JP4027741B2 - Plastic molded product - Google Patents

Description

【０１１２】
（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（Ｉ）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。
【０１１３】
上記式（Ｉ）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（Ｉ）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。
【０１１４】
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。
【０１１５】
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、樹脂組成物の成形性の低下を招く。
【０１１６】
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。
【０１１７】
本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物は、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。
【０１１８】
また本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物は離型剤を含むことが好ましい。かかる離型剤としては公知のものが使用できる。例えば、脂肪酸エステル、ポリオレフィン系ワックス（ポリエチレンワックス、１−アルケン重合体など。酸変性などの官能基含有化合物で変性されているものも使用できる）、シリコーン化合物（特にフェニル基およびメチル基などのアルキル基の双方を有するオルガノシロキサン化合物などに代表される）、フッ素オイル（ポリフルオロアルキルエーテルなどに代表される）、パラフィンワックス、並びに蜜蝋などを挙げることができる。
【０１１９】
中でも脂肪酸エステルおよびシリコーン化合物が好ましく、特に脂肪酸エステルが、離型性、成形品の透明性およびハードコート層との密着性などの点から好ましく使用される。脂肪酸エステルはアルコールと脂肪族カルボン酸とのエステルであるが、アルコールとしては一価アルコールおよび二価以上の多価アルコールのいずれも使用可能である。本発明では脂肪酸エステルは多価アルコールを主体とすることがより好適である。
【０１２０】
一価アルコールとしては、例えばドデカノール、テトラデカノール、ヘキサデカノール、オクタデカノール、エイコサノール、テトラコサノール、セリルアルコール、およびトリアコンタノールなどが例示される。
【０１２１】
多価アルコールの具体例としては、グリセリン、ジグリセリン、ポリグリセリン（例えばデカグリセリンなど）、ペンタエリスリトール、ジペンタエリスリトール、ジエチレングリコール、およびプロピレングリコールなどが挙げられ、中でもペンタエリスリトールが好ましい。
【０１２２】
脂肪酸エステルに使用される脂肪族カルボン酸は、その炭素原子数が３〜３２であるものが好ましい。かかる炭素原子数３〜３２の脂肪族カルボン酸としては、例えばヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ウンデカン酸、ドデカン酸、トリデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸（パルミチン酸）、ヘプタデカン酸、オクタデカン酸（ステアリン酸）、ノナデカン酸、イコサン酸、ドコサン酸、およびヘキサコサン酸などの飽和脂肪族カルボン酸、並びにパルミトレイン酸、オレイン酸、リノール酸、リノレン酸、エイコセン酸、エイコサペンタエン酸、およびセトレイン酸などの不飽和脂肪族カルボン酸を挙げることができる。
【０１２３】
上記の中でも脂肪族カルボン酸は炭素原子数１０〜２２であるものが好ましく、炭素原子数１４〜２０であるものがより好ましい。更に好ましくはかかる飽和脂肪族カルボン酸である。特にステアリン酸およびパルミチン酸が好ましい。
【０１２４】
ステアリン酸やパルミチン酸などの脂肪族カルボン酸は通常、動物性油脂（牛脂および豚脂など）や植物性油脂（パーム油など）などの天然油脂類から製造される。したがってステアリン酸などの脂肪族カルボン酸は通常炭素原子数の異なる他のカルボン酸成分を含む混合物である。本発明の脂肪酸エステルの製造においてもかかる天然油脂類から製造され、他のカルボン酸成分を含む混合物の形態からなるステアリン酸やパルミチン酸が好ましく使用される。かかる混合物における各成分の組成割合の好ましい態様は次のとおりである。
【０１２５】
すなわち、該脂肪族カルボン酸はパルミチン酸成分とステアリン酸成分とを含み、その熱分解メチル化ＧＣ／ＭＳ（ガスクロマト−質量分析）法におけるピーク面積において、パルミチン酸成分の面積（Ｓｐ）とステアリン酸成分の面積（Ｓｓ）との合計が全脂肪族カルボン酸中８０％以上であり、かつ両者の面積比（Ｓｓ／Ｓｐ）が１．２以上であるものが好ましい。ここで熱分解メチル化ＧＣ／ＭＳ法とは、パイロフィル上において試料である脂肪酸エステルと反応試剤である水酸化メチルアンモニウムを反応させて脂肪酸エステルを分解すると共に脂肪酸のメチルエステル誘導体を生成させ、かかる誘導体に対してＧＣ／ＭＳ測定を行う方法である。
【０１２６】
かかるＳｐおよびＳｓの合計は、全脂肪族カルボン酸成分中８５％以上が好ましく、９０％以上がより好ましく、９１％以上が更に好ましい。また一方で上記のＳｐおよびＳｓの合計は１００％とすることも可能であるが、製造コストなどの観点から９８％以下が好ましく、９６％以下がより好ましい。また上記の面積比（Ｓｓ／Ｓｐ）は、１．３〜３０の範囲がより好ましい。更にその上限は１０がより好ましく、４が更に好ましく、更に３が特に好ましい。尚、これらの混合比率は単独の脂肪族カルボン酸で満足する必要はなく、２種以上の脂肪族カルボン酸を混合することにより満足するものであってもよい。また上記の混合比率を満足する脂肪族カルボン酸の原料となる油脂としては、例えば牛脂および豚脂などの動物性油脂、並びにアマニ油、サフラワー油、ヒマワリ油、大豆油、トウモロコシ油、落花生油、綿実油、ゴマ油、およびオリーブ油などの植物性油脂を挙げることができる。上記の中でもステアリン酸をより多く含む点で動物性油脂が好ましく、更に牛脂がより好ましい。更に牛脂の中でもステアリン酸およびパルミチン酸などの飽和成分を多く含むオレオステアリンが好ましい。
【０１２７】
本発明で脂肪酸エステルは、そのエステル化率は特に制限されないものの、エステル化率は６０％以上が好ましく、８０％以上がより好ましく、８５％以上が更に好ましい。エステル化率が低く、水酸基価が高い脂肪酸エステルはポリカーボネート樹脂を劣化させやすく、成形品の割れが生じやすくなる。上記より本発明の脂肪酸エステルは多価アルコールと脂肪族カルボン酸とのフルエステルが好ましい。但し、本発明においてフルエステルとは、そのエステル化率が必ずしも１００％である必要はなく、８０％以上であればよく、好ましくは８５％以上である。
【０１２８】
脂肪酸エステルにおける酸価、水酸基価、ヨウ素価、およびＴＧＡ（熱重量解析）測定における５％重量減少温度などについて説明する。
【０１２９】
脂肪酸エステルの酸価は、熱安定性や成形品の割れへの影響の点からは低いことが好ましく、一方離型力の低減（離型性の向上）の点からは比較的高いことが好ましい。脂肪酸エステルの酸価は０．１〜２０の範囲が適切であり、２〜１８の範囲がより好ましく、５〜１５の範囲が更に好ましい。酸価はＪＩＳ Ｋ ００７０に規定された方法により求めることができる。
【０１３０】
脂肪酸エステルの水酸基価は、熱安定性、離型力低減および成形品の割れへの影響の点からは低いことが好ましく、一方あまりに低いことは製造時間の増大によりコストが増大するため好ましくない。脂肪酸エステルの水酸基価は、０．１〜４０の範囲が適切であり、１〜３０の範囲が好ましく、２〜２０の範囲がより好ましい。水酸基価はＪＩＳ Ｋ ００７０に規定された方法により求めることができる。
【０１３１】
脂肪酸エステルのヨウ素価は、熱安定性の点から低いことが好ましい。脂肪酸エステルのヨウ素価は１０以下が好ましく、１以下がより好ましい。かかるヨウ素価はＪＩＳ Ｋ ００７０に規定された方法により求めることができる。
【０１３２】
脂肪酸エステルなどの離型剤は、ポリカーボネート樹脂１００重量部に対して０．００５〜２重量部が好ましく、０．０１〜１重量部がより好ましく、０．０５〜０．５重量部が更に好ましい。離型剤が上記範囲を超えて少なすぎる場合には離型性の改善が十分でない。一方離型剤が上記範囲を超えて多すぎる場合には成形品の透明性を損ないやすい。
【０１３３】
また、本発明の樹脂成形品を車輌用透明部材として用いるためには、良好な耐候性が求められる場合が多いことから、樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物は更に紫外線吸収剤を含むものであることが好ましい。
【０１３４】
紫外線吸収剤としては、具体的にはベンゾフェノン系では、例えば、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−オクトキシベンゾフェノン、２−ヒドロキシ−４−ベンジロキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−５−スルホキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−５−スルホキシトリハイドライドレイトベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシ−５−ソジウムスルホキシベンゾフェノン、ビス（５−ベンゾイル−４−ヒドロキシ−２−メトキシフェニル）メタン、２−ヒドロキシ−４−ｎ−ドデシルオキシベンソフェノン、および２−ヒドロキシ−４−メトキシ−２’−カルボキシベンゾフェノンなどが例示される。
【０１３５】
紫外線吸収剤化合物は、具体的に、ベンゾトリアゾール系では、例えば、２−（２−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾ−ル、２−（２−ヒドロキシ−５−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾ−ル、２−（２−ヒドロキシ−３，５−ジクミルフェニル）フェニルベンゾトリアゾール、２−（２−ヒドロキシ−３−ｔｅｒｔ−ブチル−５−メチルフェニル）−５−クロロベンゾトリアゾール、２，２’−メチレンビス［４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール］、２−（２−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾ−ル、２−（２−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２−ヒドロキシ−３，５−ジ−ｔｅｒｔ−アミルフェニル）ベンゾトリアゾ−ル、２−（２−ヒドロキシ−５−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾ−ル、２−（２−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾ−ル、２−（２−ヒドロキシ−４−オクトキシフェニル）ベンゾトリアゾ−ル、２，２’−メチレンビス（４−クミル−６−ベンゾトリアゾールフェニル）、２，２’−ｐ−フェニレンビス（１，３−ベンゾオキサジン−４−オン）、および２−［２−ヒドロキシ−３−（３，４，５，６−テトラヒドロフタルイミドメチル）−５−メチルフェニル］ベンゾトリアゾ−ル、並びに２−（２’−ヒドロキシ−５−メタクリロキシエチルフェニル）−２Ｈ−ベンゾトリアゾールと該モノマーと共重合可能なビニル系モノマーとの共重合体や２−（２’―ヒドロキシ−５−アクリロキシエチルフェニル）―２Ｈ―ベンゾトリアゾールと該モノマーと共重合可能なビニル系モノマーとの共重合体などの２−ヒドロキシフェニル−２Ｈ−ベンゾトリアゾール骨格を有する重合体などが例示される。
【０１３６】
紫外線吸収剤化合物は、具体的に、ヒドロキシフェニルトリアジン系では、例えば、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−ヘキシルオキシフェノール、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−メチルオキシフェノール、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−エチルオキシフェノール、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−プロピルオキシフェノール、および２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−ブチルオキシフェノールなどが例示される。更に２−（４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン−２−イル）−５−ヘキシルオキシフェノールなど、上記フェニル基が２，４−ジメチルフェニル基である化合物が例示される。
【０１３７】
上記の中でもベンゾトリアゾール系およびヒドロキシフェニルトリアジン系が好ましい。上記紫外線吸収剤は単独であるいは２種以上の混合物で用いてもよい。紫外線吸収剤の使用量は、芳香族ポリカーボネート樹脂１００重量部に対して０．０００５〜３重量部が好ましく、０．０１〜２重量部がより好ましく、０．０２〜１重量部が更に好ましく、０．０５〜０．５重量部が特に好ましい。
【０１３８】
また本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物は、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、ポリ｛［６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル］［（２，２，６，６−テトラメチルピペリジル）イミノ］ヘキサメチレン［（２，２，６，６−テトラメチルピペリジル）イミノ］｝、およびポリメチルプロピル３−オキシ−［４−（２，２，６，６−テトラメチル）ピペリジニル］シロキサンなどに代表されるヒンダードアミン系の光安定剤も含むことができる。更にヒンダードアミン系光安定剤とベンゾトリアゾール系および／またはトリアジン系紫外線吸収剤との併用が耐候性を効果的に向上させる。かかる併用では両者の重量比（光安定剤／紫外線吸収剤）は９５／５〜５／９５の範囲が好ましく、８０／２０〜２０／８０の範囲が更に好ましい。
【０１３９】
上記光安定剤は単独であるいは２種以上の混合物で用いてもよい。光安定剤の使用量は芳香族ポリカーボネート樹脂１００重量部に対して０．０００５〜３重量部が好ましく、０．０１〜２重量部がより好ましく、０．０２〜１重量部が更に好ましく、０．０５〜０．５重量部が特に好ましい。
【０１４０】
本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物は、更にブルーイング剤を芳香族ポリカーボネート樹脂組成物中０．０５〜３ｐｐｍ（重量割合）含んでなることが好ましい。ポリカーボネート樹脂成形品の黄色味を消すために有効である。特に耐候性を付与した成形品の場合は、一定量の紫外線吸収剤が使用されているため「紫外線吸収剤の作用や色」によって樹脂製品が黄色味を帯びやすい現実があり、したがって成形品に自然な透明感を付与するためにはブルーイング剤の使用は非常に有効である。
【０１４１】
ここでブルーイング剤とは、橙色ないし黄色の光線を吸収することにより青色ないし紫色を呈する着色剤をいい、特に染料が好ましい。ブルーイング剤の配合により本発明のポリカーボネート樹脂組成物は、更に良好な色相を達成する。ここで重要な点はかかるブルーイング剤の配合量である。樹脂組成物中、ブルーイング剤が０．０５ｐｐｍ未満では色相の改善効果が不十分な場合がある一方、３ｐｐｍを超える場合には光線透過率が低下し適当ではない。より好ましいブルーイング剤の配合量は樹脂組成物中０．５〜２．５ｐｐｍ、更に好ましくは０．５〜２ｐｐｍの範囲である。
【０１４２】
ブルーイング剤としては代表例として、バイエル社のマクロレックスバイオレットＢおよびマクロレックスブルーＲＲや、サンド社のテラゾールブルーＲＬＳ、並びに有本化学工業社のプラストブルー８５８０などが挙げられる。
【０１４３】
本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物には、発明の目的を損なわない範囲で上記ブルーイング剤以外にも各種の染顔料を使用することができる。特に透明性を維持する点から、染料が好適である。好ましい染料としてはペリレン系染料、クマリン系染料、チオインジゴ系染料、アンスラキノン系染料、チオキサントン系染料、紺青等のフェロシアン化物、ペリノン系染料、キノリン系染料、キナクリドン系染料、ジオキサジン系染料、イソインドリノン系染料、およびフタロシアニン系染料などを挙げることができる。更にビスベンゾオキサゾリル−スチルベン誘導体、ビスベンゾオキサゾリル−ナフタレン誘導体、ビスベンゾオキサゾリル−チオフェン誘導体、およびクマリン誘導体などの蛍光増白剤を使用することができる。これら染料および蛍光増白剤の使用量は、芳香族ポリカーボネート樹脂１００重量部あたり、０．０００１〜１重量部が好ましく、０．０００５〜０．５重量部がより好ましい。
