JP3976416B2 - Aromatic polycarbonate resin composition - Google Patents

Description

【００２８】
この残存触媒活性指数は、１％以下であり、更に好ましくは０．５％以下、最も好ましくは０．２％以下である。残存触媒活性指数がこの範囲を越えると芳香族ポリカーボネート樹脂が経時変化して好ましくない。
【００２９】
芳香族ポリカーボネート樹脂の分子量は、粘度平均分子量（Ｍ）で１２，０００〜３０，０００が好ましく、１４，０００〜２７，０００がより好ましく、１５，０００〜２５，０００が特に好ましい。かかる粘度平均分子量を有する芳香族ポリカーボネート樹脂は、組成物として十分な強度が得られ、また、成形時の溶融流動性も良好であり成形歪みが発生せず好ましい。本発明でいう粘度平均分子量は塩化メチレン１００ｍＬにポリカーボネート樹脂０.７ｇを２０℃で溶解した溶液から求めた比粘度（ηsp）を次式に挿入して求めたものである。
【００３０】
η_ｓｐ／ｃ＝［η］＋０.４５×［η］^２ｃ（但し［η］は極限粘度）
［η］＝１.２３×１０^−４Ｍ^０．８３
ｃ＝０．７
本発明の芳香族ポリカーボネート樹脂組成物に用いる板状充填材としては、ガラスフレーク、マイカ、タルクである。
【００３１】
本発明で使用するガラスフレークとしては、平均粒径が１０〜１０００μｍのものが好ましく、かつその平均粒径を（ａ）、厚さを（ｃ）とした時、（ａ）／（ｃ）比が５〜５００のものが好ましく、６〜４５０のものがより好ましく、７〜４００のものがさらに好ましい。平均粒径が１０μｍ未満もしくは（ａ）／（ｃ）比が５未満であると剛性が十分でなく、平均粒径が１０００μｍを越えるかもしくは（ａ）／（ｃ）比が５００を越えると成形品の外観、及びウエルド強度が悪くなり好ましくない。ここでいうガラスフレークの平均粒径とは、標準ふるい法により求められる粒度の重量分布のメジアン径として算出されるものである。
【００３２】
ガラスフレークは、現在公知のエポキシ系、ウレタン系、アクリル系などの各種化合物により集束処理することができ、また後述するシランカップリング剤等で表面処理されたものが好ましい。
【００３３】
また、本発明で使用するガラスフレークとして、金属コートガラスフレークを使用することもできる。ガラスフレークにコーティングする金属は、ガラスにコーティング可能な金属であればよく、例えば金、銀、ニッケル、アルミニウム等があげられる。また、コーティングする方法には特に制限がなく、任意の方法が採用される。例えば無電解メッキによる方法が好ましく、コーティングの膜厚は通常０．００００１〜１０μｍであり、ガラスフレークの平滑面、好ましくは更に端面にも均一にコーティングする。かかる金属をコーティングしたガラスフレークは、そのまま使用できるが、更にその表面に、酸化防止剤等のために、処理剤をコーティングしてもよい。
【００３４】
本発明におけるマイカとしては、剛性確保の面から、平均粒径が１〜８０μｍの粉末状のものが好ましい。 マイカとは、アルミニウム、カリウム、マグネシウム、ナトリウム、鉄等を含んだケイ酸塩鉱物の粉砕物である。マイカには白雲母、金雲母、黒雲母、人造雲母等があり、本発明のマイカとしてはいずれのマイカも使用できるが、金雲母、黒雲母は白雲母に比べてそれ自体が柔軟であり、また、金雲母、黒雲母は白雲母に比べて主成分中にＦｅが多く含まれているためそれ自体の色相が黒っぽくなるため、更に人造雲母は天然金雲母のＯＨ基がＦに置換されたものであるがそれ自体が高価であり実用的ではない。好ましくは白雲母である。また、マイカの製造に際しての粉砕法としては、マイカ原石を乾式粉砕機にて粉砕する乾式粉砕法とマイカ原石を乾式粉砕機にて粗粉砕した後、水を加えてスラリー状態にて湿式粉砕機で本粉砕し、その後脱水、乾燥を行う湿式粉砕法があり、乾式粉砕法の方が低コストで一般的であるがマイカを薄く細かく粉砕することが困難であるため本発明においては湿式粉砕法により製造されたマイカを使用するのが好ましい。
【００３５】
マイカの平均粒径としては、マイクロトラックレーザー回折法により測定した平均粒径が１０〜１００μｍのものを使用できる。好ましくは平均粒径が２０〜５０μｍのものである。マイカの平均粒径が１０μｍ未満では剛性に対する改良効果が十分ではなく、１００μｍを越えても剛性の向上が十分でなく、ウエルド強度も十分ではない。
【００３６】
マイカの厚みとしては、電子顕微鏡の観察により実測した厚みが０．０１〜１μｍのものを使用できる。好ましくは厚みが０．０３〜０．３μｍである。マイカの厚みが０．０１μｍ未満のものは溶融加工の段階でマイカが割れ易くなるためそれ以上の剛性の向上が認められず、１μｍを越えると剛性に対する改良効果が十分ではない。更にかかるマイカは、シランカップリング剤等で表面処理されていてもよく、更に結合剤で造粒し顆粒状とされていても良い。マイカの具体例としては、株式会社山口雲母工業所 雲母粉（マイカ粉） Ａ−４１、等があり、これらは市場で容易に入手できる。
【００３７】
また、本発明で使用するマイカとして、金属コートマイカを使用することもできる。マイカにコーティングする金属は、マイカにコーティング可能な金属であればよく、例えば金、銀、ニッケル、アルミニウム等があげられる。また、コーティングする方法には特に制限がなく、任意の方法が採用される。例えば無電解メッキによる方法が好ましく、コーティングの膜厚は通常０．００００１〜１０μｍであり、マイカの平滑面、好ましくは更に端面にも均一にコーティングする。かかる金属をコーティングしたマイカは、そのまま使用できるが、更にその表面に、酸化防止剤等のために、処理剤をコーティングしてもよい。
【００３８】
本発明におけるタルクとしては、層状構造を持つ含水ケイ酸マグネシウムであり、化学式４ＳｉＯ₂・３ＭｇＯ・２Ｈ₂Ｏで表され、通常ＳｉＯ₂ 約６３重量％、ＭｇＯ 約３２％、Ｈ₂Ｏ 約５重量％、その他Ｆｅ₂Ｏ₃、Ａｌ₂Ｏ₃などを含有しており、比重は約２．７である。本発明においては、剛性確保の面から、平均粒径が０.０１〜２０μｍの粉末状のものが好ましい。ここでいうタルクの平均粒径とはレーザー回折法により測定された値をいう。タルクの場合には、平均粒径がこの範囲より小さくなると剛性が不十分となり、この範囲を越えると成形品の外観が悪くなり好ましくない。
【００４０】
かかる板状充填材はシランカップリング剤等で表面処理されているものが好ましい。この表面処理により、芳香族ポリカーボネート樹脂の分解が抑制されるとともに、密着性をより向上させることにより、本発明の目的である湿熱疲労性やウエルド強度をより良好なものとすることができる。ここでいうシランカップリング剤とは下記式
【００４１】
【化１】

