JP4506922B2 - Polycarbonate oligomer and resin composition thereof - Google Patents

Description

（式中、Ｒ₁ 〜Ｒ₄ は、各々独立して水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基を表す。）
【０００９】
【化６】

（式中、Ｒ₅ 及びＲ₆ は、炭素数１〜６の脂肪族基を表し、Ｘはジメチルシロキサン、メチルフェニルシロキサン及びジフェニルシロキサンの中から選ばれた少なくとも２種類のランダム共重合体であり、重合度は２〜２００を表す。）
【００１０】
【化７】

（式中Ｒ₇ 〜Ｒ₁₀は、各々独立して、水素、炭素数１〜１０のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、又は炭素数１〜５のアルコキシ基を有することもできる。Ｙは、
【化８】

であり、ここにＲ₁₁及びＲ₁₂はそれぞれ、水素、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数１〜１０のアルコキシ基又は炭素数６〜１２のアリール基を表すか、Ｒ₁₁及びＲ₁₂が一緒に結合して、脂肪族環または複素環を形成する基を表す。これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、又は炭素数１〜５のアルコキシ基を有することもできる。ａは０〜２０の整数を表す。）
【００１１】
本発明の共重合オリゴマーは、前記一般式（Ａ）及び（Ｂ）及び（Ｃ）と炭酸エステル形成化合物を反応させることによって、製造することができる。即ち、ビスフェノールＡから誘導されるポリカーボネートを製造する際に用いられている公知の方法、例えば二価フェノールとホスゲンとの直接反応（ホスゲン法）、あるいは二価フェノールとビスアリールカーボネートとのエステル交換反応（エステル交換法）などの方法を採用することができる。
【００１２】
炭酸エステル形成性化合物としては、例えばホスゲンや、ジフェニルカーボネート、ジ−ｐ−トリルカーボネート、フェニル−ｐ−トリルカーボネート、ジ−ｐ−クロロフェニルカーボネート、ジナフチルカーボネートなどのビスアリルカーボネートが挙げられる。
【００１３】
前記一般式（Ａ）で表される化合物としては、具体的には９，９−ビス（４−ヒドロキシ−２−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシフェニル）フルオレン、３，６−ジメチル−９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−メトキシ−４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−エトキシ−４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−エチル−４−ヒドロキシフェニル）フルオレン、４，５−ジメチル−９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−フェニル−４−ヒドロキシフェニル）フルオレン、３，６−ジメチル−９，９−ビス（３−メチル−４−ヒドロキシフェニル）フルオレン及び３，６−ジフェニル−９，９−ビス（４−ヒドロキシフェニル）フルオレン等を挙げることができる。特に、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−２−メチルフェニル）フルオレンが好ましい。
【００１４】
前記一般式（Ｂ）で表される化合物としては、具体的には式中のＲ₅ 及びＲ₆ がジメチレン、トリメチレン、テトラメチレン、ペンタメチレン及びヘキサメチレンであり、Ｘがジメチルシロキサン、メチルフェニルシロキサン及びジフェニルシロキサンの中から選ばれた少なくとも２種類からなるランダム共重合体であり、重合度は２〜２００である。好ましくは、該ランダム共重合体中にジフェニルシロキサンが２個以上で、重合度が３〜１００のものである。
【００１５】
前記一般式（Ｃ）で表される化合物としては、具体的には４，４’−ビフェニルジオール、ビス（４−ヒドロキシフェニル）メタン、ビス（４−ヒドロキシフェニル）エーテル、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシ−３−メチルフェニル）スルホン、ビス（４−ヒドロキシフェニル）スルホキシド、ビス（４−ヒドロキシフェニル）スルファイド、ビス（４−ヒドロキシフェニル）ケトン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ；ＢＰＡ）、２，２−ビス（４−ヒドロキシフェニル）ブタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（ビスフェノールＺ；ＢＰＺ）、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン（ジメチルビスフェノールＡ）、２，２−ビス（４−ヒドロキシ−３、５−ジメチルフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン（ビスフェノールＡＰ；ＢＰＡＰ）、ビス（４−ヒドロキシフェニル）ジフェニルメタン、２，２−ビス（４−ヒドロキシ−３−アリルフェニル）プロパン、３，３，５−トリメチル−１，１−ビス（４−ヒドロキシフェニル）シクロヘキサンなどが例示される。これらは、２種類以上併用することも可能である。また、これらの中でも特に２，２−ビス（４−ヒドロキシフェニル）プロパンが好ましい。