【０１４４】
本発明の樹脂成形品には、帯電防止性能が求められる場合があり、かかる場合帯電防止剤を含む芳香族ポリカーボネート樹脂組成物から形成されることが好ましい。かかる帯電防止剤としては、例えば（ｉ）ドデシルベンゼンスルホン酸ホスホニウム塩に代表されるアリールスルホン酸ホスホニウム塩、およびアルキルスルホン酸ホスホニウム塩などの有機スルホン酸ホスホニウム塩が挙げられる。該ホスホニウム塩は、Ａ成分１００重量部あたり５重量部以下の組成割合が適切であり、０．０５〜５重量部が好ましく、１〜３．５重量部がより好ましく、１．５〜３重量部の範囲が更に好ましい。
【０１４５】
帯電防止剤としては例えば、（ｉｉ）有機スルホン酸リチウム、有機スルホン酸ナトリウム、有機スルホン酸カリウム、有機スルホン酸セシウム、有機スルホン酸ルビジウム、有機スルホン酸カルシウム、有機スルホン酸マグネシウム、有機スルホン酸バリウムなどの有機スルホン酸アルカリ（土類）金属塩が挙げられる。具体的には例えばドデシルベンゼンスルホン酸の金属塩やパーフルオロアルカンスルホン酸の金属塩などが例示される。有機スルホン酸アルカリ（土類）金属塩は、Ａ成分１００重量部あたり０．５重量部以下の組成割合が適切であり、０．００１〜０．３重量部が好ましく、０．００５〜０．２重量部がより好ましい。特にカリウム、セシウム、およびルビジウムなどのアルカリ金属塩が好適である。
【０１４６】
帯電防止剤としては、例えば（ｉｉｉ）アルキルスルホン酸アンモニウム塩、およびアリールスルホン酸アンモニウム塩などの有機スルホン酸アンモニウム塩が挙げられる。該アンモニウム塩は、Ａ成分１００重量部あたり０．０５重量部以下の組成割合が適切である。帯電防止剤としては、例えば（ｉｖ）グリセリンモノステアレート、無水マレイン酸モノグリセライド、および無水マレイン酸ジグリセライドなどのグリセリン誘導体エステルが挙げられる。該エステルはＡ成分１００重量部あたり０．５重量部以下の組成割合が適切である。帯電防止剤としては、例えば（ｖ）ポリエーテルエステルアミドなどのポリ（オキシアルキレン）グリコール成分をその構成成分として含有するポリマーが挙げられる。該ポリマーはＡ成分１００重量部あたり５重量部以下が適切である。他の帯電防止剤としては、例えば、（ｖｉ）カーボンブラック、カーボンファイバー、カーボンナノチューブ、グラファイト、金属粉末、金属酸化物粉末などの非有機化合物が挙げられる。該非有機化合物は、Ａ成分１００重量部あたり０．０５重量部以下の組成割合が適切である。またこれらの（ｖｉ）に例示された非有機化合物は、帯電防止性能以外にも、熱線吸収剤として配合される場合がある。
【０１４７】
本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物には、本発明の目的が損なわれない量の熱線吸収能を有する化合物を使用することができる。該化合物としてはフタロシアニン系近赤外線吸収剤および炭素フィラーが好適に例示される。かかるフタロシアニン系近赤外線吸収剤としては例えば三井化学（株）製ＭＩＲ−３６２が市販され容易に入手可能である。炭素フィラーとしてはカーボンブラック、グラファイト（天然および人工のいずれも含み、更にウイスカーを含む）、カーボンファイバー（気相成長法によるものを含む）、カーボンナノチューブ、およびフラーレンなどが例示され、好ましくはカーボンブラックおよびグラファイトである。これらは単独でまたは２種以上併用して使用することができる。フタロシアニン系近赤外線吸収剤は、ポリカーボネート樹脂１００重量部に対して０．００５〜０．２重量部が好ましく、０．００８〜０．１重量部がより好ましく、０．０１〜０．０７重量部が更に好ましい。炭素フィラーは本発明の樹脂組成物中、０．１〜２００ｐｐｍ（重量割合）の範囲が好ましく、０．５〜１００ｐｐｍの範囲がより好ましく、１〜５０ｐｐｍの範囲が更に好ましい。
【０１４８】
本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物には、本発明の目的が損なわれない量の難燃剤を使用することができる。難燃剤としては、ハロゲン化ビスフェノールＡのポリカーボネート型難燃剤、有機塩系難燃剤、芳香族リン酸エステル系難燃剤、あるいは、ハロゲン化芳香族リン酸エステル型難燃剤等が挙げられ、それらを一種以上使用することができる。
【０１４９】
具体的にハロゲン化ビスフェノールＡのポリカーボネート型難燃剤は、テトラブロモビスフェノールＡのポリカーボネート型難燃剤、テトラブロモビスフェノールＡとビスフェノールＡとの共重合ポリカーボネート型難燃剤等である。
【０１５０】
具体的に有機塩系難燃剤は、ジフェニルスルホン−３，３’−ジスルホン酸ジカリウム、ジフェニルスルホン−３−スルホン酸カリウム、２，４，５−トリクロロベンゼンスルホン酸ナトリウム、２，４，５−トリクロロベンゼンスルホン酸カリウム、ビス（２，６−ジブロモ−４−クミルフェニル）リン酸カリウム、ビス（４−クミルフェニル）リン酸ナトリウム、ビス（ｐ−トルエンスルホン）イミドカリウム、ビス（ジフェニルリン酸）イミドカリウム、ビス（２，４，６−トリブロモフェニル）リン酸カリウム、ビス（２，４−ジブロモフェニル）リン酸カリウム、ビス（４−ブロモフェニル）リン酸カリウム、ジフェニルリン酸カリウム、ジフェニルリン酸ナトリウム、パーフルオロブタンスルホン酸カリウム、ラウリル硫酸ナトリウムあるいはカリウム、ヘキサデシル硫酸ナトリウムあるいはカリウム等である。
【０１５１】
具体的にハロゲン化芳香族リン酸エステル型難燃剤は、トリス（２，４，６−トリブロモフェニル）ホスフェート、トリス（２，４−ジブロモフェニル）ホスフェート、トリス（４−ブロモフェニル）ホスフェート等である。
【０１５２】
具体的に芳香族リン酸エステル系難燃剤は、トリフェニルホスフェート、トリス（２，６−キシリル）ホスフェート、テトラキス（２，６−キシリル）レゾルシンジホスフェート、テトラキス（２，６−キシリル）ヒドロキノンジホスフェート、テトラキス（２，６−キシリル）−４，４’−ビフェノールジホスフェート、テトラフェニルレゾルシンジホスフェート、テトラフェニルヒドロキノンジホスフェート、テトラフェニル−４，４’−ビフェノールジホスフェート、芳香環ソースがレゾルシンとフェノールでありフェノール性ＯＨ基を含まない芳香族ポリホスフェート、芳香環ソースがレゾルシンとフェノールでありフェノール性ＯＨ基を含む芳香族ポリホスフェート、芳香環ソースがヒドロキノンとフェノールでありフェノール性ＯＨ基を含まない芳香族ポリホスフェート、同様のフェノール性ＯＨ基を含む芳香族ポリホスフェート、（以下に示す「芳香族ポリホスフェート」は、フェノール性ＯＨ基を含む芳香族ポリホスフェートと含まない芳香族ポリホスフェートの両方を意味するものとする）芳香環ソースがビスフェノールＡとフェノールである芳香族ポリホスフェート、芳香環ソースがテトラブロモビスフェノールＡとフェノールである芳香族ポリホスフェート、芳香環ソースがレゾルシンと２，６−キシレノールである芳香族ポリホスフェート、芳香環ソースがヒドロキノンと２，６−キシレノールである芳香族ポリホスフェート、芳香環ソースがビスフェノールＡと２，６−キシレノールである芳香族ポリホスフェート、芳香環ソースがテトラブロモビスフェノールＡと２，６−キシレノールである芳香族ポリホスフェート等である。
【０１５３】
本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物には、Ｃ成分以外の樹脂やエラストマーを適宜目的に応じて配合することもできる。
【０１５４】
かかる他の樹脂としては、例えば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等のポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリウレタン樹脂、シリコーン樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、ポリスチレン樹脂、アクリロニトリル／スチレン共重合体（ＡＳ樹脂）、アクリロニトリル／ブタジエン／スチレン共重合体（ＡＢＳ樹脂）、ポリメタクリレート樹脂、フェノール樹脂、エポキシ樹脂等の樹脂が挙げられる。
【０１５５】
また、エラストマーとしては、例えばイソブチレン／イソプレンゴム、スチレン／ブタジエンゴム、エチレン／プロピレンゴム、アクリル系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、コアシェル型のエラストマーであるＭＢＳ（メタクリル酸メチル／ステレン／ブタジエン）ゴム、ＭＡＳ（メタクリル酸メチル／アクリロニトリル／スチレン）ゴム等が挙げられる。
【０１５６】
本発明の樹脂成形品を形成する芳香族ポリカーボネート樹脂組成物には、適宜目的に応じて各種離型剤、無機充填材、流動改質剤、抗菌剤、光触媒系防汚剤、メタリック剤およびフォトクロミック剤などを、本発明の効果が損なわれない範囲で配合することができる。
【０１５７】
本発明の樹脂成形品を形成する芳香族ポリカーボネート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。
【０１５８】
更に、本発明の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成分の芳香族ポリカーボネート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系重合体（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成分の芳香族ポリカーボネート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芳香族ポリカーボネート樹脂の熱安定性を向上させるため好ましい。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。
【０１５９】
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。
【０１６０】
本発明の樹脂成形品は通常上記の如く製造されたペレットを射出成形して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、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。
【０１６１】
また本発明の樹脂成形品は、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製造することもできる。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。また本発明の樹脂成形品を回転成形やブロー成形などにより中空成形品として製造することも可能である。
【０１６２】
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、かつ良好な表面平滑性、良好な表面硬度、および良好な剛性を有する。より具体的には、▲１▼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、▲２▼ＪＩＳ Ｋ５４００に準拠して測定された手かき法による鉛筆引っかき値が、ＨＢ以上、▲３▼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得られ、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。
【０１６３】
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。鉛筆引っかき値は、より好ましくはＦ以上であり、その上限は４Ｈ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。
【０１６４】
本発明の樹脂成形品は、その樹脂組成物から形成された厚み１ｍｍの平滑平板状成形品におけるＪＩＳ Ｋ７１０５に準拠して測定された全光線透過率が７５％以上であることが好ましく、８０％以上であることがより好ましい。上限は９１．５％が好ましく、９１％がより好ましい。かかる条件を満足する組成物はより良好な光透過性を有する樹脂成形品の提供を可能とする。更に本発明の樹脂成形品は、その厚みが１〜５ｍｍであることが好ましく、１〜３ｍｍがより好ましく、１〜２ｍｍが更に好ましい。本発明の樹脂成形品はかかる厚みにおいても良好な光透過性を有し、かかる厚みを有する透明性の樹脂成形品を提供する。
【０１６５】
本発明の樹脂成形品は、高い曲げ弾性率の値を有するが、通常の無機強化材で補強した場合に比べて、比重の増加が小さいという特徴も有する。即ち、同一重量で比較すればより高い曲げ剛性を成形品に付与できることを意味する。この効果は、例えば、［（曲げ弾性率）／（比重）³］で表される指標で比較することができ、この値が大きいほど、軽量で剛性の高い樹脂成形品が得られることになる。ビスフェノールＡ型芳香族ポリカーボネート樹脂の場合、曲げ弾性率が２，１５０ＭＰａ、比重が１．２０であるため、上記指標値は１，２４４となる。一方、本発明によれば、このましくはかかる指標値が好ましくは１，５００以上、更に好ましくは１，６００以上である樹脂組成物からなる成形品が提供される。したがってビスフェノールＡ型芳香族ポリカーボネート樹脂に対して、１．２倍を超える剛性を同一重量において付与することが可能となる。他方かかる特性は製品の軽量化に寄与する。
【０１６６】
本発明の樹脂成形品には、各種の表面処理を行うことが可能である。表面処理としては、ハードコート、撥水・撥油コート、親水性コート、帯電防止コート、紫外線吸収コート、赤外線吸収コート、並びにメタライジング（蒸着など）などの各種の表面処理を行うことができる。表面処理方法としては、液剤のコーティングの他、蒸着法、溶射法、およびメッキ法が挙げられる。蒸着法としては物理蒸着法および化学蒸着法のいずれも使用できる。物理蒸着法としては真空蒸着法、スパッタリング、およびイオンプレーティングが例示される。化学蒸着（ＣＶＤ）法としては、熱ＣＶＤ法、プラズマＣＶＤ法、および光ＣＶＤ法などが例示される。例えばメタライジングすることでミラーやリフレクターなどの用途に好適な成形品が提供される。
【０１６７】
本発明の樹脂成形品は、良好な表面硬度を有しているが、ハードコートを施すことにより更に車輌用透明部材に適したものとなる。すなわち基体成形品が良好な表面硬度を有することから、ハードコート層の特性をより有効に発現できる。更に本発明の樹脂成形品は線膨張係数も低減されていることから、ハードコート層との膨張率の差異による密着性の低下においても低減されている。
【０１６８】
本発明で使用するハードコート剤としては、シリコーン樹脂系ハードコート剤や有機樹脂系ハードコート剤などが例示される。シリコーン樹脂系ハードコート剤は、シロキサン結合をもった硬化樹脂層を形成するものであり、例えば、３官能シロキサン単位に相当する化合物（トリアルコキシシラン化合物など）を主成分とする化合物の部分加水分解縮合物、好ましくは更に４官能シロキサン単位に相当する化合物（テトラアルコキシシラン化合物など）を含む部分加水分解縮合物、並びに更にこれらにコロイダルシリカなどの金属酸化物微粒子を充填した部分加水分解縮合物などが挙げられる。シリコーン樹脂系ハードコート剤は更に２官能性のシロキサン単位および１官能性のシロキサン単位を含んでよい。これらには縮合反応時に発生するアルコール（アルコキシシランの部分加水分解縮合物の場合）などが含まれるが、更に必要に応じて任意の有機溶剤、水、あるいはこれらの混合物に溶解ないしは分散させてもよい。そのための有機溶剤としては、低級脂肪酸アルコール類、多価アルコールとそのエーテル、エステル類などが挙げられる。なお、ハードコート層には平滑な表面状態を得るため各種界面活性剤、例えば、シロキサン系、フッ化アルキル系界面活性剤などを添加してもよい。
【０１６９】
有機樹脂系ハードコート剤としては、例えば、メラミン樹脂、ウレタン樹脂、アルキド樹脂、アクリル樹脂、多官能アクリル樹脂などが挙げられる。ここで多官能アクリル樹脂としてはポリオールアクリレート、ポリエステルアクリレート、ウレタンアクリレート、エポキシアクリレート、ホスファゼンアクリレートなどの樹脂が挙げられる。
【０１７０】
これらハードコート剤のうち長期間の耐久性に優れ、かつ表面硬度が比較的高いシリコーン樹脂系ハードコート剤、または処理が比較的簡便でかつ良好なハードコート層が形成される紫外線硬化型のアクリル樹脂または多官能アクリル樹脂が好ましい。シリコーン樹脂系ハードコート剤はプライマー層とトップ層から構成されるいわゆる２コートタイプ、並びに１層のみから形成されるいわゆる１コートタイプのいずれも選択できる。
【０１７１】
かかるプライマー層（第１層）を形成する樹脂としては、各種ブロックイソシアネート成分およびポリオール成分からなるウレタン樹脂、アクリル樹脂、ポリエステル樹脂、エポキシ樹脂、メラミン樹脂、アミノ樹脂、およびポリエステルアクリレート、ウレタンアクリレート、エポキシアクリレート、ホスファゼンアクリレート、メラミンアクリレート、アミノアクリレートなどの各種多官能アクリル樹脂を挙げることができ、これらは単独でも２種以上を併用して使用することもできる。これらの中でも好ましくはアクリル樹脂、多官能アクリル樹脂が５０重量％、より好ましくは６０重量％以上含有するものを挙げることができ、特にアクリル樹脂およびウレタンアクリレートからなるものが好ましい。これらは未反応状態のものを塗布後所定の反応をさせて硬化樹脂とすること、並びに反応後の樹脂を直接塗布し硬化樹脂層を形成することのいずれも適用可能である。後者は通常樹脂を溶媒に溶解し溶液とした後、塗布されその後溶媒が除去される。また前者の場合も溶媒を使用することが一般的である。