【００４２】
［ここでＹはアミノ基、エポキシ基、カルボン酸基、ビニル基、メルカプト基、ハロゲン原子等の樹脂マトリックスと反応性または親和性を有する基、Ｒ¹、Ｒ²、Ｒ³はそれぞれ単結合または炭素数１〜７のアルキレン基を表わし、そのアルキレン分子鎖中に、アミド結合、エステル結合、エーテル結合あるいはイミノ結合が介在してもよく、Ｘ¹、Ｘ²、Ｘ³はそれぞれアルコキシ基好ましくは炭素数１〜４のアルコキシ基またはハロゲン原子］で表わされるシラン化合物をいい、具体的には、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシランおよびγ−クロロプロピルトリメトキシシランなどが挙げられる。
【００４３】
本発明における板状充填材の配合割合は、芳香族ポリカーボネート樹脂１００重両部に対して、５〜２００重量部、好ましくは１０〜１００重量部である。５重量部未満だと、組成物の剛性が不十分であり、２００重量部を超えると、得られる組成物の押出が困難であり、実用的でない。
【００４４】
本発明の芳香族ポリカーボネート樹脂組成物には、成形時における分子量の低下や色相の悪化を防止するために熱安定剤を配合することができる。かかる熱安定剤としては、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸およびこれらのエステル等が挙げられ、具体的には、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、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、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、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、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、ジステアリルペンタエリスリトールジホスファイト、トリブチルホスフェート、トリエチルホスフェート、トリメチルホスフェート、トリフェニルホスフェート、ジフェニルモノオルソキセニルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、ジイソプロピルホスフェート、４，４’−ビフェニレンジホスホスフィン酸テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）、ベンゼンホスホン酸ジメチル、ベンゼンホスホン酸ジエチル、ベンゼンホスホン酸ジプロピル等が挙げられる。なかでも、トリスノニルフェニルホスファイト、トリメチルホスフェート、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイトおよびベンゼンホスホン酸ジメチルが好ましく使用される。これらの熱安定剤は、単独でもしくは２種以上混合して用いてもよい。かかる熱安定剤の配合量は、芳香族ポリカーボネート樹脂１００重量部に対して０．０００１〜１重量部が好ましく、０．０００５〜０．５重量部がより好ましく、０．００１〜０．１重量部が更に好ましい。
【００４５】
本発明の芳香族ポリカーボネート樹脂組成物には、酸化防止の目的で通常知られた酸化防止剤を配合することもできる。かかる酸化防止剤としては、例えばペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３−ラウリルチオプロピオネート）、グリセロール−３−ステアリルチオプロピオネート、トリエチレングリコール−ビス［３−（３−ｔｅｒｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、ペンタエリスリトール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、Ｎ，Ｎ−ヘキサメチレンビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ヒドロシンナマイド）、３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ベンジルホスホネート−ジエチルエステル、トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、４，４’−ビフェニレンジホスホスフィン酸テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）、３，９−ビス｛１，１−ジメチル−２−［β−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル｝−２，４，８，１０−テトラオキサスピロ（５，５）ウンデカン等が挙げられる。これら酸化防止剤の配合量は、芳香族ポリカーボネート樹脂１００重量部に対して０．０００１〜０．０５重量部が好ましい。
【００４６】
本発明の芳香族ポリカーボネート樹脂組成物には、溶融成形時の金型からの離型性をより向上させるために、本発明の目的を損なわない範囲で離型剤を配合することも可能である。かかる離型剤としては、オレフィン系ワックス、シリコーンオイル、オルガノポリシロキサン、一価又は多価アルコールの高級脂肪酸エステル、パラフィンワックス、蜜蝋等が挙げられる。かかる離型剤の配合量は、Ａ成分の芳香族ポリカーボネート樹脂１００重量部に対し、０．０１〜２重量部が好ましい。
【００４７】
オレフィン系ワックスとしては、特にポリエチレンワックスおよび／または１−アルケン重合体の使用が好ましくきわめて良好な離型効果が得られる。ポリエチレンワックスとしては現在一般に広く知られているものが使用でき、エチレンを高温高圧下で重合したもの、ポリエチレンを熱分解したもの、ポリエチレン重合物より低分子量成分を分離精製したもの等が挙げられる。また分子量、分岐度等は特に制限されるものではないが、分子量としては数平均分子量で１，０００以上が好ましい。更にポリエチレンワックスをマレイン酸および／または無水マレイン酸で変性したタイプも使用できる。１−アルケン重合体としては炭素数５〜４０の１−アルケンを重合したものが使用でき、更にマレイン酸および／または無水マレイン酸を同時に共重合したタイプも使用できる。マレイン酸および／または無水マレイン酸を同時に共重合したタイプでは摺動性向上効果と共に、衝撃強度が向上する特徴がある。１−アルケン重合体の分子量としては数平均分子量で１，０００以上が好ましい。かかる場合には強度を維持しながら良好な離型性が得られる。
【００４８】
高級脂肪酸エステルとしては、炭素原子数１〜２０の一価又は多価アルコールと炭素原子数１０〜３０の飽和脂肪酸との部分エステル又は全エステルであるのが好ましい。かかる一価又は多価アルコールと飽和脂肪酸との部分エステル又は全エステルとしては、ステアリン酸モノグリセリド、ステアリン酸ジグリセリド、ステアリン酸トリグリセリド、ステアリン酸モノソルビテート、ベヘニン酸モノグリセリド、ペンタエリスリトールモノステアレート、ペンタエリスリトールテトラステアレート、ペンタエリスリトールテトラペラルゴネート、プロピレングリコールモノステアレート、ステアリルステアレート、パルミチルパルミテート、ブチルステアレート、メチルラウレート、イソプロピルパルミテート、ビフェニルビフェネ−ト、ソルビタンモノステアレート、２−エチルヘキシルステアレート等が挙げられ、なかでも、ステアリン酸モノグリセリド、ステアリン酸トリグリセリド、ペンタエリスリトールテトラステアレートが好ましく用いられる。
【００４９】
本発明の芳香族ポリカーボネート樹脂組成物には、本発明の目的を損なわない範囲で、光安定剤を配合することができる。かかる光安定剤としては、例えば２−（２’−ヒドロキシ−５’−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾール、２−（３−ｔｅｒｔ−ブチル−５−メチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール、２−（５−メチル−２−ヒドロキシフェニル）ベンゾトリアゾール、２−［２−ヒドロキシ−３，５−ビス（α，α−ジメチルベンジル）フェニル］−２Ｈ−ベンゾトリアゾール、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）等が挙げられる。かかる光安定剤の配合量は、芳香族ポリカーボネート樹脂１００重量部に対して０．０１〜２重量部が好ましい。
【００５０】
本発明の芳香族ポリカーボネート樹脂組成物には、本発明の目的を損なわない範囲で、帯電防止剤を配合することができる。かかる帯電防止剤としては、例えばポリエーテルエステルアミド、グリセリンモノステアレート、ドデシルベンゼンスルホン酸アンモニウム塩、ドデシルベンゼンスルホン酸ホスホニウム塩、無水マレイン酸モノグリセライド、無水マレイン酸ジグリセライド等が挙げられる。
【００５１】
本発明の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配合することができる。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あげられ、それらを一種以上配合することができる。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、テトラクロロビスフェノールＡのポリカーボネート型難燃剤、テトラクロロビスフェノール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。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。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。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。
【００５２】
これらの難燃剤の中で、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として、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が好ましく、更に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が好ましい。有機塩系難燃剤として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が好ましい。芳香族リン酸エステル系難燃剤としては、トリフェニルホスフェート、トリクレジルフスフェート、クレジルジフェニルホスフェート、レズルシノールビス（ジキシレニルホスフェート）、ビス（２，３ジブロモプロピル）ホスフェート、トリス（２，３ジブロモプロピル）ホスフェートが好ましい。これらの中でも、オゾン層破壊しない芳香族リン酸エステル系難燃剤であるトリフェニルホスフェート、トリクレジルフスフェート、レズルシノールビス（ジキシレニルホスフェート）が最も好ましい。
【００５３】
本発明の芳香族ポリカーボネート樹脂組成物には、他の樹脂やエラストマーを本発明の目的が損なわれない範囲で、すなわち極めて少割合であれば配合することもできる。
【００５４】
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、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。
【００５５】
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、シリコーンゴム、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／スチレン／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。
【００５６】
本発明の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。例えばタンブラー、Ｖ型ブレンダー、スーパーミキサー、ナウターミキサー、バンバリーミキサー、混練ロール、押出機等で混合する方法が適宜用いられる。こうして得られる芳香族ポリカーボネート樹脂組成物は、そのまま又は溶融押出機で一旦ペレット状にしてから、射出成形法、押出成形法、圧縮成形法等の通常知られている方法で成形品にすることができる。なお、芳香族ポリカーボネート樹脂への配合成分の分散を高めて安定した離型性や各物性を得るためには、溶融押出において二軸押出機を使用するのが好ましい。更に本発明の板状充填材は直接押出機ホッパー口あるいは押出機途中から投入する方法、芳香族ポリカーボネート樹脂と予め混合する方法、一部の芳香族ポリカーボネート樹脂と予め混合してマスターを作成し投入する方法、かかるマスターを押出機途中から投入する方法のいずれの方法も取ることができる。
【００５７】
かくして得られた本発明の芳香族ポリカーボネート樹脂組成物は、パソコン、ワープロ、ファクス、コピー機、プリンター等のＯＡ機器のシャーシ、機構部品、ＣＤ−ＲＯＭ用ドライブのトレー、シャーシー、ターンテーブル、ピックアップシャーシ、各種ギア等のＯＡ内部部品、テレビ、ビデオ、電気洗濯機、電気乾燥機、電気掃除機等の家庭電器製品の内部部品、電気鋸、電動ドリル等の電動工具、望遠鏡鏡筒、顕微鏡鏡筒、カメラボディ、カメラハウジング、カメラ鏡筒等の光学機器部品、ドアーハンドル、ピラー、バンパー、計器パネル等の自動車用部品に有用である。
【００５８】
中でも本発明の芳香族ポリカーボネート樹脂とガラスフレークからなる芳香族ポリカーボネート樹脂組成物は、その強度、剛性、寸法精度の良さの点でパソコン、ワープロ、ファクス、コピー機、プリンター等のＯＡ機器のハウジング及びシャーシ、ＣＤ−ＲＯＭ、ＤＶＤ用ドライブのトレー、シャーシー、ターンテーブル、等のＯＡ内部部品、テレビ、ビデオ、電気洗濯機、電気乾燥機、電気掃除機等の家庭電器製品のハウジングや部品、電動ドリル等の電動工具、望遠鏡鏡筒、顕微鏡鏡筒、カメラボディ、カメラハウジング、カメラ鏡筒等の光学機器部品に有用である。
【００５９】
また、本発明の芳香族ポリカーボネート樹脂とマイカからなる芳香族ポリカーボネート樹脂組成物は、ガラスフレークと比べて高剛性、及び高い寸法精度の点からパソコン、ワープロ、ファクス、コピー機、プリンター等のＯＡ機器のシャーシ、ＣＤ−ＲＯＭ、ＤＶＤ用ドライブのトレー、シャーシー、ターンテーブル、等のＯＡ内部部品、レーザービームプリンターの内部部品等の光学機器部品等に有用である。
【００６０】
更に、本発明の芳香族ポリカーボネート樹脂とタルクからなる芳香族ポリカーボネート樹脂組成物は、ガラスフレークと比べて適度な剛性、寸法安定性、表面外観性（平滑性）の点でパソコン、ワープロ、ファクス、コピー機、プリンター等のＯＡ機器のハウジング、ＣＤ−ＲＯＭ、ＤＶＤ用ドライブのトレー、シャーシー、ターンテーブル、等のＯＡ内部部品、テレビ、ビデオ、電気洗濯機、電気乾燥機、電気掃除機等の家庭電器製品のハウジングや部品、望遠鏡鏡筒、顕微鏡鏡筒、カメラボディ、カメラハウジング、カメラ鏡筒等の光学機器部品、ドアーハンドル、ピラー、バンパー、計器パネル等の自動車用部品に有用である。
【００６１】
【実施例】
以下に実施例をあげて更に説明する。実施例中の「部」または「％」は重量部または重量％を示し、また評価項目および組成物中の各成分の記号は下記の内容を意味する。
【００６２】
（Ｉ）評価項目
（１）残存触媒活性指数
残存触媒活性量は以下のように測定した。サンプルは測定前に１２０℃、４時間の減圧乾燥を行い測定に供した。測定機としてレオメトリックス（株）製ＲＤＡ−ＩＩ型粘弾性測定器を使用し、直径２５ｍｍの円錐円板型の治具を装着し、測定中サンプルの本機器の適正条件を満足した窒素気流中、測定温度である２７０℃に設定した。測定温度はオーブン内の温度を測定することにより設定した。その後乾燥した測定用サンプルをセットし、サンプル全体が十分に測定温度となるよう静置の後、その後角速度１ｒａｄ／秒の回転をすることで測定を開始し、これを３０分間続け、その間の溶融粘度の変化を観察した。この測定より回転開始後５分後及び３０分後の溶融粘度を求め、それらの値を下記式（ｉ）より計算することにより、１分間当たりの溶融粘度変化を残存触媒活性指数として表した。
【００６３】
【数２】

