JP2004051858A - Resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molding which contains a finely dispersed philo-silicate, has good transparency and surface properties (surface smoothness and surface hardness), is lightweight and highly rigid, and has good heat stability in molding. <P>SOLUTION: The resin molding is formed from an aromatic polycarbonate resin composition comprising (A) 100 pts. wt. aromatic polycarbonate resin (component A), (B) 0.1-50 pts. wt. philo-silicate (component B) satisfying requirements (i) and (ii): (i) component B has an ion exchange capacity of 50-200 meq/100 g, and (ii) at least 70% (in terms of a numerical ratio) of component B have thicknesses of 100 nm or smaller, and (C) 0.1-50 pts. wt. compound (component C) having an affinity for the aromatic polycarbonate and having a hydrophilic component and has a total light transmittance of 75% or higher as measured in accordance with JIS K7105. <P>COPYRIGHT: (C)2004,JPO

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−ＣＨ_３、−ＣＨ_２Ｃｌ、−ＣＨ_２Ｂｒ、−ＣＨ_２Ｉ、および−ＣＨ_２ＯＣＨ_３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]
TECHNICAL FIELD OF THE INVENTION
The present invention comprises an aromatic polycarbonate resin, a layered silicate, particularly 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. 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 thus are widely used in electrical, mechanical, automotive, medical, and other applications. Above all, application to transparent members for vehicles for the purpose of weight reduction has been widely attempted. As such a transparent member for a vehicle, a member requiring high transparency such as a headlamp lens, a resin window glass, a rear lamp lens, and a meter cover, and a sunroof, a moonroof, a detachable top, a window reflector, a turn signal lamp lens, Examples of such members include a room lamp lens, a front plate for display display, and other members that require a slightly lower degree of transparency. These members have been replaced with aromatic polycarbonates for the purpose of reducing the weight of the vehicle, instead of those made of conventional glass.However, the bending rigidity is inferior to that of glass. May be In particular, there is a high demand for an external member that receives a 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 can further reduce the weight of the member. In the case of a thermoplastic resin, it is common to mix an inorganic reinforcing material to improve the mechanical properties, but by doing so, the mechanical properties are improved, but the specific gravity is increased, and the advantage of weight reduction is reduced. In addition, the transparency and the surface smoothness are reduced. Further, the aromatic polycarbonate resin has poor scratch resistance, so that improvement in surface hardness may be required.
[0003]
In recent years, clay minerals, especially layered silicates, have been used as inorganic fillers, and their interlayer ions have been ion-exchanged into various organic onium ions to facilitate dispersion in the resin, thereby improving the specific gravity and surface appearance of molded products. Many attempts have been made to improve the mechanical properties while maintaining the above properties, particularly for polyamide resins and polyolefin resins, and some of them have been put to practical use.
[0004]
Similar techniques are also used for the aromatic polycarbonate resin composition 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, JP-A-2001-131400, and the like.
[0005]
In particular, in JP-A-07-331092, a resin composition comprising an aromatic polycarbonate resin and a layered silicate is used. By subjecting the layered silicate to a specific treatment, the strength of a molded article is maintained while maintaining a certain degree of transparency. Attempts have been made to improve. In addition, JP-A-11-71509 and JP-A-2001-131400 propose an optical film comprising an aromatic polycarbonate resin and a specific layered silicate.
[0006]
However, resin molded products of aromatic polycarbonate resins in which these layered silicates or the like are finely dispersed do not only exhibit sufficient mechanical properties and surface characteristics, but also large molded products such as members for vehicles. At the present time, it does not have thermal stability for injection molding, and is not practical. That is, a transparent member for vehicles (especially, having excellent transparency, lightweight and improved rigidity, excellent surface smoothness and surface hardness, and showing practically sufficient thermal stability during molding) At present, an aromatic polycarbonate resin molded product suitable for the injection molded product) has not been obtained so far.
[0007]
[Problems to be solved by the invention]
In view of the above problems, an object of the present invention is a resin molded product in which a layered silicate is finely dispersed, which has good transparency, surface characteristics (surface smoothness and surface hardness), and is lightweight. It is an object of the present invention to provide a resin molded product having high rigidity and having good thermal stability during molding.
[0008]
The present inventors have conducted intensive studies to achieve such an object, and as a result, blended an aromatic polycarbonate resin, a layered silicate, and a specific compound, and dispersed the layered silicate into a specific dispersion in an aromatic polycarbonate resin molded article. It has been found that the above problem can be solved by setting the state. The present inventors have conducted further intensive studies based on such a finding, and have completed the present invention.
[0009]
[Means for Solving the Problems]
The present invention relates to (1) 100 parts by weight of (A) an aromatic polycarbonate resin (component A), and (B) 0.1 to 50 parts by weight of a layered silicate (component B) satisfying the following (i) and (ii). Department,
(I) having a cation exchange capacity of 50 to 200 meq / 100 g;
(Ii) in the resin composition, 70% or more of the number ratio has a thickness of 100 nm or less;
And (C) a compound having an affinity for an aromatic polycarbonate and having a hydrophilic component (component (C)), which is formed from an aromatic polycarbonate resin composition comprising 0.1 to 50 parts by weight, and conforms to JIS K7105. The present invention relates to a resin molded product having a measured total light transmittance of 75% or more.
[0010]
According to the above configuration (1), a resin molded product having good transparency and surface characteristics (surface smoothness and surface hardness), light weight, high rigidity, and good thermal stability during molding is provided. Is done. Conventionally, a polycarbonate resin material having both high rigidity and transparency by mixing a glass filler having a refractive index close to that of a polycarbonate resin has been proposed. However, such materials are still insufficient in surface smoothness, and a special molding method was required to achieve surface smoothness close to that of a glass material. On the other hand, the present invention has excellent surface smoothness, and since the improvement in bending elastic modulus is achieved at an extremely low specific gravity, the bending rigidity is excellent and the product contributes to weight reduction. The present invention also provides a highly practical resin molded product exhibiting improved thermal stability with respect to a conventional resin composition using a specific layered silicate and capable of coping with a large injection molded product.
[0011]
One preferred embodiment of the present invention is (2) the above resin composition, which has a total light transmittance of a 1 mm-thick smooth flat molded article formed from the resin composition, which is measured according to JIS K7105. Is 75% or more of the resin molded article according to the above (1). According to the configuration (2), a resin molded product having more excellent light transmittance is provided.
[0012]
One preferred aspect 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 the configuration (3), a resin molded product in which a glass member is substituted is provided.
[0013]
In a preferred embodiment of the present invention, (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. The resin molded article according to the above. According to the configuration (4), there is provided a resin molded product having excellent dispersibility that more easily satisfies the above condition (ii), and having good transparency and flexural modulus.
[0014]
One of preferred embodiments of the present invention is (5) the component B, wherein the organic group forming the organic onium ion contains at least an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. The resin molded product according to the above (4). According to the configuration (5), a resin molded product excellent in dispersibility and thermal stability of the layered silicate of the B component is further provided.
[0015]
In one preferred embodiment of the present invention, (6) the B component is such that 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 at least one carbon atom. The resin molded product according to the above (4), which is 6 to 10. According to the configuration (6), the dispersibility of the layered silicate in the resin molded product and the thermal stability are further improved.
[0016]
One of the preferred embodiments of the present invention is that (7) the component (C) is a polymer having an affinity for an aromatic polycarbonate resin and having a functional group consisting of a carboxyl group and / or a derivative thereof. ) The resin molded product according to any one of (1) to (6). According to the configuration (7), there is provided a resin molded product having excellent thermal stability and being practically applicable to a large injection molded product.
[0017]
One preferred embodiment of the present invention is (8) the component (C), which is a styrene-containing polymer having a functional group consisting of a carboxyl group and / or a derivative thereof. A resin molded product described in (1). According to the configuration (8), a resin molded product having further excellent dispersibility and thermal stability of the layered silicate in the resin molded product is provided.
[0018]
One preferred embodiment of the present invention is (9) the resin molded product according to any one of the above (1) to (8), wherein the C component is a styrene-maleic anhydride copolymer. . According to the configuration (9), the resin molding is extremely excellent in dispersibility and thermal stability of the layered silicate in the resin molded product, and has 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 (10) the resin molded product has (1) a value of arithmetic average roughness Ra measured in accordance with JIS B0601 of 0.1 μm or less, and (2) JISK5400. The pencil scratch value measured by the handwriting method measured in accordance with the above method is HB or more, and the value of the flexural modulus measured in accordance with (3) ASTM D790 is 2,500 MPa or more. The resin molded product according to any one of (1) to (9) is provided. According to the configuration (10), more specifically, a resin molded product satisfying the above (1) to (3) is provided.
[0020]
According to a preferred aspect of the present invention, (11) the resin molded article has a surface subjected to a hard coat treatment, wherein the resin molded article has a hard coat treatment. It is a resin molded product. According to the configuration (11), a transparent member having excellent surface hardness and excellent adhesion to the hard coat layer is provided.
[0021]
According to a preferred aspect of the present invention, (12) the resin molded product is the resin molded product according to any one of (1) to (11), which is a transparent member for a vehicle. According to the configuration (12), a resin molded product suitable for a transparent member for a vehicle, in which the bending rigidity and the surface hardness of a 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]
Hereinafter, the present invention will be described in detail.
[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%, and more preferably 91%. If the total light transmittance is 75% or more, it can be used for some transparent members for vehicles. In the resin composition of the present invention, the fine dispersion of the component B is assisted by the component C, and the thermal stability is also improved. Thereby, it is possible to obtain a better light transmittance as compared with the component B alone. The higher the proportion of the B component, the lower the total light transmittance, but on the other hand, the improvement of the flexural modulus allows the product thickness to be reduced, so that the configuration of the present invention provides a resin molded product satisfying a predetermined transparency. It is possible.
