている。
【００８３】
また反応型では、相溶化剤において非晶性熱可塑性樹脂と反応性を有する官能基として知られた各種を挙げることができる。例えば非晶性熱可塑性樹脂として好適な芳香族ポリカーボネート樹脂に対しては、カルボキシル基、カルボン酸無水物基、エポキシ基、オキサゾリン基、エステル基、エステル結合、カーボネート基、およびカーボネート結合などを例示することができる。
【００８４】
一方で、非晶性熱可塑性樹脂とαが良好な親和性を得た場合、その結果として非晶性熱可塑性樹脂とαとの混合物において単一のガラス転移温度（Ｔｇ）を示すか、または非晶性熱可塑性樹脂のＴｇがαのＴｇの側に移動する挙動が認められることも広く知られるところである。本発明において親和性を有する成分（α）として、かかる挙動を有する成分をその態様の１つとして挙げることができる。
【００８５】
上記の如く、本発明のＣ成分における非晶性熱可塑性樹脂と親和性を有する成分（α）は、各種の要因によりその親和性を発揮することが可能である。中でもαは非反応型であることが好ましく、殊に溶解度パラメータが近似することは、良好な親和性を発揮するので好ましい。これは反応型に比較して非晶性熱可塑性樹脂との親和性により優れるためである。また反応型は過度に反応性を高めた場合、副反応によって重合体の熱劣化が促進される欠点がある。
【００８６】
非晶性熱可塑性樹脂およびαの溶解度パラメータは次の関係を有することが好ましい。即ち、非晶性熱可塑性樹脂（Ａ成分）の溶解度パラメータをδ_A（（ＭＰａ）^1/2）、およびＣ成分におけるαの溶解度パラメータまたはＣ成分全体の溶解度パラメータをδα（（ＭＰａ）^1/2）としたとき、
δα＝δ_A±２ （（ＭＰａ）^1/2）
であることが好ましい。
【００８７】
例えば、Ａ成分として好適な芳香族ポリカーボネート樹脂の溶解度パラメータは通常約１０（ｃａｌ／ｃｍ³）^1/2（即ち約２０．５（（ＭＰａ）^1/2））とされていることから、かかるＡ成分におけるδαは１８．５〜２２．５（（ＭＰａ）^1/2）の範囲が好ましく、１９〜２２（（ＭＰａ）^1/2）の範囲がより好ましい。
【００８８】
例えばＡ成分として好適な芳香族ポリカーボネート樹脂におけるかかる溶解度パラメータδαを満足する重合体成分の具体例は、芳香族ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、およびシクロヘキサンジメタノール共重合ポリエチレンテレフタレートなどに代表される）、および脂肪族ポリエステル（ポリカプロラクトンに代表される）などのポリエステル系重合体が挙げられる。またかかる具体例としては、スチレンポリマー、アルキル（メタ）アクリレートポリマー、およびアクリロニトリルポリマー（ポリスチレン、スチレン−無水マレイン酸共重合体、ポリメチルメタクリレート、スチレン−メチルメタクリレート共重合体、およびスチレン−アクリロニトリル共重合体などに代表される）などのビニル系重合体を挙げることができる。本発明の組成物の耐熱性の保持のためには、Ｔｇの高い重合体成分を用いることが好ましい。
【００８９】
ここで溶解度パラメータは、「ポリマーハンドブック 第４版」（Ａ ＷＩＬＥＹ−ＩＮＴＥＲＳＣＩＥＮＣＥ ＰＵＢＬＩＣＡＴＩＯＮ，１９９９年）中に記載されたＳｍａｌｌの値を用いた置換基寄与法（Ｇｒｏｕｐ ｃｏｎｔｒｉｂｕｔｉｏｎ ｍｅｔｈｏｄｓ）による理論的な推算方法が利用できる。また非晶性熱可塑性樹脂のＴｇはＪＩＳ Ｋ７１２１に準拠した示差走査熱量計（ＤＳＣ）測定により求めることが可能である。
【００９０】
上記のＡ成分の非晶性熱可塑性樹脂に親和性を有する成分αは、Ｃ成分中５重量％以上であることが好ましく、１０重量％以上がより好ましく、３０重量％以上が更に好ましく、５０重量％以上が特に好ましい。Ｃ成分全体をαとする態様も可能であることから上限は１００重量％であってよい。
【００９１】
一方、Ｃ成分における親水性成分（以下、βと称する場合がある）は、親水基（水との相互作用の強い有機性の原子団）を有する単量体及び親水性重合体成分（重合体セグメント）より選択される。親水基はそれ自体広く知られ、下記の基が例示される。
１）強親水性の基：−ＳＯ₃Ｈ、−ＳＯ₃Ｍ、−ＯＳＯ₃Ｈ、−ＯＳＯ₃Ｈ、−ＣＯＯＭ、−ＮＲ₃Ｘ（Ｒ：アルキル基、Ｘ：ハロゲン原子、Ｍ：アルカリ金属、−ＮＨ₄） 等、
２）やや小さい親水性を有する基：−ＣＯＯＨ、−ＮＨ₂、−ＣＮ、−ＯＨ、−ＮＨＣＯＮＨ₂ 等、
３）親水性が無いか又は小さい基：−ＣＨ₂ＯＣＨ₃、−ＯＣＨ₃、−ＣＯＯＣＨ₃、−ＣＳ 等
上記１）〜３）の群の中で本発明における親水基は１）および２）に分類されるものが使用される。上記の例示以外にも、１）強親水性の基としてはスルフィン基などが例示され、２）あまり親水性の強くない基としては、カルボン酸無水物基、オキサゾリン基、ホルミル基およびピロリドン基などが例示される。
【００９２】
上記２）の親水基は非晶性熱可塑性樹脂、殊に本発明において好適な芳香族ポリカーボネート樹脂の溶融加工時の熱安定性により優れるため好ましい。親水性が高すぎる場合には芳香族ポリカーボネート樹脂などの熱劣化が生じやすくなる。これはかかる親水基が直接カーボネート結合と反応し、熱分解反応を生じるためである。
【００９３】
尚、本発明の親水基は１価および２価以上のいずれも含む。Ｃ成分が重合体の場合、２価以上の官能基とは該基が主鎖を構成しないものをを指し、主鎖を構成するものは結合として官能基とは区別する。具体的には、主鎖を構成する炭素などの原子に付加した基、側鎖の基、および分子鎖末端の基は、２価以上であっても官能基である。
【００９４】
親水基のより具体的な指標は、溶解度パラメータである。溶解度パラメータの値が大きいほど親水性が高くなることは広く知られている。基ごとの溶解度パラメータは、Ｆｅｄｏｒｓによる基ごとの凝集エネルギー（Ｅ_coh）および基ごとのモル体積（Ｖ）より算出することができる（「ポリマー・ハンドブック 第４版」（Ａ ＷＩＬＥＹ−ＩＮＴＥＲＳＣＩＥＮＣＥ ＰＵＢＬＩＣＡＴＩＯＮ），ＶＩＩ／６８５頁、１９９９年、またはＰｏｌｙｍ．Ｅｎｇ．Ｓｃｉ．，第１４巻，１４７および４７２頁，１９７４年等参照）。かかる算出方法は簡便であり広く知られる。更に親水性の大小関係のみを比較する観点からは、凝集エネルギー（Ｅ_coh）をモル体積（Ｖ）で除した数値（Ｅ_coh／Ｖ；以下単位は“Ｊ／ｃｍ³”とする）を親水性の指標として使用できる。
【００９５】
本発明のＣ成分におけるβに含まれる親水基は、Ｅ_coh／Ｖが６００以上であることが必要である。好ましくはＥ_coh／Ｖは８００以上であり、８００以上の場合には本発明のＡ成分として好適な芳香族ポリカーボネート樹脂におけるカーボネート結合のＥ_coh／Ｖを超え、カーボネート結合よりも高い親水性を有する。更にＥ_coh／Ｖは９００以上がより好ましく、９５０以上が更に好ましい。一方、親水性が高すぎる場合には、既に述べたように芳香族ポリカーボネート樹脂の熱劣化が生じ易くなる。このため、Ｅ_coh／Ｖは２，５００以下が好ましく、２，０００以下がより好ましく、１，５００以下がさらに好ましい。
【００９６】
Ｃ成分の親水性成分（β）として、親水性重合体成分（重合体セグメント）も選択される。したがってＣ成分の重合体中に含まれる親水性重合体のセグメントはβとなる、親水性重合体としては、例えばポリアルキレンオキシド、ポリビニルアルコール、ポリアクリル酸、ポリアクリル酸金属塩（キレート型を含む）、ポリビニルピロリドン、ポリアクリルアミド、およびポリヒドロキシエチルメタクリレートなどが例示される。これらの中でもポリアルキレンオキシド、ポリビニルアルコール、ポリアクリル酸、ポリビニルピロリドン、およびポリヒドロキシエチルメタクリレートが好ましく例示される。これらは良好な親水性と本発明において好適な芳香族ポリカーボネート樹脂に対する熱安定性（溶融加工時の芳香族ポリカーボネート樹脂の分解の抑制）とを両立できるためである。尚、ポリアルキレンオキシドとしては、ポリエチレンオキシドおよびポリプロピレンオキシドが好ましい。
【００９７】
親水基を有する単量体および親水性重合体成分のいずれにおいても、βは酸性の官能基（以下単に“酸性基”と称する場合がある）を有することが好ましい。酸性基は本発明において好適な芳香族ポリカーボネート樹脂を主成分とする熱可塑性樹脂組成物の溶融加工時の熱劣化を抑制する。とりわけ、窒素原子を含まない酸性基がより好適である。好適な酸性基としては、カルボキシル基、カルボン酸無水物基、スルホン酸基、スルフィン酸基、ホスホン酸基及びホスフィン酸基等が例示される。
【００９８】
これに比して、アミド基やイミド基等の窒素原子を含む官能基は溶融加工時の芳香族ポリカーボネート樹脂の熱劣化を十分には抑制しない場合がある。これは窒素原子が局所的に塩基性を有しカーボネート結合の熱分解を生じさせるためと考えられる。
【００９９】
Ｃ成分におけるβの割合は、βが親水基を有する単量体の場合、官能基１つ当たりの分子量である官能基当量として６０〜１０，０００であり、７０〜８，０００が好ましく、８０〜６，０００がより好ましく、１００〜３，０００が更に好ましい。またβが親水性重合体セグメントの場合、Ｃ成分１００重量％中βが５〜９５重量％の範囲にあることが適当であり、１０〜９０重量％が好ましい。とりわけ、３０〜７０重量％がより好ましく、３０〜５０重量％が更に好ましい。
【０１００】
非晶性熱可塑性樹脂に親和性を有する成分（α）と親水性成分（β）とを有する化合物の製造方法としては、βの単量体とαを構成する単量体とを共重合する方法、βの重合体成分をαとブロックまたはグラフト共重合する方法、およびβをαに直接反応させて付加する方法などが例示される。
【０１０１】
本発明のＣ成分の好ましい態様として、“Ａ成分の樹脂との親和性を有しかつ酸性の官能基を有する重合体”、“Ａ成分の樹脂との親和性を有しかつポリアルキレンオキシドセグメントを有する重合体”、“Ａ成分の樹脂との親和性を有しかつオキサゾリン基を有する重合体”、または“Ａ成分の樹脂との親和性を有しかつ水酸基を有する重合体”が例示される。これらのＣ成分として好ましい態様の重合体においては、その分子量は重量平均分子量において１万〜１００万の範囲が好ましく、５万〜５０万の範囲がより好ましい。かかる重量平均分子量は標準ポリスチレン樹脂による較正直線を使用したＧＰＣ測定によりポリスチレン換算の値として算出されるものである。
【０１０２】
上記の中でもＡ成分の樹脂との（より好適には芳香族ポリカーボネート樹脂との）親和性を有しかつ酸性の官能基を有する重合体が好ましく、更に好ましくは芳香族ポリカーボネート樹脂との親和性を有しかつカルボキシル基及び／又はその誘導体からなる官能基とを有する重合体である。また、芳香族ポリカーボネート樹脂の耐熱性保持効果の観点から、重合体は芳香環成分を主鎖に有するもの、およびスチレン成分を主鎖に有するものが好ましい。上記の点からカルボキシル基及び／又はその誘導体からなる官能基を有するスチレン含有重合体（Ｃ１成分）が本発明のＣ成分として特に好適である。ここでスチレン含有重合体とはスチレン等の芳香族ビニル化合物を重合した繰返し単位を重合体成分として含有する重合体を指す。
【０１０３】
本発明のＣ成分として特に好適なカルボキシル基及び／又はその誘導体からなる官能基を有するスチレン含有重合体（Ｃ１成分）について詳述する。かかるカルボキシル基及び／又はその誘導体からなる官能基の割合としては、０．１〜１２ミリ当量／ｇが好ましく、０．５〜５ミリ当量／ｇがより好ましい。ここでＣ１成分における１当量とは、カルボキシル基が１モル存在することをいい、かかる値は水酸化カリウムなどの逆滴定により算出することが可能である。
【０１０４】
カルボキシル基の誘導体からなる官能基としては、カルボキシル基の水酸基を（ｉ）金属イオンで置換した金属塩（キレート塩を含む）、（ｉｉ）塩素原子で置換した酸塩化物、（ｉｉｉ）−ＯＲで置換したエステル（Ｒは一価の炭化水素基）、（ｉｖ）−Ｏ（ＣＯ）Ｒで置換した酸無水物（Ｒは一価の炭化水素基）、（ｖ）−ＮＲ₂で置換したアミド（Ｒは水素又は一価の炭化水素基）、並びに（ｖｉ）２つのカルボキシル基の水酸基を＝ＮＲで置換したイミド（Ｒは水素又は一価の炭化水素基）などを挙げることができる。
【０１０５】
カルボキシル基及び／又はその誘導体からなる官能基（以下、単に“カルボキシル基類”と称する）を有するスチレン含有重合体の製造方法としては、従来公知の各種の方法を取ることができる。例えば、▲１▼カルボキシル基類を有する単量体とスチレン系単量体とを共重合する方法、及び▲２▼スチレン含有重合体に対してカルボキシル基類を有する化合物又は単量体を結合または共重合する方法などを挙げることができる。
【０１０６】
上記▲１▼の共重合においては、ランダム共重合体の他に交互共重合体、ブロック共重合体、テーパード共重合体などの各種形態の共重合体が使用できる。また共重合の方法においても溶液重合、懸濁重合、塊状重合などのラジカル重合法の他、アニオンリビング重合法やグループトランスファー重合法などの各種重合方法を取ることができる。更に一旦マクロモノマーを形成した後重合する方法も可能である。
【０１０７】
上記▲２▼の方法は、一般的にはスチレン含有重合体又は共重合体に必要に応じて、パーオキサイドや２，３−ジメチル−２，３ジフェニルブタン（ジクミル）などのラジカル発生剤を加えて、高温化で反応又は共重合する方法を挙げることができる。かかる方法はスチレン含有重合体または共重合体に熱的に反応活性点を生成し、かかる活性点に反応する化合物または単量体を反応させるものである。反応に要する活性点を生成するその他の方法として、放射線や電子線の照射やメカノケミカル手法による外力の付与などの方法も挙げられる。更にスチレン系共重合体中に予め反応に要する活性点を生成する単量体を共重合しておく方法も挙げられる。反応のための活性点としては不飽和結合、パーオキサイド結合、および立体障害が高く熱的に安定なニトロオキシドラジカルなどを挙げることができる。
【０１０８】
上記カルボキシル基類を有する化合物又は単量体としては、例えば、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド等の不飽和モノカルボン酸及びその誘導体、無水マレイン酸、無水シトラコン酸、Ｎ−フェニルマレイミド、Ｎ−メチルマレイミド等の無水マレイン酸の誘導体、並びにグルタルイミド構造やアクリル酸と多価の金属イオンで形成されたキレート構造等が挙げられる。これらの中でも金属イオンや窒素原子を含まない官能基を有する単量体が好適であり、カルボキシル基およびカルボン酸無水物基を有する単量体がより好適である。これらの中でも特に好ましくは無水マレイン酸である。