【００１６】
ホスゲン法とエステル交換法では、一般式（Ａ）、（Ｂ）及び（Ｃ）で表される化合物の反応性を考慮した場合、ホスゲン法の方が好ましい。
【００１７】
前者のホスゲン法においては、通常酸結合剤および溶媒の存在下において、本発明における上記一般式（Ａ）、（Ｂ）及び（Ｃ）とホスゲンを反応させる。酸結合剤としては、例えば、ピリジンや、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物などが用いられ、また溶媒としては、例えば、塩化メチレン、クロロホルム、クロロベンゼン、キシレンなどが用いられる。さらに、縮重合反応を促進するために、トリエチルアミンのような第三級アミン触媒などが使用される。また重合度調節には、フェノール、ｐ−ｔ−ブチルフェノール、ｐ−クミルフェノールなどのフェノール類等一官能基化合物を分子量調節剤として加える。さらに、所望に応じ亜硫酸ナトリウム、ハイドロサルファイトなどの酸化防止剤や、フロログルシン、イサチンビスフェノール、１，１，１−トリス（４−ヒドロキシフェニル）エタン、α，α’，α”−トリス（４−ヒドロキシフェニル）−１，３，５−トリイソプロピルベンゼンなど分岐化剤を小量添加してもよい。反応は通常０〜１５０℃、好ましくは５〜４０℃の範囲とするのが適当である。反応時間は反応温度によって左右されるが、通常０．５分〜１０時間、好ましくは１分〜２時間である。また、反応中は、反応系のｐＨを１０以上に保持することが望ましい。
【００１８】
一方、後者のエステル交換法においては、前記一般式（Ａ）、（Ｂ）及び（Ｃ）のビスフェノール類とビスアリールカーボネートとを混合し、減圧下で高温において反応させる。この時、フェノール、ｐ−ｔ−ブチルフェノール、ｐ−クミルフェノールなどのフェノール類等一官能基化合物を分子量調節剤として加えてもよい。反応は通常１５０〜３５０℃、好ましくは２００〜３００℃の範囲の温度において行われ、また減圧度は最終で好ましくは１ｍｍＨｇ以下にして、エステル交換反応により生成した該ビスアリールカーボネートから由来するフェノール類を系外へ留去させる。反応時間は反応温度や減圧度などによって左右されるが、通常１〜６時間程度である。反応は窒素やアルゴンなどの不活性ガス雰囲気下で行うことが好ましく。また、所望に応じ、酸化防止剤や分岐化剤を添加して反応を行ってもよい。
【００１９】
本発明においてホスゲン法を採用する場合は、ビスフェノール類とホスゲンの反応を効率よく行うため、ホスゲン吹き込み終了後に、トリエチルアミンのような三級アミンが使用される。また、所望によりトリエチルベンジルアンモニウムクロライドのような第四級アンモニウム塩も使用されることがある。これらアミン類の添加量は、全ビスフェノールに対して、０．０１〜１．０ｍｏｌ％である。
【００２０】
更に、本発明の分子量調節剤としては、特に一価フェノールが好ましく、具体的には、ブチルフェノール、オクチルフェノール、ノニルフェノール、デカニルフェノール、テトラデカニルフェノール、ヘプタデカニルフェノール、オクタデカニルフェノール等の長鎖アルキル置換フェノール；ヒドロキシ安息香酸ブチル、ヒドロキシ安息香酸オクチル、ヒドロキシ安息香酸ノニル、ヒドロキシ安息香酸デカニル、ヒドロキシ安息香酸ヘプタデカニル等のヒドロキシ安息香酸長鎖アルキルエステル；ブトキシフェノール、オクチルオキシフェノール、ノニルオキシフェノール、デカニルオキシフェノール、テトラデカニルオキシフェノール、ヘプタデカニルオキシフェノール、オクタデカニルオキシフェノール等の長鎖アルキルオキシフェノール類が例示される。この分子量調節剤の添加量は全ビスフェノール類に対して３〜７０ｍｏｌ％である。
【００２１】
これらの反応で合成された共重合ポリカーボネートオリゴマーは、芳香族ポリカーボネートと混合して、そのまま、あるいは一旦ペレット化して、押出成形、射出成形、ブロ−成形、圧縮成形、湿式成形など公知の成形法で成形可能である。
【００２２】
また、前記一般式（Ａ）の使用量は、混合する芳香族ポリカーボネートの成形品の透明性、難燃性を考慮すると、前記一般式（Ａ）、（Ｂ）及び（Ｃ）の合計量に対して、１０〜８０重量％である。前記一般式（Ａ）が１０重量％未満では、芳香族ポリカーボネートと混合した場合、白濁が生じる。前記一般式（Ａ）が８０重量％を越えると難燃性が不充分となる。
【００２３】
前記一般式（Ｂ）の使用量は、混合する芳香族ポリカーボネートの成形品の透明性、難燃性を考慮すると、前記一般式（Ａ）、（Ｂ）及び（Ｃ）の合計量に対して、１０〜８０重量％である。前記一般式（Ｂ）が１０重量％未満では、芳香族ポリカーボネートと混合した場合、白濁が生じる。前記一般式（Ｂ）が８０重量％を越えると難燃性が不充分となる。
【００２４】
前記一般式（Ｃ）の使用量は、混合する芳香族ポリカーボネートの成形品の透明性、難燃性を考慮すると、前記一般式（Ａ）、（Ｂ）及び（Ｃ）の合計量に対して１〜８０重量％である。前記一般式（Ｃ）が１重量％未満では、芳香族ポリカーボネートと混合した場合、著しい白濁が生じる。前記一般式（Ｃ）が８０重量％を越えると難燃性が不充分となる。