[0024]
The aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol with 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 known as bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisoprop 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. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, and among them, bisphenol A is particularly preferred from the viewpoint of impact resistance.
[0026]
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate and the like are used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.
[0027]
In producing the aromatic polycarbonate resin by the interfacial polymerization method of the dihydric phenol and the carbonate precursor, if necessary, a catalyst, a terminal stopper, an antioxidant for preventing the dihydric phenol from being oxidized. May be used. The aromatic polycarbonate resin of the present invention may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. Includes carbonate resins, copolymerized polycarbonate resins obtained by copolymerizing difunctional alcohols (including alicyclic groups), and polyester carbonate resins obtained by copolymerizing such difunctional carboxylic acids and difunctional alcohols together. Further, a mixture of two or more of the obtained polycarbonate resins may be used.
[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 producing a branched polycarbonate is contained, such a ratio is preferably 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0 mol%, 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, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0. Those having 9 mol%, particularly preferably 0.01 to 0.8 mol%, are preferred. The ratio is¹It can be calculated by 1 H-NMR measurement.
[0030]
The aliphatic difunctional carboxylic acid is preferably an α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icosandioic acid, and cyclohexanedicarboxylic acid. And alicyclic dicarboxylic acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.
[0031]
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane unit can be used.
[0032]
The reaction by the interfacial polymerization method is usually a reaction between dihydric phenol and phosgene, and is performed 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]
Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction, and a monofunctional phenol such as phenol, p-tert-butylphenol or p-cumylphenol can be used as a molecular weight regulator. It is preferred to use Further, examples of the monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and tricontylphenol. These monofunctional phenols having a relatively long-chain alkyl group are effective when improved fluidity and hydrolysis resistance are required.
[0035]
The reaction temperature is usually 0 to 40 ° C., the reaction time is preferably several minutes to 5 hours, and the pH during the reaction is generally 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. The dihydric phenol and the carbonic acid diester are mixed in the presence of an inert gas, and the mixture is reacted under reduced pressure, usually at 120 to 350 ° C. The degree of pressure reduction is changed stepwise, and finally, the phenols generated are reduced to 133 Pa or less to remove the phenols out of 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. Of these, diphenyl carbonate is preferable.
[0038]
A polymerization catalyst can be used to increase the polymerization rate.Examples of the polymerization catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, hydroxides of boron and aluminum, Alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkoxides of alkali metals and alkaline earth metals, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, silicon compounds, germanium compounds, Examples of the catalyst include those usually used for esterification and transesterification of organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, and the like. The catalyst may be used alone or in combination of two or more. These polymerization catalysts are used in an amount of preferably 1 × 10^-8~ 1 × 10^-3Equivalent, more preferably 1 × 10^-7~ 5 × 10^-4It is selected within the range of equivalents.
[0039]
In the polymerization reaction, in order to reduce the number of phenolic terminal groups, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonylphenylphenyl carbonate, etc. Compounds can be added.
[0040]
Further, in the melt transesterification method, it is preferable to use a deactivator for neutralizing the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol per 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, particularly preferably 0.01 to 100 ppm, based on the aromatic polycarbonate after polymerization. Preferable examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
[0041]
Details of the reaction modes other than those described above are well known in books and patent publications.
[0042]
When the viscosity average molecular weight of the aromatic polycarbonate resin is less than 10,000, the strength and the like decrease, and when the viscosity average molecular weight exceeds 50,000, the molding processing characteristics decrease, so that the range of 10,000 to 50,000 is preferred. Preferably, the range is 12,000 to 30,000, and more preferably, the range is 15,000 to 28,000. Incidentally, 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 determined at 20 ° C. from a solution in which 0.7 g of the polycarbonate resin was dissolved in 100 ml of methylene chloride._sp) In the following equation.
η_sp/C=[η]+0.45×[η]²c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10^-4M^0.83
c = 0.7
[0044]
Embodiments of the polycarbonate resin in the present invention include the following. That is, it is composed of an aromatic polycarbonate having a viscosity average molecular weight of 70,000 to 300,000 (PC 1) and an aromatic polycarbonate having a viscosity average molecular weight of 10,000 to 30,000 (PC 2). 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 product. For example, appearance defects such as hesitation marks can be further reduced, and the condition width of injection press molding can be increased accordingly. On the other hand, a low molecular weight component of the PC (2) component lowers the overall melt viscosity, promotes relaxation of the resin, and enables molding with lower distortion. Note that the same 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 is performed 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 filtration through celite, the solution is removed and dried sufficiently, and the solid component soluble in methylene chloride is removed. obtain. From a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride, the specific viscosity at 20 ° C. calculated by the above equation is measured by using an Ostwald viscometer.
[0047]
The B component used in the aromatic polycarbonate resin composition forming the resin molded product 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 an organic onium ion is present between the layers in an amount of 40% or more of the cation exchange capacity. It is a layered silicate that has been exchanged. Hereinafter, the “layered silicate having a cation exchange capacity and formed by ion exchange between organic onium ions between layers” may be simply referred to as “organized layered silicate”.
[0048]
The layered silicate of the B component is SiO 2₂SiO consisting of chains₄It is a layer composed of a combination of a tetrahedral sheet structure and an octahedral sheet structure containing Al, Mg, Li, etc., and is a silicate (silicate) or clay mineral (clay) in which an exchangeable cation is coordinated between the layers. . These are represented, for example, by smectite minerals, vermiculite, halloysite, and swelling mica. Specifically, as smectite-based minerals, montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, stevensite, etc., and as swelling mica, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica And swellable synthetic mica such as Li-type tetrasilicon fluorine mica. These layered silicates can be either natural or synthetic. The synthetic product can be obtained by, for example, hydrothermal synthesis, melt synthesis, or solid-state 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, and more preferably 100 to 150 meq / 100 g. The cation exchange capacity is measured as a CEC value by the Schollenberger improved method, which is the official method in Japan 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, especially an aromatic polycarbonate resin. However, when it is larger than 200 meq / 100 g, the influence on the thermal deterioration of the aromatic polycarbonate resin increases.
[0050]
The layered silicate preferably has a pH value of 7 to 10. When the pH value is larger than 10, the thermal stability of the aromatic polycarbonate resin tends to decrease.
[0051]
Among these layered silicates, swelling properties of smectite clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine mica from the viewpoint of cation exchange capacity and the like. Fluorine mica is preferably used, and montmorillonite and synthetic fluoromica obtained by purifying bentonite are more preferable in terms of purity and the like. Further, synthetic fluorine mica which can obtain good mechanical properties is particularly preferable.
[0052]
The layered silicate of component B is preferably a layered silicate in which organic onium ions are ion-exchanged between layers of the layered silicate (organized layered silicate). Such an organically modified layered silicate helps to more easily achieve the dispersion state of "(ii) in which 70% or more of the silicate has a thickness of 100 nm or less in the resin composition" of the present invention. The organic onium ion is usually handled as a salt with a halogen ion or the like. Here, examples of the organic onium ion include an ammonium ion, a phosphonium ion, a sulfonium ion, an onium ion derived from a heteroaromatic ring, and the like. As the onium ion, any of primary, secondary, tertiary, and quaternary can be used. However, a quaternary onium ion is preferable. As the organic onium ion, an ammonium ion and a phosphonium ion are preferable. Generally, ammonium ions are superior in dispersibility, and phosphonium ions are somewhat advantageous in thermal stability. In the present invention, an ammonium ion is particularly preferred.
[0053]
As the ionic compound, those in which various organic groups are bonded can be used. The organic group is typically an alkyl group, but may have an aromatic group, or may have an ether group, an ester group, a double bond, a triple bond, a glycidyl group, a carboxylic acid group, or an acid anhydride group. And those containing various functional groups such as a hydroxyl group, an amino group, an amide group, and an oxazoline group.
[0054]
Specific examples of the organic onium ion include quaternary ammoniums having the same alkyl group such as tetraethylammonium and tetrabutylammonium; trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyl Trimethylalkylammonium such as octadecyl ammonium and trimethylicosanilammonium; trimethylalkenylammonium such as trimethyloctadecenylammonium; trimethylalkadienylammonium such as trimethyloctadecadienylammonium; triethyldodecylammonium, triethyltetradecylammonium; Triethylhexadecylane And triethylalkyl ammonium such as triethyloctadecyl ammonium; tributyl alkyl ammonium such as tributyl dodecyl ammonium, tributyl tetradecyl ammonium, tributyl hexadecyl ammonium, and tributyl octadecyl ammonium; dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl ditetradecyl ammonium Dimethyldialkylammonium, such as dimethyldihexadecylammonium, and dimethyldioctadecylammonium; dimethyldialkenylammonium, such as dimethyldioctadecenylammonium; dimethyldialkadienylammonium, such as dimethyldioctadecadienylammonium; Ammo Dialkylammonium, such as ammonium, 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; trioctylethyl ammonium And trialkylethylammonium such as tridodecylethylammonium; trialkylbutylammonium such as trioctylbutylammonium and tridecylbutylammonium; quaternary ammonium having an aromatic ring such as trimethylbenzylammonium; fragrance such as trimethylphenylammonium Quaternary ammonium derived from an aromatic amine; trialkyl [PAG] ammonium such as methyl diethyl [PEG] ammonium and methyl diethyl [PPG]; dialkyl bis [PAG] ammonium such as methyl dimethyl bis [PEG] ammonium; ethyl tris [PEG] Alkyltris [PAG] ammonium, such as ammonium, and phosphonium in which the nitrogen atom of the ammonium ion is replaced by a phosphorus atom Ion, and the like. These organic onium ions can be used either singly or in combination of two or more. The notation “PEG” indicates polyethylene glycol, the notation “PPG” indicates polypropylene glycol, and the notation “PAG” indicates polyalkylene glycol. Polyalkylene glycol having a molecular weight of 100 to 1,500 can be used.