【００６４】
（２）末端水酸基濃度
サンプル０．０２ｇを０．４ｍｌのクロロホルムに溶解し、２０℃で１Ｈ−ＮＭＲ（日本電子社製ＥＸ−２７０）を用いて末端水酸基および末端フェニル基を測定し、下記式（ii）により末端水酸基濃度を測定した。
【００６５】
末端水酸基濃度（モル％）＝（末端水酸基数／全末端数）×１００・・・（ii）
（式中、全末端数は、末端水酸基数と末端フェニル基数との合計量である。）
【００６６】
（３）湿熱疲労性
図１に示したいわゆるＣ型の測定用サンプルを用いて、８０℃、９０％ＲＨの雰囲気で、正弦波で振動数１Ｈｚ、最大荷重５ｋｇの条件で、以下の疲労試験機［（株）島津製作所製 島津サーボパルサー ＥＨＦ−ＥＣ５型］を用いて、測定用サンプルが破断するまでの回数を測定した。
【００６７】
（４）ウエルド強度
ＡＳＴＭ Ｄ６３８に従いＴＹＰＥ−１試験片を用いて引張り強度（Ｓ１）を測定した。次にＴＹＰＥ−１試験片と同様の形状であり、試験片中央部にウエルドラインがある試験片（ＴＹＰＥ−１試験片と同一の金型で試験片の両端にゲートを設けたもの）により同様にして引張り強度（Ｓ２）を測定した。Ｓ１、Ｓ２よりウエルド部の保持率（強度保持率（％）＝（Ｓ２／Ｓ１）×１００％）を算出し、ウエルド部の強度を評価した。
【００６８】
（５）剛性
ＡＳＴＭ Ｄ７９０により、曲げ弾性率を測定した。
【００６９】
（６）引張強度
ＡＳＴＭ Ｄ６３８に従い、引張試験を実施し、引張破断強度を測定した。
【００７０】
（７）ノッチ付衝撃値
ＡＳＴＭ Ｄ２５６により厚み３．２ｍｍの試験片を用いノッチ側からおもりを衝撃させ衝撃値を測定した。
【００７１】
（８）比 重
ＪＩＳ Ｋ７１１２に従い、比重を測定した。
【００７２】
（II）組成物中の各成分の記号
（ａ）芳香族ポリカーボネート樹脂
▲１▼ＥＸ−ＰＣ
［参照例１］本発明の芳香族ポリカーボネート樹脂の製造
撹拌機及び蒸留塔を備えた反応器に２,２−ビス（４−ヒドロキシフェニル）プロパン２２８部（約１モル）、ジフェニルカーボネート（バイエル社製）２２０部（約１．０３モル）及び触媒として水酸化ナトリウム０.００００２４部（約６×１０^-7モル／ビスフェノールＡ１モル）とテトラメチルアンモニウムヒドロキシド０.００７３部（約８×１０^-5モル／ビスフェノールＡ１モル）を仕込み、窒素置換した。この混合物を２００℃まで加熱して撹拌しながら溶解させた。次いで、減圧度を３０Ｔｏｒｒとして加熱しながら１時間で大半のフェノールを留去し、更に２７０℃まで温度を上げ、減圧度を１Ｔｏｒｒとして２時間重合反応を行ったところで、末端停止剤として２−メトキシカルボニルフェニルフェニルカーボネート３．１部を添加した。その後２７０℃、１Ｔｏｒｒ以下で５分間末端封鎖反応を行った。次に溶融状態のままで、触媒中和剤としてドデシルベンゼンスルホン酸テトラブチルホスホニウム塩０．００３５部（約６×１０^-6モル／ビスフェノールＡ１モル）添加して２７０℃、１０Ｔｏｒｒ以下で反応を継続し、粘度平均分子量２３３００、末端水酸基濃度５モル％、残存触媒活性指数０．０１％の芳香族ポリカーボネート樹脂を得た。この芳香族ポリカーボネート樹脂をギアポンプでエクストルーダーに送った。エクストルーダー途中でトリスノニルフェニルホスファイトを０.００３重量％、トリメチルホスフェートを０.０５重量％加え、芳香族ポリカーボネート樹脂ペレットを得た。
【００７３】
▲２▼ＣＥＸ−ＰＣ
［参照例２］比較のための芳香族ポリカーボネート樹脂の製造
末端停止剤として２−メトキシカルボニルフェニルフェニルカーボネート及び触媒失活剤としてドデシルベンゼンスルホン酸テトラブチルホスホニウム塩を用いない以外は参照例１と同様な条件で芳香族ポリカーボネート樹脂を製造した。尚、この芳香族ポリカーボネート樹脂の粘度平均分子量２３０００、末端水酸基濃度５２モル％、残存触媒活性指数２．５であった。
【００７４】
（ｂ）充填材
（ｉ）ＧＦＬ：ガラスフレークＲＥＦＧ−１０１；日本板硝子（株）製、平均粒径Ｌ＝４０μｍ、Ｌ／Ｄ＝８
（ ii ）マイカ：Ａ−４１；山口雲母工業所（株）製、平均粒径Ｌ＝４０μｍ、Ｌ／Ｄ＝７０
（ iii ）タルク：Ｐ−３；日本タルク（株）製、平均粒径Ｌ＝０．４μｍ、Ｌ／Ｄ＝８
【００７５】
［実施例１〜３、比較例１及び２］
上記で得られた芳香族ポリカーボネート樹脂及び表１記載の各成分を、タンブラーを使用して均一に混合した後、３０ｍｍφベント付き二軸押出機（神戸製鋼（株）製ＫＴＸ−３０）により、シリンダー温度２７０℃、１０ｍｍＨｇの真空度で脱気しながらペレット化し、得られたペレットを１２０℃で５時間乾燥後、射出成形機（住友重機械工業（株）製ＳＧ１５０Ｕ型）を使用して、シリンダー温度３３０℃、金型温度１００℃の条件で測定用の成形板を作成した。
【００７６】
表１から明らかな如く本発明の実施例である残存触媒活性指数を有する芳香族ポリカーボネート樹脂とガラスフレークからなる芳香族ポリカーボネート樹脂組成物は、比較例の残存触媒活性が残っている芳香族ポリカーボネート樹脂を用いたものに比較して、ガラスフレークを含有した樹脂組成物本来期待される特性が優る上に更に湿熱疲労性、ウエルド強度が特に優れている。
【００７７】
【表１】