【０１７２】
更に、ハードコート層を形成する樹脂には、上述した光安定剤や紫外線吸収剤、並びに触媒、熱・光重合開始剤、重合禁止剤、シリコーン消泡剤、レベリング剤、増粘剤、沈殿防止剤、垂れ防止剤、難燃剤、有機・無機顔料・染料の各種添加剤および添加助剤を含むことができる。
【０１７３】
コート方法としては、バーコート法、ディップコート法、フローコート法、スプレーコート法、スピンコート法、ローラーコート法等の方法を、塗装される基材となる成形品の形状に応じて適宜選択することができる。中でも複雑な成形品形状に対応しやすいディップコート法、フローコート法、およびスプレーコート法が好ましい。
【０１７４】
本発明の樹脂成形品は、透明性、表面平滑性、および表面硬度に優れる。更に本発明の樹脂成形品は、成形品重量の増加なく曲げ剛性の大幅な向上を可能としており、かかる特性は製品の軽量化にも寄与する。更なる特徴は、本発明の樹脂成形品を構成する樹脂組成物は熱安定性に優れ、これにより大型の射出成形品にも適用可能な点である。これらの特性から、本発明の樹脂成形品は、各種の透明部材において好適である。かかる透明部材としては例えば、各種車輌用透明部材（ヘッドランプレンズ、ウインカーランプレンズ、テールランプレンズ、樹脂窓ガラス、メーターカバー、サンルーフ、ムーンルーフ、デタッチャブルトップ、ウインドーリフレクター、ウインカーランプレンズ、ルームランプレンズ、およびディスプレー表示用前面板など）、照明灯カバー、樹脂窓ガラス（建築用など）、太陽電池カバーまたは太陽電池基材、ディスプレー装置用レンズ、タッチパネル、ミラーおよび遊技機（パチンコ機など）用部品（回路カバー、シャーシ、パチンコ玉搬送ガイドなど）などを挙げることができる。更にこれらの中でもハードコート処理がなされる成形品が、本発明の樹脂成形品に対し特に適するものである。
【０１７５】
【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）層状珪酸塩（無機分）の含有量
樹脂成形品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）量を測定した。
（２）全光線透過率
ヘーズメーター ＨＲ−１００（村上色彩技術研究所（株）製）を用い、ＪＩＳ Ｋ７１０５に準拠して、樹脂成形品（厚み１ｍｍの平滑平板状成形品）について測定した。
（３）層状珪酸塩の分散厚み
ミクロトームにて、５０〜１００ｎｍの切片を作成し、透過型電子顕微鏡（ＬＥＭ−１００：トプコン（株）製）を用いて、加速電圧１００ｋＶにて観察し、倍率１０，０００倍で写真撮影した。撮影した写真を画像解析し層状珪酸塩の厚みを計測することにより、その分散厚みを求めた。
（４）粘度平均分子量
樹脂成形品（下記曲げ試験片）の粘度平均分子量は、本文中記載の方法にて測定した。
（５）算術平均粗さ（Ｒａ）
表面粗さ形状測定機（サーフコム１４００Ａ：（株）東京精密製）を用い、ＪＩＳ Ｂ０６０１−１９９４に準拠して、樹脂成形品（厚み１ｍｍの平滑平板状成形品）の算術平均粗さＲａを測定した。
（６）曲げ弾性率
ＡＳＴＭ Ｄ７９０に準拠して曲げ試験を行った。曲げ試験片は、射出成形により作成された長さ１２７ｍｍ×幅１２．７ｍｍ×厚み６．４ｍｍの寸法を有するものを使用した。
（７）比重
ＡＳＴＭ Ｄ７９２に準拠して測定した。試験片は上記曲げ試験片を使用した。
（８）鉛筆引っかき値
ＪＩＳ Ｋ５４００中に定められた方法に準拠し、厚み１ｍｍの平滑平板状成形品を用い手かき法にて、鉛筆引っかき値を測定した。
（９）ハードコート密着性
樹脂成形品（厚み１ｍｍの平滑平板状成形品）のほぼ中央部において、ハードコート層にカッターナイフで１ｍｍ間隔の１００個の碁盤目を作りニチバン製粘着テープ（商品名“セロテープ”）を圧着し、垂直に強く引き剥がして樹脂成形品にすべて残るか否かを観察した。１０枚の樹脂成形品中、全て残らなかった成形品数ｎを求めた。
【０１７６】
［原料］
原料としては、以下のものを用いた。
（Ａ成分）
ホスゲン法で作成されたビスフェノールＡ及び末端停止剤としてｐ−ｔｅｒｔ−ブチルフェノールからなる、粘度平均分子量２３，７００の直鎖状ポリカーボネート樹脂パウダー（帝人化成（株）製：パンライトＬ−１２５０ＷＰおよびＬ−１２２５ＷＰを１：１（重量比）で混合したもの）
【０１７７】
（Ｂ成分）
Ｂ成分（Ｂ−１およびＢ−２）の内容は表１に示す。尚、使用された層状珪酸塩は、合成フッ素雲母（コープケミカル（株）製：ソマシフ ＭＥ−１００、陽イオン交換容量：１１０ミリ当量／１００ｇ）であり、また層状珪酸塩の層間陽イオンをイオン交換するのに用いた有機オニウムイオンは次のとおりであった。
▲１▼ジステアリルジメチルアンモニウムクロライド（東京化成工業（株）製：１級試薬）
▲２▼トリ−ｎ−オクチルメチルアンモニウムクロライド（東京化成工業（株）製：１級試薬）
【０１７８】
（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％）
Ｃ−２：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 ２３２、無水マレイン酸量約８重量％）
【０１７９】
（その他）
ＴＭＰ：リン酸トリメチル（大八化学工業（株）製：ＴＭＰ）
ＥＰＱ：ホスホナイト系熱安定剤（Ｓａｎｄｏｚ社製：サンドスタブＰ−ＥＰＱ）
ＥＷ：脂肪酸フルエステル（理研ビタミン（株）製：リケスターＥＷ−４００）
ＵＶＡ：紫外線吸収剤（チバ・スペシャリティ・ケミカルズ製：Ｔｉｎｕｖｉｎ１５７７）
ＨＰ：ヒンダードフェノール系酸化防止剤（チバ・スペシャリティ・ケミカルズ製：Ｉｒｇａｎｏｘ１０７６）
ＩＲ：フタロシアニン系近赤外線吸収剤（三井化学（株）製：ＭＩＲ−３６２、ＴＧＡ５％重量減少温度２８２℃）
ＣＢ：カーボンブラック（三菱化学（株）製：ファーネスブラック ＭＡ−１００、ｐＨ＝３．５）
ＦＲ：ペリレン系赤蛍光染料（ＢＡＳＦ社製：Ｌｕｍｏｇｅｎ Ｆ Ｒｅｄ ３００）
ＯＢ：クマリン系蛍光増白剤（ハッコールケミカル（株）製：ハッコールＰＳＲ）
タルク：タルク（林化成（株）製：Ｕ_PN ＨＳ−Ｔ_0.8）
［層間化合物の作製方法］
合成フッ素雲母への、上記有機オニウムのイオン交換を次の方法により行った。
【０１８０】
合成フッ素雲母約１００ｇを精秤しこれを室温の水１０リットルに撹拌分散し、ここにオニウムイオンのクロライドまたはブロマイドを合成フッ素雲母の陽イオン交換当量に対して種々当量を添加して６時間撹拌した。生成した沈降性の固体を濾別し、次いで３０リットルの脱塩水中で撹拌洗浄後再び濾別した。この洗浄と濾別の操作を３回行った。得られた固体は３〜７日の風乾後乳鉢で粉砕し、更に５０℃の温風乾燥を３〜１０時間行い（ゲストのオニウムイオンの種類により異なる）、再度乳鉢で最大粒径が１００μｍ程度となるまで粉砕した。かかる温風乾燥により残留水分量を２〜３重量％とした（残留水分量は、窒素気流下１２０℃で１時間保持した場合の熱重量減少で評価した）。オニウムイオンのイオン交換割合については、イオン交換された層状珪酸塩の、窒素気流下５００℃で３時間保持した場合の残渣の重量分率を測定することにより求めた。上記操作を数回繰り返し必要量を得た。作製した有機オニウムイオン交換合成フッ素雲母を表１に示す。
【０１８１】
【表１】

【０１８２】
［ハードコート用組成物の調整］
（１）コーティング用組成物（ｉ−１）
還流冷却器及び撹拌装置を備え、窒素置換したフラスコ中にメチルメタクリレート（以下ＭＭＡと略称する）７０部、２−ヒドロキシエチルメタクリレート（以下ＨＥＭＡと略称する）３９部、アゾビスイソブチロニトリル（以下ＡＩＢＮと略称する）０．１８部及び１，２−ジメトキシエタン２００部を添加混合し、溶解させた。次いで、窒素気流中７０℃で６時間攪拌下に反応させた。得られた反応液をｎ−ヘキサンに添加して再沈精製し、ＭＭＡ／ＨＥＭＡの組成比７０／３０（モル比）のコポリマー（アクリル樹脂（Ｉ））９０部を得た。該コポリマーの重量平均分子量はＧＰＣの測定（カラム；Ｓｈｏｄｅｘ ＧＰＣＡ−８０４、溶離液；ＴＨＦ）からポリスチレン換算で８０，０００であった。
【０１８３】
次にハードコート第１層用組成物として、前記アクリル樹脂（Ｉ）８部をメチルエチルケトン４０部、メチルイソブチルケトン２０部、エタノール５．２部、イソプロパノール１４部および２−エトキシエタノール１０部からなる混合溶媒に溶解し、次いでこの溶液にメチルトリメトキシシラン加水分解縮合物溶液（Ｘ）１０部を添加して２５℃で５分間攪拌し、さらにかかる溶液にメラミン樹脂（三井サイテック（株）製サイメル３０３）１部を添加して２５℃で５分間攪拌し、コーティング用組成物（ｉ−１）を調製した。
【０１８４】
（２）コーティング用組成物（ｉｉ−１）
上記と同様の装置を用いて、メチルトリメトキシシラン１４２部、蒸留水７２部、酢酸２０部を氷水で冷却下混合し、この混合液を２５℃で１時間攪拌し、イソプロパノール１１６部で希釈してメチルトリメトキシシラン加水分解縮合物溶液（Ｘ）３５０部を得た。一方、テトラエトキシシラン２０８部、０．０１Ｎ塩酸８１部を氷水で冷却下混合し、この混合液を２５℃で３時間攪拌し、イソプロパノール１１部で希釈してテトラエトキシシラン加水分解縮合物溶液（Ｙ）３００部を得た。
【０１８５】
更にハードコート第２層用組成物として、水分散型コロイダルシリカ分散液（日産化学工業（株）製 スノーテックス３０ 固形分濃度３０重量％）１００部に蒸留水１２部、酢酸２０部を加えて攪拌し、この分散液に氷水浴で冷却下メチルトリメトキシシラン１３４部を加えた。この混合液を２５℃で１時間攪拌して得られた反応液に、テトラエトキシシラン加水分解縮合物溶液（Ｙ）２０部および硬化触媒として酢酸ナトリウム１部を加えイソプロパノール２００部で希釈してコーティング用組成物（ｉｉ−１）を調製した。
【０１８６】
［実施例１〜７、比較例１〜４］
各成分を表２記載の配合割合で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。
【０１８７】
なお、Ｃ成分を用いる場合には、Ｂ成分とＣ成分を、表２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℃にて溶融混練して押出し、ストランドカットしてペレットを得た後、得られたペレットを用いて、最終割合が表２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。
【０１８８】
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、１５０ｍｍ角×１ｍｍ厚の平滑平板状成形品および曲げ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３００℃、金型温度８０℃、成形サイクル４０秒で成形した。
【０１８９】
また上記平滑平板状成形品を１２０℃で２時間アニール処理した後、上記コーティング用組成物（ｉ−１）をディップコート法により塗布し、２５℃で２０分間静置後、１２０℃で３０分間熱硬化させた。次いで該樹脂成形品に上記コーティング用組成物（ｉｉ−１）を更にディップコート法により塗布し、２５℃で２０分間静置後、１２０℃で２時間熱硬化させ、ハードコート処理を行った。得られた樹脂成形品を観察したところ割れの発生はなかった。
【０１９０】
これらについての測定結果を表３に示す。
【０１９１】
【表２】

【０１９２】
【表３】

【０１９３】
上記表３の結果から明らかなように、特定の分散形態を満足する芳香族ポリカーボネート樹脂組成物は、良好な成形時における熱安定性を有しており、それらから形成された樹脂成形品は、良好な透明性、表面特性（表面平滑性および表面硬度）を有していることがわかる。更に各種の機能性添加剤を付与した組成物においても同様の良好な特性を維持し、透明性部材に求められる各種の機能が問題なく付与できることが分かる。一方、芳香族ポリカーボネート樹脂単独（比較例１）、タルクを配合した樹脂成形品（比較例２）、並びにＣ成分を含まない樹脂成形品（比較例３〜４）などの通常の樹脂組成物は、上記のいずれをも満足する樹脂組成物は得られていない。
【０１９４】
【発明の効果】
本発明の樹脂成形品は、良好な透明性、表面特性（表面平滑性および表面硬度）を有し、軽量で剛性が高く、更に良好な成形時における熱安定性を有する樹脂成形品である。したがって本発明の樹脂成形品は、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、および雑貨分野などといった幅広い分野において有用であるが、特に車輌用透明部材として有用であり、その奏する工業的効果は格別である。[0001]
BACKGROUND OF THE INVENTION
The present invention comprises an aromatic polycarbonate resin, a layered silicate, especially an organically layered silicate, and a compound having an affinity for an aromatic polycarbonate and having a hydrophilic component, and the layered silicate is specified The present invention relates to a resin molded article comprising an aromatic polycarbonate resin composition having a dispersion structure of
[0002]
[Prior art]
Aromatic polycarbonate resins have excellent transparency, heat resistance, mechanical strength, and the like, and are therefore widely used in electrical, mechanical, automotive, medical applications and the like. In particular, application to a transparent member for vehicles for the purpose of weight reduction has been widely attempted. Examples of such a transparent member for vehicles include a headlamp lens, a resin window glass, a rear lamp lens, a meter cover such as a meter cover, a sunroof, a moon roof, a detachable top, a window reflector, a winker lamp lens, Examples include a room lamp lens and a member with a slightly low degree of transparency, such as a display display front plate. These members have been replaced with aromatic polycarbonate for the purpose of reducing the weight of the vehicle body, but the bending rigidity is inferior to that of glass. May be. In particular, the demand is high for an external member that receives wind pressure and is loaded during traveling. On the other hand, the improvement of the flexural modulus can reduce the thickness of the product and further reduce the weight of the member. In the case of thermoplastic resins, it is common practice to add inorganic reinforcements to improve mechanical properties, but this improves mechanical properties, but the specific gravity increases, so the benefits of weight reduction are reduced. In addition, the transparency and surface smoothness are lowered. In addition, since the aromatic polycarbonate resin has poor scratch resistance, it may be required to improve the surface hardness.