【００２５】
本発明の共重合ポリカーボネートオリゴマーの極限粘度は、混合する芳香族ポリカーボネートに対する分散性を考慮すると０．０１ｄｌ／ｇ以上で０．２ｄｌ／ｇ未満である。
【００２６】
また、本発明の共重合ポリカーボネートオリゴマーは、臭素化合物、フッ素化合物、塩素化合物等のハロゲン化合物、燐化合物、有機スルホン酸金属塩など、他の公知の難燃剤と併用して用いることができる。本発明の共重合ポリカーボネートオリゴマーは、極めて高度な耐ドリッピング炎上性を有するため、ハロゲン化合物、燐化合物などの消火効果の高い難燃剤と併用するのが好ましい。特に臭素化ビスフェノールＡのカーボネート化合物と併用すると優れた難燃性を発揮できる。
【００２７】
本発明の難燃剤は成形時に必要な安定性や離型性を確保するため、所望に応じて、ヒンダードフェノール系やホスファイト系酸化防止剤；シリコン系、脂肪酸エステル系、脂肪酸系、脂肪酸グリセリド系、密ろう等天然油脂などの滑剤や離型剤；ベンゾトリアゾール系、ベンゾフェノン系、ジベンゾイルメタン系、サリチレート系等の光安定剤；ポリアルキレングリコール、脂肪酸グリセリド等帯電防止剤などを適宜併用してよい。
【００２８】
【実施例】
次に実施例により、本発明をさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
【００２９】
合成例１
８．８％（ｗ／ｖ）の水酸化ナトリウム水溶液４９リットルに、９，９−ビス（３−メチル４−ヒドロキシフェニル）フルオレン３．９０６ｋｇ（以下ＢＣＦＬと略称、）とポリオルガノシロキサン〔一般式（Ｂ）において、Ｒ₅ 及びＲ₆ がトリメチレン基であり、Ｘとしてジメチルシロキサンが平均２６個とジフェニルシロキサンが平均１３個からなるランダム共重合体であるもの〕２．６０４ｋｇ（以下Ｓｉモノマーと略称）、２，２−ビス（４−ヒドロキシフェニル）プロパン０．４９０ｋｇ（以下ＢＰＡと略称）及びハイドロサルファイト２０ｇを加え溶解した。これにメチレンクロライド３６リットルを加え、１５℃に保ちながら撹拌しつつ、ホスゲン１．８１５ｋｇを０．１２ｋｇ／分の速度で吹き込んだ。
吹き込み終了後、ｐ−ターシャルブチルフェノール１２３ｇ（以下ＰＴＢＰと略称）を加え、１０分間激しく撹拌して、さらに１０ｍｌのトリエチルアミンを加え、約１時間撹拌し重合させた。
重合液を水相と有機相に分離し、有機相をリン酸で中和し、洗液の導電率が１０μＳ／ｃｍ以下になるまで水洗を繰り返した後、精製樹脂液を得た。得られた精製樹脂液を、強攪拌されている６０℃の温水に樹脂液をゆっくり滴下し、溶媒を除去しつつ重合物を固形化した。固形物を濾過後、乾燥して白色粉末状重合体を得た。
この重合体は、塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌの溶液の温度２０℃における極限粘度［η］は０．１３ｄｌ／ｇであった。
得られた上記重合体を赤外線吸収スペクトルより分析した結果、１７７０cm^-1付近の位置にカルボニル基による吸収、１２４０cm^-1付近の位置にエーテル結合による吸収が認められ、カーボネート結合を有することが確認された。また、３６５０〜３２００cm^-1の位置に水酸基由来の吸収はほとんど認められなかった。
このポリカーボネート中のモノマーをＧＰＣ分析で測定した場合、いずれのモノマーも２０ｐｐｍ以下であった。
これらを総合した結果、このポリカーボネートのＢＣＦＬとＳｉモノマーとＢＰＡの比率は、仕込み比率とほぼ同じであった。
【００３０】
合成例２
ＰＴＢＰを１００ｇに変更した以外は合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は極限粘度以外は実施例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３１】
合成例３
ＢＣＦＬを４．１３０ｋｇ、Ｓｉモノマーを２．８００ｋｇ、ホスゲンを１．６３７ｋｇ、ＰＴＢＰを９１ｇに変更した以外は、合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は合成例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３２】
合成例４
ＢＣＦＬを０．８４０ｋｇ、Ｓｉモノマーを０．５６０ｋｇ、ＢＰＡを５．６００ｋｇ、ホスゲンを３．４６１ｋｇ、ＰＴＢＰを４４８ｇに変更した以外は、合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は合成例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３３】
合成例５
ＢＣＦＬを５．１８０ｋｇ、Ｓｉモノマーを１．３３０ｋｇ、ホスゲンを２．２３５ｋｇ、ＰＴＢＰを１２４ｇに変更した以外は、合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は合成例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３４】
合成例６