【００７８】
［実施例４〜６、比較例３及び４］
上記で得られた芳香族ポリカーボネート樹脂及び表２記載の各成分を、タンブラーを使用して均一に混合した後、以下実施例１と同様な方法で測定用の成形板を作成した。
【００７９】
表２から明らかな如く本発明の実施例である残存触媒活性指数を有する芳香族ポリカーボネート樹脂とマイカからなる芳香族ポリカーボネート樹脂組成物は、比較例の残存触媒活性が残っている芳香族ポリカーボネート樹脂を用いたものに比較して、マイカを含有した樹脂組成物本来期待される特性が優る上に更に湿熱疲労性、ウエルド強度が特に優れている。
【００８０】
【表２】

【００８１】
［実施例７〜９、比較例５及び６］
上記で得られた芳香族ポリカーボネート樹脂及び表３記載の各成分を、タンブラーを使用して均一に混合した後、以下実施例１と同様な方法で測定用の成形板を作成した。
【００８２】
表３から明らかな如く本発明の実施例である残存触媒活性指数を有する芳香族ポリカーボネート樹脂とタルクからなる芳香族ポリカーボネート樹脂組成物は、比較例の残存触媒活性が残っている芳香族ポリカーボネート樹脂を用いたものに比較して、タルクを含有した樹脂組成物本来期待される特性が優る上に更に湿熱疲労性、ウエルド強度が特に優れている。
【００８３】
【表３】