[0055]
The molecular weight of these organic onium ion compounds is more preferably from 100 to 600. More preferably, it is 150 to 500. When the molecular weight is more than 600, the aromatic polycarbonate resin tends to accelerate the thermal deterioration in some cases, or tends to impair the heat resistance of the resin composition. The molecular weight of such an organic onium ion refers to the molecular weight of a single organic onium ion not including a counter ion such as a halogen ion. The organic group in the organic onium ion compound structure preferably contains at least one alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. In particular, using an alkyl group having 10 or less carbon atoms is also a preferable method for suppressing thermal deterioration of the aromatic polycarbonate resin. In this 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. It is particularly preferred that the number of carbon atoms is 6 to 8.
[0056]
Preferred embodiments of the organic onium ion include trimethyl-n-octyl ammonium, trimethyl-n-decyl ammonium, trimethyl-n-dodecyl ammonium, trimethyl-n-hexadecyl ammonium, trimethyl-n-octadecyl ammonium, methyl tri-n-octyl. Ammonium, ethyl tri-n-octyl ammonium, butyl tri-n-octyl ammonium, triphenylmethyl ammonium, 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 an organic onium ion compound to a layered silicate dispersed in a polar solvent and collecting the precipitated ion exchange compound. . 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 into the organic onium ion. It is common to exchange them. However, controlling the exchange ratio with respect to the ion exchange capacity within a certain range is also effective in suppressing thermal deterioration of the aromatic polycarbonate resin. For example, the fact that the ratio of ion exchange with organic onium ions is 80% or less of the ion exchange capacity is one means of suppressing thermal deterioration. Further, since organic onium ions also cause a decrease in transparency, reducing the ion exchange ratio by organic onium ions can also be expected to improve transparency.
[0058]
The exchange rate of the organic onium ion can be calculated for the compound after the exchange by determining the weight loss due to the thermal decomposition of the organic onium ion using a thermogravimeter or the like.
[0059]
The composition ratio of the layered silicate of the component B to the component A used in the present invention is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the component A. It is 5 to 10 parts by weight. When this composition ratio is less than 0.1 part by weight, the effect of improving the flexural modulus of the aromatic polycarbonate resin is not seen, and when it is more than 50 parts by weight, the thermal stability and mechanical strength of the composition decrease, It is difficult to obtain a practical resin molded product having a predetermined transparency. More preferably, the unit area of the molded article (1 cm²), The ratio of the component B is preferably 1 to 10 mg / cm²And more preferably 2 to 8 mg / cm²And more preferably 3 to 6 mg / cm.²It is.
[0060]
The component B of the present invention is further characterized in that 70% or more of the components have a thickness of 100 nm or less.
[0061]
The above characteristics can be determined from transmission electron micrographs of the thermoplastic resin composition. That is, the thermoplastic resin composition is used as 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, it is possible to obtain knowledge on the above characteristics.
[0062]
In the above characteristics, the component B preferably has a thickness of 80% or more having a thickness of 100 nm or less, and more preferably 85% or more of a component having a thickness of 100 nm or less. If the number ratio of the layer having a thickness of 100 nm or less is less than 70%, good transparency, surface smoothness, rigidity, and the like, which are features 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 the C component produces good affinity for both the aromatic polycarbonate resin and the phyllosilicate, especially the organized phyllosilicate. The affinity for both the aromatic polycarbonate resin and the layered silicate, especially the organically modified layered silicate, enhances 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 with respect to the dispersion of the organically modified layered silicate is considered to be the same as that of a compatibilizer for polymer alloy (compatibilityizer) used for compatibilizing different kinds of polymers. Therefore, the component C is preferably a polymer rather than a low molecular compound. Further, the polymer also has excellent thermal stability during kneading. The average number of repeating units of the polymer needs to be 2 or more, preferably 5 or more, 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 is obtained.
[0065]
When the component C of the present invention is a polymer, examples of its basic structure 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 composed of α and β (the main chain is α, the graft chain is β, The chain can be any of β and the graft chain can be either α) or a block copolymer composed of α and β (the number of block segments such as di-, tri-, etc. can be 2 or more, including radial block type) ), And a random copolymer comprising α and β. α and β may be not only single polymers but also copolymers.
[0067]
Here, α and β represent both a polymer segment unit and a monomer unit. 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 affinity for the aromatic polycarbonate resin is α and the hydrophilic component is β, the function of α is expressed by the entire polymer, and β is a polymer having a structure contained in α. Coalescing.
[0069]
That is, although α alone does not have sufficient affinity with the aromatic polycarbonate resin, α and β are combined and integrated to exhibit good affinity with the aromatic polycarbonate resin. Even when α alone is used, the affinity with the aromatic polycarbonate resin is good, and the combination with β sometimes further improves the affinity. Such an embodiment is included in the above structure (i). Thus, structures (i) and (ii) may partially overlap. On the other hand, in the structure (i), α alone has a sufficient affinity with the aromatic polycarbonate resin, but by combining and integrating α and β, the good affinity with the aromatic polycarbonate resin is reversed. There can be some embodiments in which it decreases. Naturally, such an embodiment is included in the C component.
[0070]
The above structures (i) and (ii) can be selected in the present invention. In particular, an embodiment that satisfies both the condition of the structure (i) and the condition of the structure (ii), that is, even if only α is used, the affinity for the aromatic polycarbonate resin is high, and the affinity is further increased for the entire C component to which β is added. Embodiments are preferred.
[0071]
The component having an affinity for the aromatic polycarbonate resin in the component C of the present invention (hereinafter, may be referred to as α in the above description) will be described. As described above, the component C functions in the same manner as the compatibilizer in the polymer alloy, so that 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]
In the non-reaction type, the affinity is good when the following factors are present. That is, (1) similarity in chemical structure, (2) similarity of solubility parameter (difference in solubility parameter is 1 (cal / cm) between the aromatic polycarbonate resin and α.³)^1/2Within, that is, about 2.05 (MPa)^1/2It is desirable to have factors such as (3) intermolecular interactions (hydrogen bonding, ionic interactions, etc.), and pseudo-attractive interactions peculiar to random polymers. These factors are also known as indices for judging the affinity between the compatibilizer and the polymer on which the polymer alloy is based.
[0073]
In the reaction type, various types known as functional groups having reactivity with the aromatic polycarbonate resin in the compatibilizer can be used. For example, a carboxyl group, a carboxylic 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 obtain a good affinity, the mixture of the aromatic polycarbonate resin and α shows a single glass transition temperature (Tg), It is also widely known that a behavior in which Tg of α moves toward Tg of α is recognized. In the present invention, as the component (α) having affinity, a component having such behavior can be mentioned as one of the embodiments.
[0075]
As described above, the component (α) having an affinity with the aromatic polycarbonate resin in the component C of the present invention can exert its affinity due to various factors. Above all, α is preferably a non-reactive type, and particularly preferably exhibits good affinity by approximating the solubility parameter. This is because it has better affinity with the aromatic polycarbonate resin than the reaction type. In addition, the reaction type has a disadvantage that when the reactivity is excessively increased, thermal degradation of the polymer is promoted by a side reaction.
[0076]
Preferably, the solubility parameters of the aromatic polycarbonate resin and α have the following relationship. That is, the solubility parameter of the aromatic polycarbonate resin (component A) is set to δ_A((MPa)^1/2) And the solubility parameter of α in the C component or the solubility parameter of the entire C component is 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 / cm³)^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 preferable, and 19 to 22 ((MPa)^1/2Is 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 cyclohexane dimethanol copolymerized polyethylene terephthalate), and aliphatic polyester ( And polyester-based polymers such as polycaprolactone. Specific examples thereof include styrene polymer, alkyl (meth) acrylate polymer, and acrylonitrile polymer (for example, polystyrene, styrene-maleic anhydride copolymer, polymethyl methacrylate, styrene-methyl methacrylate copolymer, and styrene-acrylonitrile copolymer). And a vinyl polymer represented by a polymer. 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 determined by a theoretical estimation method based on a 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 a differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.
[0080]
The component α having an affinity for the aromatic polycarbonate resin of the component A is preferably 5% by weight or more, more preferably 10% by weight or more, further preferably 30% by weight or more, and more preferably 50% by weight in the component C. The above is particularly preferred. Since an embodiment in which the entire C component is set to α is also possible, the upper limit may be 100% by weight.
[0081]
Next, the hydrophilic component of component C in the present invention (hereinafter sometimes referred to as β as described above) will be described. Such a hydrophilic component is selected from a monomer having a hydrophilic group (organic atomic group having strong interaction with water) and a hydrophilic polymer component (polymer segment). Hydrophilic groups are widely known per se. For example, according to the Chemical Dictionary (Kyoritsu Shuppan, 1989), the following groups are exemplified.
[0082]
1) Strongly hydrophilic group:
-SO₃H, -SO₃M, -OSO₃H, -OSO₃H, -COOM, -NR₃X (R: alkyl group, X: halogen atom, M: alkali metal, -NH₄) Such
2) Less hydrophilic groups:
-COOH, -NH₂, -CN, -OH, -NHCONH₂ Such
3) Small hydrophilic group:
-CH₂OCH₃, -OCH₃, -COOCH₃, -CS, etc.
[0083]
Among the above 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) a strongly hydrophilic group includes a sulfine group and the like, and 2) a group having a low hydrophilicity includes a carboxylic anhydride group, an oxazoline group, a formyl group and a pyrrolidone group. Is exemplified.