[0003]
In recent years, clay minerals, particularly layered silicates, have been used as inorganic fillers, and the specific gravity and surface appearance of molded products have been improved by facilitating dispersion in the resin 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 resins and polyolefin resins, and some of them have been put into practical use.
[0004]
In the aromatic polycarbonate resin composition, similar techniques are disclosed in JP-A-03-215558, JP-A-07-207134, JP-A-07-228762, JP-A-07-331092, JP-A-09-143359, It has been proposed in Kaihei 10-60160, JP-A-11-71509, and JP-A-2001-131400.
[0005]
In particular, in Japanese Patent Application Laid-Open No. 07-331092, a resin composition comprising an aromatic polycarbonate resin and a layered silicate is used to increase the strength of the molded product while maintaining a certain degree of transparency by applying a specific treatment to the layered silicate. Attempts have been made to improve. JP-A-11-71509 and JP-A-2001-131400 propose an optical film made of an aromatic polycarbonate resin and a specific layered silicate.
[0006]
However, the resin molded products of aromatic polycarbonate resin in which these layered silicates are finely dispersed do not show sufficient mechanical properties and surface properties, but also large molded products such as vehicle members. At present, it does not have the thermal stability for injection molding, and its practicality is poor. That is, a transparent member for a vehicle (particularly a transparent member for vehicles (especially, having lightness, improved rigidity, excellent surface smoothness, surface hardness, and thermal stability during practically sufficient molding). At present, an aromatic polycarbonate resin molded article suitable for an injection molded article) has not been obtained so far.
[0007]
[Problems to be solved by the invention]
An object of the present invention is a resin molded product in which a layered silicate is finely dispersed in view of the above problems, and has good transparency, surface characteristics (surface smoothness and surface hardness), and is lightweight. Another object of the present invention is to provide a resin molded product having high rigidity and high thermal stability during molding.
[0008]
As a result of intensive investigations to achieve the above object, the present inventors have blended an aromatic polycarbonate resin, a layered silicate, and a specific compound, so that the layered silicate is dispersed in the molded product of the aromatic polycarbonate resin. It has been found that the above-described problems can be solved by setting the state. The inventors of the present invention have made further studies from this discovery and have completed the present invention.
[0009]
[Means for Solving the Problems]
The present invention relates to (1) (A) aromatic polycarbonate resin (component A) 100 parts by weight, and (B) layered silicate (component B) 0.1 to 50 weights satisfying the following (i) and (ii): Part,
(I) having a cation exchange capacity of 50 to 200 meq / 100 g,
(Ii) In the resin composition, a number ratio of 70% or more has a thickness of 100 nm or less.
And (C) an aromatic polycarbonate resin composition comprising 0.1 to 50 parts by weight of a compound (component C) having an affinity for an aromatic polycarbonate and having a hydrophilic component, and in accordance with JIS K7105 It is applied to a resin molded product having a measured total light transmittance of 75% or more.
[0010]
According to the configuration (1), there is provided a resin molded product having good transparency, surface characteristics (surface smoothness and surface hardness), light weight and high rigidity, and good thermal stability during molding. Is done. Conventionally, a polycarbonate resin material having both high rigidity and transparency has been proposed by blending a glass filler having a refractive index close to that of a polycarbonate resin. However, such a material is still insufficient in surface smoothness, and a special molding method is required to achieve surface smoothness close to that of a glass material. On the other hand, the present invention has good surface smoothness, and an improvement in flexural modulus is achieved with a very low specific gravity. Therefore, the present invention is excellent in bending rigidity efficiency and contributes to weight reduction of the product. In addition, the present invention provides a resin molded product having a high practicality that exhibits improved thermal stability and is compatible with a large-sized injection molded product with respect to a resin composition using a specific layered silicate.
[0011]
One of the preferred embodiments of the present invention is that (2) the resin composition is a total light transmittance measured in accordance with JIS K7105 in a smooth flat plate-shaped molded article having a thickness of 1 mm formed from the resin composition. Is a resin molded product according to the above (1), which is 75% or more. According to this configuration (2), a resin molded product having more excellent light transmittance is provided.
[0012]
One of the suitable aspects of the present invention is (3) the resin molded product according to any one of (1) and (2), wherein the resin molded product has a thickness of 1 to 5 mm. According to this structure (3), the resin molded product with which a glass member is substituted is provided.
[0013]
One of the preferred embodiments of the present invention is that (4) the component B is any one of the above (1) to (3), wherein at least 40% of its cation exchange capacity is exchanged with an organic onium ion. It is a resin molded product described in 1. According to the configuration (4), a resin molded product having excellent dispersibility that satisfies the above condition (ii) more easily, and thus excellent transparency and flexural modulus is provided.
[0014]
One of the preferred embodiments of the present invention is that (5) the component B contains at least an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms as an organic group forming an organic onium ion. The resin molded product according to (4) above. According to this configuration (5), a resin molded product having further excellent dispersibility and thermal stability of the B component layered silicate is provided.
[0015]
One preferred embodiment of the present invention is that (6) the component B is an organic group in which an organic onium ion is an alkyl group having 10 or less carbon atoms, and at least one of the alkyl groups has a carbon number The resin molded product according to (4) above, which is 6 to 10. According to this configuration (6), the dispersibility and thermal stability of the layered silicate in the resin molded product are further improved.
[0016]
One of the preferred embodiments of the present invention is (7) the above component (1), wherein the component C is a polymer having an affinity for an aromatic polycarbonate resin and having a functional group comprising a carboxyl group and / or a derivative thereof. ) To (6). According to such a configuration (7), a resin molded product with excellent practicality that is more excellent in thermal stability and is compatible with a large injection molded product is provided.
[0017]
One of the preferred embodiments of the present invention is (8) any one of the above (1) to (7), wherein the component C is a styrene-containing polymer having a functional group comprising a carboxyl group and / or a derivative thereof. The resin molded product described in 1. According to the configuration (8), a resin molded product further excellent in dispersibility of the layered silicate in the resin molded product and thermal stability is provided.
[0018]
One of the preferred embodiments of the present invention is (9) the resin molded article according to any one of the above (1) to (8), wherein the component C is a styrene-maleic anhydride copolymer. . According to the configuration (9), the resin molding having excellent dispersibility and thermal stability of the layered silicate in the resin molded article, and having better transparency, low specific gravity, high rigidity, and good surface hardness. Goods are provided.
[0019]
One of the preferred embodiments of the present invention is that (10) the resin molded product has an arithmetic mean roughness Ra value of 0.1 μm or less measured according to (1) JIS B0601, and (2) JISK5400. The pencil scratch value measured in accordance with the hand-drawn method is HB or more, and (3) the flexural modulus value measured in accordance with ASTM D790 is 2,500 MPa or more. A resin molded product according to any one of (1) to (9) is provided. According to this configuration (10), more specifically, a resin molded product satisfying the above-mentioned (1) to (3) is provided.
[0020]
One of the preferable aspects of the present invention is as described in any one of (1) to (10) above, wherein (11) the resin molded product is subjected to a hard coat treatment on the surface thereof. This is a resin molded product. According to this configuration (11), a transparent member having further excellent surface hardness and excellent adhesion to the hard coat layer is provided.
[0021]
One of the suitable aspects of the present invention is (12) the resin molded product according to any one of (1) to (11), wherein the resin molded product is a vehicle transparent member. According to this configuration (12), a resin molded product suitable for a transparent member for a vehicle in which the bending rigidity and surface hardness of the polycarbonate resin are improved without impairing the surface smoothness and thermal stability of the molded product, particularly the injection molded product thereof. Therefore, according to the present invention, such a transparent member for a vehicle is provided.
[0022]
Details of the present invention will be described below.
[0023]
The present invention is a resin molded article formed from an aromatic polycarbonate resin composition and having a total light transmittance of 75% or more, preferably 80% or more, measured according to JIS K7105. On the other hand, the upper limit is suitably 92%, more preferably 91%. If the total light transmittance is 75% or more, it can be used for some transparent members for vehicles. The resin composition of the present invention assists the fine dispersion of the B component by the C component and improves the thermal stability. Thereby, it is possible to obtain a favorable light transmittance as compared with the component B alone. The higher the proportion of component B, the lower the total light transmittance. On the other hand, the thickness of the product can be reduced by improving the flexural modulus. Therefore, the configuration of the present invention provides a resin molded product that satisfies a predetermined transparency. Is possible.
[0024]
The aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
[0025]
Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called 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-phenylenediisopropyl Pyridene) diphenol, 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 and 9,9-bis (4-hydroxy-3-methylphenyl) ) Fluorene and the like. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance.
[0026]
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
[0027]
In producing an aromatic polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resins, copolymerized polycarbonate resins copolymerized with bifunctional alcohols (including alicyclics), and polyester carbonate resins copolymerized with such bifunctional carboxylic acids and difunctional alcohols are included. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.
[0028]
Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.
[0029]
When a polyfunctional compound that produces a branched polycarbonate is included, the ratio is 0.001-1 mol%, preferably 0.005-0.9 mol%, particularly preferably 0.01-0, based on the total amount of the aromatic polycarbonate. 0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.005% in the total amount of the aromatic polycarbonate. Those having 9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. About this ratio¹It is possible to calculate by H-NMR measurement.
[0030]
The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, and other straight-chain saturated aliphatic dicarboxylic acids, 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.
[0031]
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.
[0032]
The reaction by the interfacial polymerization 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, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used.
[0033]
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
[0034]
In addition, catalysts such as tertiary amines and quaternary ammonium salts can be used for promoting the reaction, and monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, etc. as molecular weight regulators. Are preferably used. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. These monofunctional phenols having a relatively long chain alkyl group are effective when improvement in fluidity and hydrolysis resistance is required.
[0035]
The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually preferably maintained at 10 or higher.
[0036]
The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonic acid diester, and the dihydric phenol and the carbonic acid diester are mixed in the presence of an inert gas and reacted at 120 to 350 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the phenols produced at 133 Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.
[0037]
Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.
[0038]
A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, boron and aluminum hydroxides, Alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, alkoxide of alkali metal or alkaline earth metal, organic acid salt of alkali metal or alkaline earth metal, zinc compound, boron compound, silicon compound, germanium compound, Examples thereof include catalysts usually used for esterification and transesterification of organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. A catalyst may be used independently and may be used in combination of 2 or more types. The amount of these polymerization catalysts used is preferably 1 × 10 with respect to 1 mol of dihydric phenol as a raw material.^-8~ 1x10^-3Equivalent weight, more preferably 1 × 10^-7~ 5x10^-FourIt is selected in the range of equivalents.
[0039]
In the polymerization reaction, in order to reduce phenolic end groups, for example, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate, 2-ethoxycarbonylphenyl phenyl carbonate, etc. Compounds can be added.
[0040]
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. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm with respect to the aromatic polycarbonate after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
[0041]
The details of reaction formats other than those described above are also well known in books and patent publications.