ＢＣＦＬを１．３３０ｋｇ、Ｓｉモノマーを５．１８０ｋｇ、ホスゲンを０．９３４ｋｇ、ＰＴＢＰを５２ｇに変更した以外は、合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は合成例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３５】
合成例７
ＢＣＦＬを０．４２０ｋｇ、Ｓｉモノマーを０．２８０ｋｇ、ホスゲンを３．４２１ｋｇ、ＰＴＢＰを５７６ｇに変更した以外は、合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は合成例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３６】
合成例８
ＢＣＦＬを４．１７９ｋｇ、Ｓｉモノマーを２．７８６ｋｇ、ＢＰＡを０．０３５ｋｇ、ホスゲンを１．６３３ｋｇ、ＰＴＢＰを９１ｇに変更した以外は、合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は合成例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３７】
合成例９
ＢＣＦＬを５．８８０ｋｇ、Ｓｉモノマーを０．６３０ｋｇ、ホスゲンを２．４７２ｋｇ、ＰＴＢＰを１３７ｇに変更した以外は、合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は合成例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３８】
合成例１０
ＢＣＦＬを０．６３０ｋｇ、Ｓｉモノマーを５．８８０ｋｇ、ホスゲンを０．６８９ｋｇ、ＰＴＢＰを３９ｇに変更した以外は、合成例１と同様に行った。
得られた重合体の極限粘度［η］は０．１９ｄｌ／ｇで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は合成例１と同等のポリカーボネート重合体構造を有することが認められた。
【００３９】
合成例１１
撹拌装置、冷却装置、温度計を取り付けた１Ｌフラスコに、水４５０ｇとトルエン１４３ｇを仕込み、オイルバスで内温８０℃まで加熱した。滴下ロートにフェニルトリクロロシラン１４８ｇ、ジフェニルジクロロシラン２３ｇ、メチルフェニルジクロロシラン２１ｇ及びテトラクロロシラン１７ｇを仕込み、フラスコ内へ攪拌しながら１時間で滴下し、滴下終了後、更に内温８０℃で攪拌を１時間続けて熟成した。室温まで冷却しながら静置して分離してきた水相を除去し、引き続き１０％硫酸ナトリウム水溶液を混合して１０分間攪拌後、３０分間静置し、分離してきた水槽を除去する水洗操作をトルエン相が中性になるまで繰り返して反応を停止した。エステルアダプターを取り付け、オルガノポリシロキサンを含むトルエン相を加熱環流してトルエン相から水を除去し、内温が１１０℃に達してから更に１時間続けた後、室温まで冷却した。得られたポリオルガノシロキサン溶液を濾過して不要物を除去し、引き続き減圧蒸留によりトルエンを除去して、固体のポリオルガノシロキサン１１０ｇを得た。
【００４０】
【表１】

【００４１】
〔表１の説明〕
ＢＣＦＬ共重合比：ＢＣＦＬ、Ｓｉモノマー、及びＢＰＡの合計量に対するＢＣＦＬの共重合比（重量％）
Ｓｉモノマー共重合比：ＢＣＦＬ、Ｓｉモノマー、及びＢＰＡの合計量に対するＳｉモノマーの共重合比（重量％）
ＢＰＡ共重合比：ＢＣＦＬ、Ｓｉモノマー、及びＢＰＡの合計量に対するＢＰＡの共重合比（重量％）
極限粘度：０．５ｇ／１００ｃｃジクロロメタン樹脂溶液を２０℃、ハギンズ定数０．４５で極限粘度［η］（ｄｌ／ｇ）を求めた。
【００４２】
実施例１
市販ＢＰＡ型ポリカーボネート（三菱瓦斯化学（株）製Ｅ−１０００、［η］＝０．６４ｄｌ／ｇ、以下Ｅ−１０００と略す）４．９５ｋｇに合成例１で得られた難燃剤０．０５ｋｇを添加し、ベント付き２０ｍｍ押出機にて３００℃で溶融ペレット化を行った。得られたペレットで０．４ｍｍ厚スペーサーを用いて、成形温度３００℃、プレス圧１００ｋｇｆ／ｃｍ² で２００ｍｍ×２００ｍｍ×厚さ０．４ｍｍの板状片を３０枚、圧縮成形した。動力プレス機を用いて板状片から、０．４ｍｍ厚燃焼試験片を打ち抜き、ＵＬ９４―１９９３の燃焼試験片に適合するものを選んだ。選ばれた燃焼試験片をＵＬ９４―１９９３の方法に準じて燃焼試験した。ただし、試験片の耐ドリッピング炎上性を正確に評価するため、１試験片に対する着火は１回のみとし、燃焼試験片がドリッピングし、試験片の下部に置かれた脱脂綿が炎上するまで試験片に接炎を続けた。そして、接炎開始から脱脂綿が炎上するまでの時間を測定した。合計１０回の測定を行い、平均値をドリッピング炎上までの時間とした。ドリッピング炎上までの時間は６秒であった。また、動力プレスを用いて、上記の板状片から、５０ｍｍ×５０ｍｍ×厚さ０．４ｍｍ（±０．００２ｍｍ）の試験片を１０枚打ち抜いた。得られた試験片１０枚の全光線透過率とヘーズを村上色彩技術研究所製ＨＭ−１００を用いて測定し、それぞれ１０枚測定の平均値を全光線透過率、ヘーズとした。全光線透過率は９１．０％、ヘーズは０．９％であった。
【００４３】
但し、全光線透過率とヘーズの関係は、全光線透過率をＴ_t 、平行光線透過率をＴ_p 、拡散透過率をＴ_d 、ヘーズをＨとすると、以下の関係となる。
Ｔ_p ＝Ｔ_t −Ｔ_d
Ｈ ＝（Ｔ_d ／Ｔ_t ）×１００
【００４４】