【０１０９】
また、スチレン系単量体化合物としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｔｅｒｔ−ブチルスチレン、α−メチルビニルトルエン、ジメチルスチレン、クロルスチレン、ジクロルスチレン、ブロムスチレン、ジブロムスチレン、ビニルナフタレン等を用いることができるが、特にスチレンが好ましい。
【０１１０】
さらに、これらの化合物と共重合可能な他の化合物、例えばアクリロニトリル、メタクリロニトリル等を共重合成分として使用しても差し支えない。
【０１１１】
本発明におけるＣ成分として好ましいものは、カルボキシル基類を有する単量体を共重合してなるスチレン含有共重合体である。かかる共重合体においては比較的多くのカルボキシル基類を安定してスチレン含有重合体中に含むことが可能となるためである。より好適な態様としてカルボキシル基類を有する単量体とスチレン系単量体とを共重合してなるスチレン含有共重合体を挙げることができる。そして殊に好適な態様はスチレン−無水マレイン酸共重合体である。スチレン−無水マレイン酸共重合体は、層状珪酸塩中のイオン成分及び芳香族ポリカーボネート樹脂のいずれに対しても高い相溶性を有することから、層状珪酸塩（Ｂ成分）を良好に微分散させる。さらに、カルボン酸無水物基の作用により層状珪酸塩、殊に有機化層状珪酸塩を含有する樹脂組成物において良好な熱安定性が得られる。またかかる共重合体それ自体の熱安定性が良好であるため、芳香族ポリカーボネート樹脂の溶融加工に必要な高温条件に対しても高い安定性を有する。
【０１１２】
上記カルボキシル基類を有する単量体を共重合してなるスチレン含有共重合体の組成については上述のβの割合における条件を満足する限り制限されないが、カルボキシル基類を有する単量体からの成分を１〜３０重量％（特に５〜２５重量％）、スチレン系単量体化合物成分９９〜７０重量％（特に９５〜７５重量％）を含み、共重合可能な他の化合物成分を０〜２９重量％を含むものを用いるのが好ましく、カルボキシル基類を有する単量体を１〜３０重量％（特に５〜２５重量％）、スチレン系単量体化合物９９〜７０重量％（特に９５〜７５重量％）含む共重合体が特に好ましい。
【０１１３】
また、本発明のＣ成分の好ましい態様であるＣ１成分の分子量は特に制限されない。Ｃ１成分の重量平均分子量は１万〜１００万の範囲にあることが好ましく、５万〜５０万の範囲がより好ましい。尚、ここで示す重量平均分子量は、標準ポリスチレン樹脂による較正直線を使用したＧＰＣ測定によりポリスチレン換算の値として算出されたものである。
【０１１４】
本発明のＣ成分として好適なポリアルキレンオキシドセグメントを有する重合体、殊に好ましいポリエーテルエステル共重合体（Ｃ２成分）について説明する。
【０１１５】
ポリエーテルエステル共重合体は、ジカルボン酸、アルキレングリコール、およびポリ（アルキレンオキシド）グリコール、並びにこれらの誘導体から重縮合を行うことで製造される重合体である。殊に好適な例としては、下記式（ＩＩ）で示されるポリアルキレンオキシド単位を有するポリ（アルキレンオキシド）グリコールあるいはその誘導体（Ｃ２▲１▼成分）、テトラメチレングリコールを６５モル％以上含有するアルキレングリコールあるいはその誘導体（Ｃ２▲２▼成分）、およびテレフタル酸を６０モル％以上含有するジカルボン酸あるいはその誘導体（Ｃ２▲３▼成分）から製造される共重合体である。
【０１１６】
【化２】

【０１１７】
（ここで、Ｘは一価の有機基を表し、ｎおよびｍはいずれも０を含む整数であり、かつ１０≦（ｎ＋ｍ）≦１２０である。ｍが２以上の場合Ｘは互いに同一および異なる態様のいずれも選択できる。）
上記式（ＩＩ）においてＸは−ＣＨ₃、−ＣＨ₂Ｃｌ、−ＣＨ₂Ｂｒ、−ＣＨ₂Ｉ、および−ＣＨ₂ＯＣＨ₃から選択される少なくとも１種の置換基が好ましい。Ｘがこれら以外の場合には置換基による立体障害が大きくなり共重合体の重合度を上げることが困難となる。またｎ＋ｍが１０未満の場合には層状珪酸塩が十分に分散しない場合があり、ｎ＋ｍが１２０を超える場合には、重合度の高いポリエーテルエステル共重合体が得られ難くなり、Ｃ２成分の相溶化機能が低下する場合がある。
【０１１８】
上記式（ＩＩ）におけるポリアルキレンオキシド成分は、ポリエチレンオキシド成分と置換基Ｘを有する成分とのランダム共重合体、テーパード共重合体およびブロック共重合体のいずれも選択できる。上記式（ＩＩ）におけるポリアルキレンオキシドは、特にｍ＝０、すなわちポリエチレンオキシド成分のみからなる重合体成分が好ましい。
【０１１９】
Ｃ２▲１▼成分の共重合割合は、全グリコール成分の３０〜８０重量％であり、より好適には４０〜７０重量％である。Ｃ２▲１▼成分が３０重量％より少ない場合には層状珪酸塩は十分に分散されず、機械特性の低下や外観の悪化を生ずる場合がある。Ｃ２▲１▼成分が８０重量％より多い場合にも層状珪酸塩は十分に分散されず、またポリエーテルエステル共重合体自身の強度低下も加わることで、機械特性の低下や外観の悪化を生ずる場合がある。
【０１２０】
Ｃ２成分のポリエーテルエステル共重合体のＣ２▲２▼成分においては、テトラメチレングリコール以外のジオールを共重合することができる。かかるジオールとしては、エチレングリコール、トリメチレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノールが例示される。Ｃ２▲２▼成分中テトラメチレングリコールは６５モル％以上であり、７５モル％以上が好ましく、８５モル％以上がより好ましい。テトラメチレングリコールが６５モル％未満のポリエーテルエステル共重合体は、熱可塑性樹脂組成物の成形性の低下を招く。
【０１２１】
ポリエーテルエステル共重合体のジカルボン酸あるいはその誘導体（Ｃ２▲３▼成分においては、テレフタル酸以外のジカルボン酸（カルボキシル基が２を超えるものを含む）を共重合することができる。かかるジカルボン酸としては、イソフタル酸、フタル酸、アジピン酸、セバシン酸、アゼライン酸、ドデカン二酸、トリメリット酸、ピロメリット酸、ナフタレンジカルボン酸、シクロヘキサンジカルボン酸が例示される。イソフタル酸を共重合したポリエーテルエステル共重合体はＣ成分として特に好適である。Ｃ２▲３▼成分中テレフタル酸は６０モル％以上であり、７０モル％以上が好ましく、７５〜９５モル％がより好ましい。テレフタル酸が６０モル％未満のポリエーテルエステル共重合体は、共重合体の重合度が低下しやすく、十分な重合度のポリエーテルエステル共重合体の製造が困難となるため好ましくない。
【０１２２】
他の好適なＣ成分としては、親水基としてオキサゾリン基を含有するスチレン含有共重合体が挙げられる。かかる共重合体を形成するスチレン系単量体化合物としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｔｅｒｔ−ブチルスチレン、α−メチルビニルトルエン、ジメチルスチレン、クロルスチレン、ジクロルスチレン、ブロムスチレン、ジブロムスチレン、ビニルナフタレン等を用いることができる。さらに、これらの化合物と共重合可能な他の化合物、例えばアクリロニトリル、メタクリロニトリル等、を共重合成分として使用しても差し支えない。中でも、特に好適なものとして、スチレン（２−イソプロペニル−２−オキサゾリン）−スチレン−アクリロニトリル共重合体が例示される。
【０１２３】
本発明のＣ成分の組成割合は、Ａ成分１００重量部あたり０．５〜５０重量部が好ましく、０．５〜２０重量部がより好ましい。０．５重量部より少ない場合には層状珪酸塩の分散効果が十分でなく、また芳香族ポリカーボネート樹脂の熱劣化を抑制する効果も不十分となる場合がある。また５０重量部を超えると耐衝撃性および耐熱性などが低下する場合がある。
【０１２４】
本発明の熱可塑性樹脂組成物には、本発明の効果を発揮する範囲で、Ｂ成分以外の強化充填材を更に配合することができる。強化充填材としては、ガラス繊維、炭素繊維、ガラスフレーク、ワラストナイト、カオリンクレー、マイカ、タルクおよび各種ウイスカー類（チタン酸カリウムウイスカー、ホウ酸アルミニウムウイスカーなど）といった一般に知られている各種フィラーを併用することができる。形状は繊維状、フレーク状、球状、中空状を自由に選択できる。ガラス繊維、炭素繊維およびガラスフレークなどは熱可塑性樹脂組成物の強度や耐衝撃性の向上のためには好適である。一方本発明の樹脂組成物が有する極めて良好な表面外観（表面平滑性）をより有効に活用する場合には、強化充填材の大きさは微小であることが好ましい。具体的には繊維状充填材の場合にはその繊維径が、また板状充填材や粒状充填材の場合にはその大きさが、５μｍ以下が好ましく、４μｍ以下がより好ましく、３μｍ以下が更に好ましい。下限は０．０５μｍ程度が適切である。かかる微小な強化充填材としてはタルク、ワラストナイト、カオリンクレー、および各種ウイスカー類が例示される。強化充填材の配合量は、全熱可塑性樹脂組成物１００重量％あたり５０重量％以下が適切であり、０．５〜５０重量％の範囲が好ましく、１〜３５重量％の範囲がより好ましい。かかる配合量が５０重量％を超えると、成形加工性が悪化し、本発明の効果が得られないため好ましくない。
【０１２５】
さらに本発明の目的を損なわない範囲で、他の熱可塑性樹脂（例えば、ポリアミド樹脂、ポリアセタール樹脂、芳香族ポリエステル樹脂、液晶ポリエステル樹脂、ポリオレフィン樹脂、シンジオタクチックポリスチレン樹脂およびポリフェニレンサルファイド樹脂等の結晶性熱可塑性樹脂）、難燃剤（例えば、臭素化エポキシ樹脂、臭素化ポリスチレン、臭素化ポリカーボネート、臭素化ポリアクリレート、モノホスフェート化合物、ホスフェートオリゴマー化合物、ホスホネートオリゴマー化合物、ホスホニトリルオリゴマー化合物、ホスホン酸アミド化合物、有機スルホン酸アルカリ（土類）金属塩、シリコーン系難燃剤等）、難燃助剤（例えば、アンチモン酸ナトリウム、三酸化アンチモン等）、滴下防止剤（フィブリル形成能を有するポリテトラフルオロエチレン等）、核剤（例えば、ステアリン酸ナトリウム、エチレン−アクリル酸ナトリウム等）、酸化防止剤（例えば、ヒンダ−ドフェノ−ル系化合物、イオウ系酸化防止剤等）、衝撃改良剤、紫外線吸収剤、光安定剤、離型剤、滑剤、着色剤（染料、無機顔料等）、および蛍光増白剤等を配合してもよい。これら各種の添加剤は、芳香族ポリカーボネート樹脂に配合する際の周知の配合量で利用することができる。
【０１２６】
本発明の熱可塑性樹脂組成物は、リン系熱安定剤を含むことが好ましい。かかるリン系熱安定剤としてはトリメチルホスフェート等のリン酸エステル、トリフェニルホスファイト、トリスノニルフェニルホスファイト、ジステアリルペンタエリスリト−ルジホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリト−ルジホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト、およびビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト等の亜リン酸エステル、並びにテトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト等の亜ホスホン酸エステルなど、芳香族ポリカーボネート樹脂のリン系熱安定剤として広く知られた化合物が好適に例示される。かかるリン系熱安定剤は全組成物１００重量％中０．００１〜１重量％を含むことが好ましく、０．０１〜０．５重量％を含むことがより好ましく、０．０１〜０．２重量％を含むことが更に好ましい。かかるリン系熱安定剤の配合によりさらに熱安定性が向上し良好な成形加工特性を得ることができる。
【０１２７】
本発明の熱可塑性樹脂組成物を製造するには、任意の方法が採用される。例えば各成分、並びに任意に他の成分を予備混合し、その後溶融混練し、ペレット化する方法を挙げることができる。予備混合の手段としては、ナウターミキサー、Ｖ型ブレンダー、ヘンシェルミキサー、メカノケミカル装置、押出混合機などを挙げることができる。予備混合においては場合により押出造粒器やブリケッティングマシーンなどにより造粒を行うこともできる。予備混合後、ベント式二軸押出機に代表される溶融混練機で溶融混練、およびペレタイザー等の機器によりペレット化する。溶融混練機としては他にバンバリーミキサー、混練ロール、恒熱撹拌容器などを挙げることができるが、ベント式二軸押出機に代表される多軸押出機が好ましい。かかる多軸押出機を用いることにより強力なせん断力で有機化層状珪酸塩は基体樹脂中に微分散させられる。一方その分散は層間を縮小させる作用が存在する下で行われることにより、層間のイオンの外部への露出は抑制される。結果して良好な分散と熱安定性とのより高度な両立が達成される。
【０１２８】
更に、本発明の熱可塑性樹脂組成物の溶融混練機による溶融混練において次の態様がより好適である。すなわち、５０〜２００ミリ当量／１００ｇの陽イオン交換能を有する層状珪酸塩（Ｂ成分）と、Ａ成分の非晶性熱可塑性樹脂との親和性を有しかつ親水性成分を有する化合物（Ｃ成分）、殊に好適にはカルボキシル基及び／又はその誘導体からなる官能基を有するスチレン含有重合体（Ｃ１成分）とを予め溶融混練しておく。その後該溶融混練物とＡ成分の非晶性熱可塑性樹脂、殊に好適には芳香族ポリカーボネート樹脂とを多軸押出機により溶融混練する。かかる溶融混練方法は非晶性熱可塑性樹脂の熱安定性を向上させるため好ましい。芳香族ポリカーボネート樹脂においてはその分子量低下が特に抑制されるため好ましい溶融混練方法である。これはＢ成分とＣ成分とが予め溶融混練されることによりＢ成分に対してＣ成分が十分に相互作用し、所定の効果が効率的に得られているためと考えられる。したがって本発明によれば上記Ｂ成分とＣ成分とを予め溶融混練した後に、該溶融混練物とＡ成分とを多軸押出機を用いて溶融混練してなる、本発明の樹脂組成物および該樹脂組成物の製造方法が提供される。
【０１２９】
より具体的には、例えば、（ｉ）Ｂ成分とＣ成分をベント式二軸押出機にて溶融混練しペレット化したものを、再度Ａ成分と溶融混練する方法や、（ｉｉ）Ｂ成分とＣ成分をベント式二軸押出機の主供給口より投入し、Ａ成分の一部または全部を二軸押出機の途中段階に設けられた供給口から、Ｂ成分とＣ成分が既に溶融混練された状態の中へ投入する方法などが挙げられる。これらＢ成分とＣ成分を予め溶融混練する方法においては、その溶融混練時に、Ａ成分の一部を含んでいても構わない。
【０１３０】