【００８４】
【発明の効果】
本発明の芳香族ポリカーボネート樹脂組成物は、芳香族ポリカーボネート樹脂が本来有する特性を生かし、且つ板状充填材を加えることで剛性等の特性を向上させた上、湿熱疲労性やウエルド強度に優れた板状充填材を含有した芳香族ポリカーボネート樹脂組成物を提供することが可能である。
【図面の簡単な説明】
【図１】湿熱疲労性を評価するために使用した、いわゆるＣ型サンプルの正面図である。なおサンプルの厚みは３ｍｍである。符号６で示される孔の部分に試験機の治具を通し、符号７で示される垂直方向に所定の荷重をかけて試験を行う。
【符号の説明】
１ Ｃ型形状の二重円の中心
２ 二重円の内側円の半径（２０ｍｍ）
３ 二重円の外側円の半径（３０ｍｍ）
４ 治具装着用孔の位置を示す中心角（６０°）
５ サンプル端面の間隙（１３ｍｍ）
６ 治具装着用孔（直径４ｍｍの円であり、サンプル幅の中央に位置する）
７ 疲労試験時におけるサンプルに課される荷重の方向[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aromatic polycarbonate resin composition containing a plate-like filler excellent in wet heat fatigue and weld strength. In more detail, taking advantage of the characteristics inherent in aromatic polycarbonate resin and adding plate fillers, the properties such as rigidity were improved, and plate fillers with excellent wet heat fatigue and weld strength were included. The present invention relates to an aromatic polycarbonate resin composition.
[0002]
[Prior art]
Aromatic polycarbonate resins are widely used because they are excellent in mechanical properties such as impact resistance, heat resistance, and transparency. As a method for producing such an aromatic polycarbonate resin, a method in which phosgene is directly reacted with a dihydric phenol such as bisphenol A (interfacial polymerization method), or a dihydric phenol such as bisphenol and diallyl carbonate such as diphenyl carbonate is melted. A method of polymerizing by transesterification in a state (hereinafter sometimes referred to as a melting method) is known. Among such production methods, the transesterification reaction of dihydric phenol and diallyl carbonate has no problem of using halogen compounds such as phosgene and methylene chloride as compared with the production by interfacial polymerization, and is environmentally friendly. This is a promising technology because it has an advantage that it can be manufactured at low cost with low load.
[0003]
An aromatic polycarbonate resin composition using an aromatic polycarbonate resin and a glass filler is described in Japanese Patent No. 2668362, suggesting application of glass flakes and the like. This aromatic polycarbonate resin is an aromatic polycarbonate resin produced substantially by a melting method. It is disclosed that this composition is superior in Izod impact resistance to the aromatic polycarbonate resin composition of the solution method. However, the melt-process aromatic polycarbonate resin used in such a composition has not been subjected to a catalyst deactivation treatment, and has a drawback of being inferior in wet heat fatigue and weld strength.
[0004]
[Problems to be solved by the invention]
The purpose of the present invention is to make use of the inherent properties of aromatic polycarbonate resin and improve the properties such as rigidity by adding a plate-like filler, and also contains a plate filler excellent in wet heat fatigue and weld strength It is an object of the present invention to provide an aromatic polycarbonate resin composition.
[0005]
As a result of intensive studies on such a resin composition, the polymerization catalyst remaining in the aromatic polycarbonate resin in the melting method is deactivated, and the above object is discovered by using this aromatic polycarbonate resin, thereby completing the present invention. It came to.
[0006]
[Means for Solving the Problems]
In the present invention, (A) the residual catalyst activity index obtained by reacting a dihydric phenol and a carbonate ester by a melting method is 1% or less, and the hydroxyl terminal is 0 to 40 mol% with respect to all terminals. When 100 parts by weight of an aromatic polycarbonate resin and (B) the plate-like filler is glass flake, mica or talc, the average particle size of the plate-like filler is (a) and the thickness is (c) , (A) / (c) The present invention relates to an aromatic polycarbonate resin composition comprising 5 to 200 parts by weight of a plate-like filler having a ratio of 5 to 500 .
[0007]
The aromatic polycarbonate resin used in the present invention is usually obtained by reacting a dihydric phenol and a carbonate ester by a melting method. Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, and bis (4-hydroxyphenyl) methane. 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5 -Dimethyl) phenyl} propane, 2,2-bis {(3,5-dibromo-4-hydroxy) phenyl} propane, 2,2-bis {(3,5-dichloro-4-hydroxy) phenyl} propane, , 2-bis {(3-bromo-4-hydroxy) phenyl} propane, 2,2-bis {(3-chloro-4-hydroxy) phenyl} propane, 4-bromoresorcinol, 2,2-bis {(3 -Isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-phenyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-ethyl-4-hydroxy) Roxy) phenyl} propane, 2,2-bis {(3-n-propyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-sec-butyl-4-hydroxy) phenyl} propane, 2, 2-bis {(3-tert-butyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-cyclohexyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-methoxy-4 -Hydroxy) phenyl} propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-dibromo-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dichloro-2,2 -Bis {(3-phenoxy-4-hydroxy) phenyl} ethylene, ethylene glycol bis (4-hydroxyphenyl) ether, 2,2-bi (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4 -Hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cycl Rhododecane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α'-bis (4-hydroxyphenyl) -o-diisopropyl Benzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl)- 5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, bis {(3,5-dimethyl-4-hydroxy) phenyl} sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ketone And 4,4'-like dihydroxydiphenyl ester and the like, they can be used alone or in combination.
[0008]
Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(3,5-dibromo-4-hydroxy) phenyl} propane, ethylene glycol bis (4 -Hydroxyphenyl) ether, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfone, bis {(3,5-dimethyl-4-hydroxy) phenyl} sulfone, 4,4'-dihydroxy Diphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, and 4,4′-dihy A homopolymer or copolymer obtained from at least one bisphenol selected from the group consisting of droxydiphenyl ketones is preferred, and a bisphenol A homopolymer is particularly preferred.
[0009]
Specific examples of the carbonate ester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. However, it is not limited to these. Preferably, diphenyl carbonate is used. These carbonate esters may also be used alone or in combination of two or more.
[0010]
When the polycarbonate resin is produced by reacting the dihydric phenol and the carbonate ester by a melting method, a catalyst, a terminal terminator, a dihydric phenol antioxidant, or the like may be used as necessary. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.
[0011]
Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2. , 4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1- Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis (4- Hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihi Droxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, 2- (4-hydroxyphenyl) -2- (3′-phenoxycarbonyl-4′-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3′-carboxy-4′-hydroxyphenyl) propane, and the like. 1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferred, especially 1,1,1-tris (4-hydroxyphenyl) Ethane is preferred.
[0012]
The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonate ester. The dihydric phenol and the carbonate ester are mixed with heating in the presence of an inert gas, and the resulting alcohol or phenol is distilled. It is done by the method of making it come out. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is evacuated to about 10 to 0.1 Torr to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.
[0013]
In addition, a polymerization catalyst can be used in order to increase the polymerization rate in the melting method, and as such a polymerization catalyst, for example, condensation is performed using a catalyst comprising (i) an alkali metal compound and / or (ii) a nitrogen-containing basic compound. Is done.
[0014]
Examples of the alkali metal compound used as the catalyst include alkali metal hydroxides, hydrocarbons, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, hydrogens. Examples thereof include boron halide salts, benzoates, hydrogen phosphates, bisphenols, and phenol salts.
[0015]
Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium nitrate, Potassium nitrate, lithium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, sodium sulfite, potassium sulfite, lithium sulfite, sodium cyanate, potassium cyanate, lithium cyanate, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, stearin Sodium phosphate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, potassium borohydride, sodium phenyl borohydride, sodium benzoate, benzoate Examples include potassium acid, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt, dipotassium salt, dilithium salt of bisphenol A, sodium salt of potassium, potassium salt, and lithium salt. .
[0016]
The alkali metal compound as a catalyst can be used in the range of 10 ⁻⁸ to 10 ⁻⁵ mol with ^respect to 1 mol of dihydric phenol. Deviating from the above-mentioned range is not preferred because there are problems such as adversely affecting various physical properties of the obtained polycarbonate, and the transesterification reaction does not proceed sufficiently, resulting in failure to obtain a high molecular weight polycarbonate.
[0017]
Examples of the nitrogen-containing basic compound as a catalyst include tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), and benzyltrimethylammonium hydroxide. (Φ-CH ₂ (Me) ₃ NOH), ammonium hydroxides having alkyl, aryl, alkylaryl groups, such as hexadecyltrimethylammonium hydroxide, triethylamine, tributylamine, dimethylbenzylamine, hexadecyldimethylamine, etc. tertiary amines, or tetramethylammonium borohydride (Me ₄ NBH _4), tetrabutylammonium borohydride (Bu ₄ NBH _4), tetrabutyl Nmo tetraphenylborate (Bu ₄ NBPh _4), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄₎ and the like basic salts such as. Among these, tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), and tetrabutylammonium hydroxide (Bu ₄ NOH) are preferable, and tetramethylammonium hydroxide (Me ₄ NOH) is particularly preferable. Is preferred.
[0018]
The nitrogen-containing basic compound is preferably used in such a ratio that the ammonium nitrogen atom in the nitrogen-containing basic compound is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ equivalent per mole of dihydric phenol. A more desirable ratio is a ratio of 2 × 10 ^{−5 to} 7 × 10 ⁻⁴ equivalents with respect to the same standard. A particularly desirable ratio is a ratio of 5 × 10 ^{−5 to} 5 × 10 ⁻⁴ equivalents with respect to the same standard. In the present invention, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal organic acid salts, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, if desired. Catalysts usually used in esterification reactions and transesterification reactions such as organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like can be used. A catalyst may be used independently and may be used in combination of 2 or more types. These polymerization catalysts are preferably used in an amount of 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, relative to 1 mol of the raw material dihydric phenol. Selected by range.
[0019]
Further, in this polymerization reaction, in order to reduce the phenolic end group, for example, phenol, pt-butylphenol, pt-butylphenylphenyl carbonate, pt-butyl may be used at the later stage or after completion of the polycondensation reaction. Phenyl carbonate, p-cumylphenol, p-cumylphenylphenyl carbonate, p-cumylphenyl carbonate, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis (phenylphenyl) carbonate , Chlorophenyl phenyl carbonate, bromophenyl phenyl carbonate, nitrophenyl phenyl carbonate, diphenyl carbonate, methoxycarbonylphenyl phenyl carbonate, 2,2,4-trimethyl 4- (4-hydroxyphenyl) it is preferable to add a chroman 2,4,4-trimethyl-2- (4-hydroxyphenyl) compounds such as chroman and ethoxycarbonyl phenyl carbonate. Of these, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate are preferable, and 2-methoxycarbonylphenyl phenyl carbonate is particularly preferably used.
[0020]
In this invention, it is preferable to block the terminal of aromatic polycarbonate resin using a terminal blocker. Further, it is preferable to control the hydroxyl terminal of the aromatic polycarbonate resin before adding the end-blocking agent to 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more with respect to all terminals. By doing so, specific end groups can be introduced at a high rate, and the modification effect of the aromatic polycarbonate resin can be enhanced. Usually, it is advantageous to use a terminal blocking agent for an aromatic polycarbonate resin in which the ratio of the hydroxyl terminal of the aromatic polycarbonate resin is in the range of 30 to 95 mol% of the hydroxyl groups among all the terminals. Moreover, the terminal ratio of the aromatic polycarbonate resin hydroxyl group before adding the terminal blocking agent can be controlled by the charging ratio of dihydric phenol and diphenyl carbonate as raw materials. Here, the number of moles of the terminal hydroxyl group in a certain amount of the aromatic polycarbonate resin can be determined by ¹ H-NMR by a conventional method.
[0021]
The hydroxyl terminal of the aromatic polycarbonate resin of the present invention is controlled to 0 to 40 mol%, preferably 0 to 18 mol%, more preferably 0 to 9 mol%, and most preferably 0 to 7 mol% with respect to all terminals. It is preferable to do. Here, 0 mol% represents that detection is impossible when measured by ¹ H-NMR method. When the hydroxyl terminal is in such a range, wet heat fatigue and surface impact properties are further improved.
[0022]
In the present invention, it is preferable to use a deactivator that neutralizes the activity of the catalyst in the aromatic polycarbonate resin. Specific examples of the deactivator include, for example, benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acid, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonate-2-phenyl-2-propyl, dodecylbenzenesulfonate-2-phenyl-2-butyl, octylsulfonate tetrabutylphospho Salts, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetradecylbenzenesulfonate tetra Octyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate Over DOO, decyl trimethyl ammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.
[0023]
Among the deactivators, phosphonium or ammonium salt type deactivators themselves are particularly stable even at 200 ° C. or higher. When the deactivator is added to the aromatic polycarbonate resin, the polycondensation reaction catalyst can be quickly neutralized to obtain the desired aromatic polycarbonate resin. That is, the deactivator is preferably used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm with respect to the polycarbonate produced after the polymerization blocking reaction. .
[0024]
Moreover, it is preferable to use this deactivator in the ratio of 0.5-50 mol with respect to 1 mol of polycondensation reaction catalysts in the ratio with respect to a polycondensation reaction catalyst. There is no particular limitation on the method of adding the quencher to the aromatic polycarbonate resin after end-capping. For example, these may be added while the aromatic polycarbonate resin as a reaction product is in a molten state, or may be added after being once melted and then remelted. In the former, while the aromatic polycarbonate resin, which is a reaction product in the molten reactor or the extruder obtained by the end-capping reaction, is in the molten state, these are added to add the aromatic polycarbonate resin. After forming, a quenching agent may be added while the aromatic polycarbonate resin obtained by the polymerization blocking reaction is pelletized from the reactor through the extruder. An aromatic polycarbonate resin can be obtained by kneading.
[0025]
In the melt-polymerized aromatic polycarbonate resin of the present invention, since a polymerization catalyst is used to accelerate the reaction, the polymerization catalyst often remains after the polymerization reaction. If the remaining catalyst is left as it is after completion of the polymerization reaction, there is a problem that the aromatic polycarbonate resin is decomposed or re-reacted due to the catalytic activity of the polymerization catalyst. Further, in the aromatic polycarbonate resin composition of the aromatic polycarbonate resin having the residual catalytic activity and the plate-like filler, the influence is enlarged, and new problems such as a decrease in weld strength occur.
[0026]
In the present invention, it is necessary to suppress such residual catalyst activity. Using the residual catalyst activity index as an index for suppressing the residual catalyst activity, the measurement is performed as follows. A rotating rheometer capable of measuring the melt viscosity range of the sample to be measured is used as the measuring instrument, and the resin to be measured is melted in a sufficient nitrogen stream so that the sample is not oxidized by external oxygen. Under temperature conditions, the sample is rotated in a constant direction and at a constant angular velocity, and the change in melt viscosity is observed. As the jig of the viscoelasticity measuring instrument when measuring the sample, a conical disk-shaped jig is used so that the strain of the entire sample is constant, that is, the shear rate is constant. That is, the change in melt viscosity per minute calculated by the following formula (i) was used as the residual catalyst activity index.
[0027]
[Expression 1]