[0042]
If the viscosity average molecular weight of the aromatic polycarbonate resin is less than 10,000, the strength and the like are lowered, and if it exceeds 50,000, the molding process characteristics are lowered. Therefore, the range of 10,000 to 50,000 is included. Preferably, the range of 12,000 to 30,000 is more preferable, and the range of 15,000 to 28,000 is more preferable. The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range.
[0043]
The viscosity average molecular weight (M) of the polycarbonate resin was a specific viscosity (η determined at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride._sp) Is inserted into the following equation.
η_sp/C=[η]+0.45×[η]²c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10^-FourM^0.83
c = 0.7
[0044]
The following can be mentioned as an aspect of the polycarbonate resin in this invention. That is, it consists of an aromatic polycarbonate (PC 1) having a viscosity average molecular weight of 70,000 to 300,000 and an aromatic polycarbonate (PC 2) having a viscosity average molecular weight of 10,000 to 30,000. An aromatic polycarbonate having a molecular weight of 15,000 to 40,000, preferably 20,000 to 30,000 (hereinafter sometimes referred to as “high molecular weight component-containing aromatic polycarbonate”) can also be used.
[0045]
Such an aromatic polycarbonate containing a high molecular weight component increases the entropy elasticity of the polymer due to the presence of PC (1), and is more advantageous in injection press molding suitable for molding a large molded article. For example, appearance defects such as hesitation marks can be further reduced, and the range of conditions for injection press molding can be expanded accordingly. On the other hand, the low molecular weight component of the PC (2) component lowers the overall melt viscosity, promotes relaxation of the resin, and enables molding with lower strain. A similar effect is also observed in a polycarbonate resin containing a branched component.
[0046]
In addition, when measuring the viscosity average molecular weight in the 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.
[0047]
The B component used in the aromatic polycarbonate resin composition forming the resin molded article 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. 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”.
[0048]
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 are represented by, for example, smectite minerals, vermiculite, halloysite, and swellable mica. Specifically, montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, stevensite, etc. are used as smectite minerals. And swelling synthetic mica such as Li-type tetrasilicon fluorine mica. These layered silicates can be either natural or synthesized. The synthetic product can be obtained by, for example, hydrothermal synthesis, melt synthesis, or solid reaction.
[0049]
The cation exchange capacity of the layered silicate needs to be 50 to 200 meq / 100 g, preferably 80 to 150 meq / 100 g, more preferably 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. The cation exchange capacity of the layered silicate requires a cation exchange capacity of 50 meq / 100 g or more in order to obtain good dispersibility in an amorphous thermoplastic resin, particularly an aromatic polycarbonate resin. However, when it becomes larger than 200 meq / 100 g, the influence on the thermal deterioration of the aromatic polycarbonate resin becomes large.
[0050]
The layered silicate preferably has a pH value of 7-10. When the pH value is larger than 10, a tendency to lower the thermal stability of the aromatic polycarbonate resin appears.
[0051]
Among these layered silicates, they have swelling properties such as smectite clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluoromica from the viewpoint of cation exchange capacity. Fluorine mica is preferably used, and montmorillonite obtained by purifying bentonite and synthetic fluorine mica are more preferable in terms of purity. Furthermore, synthetic fluorine mica, which can obtain good mechanical properties, is particularly preferable.
[0052]
The layered silicate of component B is preferably an organic onium ion ion-exchanged between layered silicate layers (organized layered silicate). Such an organic layered silicate is useful for more easily achieving a dispersion state of “(ii) a resin composition having a thickness ratio of 70% or more of which has a thickness of 100 nm or less” in the present invention. The organic onium ion is usually handled as a salt with a halogen ion or the like. 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. As organic onium ions, ammonium ions and phosphonium ions are preferred. In general, ammonium ions are excellent in dispersibility, and phosphonium ions are somewhat advantageous in thermal stability. In the present invention, ammonium ions are particularly preferable.
[0053]
As the ionic 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 group and other functional groups.
[0054]
Specific examples of organic onium ions include quaternary ammonium having the same alkyl group such as tetraethylammonium and tetrabutylammonium; trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, 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; Triethylhexadecylan Triethylalkylammonium such as nitro and triethyloctadecylammonium; tributylalkylammonium such as tributyldodecylammonium, tributyltetradecylammonium, tributylhexadecylammonium and tributyloctadecylammonium; dimethyldioctylammonium, dimethyldidecylammonium, dimethylditetradecylammonium Dimethyldialkylammonium such as dimethyldihexadecylammonium and dimethyldioctadecylammonium; dimethyldialkenylammonium such as dimethyldioctadecenylammonium; dimethyldialkadienylammonium such as dimethyldioctadecadienylammonium; Ammo Diethyldialkylammonium such as dimethyl, diethylditetradecylammonium, diethyldihexadecylammonium, and diethyldioctadecylammonium; dibutyl such as dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, and dibutyldioctadecylammonium Dialkylammonium; methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium; dibenzyldialkylammonium such as dibenzyldihexadecylammonium; trialkylmethyl such as trioctylmethylammonium, tridodecylmethylammonium and tritetradecylmethylammonium Ammonium; trioctylethylammoni And trialkylethylammonium such as tridodecylethylammonium; trialkylbutylammonium such as trioctylbutylammonium; quaternary ammonium having an aromatic ring such as trimethylbenzylammonium; aroma such as trimethylphenylammonium Quaternary ammonium from group amines; methyldiethyl [PEG] ammonium and trialkyl [PAG] ammonium such as methyldiethyl [PPG]; dialkylbis [PAG] ammonium such as methyldimethylbis [PEG] ammonium; ethyltris [PEG] Alkyltris [PAG] ammonium such as ammonium, and phosphonic acid in which the nitrogen atom of the ammonium ion is replaced with a phosphorus atom. Ion, and the like. 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.
[0055]
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 higher than 600, there is a tendency that the thermal degradation of the aromatic polycarbonate resin is accelerated or the heat resistance of the 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. The organic group in the organic onium ion compound structure preferably contains at least one alkyl group having 6 to 20 carbon atoms or aryl group having 6 to 12 carbon atoms. In particular, use of an alkyl group having 10 or less carbon atoms is also a preferable method for suppressing thermal degradation of the aromatic polycarbonate resin. In that case, for good dispersion of the layered silicate, the organic group forming the organic onium ion is an alkyl group having 10 or less carbon atoms, and at least one of the alkyl groups has 6 to 10 carbon atoms. In particular, the carbon number is preferably 6 to 8.
[0056]
Preferred embodiments of the organic onium ion include trimethyl-n-octylammonium, trimethyl-n-decylammonium, trimethyl-n-dodecylammonium, trimethyl-n-hexadecylammonium, trimethyl-n-octadecylammonium, methyltri-n-octyl. Ammonium, ethyltri-n-octylammonium, butyltri-n-octylammonium, triphenylmethylammonium, trimethyl-n-octylphosphonium, trimethyl-n-decylphosphonium, trimethyl-n-dodecylphosphonium, trimethyl-n-hexadecylphosphonium, Trimethyl-n-octadecylphosphonium, methyltri-n-octylphosphonium, ethyltri-n-octylphosphonium, butyltri n- octyl phosphonium, triphenylmethyl phosphonium, and the like.
[0057]
Ion exchange of organic onium ions into layered silicates can be made by adding organic onium ion compounds to layered silicates dispersed in a polar solvent and collecting the precipitated ion exchange compounds. . Usually, this ion exchange reaction is performed by adding 1.0 to 1.5 equivalents of the organic onium ion compound to 1 equivalent of the ion exchange capacity of the layered silicate, and converting almost all of the metal ions between the layers to the organic onium ion. It is common to exchange with. 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. For example, the fact that the rate of ion exchange with organic onium ions is 80% or less of the ion exchange capacity is one means of suppressing thermal degradation. Furthermore, since organic onium ions also cause a decrease in transparency, reducing the rate of ion exchange with organic onium ions can be expected to improve transparency.
[0058]
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 measuring device or the like for the compound after the exchange.
[0059]
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 flexural modulus of the aromatic polycarbonate resin is not seen, and when it exceeds 50 parts by weight, the thermal stability and mechanical strength of the composition are reduced, It is difficult to obtain a practical resin molded product having a predetermined transparency. More preferably, the molded product unit area (1 cm²), The ratio of component B is preferably 1-10 mg / cm²And more preferably 2-8 mg / cm²And more preferably 3-6 mg / cm²It is.
[0060]
The B component of the present invention is further characterized in that a number ratio of 70% or more has a thickness of 100 nm or less.
[0061]
Said characteristic can be calculated | required from the transmission electron microscope imaging | photography of a thermoplastic resin composition. That is, the thermoplastic resin composition is made into an observation sample having a thickness of 50 to 100 nm using a microtome, and the observation sample is observed at a magnification of about 10,000 times. By analyzing the image from the observed photograph and measuring the thickness of the layered silicate, knowledge about the above characteristics can be obtained.
[0062]
In the above characteristics, the B component preferably has a thickness ratio of 80% or more and a thickness of 100 nm or less, and more preferably a number ratio of 85% or more has a thickness of 100 nm or less. When the number ratio of the thickness of 100 nm or less is less than 70%, it is not preferable because good transparency, surface smoothness, rigidity and the like, which are the characteristics of the present invention, cannot be obtained.
[0063]
The C component used in the aromatic polycarbonate resin composition forming the resin molded article of the present invention is a compound having an affinity for the aromatic polycarbonate resin (A component) and having a hydrophilic component. Such a configuration of component C produces good affinity for both aromatic polycarbonate resins and layered silicates, especially organically layered silicates. The affinity for both the aromatic polycarbonate resin and the layered silicate, especially the organically modified layered silicate, improves the compatibility of the two components so that the layered silicate is finely and stably dispersed in the aromatic polycarbonate resin. become.
[0064]
The function of the component C relating to the dispersion of the organically modified layered silicate is considered to be the same as that of a compatibilizer for a polymer alloy used to compatibilize different polymers. Therefore, the component C is preferably a polymer 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.
[0065]
When the C component of the present invention is a polymer, examples of the basic structure thereof include the following structures (i) and (ii).
[0066]
Structure (i): When the component having affinity for the aromatic polycarbonate resin is α and the hydrophilic component is β, a graft copolymer comprising α and β (the main chain is α, the graft chain is β, and the main The chain can be selected from β and the graft chain can be selected from α.), Block copolymer consisting of α and β (di-, tri-, etc., the number of block segments can be 2 or more, including radial block type) ), And a random copolymer comprising α and β. α and β may be not only a single polymer but also a copolymer.
[0067]
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 aromatic polycarbonate resin.
[0068]
Structure (ii): When the component having an affinity for the aromatic polycarbonate resin is α and the hydrophilic component is β, the function of α is expressed by the whole polymer, and β is a weight having a structure contained in the α. Coalescence.
[0069]
In other words, α alone does not have sufficient affinity with the aromatic polycarbonate resin, but α and β are combined and integrated, thereby exhibiting good affinity with the aromatic polycarbonate resin. Even when α alone is used, the affinity with the aromatic polycarbonate resin is good, and the affinity may be further improved by combination with β. Such an embodiment is included in the structure (i). Thus, structures (i) and (ii) may overlap in part. On the other hand, in the structure (i), α alone has sufficient affinity with the aromatic polycarbonate resin, but α and β are combined and integrated to reverse the good affinity with the aromatic polycarbonate resin. There may be a mode of reduction. Naturally, such an embodiment is included in the C component.
[0070]
Any of the structures (i) and (ii) can be selected in the present invention. In particular, an embodiment that satisfies both the conditions of the structure (i) and the conditions of the structure (ii), that is, α alone has a high affinity for the aromatic polycarbonate resin, and the affinity for the entire C component added with β is further increased. Embodiments are preferred.
[0071]
The component having an affinity for the aromatic polycarbonate resin in the component C 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.
[0072]
The non-reactive type has good affinity when it has the following factors. That is, between the aromatic polycarbonate resin and α, (1) chemical structure similarity, (2) solubility parameter approximation (solubility parameter difference is 1 (cal / cm^Three)^1/2Within, that is, about 2.05 (MPa)^1/2It is desirable to have factors such as (3) intermolecular interactions (hydrogen bonds, ionic interactions, etc.), and pseudo-attractive interactions peculiar to random polymers. These factors are also known as indicators for judging the affinity between the compatibilizing agent and the polymer which is the base of the polymer alloy.
[0073]
In the reactive type, various known functional groups having reactivity with the aromatic polycarbonate resin in the compatibilizing agent can be exemplified. For example, 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 can be exemplified.
[0074]
On the other hand, when the aromatic polycarbonate resin and α have a good affinity, as a result, the mixture of the aromatic polycarbonate resin and α exhibits a single glass transition temperature (Tg) or the aromatic polycarbonate resin. It is also widely known that the behavior of the Tg of α moves to the Tg side of α. In the present invention, as the component (α) having affinity, a component having such behavior can be mentioned as one of its embodiments.
[0075]
As described above, the component (α) having an affinity for the aromatic polycarbonate resin in the component C of the present invention can exhibit its affinity due to various factors. Of these, α is preferably non-reactive, and particularly preferably exhibits good affinity when the solubility parameter is approximated. This is because the affinity with the aromatic polycarbonate 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 side reaction.
[0076]
The solubility parameters of the aromatic polycarbonate resin and α preferably have the following relationship. That is, the solubility parameter of the aromatic polycarbonate resin (component A) is 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
[0077]
The solubility parameter of the aromatic polycarbonate resin 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.
[0078]
Specific examples of the polymer component satisfying the solubility parameter δα include aromatic polycarbonate, aromatic polyester (typified by polyethylene terephthalate, polybutylene terephthalate, and cyclohexanedimethanol copolymerized polyethylene terephthalate), and aliphatic polyester ( And polyester polymers such as polycaprolactone). Specific examples include styrene polymers, alkyl (meth) acrylate polymers, and acrylonitrile polymers (eg, polystyrene, styrene-maleic anhydride copolymer, polymethyl methacrylate, styrene-methyl methacrylate copolymer, and styrene-acrylonitrile copolymer). And vinyl-based polymers such as polymers). 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.
[0079]
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.
[0080]
The component α having an affinity for the aromatic polycarbonate resin of component A is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 30% by weight or more, and 50% by weight in the C component. The above is particularly preferable. Since the aspect which makes (alpha) the whole C component is also possible, an upper limit may be 100 weight%.