本発明の熱可塑性樹脂組成物は通常上記の如く製造されたペレットを射出成形して各種製品を製造することができる。かかる射出成形においては、通常の成形方法だけでなく、適宜目的に応じて、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、発泡成形（超臨界流体の注入によるものを含む）、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、サンドイッチ成形、および超高速射出成形などの射出成形法を用いて成形品を得ることができる。これら各種成形法の利点は既に広く知られるところである。また成形はコールドランナー方式およびホットランナー方式のいずれも選択することができる。
【０１３１】
また本発明の熱可塑性樹脂組成物は、押出成形により各種異形押出成形品、シート、フィルムなどの形で使用することもできる。またシート、フィルムの成形にはインフレーション法や、カレンダー法、キャスティング法なども使用可能である。更に特定の延伸操作をかけることにより熱収縮チューブとして成形することも可能である。また本発明の熱可塑性樹脂組成物を回転成形やブロー成形などにより中空成形品とすることも可能である。
【０１３２】
本発明の熱可塑性樹脂組成物は、良好な剛性を有し、良好な耐加水分解性を有し、更に良好な熱安定性を有する。したがって上記の如く得られた樹脂成形品は、実用上問題のない幅広い成形加工条件の下で製造され、かつ良好な剛性および良好な表面外観を有する。より具体的には本発明によれば、本発明の熱可塑性樹脂組成物より形成された樹脂成形品であって、その表面のＪＩＳ Ｂ０６０１に準拠して測定された算術平均粗さＲａの値が、０．１μｍ以下、かつＡＳＴＭ Ｄ７９０に準拠して測定された曲げ弾性率の値が、２，５００ＭＰａ以上であることを特徴とする樹脂成形品が提供され、かかる樹脂成形品はその工業的価値が更に高い。従来、樹脂成形品の曲げ弾性率を向上させるためには、繊維上強化材や無機充填材を配合するのが一般的であったが、その場合にはその表面粗さは顕著に低下し、上記のバランスをとることができるものが得られていなかったためである。
【０１３３】
樹脂成形品の算術表面粗さＲａの値は、より好ましくは０．０８μｍ以下であり、更に好ましくは０．０５μｍ以下である。かかる下限は成形を行う金型によるところが大きいが約０．００１μｍ程度が適切である。また、曲げ弾性率の値は、より好ましくは２，８００ＭＰａ以上であり、更に好ましくは３，０００ＭＰａ以上である。一方、その上限は８，０００ＭＰａが適切であり、７，０００ＭＰａが好ましく、６，０００ＭＰａがより好ましい。
【０１３４】
本発明の樹脂成形品には、表面改質を施すことにより、平滑性に優れた表面改質成形品を得ることができる。ここでいう表面改質とは、蒸着（物理蒸着、化学蒸着など）、メッキ（電気メッキ、無電解メッキ、溶融メッキなど）、塗装、コーティング、印刷などの樹脂成形品の表層上に新たな層を形成させるものであり、通常の芳香族ポリカーボネート樹脂に用いられる方法が適用できる。これら表面改質では、改質される樹脂成形品の表面平滑性が、改質後の表面性に大きな影響を与えるが、本発明の樹脂成形品を使用すると、表面平滑性に優れた成形品を得ることができる。一般にこれらの表面改質は、表面修飾や機能付与だけでなく、樹脂成形品の表面平滑性を高める目的で施されることもあり、表面平滑性が悪いと改質の厚さを大きくとる必要があるが、本発明の樹脂成形品では、薄い厚みにて効率よく改質することができる。すなわち、５０μｍ以下であることが本発明の効果が発揮され好ましい。更にかかる厚みは２０μｍ以下がより好ましく、５μｍ以下が更に好ましく、２μｍ以下が更に好ましい。下限値としては０．００１μｍ以上が適切である。更に、金属層または金属酸化物層を有しない樹脂成形品単体におけるＪＩＳ Ｂ０６０１に準拠して測定される算術平均粗さＲａの値に対して、かかるＲａの５００倍以内の厚みで表面改質を行うと、本発明の樹脂成形品の特長が生かされ、かかるＲａの２００倍以内の値の厚みであればより好ましく、１００倍以内は更に好ましく、５０倍以内は特に好ましい。本発明において好ましい表面改質方法は、蒸着、メッキなどの改質厚みの小さい手法である。
【０１３５】
本発明の熱可塑性樹脂組成物は、上記の特性を生かし樹脂材料として従来使用できなかった部品に用途展開が可能である。殊に従来ガラス成形品または金属の精密切削品でなければ達成できなかった極めて高い耐加水分解性と剛性が要求される用途に使用可能である。かかる用途としては例えば光学精密機器内に配されたミラー、レーザー式複写・印刷装置などに配されたポリゴンミラー、およびハードディスクなどが例示される。
【０１３６】
更に本発明の熱可塑性樹脂組成物は、各種電子・電気機器、ＯＡ機器、車両部品、機械部品、その他農業資材、漁業資材、搬送容器、包装容器、および雑貨などの各種用途にも有用である。本発明の熱可塑性樹脂組成物は成形加工性にも優れていることから、各種薄肉成形品にも好適であり、薄肉射出成形品の具体例としては、電池ハウジングなどの各種ハウジング成形品、鏡筒、メモリーカード、スピーカーコーン、ディスクカートリッジ、面発光体、マイクロマシン用機構部品、銘板、パソコンのハウジング、ＣＤやＤＶＤドライブのトレーやシャシー、複写機のトレーやシャシー、液晶装置の直下型バックライト用光拡散板（特に大型液晶表示装置（１５インチ以上の大型液晶テレビ）用直下型バックライト用光拡散板）およびＩＣカードなどが例示される。
【０１３７】
【実施例】
以下、実施例により本発明を詳述する。ただし、本発明はこれらに限定されるものではない。なお、実施例中の各種特性の測定は、以下の方法によった。原料は以下の原料を用いた。
（１）熱可塑樹脂組成物中の層状珪酸塩（無機分）の含有量
試験片を射出成形機（東芝機械（株）製：ＩＳ−１５０ＥＮ）によりシリンダー温度２６０℃、金型温度８０℃、成形サイクル４０秒で成形し、成形した試験片を切削してるつぼに入れて秤量し、６００℃まで昇温し、そのまま６時間保持した後で放冷し、るつぼに残った灰化残渣を秤量することで層状珪酸塩（無機分）の量を測定した。すなわち、樹脂組成物の曲げ弾性率（剛性）等の特性は無機分の割合によって影響されるため、各実施例および比較例２、３では、試験片中の無機分の割合を測定し、表１にＢ成分の無機分の割合（重量％）として表示した。
（２）熱可塑樹脂組成物中の層状珪酸塩のシリケート層の底面間隔および平均積層数
粉末Ｘ銭回折装置（ＲＩＧＡＫＵ ＲＯＴＡＦＬＥＸ ＲＵ３００：（株）リガク製）を用いて測定を行った。厚み６．４ｍｍの棒状試験片を（１）と同条件にて成形し、長さ２０ｍｍに切断した測定成形品を、試料台の開口部に測定基準面と同一面になるように固定して測定に供した。測定によって得られた回折ピークは層状珪酸塩の底面ピークであるが、そのうち、最も小角側の回折ピークが（００１）面の底面間隔に対応するピークであるとして、下記Ｂｒａｇｇの式により底面間隔を算出した。
ｄ＝λ／（２ｓｉｎθ）
（但し、式中 ｄ：底面間隔（層間距離）（ｎｍ）、２θ：回折ピークの回折角度（°）、λ：Ｘ線測定波長（ｎｍ））
更に、下記式から平均積層数（Ｎ）を求めた。
Ｎ＝（Ｄ／ｄ）＋１
（但し、式中 Ｎ：積層数（枚）、Ｄ：積層厚み（ｎｍ）、ｄ：底面間隔（ｎｍ））
Ｄ＝０．９＊λ／（βｃｏｓΘ）
（但し、式中 Ｄ：積層厚み（ｎｍ）、λ：Ｘ線測定波長（ｎｍ）、β：半値幅（ｒａｄ）、２Θ：回折ピークの回折角度（ｒａｄ）、ここで半値幅は回折ピークの最大値Ｉ₀の１／２の高さにおける２Θ（ｒａｄ）の幅であり、回折ピークの回折角度とはピークの最大値Ｉ₀部分での２Θの値を指す）
尚、測定の条件については以下に示す。
Ｘ−ｒａｙ ｓｏｕｒｃｅ：Ｃｕ−Ｋα（Ｘ線測定波長１．５４１８×１０^-10ｍ）、５０ｋＶ−２００ｍＡ
Ｓｌｉｔ：ＤＳ／ＳＳ １／２°
Ｒｓ ０．１５ｍｍ−ｇｒａｐｈｉｔｅ ｍｏｎｏｃｈｒｏｍｅｔｅｒ−０．４５ｍｍ
Ｍｅｔｈｏｄ：２θ−θ
Ｓｃａｎ：０．０５ｓｔｅｐ／１〜４ｓｅｃ
Ｓｃａｎ範囲：１〜２０°
【０１３８】
（３）熱可塑性樹脂組成物における粘度平均分子量
試験片を上記（１）と同条件で成形し、試験片の粘度平均分子量を本文中記載の方法にて測定した。
（４）曲げ弾性率
前記（１）と同条件で成形した同形状の試験片（寸法：長さ１２７ｍｍ×幅１２．７ｍｍ×厚み６．４ｍｍ）を、温度２３℃および相対湿度５０％ＲＨの雰囲気下においてＡＳＴＭ−Ｄ７９０に準拠の方法により曲げ弾性率（ＭＰａ）を測定した。この数値が大きいほど成形した樹脂組成物の剛性が優れていることを意味する。
（５）高温高湿試験後の粘度平均分子量の低下率（ΔＭ_ratio）
前記（１）と同条件で成形した同形状の試験片（寸法：長さ１２７ｍｍ×幅１２．７ｍｍ×厚み６．４ｍｍ）を温度１０５℃、相対湿度１００％のプレッシャークッカーに１０時間放置して処理した後、温度２３℃、相対湿度５０％の環境下で２４時間放置した試験片（処理後の試験片）を用いて測定した粘度平均分子量と、温度２３℃、相対湿度５０％の環境下で７４時間放置した試験片（処理前の試験片）を用いて測定した粘度平均分子量を、下記数式にしたがって計算し、恒温恒湿試験後の粘度平均分子量の低下率（ΔＭ_ratio）を算出した。
ΔＭ_ratio＝１００×［（処理前の試験片の粘度平均分子量）−（処理後の試験片の粘度平均分子量）］／（処理前の試験片の粘度平均分子量）
この数値が小さいほど成形した樹脂組成物の耐加水分解性が良好であることを示す。
【０１３９】
［原料］
原料としては、以下のものを用いた。
（Ａ成分：ポリカーボネート樹脂）
粘度平均分子量２３，８００のビスフェノールＡ型芳香族ポリカ−ボネ−ト樹脂パウダー［帝人化成（株）製「パンライトＬ−１２５０ＷＰ」］
【０１４０】
（Ｂ成分およびＢ成分以外）
Ｂ−１：合成雲母（ソマシフ ＭＥ−１００：コープケミカル（株）製、陽イオン交換容量：１１０ミリ当量／１００ｇ）
Ｂ−２：合成雲母（ソマシフ ＭＥ−１００：コープケミカル（株）製）にトリオクチルメチルアンモニウムクロライドをほぼ完全にイオン交換したもの
Ｂ−３：合成雲母（ソマシフ ＭＥ−１００：コープケミカル（株）製）にジデシルジメチルアンモニウムクロライドをほぼ完全にイオン交換したもの
Ｂ−４：合成雲母（ソマシフ ＭＥ−１００：コープケミカル（株）製）にトリフェニルメチルアンモニウムクロライドをほぼ完全にイオン交換したもの
Ｂ−５：合成雲母（ソマシフ ＭＥ−１００：コープケミカル（株）製）にジオクタデシルジメチルアンモニウムクロライドをほぼ完全にイオン交換したもの
【０１４１】
（Ｃ成分）
Ｃ−１：スチレン−無水マレイン酸共重合体（ノヴァケミカルジャパン（株）製：「ＤＹＬＡＲＫ ３３２−８０」、無水マレイン酸量約１５重量％）
（その他の成分）
ＴＭＰ：トリメチルホスフェート（大八化学工業（株）製：ＴＭＰ）、添加量は全ての組成物でＡ成分１００重量部当り０．１重量部。
【０１４２】
［実施例１、２、比較例１〜３］
Ｂ成分とＣ成分を、表１の量割合にて、径３０ｍｍφ、Ｌ／Ｄ＝３３．２、混練ゾーン２箇所のスクリューを装備したベント付き二軸押出機（（株）神戸製鋼所製：ＫＴＸ３０）を用い、シリンダー温度２００℃にて溶融混練し、押出し、ストランドカットしてペレットを得た。得られたペレットを用い、最終割合が表３に示す割合になるよう、上記Ｂ成分とＣ成分の混合物と、Ａ成分などをドライブレンドした後、径３０ｍｍφ、Ｌ／Ｄ＝３３．２、混練ゾーン２箇所のスクリューを装備したベント付き二軸押出機（（株）神戸製鋼所製：ＫＴＸ３０）を用い、シリンダー温度２８０℃にて溶融混練し、押出し、ストランドカットしてペレットを得た。
【０１４３】
得られたペレットを１００℃で５時間熱風循環式乾燥機により乾燥した。乾燥後、試験片を射出成形機（東芝機械（株）製：ＩＳ−１５０ＥＮ）によりシリンダー温度２６０℃、金型温度８０℃、成形サイクル４０秒で成形した。これらについての測定結果を表１に示す。
【０１４４】
【表１】

【０１４５】
上記表から明らかなように、本発明の熱可塑性樹脂組成物は特定の分散形態を満足することにより、良好な剛性および極めて良好な耐加水分解性を有し、更に良好な熱安定性を有する熱可塑性樹脂組成物を提供することがわかる。殊に熱安定性はＢ成分の層状珪酸塩とＣ成分とを予め混練した場合において特に良好である。これにより実用的であり幅広い分野において適用可能な層状珪酸塩を含んでなる熱可塑性樹脂組成物、殊に芳香族ポリカーボネート樹脂組成物が提供される。上記の特有の効果は具体的には本発明の特異な分散状態で得られていることが判る。この分散状態によって、剛性、耐加水分解性の向上が顕著になる。
【０１４６】
【発明の効果】
本発明の熱可塑性樹脂組成物は、良好な剛性を有し、良好な耐加水分解性を有し、更に良好な熱安定性を有する熱可塑性樹脂組成物、殊に芳香族ポリカーボネート樹脂からなる熱可塑性樹脂組成物である。更に本発明の熱可塑性樹脂組成物は射出成形および押出成形の双方に適した溶融粘度特性を有しており成形加工性に優れる。したがって本発明の熱可塑性樹脂組成物、電気電子部品分野、ＯＡ機器部品分野、自動車部品分野、農業資材分野、漁業資材分野、搬送容器分野、包装容器分野、および雑貨分野等の幅広い分野において有用であり、特に電気電子部品分野、のＯＡ機器部品分野、自動車部品分野に有用であり、その奏する工業的効果は格別である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin composition comprising an amorphous thermoplastic resin and a layered silicate, in particular, an organized layered silicate, wherein the layered silicate has a specific dispersion structure. In particular, the present invention is a thermoplastic resin composition having a high rigidity formed by finely dispersing a layered silicate, having a low molecular weight reduction, excellent thermal stability, and environmental stability under high temperature and high humidity, that is, The present invention relates to a novel thermoplastic resin composition having greatly improved hydrolysis resistance.