[0084]
The group 2) is preferable because it is more excellent in thermal stability during melt processing of the aromatic polycarbonate resin. If the hydrophilicity is too high, thermal deterioration of the 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]
In addition, the hydrophilic group of the present invention includes both monovalent and divalent or higher. When the component C is a polymer, a divalent or higher valent functional group refers to a group in which the group does not form a main chain, and a group that forms a 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 group at a molecular chain terminal are functional groups even if they are divalent or higher.
[0086]
A more specific indicator of a hydrophilic group is a solubility parameter. It is widely known that the greater the value of the solubility parameter, the higher the hydrophilicity. The solubility parameter per group is determined by the aggregation energy (E_coh) And the molar volume (V) of each group (“A Polymer Handbook 4th Edition” (A @ WILEY-INTERSCIENCE @ PUBLICATION), VII / 685, 1999, or Polym. Eng. Sci., No. 14, 147 and 472, 1974). Such a calculation method is simple and widely known. Further, from the viewpoint of comparing only the magnitude relation of hydrophilicity, the cohesive energy (E_coh) Divided by the molar volume (V) (E)_coh/ V; the unit is “J / cm³") Can be used as an index of hydrophilicity.
[0087]
The hydrophilic group contained in β in component C of the present invention is E_coh/ V needs to be 600 or more. Preferably E_coh/ V is 800 or more, and when it is 800 or more, E of the carbonate bond in the aromatic polycarbonate resin of the component A of the present invention is_coh/ V and has a higher hydrophilicity than a carbonate bond. Further E_coh/ V is more preferably 900 or more, and even more preferably 950 or more.
[0088]
As described above, when the hydrophilicity is too high, the aromatic polycarbonate resin is likely to be thermally degraded. Therefore E_coh/ V is preferably 2,500 or less, more preferably 2,000 or less, and still more preferably 1,500 or less.
[0089]
A hydrophilic polymer component (polymer segment) is also selected as the hydrophilic component (β) of the component C. Therefore, the segment of the hydrophilic polymer contained in the polymer of the component C is β. Hydrophilic polymers are widely known and include, for example, polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyacrylic acid metal salts (including chelate type), polyvinylpyrrolidone, polyacrylamide, polyhydroxyethyl methacrylate, and the like. Among these, polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyvinyl pyrrolidone, and polyhydroxyethyl methacrylate are preferably exemplified. These are because good hydrophilicity and thermal stability to the aromatic polycarbonate resin (suppression of decomposition of the aromatic polycarbonate during melt processing) can be achieved at the same time. Incidentally, as the polyalkylene oxide, polyethylene oxide and polypropylene oxide are preferable.
[0090]
In both the monomer having a hydrophilic group and the hydrophilic polymer component, β preferably has an acidic functional group (hereinafter sometimes simply referred to as “acid group”). The acidic group suppresses thermal deterioration of the aromatic polycarbonate resin during melt processing. This is considered to be because such an acidic group has an excellent effect of reducing the size of the interlayer by electric action.
[0091]
Among them, an acidic group containing no nitrogen atom is more preferable. A functional group containing a nitrogen atom such as an amide group or an imide group may not sufficiently suppress thermal deterioration of the aromatic polycarbonate resin during melt processing. This is considered to be because the nitrogen atom has local basicity and causes thermal decomposition of the carbonate bond.
[0092]
Examples of the acidic group include a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, and a sulfinic acid group, as well as a phosphonic acid group and a phosphinic acid group.
[0093]
When β is a monomer having a hydrophilic group, the ratio of β in the component C of the present invention is 60 to 10,000 as a functional group equivalent, which is the molecular weight per functional group, and 70 to 8,000 Preferably, it is more preferably from 80 to 6,000, and still more preferably from 100 to 3,000. When β is a hydrophilic polymer segment, β in the C component is 5 to 95% by weight in 100% by weight of the C component, preferably 10 to 90% by weight, more preferably 30 to 70% by weight. Preferably, it is 30 to 50% by weight.
[0094]
As a method for producing a compound having a component (α) having an 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 of block- or graft-copolymerizing a polymer component of β with α, and a method of directly reacting β with α to add it.
[0095]
As preferred embodiments of the component C of the present invention, “a polymer having an affinity for an aromatic polycarbonate and having an acidic functional group”, “having an affinity for an aromatic polycarbonate and having a polyalkylene oxide segment” "Polymer", "Polymer having affinity for aromatic polycarbonate and having oxazoline group", or "Polymer having affinity for aromatic polycarbonate and having hydroxyl group" is exemplified. In the polymer of the preferred embodiment as the C component, its molecular weight is preferably in the range of 10,000 to 1,000,000 in weight average molecular weight, more preferably in the range of 50,000 to 500,000. 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 component C are mixed is also a preferable embodiment when the resin molded article is used as a transparent member for a vehicle.
[0096]
Among them, a polymer having an affinity for an aromatic polycarbonate and having an acidic functional group is preferable, and a functional group having an affinity for an aromatic polycarbonate and comprising a carboxyl group and / or a derivative thereof is more preferable. And a polymer having: From the viewpoint of the effect of maintaining the heat resistance of the aromatic polycarbonate, the polymer is preferably one having an aromatic ring component in the main chain and one having a styrene component in the main chain. In view of the above, a styrenic polymer (component C1) having a functional group consisting of a carboxyl group and / or a derivative thereof is particularly suitable as the component C of the present invention.
[0097]
The composition ratio of the component C of the present invention is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, and still more preferably 1 to 12 parts by weight, per 100 parts by weight of the component A. If the amount is less than 0.5 part by weight, the effect of dispersing the layered silicate may not be sufficient, and the effect of suppressing the thermal deterioration of the aromatic polycarbonate may be insufficient. If it exceeds 50 parts by weight, impact resistance and heat resistance may be reduced.
[0098]
The styrene polymer (component C1) having a functional group comprising a carboxyl group and / or a derivative thereof particularly suitable as the component C of the present invention will be described in detail. The ratio of the functional group comprising a carboxyl group and / or a derivative thereof is preferably from 0.1 to 12 meq / g, more preferably from 0.5 to 5 meq / g. Here, one equivalent in the C1 component means that one mole of a carboxyl group is present, and such a value can be calculated by back titration with potassium hydroxide or the like.
[0099]
Examples of the functional group comprising a derivative of a carboxyl group include (i) a metal salt (including a chelate salt) in which a hydroxyl group of a carboxyl group is substituted with a metal ion, (ii) an acid chloride in which a chlorine atom is substituted, (iii) -OR (R is a monovalent hydrocarbon group), (iv) an acid anhydride (R is a monovalent hydrocarbon group) substituted with -O (CO) R, (v) -NR₂(R is hydrogen or a monovalent hydrocarbon group), and (vi) an imide (R is hydrogen or a monovalent hydrocarbon group) in which two carboxyl groups are substituted with ＝ NR. Can be.
[0100]
As a method for producing a styrene-based polymer having a functional group composed of a carboxyl group and / or a derivative thereof (hereinafter, simply referred to as “carboxyl groups”), various conventionally known methods can be used. For example, (1) a method of copolymerizing a monomer having a carboxyl group and a styrene-based monomer, and (2) a method of bonding or copolymerizing a compound or monomer having a carboxyl group to a styrene-based polymer. Examples of the method include polymerization.
[0101]
In the copolymerization of the above (1), various copolymers such as alternating copolymers, block copolymers and tapered copolymers can be used in addition to random copolymers. In addition, in the method of copolymerization, 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. Further, a method of polymerizing once after forming a macromonomer 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-based polymer or copolymer as required. In addition, there can be mentioned a method of reacting or copolymerizing at a high temperature. In such a method, a reactive active site is thermally generated in a styrene-based 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 irradiation with radiation or an electron beam, and application of an external force by a mechanochemical technique. Further, there is a method in which a monomer that generates an active site required for the reaction is previously copolymerized in the styrene-based copolymer. Examples of the active site for the reaction include an unsaturated bond, a peroxide bond, and a thermally stable nitroxide radical having high steric hindrance.
[0103]
As the compound or monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, acrylamide, unsaturated monocarboxylic acids such as methacrylamide and derivatives thereof, maleic anhydride, citraconic anhydride, N-phenylmaleimide, Derivatives of maleic anhydride, such as N-methylmaleimide, as well as glutarimide structures and chelate structures formed of acrylic acid and polyvalent metal ions. Among these, a monomer having a functional group containing no metal ion or 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 preferred.
[0104]
Examples of the styrene compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, and dichlorostyrene. , Bromostyrene, dibromostyrene, vinylnaphthalene and the like can be used, and styrene is particularly preferable.
[0105]
Further, other compounds copolymerizable with these compounds, such as acrylonitrile and methacrylonitrile, may be used as a copolymerization component.
[0106]
Among the styrenic polymers having carboxyl groups, preferred in the present invention are styrenic copolymers obtained by copolymerizing a monomer having a functional group consisting of a carboxyl group and / or a derivative thereof. is there. This is because in such a copolymer, a relatively large number of carboxyl groups can be stably contained in the styrene-based polymer. A more preferred embodiment is a styrene-based copolymer obtained by copolymerizing a monomer having a carboxyl group and a styrene-based monomer. A particularly preferred embodiment is a styrene-maleic anhydride copolymer. The styrene-maleic anhydride copolymer has high compatibility with both the ionic component in the layered silicate and the aromatic polycarbonate resin, and thus finely disperses the layered silicate. Further, the action of the carboxylic acid anhydride group effectively reduces the interlayer of the layered silicate, especially the layered silicate of the organic layer, thereby giving the resin composition good thermal stability. Further, since the copolymer itself has good thermal stability, it has high stability even at the 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 a carboxyl group is not particularly limited as long as the above-mentioned condition of the ratio of β is satisfied. It is preferable to use a monomer having a carboxyl group content of 1 to 30% by weight, a styrene compound of 99 to 70% by weight and a copolymerizable other compound of 0 to 29% by weight. Those having 30% by weight and 99 to 70% by weight of a styrene compound are particularly preferred.