実施例２
合成例１で得られた難燃剤を合成例２で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は７秒、全光線透過率は９１．０％、ヘーズは０．８％であった。
【００４５】
実施例３
合成例１で得られた難燃剤を合成例３で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は７秒、全光線透過率は９１．０％、ヘーズは１．０％であった。
【００４６】
実施例４
合成例１で得られた難燃剤を合成例４で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は５秒、全光線透過率は９１．２％、ヘーズは０．５％であった。
【００４７】
実施例５
合成例１で得られた難燃剤を合成例５で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は５秒、全光線透過率は９１．３％、ヘーズは０．５％であった。
【００４８】
実施例６
合成例１で得られた難燃剤を合成例６で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は１２秒、全光線透過率は９０．０％、ヘーズは１．５％であった。
【００４９】
実施例７
Ｅ−１０００（三菱瓦斯化学（株）製）３．９５ｋｇにテトラブロムビスフェノールＡ型ポリカーボネートオリゴマー（三菱瓦斯化学（株）製ＦＲ−５３、以下ＦＲ−５３と略す）１ｋｇ（２０ｗｔ％）及び合成例１で得られた難燃剤０．０５ｋｇを添加し、ベント付き２０ｍｍ押出機にて３００℃で溶融ペレット化を行った。得られたペレットで０．４ｍｍ厚スペーサーを用いて、成形温度３００℃、プレス圧１００ｋｇｆ／ｃｍ² で２００ｍｍ×２００ｍｍ×厚さ０．４ｍｍの板状片を３０枚を、圧縮成形した。動力プレス機を用いて板状片から、０．４ｍｍ厚燃焼試験片を打ち抜き、ＵＬ９４―１９９３の燃焼試験片に適合するものを選んだ。選ばれた燃焼試験片をＵＬ９４―１９９３の方法に準じて燃焼試験した。ＵＬ９４―１９９３における難燃性はＶ−０であった。また、動力プレスを用いて、上記の板状片から、５０ｍｍ×５０ｍｍ×厚さ０．４ｍｍ（±０．００２ｍｍ）の試験片を１０枚打ち抜いた。得られた試験片１０枚の全光線透過率とヘーズを村上色彩技術研究所製ＨＭ−１００を用いて測定し、それぞれ１０枚測定の平均値を全光線透過率、ヘーズとした。全光線透過率は９１．０％、ヘーズは０．７％であった。
【００５０】
実施例８
合成例１で得られた難燃剤を合成例２で得られた難燃剤に変更した以外は、実施例７と同様の試験を行った。ＵＬ９４―１９９３における難燃性はＶ−０、全光線透過率は９１．０％、ヘーズは０．８％であった。
【００５１】
実施例９
Ｅ−１０００を４．２５ｋｇ、ＦＲ−５３を０．５ｋｇ（１０ｗｔ％）、合成例１で得られた難燃剤を０．２５ｋｇ（５ｗｔ％）に変更した以外は、実施例７と同様の試験を行った。ＵＬ９４―１９９３における難燃性はＶ−０、全光線透過率は９１．０％、ヘーズは１．０％であった。
【００５２】
実施例１０
合成例１で得られた難燃剤を合成例２で得られた難燃剤に変更した以外は、実施例９と同様の試験を行った。ＵＬ９４―１９９３における難燃性はＶ−０、全光線透過率は９１．２％、ヘーズは１．０％であった。
【００５３】
比較例１
合成例１で得られた難燃剤を使用しない以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は３秒、全光線透過率は９１．３％、ヘーズは０．６％であった。
【００５４】
比較例２
合成例１で得られた難燃剤を合成例７で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は３秒、全光線透過率は９１．７％、ヘーズは１．０％であった。
【００５５】
比較例３
合成例１で得られた難燃剤を合成例８で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は７秒、全光線透過率は８９．０％、ヘーズは７０．０％であった。
【００５６】
比較例４
合成例１で得られた難燃剤を合成例９で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は４秒、全光線透過率は９１．２％、ヘーズは０．７％であった。
【００５７】
比較例５
合成例１で得られた難燃剤を合成例１０で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は１２秒、全光線透過率は９０．０％、ヘーズは１３．１％であった。
【００５８】
比較例６
合成例１で得られた難燃剤を合成例１で使用したＳｉモノマーに変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は４秒、全光線透過率は８８．９％、ヘーズは７６．５％であった。
【００５９】
比較例７
合成例１で得られた難燃剤を合成例１１で得られた難燃剤に変更した以外は、実施例１と同様の試験を行った。ドリッピング炎上までの時間は４秒、全光線透過率は８９．０％、ヘーズは７０．０％であった。
【００６０】
比較例８