[0002]
[Prior art]
In recent years, clay minerals, especially layered silicates, have been used as inorganic fillers, and the surface appearance and specific gravity of molded products have been improved by facilitating dispersion in resins by ion-exchange of the interlayer ions with various organic onium ions. Many attempts have been made to improve the mechanical properties while maintaining the above, particularly in polyamide-based resins and polyolefin-based resins, and in these cases, practical examples can be seen.
[0003]
However, none of these aromatic polycarbonate resin compositions in which layered silicates or the like are finely dispersed have sufficient thermal stability and are not practical. In other words, it has a good surface appearance equivalent to that of a single resin that does not contain inorganic fillers, etc., has the same rigidity as a resin reinforced with reinforcing fillers, and has practically sufficient thermal stability. The present condition is that the thermoplastic resin composition which consists of a thermoplastic resin is not obtained.
[0004]
In general, as a means for improving the rigidity (flexural modulus) of a thermoplastic resin, mixing of a fibrous reinforcing material such as glass fiber or an inorganic filler has been performed. There are drawbacks in that the specific gravity is increased and the surface appearance of the product is impaired.
[0005]
On the other hand, as one of the techniques for achieving a high flexural modulus with a relatively small amount of filler, layer exchange silicate as an inorganic filler, and more preferably ion exchange of interlayer ions of such layer silicate with various organic onium ions A layered silicate obtained by finely dispersing a layered silicate in a thermoplastic resin has been proposed, and the interlayer ions of the aromatic polycarbonate resin and the layered silicate are ion-exchanged with various organic onium ions. There are also known resin compositions in combination with (see Patent Documents 1 to 6).
[0006]
And as an organic onium ion for ion-exchange of the interlayer ion of such a layered silicate, an organic onium ion having a C 12 or more alkyl group represented by dimethyldioctadecyl ammonium ion or a polyethylene glycol chain is used. The ammonium ion etc. which have are proposed (refer patent document 2 and patent document 3). Further, for thermoplastic resins in general, a proposal that a quaternary ammonium ion having 15 to 30 carbon atoms is preferable as an organic onium ion (see Patent Document 7), or a quaternary ammonium ion (or phosphonium ion). It has also been proposed that one of the organic groups has 8 or more carbon atoms, and the other three organic groups are preferably organic onium ions having 1 to 4 carbon atoms (see Patent Document 8). ).
[0007]
In any of these proposals, there is no suggestion about the hydrolysis resistance in the thermoplastic resin composition, and in fact, in the thermoplastic resin composition containing a layered silicate ion-exchanged with such an organic onium ion, Since there is a problem with hydrolysis resistance, improvement in hydrolysis resistance in an amorphous thermoplastic resin composition such as an aromatic polycarbonate resin containing a layered silicate is important for further increasing its practicality. Technical issues.
[0008]
In Non-Patent Documents 1 to 3, a polycarbonate resin / compatibility agent / organic fluoromica-based resin composition has been studied by melt-kneading, and the composition has a relatively small decrease in molecular weight and heat resistance. Discloses that it has excellent flexural modulus. Further, Non-Patent Documents 2 and 3 also disclose that fluoromica is dispersed in 3 to 4 layers. However, such non-patent literature does not describe the bottom surface spacing, and further, the moderately dispersed state of the present invention and the hydrolysis resistance of the molded product, which is one of the effects thereof, under good high temperature and high humidity (hereinafter referred to as the following). , Sometimes simply referred to as hydrolysis resistance). In addition, the composition does not completely suppress the decrease in molecular weight, and is inferior in hydrolysis resistance under high temperature and high humidity, lowering the melting temperature during pelletization, Care was required not to get wet.
[0009]
[Patent Document 1]
JP-A-3-215558
[Patent Document 2]
JP-A-7-207134
[Patent Document 3]
JP-A-7-228762
[Patent Document 4]
JP 7-331092 A
[Patent Document 5]
JP 9-143359 A
[Patent Document 6]
Japanese Patent Laid-Open No. 10-60160
[Patent Document 7]
JP 2002-88255 A
[Patent Document 8]
WO99 / 32403 (Japanese Patent Publication No. 2001-526313)
[Non-Patent Document 1]
51st Annual Meeting of the Society of Polymer Science, Japan, Volume 51 (No. 3), 669 pages, 2002
[Non-Patent Document 2]
Molding '02, page 15, 2002
[Non-Patent Document 3]
51st Annual Meeting of the Society of Polymer Science, Japan, Volume 51 (No. 11), 2645, 2002
[0010]
[Problems to be solved by the invention]
An object of the present invention is a thermoplastic resin composition that achieves an unprecedented finely dispersed state of a layered silicate in view of the above-mentioned problems, and has a good rigidity and a good hydrolysis resistance It is another object of the present invention to provide a thermoplastic resin composition, particularly a thermoplastic resin composition comprising an aromatic polycarbonate resin.
[0011]
As a result of intensive studies to achieve the above object, the present inventors have dispersed a layered silicate in a thermoplastic resin, and the average number of layers and the bottom surface interval of the layered silicate layer are specified. It has been found that the above-mentioned problems can be solved by creating a dispersion state that cannot be achieved by a resin composition containing a conventional layered silicate. The inventors of the present invention have made further studies from this discovery and have completed the present invention. That is, the properties of the thermoplastic resin composition of the present invention are characterized by means of using a specific raw material, means of using a high-purity raw material, means of setting the composition ratio of the thermoplastic resin composition in a specific range, and preparing a master batch in advance. It cannot be achieved even if a means for applying a shearing force at the time of melt kneading is used alone. This was achieved for the first time by obtaining the dispersion state of the present invention by using a plurality of these various means.
[0012]
[Means for Solving the Problems]
The present invention relates to (1) (A) a layered silicate (B component) 0 having a cation exchange capacity of 50 to 200 meq / 100 g per 100 parts by weight of an amorphous thermoplastic resin (A component). A thermoplastic resin composition comprising 1 to 50 parts by weight, wherein the B component has an average number of laminated silicate layers of 5 to 40 determined by X-ray diffraction in the resin composition, and the bottom surface spacing is It relates to a thermoplastic resin composition in the range of 1.3 to 2.3 nm.
[0013]
One of the preferred embodiments of the present invention is that (2) the organic layered silicate in which the component B is ion-exchanged between layers with an organic onium ion at a ratio of 40% or more of the cation exchange capacity of the layered silicate. The thermoplastic resin composition of (1) above.
[0014]
One preferred embodiment of the present invention is that (3) the thermoplastic resin composition further has an affinity for (C) the amorphous thermoplastic resin of component A per 100 parts by weight of component A, and The thermoplastic resin composition according to any one of (1) and (2) above, comprising 0.1 to 50 parts by weight of a compound having a hydrophilic component (C component).
[0015]
One of the preferred embodiments of the present invention is (4) the thermoplastic resin composition according to any one of the above (1) to (3), wherein the component A is at least 50% by weight of an aromatic polycarbonate resin.
[0016]
One of the preferred embodiments of the present invention is that (5) the component C is a styrene-containing polymer having a functional group consisting of a carboxyl group and / or a derivative thereof. It is a thermoplastic resin composition.
[0017]
One of the preferred embodiments of the present invention is (6) the above-mentioned product obtained by melt-kneading the B component and the C component in advance and then melt-kneading the melt-kneaded product and the A component using a multi-screw extruder (3) It is a thermoplastic resin composition in any one of (5).
[0018]
Details of the present invention will be described below.
<About component A>
In the present invention, the amorphous thermoplastic resin (component A) is, for example, polystyrene, acrylic resin, AS resin (resin mainly composed of acrylonitrile-styrene copolymer), SMA resin (mainly composed of styrene-maleic anhydride copolymer). Resin, MS resin (resin consisting mainly of methyl methacrylate-styrene copolymer) and ABS resin (resin consisting mainly of acrylonitrile-styrene-butadiene copolymer), and amorphous engineering plastics such as aromatic polycarbonate resin, etc. Is exemplified.
[0019]
Furthermore, a preferred amorphous thermoplastic resin in the present invention is an amorphous thermoplastic resin having a glass transition temperature (Tg) of 120 ° C. or higher. Such Tg is more preferably 130 ° C. or higher, and still more preferably 140 ° C. or higher. On the other hand, the Tg is suitably 280 ° C. or lower, and preferably 250 ° C. or lower. Such a high Tg amorphous thermoplastic resin requires a high molding processing temperature, and improvement in its thermal stability is more demanded. In addition, the glass transition temperature in this invention is measured by the method prescribed | regulated to JISK7121.
[0020]
Preferred embodiments of the above amorphous thermoplastic resin include, for example, aromatic polycarbonate resin, polyphenylene oxide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, cyclic polyolefin resin, polyetherimide resin, polyamideimide resin, Examples include polyimide resins and polyamino bismaleimide resins. More preferably, among these, aromatic polycarbonate resins, polyarylate resins, and cyclic polyolefin resins that are excellent in moldability and applicable to a wider range of fields are exemplified. Among the above, the amorphous thermoplastic resin of the present invention is preferably an aromatic polycarbonate resin that is particularly excellent in mechanical strength. Therefore, it is preferable that at least 50% by weight of the component A is an aromatic polycarbonate resin. Also, the aromatic polycarbonate resin can be used by combining one or more other thermoplastic resins such as ABS resin and aromatic polyester resin.
[0021]
An aromatic polycarbonate resin particularly suitable as the amorphous thermoplastic resin of the component A of the present invention will be described.
[0022]
The representative aromatic polycarbonate resin of the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. The reaction may be carried out by an interfacial polycondensation method, a melt transesterification method, a carbonate prepolymer solid solution. Examples thereof include a phase transesterification method and a ring-opening polymerization method of a cyclic carbonate compound.
[0023]
Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly known as “bisphenol”). A ″), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, particularly bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.
[0024]
In the present invention, in addition to the bisphenol A-based polycarbonate resin, which is a general-purpose aromatic polycarbonate resin, a special aromatic polycarbonate resin using other dihydric phenols is used for the purpose of obtaining better hydrolysis resistance. It can be used as the A component.
[0025]
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) An aromatic polycarbonate resin (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes referred to as “BCF”) is a polymer itself. Since it has good hydrolysis resistance, it is suitable for applications in which dimensional changes due to water absorption and requirements for form stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the aromatic polycarbonate resin.
[0026]
In particular, when high rigidity and better hydrolysis resistance are required, the component A constituting the aromatic polycarbonate resin composition is the following (1) to (3) copolymer polycarbonate resin. Is particularly preferred.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate resin. And BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, and further preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate resin. And a BCF of 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate resin. And Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
[0027]
These special aromatic polycarbonate resins may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type aromatic polycarbonate resin generally used.
[0028]
For the production method and characteristics of these special aromatic polycarbonate resins, see, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. It is described in detail.
[0029]
Among the various aromatic polycarbonate resins described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc., are resistant to hydrolysis of the polymer itself. Since it is excellent and has excellent remarkably low warpage after molding, it is particularly suitable in the field of, for example, a mirror or the like where shape stability is required.
(I) an aromatic polycarbonate resin having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C., or
(Ii) Tg is 160 to 250 ° C., preferably 170 to 230 ° C., and water absorption is 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to Aromatic polycarbonate resin that is 0.27%.
[0030]
Here, the water absorption of the aromatic polycarbonate resin is measured by measuring the water content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. It is the value. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.
[0031]
On the other hand, as the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
[0032]
In producing a polycarbonate resin from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, an antioxidant for preventing the oxidation of the catalyst, the terminal terminator, and the dihydric phenol as necessary. An agent or the like may be used. The aromatic polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.
[0033]
When a polyfunctional compound that produces a branched polycarbonate resin is included, the ratio is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 in the total amount of the aromatic polycarbonate resin. -0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may be generated as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to the total amount of the aromatic polycarbonate resin. Those having 0.9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. Regarding the ratio of such branched structures¹It is possible to calculate by H-NMR measurement.
[0034]
The aromatic polycarbonate resin as the component A is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, and a bifunctional alcohol (including alicyclic). Polymerized copolymer polycarbonate resin and polyester carbonate obtained by copolymerizing such a bifunctional carboxylic acid and a bifunctional alcohol may also be used. Further, a mixture obtained by blending two or more of the obtained aromatic polycarbonate resins may be used.
[0035]
The aliphatic bifunctional carboxylic acid used here is preferably an α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and the like, and saturated aliphatic dicarboxylic acid and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
[0036]
Further, in the present invention, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.
[0037]
The aromatic polycarbonate resin as the component A in the resin composition of the present invention includes various fragrances such as the above-described polycarbonate resins having different dihydric phenols, polycarbonate resins containing branched components, polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. It may be a mixture of two or more group polycarbonate resins. Furthermore, what mixed 2 or more types of polycarbonate resin from which a manufacturing method differs, polycarbonate resin from which a terminal stopper differs, etc. can also be used.