[0108]
The molecular weight of the component C1, which is a preferred embodiment of the component C 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. The weight average molecular weight shown here is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line with a standard polystyrene resin.
[0109]
Next, a polymer having a polyalkylene oxide segment, which is another embodiment of the component C, particularly a preferable polyetherester copolymer (component C2) will be described.
[0110]
The polyetherester copolymer is a polymer produced by performing 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 (component C2), and alkylene containing tetramethylene glycol in an amount of 65 mol% or more. It is a copolymer produced from glycol or a derivative thereof (C2 component), and a dicarboxylic acid or a derivative thereof containing 60% by mole or more of terephthalic acid (C2 component).
[0111]
Embedded image

[0112]
(Where X represents a monovalent organic group, n and m are each an integer including 0, and 10 ≦ (n + m) ≦ 120. When m is 2 or more, Xs are the same or different from each other Any of the embodiments can be selected.)
In the above formula (I), X is -CH₃, -CH₂Cl, -CH₂Br, -CH₂I, and -CH₂OCH₃At least one substituent selected from When X is other than these, steric hindrance by the substituent becomes large, and it becomes difficult to increase the degree of polymerization of the copolymer. When n + m is less than 10, the layered silicate may not be sufficiently dispersed. When n + m exceeds 120, a polyetherester copolymer having a high degree of polymerization is hardly obtained, and the phase of the C2 component is hardly obtained. The solubilizing 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. If the amount of the component C2 (1) is less than 30% by weight, the layered silicate is not sufficiently dispersed, which may cause a decrease in mechanical properties and a deterioration in appearance. Even when the content of the C2 component (1) is more than 80% by weight, the layered silicate is not sufficiently dispersed and the strength of the polyetherester copolymer itself is reduced, thereby deteriorating mechanical properties and deteriorating appearance. There are cases.
[0115]
In the C2 component of the polyetherester copolymer of the C2 component, a diol other than tetramethylene glycol can be copolymerized. Examples of such a diol include ethylene glycol, trimethylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. The content of tetramethylene glycol in the component C2 (2) is 65 mol% or more, preferably 75 mol% or more, and more preferably 85 mol% or more. A polyetherester copolymer having less than 65 mol% of tetramethylene glycol causes a reduction in the moldability of the resin composition.
[0116]
A dicarboxylic acid of a polyetherester copolymer or a derivative thereof (in the component C2-3), such a dicarboxylic acid capable of copolymerizing a dicarboxylic acid other than terephthalic acid (including those having a carboxyl group exceeding 2) Examples thereof include isophthalic acid, phthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid and cyclohexanedicarboxylic acid. The copolymer is particularly suitable as the component C. In the component C2-3, terephthalic acid is at least 60 mol%, preferably at least 70 mol%, more preferably from 75 to 95 mol%, and preferably at least 60 mol%. The polyetherester copolymer of less than tends to lower 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. Examples of such a phosphorus-based heat stabilizer include phosphate esters such as trimethyl phosphate, triphenyl phosphite, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, and 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, and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite Aromatic polycarbonate such as phosphonite Compounds widely known as the phosphorus-based heat stabilizer is preferably exemplified. The phosphorus-based heat stabilizer preferably contains 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, and more preferably 0.01 to 0.2% by weight, based on 100% by weight of the total composition. It is even more preferred that it comprises% by weight. By adding such a phosphorus-based heat stabilizer, the heat stability is further improved, and good molding characteristics can be obtained.
[0118]
Further, the aromatic polycarbonate resin composition forming the resin molded article of the present invention preferably contains a release agent. Known release agents can be used. For example, fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc .; those modified with a functional group-containing compound such as acid modification can also be used), silicone compounds (especially alkyls such as phenyl and methyl groups) Fluorinated oil (typified by polyfluoroalkyl ether, etc.), paraffin wax, and beeswax.
[0119]
Among them, fatty acid esters and silicone compounds are preferable, and fatty acid esters are particularly preferably used in terms of mold releasability, transparency of a molded article, adhesion to a hard coat layer, and the like. The fatty acid ester is an ester of an alcohol and an aliphatic carboxylic acid. As the alcohol, any of a monohydric alcohol and a dihydric or higher polyhydric alcohol can be used. In the present invention, it is more preferable that the fatty acid ester is mainly composed of a polyhydric alcohol.
[0120]
Examples of the monohydric alcohol include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol.
[0121]
Specific examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin (for example, decaglycerin), pentaerythritol, dipentaerythritol, diethylene glycol, and propylene glycol, among which pentaerythritol is preferable.
[0122]
The aliphatic carboxylic acid used for the fatty acid ester preferably has 3 to 32 carbon atoms. Examples of such aliphatic carboxylic acids 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, and hexadecanoic acid (palmitin). Acids), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, and saturated aliphatic carboxylic acids such as hexacosanoic acid, and palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, Mention may be made of unsaturated aliphatic carboxylic acids such as eicosapentaenoic acid and setrenic 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 are such saturated aliphatic carboxylic acids. Particularly preferred are stearic acid and palmitic acid.
[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 tallow and lard) and vegetable fats (such as palm oil). Thus, aliphatic carboxylic acids such as stearic acid are usually mixtures 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 or palmitic acid which is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components is preferably used. Preferred embodiments of the composition ratio of each component in such a mixture are 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 methylation GC / MS (gas chromatography-mass spectrometry) method indicates that the area of the palmitic acid component (Sp) and the stearic acid component are different. It is preferable that the sum of the area of the acid component and the area (Ss) is 80% or more of the total aliphatic carboxylic acid and the area ratio (Ss / Sp) of both is 1.2 or more. Here, the pyrolysis methylation 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 generate a methyl ester derivative of the fatty acid. This is a method of performing GC / MS measurement on the derivative.
[0126]
The total of Sp and Ss is preferably at least 85%, more preferably at least 90%, even more preferably at least 91% of the total aliphatic carboxylic acid component. On the other hand, the sum of the above Sp and Ss can be set to 100%, but is preferably 98% or less, more preferably 96% or less from the viewpoint of manufacturing cost and the like. 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. The mixing ratio of these aliphatic carboxylic acids does not need to be satisfied, but may be satisfied by mixing two or more aliphatic carboxylic acids. Examples of the fats and oils as the raw material of the aliphatic carboxylic acid satisfying the above mixing ratio include animal fats and oils such as beef tallow and lard, 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 the above, animal fats and oils are preferable in that they contain more stearic acid, and beef tallow is more preferable. Further, among tallow, oleostearin containing a large amount 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 even more preferably 85% or more. A fatty acid ester having a low esterification rate and a high hydroxyl value easily deteriorates the polycarbonate resin, and the molded product is liable 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 is not necessarily required to have an esterification ratio of 100%, but may be at least 80%, preferably at least 85%.
[0128]
The acid value, hydroxyl value, iodine value, and 5% weight loss temperature in TGA (thermogravimetric analysis) measurement of the fatty acid ester are described.
[0129]
The acid value of the fatty acid ester is preferably low from the viewpoint of thermal stability and the effect on cracking of the molded product, and is preferably relatively high from the viewpoint of reducing the releasing force (improving the releasing property). . The acid value of the fatty acid ester is suitably in the range of 0.1 to 20, more preferably 2 to 18, and still more preferably 5 to 15. The acid value can be determined by the method specified in JIS K 0070.
[0130]
The hydroxyl value of the fatty acid ester is preferably low from the viewpoint of thermal stability, reduction of the releasing force and influence on cracking of the molded product, while too low is not preferable because the production time increases and the cost increases. The hydroxyl value of the fatty acid ester is suitably in the range of 0.1 to 40, preferably in the range of 1 to 30, and more preferably in the range of 2 to 20. The hydroxyl value can be determined by the method specified 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, more preferably 1 or less. Such an iodine value can be determined by the method specified in JIS K 0070.
[0132]
The release agent such as a 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 based on 100 parts by weight of the polycarbonate resin. . If the amount of the release agent exceeds the above range and is too small, the release property is not sufficiently improved. On the other hand, when the amount of the release agent exceeds the above range and is too large, the transparency of the molded article is easily damaged.
[0133]
Further, in order to use the resin molded article of the present invention as a transparent member for vehicles, good weather resistance is often required, so that the aromatic polycarbonate resin composition forming the resin molded article further contains an ultraviolet absorber. It is preferable that it contains.
[0134]
As the ultraviolet absorber, specifically, in the case of benzophenones, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate 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]
Specific examples of the ultraviolet absorber compound include benzotriazole-based compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole. , 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-chlorobenzotriazole 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 copolymer with the monomer Such as a copolymer with a possible vinyl monomer or a copolymer of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer. And a polymer having a -hydroxyphenyl-2H-benzotriazole skeleton.
[0136]
Specific examples of the ultraviolet absorber compound include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4 , 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- Il) -5-butyloxyphenol and the like. Further, the above 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. Certain compounds are exemplified.
[0137]
Among them, benzotriazole and hydroxyphenyltriazine are preferable. The ultraviolet absorbers may be used alone or as a mixture of two or more. The use amount of the ultraviolet absorber 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 part by weight is particularly preferred.
[0138]
The aromatic polycarbonate resin composition forming the resin molded product of the present invention comprises 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. Further, the combined use of a hindered amine-based light stabilizer and a benzotriazole-based and / or triazine-based UV absorber effectively improves 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]
The light stabilizers may be used alone or as a mixture of two or more. 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 part by weight is particularly preferred.