Ｅ−１０００を４．００ｋｇ（８０ｗｔ％）、ＦＲ−５３を１．００ｋｇ（２０ｗｔ％）、合成例１で得られた難燃剤を０ｋｇ（０ｗｔ％）に変更した以外は、実施例７と同様の試験を行った。ＵＬ９４―１９９３における難燃性はＶ−２、全光線透過率は９１．３％、ヘーズは０．６％であった。
【００６１】
比較例９
Ｅ−１０００を３．５０ｋｇ（７０ｗｔ％）、ＦＲ−５３を１．００ｋｇ（２０ｗｔ％）、合成例１で得られた難燃剤を合成例７で得られた難燃剤０．５ｋｇ（１０ｗｔ％）に変更した以外は、実施例７と同様の試験を行った。ＵＬ９４―１９９３における難燃性はＶ−２、全光線透過率は９１．７％、ヘーズは１．０％であった。
【００６２】
比較例１０
Ｅ−１０００を３．５０ｋｇ（７０ｗｔ％）、ＦＲ−５３を１．００ｋｇ（２０ｗｔ％）、合成例１で得られた難燃剤を合成例９で得られた難燃剤０．５ｋｇ（１０ｗｔ％）に変更した以外は、実施例７と同様の試験を行った。ＵＬ９４―１９９３における難燃性はＶ−２、全光線透過率は９１．２％、ヘーズは０．７％であった。
【００６３】
【表２】

【００６４】
〔表２の説明〕
成形機（板状品）：（株）神藤金属工業所製、圧縮成形機ＳＦ．３７を使用。
ドリッピング炎上までの時間：ＵＬ９４−１９９３の設備等を用いて試験片に着火した時の接炎開始から脱脂綿が炎上するまでの時間。
全光線透過率：厚さ０．４ｍｍの試験片１０枚の全光線透過率を村上色彩技術研究所製ＨＭ−１００を用いて１９ｍｍφ透過光で測定し、その平均値を全光線透過率とした。
ヘーズ：厚さ０．４ｍｍの試験片１０枚のヘーズを村上色彩技術研究所製ＨＭ−１００を用いて１９ｍｍφ透過光で測定し、その平均値をヘーズとした。
【００６５】
【表３】

【００６６】
〔表３の説明〕
難燃剤添加率：Ｅ−１０００、合成例１〜１０の難燃剤及びＦＲ−５３の合計量に対する該難燃剤の重量比（ｗｔ％）
成形機（板状品）：（株）神藤金属工業所製、圧縮成形機ＳＦ．３７を使用。
ＵＬ９４難燃性：ＵＬ９４−１９９３の方法で０．４ｍｍ厚試験片の難燃性を評価した。
全光線透過率：厚さ０．４ｍｍの試験片１０枚の全光線透過率を村上色彩技術研究所製ＨＭ−１００を用いて１９ｍｍφ透過光で測定し、その平均値を全光線透過率とした。
ヘーズ：厚さ０．４ｍｍの試験片１０枚のヘーズを村上色彩技術研究所製ＨＭ−１００を用いて１９ｍｍφ透過光で測定し、その平均値をヘーズとした。
【００６７】
【発明の効果】
本発明の共重合ポリカーボネートオリゴマーは芳香族ポリカーボネートに添加することで該芳香族ポリカーボネートの透明性を損なわず、特に薄肉での耐ドリッピング炎上性を飛躍的に向上できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polycarbonate oligomer that can add flame retardancy by being contained in an aromatic polycarbonate, and a resin composition containing the oligomer.
[0002]
[Prior art]
Aromatic polycarbonates are widely used in the OA equipment field, the electric / electronic field, the automobile field, the building field, the optical field, etc., taking advantage of their transparency, heat resistance, impact resistance, and electrical characteristics. In these fields, there are fields that require extremely high flame retardancy, such as the OA equipment field and the electrical / electronic field.
[0003]
However, the flame retardancy of aromatic polycarbonates is not sufficient, and their use in fields where extremely high flame retardancy is required has been limited. In order to improve the flame retardancy of these aromatic polycarbonates, a flame retardant polycarbonate resin composition containing a polycarbonate of tetrabromobisphenol A end-capped with a halogenated phenol is disclosed (Japanese Patent Laid-Open No. 47-41422). ). However, although the composition can provide a fire extinguishing effect by adding a halogen compound, it has not been possible to avoid the danger of flames due to dripping. In particular, in the OA equipment field and the electric / electronic field, which have recently become more compact and light in weight, there has been a demand for a material that does not easily cause flames by dripping even if the thickness of the molded product is small.