[0081]
Next, the hydrophilic component of component C in the present invention (hereinafter sometimes referred to as β in accordance with the above) will be described. Such a hydrophilic component is selected from 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. For example, according to the Dictionary of Chemistry (Kyoritsu Shuppan, 1989), the following groups are exemplified.
[0082]
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) Such
2) Groups that are not very hydrophilic:
-COOH, -NH₂, -CN, -OH, -NHCONH₂    Such
3) Small hydrophilic group:
-CH₂OCH_Three, -OCH_Three, -COOCH_Three, -CS, etc.
[0083]
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) sulfine groups are exemplified as strongly hydrophilic groups, and 2) carboxylic anhydride groups, oxazoline groups, formyl groups, pyrrolidone groups, etc. Is exemplified.
[0084]
The group 2) is preferable because it is superior in thermal stability during the melt processing of the aromatic polycarbonate resin. If the hydrophilicity is too high, thermal degradation of an aromatic polycarbonate or the like tends to occur. This is because such a hydrophilic group directly reacts with a carbonate bond to cause a thermal decomposition reaction.
[0085]
The hydrophilic group of the present invention includes both monovalent and divalent or more. When the component C is a polymer, a divalent or higher functional group means a group in which the main chain does not constitute a main chain, and a constituent constituting the main chain is distinguished from a 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.
[0086]
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). 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.
[0087]
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 of 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.
[0088]
As described above, when the hydrophilicity is too high, the aromatic polycarbonate resin is likely to be thermally deteriorated. Therefore E_coh/ V is preferably 2,500 or less, more preferably 2,000 or less, and even more preferably 1,500 or less.
[0089]
As the hydrophilic component (β) of component C, a hydrophilic polymer component (polymer segment) is also selected. Therefore, the segment of the hydrophilic polymer contained in the polymer of component C is β. Hydrophilic polymers are widely known, and examples include polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyacrylic acid metal salts (including chelate type), polyvinyl pyrrolidone, polyacrylamide, and polyhydroxyethyl methacrylate. Among these, polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyvinyl pyrrolidone, and polyhydroxyethyl methacrylate are preferably exemplified. This is because both good hydrophilicity and thermal stability with respect to the aromatic polycarbonate resin (inhibition of decomposition of the aromatic polycarbonate during melt processing) can be achieved. Polyalkylene oxide is preferably polyethylene oxide or polypropylene oxide.
[0090]
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 the aromatic polycarbonate resin. This is presumably because such an acidic group is excellent in the effect of contracting the layers by electrical action.
[0091]
Of these, acidic groups containing no nitrogen atom are more preferred. A functional group containing a nitrogen atom such as an amide group or an imide group may not sufficiently suppress 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.
[0092]
Examples of acidic groups include phosphonic acid groups and phosphinic acid groups in addition to carboxyl groups, carboxylic acid anhydride groups, sulfonic acid groups, and sulfinic acid groups.
[0093]
The ratio of β in the C component of the present invention is 60 to 10,000 as a functional group equivalent which is a molecular weight per functional group when β is a monomer having a hydrophilic group, and 70 to 8,000 is Preferably, 80 to 6,000 is more preferable, and 100 to 3,000 is still more preferable. Further, the ratio of β in the C component is that when β is a hydrophilic polymer segment, β is 5 to 95 wt%, preferably 10 to 90 wt%, more preferably 30 to 70 wt% in 100 wt% of the C component. Preferably, 30 to 50% by weight is more preferable.
[0094]
As a method for producing a compound having a component (α) having affinity for an aromatic polycarbonate 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.
[0095]
As a preferred embodiment of the component C of the present invention, “a polymer having affinity with an aromatic polycarbonate and having an acidic functional group”, “having affinity with an aromatic polycarbonate and having a polyalkylene oxide segment” Examples thereof include “polymer”, “polymer having affinity with aromatic polycarbonate and having oxazoline group”, and “polymer having affinity with aromatic polycarbonate and having hydroxyl group”. In the polymer of a preferred embodiment 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. In addition, maintaining the transparency when the aromatic polycarbonate and the C component are mixed is also a preferable aspect when the resin molded product is used as a vehicle transparent member.
[0096]
Among them, a polymer having an affinity for an aromatic polycarbonate and an acidic functional group is preferred, and more preferably a functional group having an affinity for an aromatic polycarbonate and comprising a carboxyl group and / or a derivative thereof. It is a polymer which has. From the viewpoint of the heat resistance retention effect of the aromatic polycarbonate, the polymer preferably has an aromatic ring component in the main chain and a polymer having a styrene component in the main chain. In view of the above, a styrene polymer (C1 component) having a functional group comprising a carboxyl group and / or a derivative thereof is particularly suitable as the C component of the present invention.
[0097]
The composition ratio of the C component of the present invention is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, and further preferably 1 to 12 parts by weight per 100 parts by weight of the A component. When the amount is less than 0.5 part by weight, the dispersion effect of the layered silicate is not sufficient, and the effect of suppressing the thermal degradation of the aromatic polycarbonate may be insufficient. On the other hand, if it exceeds 50 parts by weight, impact resistance and heat resistance may be lowered.
[0098]
The styrenic polymer (C1 component) having a functional group comprising a carboxyl group and / or a derivative thereof particularly suitable as the C component 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.
[0099]
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.
[0100]
As a method for producing a styrenic 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 styrenic monomer, and (2) a compound or monomer having a carboxyl group is bonded to or co-polymerized with a styrene polymer. The method of superposing | polymerizing can be mentioned.
[0101]
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.
[0102]
In the method (2), a radical generator such as peroxide or 2,3-dimethyl-2,3-diphenylbutane (dicumyl) is generally added to the styrene polymer or copolymer as required. In addition, a method of reacting or copolymerizing at a high temperature can be mentioned. In this method, a reactive site is thermally generated in a styrene polymer or copolymer, and a compound or monomer that reacts with the active site is reacted. 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.
[0103]
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.
[0104]
Examples of the styrene compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene. Bromine styrene, dibromostyrene, vinyl naphthalene and the like can be used, and styrene is particularly preferable.
[0105]
Furthermore, other compounds copolymerizable with these compounds, such as acrylonitrile and methacrylonitrile, may be used as the copolymerization component.
[0106]
Among the styrenic polymers having the above carboxyl groups, those suitable in the present invention are styrenic copolymers obtained by copolymerizing monomers having a functional group comprising a carboxyl group and / or a derivative thereof. is there. This is because such a copolymer can stably contain a relatively large number of carboxyl groups in the styrenic polymer. A more preferred embodiment is a styrene 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 in the layered silicate and the aromatic polycarbonate resin, the layered silicate is finely dispersed well. Further, the layer of the layered silicate, particularly the organically modified layered silicate is effectively reduced by the action of the carboxylic acid anhydride group, and as a result, good thermal stability is given to the resin composition. 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.
[0107]
The composition of the styrenic copolymer obtained by copolymerizing the monomer having the carboxyl group is not limited as long as the above-mentioned condition for the ratio of β is satisfied. It is preferable to use 1 to 30% by weight of the product, 99 to 70% by weight of the styrenic compound and 0 to 29% by weight of the other copolymerizable compound. Particularly preferred are 30% by weight and 99 to 70% by weight of a styrene-based compound.
[0108]
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.
[0109]
Next, a polymer having a polyalkylene oxide segment, which is another embodiment of the C component, particularly a preferred polyetherester copolymer (C2 component) will be described.
[0110]
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 (I) 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.
[0111]
[Chemical 1]

[0112]
(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 (I), 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.
[0113]
As the polyalkylene oxide component in the above formula (I), 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 (I) is particularly preferably m = 0, that is, a polymer component comprising only a polyethylene oxide component.
[0114]
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.
[0115]
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 resin composition.
[0116]
As a dicarboxylic acid of a polyetherester 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, and 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.
[0117]
The aromatic polycarbonate resin composition forming the resin molded article 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 heat stability and obtain good molding characteristics.
[0118]
Moreover, it is preferable that the aromatic polycarbonate resin composition which forms the resin molded product of this invention contains a mold release agent. Known release agents can be used. For example, fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which can be modified with a functional group-containing compound such as acid modification), silicone compound (especially alkyl such as phenyl group and methyl group) And a fluorine oil (represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like.
[0119]
Of these, fatty acid esters and silicone compounds are preferred, and fatty acid esters are particularly preferred from the viewpoints of releasability, transparency of molded products, adhesion to the hard coat layer, and the like. The fatty acid ester is an ester of an alcohol and an aliphatic carboxylic acid. As the alcohol, either a monohydric alcohol or a dihydric or higher polyhydric alcohol can be used. In the present invention, the fatty acid ester is more preferably composed mainly of a polyhydric alcohol.
[0120]
Examples of monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol.
[0121]
Specific examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin (such as decaglycerin), pentaerythritol, dipentaerythritol, diethylene glycol, and propylene glycol. Among them, pentaerythritol is preferable.
[0122]
The aliphatic carboxylic acid used in the fatty acid ester is preferably one having 3 to 32 carbon atoms. Examples of the aliphatic carboxylic acid having 3 to 32 carbon atoms include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitin) Acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, and hexacosanoic acid, as well as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, e Mention may be made of unsaturated aliphatic carboxylic acids such as icosapentaenoic acid and cetreic acid.
[0123]
Among them, the aliphatic carboxylic acid preferably has 10 to 22 carbon atoms, and more preferably has 14 to 20 carbon atoms. More preferred is such a saturated aliphatic carboxylic acid. In particular, stearic acid and palmitic acid are preferred.
[0124]
Aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats (such as palm oil). Accordingly, an aliphatic carboxylic acid such as stearic acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. In the production of the fatty acid ester of the present invention, stearic acid and palmitic acid which are produced from such natural oils and fats and are in the form of a mixture containing other carboxylic acid components are preferably used. The preferable aspect of the composition ratio of each component in this mixture is as follows.
[0125]
That is, the aliphatic carboxylic acid contains a palmitic acid component and a stearic acid component, and the peak area in the pyrolysis methylated GC / MS (gas chromatography-mass spectrometry) method shows the area (Sp) of the palmitic acid component and stearin. The total of the acid component area (Ss) is preferably 80% or more in the total aliphatic carboxylic acid, and the area ratio (Ss / Sp) of both is 1.2 or more. Here, the pyrolysis methylated GC / MS method means that a fatty acid ester as a sample is reacted with methylammonium hydroxide as a reaction reagent on a pyrofil to decompose the fatty acid ester and produce a methyl ester derivative of the fatty acid. This is a method of performing GC / MS measurement on a derivative.
[0126]
The total of Sp and Ss is preferably 85% or more, more preferably 90% or more, and still more preferably 91% or more in the total aliphatic carboxylic acid component. On the other hand, the total of Sp and Ss can be set to 100%, but is preferably 98% or less and more preferably 96% or less from the viewpoint of manufacturing cost. The area ratio (Ss / Sp) is more preferably in the range of 1.3 to 30. Further, the upper limit is more preferably 10, more preferably 4, and still more preferably 3. These mixing ratios do not need to be satisfied with a single aliphatic carboxylic acid, and may be satisfied by mixing two or more aliphatic carboxylic acids. Examples of the fats and oils that can be used as the raw material for the aliphatic carboxylic acid satisfying the above mixing ratio include animal fats and oils such as beef tallow and lard, and linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, and peanut oil. And vegetable oils such as cottonseed oil, sesame oil, and olive oil. Among these, animal fats and oils are preferable in view of containing more stearic acid, and beef tallow is more preferable. Furthermore, among the beef tallow, oleostearin containing a lot of saturated components such as stearic acid and palmitic acid is preferable.
[0127]
In the present invention, the esterification rate of the fatty acid ester is not particularly limited, but the esterification rate is preferably 60% or more, more preferably 80% or more, and still more preferably 85% or more. A fatty acid ester having a low esterification rate and a high hydroxyl value tends to deteriorate the polycarbonate resin, and the molded product tends to crack. From the above, the fatty acid ester of the present invention is preferably a full ester of a polyhydric alcohol and an aliphatic carboxylic acid. However, in the present invention, the full ester does not necessarily have an esterification rate of 100%, may be 80% or more, and preferably 85% or more.
[0128]
The acid value, hydroxyl value, iodine value, fatty acid ester, 5% weight reduction temperature in TGA (thermogravimetric analysis) measurement, etc. will be described.
[0129]
The acid value of the fatty acid ester is preferably low from the viewpoint of the effect on thermal stability and cracking of the molded product, while it is preferably relatively high from the viewpoint of reducing the releasing force (improving the releasing property). . The range of 0.1-20 is suitable for the acid value of fatty acid ester, the range of 2-18 is more preferable, and the range of 5-15 is still more preferable. The acid value can be determined by the method defined in JIS K 0070.
[0130]
The hydroxyl value of the fatty acid ester is preferably low from the viewpoints of thermal stability, reduction of mold release force and influence on cracking of the molded product, while too low is not preferable because the cost increases due to an increase in production time. The range of 0.1-40 is suitable for the hydroxyl value of fatty acid ester, the range of 1-30 is preferable, and the range of 2-20 is more preferable. The hydroxyl value can be determined by the method defined in JIS K 0070.
[0131]
The iodine value of the fatty acid ester is preferably low from the viewpoint of thermal stability. The iodine value of the fatty acid ester is preferably 10 or less, and more preferably 1 or less. Such iodine value can be determined by the method defined in JIS K 0070.
[0132]
The mold release agent such as fatty acid ester is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight of the polycarbonate resin. . If the release agent exceeds the above range and is too small, improvement of the release property is not sufficient. On the other hand, when there are too many mold release agents exceeding the said range, it is easy to impair the transparency of a molded article.
[0133]
Further, in order to use the resin molded product of the present invention as a transparent member for vehicles, good weather resistance is often required. Therefore, the aromatic polycarbonate resin composition forming the resin molded product further contains an ultraviolet absorber. It is preferable that it is included.
[0134]
Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5- Benzoyl-4-hydroxy-2 Methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.
[0135]
Specifically, the ultraviolet absorber compound is, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole or 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.
[0136]
Specifically, the ultraviolet absorber compound is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4) in the hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Further, the phenyl group is a 2,4-dimethylphenyl group such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol. Some compounds are exemplified.
[0137]
Of these, benzotriazole and hydroxyphenyltriazine are preferred. You may use the said ultraviolet absorber individually or in mixture of 2 or more types. The amount of the ultraviolet absorber used is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin. 0.05 to 0.5 parts by weight is particularly preferable.