[0140]
The aromatic polycarbonate resin composition forming the resin molded product of the present invention preferably further contains a bluing agent in an amount of 0.05 to 3 ppm (weight ratio) in the aromatic polycarbonate resin composition. It is effective for eliminating the yellow tint of a polycarbonate resin molded product. In particular, in the case of molded articles with weather resistance, a certain amount of ultraviolet absorber is used, so there is a reality that resin products tend to take on a yellow tint due to the "action and color of the ultraviolet absorber". The use of a bluing agent is very effective for imparting a natural transparency.
[0141]
Here, the bluing agent refers to a colorant that exhibits a blue color or a purple color by absorbing orange or yellow light, and is particularly preferably a dye. By blending the bluing agent, the polycarbonate resin composition of the present invention achieves a better hue. The important point here is the amount of the bluing agent. If the amount of the bluing agent in the resin composition is less than 0.05 ppm, the effect of improving the hue may be insufficient. On the other hand, if the amount exceeds 3 ppm, the light transmittance is lowered, which is not suitable. More preferably, the compounding 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, Terazol Blue RLS from Sando, and Plast Blue 8580 from Arimoto Chemical Industries.
[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-mentioned bluing agents, as long as the object of the present invention is not impaired. Dyes are particularly preferred from the viewpoint of maintaining transparency. Preferred dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, and isoindians. Linone dyes and phthalocyanine dyes can be exemplified. Further, fluorescent whitening agents such as bisbenzooxazolyl-stilbene derivatives, bisbenzooxazolyl-naphthalene derivatives, bisbenzooxazolyl-thiophene derivatives, and coumarin derivatives can be used. The amount of the dye and the fluorescent whitening agent to be 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]
In some cases, the resin molded product of the present invention is required to have antistatic performance. In such a case, the resin molded product is preferably formed from an aromatic polycarbonate resin composition containing an antistatic agent. Examples of such antistatic agents include (i) phosphonium salts of organic sulfonates such as phosphonium salts of arylsulfonic acids represented by phosphonium salts of dodecylbenzenesulfonic acid, and phosphonium salts of alkylsulfonic acids. The phosphonium salt is suitably in a composition ratio of 5 parts by weight or less per 100 parts by weight of the 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. The range of parts is more preferred.
[0145]
Examples of the antistatic agent include (ii) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, organic cesium sulfonate, organic rubidium sulfonate, organic calcium sulfonate, organic magnesium sulfonate, organic barium sulfonate and the like. And alkali (earth) metal salts of organic sulfonic acids. Specifically, for example, metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid are exemplified. The alkali (earth) metal salt of organic sulfonic acid is suitably in a composition ratio of 0.5 part by weight or less per 100 parts by weight of the component A, preferably 0.001 to 0.3 part by weight, more preferably 0.005 to 0.5 part by weight. 2 parts by weight is more preferred. Particularly, alkali metal salts such as potassium, cesium, and rubidium are preferred.
[0146]
Examples of the antistatic agent include (iii) ammonium salts of organic sulfonates such as ammonium salts of alkyl sulfonates and ammonium salts of aryl sulfonates. It is appropriate that the ammonium salt has a composition ratio of 0.05 part 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 proportion of the ester is preferably 0.5 part by weight or less per 100 parts by weight of the component A. Examples of the antistatic agent include (v) a polymer containing a poly (oxyalkylene) glycol component such as polyetheresteramide as a constituent component thereof. The amount of the polymer is suitably 5 parts by weight or less per 100 parts by weight of the 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 proportion of the non-organic compound is suitably 0.05 parts by weight or less per 100 parts by weight of the component A. Further, the non-organic compounds exemplified in (vi) may be blended as a heat ray absorbent in addition to the antistatic performance.
[0147]
In the aromatic polycarbonate resin composition forming the resin molded article of the present invention, a compound having an ability to absorb heat rays that does not impair the object of the present invention can be used. Preferable examples of the compound include a phthalocyanine-based near-infrared absorbing agent and a carbon filler. 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 (both natural and artificial, and further including whiskers), carbon fiber (including those obtained by a vapor phase growth method), carbon nanotube, and fullerene. 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 part by weight, more preferably 0.008 to 0.1 part by weight, and 0.01 to 0.07 part by weight based on 100 parts by weight of the polycarbonate resin. Is more preferred. In the resin composition of the present invention, 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.
[0148]
In the aromatic polycarbonate resin composition forming the resin molded article of the present invention, a flame retardant can be used in an amount that does not impair the object of the present invention. Examples of the flame retardant include a halogenated bisphenol A polycarbonate flame retardant, an organic salt flame retardant, an aromatic phosphate ester flame retardant, and a halogenated aromatic phosphate ester flame retardant. The above can be used.
[0149]
Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrabromobisphenol A, a copolymerized polycarbonate type flame retardant of tetrabromobisphenol A and bisphenol A, and the like.
[0150]
Specifically, organic salt-based flame retardants include dipotassium diphenylsulfone-3,3'-disulfonate, potassium diphenylsulfon-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 perfluorobutanesulfonate, sodium lauryl sulfate Um or potassium hexadecyl sulfate, sodium or potassium.
[0151]
Specifically, the halogenated aromatic phosphate ester type flame retardants include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate and the like. is there.
[0152]
Specifically, aromatic phosphate ester-based flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, and tetrakis (2,6-xylyl) hydroquinone diphosphate. , Tetrakis (2,6-xylyl) -4,4'-biphenol diphosphate, tetraphenyl resorcin diphosphate, tetraphenyl hydroquinone diphosphate, tetraphenyl-4,4'-biphenol diphosphate, and the aromatic ring source is resorcin and phenol Aromatic polyphosphate containing no phenolic OH group, aromatic polyphosphate containing resorcinol and phenol as aromatic ring sources, and aromatic polyphosphate containing phenolic OH group, and hydroquinone and phenol as aromatic ring sources. Aromatic polyphosphate containing no H group, similar aromatic polyphosphate containing phenolic OH group, ("Aromatic polyphosphate" shown below means aromatic polyphosphate containing phenolic OH group and aromatic polyphosphate not containing Aromatic polyphosphate whose aromatic ring source is bisphenol A and phenol, aromatic polyphosphate whose aromatic ring source is tetrabromobisphenol A and phenol, and whose aromatic ring source is resorcinol and 2 Aromatic polyphosphate whose aromatic ring source is hydroquinone and 2,6-xylenol, aromatic polyphosphate whose aromatic ring source is bisphenol A and 2,6-xylenol, aromatic ring The source is tetrabromobisph Aromatic polyphosphates such a Nord A and 2,6-xylenol.
[0153]
The aromatic polycarbonate resin composition forming the resin molded article of the present invention may contain a resin or an elastomer other than the component C as appropriate according to the purpose.
[0154]
As such other resins, for example, polyethylene terephthalate, polyester resins such as polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, polypropylene 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]
Examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber and the like.
[0156]
The aromatic polycarbonate resin composition forming the resin molded article of the present invention may contain various release agents, inorganic fillers, flow modifiers, antibacterial agents, photocatalytic antifouling agents, metallic agents, and photochromics, as appropriate. Agents and the like can be blended as long as the effects of the present invention are not impaired.
[0157]
For producing the aromatic polycarbonate resin composition forming the resin molded article of the present invention, any method is employed. For example, there can be mentioned a method in which each component and optionally other components are premixed, then melt-kneaded, and pelletized. Examples of premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. In the pre-mixing, granulation can also be carried out by an extrusion granulator or a briquetting machine, if necessary. 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 thermostatic stirring vessel. A multi-screw extruder represented by a vented 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]
Further, in the melt kneading of the resin composition of the present invention by a melt kneader, the following embodiment is more preferable. That is, a compound having an affinity between the layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g (component B) and the aromatic polycarbonate resin of component A and having a hydrophilic component (component C) Particularly preferably, a styrene-based polymer (component C1) having a functional group comprising a carboxyl group and / or a derivative thereof is melt-kneaded in advance. Thereafter, the melt-kneaded product and the aromatic polycarbonate of the component A are melt-kneaded by a multi-screw extruder. Such a melt-kneading method is preferable for improving the thermal stability of the aromatic polycarbonate resin. This is considered to be because the C component sufficiently interacts with the B component when the B component and the C component are melt-kneaded in advance, and a predetermined effect is efficiently obtained.
[0159]
More specifically, for example, (i) a method of melt-kneading the components B and C with a vented twin-screw extruder to form a pellet, and then melt-kneading with the component A again, or (ii) mixing the component B with the component B The component C is introduced from the main supply port of the vented twin-screw extruder, and part or all of the component A is already melt-kneaded with the components B and C from the supply port provided in the middle stage of the twin-screw extruder. The method of throwing into the state where it was put is mentioned. In the method in which the components B and C are melt-kneaded in advance, a part of the component A may be included during the melt-kneading.
[0160]
The resin molded product of the present invention can be usually produced by injection molding the pellet produced as described above. In such injection molding, not only a usual molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, an insert molding, an in-mold coating molding, an adiabatic mold molding, a rapid heating and cooling mold according to an appropriate purpose. A molded article can be obtained by using an injection molding method 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. For the molding, either a cold runner method or a hot runner method can be selected.
[0161]
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 a sheet or film, an inflation method, a calendar method, a casting method, or the like can be used. Furthermore, it is also possible to form a heat-shrinkable tube by performing a specific stretching operation. It is also possible to produce the resin molded product of the present invention as a hollow molded product by rotational molding or blow molding.