[0038]
In the polymerization reaction of the aromatic polycarbonate resin, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to promote the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound is used. You can also. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.
[0039]
In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As monofunctional phenols, it is preferable to use monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, and the like. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. Such end terminators may be used alone or in admixture of two or more.
[0040]
The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester. The dihydric phenol and the carbonate ester are mixed with heating in the presence of an inert gas to produce an alcohol or It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but in most cases is in the range of 120 to 350 ° C. In the late stage of the reaction, the reaction system was 1.33 × 10^ThreeDistillation of alcohol or phenol produced by reducing the pressure to about ˜13.3 Pa is facilitated. The reaction time is about 1 to 4 hours.
[0041]
Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms which may have a substituent, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms, and among them, diphenyl carbonate is preferable. .
[0042]
A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, divalent phenol sodium salt and potassium salt; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; tetra Catalysts such as nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. Furthermore, alkoxides of alkali (earth) metals, organic acid salts of alkali (earth) metals, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc., esterification reaction, transesterification The catalyst used for the reaction can be used. A catalyst may be used independently and may be used in combination of 2 or more type. These polymerization catalysts are preferably used in an amount of 1 × 10 with respect to 1 mol of the raw material dihydric phenol.^-8~ 1x10^-3Equivalent weight, more preferably 1 × 10^-7~ 5x10^-FourIt is selected in the range of equivalents.
[0043]
In the reaction by the melt transesterification method, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonyl is used at the later stage or after completion of the polycondensation reaction for the purpose of reducing the phenolic end groups of the produced polycarbonate resin. Compounds such as phenylphenyl carbonate can be added.
[0044]
Further, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Moreover, it is appropriate to use in the ratio of 0.01-500 ppm with respect to the polycarbonate resin after superposition | polymerization, More preferably, it is 0.01-300 ppm, Most preferably, it is a ratio of 0.01-100 ppm. Examples of preferable quenching agents include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
[0045]
The viscosity average molecular weight of the aromatic polycarbonate resin to be the component A is not limited. However, when the viscosity average molecular weight is less than 10,000, the strength and the like are lowered, and when it exceeds 50,000, the molding process characteristics are lowered. Therefore, the range of 10,000 to 50,000 is preferable. The range of 3,000 to 30,000 is more preferable, and the range of 14,000 to 28,000 is more preferable. In this case, it is also possible to mix a polycarbonate resin having a viscosity average molecular weight outside the above range within a range in which moldability and the like are maintained. For example, a high molecular weight aromatic polycarbonate resin component having a viscosity average molecular weight exceeding 50,000 can be blended.
[0046]
In the present invention, the viscosity average molecular weight is first calculated by the specific viscosity (η_SP) At 20 ° C. using an Ostwald viscometer from a solution of 0.7 g of aromatic polycarbonate resin in 100 ml of methylene chloride.
Specific viscosity (η_SP) = (T−t₀) / T₀
[T₀Is the drop time of methylene chloride, t is the drop time of the sample solution]
Calculated specific viscosity (η_SP) To calculate the viscosity average molecular weight M by the following formula.
η_SP/C=[η]+0.45×[η]²c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10^-FourM^0.83
c = 0.7
[0047]
In addition, when measuring the viscosity average molecular weight in the thermoplastic resin composition of this invention, it carries out in the following way. That is, the composition is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble component is collected by celite filtration, and then the solution is removed and dried sufficiently to obtain a methylene chloride soluble solid. obtain. The specific viscosity at 20 ° C. calculated by the above formula is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride by using an Ostwald viscometer.
[0048]
<About B component>
The B component of the present invention is a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g. Further preferably, in the present invention, the component B of the present invention has a cation exchange capacity of 50 to 200 meq / 100 g, and organic onium ions are ionized between layers at a ratio of 40% or more of the cation exchange capacity. It is a layered silicate that is exchanged. Here, the ratio of 40% means that, for example, when the cation exchange capacity of the layered silicate is 110 meq / 100 g, 44 meq / 100 g, which is 40%, is ion-exchanged with organic onium ions. It points to that. Hereinafter, “a layered silicate having a cation exchange capacity and having an organic onium ion exchanged between layers” may be simply referred to as “organized layered silicate”.
[0049]
The organic onium ion compound in the organically modified layered silicate of the present invention is usually handled as a salt with anions such as halogen ions, hydroxide ions and acetate ions. It can be obtained by reacting a salt compound of such an organic onium ion with a layered silicate. Examples of organic onium ions include ammonium ions, phosphonium ions, sulfonium ions, onium ions derived from heteroaromatic rings, and the like, and any of primary, secondary, tertiary, and quaternary ions can be used. However, a quaternary onium ion is preferable.
[0050]
As the onium ion compound, those having various organic groups bonded thereto can be used. The organic group is typically an alkyl group, but may have an aromatic group, and may be an ether group, ester group, double bond portion, triple bond portion, glycidyl group, carboxylic acid group, or acid anhydride group. , Hydroxyl group, amino group, amide group, oxazoline ring and other functional groups.
[0051]
Specific examples of organic onium ions include quaternary ammonium having the same alkyl group such as tetraethylammonium and tetrabutylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium and trimethyl. Octadecyl ammonium, and trimethyl alkyl ammonium such as trimethyl icosanyl ammonium, trimethyl alkenyl ammonium such as trimethyl octadecenyl ammonium, trimethyl alkadienyl ammonium such as trimethyl octadecadienyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium, Triethyl hexadecyl ammonium And triethylalkyl ammonium such as triethyl octadecyl ammonium, tributyl dodecyl ammonium, tributyl tetradecyl ammonium, tributyl hexadecyl ammonium, and tributyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl Dihexadecylammonium, dimethyldioctadecylammonium, dimethyldialkylammonium such as dimethyldidodecylammonium, dimethyldialkenylammonium such as dimethyldioctadecenylammonium, dimethyldialkadienylammonium such as dimethyldioctadecadienylammonium, Diethyldi Diethyl dialkyl ammonium such as decyl ammonium, diethyl ditetradecyl ammonium, diethyl dihexadecyl ammonium, and diethyl dioctadecyl ammonium, dibutyl dioctyl ammonium, dibutyl didecyl ammonium, dibutyl didodecyl ammonium, dibutyl ditetradecyl ammonium, dibutyl dihexadecyl Ammonium and dibutyldialkylammonium such as dibutyldioctadecylammonium, methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium, dibenzyldialkylammonium such as dibenzyldihexadecylammonium, trioctylmethylammonium, tridodecylmethylammonium, and Tritetradecylmethylammoni Aromatic rings such as trialkylmethylammonium such as um, trialkylethylammonium such as trioctylethylammonium and tridodecylethylammonium, trialkylbutylammonium such as trioctylbutylammonium and tridecylbutylammonium, and trimethylbenzylammonium Having quaternary ammonium, quaternary ammonium derived from aromatic amines such as trimethylphenylammonium, trimethyl [PAG] ammonium such as methyldiethyl [PEG] ammonium and methyldiethyl [PPG], methyldimethylbis [PEG] ammonium and the like Alkyltris [PAG] ammonium such as dialkylbis [PAG] ammonium, ethyltris [PEG] ammonium, and the above ammonia Nitrogen atom-ion can be cited phosphonium ion replacing a phosphorus atom. These organic onium ions can be used either alone or in combination of two or more. The notation of “PEG” indicates polyethylene glycol, the notation of “PPG” indicates polypropylene glycol, and the notation of “PAG” indicates polyalkylene glycol. The molecular weight of the polyalkylene glycol can be 100 to 1,500.
[0052]
The molecular weight of these organic onium ion compounds is more preferably 100 to 600. More preferably, it is 150-500. When the molecular weight is more than 600, there is a tendency that the thermal deterioration of an amorphous thermoplastic resin such as an aromatic polycarbonate resin is accelerated or the heat resistance of the thermoplastic resin composition is impaired. The molecular weight of the organic onium ion refers to the molecular weight of a single organic onium ion that does not include counter ions such as halogen ions.
[0053]
Preferred embodiments of the organic onium ion include trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium, methyltrioctylammonium, ethyltrioctylammonium, butyltrioctylammonium, triphenylmethylammonium, Organic onium ions such as trimethyloctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, methyltrioctylphosphonium, ethyltrioctylphosphonium, butyltrioctylphosphonium, triphenylmethylphosphonium, etc. in one molecule Charcoal An alkyl group having 6 to 16 atoms (preferably having 7 to 14 carbon atoms, more preferably 7 to 11 carbon atoms) and an alkyl group having 1 to 4 carbon atoms (preferably having 1 to 3 carbon atoms). More preferably a methyl group or an ethyl group, and still more preferably an organic onium ion having a methyl group.
[0054]
In the present invention, a more preferable embodiment of the component B is a layered silicate ion-exchanged with an organic onium ion represented by the following general formula (I).
[0055]
[Chemical 1]

[0056]
The general formula (I) satisfies the following conditions. That is, M is a nitrogen atom or a phosphorus atom, and R¹And R²Are each an alkyl group having 6 to 16 carbon atoms. R^ThreeIs an alkyl group having 1 to 16 carbon atoms and R^FourIs an alkyl group having 1 to 4 carbon atoms. R¹And R²And may be the same group or different groups, and R^ThreeAnd R^FourAnd may be the same group or different groups.
[0057]
A more preferred embodiment of the organic onium ion represented by the general formula (I) is (i) the R^ThreeIs an alkyl group having 1 to 4 carbon atoms. More preferably (ii) R^ThreeAnd R^FourAre each an alkyl group having 1 to 4 carbon atoms, and R¹And R²Are each an alkyl group having 7 to 14 carbon atoms. More preferably, (iii) R^ThreeAnd R^FourAre each an alkyl group having 1 to 4 carbon atoms and R¹And R²Is the case of an alkyl group having 7 to 11 carbon atoms. Of these, R^ThreeAnd R^FourIs particularly preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a quaternary ammonium ion of a methyl group.
[0058]
According to these more preferred embodiments (including further preferred embodiments) of (i) to (iii), the hydrolysis resistance of the resin composition is particularly excellent, which is favorable for the thermoplastic resin composition of the present invention. Gives long-term practical characteristics.
[0059]
In the above formula (I), R¹~ R^FourBoth can be selected from linear and branched.
[0060]
Examples of such suitable quaternary ammonium ions include dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl didodecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexadecyl ammonium, diethyl didodecyl ammonium, diethyl ditetradecyl ammonium, diethyl Examples include dihexadecyl ammonium, dibutyl dioctyl ammonium, dibutyl didecyl ammonium, dibutyl didodecyl ammonium and the like.
[0061]
B component layered silicate is SiO₂Chain SiO_FourIt is a silicate (silicate) or clay mineral (clay) consisting of a layer composed of a combination of a tetrahedral sheet structure and an octahedral sheet structure containing Al, Mg, Li, etc., with coordinated exchangeable cations between the layers. . These silicates (silicates) or clay minerals (clays) are typified by smectite minerals, vermiculite, halloysite, and swellable mica. Specifically, examples of the smectite mineral include montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, and stevensite. Examples of the swellable mica include Li type fluorine teniolite, Na type fluorine teniolite, and Na type tetrasilicon. Examples include swellable synthetic mica such as fluorine mica and Li-type tetrasilicon fluorine mica. These layered silicates can be either natural products or synthetic products. The synthetic product is produced by, for example, hydrothermal synthesis, melt synthesis, or solid reaction.
[0062]
Among the layered silicates, from the viewpoint of cation exchange capacity, etc., smectite clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica have swelling properties. Fluorine mica is preferably used, and montmorillonite obtained by purifying bentonite and synthetic fluorine mica are more preferable in terms of purity and the like. Among these, synthetic fluorine mica that can provide good mechanical properties is particularly preferable.
[0063]
The cation exchange capacity (also referred to as cation exchange capacity) of the layered silicate as the component B is required to be 50 to 200 meq / 100 g, preferably 80 to 150 meq / 100 g, more preferably Is 100 to 150 meq / 100 g. The cation exchange capacity is measured as a CEC value by the modified Schöllenberger method, which is a domestic official method as a soil standard analysis method. That is, the cation exchange capacity of the layered silicate is required to be 50 meq / 100 g or more in order to obtain good dispersibility in the amorphous thermoplastic resin as the component A, but from 200 meq / 100 g. When it becomes large, the thermal deterioration of the thermoplastic resin composition (especially the aromatic polycarbonate resin composition) becomes large, and accordingly, the influence on the thermal deterioration of the amorphous thermoplastic resin composition of the present invention becomes large. The layered silicate preferably has a pH value of 9 to 10.5. When the pH value is greater than 10.5, the thermal stability of the thermoplastic resin composition of the present invention tends to decrease.
[0064]
For the ion exchange of organic onium ions to layered silicate, add organic onium ion compound (salt compound of organic onium ion) to layered silicate dispersed in polar solvent and collect the deposited ion exchange compound Can be created by doing. Usually, this ion exchange reaction is carried out by adding an organic onium ion compound at a ratio of 1.0 to 1.5 equivalents to 1 equivalent of the ion exchange capacity of the layered silicate, and almost all of the metal ions between the layers are added to the organic onium. It is common to exchange with ions. However, controlling the exchange rate with respect to the ion exchange capacity within a certain range is also effective in suppressing thermal degradation of the aromatic polycarbonate resin. Here, the ratio of ion exchange with organic onium ions is preferably 40% or more with respect to the ion exchange capacity of the layered silicate. The proportion of such ion exchange capacity is preferably 40 to 95%, particularly preferably 40 to 80%. Here, the exchange rate of the organic onium ions can be calculated by obtaining a weight reduction due to thermal decomposition of the organic onium ions using a thermogravimetric apparatus or the like for the compound after the exchange.
[0065]
The average number of layers of the silicate layer obtained from the X-ray diffraction of the layered silicate (component B) of the present invention is 5 to 40 (feature A), preferably 5 to 30, more preferably 5 to 20, and most preferably. 5-15. If the average number of layers is less than 5, the thermal stability of the thermoplastic resin composition may be reduced, and if it exceeds 40, the rigidity improvement effect is reduced.
[0066]
A thermoplastic resin composition in which a layered silicate is finely dispersed in an amorphous thermoplastic resin such as an aromatic polycarbonate resin has conventionally been made by simply peeling off the organically layered layered silicate at the interlayer portion and making it as fine as possible in the base resin. The problem was to disperse. However, if the dispersion is excessively advanced, the effect of improving the rigidity is reduced, and the thermal stability is deteriorated. Therefore, an appropriate dispersion state of the present invention is required for improving rigidity and maintaining thermal stability.