[0138]
In addition, the aromatic polycarbonate resin composition forming the resin molded product of the present invention includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl). -4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6- Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2, 4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-o Shi - [4- (2,2,6,6-tetramethyl) piperidinyl] hindered amine light stabilizer typified by siloxane can also be included. Furthermore, the combined use of a hindered amine light stabilizer and a benzotriazole-based and / or triazine-based ultraviolet absorber effectively improves the weather resistance. In such a combination, the weight ratio (light stabilizer / ultraviolet absorber) of both is preferably in the range of 95/5 to 5/95, more preferably in the range of 80/20 to 20/80.
[0139]
You may use the said light stabilizer individually or in mixture of 2 or more types. The amount of the light stabilizer used is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin. 0.05 to 0.5 parts by weight is particularly preferable.
[0140]
The aromatic polycarbonate resin composition forming the resin molded article of the present invention preferably further comprises 0.05 to 3 ppm (weight ratio) of a blueing agent in the aromatic polycarbonate resin composition. This is effective for eliminating the yellow color of the polycarbonate resin molded product. In particular, in the case of molded products with weather resistance, since a certain amount of UV absorber is used, there is a reality that resin products tend to be yellowish due to the `` action and color of the UV absorber ''. The use of a bluing agent is very effective for imparting natural transparency.
[0141]
Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. By blending the bluing agent, the polycarbonate resin composition of the present invention achieves an even better hue. The important point here is the blending amount of the bluing agent. In the resin composition, if the bluing agent is less than 0.05 ppm, the hue improving effect may be insufficient. On the other hand, if it exceeds 3 ppm, the light transmittance is not suitable. A more preferable blending amount of the bluing agent is in the range of 0.5 to 2.5 ppm, more preferably 0.5 to 2 ppm in the resin composition.
[0142]
Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR from Bayer, Terrasol Blue RLS from Sand, and Plast Blue 8580 from Arimoto Chemical Industry.
[0143]
In the aromatic polycarbonate resin composition forming the resin molded article of the present invention, various dyes and pigments can be used in addition to the above bluing agent as long as the object of the invention is not impaired. In particular, a dye is preferable from the viewpoint of maintaining transparency. Preferred dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindo Examples thereof include linone dyes and phthalocyanine dyes. Furthermore, fluorescent whitening agents such as bisbenzoxazolyl-stilbene derivatives, bisbenzoxazolyl-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives can be used. The amount of these dyes and fluorescent whitening agent used is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight per 100 parts by weight of the aromatic polycarbonate resin.
[0144]
The resin molded product of the present invention may be required to have antistatic performance, and in such a case, it is preferably formed from an aromatic polycarbonate resin composition containing an antistatic agent. Examples of the antistatic agent include (i) an organic sulfonic acid phosphonium salt such as an aryl sulfonic acid phosphonium salt typified by dodecylbenzenesulfonic acid phosphonium salt and an alkyl sulfonic acid phosphonium salt. The phosphonium salt has an appropriate composition ratio of 5 parts by weight or less per 100 parts by weight of component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and 1.5 to 3 parts by weight. A range of parts is more preferred.
[0145]
Examples of the antistatic agent include (ii) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Organic sulfonate alkali (earth) metal salts of Specifically, for example, metal salts of dodecylbenzenesulfonic acid, metal salts of perfluoroalkanesulfonic acid, and the like are exemplified. The organic sulfonate alkali (earth) metal salt has a composition ratio of 0.5 parts by weight or less per 100 parts by weight of component A, preferably 0.001 to 0.3 parts by weight, and 0.005 to 0.005. 2 parts by weight is more preferred. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.
[0146]
Examples of the antistatic agent include (iii) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The composition ratio of the ammonium salt is 0.05 parts by weight or less per 100 parts by weight of the component A. Examples of the antistatic agent include (iv) glycerin derivative esters such as glycerin monostearate, maleic anhydride monoglyceride, and maleic anhydride diglyceride. The ester has a composition ratio of 0.5 parts by weight or less per 100 parts by weight of component A. Examples of the antistatic agent include (v) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less per 100 parts by weight of component A. Examples of other antistatic agents include (vi) non-organic compounds such as carbon black, carbon fiber, carbon nanotube, graphite, metal powder, and metal oxide powder. The composition ratio of the non-organic compound is 0.05 parts by weight or less per 100 parts by weight of the component A. In addition to the antistatic performance, the non-organic compounds exemplified in (vi) may be blended as a heat ray absorbent.
[0147]
In the aromatic polycarbonate resin composition forming the resin molded article of the present invention, an amount of a compound having a heat ray absorbing ability that does not impair the object of the present invention can be used. Preferred examples of the compound include phthalocyanine-based near infrared absorbers and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial, and whisker), carbon fiber (including those produced by vapor phase growth), carbon nanotubes, and fullerenes, preferably carbon black. And graphite. These can be used alone or in combination of two or more. The phthalocyanine-based near infrared absorber is preferably 0.005 to 0.2 parts by weight, more preferably 0.008 to 0.1 parts by weight, and 0.01 to 0.07 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Is more preferable. The carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio), more preferably in the range of 0.5 to 100 ppm, and still more preferably in the range of 1 to 50 ppm in the resin composition of the present invention.
[0148]
In the aromatic polycarbonate resin composition forming the resin molded article of the present invention, an amount of flame retardant that does not impair the object of the present invention can be used. Examples of flame retardants include halogenated bisphenol A polycarbonate flame retardants, organic salt flame retardants, aromatic phosphate ester flame retardants, and halogenated aromatic phosphate ester flame retardants. It can be used above.
[0149]
Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrabromobisphenol A, a copolymer polycarbonate type flame retardant of tetrabromobisphenol A and bisphenol A, or the like.
[0150]
Specifically, organic salt flame retardants include dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfonate. Potassium chlorobenzenesulfonate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, Potassium bis (2,4,6-tribromophenyl) phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, Potassium perfluorobutane sulfonate, sodium lauryl sulfate Um or potassium hexadecyl sulfate, sodium or potassium.
[0151]
Specifically, the halogenated aromatic phosphate ester type flame retardant is tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, etc. is there.
[0152]
Specifically, the aromatic phosphate ester flame retardant is triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate. , Tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4′-biphenol diphosphate, aromatic ring source is resorcin and phenol Aromatic polyphosphates that do not contain phenolic OH groups, aromatic ring sources are resorcin and phenol, aromatic polyphosphates that contain phenolic OH groups, aromatic ring sources are hydroquinone and phenol, and are phenolic Aromatic polyphosphates containing no H groups, aromatic polyphosphates containing similar phenolic OH groups, ("Aromatic polyphosphates" shown below are aromatic polyphosphates containing phenolic OH groups and aromatic polyphosphates not containing Aromatic polyphosphates whose aromatic ring sources are bisphenol A and phenol, aromatic polyphosphates whose aromatic ring source is tetrabromobisphenol A and phenol, aromatic ring sources are resorcin and 2 , 6-xylenol aromatic polyphosphate, aromatic polyphosphates whose aromatic ring sources are hydroquinone and 2,6-xylenol, aromatic polyphosphates whose aromatic ring sources are bisphenol A and 2,6-xylenol, aromatic rings The source is tetrabromobisph Aromatic polyphosphates such a Nord A and 2,6-xylenol.
[0153]
In the aromatic polycarbonate resin composition forming the resin molded product of the present invention, resins and elastomers other than the component C can be appropriately blended according to the purpose.
[0154]
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.
[0155]
As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.
[0156]
The aromatic polycarbonate resin composition forming the resin molded article of the present invention includes various release agents, inorganic fillers, flow modifiers, antibacterial agents, photocatalytic antifouling agents, metallic agents, and photochromics depending on purposes. An agent etc. can be mix | blended in the range which does not impair the effect of this invention.
[0157]
In order to produce the aromatic polycarbonate resin composition forming the resin molded article of the present invention, any method is adopted. 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.
[0158]
Furthermore, in the melt kneading by the melt kneader of the resin composition of the present invention, the following mode is more preferable. That is, a compound (C component) having an affinity between the layered silicate (B component) having a cation exchange capacity of 50 to 200 meq / 100 g and the aromatic polycarbonate resin of the A component and having a hydrophilic component Particularly preferably, a styrene polymer (C1 component) having a functional group comprising a carboxyl group and / or a derivative thereof is melt-kneaded in advance. Thereafter, the melt-kneaded product and component A aromatic polycarbonate are melt-kneaded by a multi-screw extruder. Such a melt-kneading method is preferable because it improves the thermal stability of the aromatic polycarbonate resin. 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.
[0159]
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.
[0160]
The resin molded product of the present invention can be usually produced by injection molding the pellets produced as described above. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, insert molding, in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold, depending on the purpose as appropriate. Molded articles can be obtained using injection molding methods such as mold molding, two-color molding, sandwich molding, and ultra-high 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.
[0161]
In addition, the resin molded product of the present invention can also be produced 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. The resin molded product of the present invention can also be produced as a hollow molded product by rotational molding, blow molding, or the like.
[0162]
The resin molded product obtained as described above is manufactured under a wide range of molding processing conditions having no practical problem, and has good surface smoothness, good surface hardness, and good rigidity. More specifically, (1) the value of arithmetic average roughness Ra measured in accordance with JIS B0601 is 0.1 μm or less, and (2) pencil scribing by a hand-drawn method measured in accordance with JIS K5400. A resin molded product characterized in that the value is HB or more and (3) the value of the flexural modulus measured in accordance with ASTM D790 is 2,500 MPa or more. The target 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.
[0163]
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. The pencil scratch value is more preferably F or more, and the upper limit is 4H. 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.
[0164]
The resin molded article of the present invention preferably has a total light transmittance of 75% or more measured in accordance with JIS K7105 in a 1 mm-thick smooth flat molded article formed from the resin composition, and 80% More preferably. The upper limit is preferably 91.5%, more preferably 91%. A composition satisfying such conditions makes it possible to provide a resin molded product having better light transmittance. Furthermore, the resin molded product of the present invention preferably has a thickness of 1 to 5 mm, more preferably 1 to 3 mm, and still more preferably 1 to 2 mm. The resin molded product of the present invention has good light transmittance even at such a thickness, and provides a transparent resin molded product having such a thickness.
[0165]
The resin molded product of the present invention has a high value of flexural modulus, but also has a feature that the increase in specific gravity is small as compared with the case where it is reinforced with a normal inorganic reinforcing material. That is, it means that higher bending rigidity can be imparted to a molded product when compared with the same weight. This effect is, for example, [(flexural modulus) / (specific gravity)^Three], And a larger value means that a lighter and more rigid resin molded product can be obtained. In the case of the bisphenol A type aromatic polycarbonate resin, since the flexural modulus is 2,150 MPa and the specific gravity is 1.20, the index value is 1,244. On the other hand, according to the present invention, there is preferably provided a molded article comprising a resin composition having such an index value of preferably 1,500 or more, more preferably 1,600 or more. Therefore, it is possible to impart rigidity exceeding 1.2 times to the bisphenol A type aromatic polycarbonate resin at the same weight. On the other hand, such characteristics contribute to weight reduction of the product.
[0166]
The resin molded product of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method. For example, by metallizing, a molded product suitable for applications such as a mirror and a reflector is provided.
[0167]
The resin molded product of the present invention has a good surface hardness, but is further suitable for a transparent member for vehicles by applying a hard coat. That is, since the base molded article has a good surface hardness, the characteristics of the hard coat layer can be expressed more effectively. Furthermore, since the linear expansion coefficient of the resin molded product of the present invention is also reduced, the adhesiveness is also reduced due to the difference in expansion coefficient from the hard coat layer.
[0168]
Examples of the hard coat agent used in the present invention include a silicone resin hard coat agent and an organic resin hard coat agent. The silicone resin hard coat agent forms a cured resin layer having a siloxane bond. For example, partial hydrolysis of a compound mainly composed of a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound, etc.). Condensates, preferably partially hydrolyzed condensates further containing compounds corresponding to tetrafunctional siloxane units (tetraalkoxysilane compounds etc.), and further partially hydrolyzed condensates filled with metal oxide fine particles such as colloidal silica Is mentioned. The silicone resin hard coat agent may further contain a bifunctional siloxane unit and a monofunctional siloxane unit. These include alcohol generated during the condensation reaction (in the case of a partially hydrolyzed condensate of alkoxysilane), etc., but if necessary, may be dissolved or dispersed in any organic solvent, water, or a mixture thereof. Good. Examples of the organic solvent for this purpose include lower fatty acid alcohols, polyhydric alcohols and ethers thereof, and esters. In addition, in order to obtain a smooth surface state, various surfactants such as siloxane-based and alkyl fluoride-based surfactants may be added to the hard coat layer.
[0169]
Examples of the organic resin hard coat agent include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate.
[0170]
Among these hard coat agents, silicone resin hard coat agents with excellent long-term durability and relatively high surface hardness, or UV curable acrylics that can be processed with a relatively simple and good hard coat layer. A resin or a polyfunctional acrylic resin is preferred. The silicone resin hard coat agent can be selected from a so-called two-coat type composed of a primer layer and a top layer and a so-called one-coat type formed from only one layer.
[0171]
Examples of the resin that forms such a primer layer (first layer) include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, and polyester acrylates, urethane acrylates, and epoxy resins, which are composed of various blocked isocyanate components and polyol components. Various polyfunctional acrylic resins such as acrylate, phosphazene acrylate, melamine acrylate, amino acrylate and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, an acrylic resin and a polyfunctional acrylic resin preferably include 50% by weight, more preferably 60% by weight or more, and those composed of an acrylic resin and a urethane acrylate are particularly preferable. These can be applied either by applying a predetermined reaction after application of an unreacted material to obtain a cured resin, or by directly applying the reacted resin to form a cured resin layer. In the latter case, the resin is usually dissolved in a solvent to form a solution, which is then applied and then the solvent is removed. In the former case, a solvent is generally used.
[0172]
Furthermore, the resin forming the hard coat layer includes the above-mentioned light stabilizer and ultraviolet absorber, catalyst, thermal / photopolymerization initiator, polymerization inhibitor, silicone antifoaming agent, leveling agent, thickener, precipitation prevention. Agents, sag-preventing agents, flame retardants, various additives of organic / inorganic pigments / dyes, and auxiliary additives can be included.
[0173]
As a coating method, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method is appropriately selected depending on the shape of a molded product to be coated. be able to. Of these, the dip coating method, the flow coating method, and the spray coating method, which can easily cope with complicated molded product shapes, are preferable.