[0162]
The resin molded product obtained as described above is manufactured under a wide range of molding processing conditions having no practical problems, and has good surface smoothness, good surface hardness, and good rigidity. More specifically, (1) the value of the arithmetic average roughness Ra measured in accordance with JIS B0601 is 0.1 μm or less, and (2) the pencil scratching by the handwriting method measured in accordance with JIS K5400. A resin molded product having a value of HB or more and (3) a value of flexural modulus measured in accordance with ASTM D790 of 2,500 MPa or more is obtained. The target value is even higher. Conventionally, in order to improve the bending elastic modulus of a resin molded product, it was common to mix a reinforcing material on a fiber or an inorganic filler, but in that case, the surface roughness is 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 further preferably 0.05 μm or less. The lower limit largely depends on the mold used for molding, but about 0.001 μm is appropriate. The pencil scratch value is more preferably F or more, and its upper limit is 4H. The value of the flexural modulus is more preferably 2,800 MPa or more, and still more 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 product of the present invention preferably has a total light transmittance of 75% or more, as measured according to JIS K7105, of a flat plate-shaped molded product having a thickness of 1 mm formed from the resin composition, and is preferably 80% or more. 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 article having better light transmittance. Furthermore, the thickness of the resin molded product of the present invention is preferably 1 to 5 mm, more preferably 1 to 3 mm, and still more preferably 1 to 2 mm. The resin molded article of the present invention has good light transmittance even at such a thickness, and provides a transparent resin molded article having such a thickness.
[0165]
The resin molded product of the present invention has a high flexural modulus, but also has a feature that the increase in specific gravity is small as compared with the case where the resin molded product is reinforced with an ordinary inorganic reinforcing material. That is, it means that a 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)³], And the larger the value, the higher the weight of the resin molded article with higher rigidity. In the case of bisphenol A type aromatic polycarbonate resin, the flexural modulus is 2,150 MPa and the specific gravity is 1.20, so the above index value is 1,244. On the other hand, according to the present invention, there is provided a molded article comprising a resin composition having such an index value preferably at least 1,500, more preferably at least 1,600. Therefore, it is possible to provide the bisphenol A type aromatic polycarbonate resin with more than 1.2 times the rigidity at the same weight. On the other hand, such characteristics contribute to the weight reduction of the product.
[0166]
The resin molded article 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 metallizing (e.g., vapor deposition) can be performed. Examples of the surface treatment method include a vapor deposition method, a thermal spraying method, and a plating method, in addition to coating with a liquid agent. Either a physical vapor deposition method or a chemical vapor deposition method can be used as the vapor deposition method. Examples of the physical vapor deposition method include a vacuum vapor deposition method, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and an optical CVD method. For example, by performing metallizing, a molded product suitable for applications such as a mirror and a reflector is provided.
[0167]
Although the resin molded article of the present invention has good surface hardness, it becomes more suitable for a transparent member for vehicles by applying a hard coat. That is, since the molded substrate has a good surface hardness, the properties of the hard coat layer can be more effectively exhibited. Further, since the resin molded article of the present invention has a reduced coefficient of linear expansion, the decrease in adhesion due to a difference in expansion coefficient with the hard coat layer is also reduced.
[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-based hard coat agent forms a cured resin layer having a siloxane bond, and for example, partially hydrolyzes a compound mainly containing a compound corresponding to a trifunctional siloxane unit (such as a trialkoxysilane compound). Condensates, preferably partially hydrolyzed condensates further containing a compound corresponding to a tetrafunctional siloxane unit (such as a tetraalkoxysilane compound), and partially hydrolyzed condensates further filled with metal oxide fine particles such as colloidal silica Is mentioned. The silicone resin-based hard coat agent may further contain a difunctional siloxane unit and a monofunctional siloxane unit. These include alcohols generated during the condensation reaction (in the case of partially hydrolyzed condensate of alkoxysilane) and the like, and may be further dissolved or dispersed in any organic solvent, water, or a mixture thereof as necessary. Good. Examples of the organic solvent therefor include lower fatty alcohols, polyhydric alcohols and ethers and esters thereof. In order to obtain a smooth surface state, various surfactants, for example, a siloxane-based or alkyl fluoride-based surfactant may be added to the hard coat layer.
[0169]
Examples of the organic resin-based hard coating agent include a melamine resin, a urethane resin, an alkyd resin, an acrylic resin, and a 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, a silicone resin-based hard coat agent having excellent long-term durability and a relatively high surface hardness, or an ultraviolet curable acrylic which is relatively easy to process and forms a good hard coat layer Resins or polyfunctional acrylic resins are preferred. As the silicone resin-based hard coat agent, any of a so-called two-coat type composed of a primer layer and a top layer and a so-called one-coat type formed of only one layer can be selected.
[0171]
Examples of the resin forming the 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 composed of various blocked isocyanate components and polyol components. Examples include various polyfunctional acrylic resins such as acrylate, phosphazene acrylate, melamine acrylate, and amino acrylate, and these can be used alone or in combination of two or more. Among them, preferred are those containing 50% by weight, more preferably 60% by weight or more of an acrylic resin and a polyfunctional acrylic resin. Particularly preferred are those made of an acrylic resin and urethane acrylate. These can be applied either to applying an unreacted material to a predetermined reaction after application to form a cured resin, or to directly apply the reacted resin to form a cured resin layer. The latter is usually applied by dissolving the resin in a solvent to form a solution, then applying the solution, and then removing the solvent. In the former case, a solvent is generally used.
[0172]
Further, the resin forming the hard coat layer includes the above-mentioned light stabilizer and ultraviolet absorber, as well as a catalyst, a heat / photopolymerization initiator, a polymerization inhibitor, a silicone antifoaming agent, a leveling agent, a thickener, and a sedimentation prevention agent. Agents, anti-sagging agents, flame retardants, various additives of organic / inorganic pigments / dyes and auxiliary additives.
[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, and a roller coating method is appropriately selected according to the shape of a molded article as a substrate to be coated. be able to. Among them, a dip coating method, a flow coating method, and a spray coating method, which can easily cope with a complicated molded product shape, are preferable.
[0174]
The resin molded product of the present invention is excellent in transparency, surface smoothness, and surface hardness. Furthermore, the resin molded product of the present invention enables a significant improvement in bending rigidity without increasing the weight of the molded product, and such characteristics contribute to a reduction in the weight of the product. A further feature is that the resin composition constituting the resin molded product of the present invention has excellent thermal stability, and thus can be applied to large injection molded products. From these characteristics, the resin molded product of the present invention is suitable for various transparent members. Examples of such a transparent member 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, etc.). , And front panel for display display, etc.), lighting cover, resin window glass (for architectural use), solar cell cover or base material, lens for display device, touch panel, mirror and parts for game machine (pachinko machine, etc.) (Circuit cover, chassis, pachinko ball conveyance guide, etc.). Further, among these, molded articles subjected to hard coating treatment are particularly suitable for the resin molded article of the present invention.
[0175]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these. In addition, the measurement of various characteristics in an Example was based on the following method. The following raw materials were used.
(1) Layered silicate (inorganic content) content
The resin molded product was cut into a crucible, weighed, heated to 600 ° C., kept as it was for 6 hours, allowed to cool, and weighed the incineration residue remaining in the crucible to obtain a layered silicate (inorganic component). ) The amount was measured.
(2) Total light transmittance
Using a haze meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.), measurement was performed on a resin molded product (smooth flat molded product having a thickness of 1 mm) in accordance with JIS K7105.
(3) Dispersion thickness of layered silicate
A section of 50 to 100 nm was prepared with a microtome, observed using a transmission electron microscope (LEM-100: manufactured by Topcon Corporation) at an acceleration voltage of 100 kV, and photographed at 10,000 times magnification. The thickness of the layered silicate was measured by analyzing the image of the photograph taken, and the dispersion thickness was determined.
(4) Viscosity average molecular weight
The viscosity average molecular weight of the resin molded product (bending test piece described below) was measured by the method described in the text.
(5) Arithmetic mean roughness (Ra)
The arithmetic average roughness Ra of a resin molded product (smooth flat molded product having a thickness of 1 mm) is measured using a surface roughness profile measuring device (Surfcom 1400A: manufactured by Tokyo Seimitsu Co., Ltd.) in accordance with JIS B0601-1994. did.
(6) Flexural modulus
A bending test was performed according to ASTM D790. The bending test piece used had a size of 127 mm long × 12.7 mm wide × 6.4 mm thick prepared by injection molding.
(7) Specific gravity
It was measured in accordance with ASTM D792. The test piece used was the above-described bending test piece.
(8) Pencil scratch value
According to the method specified in JIS K5400, a pencil scratch value was measured by a hand-drawing method using a flat plate-shaped molded article having a thickness of 1 mm.
(9) Hard coat adhesion
At the approximate center of the resin molded product (smooth flat plate-shaped molded product with a thickness of 1 mm), 100 squares with 1 mm intervals were made on the hard coat layer with a cutter knife, and Nichiban adhesive tape (trade name "Cellotape") was pressed. Then, it was observed whether the film was strongly peeled off vertically and remained on the resin molded product. The number n of molded articles that did not all remain out of the ten resin molded articles was determined.
[0176]
[material]
The following were used as raw materials.
(A component)
Linear polycarbonate resin powder having a viscosity average molecular weight of 23,700 (manufactured by Teijin Chemicals Ltd .: Panlite L-1250WP and L-) comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal stopper. 1225WP mixed at 1: 1 (weight ratio))
[0177]
(B component)
Table 1 shows the contents of the B components (B-1 and B-2). The layered silicate used was synthetic fluorine mica (Somasif @ ME-100, manufactured by Corp Chemical Co., Ltd., cation exchange capacity: 110 meq / 100 g), and the interlayer cation of the layered silicate was ionized. The organic onium ions used for exchange were as follows.