[0067]
The bottom surface interval of the layered silicate in the thermoplastic resin composition of the layered silicate (component B) of the present invention is 1.3 to 2.3 nm (feature B), more preferably 1.5 to 2.3 nm. Most preferably, the thickness is 1.8 to 2.3 nm. In order to obtain this bottom space, it is preferable to use an organically modified layered silicate. If the distance between the bottom surfaces is less than 1.3 nm, the rigidity improving effect may be insufficient, and if it exceeds 2.3 nm, the thermal stability of the thermoplastic resin composition may be lowered.
[0068]
The feature B is obtained from the Bragg condition from the diffraction angle of the diffraction line in the X-ray diffraction measurement. The bottom surface spacing and X-ray diffraction measurement of the layered silicate are described in, for example, “Clay Handbook” (edited by the Japan Clay Society: Gihodo Publishing). In order to perform X-ray diffraction measurement of an organic layered silicate, a sample in a powder form can be filled into a sample stage and measured, and to perform X-ray diffraction measurement of a layered silicate in a composition, After the composition is formed into a flat plate by, for example, injection molding or extrusion molding, the sample can be set and measured so that the plane portion is the same as the measurement reference plane at the sample stage opening.
[0069]
The thermoplastic resin composition of the present invention finely disperses the layered silicate, that is, by combining the above-mentioned feature A and further feature B, it has good rigidity, good hydrolysis resistance, and even better. In this way, a thermoplastic resin composition having excellent thermal stability has been obtained.
[0070]
As a method for achieving the feature A or feature B in the present invention, for example, the following method is exemplified. (1) A layered silicate having a cation exchange capacity in a specific range is used, (2) Melting and kneading with high diffusion efficiency is performed using a multi-screw extruder, (3) A specific organic layered silicate is used, (4) Mixing a non-crystalline resin and layered silicate compatibilizer (third component such as component C), (5) using a layered silicate masterbatch, etc. In particular, it is preferable to combine (1) to (4), particularly preferably (1) to (5).
[0071]
As the third component in the method (4), a compound having an affinity for the amorphous thermoplastic resin as the component A and having a hydrophilic component is preferable. Therefore, in the present invention, more preferably, the compound (C) having an affinity for the amorphous thermoplastic resin of component (A) and having a hydrophilic component (component C) is 0.1 per 100 parts by weight of component A. Mention may be made of a thermoplastic resin composition comprising -50 parts by weight.
[0072]
The composition ratio of the B component layered silicate used in the present invention to the A component is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 0.8 parts by weight per 100 parts by weight of the A component. 5 to 10 parts by weight. When this composition ratio is less than 0.1 parts by weight, the effect of improving the mechanical properties of an amorphous thermoplastic resin such as an aromatic polycarbonate resin is not observed, and when it exceeds 50 parts by weight, the thermal stability of the composition decreases. However, it is difficult to obtain a practical thermoplastic resin composition.
[0073]
<About component C>
The component C of the present invention is a compound having an affinity for an amorphous thermoplastic resin (component A) and having a hydrophilic component. Such a composition of the C component produces good affinity for both amorphous thermoplastics and layered silicates, especially organically layered silicates. Affinity for both amorphous thermoplastics and layered silicates, especially organically modified layered silicates, improves the compatibility of the two components, and layered silicates are fine and stable in amorphous thermoplastics. And become dispersed.
[0074]
The function of the component C relating to the dispersion of the organically modified layered silicate is the same as that of the compatibilizer for polymer alloy (compatibility) used to compatibilize different polymers. Therefore, the component C is preferably a polymer obtained by polymerizing a monomer rather than a low molecular compound. The polymer is also excellent in thermal stability during kneading. The average number of repeating units of the polymer needs to be 2 or more, preferably 5 or more, and more preferably 10 or more. On the other hand, at the upper limit of the average molecular weight of the polymer, the number average molecular weight is preferably 2,000,000 or less. If the upper limit is not exceeded, good moldability can be obtained.
[0075]
Examples of the basic structure of the C component of the present invention include the following structures (i) and (ii).
[0076]
Structure (i): When the component having affinity for the amorphous thermoplastic resin is α and the hydrophilic component is β, a graft copolymer composed of α and β (main chain: α, graft chain: β, In addition, the main chain: β and the graft chain: α can be selected.), Block copolymer consisting of α and β (di-, tri-, etc., the number of block segments can be 2 or more, radial block type, etc. And a random copolymer comprising α and β. α and β may be not only a single polymer but also a copolymer.
[0077]
Here, α and β represent both polymer segment units and monomer units. The α component is preferably a polymer segment unit from the viewpoint of affinity with the amorphous thermoplastic resin.
[0078]
Structure (ii): When the component having affinity for the amorphous thermoplastic resin is α and the hydrophilic component is β, the function of α is expressed by the whole polymer, and β represents the structure contained in α. Having polymer.
[0079]
In other words, α alone does not have sufficient affinity with an amorphous thermoplastic resin, but when α and β are combined and integrated, good affinity with an amorphous thermoplastic resin is expressed. is there. Even when α alone is used, the affinity with the amorphous thermoplastic resin is good, and the affinity may be further improved by combination with β. Such an embodiment is included in the structure (i). Accordingly, structures (i) and (ii) partially overlap. On the other hand, in the structure (i), α alone has sufficient affinity with an amorphous thermoplastic resin. However, α and β are combined and integrated to form a good affinity with an amorphous thermoplastic resin. On the contrary, there may be an aspect in which the sex decreases. Naturally, such an embodiment is included in the C component.
[0080]
Any of the structures (i) and (ii) can be selected in the present invention. In particular, an embodiment satisfying both the conditions of the structure (i) and the conditions of the structure (ii), that is, α alone has a high affinity for an amorphous thermoplastic resin, and the affinity for the entire C component added with β is further increased. The aspect which becomes high is suitable.
[0081]
A component having an affinity for the amorphous thermoplastic resin in the present invention (hereinafter, sometimes referred to as α) will be described. As described above, since the component C functions in the same manner as the compatibilizer in the polymer alloy, α is required to have the same affinity for the polymer as the compatibilizer. Therefore, α can be roughly classified into a non-reactive type and a reactive type.
[0082]
The non-reactive type has good affinity when it has the following factors. That is, between the amorphous thermoplastic resin and α, (1) similarity in chemical structure, (2) solubility parameter approximation (difference in solubility parameter is 1 (cal / cm^Three)^1/2Within, that is, about 2.05 (MPa)^1/2It is necessary to have factors such as (3) intermolecular interactions (hydrogen bonds, ionic interactions, etc.), and pseudo-attractive interactions peculiar to random polymers. These factors are known as indicators for judging the affinity between the compatibilizing agent and the polymer which is the base of the polymer alloy.
[0083]
In the reactive type, various types known as functional groups having reactivity with the amorphous thermoplastic resin in the compatibilizing agent can be exemplified. For example, for an aromatic polycarbonate resin suitable as an amorphous thermoplastic resin, a carboxyl group, a carboxylic acid anhydride group, an epoxy group, an oxazoline group, an ester group, an ester bond, a carbonate group, and a carbonate bond are exemplified. be able to.
[0084]
On the other hand, if the amorphous thermoplastic resin and α have good affinity, then the resulting mixture of amorphous thermoplastic resin and α exhibits a single glass transition temperature (Tg), or It is also widely known that the behavior of the amorphous thermoplastic resin moving to the Tg side of α is observed. In the present invention, as the component (α) having affinity, a component having such behavior can be mentioned as one of its embodiments.
[0085]
As described above, the component (α) having an affinity for the amorphous thermoplastic resin in the component C of the present invention can exhibit the affinity due to various factors. Of these, α is preferably non-reactive, and it is particularly preferable that the solubility parameter approximates because good affinity is exhibited. This is because the affinity with the amorphous thermoplastic resin is superior to the reaction type. In addition, the reaction type has a drawback that when the reactivity is excessively increased, thermal degradation of the polymer is promoted by a side reaction.
[0086]
The solubility parameter of the amorphous thermoplastic resin and α preferably has the following relationship. That is, the solubility parameter of the amorphous thermoplastic resin (component A) is set to δ._A((MPa)^1/2), And the solubility parameter of α in the C component or the solubility parameter of the entire C component as δα ((MPa)^1/2)
δα = δ_A± 2 ((MPa)^1/2)
It is preferable that
[0087]
For example, the solubility parameter of an aromatic polycarbonate resin suitable as the component A is usually about 10 (cal / cm^Three)^1/2(That is, about 20.5 ((MPa)^1/2)), Δα in the component A is 18.5 to 22.5 ((MPa)^1/2) Is preferred, 19-22 ((MPa)^1/2) Is more preferable.
[0088]
For example, specific examples of the polymer component that satisfies the solubility parameter δα in the aromatic polycarbonate resin suitable as the component A are represented by aromatic polyesters (polyethylene terephthalate, polybutylene terephthalate, cyclohexanedimethanol copolymer polyethylene terephthalate, and the like). ) And polyester polymers such as aliphatic polyesters (typified by polycaprolactone). Specific examples thereof include styrene polymer, alkyl (meth) acrylate polymer, and acrylonitrile polymer (polystyrene, styrene-maleic anhydride copolymer, polymethyl methacrylate, styrene-methyl methacrylate copolymer, and styrene-acrylonitrile copolymer). And vinyl polymers such as those represented by coalescence. In order to maintain the heat resistance of the composition of the present invention, it is preferable to use a polymer component having a high Tg.
[0089]
Here, the solubility parameter is a theoretical estimation method based on the substituent contribution method (Group contribution methods) using the value of Small described in “Polymer Handbook 4th Edition” (A WILEY-INTERSCIENCE PUBLICATION, 1999). Available. The Tg of the amorphous thermoplastic resin can be determined by differential scanning calorimetry (DSC) measurement based on JIS K7121.
[0090]
The component α having an affinity for the amorphous thermoplastic resin of the component A is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 30% by weight or more in the C component. A weight percent or more is particularly preferred. Since the aspect which makes (alpha) the whole C component is also possible, an upper limit may be 100 weight%.
[0091]
On the other hand, the hydrophilic component in the component C (hereinafter sometimes referred to as β) is composed of a monomer having a hydrophilic group (an organic atomic group having a strong interaction with water) and a hydrophilic polymer component (polymer). Segment). Hydrophilic groups are widely known per se, and the following groups are exemplified.
1) Strongly hydrophilic group: -SO_ThreeH, -SO_ThreeM, -OSO_ThreeH, -OSO_ThreeH, -COOM, -NR_ThreeX (R: alkyl group, X: halogen atom, M: alkali metal, —NH_Four) etc,
2) Slightly small hydrophilic group: —COOH, —NH₂, -CN, -OH, -NHCONH₂ etc,
3) Non-hydrophilic or small group: —CH₂OCH_Three, -OCH_Three, -COOCH_Three, -CS, etc.
Among the groups 1) to 3), those classified into 1) and 2) are used as the hydrophilic group in the present invention. In addition to the above examples, 1) examples of strongly hydrophilic groups include sulfine groups, and 2) groups that are not very hydrophilic include carboxylic anhydride groups, oxazoline groups, formyl groups, and pyrrolidone groups. Is exemplified.
[0092]
The hydrophilic group of 2) is preferable because it is excellent in thermal stability at the time of melt processing of an amorphous thermoplastic resin, particularly an aromatic polycarbonate resin suitable in the present invention. If the hydrophilicity is too high, thermal degradation of an aromatic polycarbonate resin or the like is likely to occur. This is because such a hydrophilic group directly reacts with a carbonate bond to cause a thermal decomposition reaction.
[0093]
The hydrophilic group of the present invention includes both monovalent and divalent or more. In the case where the component C is a polymer, the divalent or higher functional group refers to a group in which the group does not constitute a main chain, and those constituting the main chain are distinguished from the functional group as a bond. Specifically, a group added to an atom such as carbon constituting the main chain, a side chain group, and a molecular chain terminal group are functional groups even if they are divalent or higher.
[0094]
A more specific indicator of hydrophilic groups is the solubility parameter. It is widely known that the greater the solubility parameter value, the higher the hydrophilicity. The solubility parameter for each group is the cohesive energy per group (E_coh) And the molar volume per group (V) ("Polymer Handbook 4th Edition" (A WILEY-INTERSCIENCE PUBLICATION), VII / 685, 1999, or Polym. Eng. Sci., No. 1). 14, 147 and 472, 1974, etc.). Such a calculation method is simple and widely known. Furthermore, from the viewpoint of comparing only the hydrophilicity relationship, the cohesive energy (E_coh) Divided by molar volume (V) (E_coh/ V; the unit is "J / cm"^ThreeCan be used as a hydrophilicity index.
[0095]
The hydrophilic group contained in β in the C component of the present invention is E_coh/ V needs to be 600 or more. Preferably E_coh/ V is 800 or more, and in the case of 800 or more, E of carbonate bond in the aromatic polycarbonate resin suitable as the component A of the present invention._cohMore than / V, it has higher hydrophilicity than carbonate bond. E_coh/ V is more preferably 900 or more, and still more preferably 950 or more. On the other hand, when the hydrophilicity is too high, the aromatic polycarbonate resin is likely to be thermally deteriorated as already described. For this reason, E_coh/ V is preferably 2,500 or less, more preferably 2,000 or less, and even more preferably 1,500 or less.
[0096]
As the hydrophilic component (β) of component C, a hydrophilic polymer component (polymer segment) is also selected. Therefore, the hydrophilic polymer segment contained in the polymer of component C is β. Examples of the hydrophilic polymer include polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, and polyacrylic acid metal salts (including chelate type). ), Polyvinylpyrrolidone, polyacrylamide, and polyhydroxyethyl methacrylate. Among these, polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyvinyl pyrrolidone, and polyhydroxyethyl methacrylate are preferably exemplified. This is because it is possible to achieve both good hydrophilicity and thermal stability (inhibition of decomposition of the aromatic polycarbonate resin during melt processing) with respect to the aromatic polycarbonate resin suitable in the present invention. Polyalkylene oxide is preferably polyethylene oxide or polypropylene oxide.
[0097]
In any of the monomer having a hydrophilic group and the hydrophilic polymer component, β preferably has an acidic functional group (hereinafter sometimes simply referred to as “acidic group”). The acidic group suppresses thermal deterioration during the melt processing of a thermoplastic resin composition mainly composed of an aromatic polycarbonate resin suitable for the present invention. In particular, an acidic group containing no nitrogen atom is more preferable. Suitable examples of the acidic group include a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group.
[0098]
In comparison, functional groups containing nitrogen atoms such as amide groups and imide groups may not sufficiently suppress the thermal degradation of the aromatic polycarbonate resin during melt processing. This is presumably because the nitrogen atom is locally basic and causes thermal decomposition of the carbonate bond.
[0099]
When β is a monomer having a hydrophilic group, the ratio of β in component C is 60 to 10,000 as the functional group equivalent, which is the molecular weight per functional group, preferably 70 to 8,000, 80 -6,000 is more preferable, and 100-3,000 is still more preferable. When β is a hydrophilic polymer segment, it is appropriate that β is in the range of 5 to 95% by weight and preferably 10 to 90% by weight in 100% by weight of component C. In particular, 30 to 70% by weight is more preferable, and 30 to 50% by weight is still more preferable.