[0028]
The residual catalyst activity index is 1% or less, more preferably 0.5% or less, and most preferably 0.2% or less. If the residual catalyst activity index exceeds this range, the aromatic polycarbonate resin changes with time, which is not preferable.
[0029]
The molecular weight of the aromatic polycarbonate resin is preferably 12,000 to 30,000, more preferably 14,000 to 27,000, and particularly preferably 15,000 to 25,000 in terms of viscosity average molecular weight (M). An aromatic polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength as a composition can be obtained, and melt fluidity at the time of molding is good and molding distortion does not occur. The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (ηsp) obtained from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 mL of methylene chloride at 20 ° C. into the following equation.
[0030]
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7
Examples of the plate-like filler used in the aromatic polycarbonate resin composition of the present invention are glass flakes, mica and talc.
[0031]
As glass flakes used in the present invention, those having an average particle diameter of 10 to 1000 μm are preferable, and when the average particle diameter is (a) and the thickness is (c), the ratio (a) / (c) Is preferably 5 to 500, more preferably 6 to 450, and even more preferably 7 to 400. If the average particle size is less than 10 μm or the (a) / (c) ratio is less than 5, the rigidity is insufficient, and if the average particle size exceeds 1000 μm or the (a) / (c) ratio exceeds 500, molding is performed. The appearance of the product and the weld strength deteriorate, which is not preferable. The average particle diameter of the glass flake here is calculated as the median diameter of the weight distribution of the particle size obtained by the standard sieving method.
[0032]
Glass flakes can be focused with various compounds such as epoxy, urethane, and acrylic that are currently known, and those that have been surface-treated with a silane coupling agent or the like described below are preferred.
[0033]
Moreover, a metal coat glass flake can also be used as a glass flake used by this invention. The metal coated on the glass flakes may be any metal that can be coated on glass, and examples thereof include gold, silver, nickel, and aluminum. Moreover, there is no restriction | limiting in particular in the method of coating, Arbitrary methods are employ | adopted. For example, a method by electroless plating is preferable, and the film thickness of the coating is usually 0.00001 to 10 μm, and the glass flakes are evenly coated on the smooth surface, preferably the end surface. Such metal-coated glass flakes can be used as they are, but the surface thereof may be further coated with a treatment agent for an antioxidant or the like.
[0034]
The mica in the present invention is preferably a powder having an average particle diameter of 1 to 80 μm from the viewpoint of securing rigidity. Mica is a pulverized product of silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite, phlogopite, biotite, artificial mica, etc., and any mica can be used as the mica of the present invention, but phlogopite and biotite are themselves more flexible than muscovite, In addition, since phlogopite and biotite contain more Fe in the main component than muscovite, the hue of the phlogopite itself becomes darker. Although it is expensive, it itself is expensive and impractical. Preference is given to muscovite. In addition, as a pulverization method in the production of mica, a dry pulverization method in which mica rough is pulverized with a dry pulverizer, and mica rough is roughly pulverized in a dry pulverizer, then water is added and a wet pulverizer in a slurry state. There is a wet pulverization method in which the pulverization is followed by dehydration and drying, and the dry pulverization method is generally lower in cost, but it is difficult to pulverize mica thinly and finely in the present invention. It is preferable to use mica produced by
[0035]
As the average particle diameter of mica, those having an average particle diameter of 10 to 100 μm measured by a microtrack laser diffraction method can be used. The average particle size is preferably 20 to 50 μm. If the average particle diameter of mica is less than 10 μm, the effect of improving the rigidity is not sufficient, and if it exceeds 100 μm, the rigidity is not sufficiently improved and the weld strength is not sufficient.
[0036]
As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 0.3 μm. When the thickness of mica is less than 0.01 μm, the mica is easily cracked at the melt processing stage, so that no further improvement in rigidity is observed. If it exceeds 1 μm, the effect of improving the rigidity is not sufficient. Further, such mica may be surface-treated with a silane coupling agent or the like, and further granulated with a binder to be granulated. Specific examples of mica include Yamaguchi Mica Industry Co., Ltd. Mica powder (mica powder) A-41, etc., which are readily available on the market.
[0037]
Moreover, a metal coat mica can also be used as a mica used by this invention. The metal to be coated on mica may be any metal that can be coated on mica, and examples thereof include gold, silver, nickel, and aluminum. Moreover, there is no restriction | limiting in particular in the method of coating, Arbitrary methods are employ | adopted. For example, a method by electroless plating is preferable, and the film thickness of the coating is usually 0.00001 to 10 μm, and the smooth surface of mica is coated evenly on the end surface. The mica coated with such a metal can be used as it is, but the surface thereof may be further coated with a treatment agent for an antioxidant or the like.
[0038]
The talc in the present invention is a hydrous magnesium silicate having a layered structure, represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O, and usually SiO ₂ about 63 wt%, MgO about 32%, H ₂ O about 5 wt. %, Fe ₂ O ₃ , Al ₂ O _{3 and the} like, and the specific gravity is about 2.7. In the present invention, a powdery one having an average particle diameter of 0.01 to 20 μm is preferable from the viewpoint of securing rigidity. The average particle diameter of talc here is a value measured by a laser diffraction method. In the case of talc, if the average particle size is smaller than this range, the rigidity becomes insufficient, and if it exceeds this range, the appearance of the molded product is deteriorated, which is not preferable.
[0040]
Such a plate-like filler is preferably subjected to a surface treatment with a silane coupling agent or the like. By this surface treatment, the decomposition of the aromatic polycarbonate resin is suppressed and the adhesiveness is further improved, whereby the wet heat fatigue and the weld strength, which are the objects of the present invention, can be improved. The silane coupling agent here is represented by the following formula:
[Chemical 1]