[0004]
On the other hand, a flame retardant resin composition containing a specific polyorganosiloxane and having a high light transmittance is disclosed (Japanese Patent Application Laid-Open No. 11-140294). However, when polyorganosiloxane is added directly to an aromatic polycarbonate, a relatively high light transmittance can be obtained, but white turbidity is produced by addition of a very small amount, and the haze of 0.4 mm thickness increases to about 70%. As a result, the transparency, which is the most important characteristic of the aromatic polycarbonate, is significantly obstructed, and it is difficult to use it in fields where transparency is required.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to contain a polycarbonate oligomer capable of improving the dripping flame resistance in a thin wall without impairing the excellent transparency of the aromatic polycarbonate and the polycarbonate oligomer, and has excellent transparency and flame retardancy. The object is to provide a polycarbonate resin composition.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the conventional problems, the present inventors have added a copolymer polycarbonate oligomer derived from three specific types of bisphenols to the aromatic polycarbonate to add the aromatic polycarbonate. It has been found that dripping flame resistance can be dramatically improved without sacrificing transparency, and the present invention has been completed.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
That is, the present invention is a polycarbonate derived from the general formulas (A), (B) and (C), wherein the general formula (A) is 10 to 80% by weight, and the general formula (B) is 10 to 80%. The general formula (C) is 1 to 80% by weight, and the total amount thereof [general formula (A) + general formula (B) + general formula (C)] is 100% by weight, and A polycarbonate oligomer having an intrinsic viscosity of 0.01 dl / g or more and less than 0.2 dl / g, and a resin composition comprising the polycarbonate oligomer.