[0100]
As a method for producing a compound having a component (α) having affinity for an amorphous thermoplastic resin and a hydrophilic component (β), a monomer of β and a monomer constituting α are copolymerized. Examples thereof include a method, a method in which a polymer component of β is block or graft copolymerized with α, a method in which β is directly reacted with α and added.
[0101]
As a preferred embodiment of the C component of the present invention, “a polymer having an affinity for the resin of the A component and having an acidic functional group”, “a polyalkylene oxide segment having an affinity for the resin of the A component and And a polymer having an affinity with the component A resin and having an oxazoline group, or a polymer having an affinity with the component A resin and having a hydroxyl group. The In the polymer of an aspect preferable as these C components, the molecular weight is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 50,000 to 500,000 in terms of weight average molecular weight. The weight average molecular weight is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line with a standard polystyrene resin.
[0102]
Among them, a polymer having an affinity with the resin of the component A (more preferably with an aromatic polycarbonate resin) and having an acidic functional group is preferable, and an affinity with the aromatic polycarbonate resin is more preferable. And a polymer having a carboxyl group and / or a functional group comprising a derivative thereof. From the viewpoint of the heat resistance retention effect of the aromatic polycarbonate resin, the polymer preferably has an aromatic ring component in the main chain and a polymer having a styrene component in the main chain. From the above points, a styrene-containing polymer (component C1) having a functional group comprising a carboxyl group and / or a derivative thereof is particularly suitable as the component C of the present invention. Here, the styrene-containing polymer refers to a polymer containing, as a polymer component, a repeating unit obtained by polymerizing an aromatic vinyl compound such as styrene.
[0103]
A styrene-containing polymer (component C1) having a functional group comprising a carboxyl group and / or a derivative thereof particularly suitable as the component C of the present invention will be described in detail. As a ratio of the functional group which consists of this carboxyl group and / or its derivative (s), 0.1-12 milliequivalent / g is preferable and 0.5-5 milliequivalent / g is more preferable. Here, 1 equivalent in the C1 component means that 1 mol of a carboxyl group is present, and such a value can be calculated by back titration such as potassium hydroxide.
[0104]
The functional group comprising a derivative of a carboxyl group includes (i) a metal salt (including a chelate salt) in which the hydroxyl group of the carboxyl group is substituted with a metal ion, (ii) an acid chloride substituted with a chlorine atom, (iii) -OR (R is a monovalent hydrocarbon group), (iv) an acid anhydride substituted with —O (CO) R (R is a monovalent hydrocarbon group), (v) —NR₂And (vi) an imide (R is hydrogen or a monovalent hydrocarbon group) in which the hydroxyl groups of two carboxyl groups are substituted with = NR, and the like. Can do.
[0105]
As a method for producing a styrene-containing polymer having a functional group comprising a carboxyl group and / or a derivative thereof (hereinafter simply referred to as “carboxyl groups”), various conventionally known methods can be employed. For example, (1) a method of copolymerizing a monomer having a carboxyl group and a styrene monomer, and (2) a compound or monomer having a carboxyl group bonded to a styrene-containing polymer or Examples thereof include a copolymerization method.
[0106]
In the copolymerization of (1), various types of copolymers such as an alternating copolymer, a block copolymer, and a tapered copolymer can be used in addition to the random copolymer. Also in the copolymerization method, various polymerization methods such as anionic living polymerization method and group transfer polymerization method can be used in addition to radical polymerization methods such as solution polymerization, suspension polymerization and bulk polymerization. Furthermore, a method of once forming a macromonomer and then polymerizing is also possible.
[0107]
In the above method (2), a radical generator such as peroxide or 2,3-dimethyl-2,3-diphenylbutane (dicumyl) is generally added to the styrene-containing polymer or copolymer as necessary. And a method of reacting or copolymerizing at a high temperature. Such a method involves thermally generating a reactive site on a styrene-containing polymer or copolymer and reacting a compound or monomer that reacts with the active site. Other methods for generating active sites required for the reaction include methods such as irradiation with radiation and electron beams and application of external force by mechanochemical techniques. Furthermore, a method in which a monomer that generates an active site required for the reaction is copolymerized in advance in the styrene copolymer. Examples of the active site for the reaction include unsaturated bonds, peroxide bonds, and nitrooxide radicals having high steric hindrance and being thermally stable.
[0108]
Examples of the compound or monomer having a carboxyl group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, acrylamide, and methacrylamide and derivatives thereof, maleic anhydride, citraconic anhydride, N-phenylmaleimide, Examples include maleic anhydride derivatives such as N-methylmaleimide, glutarimide structures, and chelate structures formed from acrylic acid and polyvalent metal ions. Among these, a monomer having a functional group not containing a metal ion or a nitrogen atom is preferable, and a monomer having a carboxyl group and a carboxylic anhydride group is more preferable. Among these, maleic anhydride is particularly preferable.
[0109]
Examples of the styrene monomer compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, Dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene and the like can be used, and styrene is particularly preferable.
[0110]
Furthermore, other compounds copolymerizable with these compounds, such as acrylonitrile and methacrylonitrile, may be used as the copolymerization component.
[0111]
Preferred as the component C in the present invention is a styrene-containing copolymer obtained by copolymerizing a monomer having a carboxyl group. This is because such a copolymer can stably contain a relatively large number of carboxyl groups in the styrene-containing polymer. A more preferred embodiment is a styrene-containing copolymer obtained by copolymerizing a monomer having a carboxyl group and a styrene monomer. A particularly preferred embodiment is a styrene-maleic anhydride copolymer. Since the styrene-maleic anhydride copolymer has high compatibility with both the ionic component and the aromatic polycarbonate resin in the layered silicate, the layered silicate (component B) is finely dispersed well. Furthermore, good thermal stability can be obtained in a resin composition containing a layered silicate, particularly an organically modified layered silicate, by the action of the carboxylic anhydride group. Moreover, since the copolymer itself has good thermal stability, it has high stability even at high temperature conditions required for melt processing of the aromatic polycarbonate resin.
[0112]
The composition of the styrene-containing copolymer obtained by copolymerizing the monomer having a carboxyl group is not limited as long as the above-mentioned condition for the ratio of β is satisfied, but the component from the monomer having a carboxyl group 1 to 30% by weight (especially 5 to 25% by weight), 99 to 70% by weight (especially 95 to 75% by weight) of the styrenic monomer compound component, and 0 to 29 other copolymerizable components. It is preferable to use those containing 1% by weight, 1 to 30% by weight (especially 5 to 25% by weight) of monomers having carboxyl groups, and 99 to 70% by weight (especially 95 to 75%) of styrenic monomer compounds. % By weight) is particularly preferred.
[0113]
Further, the molecular weight of the C1 component which is a preferred embodiment of the C component of the present invention is not particularly limited. The weight average molecular weight of the C1 component is preferably in the range of 10,000 to 1,000,000, and more preferably in the range of 50,000 to 500,000. In addition, the weight average molecular weight shown here is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line by standard polystyrene resin.
[0114]
A polymer having a polyalkylene oxide segment suitable as the C component of the present invention, particularly a polyether ester copolymer (C2 component) will be described.
[0115]
The polyether ester copolymer is a polymer produced by polycondensation from dicarboxylic acid, alkylene glycol, and poly (alkylene oxide) glycol, and derivatives thereof. Particularly preferred examples include poly (alkylene oxide) glycol having a polyalkylene oxide unit represented by the following formula (II) or a derivative thereof (C2 (1) component), and an alkylene containing at least 65 mol% of tetramethylene glycol. It is a copolymer produced from glycol or a derivative thereof (C2 (2) component) and a dicarboxylic acid or derivative thereof (C2 (3) component) containing 60 mol% or more of terephthalic acid.
[0116]
[Chemical 2]

[0117]
(Here, X represents a monovalent organic group, n and m are both integers including 0, and 10 ≦ (n + m) ≦ 120. When m is 2 or more, X is the same and different from each other. Any of the embodiments can be selected.)
In the above formula (II), X is —CH_Three, -CH₂Cl, -CH₂Br, -CH₂I and -CH₂OCH_ThreeAt least one substituent selected from is preferred. When X is other than these, the steric hindrance by a substituent becomes large and it becomes difficult to raise the polymerization degree of a copolymer. When n + m is less than 10, the layered silicate may not be sufficiently dispersed. When n + m exceeds 120, it becomes difficult to obtain a polyether ester copolymer having a high degree of polymerization. The solubilization function may be reduced.
[0118]
As the polyalkylene oxide component in the above formula (II), any of a random copolymer, a tapered copolymer and a block copolymer of a polyethylene oxide component and a component having a substituent X can be selected. The polyalkylene oxide in the above formula (II) is particularly preferably m = 0, that is, a polymer component comprising only a polyethylene oxide component.
[0119]
The copolymerization ratio of the C2 (1) component is 30 to 80% by weight, more preferably 40 to 70% by weight of the total glycol component. When the content of C2 (1) is less than 30% by weight, the layered silicate is not sufficiently dispersed, which may cause deterioration in mechanical properties and appearance. Even when the content of C2 (1) is more than 80% by weight, the layered silicate is not sufficiently dispersed, and the strength of the polyether ester copolymer itself is reduced, resulting in deterioration of mechanical properties and appearance. There is a case.
[0120]
In the C2 component (2) of the C2 component polyether ester copolymer, a diol other than tetramethylene glycol can be copolymerized. Examples of such diols include ethylene glycol, trimethylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. In the component C2 (2), tetramethylene glycol is at least 65 mol%, preferably at least 75 mol%, more preferably at least 85 mol%. A polyether ester copolymer having a tetramethylene glycol content of less than 65 mol% causes a decrease in moldability of the thermoplastic resin composition.
[0121]
A diester of a polyether ester copolymer or a derivative thereof (in the component C2 (3), dicarboxylic acids other than terephthalic acid (including those having a carboxyl group exceeding 2) can be copolymerized. Examples include isophthalic acid, phthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, polyether ester copolymerized with isophthalic acid. The copolymer is particularly suitable as component C. In the component C2 (3), terephthalic acid is 60 mol% or more, preferably 70 mol% or more, more preferably 75 to 95 mol%, and terephthalic acid is 60 mol%. Less than polyether ester copolymer is likely to reduce the degree of polymerization of the copolymer It is not preferable because the production of sufficient degree of polymerization of the polyether ester copolymer becomes difficult.
[0122]
Another suitable C component includes a styrene-containing copolymer containing an oxazoline group as a hydrophilic group. Examples of the styrene monomer compound that forms such a copolymer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethyl Styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene, and the like can be used. Furthermore, other compounds copolymerizable with these compounds, such as acrylonitrile and methacrylonitrile, may be used as the copolymerization component. Among these, styrene (2-isopropenyl-2-oxazoline) -styrene-acrylonitrile copolymer is particularly preferable.
[0123]
The composition ratio of component C of the present invention is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 20 parts by weight per 100 parts by weight of component A. When the amount is less than 0.5 parts by weight, the dispersion effect of the layered silicate is not sufficient, and the effect of suppressing the thermal deterioration of the aromatic polycarbonate resin may be insufficient. On the other hand, if it exceeds 50 parts by weight, impact resistance and heat resistance may be lowered.
[0124]
In the thermoplastic resin composition of the present invention, a reinforcing filler other than the component B can be further blended within a range in which the effects of the present invention are exhibited. Reinforcing fillers include various commonly known fillers such as glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc and various whiskers (potassium titanate whisker, aluminum borate whisker, etc.). Can be used together. The shape can be freely selected from a fiber shape, a flake shape, a spherical shape, and a hollow shape. Glass fibers, carbon fibers and glass flakes are suitable for improving the strength and impact resistance of the thermoplastic resin composition. On the other hand, when the extremely good surface appearance (surface smoothness) of the resin composition of the present invention is utilized more effectively, the size of the reinforcing filler is preferably minute. Specifically, in the case of a fibrous filler, the fiber diameter, and in the case of a plate-like filler or granular filler, the size is preferably 5 μm or less, more preferably 4 μm or less, and further preferably 3 μm or less. preferable. A lower limit of about 0.05 μm is appropriate. Examples of such minute reinforcing fillers include talc, wollastonite, kaolin clay, and various whiskers. The blending amount of the reinforcing filler is suitably 50% by weight or less per 100% by weight of the total thermoplastic resin composition, preferably in the range of 0.5 to 50% by weight, and more preferably in the range of 1 to 35% by weight. When the blending amount exceeds 50% by weight, molding processability is deteriorated and the effects of the present invention cannot be obtained, which is not preferable.
[0125]
Furthermore, other thermoplastic resins (for example, polyamide resins, polyacetal resins, aromatic polyester resins, liquid crystal polyester resins, polyolefin resins, syndiotactic polystyrene resins, polyphenylene sulfide resins, etc.) within the range that does not impair the object of the present invention. Thermoplastic resins), flame retardants (eg brominated epoxy resins, brominated polystyrene, brominated polycarbonate, brominated polyacrylates, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, Organic sulfonate alkali (earth) metal salt, silicone flame retardant, etc.), flame retardant aid (eg sodium antimonate, antimony trioxide, etc.), anti-drip agent (have fibril forming ability) Polytetrafluoroethylene, etc.), nucleating agents (eg, sodium stearate, ethylene-sodium acrylate, etc.), antioxidants (eg, hindered phenolic compounds, sulfur-based antioxidants, etc.), impact modifiers, You may mix | blend a ultraviolet absorber, a light stabilizer, a mold release agent, a lubricant, a coloring agent (dye, an inorganic pigment etc.), a fluorescent whitening agent, etc. These various additives can be used in known blending amounts when blended with the aromatic polycarbonate resin.
[0126]
The thermoplastic resin composition of the present invention preferably contains a phosphorus-based heat stabilizer. Such phosphorus heat stabilizers include phosphate esters such as trimethyl phosphate, triphenyl phosphite, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and Phosphites such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene diphosphonite, etc. Aromatic polycarbonate trees such as phosphonites Compounds widely known as the phosphorus-based heat stabilizer is preferably exemplified. Such a phosphorus-based heat stabilizer preferably contains 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, more preferably 0.01 to 0.2% of 100% by weight of the total composition. More preferably, it contains% by weight. Addition of such a phosphorus-based heat stabilizer can further improve the thermal stability and obtain good molding characteristics.
[0127]
Arbitrary methods are employ | adopted in order to manufacture the thermoplastic resin composition of this invention. For example, each component and optionally other components can be premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a multi-screw extruder represented by a vent type twin screw extruder is preferable. By using such a multi-screw extruder, the organically modified layered silicate is finely dispersed in the base resin with a strong shearing force. On the other hand, the dispersion is performed in the presence of the action of shrinking the interlayer, thereby suppressing the exposure of ions between the layers to the outside. As a result, a higher degree of compatibility between good dispersion and thermal stability is achieved.