[0042]
[Where Y is an amino group, epoxy group, carboxylic acid group, vinyl group, mercapto group, a group having reactivity or affinity with a resin matrix such as a halogen atom, R ¹ , R ² , R ³ are each a single bond or Represents an alkylene group having 1 to 7 carbon atoms, and an amide bond, an ester bond, an ether bond or an imino bond may be interposed in the alkylene molecular chain, and X ¹ , X ² and X ³ are preferably alkoxy groups, C1-C4 alkoxy group or halogen atom], specifically, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and γ-chloropropyltri And methoxysilane.
[0043]
The mixing ratio of the plate-like filler in the present invention is 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin. If the amount is less than 5 parts by weight, the composition has insufficient rigidity. If the amount exceeds 200 parts by weight, it is difficult to extrude the resulting composition, which is not practical.
[0044]
A heat stabilizer can be blended with the aromatic polycarbonate resin composition of the present invention in order to prevent a decrease in molecular weight and a deterioration in hue during molding. Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate , Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphosphinic acid tetrakis (2,4-di-tert-butylphenyl), benzenephosphone Examples thereof include dimethyl acid, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Of these, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in admixture of two or more. The amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0.1 part by weight based on 100 parts by weight of the aromatic polycarbonate resin. Part is more preferred.
[0045]
The aromatic polycarbonate resin composition of the present invention can be blended with an antioxidant generally known for the purpose of antioxidant. Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphosphinic acid tetrakis (2 , 4-Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl}- 2,4,8,10-tetraoxaspiro (5,5) undecane and the like. The blending amount of these antioxidants is preferably 0.0001 to 0.05 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin.
[0046]
In the aromatic polycarbonate resin composition of the present invention, in order to further improve the releasability from the mold at the time of melt molding, a mold release agent can be blended within a range that does not impair the object of the present invention. . Examples of the release agent include olefin wax, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax and the like. The compounding amount of the release agent is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the A component aromatic polycarbonate resin.
[0047]
As the olefin wax, polyethylene wax and / or 1-alkene polymer is particularly preferable, and a very good release effect can be obtained. As the polyethylene wax, those generally known at present can be used, and those obtained by polymerizing ethylene under high temperature and high pressure, those obtained by thermally decomposing polyethylene, those obtained by separating and purifying low molecular weight components from polyethylene polymer, and the like can be mentioned. The molecular weight, the degree of branching, etc. are not particularly limited, but the molecular weight is preferably 1,000 or more in terms of number average molecular weight. Further, a polyethylene wax modified with maleic acid and / or maleic anhydride can also be used. As the 1-alkene polymer, a polymer obtained by polymerizing 1-alkene having 5 to 40 carbon atoms can be used, and a type obtained by copolymerizing maleic acid and / or maleic anhydride simultaneously can also be used. The type in which maleic acid and / or maleic anhydride are simultaneously copolymerized is characterized by an improvement in impact strength as well as a sliding effect. The molecular weight of the 1-alkene polymer is preferably 1,000 or more in terms of number average molecular weight. In such a case, good releasability can be obtained while maintaining the strength.
[0048]
The higher fatty acid ester is preferably a partial ester or a total ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol. Tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2- And ethyl hexyl stearate, among others, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol Le tetrastearate are preferably used.
[0049]
A light stabilizer can be blended with the aromatic polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. Examples of such a light stabilizer include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo. Triazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′- Examples include methylene bis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one) and the like. The blending amount of the light stabilizer is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin.
[0050]
The aromatic polycarbonate resin composition of the present invention can be blended with an antistatic agent as long as the object of the present invention is not impaired. Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride and the like.
[0051]
The aromatic polycarbonate resin composition of the present invention can contain a flame retardant in an amount that does not impair the object of the present invention. Examples of flame retardants include halogenated bisphenol A polycarbonate flame retardants, organic salt flame retardants, aromatic phosphate ester flame retardants, and halogenated aromatic phosphate ester flame retardants. It can mix | blend above. Specifically, the polycarbonate type flame retardant of halogenated bisphenol A includes a polycarbonate type flame retardant of tetrachlorobisphenol A, a polycarbonate type flame retardant of tetrachlorobisphenol A and bisphenol A, a polycarbonate type flame retardant of tetrabromobisphenol A, tetra A copolymer polycarbonate type flame retardant of bromobisphenol A and bisphenol A; Specifically, organic salt flame retardants include dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfonate. Potassium chlorobenzenesulfonate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, Potassium bis (2,4,6-tribromophenyl) phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, Potassium perfluorobutanesulfonate, sodium lauryl sulfate Or potassium, sodium hexadecyl sulfate or potassium. Specifically, the halogenated aromatic phosphate ester type flame retardant is tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, etc. is there. Specifically, aromatic phosphate ester flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate. Tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4′-biphenol diphosphate, aromatic ring source is resorcin and phenol Aromatic polyphosphates that do not contain phenolic OH groups, aromatic ring sources are resorcin and phenol, aromatic polyphosphates that contain phenolic OH groups, aromatic ring sources are hydroquinone and phenol, and phenolic O Aromatic polyphosphates that do not contain groups, aromatic polyphosphates that contain similar phenolic OH groups, (the "aromatic polyphosphates" shown below are aromatic polyphosphates that contain phenolic OH groups and aromatic polyphosphates that do not contain Aromatic polyphosphates whose aromatic ring source is bisphenol A and phenol, aromatic polyphosphates whose aromatic ring source is tetrabromobisphenol A and phenol, aromatic ring source is resorcin and 2, Aromatic polyphosphate that is 6-xylenol, 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 source Is tetrabromobispheno A and the aromatic polyphosphates such as 2,6-xylenol.
[0052]
Among these flame retardants, the polycarbonate-type flame retardant of halogenated bisphenol A is preferably a polycarbonate-type flame retardant of tetrabromobisphenol A, a copolymer polycarbonate of tetrabromobisphenol A and bisphenol A, and more preferably tetrabromobisphenol A. Polycarbonate flame retardants are preferred. As the organic salt flame retardant, diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium and sodium 2,4,5-trichlorobenzenesulfonate are preferable. Aromatic phosphate ester flame retardants include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resulcinol bis (dixylenyl phosphate), bis (2,3 dibromopropyl) phosphate, tris (2,3 Dibromopropyl) phosphate is preferred. Of these, triphenyl phosphate, tricresyl phosphate, and resulcinol bis (dixylenyl phosphate) which are aromatic phosphate ester flame retardants that do not destroy the ozone layer are most preferable.
[0053]
In the aromatic polycarbonate resin composition of the present invention, other resins and elastomers can be blended within a range that does not impair the object of the present invention, that is, in an extremely small proportion.
[0054]
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, polypropylene and other polyolefins. Examples thereof include resins such as resins, polystyrene resins, acrylonitrile / styrene copolymers (AS resins), acrylonitrile / butadiene / styrene copolymers (ABS resins), polymethacrylate resins, phenol resins, and epoxy resins.
[0055]
Examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, silicone rubber, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate / styrene) that is a core-shell type elastomer. / Butadiene) rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber and the like.
[0056]
Arbitrary methods are employ | adopted in order to manufacture the aromatic polycarbonate resin composition of this invention. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like is appropriately used. The aromatic polycarbonate resin composition thus obtained can be made into a molded product by a generally known method such as an injection molding method, an extrusion molding method, a compression molding method, etc., as it is or after being once pelletized with a melt extruder. it can. In order to obtain a stable release property and various physical properties by increasing the dispersion of the compounding components in the aromatic polycarbonate resin, it is preferable to use a twin screw extruder in the melt extrusion. Furthermore, the plate-like filler of the present invention is directly injected from the extruder hopper port or in the middle of the extruder, a method of pre-mixing with an aromatic polycarbonate resin, a pre-mixing with a part of the aromatic polycarbonate resin and making a master Any of the method of carrying out and the method of throwing in such a master from the middle of an extruder can be taken.
[0057]
The aromatic polycarbonate resin composition of the present invention thus obtained includes chassis, mechanism parts, CD-ROM drive trays, chassis, turntable, and pickup chassis for OA equipment such as personal computers, word processors, fax machines, copiers, and printers. OA internal parts such as various gears, internal parts of household electric appliances such as TVs, videos, electric washing machines, electric dryers, and vacuum cleaners, electric tools such as electric saws and electric drills, telescope barrels, microscope barrels It is useful for optical parts such as camera bodies, camera housings, and camera barrels, and automotive parts such as door handles, pillars, bumpers, and instrument panels.
[0058]
Among them, the aromatic polycarbonate resin composition composed of the aromatic polycarbonate resin and glass flakes of the present invention is a housing for office equipment such as personal computers, word processors, fax machines, copiers, and printers in terms of strength, rigidity, and dimensional accuracy. OA internal parts such as chassis, CD-ROM, DVD drive tray, chassis, turntable, etc., housings and parts for home appliances such as TV, video, electric washing machine, electric dryer, electric vacuum cleaner, electric drill, etc. It is useful for optical equipment parts such as electric tools such as telescopes, telescope barrels, microscope barrels, camera bodies, camera housings, and camera barrels.
[0059]
In addition, the aromatic polycarbonate resin composition comprising the aromatic polycarbonate resin and mica of the present invention is OA equipment such as personal computers, word processors, fax machines, copiers, printers, etc. in terms of higher rigidity and higher dimensional accuracy than glass flakes. It is useful for OA internal parts such as chassis, CD-ROM, DVD drive tray, chassis, turntable, etc., and optical equipment parts such as laser beam printer internal parts.
[0060]
Furthermore, the aromatic polycarbonate resin composition comprising the aromatic polycarbonate resin and talc of the present invention is suitable for personal computers, word processors, faxes, and the like in terms of moderate rigidity, dimensional stability, and surface appearance (smoothness) compared to glass flakes. OA equipment parts such as copiers, printers and other OA equipment housings, CD-ROMs, DVD drive trays, chassis, turntables, etc. Homes such as TVs, videos, electric washing machines, electric dryers, vacuum cleaners, etc. It is useful for electrical equipment housings and parts, telescope barrels, microscope barrels, camera bodies, camera housings, camera barrels and other optical equipment parts, and automotive parts such as door handles, pillars, bumpers and instrument panels.
[0061]
【Example】
Examples will be described further below. In the examples, “parts” or “%” represents parts by weight or% by weight, and the evaluation items and symbols of each component in the composition mean the following contents.
[0062]
(I) Evaluation item (1) Residual catalyst activity index The amount of residual catalyst activity was measured as follows. Before the measurement, the sample was dried under reduced pressure at 120 ° C. for 4 hours and subjected to measurement. Using a RDA-II viscoelasticity measuring instrument manufactured by Rheometrics Co., Ltd. as a measuring instrument, wearing a conical disk-shaped jig with a diameter of 25 mm, and in a nitrogen stream satisfying the appropriate conditions of the instrument being measured The measurement temperature was set to 270 ° C. The measurement temperature was set by measuring the temperature in the oven. After that, set the dried sample for measurement, and let it stand so that the entire sample is at the measurement temperature. Then, start the measurement by rotating it at an angular velocity of 1 rad / sec, and continue this for 30 minutes. The change in viscosity was observed. From this measurement, the melt viscosities after 5 minutes and 30 minutes after the start of rotation were obtained, and those values were calculated from the following formula (i) to express the change in melt viscosity per minute as the residual catalyst activity index.
[0063]
[Expression 2]