[0174]
The resin molded product of the present invention is excellent in transparency, surface smoothness, and surface hardness. Further, the resin molded product of the present invention can greatly improve the bending rigidity without increasing the weight of the molded product, and such characteristics contribute to the weight reduction of the product. A further feature is that the resin composition constituting the resin molded product of the present invention is excellent in thermal stability and can be applied to a large injection molded product. From these characteristics, the resin molded product of the present invention is suitable for various transparent members. Examples of such transparent members include transparent members for various vehicles (head lamp lens, turn signal lamp lens, tail lamp lens, resin window glass, meter cover, sun roof, moon roof, detachable top, window reflector, turn signal lamp lens, room lamp lens. , And display display front plate, etc.), lighting cover, resin window glass (for construction, etc.), solar cell cover or solar cell substrate, display device lens, touch panel, mirror, and parts for pachinko machines, etc. (Circuit cover, chassis, pachinko ball conveyance guide, etc.). Furthermore, among these, a molded product that is subjected to a hard coat treatment is particularly suitable for the resin molded product of the present invention.
[0175]
【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)
The resin molded product is cut and placed in a crucible, weighed, heated to 600 ° C., held for 6 hours, allowed to cool, and the ash residue remaining in the crucible is weighed to measure layered silicate (inorganic content). ) The amount was measured.
(2) Total light transmittance
Using a haze meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.), a resin molded product (smooth flat plate molded product having a thickness of 1 mm) was measured according to JIS K7105.
(3) Dispersion thickness of layered silicate
A section of 50 to 100 nm was prepared with a microtome, and observed at an acceleration voltage of 100 kV using a transmission electron microscope (LEM-100: manufactured by Topcon Corporation), and photographed at a magnification of 10,000 times. The photographed photograph was image-analyzed and the thickness of the layered silicate was measured to determine the dispersion thickness.
(4) Viscosity average molecular weight
The viscosity average molecular weight of the resin molded product (the following bending test piece) was measured by the method described in the text.
(5) Arithmetic mean roughness (Ra)
Using a surface roughness profile measuring machine (Surfcom 1400A: manufactured by Tokyo Seimitsu Co., Ltd.), the arithmetic average roughness Ra of the resin molded product (smooth flat plate molded product having a thickness of 1 mm) is measured in accordance with JIS B0601-1994. did.
(6) Flexural modulus
A bending test was performed in accordance with ASTM D790. As the bending test piece, one having dimensions of 127 mm in length, 12.7 mm in width, and 6.4 mm in thickness produced by injection molding was used.
(7) Specific gravity
Measured according to ASTM D792. The above-mentioned bending test piece was used as the test piece.
(8) Pencil scratch value
In accordance with a method defined in JIS K5400, a pencil scratch value was measured by a hand scratch method using a smooth flat plate-shaped molded product having a thickness of 1 mm.
(9) Hard coat adhesion
At almost the center of the resin molded product (smooth flat plate-shaped product with a thickness of 1 mm), Nichiban adhesive tape (trade name “Cero Tape”) is pressure-bonded to the hard coat layer with a 100-mm grid with a cutter knife. Then, it was strongly peeled off vertically to observe whether all remained in the resin molded product. Among the 10 resin molded products, the number n of molded products that did not remain was determined.
[0176]
[material]
The following were used as raw materials.
(A component)
A linear polycarbonate resin powder having a viscosity average molecular weight of 23,700 consisting of bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator (manufactured by Teijin Chemicals Ltd .: Panlite L-1250WP and L- 1225WP mixed at 1: 1 (weight ratio)
[0177]
(B component)
The contents of the B component (B-1 and B-2) are shown in Table 1. The layered silicate used was synthetic fluorine mica (manufactured by Co-op Chemical Co., Ltd .: Somasif ME-100, cation exchange capacity: 110 meq / 100 g), and the interlayer cation of the layered silicate was ionized. The organic onium ions used to exchange were as follows:
(1) Distearyldimethylammonium chloride (Tokyo Chemical Industry Co., Ltd .: First grade reagent)
(2) Tri-n-octylmethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd .: first grade reagent)
[0178]
(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)
C-2: Styrene-maleic anhydride copolymer (Nova Chemical Japan Co., Ltd .: DYLARK 232, maleic anhydride amount of about 8% by weight)
[0179]
(Other)
TMP: Trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP)
EPQ: Phosphonite heat stabilizer (manufactured by Sandoz: Sandstub P-EPQ)
EW: Fatty acid full ester (Riken Vitamin Co., Ltd .: Riquester EW-400)
UVA: UV absorber (Ciba Specialty Chemicals: Tinuvin 1577)
HP: hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1076)
IR: phthalocyanine-based near infrared absorber (Mitsui Chemicals, Inc .: MIR-362, TGA 5% weight loss temperature 282 ° C.)
CB: Carbon black (Mitsubishi Chemical Corporation: Furnace Black MA-100, pH = 3.5)
FR: Perylene red fluorescent dye (manufactured by BASF: Lumogen F Red 300)
OB: Coumarin-based fluorescent brightening agent (Hackol Chemical Co., Ltd .: Hackol PSR)
Talc: Talc (Made by Hayashi Kasei Co., Ltd .: U_PN  HS-T_0.8)
[Method for producing intercalation compound]
Ion exchange of the organic onium to synthetic fluorine mica was performed by the following method.
[0180]
About 100 g of synthetic fluorine mica is precisely weighed and stirred and dispersed in 10 liters of water at room temperature. To this, various equivalents of onium ion chloride or bromide are added with respect to the cation exchange equivalent of synthetic fluorine mica and stirred for 6 hours. did. The precipitated solid produced was filtered off, then stirred and washed in 30 liters of demineralized water and then filtered again. This washing and filtering operation was performed three times. The obtained solid is air-dried for 3 to 7 days and then pulverized in a mortar and further dried with hot air at 50 ° C. for 3 to 10 hours (depending on the type of guest onium ion), and the maximum particle size is again about 100 μm in the mortar. It grind | pulverized until it became. The residual moisture content was adjusted to 2 to 3 wt% by such hot air drying (the residual moisture content was evaluated by a decrease in thermal weight when held at 120 ° C. for 1 hour under a nitrogen stream). The ion exchange ratio of the onium ions was determined by measuring the weight fraction of the residue of the ion-exchanged layered silicate held at 500 ° C. for 3 hours under a nitrogen stream. The above operation was repeated several times to obtain the required amount. The produced organic onium ion exchange synthetic fluorine mica is shown in Table 1.
[0181]
[Table 1]

[0182]
[Preparation of composition for hard coat]
(1) Coating composition (i-1)
A flask equipped with a reflux condenser and a stirrer, and replaced with 70 parts of methyl methacrylate (hereinafter abbreviated as MMA), 39 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), azobisisobutyronitrile (hereinafter abbreviated as “MMA”) in a flask purged with nitrogen. 0.18 parts (abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 90 parts of a copolymer (acrylic resin (I)) having a composition ratio of MMA / HEMA of 70/30 (molar ratio). The weight average molecular weight of the copolymer was 80,000 in terms of polystyrene based on GPC measurement (column; Shodex GPCA-804, eluent: THF).
[0183]
Next, as a composition for the hard coat first layer, 8 parts of the acrylic resin (I) is mixed with 40 parts of methyl ethyl ketone, 20 parts of methyl isobutyl ketone, 5.2 parts of ethanol, 14 parts of isopropanol, and 10 parts of 2-ethoxyethanol. Then, 10 parts of methyltrimethoxysilane hydrolysis condensate solution (X) was added to this solution and stirred at 25 ° C. for 5 minutes. Further, melamine resin (Symel 303, Mitsui Cytec Co., Ltd.) was added to the solution. ) 1 part was added and stirred at 25 ° C. for 5 minutes to prepare a coating composition (i-1).
[0184]
(2) Coating composition (ii-1)
Using the same apparatus as above, 142 parts of methyltrimethoxysilane, 72 parts of distilled water and 20 parts of acetic acid were mixed with ice water while cooling, and the mixture was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol. Thus, 350 parts of methyltrimethoxysilane hydrolysis condensate solution (X) was obtained. On the other hand, 208 parts of tetraethoxysilane and 81 parts of 0.01N hydrochloric acid were mixed with cooling with ice water, and this mixed solution was stirred at 25 ° C. for 3 hours, diluted with 11 parts of isopropanol, and a tetraethoxysilane hydrolyzed condensate solution ( Y) 300 parts were obtained.
[0185]
Furthermore, as a composition for the hard coat second layer, 12 parts of distilled water and 20 parts of acetic acid are added to 100 parts of a water-dispersed colloidal silica dispersion (Snowtex 30 solid content concentration: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.). The mixture was stirred, and 134 parts of methyltrimethoxysilane was added to the dispersion while cooling in an ice-water bath. To this reaction liquid obtained by stirring this mixed liquid at 25 ° C. for 1 hour, 20 parts of tetraethoxysilane hydrolysis condensate solution (Y) and 1 part of sodium acetate as a curing catalyst were added and diluted with 200 parts of isopropanol to coat. A composition for use (ii-1) was prepared.
[0186]
[Examples 1-7, Comparative Examples 1-4]
After each component was dry blended at a blending ratio shown in Table 2, a twin screw extruder with a vent equipped with 30 mmφ diameter, L / D = 33.2, two kneading zone screws (manufactured by Kobe Steel, Ltd .: KTX30) was melt-kneaded at a cylinder temperature of 280 ° C., extruded, and strand cut to obtain pellets.
[0187]
In addition, when using C component, the B component and C component are the amount ratio of Table 2, the diameter 30mm diameter, L / D = 33.2, the twin screw extrusion with a vent equipped with the screw of the kneading zone 2 places. Using a machine (Kobe Steel Corporation: KTX30), melt-kneaded and extruded at a cylinder temperature of 200 ° C., strand-cut to obtain pellets, and then using the resulting pellets, the final ratio is shown in Table 2. The mixture of B and C components and the A component are dry blended so as to have the ratio shown in the following, and then a 30 mm diameter, L / D = 33.2, biaxial with a vent equipped with screws in two kneading zones Using an extruder (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.
[0188]
The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 5 hours. After drying, a 150 mm square × 1 mm thick smooth flat plate molded product and a bending test piece were subjected to an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 300 ° C., a mold temperature of 80 ° C., and a molding cycle of 40 seconds. Molded with
[0189]
Moreover, after annealing the said flat plate-shaped molded article at 120 degreeC for 2 hours, the said coating composition (i-1) was apply | coated by the dip coating method, and it left still at 25 degreeC for 20 minutes, Then, 120 minutes at 120 degreeC Heat cured. Next, the coating composition (ii-1) was further applied to the resin molded article by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 2 hours to perform a hard coat treatment. Observation of the obtained resin molded product revealed no occurrence of cracks.
[0190]
Table 3 shows the measurement results for these.
[0191]
[Table 2]

[0192]
[Table 3]

[0193]
As is apparent from the results of Table 3 above, the aromatic polycarbonate resin composition that satisfies the specific dispersion form has good thermal stability during molding, and the resin molded product formed from them has the following properties: It turns out that it has favorable transparency and surface characteristics (surface smoothness and surface hardness). Furthermore, it can be seen that the same good characteristics can be maintained even in the composition provided with various functional additives, and various functions required for the transparent member can be imparted without problems. On the other hand, ordinary resin compositions such as aromatic polycarbonate resin alone (Comparative Example 1), resin molded product containing talc (Comparative Example 2), and resin molded product containing no C component (Comparative Examples 3 to 4) No resin composition satisfying any of the above has been obtained.
[0194]
【The invention's effect】
The resin molded article of the present invention is a resin molded article having good transparency and surface characteristics (surface smoothness and surface hardness), light weight and high rigidity, and good thermal stability during molding. Therefore, the resin molded product of the present invention is useful in a wide range of fields such as the electric / electronic parts field, OA equipment parts field, automobile parts field, agricultural material field, fishery material field, transport container field, packaging container field, and miscellaneous goods field. However, it is particularly useful as a transparent member for vehicles, and its industrial effect is exceptional.

Claims (11)

(A) Aromatic polycarbonate resin (component A) per 100 parts by weight
(B) 0.1 to 50 parts by weight of layered silicate (component B) satisfying the following (i) and (ii):
(I) having a cation exchange capacity of 50 to 200 meq / 100 g,
(Ii) In the resin composition, a number ratio of 70% or more has a thickness of 100 nm or less.
And (C) an aromatic polycarbonate resin composition comprising 0.1 to 50 parts by weight of a styrene-containing polymer (component C) having a functional group comprising a carboxyl group and / or a derivative thereof, and conforming to JIS K7105 A resin molded product having a total light transmittance of 75% or more measured in this manner.   2. The resin molding according to claim 1, wherein the resin composition has a total light transmittance of 75% or more measured in accordance with JIS K7105 in a 1 mm-thick smooth plate-shaped molded article formed from the resin composition. Goods.   The resin molded product according to claim 1, wherein the resin molded product has a thickness of 1 to 5 mm.   The component B has a cation exchange capacity of 50 to 200 meq / 100 g, and at least 40% of the cation exchange capacity is exchanged with an organic onium ion. The resin molded product described.   5. The resin molded article according to claim 4, wherein the B component contains at least an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms in an organic group forming an organic onium ion.   5. The resin molded article according to claim 4, wherein the component B has an organic group forming an organic onium ion having an alkyl group having 10 or less carbon atoms, and at least one of the alkyl groups has 6 to 10 carbon atoms. .   The resin molded article according to any one of claims 1 to 6, wherein the component C is a polymer having an affinity for an aromatic polycarbonate resin and having a functional group comprising a carboxyl group and / or a derivative thereof. The resin component according to any one of claims 1 to 7 , wherein the component C is a styrene-maleic anhydride copolymer. The resin molded product has 1) an arithmetic average roughness Ra value measured in accordance with JIS B0601 of 0.1 μm or less, and 2) a pencil scratch value measured in accordance with JIS K5400 by a handwriting method. HB or more, 3) The value of the flexural modulus measured in accordance with ASTM D790 is 2,500 MPa or more, The resin molded product according to any one of claims 1 to 8 . The resin molded product according to any one of claims 1 to 9 , wherein the resin molded product is hard-coated on a surface thereof. The resin molded product according to any one of claims 1 to 10 , wherein the resin molded product is a vehicle transparent member.