[0128]
Furthermore, in the melt kneading by the melt kneader of the thermoplastic resin composition of the present invention, the following mode is more preferable. That is, a compound (C) having an affinity for a layered silicate (B component) having a cation exchange capacity of 50 to 200 meq / 100 g and an amorphous thermoplastic resin of component A and having a hydrophilic component Component), particularly preferably, a styrene-containing polymer (component C1) having a functional group comprising a carboxyl group and / or a derivative thereof is melt-kneaded in advance. Thereafter, the melt-kneaded product and the A component amorphous thermoplastic resin, particularly preferably an aromatic polycarbonate resin, are melt-kneaded by a multi-screw extruder. Such a melt-kneading method is preferable because it improves the thermal stability of the amorphous thermoplastic resin. The aromatic polycarbonate resin is a preferred melt-kneading method because its molecular weight reduction is particularly suppressed. This is presumably because the B component and the C component are previously melt-kneaded so that the C component sufficiently interacts with the B component, and a predetermined effect is efficiently obtained. Therefore, according to the present invention, the B composition and the C component are previously melt-kneaded, and then the melt-kneaded product and the A component are melt-kneaded using a multi-screw extruder, A method for producing a resin composition is provided.
[0129]
More specifically, for example, (i) a method in which the B component and the C component are melt-kneaded and pelletized by a vented twin screw extruder, and the component A is melt-kneaded again, or (ii) the B component C component is introduced from the main supply port of the vent type twin screw extruder, and part or all of the A component is already melt-kneaded from the supply port provided in the middle stage of the twin screw extruder. The method of throwing it into the state is mentioned. In the method of melt-kneading these B component and C component in advance, a part of the A component may be included during the melt-kneading.
[0130]
The thermoplastic resin composition of the present invention can be usually produced by injection molding the pellets produced as described above to produce various products. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.
[0131]
The thermoplastic resin composition of the present invention can also be used in the form of various shaped extruded products, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the thermoplastic resin composition of the present invention can be made into a hollow molded product by rotational molding or blow molding.
[0132]
The thermoplastic resin composition of the present invention has good rigidity, good hydrolysis resistance, and good thermal stability. Therefore, the resin molded product obtained as described above is manufactured under a wide range of molding processing conditions that have no practical problems, and has good rigidity and good surface appearance. More specifically, according to the present invention, it is a resin molded product formed from the thermoplastic resin composition of the present invention, and the value of arithmetic average roughness Ra measured on the surface according to JIS B0601 is , 0.1 μm or less, and a value of the flexural modulus measured in accordance with ASTM D790 is 2,500 MPa or more, and the resin molded product has its industrial value. Is even higher. Conventionally, in order to improve the flexural modulus of a resin molded product, it was common to add a reinforcing material on fiber or an inorganic filler, but in that case, the surface roughness was significantly reduced, This is because a product that can achieve the above balance has not been obtained.
[0133]
The value of the arithmetic surface roughness Ra of the resin molded product is more preferably 0.08 μm or less, and still more preferably 0.05 μm or less. The lower limit is largely due to the mold for molding, but about 0.001 μm is appropriate. Further, the value of the flexural modulus is more preferably 2,800 MPa or more, and further preferably 3,000 MPa or more. On the other hand, the upper limit is suitably 8,000 MPa, preferably 7,000 MPa, and more preferably 6,000 MPa.
[0134]
By subjecting the resin molded product of the present invention to surface modification, a surface modified molded product having excellent smoothness can be obtained. Surface modification here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. The method used for a normal aromatic polycarbonate resin can be applied. In these surface modifications, the surface smoothness of the resin molded product to be modified greatly affects the surface properties after the modification, but when the resin molded product of the present invention is used, the molded product has excellent surface smoothness. Can be obtained. In general, these surface modifications are applied not only for surface modification and function addition, but also for the purpose of improving the surface smoothness of resin molded products. If the surface smoothness is poor, it is necessary to increase the thickness of the modification. However, the resin molded product of the present invention can be efficiently modified with a small thickness. That is, it is preferably 50 μm or less because the effects of the present invention are exhibited. Further, the thickness is more preferably 20 μm or less, further preferably 5 μm or less, and further preferably 2 μm or less. An appropriate lower limit value is 0.001 μm or more. Furthermore, the surface modification is carried out with a thickness within 500 times of the Ra relative to the value of the arithmetic average roughness Ra measured in accordance with JIS B0601 in a resin molded product having no metal layer or metal oxide layer. If it carries out, the feature of the resin molded product of the present invention is utilized, and it is more preferable that the thickness is a value within 200 times of Ra, more preferably within 100 times, and particularly preferably within 50 times. In the present invention, a preferable surface modification method is a method having a small modified thickness such as vapor deposition and plating.
[0135]
The thermoplastic resin composition of the present invention can be applied to parts that could not be used as a resin material by taking advantage of the above characteristics. In particular, it can be used for applications requiring extremely high hydrolysis resistance and rigidity, which could only be achieved by conventional glass moldings or precision metal cuttings. Examples of such applications include a mirror disposed in an optical precision device, a polygon mirror disposed in a laser type copying / printing apparatus, and a hard disk.
[0136]
Furthermore, the thermoplastic resin composition of the present invention is also useful for various applications such as various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, fishing materials, transport containers, packaging containers, and miscellaneous goods. . Since the thermoplastic resin composition of the present invention is excellent in moldability, it is suitable for various thin molded products. Specific examples of the thin injection molded products include various housing molded products such as battery housings, mirrors, and the like. For cylinders, memory cards, speaker cones, disk cartridges, surface light emitters, mechanical parts for micromachines, nameplates, personal computer housings, trays and chassis for CD and DVD drives, trays and chassis for copiers, and direct backlights for liquid crystal devices Examples include a light diffusion plate (particularly a light diffusion plate for a direct backlight for a large liquid crystal display device (large liquid crystal television of 15 inches or more)), an IC card, and the like.
[0137]
【Example】
Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these. In addition, the measurement of the various characteristics in an Example was based on the following method. The following raw materials were used as raw materials.
(1) Content of layered silicate (inorganic content) in the thermoplastic resin composition
The test piece was molded with an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 260 ° C., a mold temperature of 80 ° C. and a molding cycle of 40 seconds, and the molded test piece was cut and placed in a crucible. Weighed, heated to 600 ° C., held as it was for 6 hours, allowed to cool, and weighed the ashing residue remaining in the crucible to measure the amount of layered silicate (inorganic content). That is, since the properties such as the flexural modulus (rigidity) of the resin composition are affected by the proportion of the inorganic component, in each Example and Comparative Examples 2 and 3, the proportion of the inorganic component in the test piece was measured, and the table 1 is expressed as a proportion (% by weight) of the inorganic component B component.
(2) Bottom spacing and average number of layers of the silicate layer of the layered silicate in the thermoplastic resin composition
Measurement was performed using a powder X-type diffractometer (RIGAKU ROTAFLEX RU300: manufactured by Rigaku Corporation). A rod-shaped test piece having a thickness of 6.4 mm was molded under the same conditions as in (1), and a measurement molded product cut to a length of 20 mm was fixed to the opening of the sample table so as to be flush with the measurement reference plane It used for the measurement. The diffraction peak obtained by the measurement is the bottom peak of the layered silicate. Of these, assuming that the diffraction peak on the smallest angle side is the peak corresponding to the bottom spacing of the (001) plane, the bottom spacing is calculated by the following Bragg equation. Calculated.
d = λ / (2 sin θ)
(Where d: bottom surface distance (interlayer distance) (nm), 2θ: diffraction angle of diffraction peak (°), λ: X-ray measurement wavelength (nm))
Furthermore, the average number of layers (N) was determined from the following formula.
N = (D / d) +1
(However, in the formula, N: number of layers (sheets), D: thickness of layers (nm), d: distance between bottom surfaces (nm))
D = 0.9 * λ / (βcosΘ)
(Wherein, D: Lamination thickness (nm), λ: X-ray measurement wavelength (nm), β: Half width (rad), 2Θ: Diffraction peak diffraction angle (rad), where the half width is the diffraction peak Maximum value I₀Of the diffraction peak and the diffraction angle of the diffraction peak is the maximum value I of the peak.₀Indicates the value of 2Θ in the part)
Measurement conditions are shown below.
X-ray source: Cu-Kα (X-ray measurement wavelength 1.5418 × 10^-Tenm), 50 kV-200 mA
Slit: DS / SS 1/2 °
Rs 0.15mm-graphite monochromator-0.45mm
Method: 2θ−θ
Scan: 0.05step / 1 ~ 4sec
Scan range: 1-20 °
[0138]
(3) Viscosity average molecular weight in the thermoplastic resin composition
A test piece was molded under the same conditions as in (1) above, and the viscosity average molecular weight of the test piece was measured by the method described in the text.
(4) Flexural modulus
A test piece of the same shape (dimensions: length 127 mm × width 12.7 mm × thickness 6.4 mm) molded under the same conditions as in (1) above is ASTM-D790 in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% RH. The flexural modulus (MPa) was measured by a method based on the above. The larger this value, the better the rigidity of the molded resin composition.
(5) Decrease rate of viscosity average molecular weight after high temperature and high humidity test (ΔM_ratio)
A test piece of the same shape (dimensions: length 127 mm × width 12.7 mm × thickness 6.4 mm) molded under the same conditions as in (1) above was left in a pressure cooker at a temperature of 105 ° C. and a relative humidity of 100% for 10 hours. After treatment, the viscosity average molecular weight measured using a test piece (test piece after treatment) that was allowed to stand for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and an environment of a temperature of 23 ° C. and a relative humidity of 50% Viscosity average molecular weight measured using a test piece left for 74 hours (test piece before treatment) was calculated according to the following formula, and the rate of decrease in viscosity average molecular weight after constant temperature and humidity test (ΔM_ratio) Was calculated.
ΔM_ratio= 100 × [(viscosity average molecular weight of test piece before treatment) − (viscosity average molecular weight of test piece after treatment)] / (viscosity average molecular weight of test piece before treatment)
The smaller this value, the better the hydrolysis resistance of the molded resin composition.
[0139]
[material]
The following were used as raw materials.
(A component: polycarbonate resin)
Bisphenol A type aromatic polycarbonate resin powder having a viscosity average molecular weight of 23,800 [“Panlite L-1250WP” manufactured by Teijin Chemicals Ltd.]
[0140]
(Other than B component and B component)
B-1: Synthetic mica (Somasif ME-100: manufactured by Coop Chemical Co., Ltd., cation exchange capacity: 110 meq / 100 g)
B-2: synthetic mica (Somasif ME-100: manufactured by Coop Chemical Co., Ltd.) trioctylmethylammonium chloride almost completely ion-exchanged
B-3: Synthetic mica (Somasif ME-100: manufactured by Coop Chemical Co., Ltd.) obtained by almost complete ion exchange of didecyldimethylammonium chloride
B-4: Synthetic mica (Somasif ME-100: manufactured by Coop Chemical Co., Ltd.) almost completely ion-exchanged with triphenylmethylammonium chloride
B-5: Synthetic mica (Somasif ME-100: manufactured by Coop Chemical Co., Ltd.) almost completely ion-exchanged with dioctadecyldimethylammonium chloride
[0141]
(C component)
C-1: Styrene-maleic anhydride copolymer (manufactured by Nova Chemical Japan Co., Ltd .: “DYLARK 332-80”, maleic anhydride amount of about 15% by weight)
(Other ingredients)
TMP: Trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP), the amount added is 0.1 part by weight per 100 parts by weight of component A in all compositions.
[0142]
[Examples 1 and 2 and Comparative Examples 1 to 3]
The B-component and C-components in the ratio of amounts shown in Table 1 are 30 mmφ in diameter, L / D = 33.2, and a twin screw extruder equipped with a screw in two kneading zones (manufactured by Kobe Steel, Ltd.) KTX30) was melt-kneaded at a cylinder temperature of 200 ° C., extruded, and strand-cut to obtain pellets. Using the obtained pellets, the above-mentioned mixture of the B and C components and the A component are dry blended so that the final ratio is as shown in Table 3, and then the diameter is 30 mmφ, L / D = 33.2, kneading Using a twin-screw extruder with a vent equipped with screws in two zones (manufactured by Kobe Steel, Ltd .: KTX30), the mixture was melt-kneaded at a cylinder temperature of 280 ° C., extruded, and strand-cut to obtain pellets.
[0143]
The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 5 hours. After drying, the test piece was molded by an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 260 ° C, a mold temperature of 80 ° C, and a molding cycle of 40 seconds. The measurement results for these are shown in Table 1.
[0144]
[Table 1]

[0145]
As is apparent from the above table, the thermoplastic resin composition of the present invention has good rigidity and extremely good hydrolysis resistance and further good thermal stability by satisfying a specific dispersion form. It can be seen that a thermoplastic resin composition is provided. The thermal stability is particularly good when the B component layered silicate and the C component are previously kneaded. This provides a thermoplastic resin composition, particularly an aromatic polycarbonate resin composition, comprising a layered silicate that is practical and applicable in a wide range of fields. It can be seen that the above-mentioned specific effect is specifically obtained in the unique dispersion state of the present invention. By this dispersed state, improvement in rigidity and hydrolysis resistance becomes remarkable.
[0146]
【The invention's effect】
The thermoplastic resin composition of the present invention has a thermoplastic resin composition, particularly an aromatic polycarbonate resin, having good rigidity, good hydrolysis resistance, and good thermal stability. It is a plastic resin composition. Furthermore, the thermoplastic resin composition of the present invention has melt viscosity characteristics suitable for both injection molding and extrusion molding, and is excellent in molding processability. Therefore, it is useful in a wide range of fields such as the thermoplastic resin composition of the present invention, electrical and electronic parts field, OA equipment parts field, automobile parts field, agricultural material field, fishery material field, transport container field, packaging container field, and sundries field. In particular, it is useful in the field of electrical and electronic parts, the field of OA equipment parts, and the field of automobile parts, and the industrial effects that it produces are exceptional.

Claims (2)

(A) per 100 parts by weight of aromatic polycarbonate resin (component A) (B) layered silicate (component B) having a cation exchange capacity of 50 to 200 meq / 100 g and (C) ) Ri carboxyl group and / or styrene-containing polymer 0.1 to 50 parts by weight Tona having a functional group consisting of a derivative thereof, does not contain a partial ester and / or full ester of polyhydric alcohol and titanium dioxide as well as higher fatty acid A thermoplastic resin composition obtained by melt-kneading the B component and the C component in advance, and then melt-kneading the melt-kneaded product, the A component and the remaining components using a multi-screw extruder , In the resin composition, the thermoplastic resin has an average number of silicate layers obtained from X-ray diffraction of 5 to 40 and a bottom surface distance of 1.3 to 2.3 nm. Composition.   The thermoplastic resin composition according to claim 1, wherein the component B is an organically modified layered silicate in which organic onium ions are ion-exchanged between layers at a ratio of 40% or more of the cation exchange capacity of the layered silicate.