(1) Distearyl dimethyl ammonium chloride (Tokyo Kasei Kogyo Co., Ltd .: First grade reagent)
(2) Tri-n-octylmethylammonium chloride (Tokyo Kasei Kogyo 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 content about 15% by weight)
C-2: Styrene-maleic anhydride copolymer (manufactured by Nova Chemical Japan Co., Ltd .: DYLARK # 232, maleic anhydride content: about 8% by weight)
[0179]
(Other)
TMP: trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP)
EPQ: phosphonite heat stabilizer (Sandoz P-EPQ)
EW: fatty acid full ester (manufactured by Riken Vitamin Co., Ltd .: RIQUESTER EW-400)
UVA: UV absorber (manufactured by Ciba Specialty Chemicals: Tinuvin 1577)
HP: Hindered phenolic antioxidant (Irganox 1076, manufactured by Ciba Specialty Chemicals)
IR: phthalocyanine-based near-infrared absorbing agent (MIR-362, manufactured by Mitsui Chemicals, Inc., TGA 5% weight loss temperature 282 ° C.)
CB: carbon black (manufactured by Mitsubishi Chemical Corporation: furnace black @ MA-100, pH = 3.5)
FR: Perylene-based red fluorescent dye (manufactured by BASF: Lumogen F Red 300)
OB: Coumarin-based fluorescent whitening agent (Hakkor Chemical Co., Ltd .: Hakkor PSR)
Talc: Talc (Hayashi Kasei Co., Ltd .: U_PNHS-T_0.8)
[Method for producing interlayer compound]
The above-mentioned organic onium was ion-exchanged to the synthetic fluorine mica by the following method.
[0180]
Approximately 100 g of synthetic fluoromica was precisely weighed, and this was stirred and dispersed in 10 liters of water at room temperature, and various equivalents of chloride or bromide of onium ion with respect to the cation exchange equivalent of synthetic fluoromica were added thereto and stirred for 6 hours. did. The resulting sedimentable solid was filtered off, washed with stirring in 30 liters of demineralized water, and then filtered off again. This washing and filtration were repeated three times. The obtained solid is air-dried for 3 to 7 days, then pulverized in a mortar, and further subjected to hot-air drying at 50 ° C. for 3 to 10 hours (depending on the type of onium ion of the guest), and the maximum particle size is again about 100 μm in the mortar. And crushed. The residual moisture content was reduced to 2 to 3% by weight by such hot air drying (the residual moisture content was evaluated by a decrease in thermogravity when kept at 120 ° C. for 1 hour under a nitrogen stream). The ion exchange ratio of onium ions was determined by measuring the weight fraction of the residue of the ion-exchanged layered silicate when it was kept at 500 ° C. for 3 hours in a nitrogen stream. The above operation was repeated several times to obtain the required amount. Table 1 shows the prepared organic onium ion-exchanged synthetic fluorine mica.
[0181]
[Table 1]

[0182]
[Preparation of composition for hard coat]
(1) Coating composition (i-1)
Equipped with a reflux condenser and a stirrer, 70 parts of methyl methacrylate (hereinafter abbreviated as MMA), 39 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), and azobisisobutyronitrile (hereinafter abbreviated as 70 parts) in a flask purged with nitrogen. 0.18 parts) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Next, the reaction was carried out in a nitrogen stream at 70 ° C. for 6 hours with stirring. 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 first layer of hard coat, 8 parts of the acrylic resin (I) was 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. After dissolving in a solvent, 10 parts of a methyltrimethoxysilane hydrolyzed condensate solution (X) was added to the solution, and the mixture was stirred at 25 ° C. for 5 minutes. Further, the melamine resin (Cymer 303 manufactured by 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 under cooling with ice water, and the mixture was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol. Thus, 350 parts of a methyltrimethoxysilane hydrolyzed condensate solution (X) was obtained. On the other hand, 208 parts of tetraethoxysilane and 81 parts of 0.01N hydrochloric acid are mixed under cooling with ice water, and the mixture is stirred at 25 ° C. for 3 hours, diluted with 11 parts of isopropanol and diluted with a tetraethoxysilane hydrolyzed condensate solution ( Y) 300 parts were obtained.
[0185]
Further, as a composition for the second layer of the hard coat, 12 parts of distilled water and 20 parts of acetic acid were added to 100 parts of a water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by weight). After stirring, 134 parts of methyltrimethoxysilane was added to this dispersion while cooling in an ice water bath. This mixture was stirred at 25 ° C. for 1 hour. To the reaction mixture obtained, 20 parts of a tetraethoxysilane hydrolyzed condensate solution (Y) and 1 part of sodium acetate as a curing catalyst were added, diluted with 200 parts of isopropanol, and coated. Composition (ii-1) was prepared.
[0186]
[Examples 1 to 7, Comparative Examples 1 to 4]
After dry-blending each component at the mixing ratio shown in Table 2, a twin-screw extruder equipped with a vent having a diameter of 30 mmφ, L / D = 33.2 and equipped with two screws in a kneading zone (manufactured by Kobe Steel Ltd.): Using KTX30), the mixture was melt-kneaded at a cylinder temperature of 280 ° C., extruded, and strand cut to obtain pellets.
[0187]
In the case where the C component is used, the B component and the C component are mixed at the ratios shown in Table 2 with a diameter of 30 mmφ, L / D = 33.2, and a twin-screw extruder equipped with a screw in two kneading zones. Using a kneader (Kobe Steel, Ltd .: KTX30), the mixture was melt-kneaded at a cylinder temperature of 200 ° C., extruded, and then subjected to strand cutting to obtain pellets. The mixture of component B and component C is dry-blended with component A and the like so as to have a ratio as shown in the following table. Then, a vented biaxial equipped with a screw having a diameter of 30 mmφ, L / D = 33.2, and two kneading zones is provided. Using an extruder (KTX30, manufactured by Kobe Steel Ltd.), 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 at 100 ° C. for 5 hours using a hot-air circulation dryer. After drying, a 150 mm square × 1 mm thick flat plate-shaped molded product and a bending test piece were subjected to an injection molding machine (manufactured by 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.
[0189]
Further, after the above-mentioned smooth plate-shaped molded article is annealed at 120 ° C. for 2 hours, the coating composition (i-1) is applied by dip coating, left at 25 ° C. for 20 minutes, and then at 120 ° C. for 30 minutes. 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 showed no occurrence of cracks.
[0190]
Table 3 shows the measurement results for these.
[0191]
[Table 2]

[0192]
[Table 3]

[0193]
As is evident from the results in Table 3, the aromatic polycarbonate resin composition satisfying the specific dispersion form has good thermal stability at the time of molding, and a resin molded article formed therefrom has: It turns out that it has good transparency and surface characteristics (surface smoothness and surface hardness). Further, it can be seen that the same good properties can be maintained in the composition to which various functional additives have been added, and the various functions required for the transparent member can be imparted without any problem. On the other hand, ordinary resin compositions such as an aromatic polycarbonate resin alone (Comparative Example 1), a resin molded product containing talc (Comparative Example 2), and a resin molded product containing no C component (Comparative Examples 3 and 4) are: However, a resin composition satisfying any of the above has not been obtained.
[0194]
【The invention's effect】
The resin molded product of the present invention has good transparency and surface characteristics (surface smoothness and surface hardness), is lightweight, has high rigidity, and has good thermal stability during molding. Therefore, the resin molded article of the present invention is useful in a wide range of fields such as electric and electronic parts, OA equipment parts, automobile parts, agricultural materials, fishery materials, transport containers, packaging containers, and miscellaneous goods. However, it is particularly useful as a transparent member for a vehicle, and the industrial effects achieved are outstanding.

Claims (12)

(A) 0.1 to 50 parts by weight of a layered silicate (component (B)) satisfying the following (i) and (ii) per 100 parts by weight of the aromatic polycarbonate resin (component (A)):
(I) having a cation exchange capacity of 50 to 200 meq / 100 g;
(Ii) in the resin composition, 70% or more of the number ratio has a thickness of 100 nm or less;
And (C) a compound having an affinity for an aromatic polycarbonate and having a hydrophilic component (component C), which is formed from an aromatic polycarbonate resin composition comprising 0.1 to 50 parts by weight, and conforming to JIS K7105. A resin molded product having a measured total light transmittance of 75% or more. The resin molding according to claim 1, wherein the resin composition has a total light transmittance of 75% or more as measured in accordance with JIS K7105 in a 1 mm-thick smooth flat molded product 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. 4. The composition according to claim 1, wherein 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 organic onium ions. A resin molded product as described in the above. 5. The resin molded product according to claim 4, wherein in the component B, an organic group forming an organic onium ion contains at least an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. The resin component according to claim 4, wherein in the component B, an organic group forming an 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. . The resin molded article according to any one of claims 1 to 6, wherein the C component 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 molded product according to any one of claims 1 to 7, wherein the C component is a styrene-containing polymer having a functional group consisting of a carboxyl group and / or a derivative thereof. The resin molded product according to any one of claims 1 to 8, wherein the C component is a styrene-maleic anhydride copolymer. The resin molded article has (1) a value of the arithmetic average roughness Ra measured in accordance with JIS B0601 of 0.1 μm or less, and (2) a pencil scratching method measured in accordance with JIS K5400. The resin according to any one of claims 1 to 9, wherein a value of the flexural modulus measured in accordance with (3) ASTM D790 is 2,500 MPa or more. Molding. The resin molded product according to any one of claims 1 to 10, wherein the surface of the resin molded product is subjected to a hard coat treatment. The resin molded product according to any one of claims 1 to 11, wherein the resin molded product is a transparent member for a vehicle.