[0064]
(2) Dissolve 0.02 g of terminal hydroxyl group sample in 0.4 ml of chloroform, and measure the terminal hydroxyl group and terminal phenyl group using 1H-NMR (EX-270 manufactured by JEOL Ltd.) at 20 ° C. The terminal hydroxyl group concentration was measured by (ii).
[0065]
Terminal hydroxyl group concentration (mol%) = (number of terminal hydroxyl groups / total number of terminals) × 100 (ii)
(In the formula, the total number of terminals is the total amount of the number of terminal hydroxyl groups and the number of terminal phenyl groups.)
[0066]
(3) Wet heat fatigue The following fatigue test using the so-called C-type measurement sample shown in FIG. 1 under the conditions of a sine wave, a frequency of 1 Hz, and a maximum load of 5 kg in an atmosphere of 80 ° C. and 90% RH. The number of times until the measurement sample broke was measured using a machine [Shimadzu Servo Pulser EHF-EC5 type, manufactured by Shimadzu Corporation].
[0067]
(4) Weld strength Tensile strength (S1) was measured using a TYPE-1 test piece in accordance with ASTM D638. Next, it is the same shape as the TYPE-1 test piece, and the same with a test piece having a weld line at the center of the test piece (the same mold as the TYPE-1 test piece and having gates at both ends of the test piece). Then, the tensile strength (S2) was measured. The retention ratio of the weld part (strength retention ratio (%) = (S2 / S1) × 100%) was calculated from S1 and S2, and the strength of the weld part was evaluated.
[0068]
(5) Flexural modulus was measured by rigidity ASTM D790.
[0069]
(6) Tensile strength In accordance with ASTM D638, a tensile test was performed to measure the tensile strength at break.
[0070]
(7) Impact value with notch Using ASTM D256, a test piece having a thickness of 3.2 mm was used to impact the weight from the notch side, and the impact value was measured.
[0071]
(8) Specific gravity Specific gravity was measured according to JIS K7112.
[0072]
(II) Symbol of each component in the composition (a) Aromatic polycarbonate resin (1) EX-PC
[Reference Example 1] Production of aromatic polycarbonate resin of the present invention In a reactor equipped with a stirrer and a distillation column, 228 parts (approximately 1 mol) of 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate (Bayer) Ltd.) 220 parts (about 1.03 moles) and 0.000024 part of sodium hydroxide as a catalyst (approximately 6 × 10 ^-7 mol / bisphenol A1 mole) and 0.0073 parts of tetramethylammonium hydroxide (about 8 × 10 ^{- 5} mol / bisphenol A 1 mol) was charged, and the atmosphere was replaced with nitrogen. The mixture was heated to 200 ° C. and dissolved with stirring. Next, most of the phenol was distilled off in 1 hour while heating at a reduced pressure of 30 Torr, the temperature was further raised to 270 ° C., and the polymerization reaction was carried out for 2 hours at a reduced pressure of 1 Torr. 3.1 parts of carbonylphenyl phenyl carbonate was added. Thereafter, end-capping reaction was carried out at 270 ° C. and 1 Torr or less for 5 minutes. Next, 0.0035 parts (about 6 × 10 ⁻⁶ mol / bisphenol A 1 mol) of dodecylbenzenesulfonic acid tetrabutylphosphonium salt was added as a catalyst neutralizing agent in the molten state, and the reaction was continued at 270 ° C. and 10 Torr or less. An aromatic polycarbonate resin having a viscosity average molecular weight of 23,300, a terminal hydroxyl group concentration of 5 mol% and a residual catalyst activity index of 0.01% was obtained. This aromatic polycarbonate resin was sent to the extruder with a gear pump. In the middle of the extruder, 0.003% by weight of trisnonylphenyl phosphite and 0.05% by weight of trimethyl phosphate were added to obtain aromatic polycarbonate resin pellets.
[0073]
(2) CEX-PC
[Reference Example 2] Production of aromatic polycarbonate resin for comparison Same as Reference Example 1 except that 2-methoxycarbonylphenylphenyl carbonate is not used as a terminal stopper and tetrabutylphosphonium dodecylbenzenesulfonate is used as a catalyst deactivator. An aromatic polycarbonate resin was produced under various conditions. The aromatic polycarbonate resin had a viscosity average molecular weight of 23,000, a terminal hydroxyl group concentration of 52 mol%, and a residual catalyst activity index of 2.5.
[0074]
(B) Filler
(I) GFL: Glass flake REFG-101; manufactured by Nippon Sheet Glass Co., Ltd., average particle diameter L = 40 μm , L / D = 8
( Ii ) Mica: A-41; manufactured by Yamaguchi Mica Industrial Co., Ltd., average particle size L = 40 μm , L / D = 70
( Iii ) Talc: P-3; manufactured by Nippon Talc Co., Ltd., average particle diameter L = 0.4 μm, L / D = 8
[0075]
[Examples 1 to 3, Comparative Examples 1 and 2]
After the aromatic polycarbonate resin obtained above and each component shown in Table 1 were uniformly mixed using a tumbler, the cylinder was moved by a twin screw extruder with a 30 mmφ vent (KTX-30 manufactured by Kobe Steel). Pelletize while degassing at a temperature of 270 ° C. and a vacuum of 10 mmHg. After drying the obtained pellets at 120 ° C. for 5 hours, use an injection molding machine (SG150U model manufactured by Sumitomo Heavy Industries, Ltd.) A molding plate for measurement was prepared under conditions of a temperature of 330 ° C. and a mold temperature of 100 ° C.
[0076]
As is apparent from Table 1, the aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin having a residual catalytic activity index and glass flakes, which is an example of the present invention, is an aromatic polycarbonate resin in which the residual catalytic activity of the comparative example remains. Compared to the resin composition using glass flakes, the resin composition containing glass flakes is superior in properties expected originally, and is further excellent in wet heat fatigue and weld strength.
[0077]
[Table 1]

[0078]
[Examples 4 to 6, Comparative Examples 3 and 4]
After the aromatic polycarbonate resin obtained above and each component shown in Table 2 were uniformly mixed using a tumbler, a measurement molding plate was prepared in the same manner as in Example 1 below.
[0079]
As is apparent from Table 2, the aromatic polycarbonate resin composition comprising the aromatic polycarbonate resin having a residual catalyst activity index and mica as an example of the present invention is the aromatic polycarbonate resin having the residual catalyst activity of the comparative example. Compared to the one used, the resin composition containing mica has excellent properties originally expected, and further has excellent wet heat fatigue and weld strength.
[0080]
[Table 2]

[0081]
[Examples 7 to 9, Comparative Examples 5 and 6]
After the aromatic polycarbonate resin obtained above and each component shown in Table 3 were uniformly mixed using a tumbler, a measurement molding plate was prepared in the same manner as in Example 1 below.
[0082]
As is apparent from Table 3, the aromatic polycarbonate resin composition comprising the aromatic polycarbonate resin having a residual catalyst activity index and talc as an example of the present invention and the aromatic polycarbonate resin having the residual catalyst activity of the comparative example remain. Compared to the one used, the resin composition containing talc is superior in properties originally expected, and is further excellent in wet heat fatigue and weld strength.
[0083]
[Table 3]

[0084]
【The invention's effect】
The aromatic polycarbonate resin composition of the present invention takes advantage of the inherent properties of the aromatic polycarbonate resin and improves properties such as rigidity by adding a plate-like filler, and is excellent in wet heat fatigue and weld strength. It is possible to provide an aromatic polycarbonate resin composition containing a plate-like filler.
[Brief description of the drawings]
FIG. 1 is a front view of a so-called C-type sample used for evaluating wet heat fatigue. The thickness of the sample is 3 mm. A jig of a testing machine is passed through the hole portion indicated by reference numeral 6 and a test is performed by applying a predetermined load in the vertical direction indicated by reference numeral 7.
[Explanation of symbols]
1 Center of C-shaped double circle 2 Radius of inner circle of double circle (20mm)
3 Radius of outer circle of double circle (30mm)
4 Center angle (60 °) indicating the position of the jig mounting hole
5 Sample end face gap (13mm)
6 Jig mounting hole (circle with a diameter of 4 mm, located at the center of the sample width)
7 Direction of load imposed on sample during fatigue test

Claims (8)

(A) An aromatic polycarbonate obtained by reacting a dihydric phenol and a carbonate ester by a melting method and having a residual catalyst activity index of 1% or less and a hydroxyl group terminal of 0 to 40 mol% with respect to all terminals. 100 parts by weight of resin and (B) the plate-like filler is glass flake, mica or talc, and when the average particle size of the plate-like filler is (a) and the thickness is (c), (a) / (C) An aromatic polycarbonate resin composition comprising 5 to 200 parts by weight of a plate-like filler having a ratio of 5 to 500 .   The aromatic polycarbonate resin composition according to claim 1, wherein the carbonate ester is diphenyl carbonate. The aromatic polycarbonate resin composition according to claim 1 , wherein the glass flake has an average particle size of 10 to 1000 μm . The aromatic polycarbonate resin composition according to claim 1, wherein the mica has an average particle diameter of 10 to 100 µm and a thickness of 0.01 to 1 µm . Talc, aromatic polycarbonate resin composition according to claim 1, wherein the average particle diameter is 0. 01~20μm.   The aromatic polycarbonate resin composition according to claim 1, wherein the dihydric phenol is bisphenol A.   The aromatic polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin has a viscosity average molecular weight of 12,000 to 30,000. A residual catalytic activity index of 1 is obtained by a method in which a dihydric phenol and a carbonate ester are melt-reacted using a polymerization catalyst comprising an alkali metal compound and / or a nitrogen-containing basic compound, and a deactivator is added after the completion of the polymerization reaction. %, And an aromatic polycarbonate resin having a hydroxyl group terminal of 0 to 40 mol% with respect to all terminals is obtained, and 100 parts by weight of the aromatic polycarbonate resin and the plate-like filler are glass flakes, mica or talc. When the average particle diameter of the plate-like filler is (a) and the thickness is (c), the ratio of (a) / (c) is 5-500 parts by weight of the plate-like filler. Is mixed in the molten state of the aromatic polycarbonate resin.

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