[0008]
[Chemical formula 5]

(Wherein R₁~ R_FourAre each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 7 to 7 carbon atoms. 17 aralkyl groups are represented. )
[0009]
[Chemical 6]

(Wherein R_FiveAnd R₆Represents an aliphatic group having 1 to 6 carbon atoms, X represents at least two random copolymers selected from dimethylsiloxane, methylphenylsiloxane and diphenylsiloxane, and the degree of polymerization represents 2 to 200. . )
[0010]
[Chemical 7]

(Where R₇~ R_TenAre each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 7 to 7 carbon atoms. 17 aralkyl groups, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Can also have. Y is
[Chemical 8]

And here R₁₁And R₁₂Each represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R₁₁And R₁₂Are bonded together to form an aliphatic ring or a heterocyclic ring. When these groups have a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. a represents an integer of 0 to 20. )
[0011]
The copolymer oligomer of the present invention can be produced by reacting the general formulas (A), (B) and (C) with a carbonate ester-forming compound. That is, a known method used for producing a polycarbonate derived from bisphenol A, for example, a direct reaction between a dihydric phenol and phosgene (phosgene method), or a transesterification reaction between a dihydric phenol and bisaryl carbonate. A method such as (transesterification method) can be employed.
[0012]
Examples of the carbonate ester-forming compound include phosgene and bisallyl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate.
[0013]
Specific examples of the compound represented by the general formula (A) include 9,9-bis (4-hydroxy-2-methylphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl). Fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methoxy-4-hydroxyphenyl) fluorene 9,9-bis (3-ethoxy-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 4,5-dimethyl-9,9-bis (4-hydroxy) Phenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (3-methyl-4-hydro) Rokishifeniru) fluorene and 3,6-diphenyl-9,9-bis (4-hydroxyphenyl) fluorene, and the like. In particular, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene are preferable. .
[0014]
Specific examples of the compound represented by the general formula (B) include R in the formula_FiveAnd R₆Is dimethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene, X is a random copolymer of at least two selected from dimethylsiloxane, methylphenylsiloxane and diphenylsiloxane, and the degree of polymerization is 2 to 2. 200. Preferably, the random copolymer has 2 or more diphenylsiloxanes and a polymerization degree of 3 to 100.
[0015]
Specific examples of the compound represented by the general formula (C) include 4,4′-biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, and bis (4-hydroxyphenyl). ) Sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4 -Hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (Bisphenol Z; BPZ), 2,2-bis (4-hydroxy-3-methyl) Phenyl) propane (dimethylbisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP; BPAP) Bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-allylphenyl) propane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane, etc. Is done. These can be used in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.
[0016]
In the phosgene method and the transesterification method, the phosgene method is preferable in consideration of the reactivity of the compounds represented by the general formulas (A), (B), and (C).
[0017]
In the former phosgene method, phosgene is reacted with the above general formulas (A), (B) and (C) in the present invention, usually in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene. . Further, a tertiary amine catalyst such as triethylamine is used to promote the condensation polymerization reaction. For the polymerization degree adjustment, monofunctional compounds such as phenols such as phenol, pt-butylphenol, and p-cumylphenol are added as molecular weight regulators. Further, if desired, an antioxidant such as sodium sulfite, hydrosulfite, phloroglucin, isatin bisphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4 A small amount of a branching agent such as -hydroxyphenyl) -1,3,5-triisopropylbenzene may be added, and the reaction is usually in the range of 0 to 150 ° C., preferably 5 to 40 ° C. Although the reaction time depends on the reaction temperature, it is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours, and it is desirable to maintain the pH of the reaction system at 10 or more during the reaction. .
[0018]
On the other hand, in the latter transesterification method, the bisphenols of the above general formulas (A), (B) and (C) and bisaryl carbonate are mixed and reacted at high temperature under reduced pressure. At this time, monofunctional compounds such as phenols such as phenol, pt-butylphenol, and p-cumylphenol may be added as molecular weight regulators. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less at the end, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the reduced pressure, but is usually about 1 to 6 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may react by adding antioxidant and a branching agent as needed.
[0019]
When the phosgene method is employed in the present invention, a tertiary amine such as triethylamine is used after the phosgene blowing is completed in order to efficiently perform the reaction between the bisphenols and phosgene. A quaternary ammonium salt such as triethylbenzylammonium chloride may also be used if desired. The addition amount of these amines is 0.01-1.0 mol% with respect to all the bisphenols.
[0020]
Furthermore, as the molecular weight regulator of the present invention, monohydric phenol is particularly preferable. Specifically, butylphenol, octylphenol, nonylphenol, decanylphenol, tetradecanylphenol, heptadecanylphenol, octadecanylphenol, etc. Long chain alkyl substituted phenols; hydroxybenzoic acid long chain alkyl esters such as butyl hydroxybenzoate, octyl hydroxybenzoate, nonyl hydroxybenzoate, decanyl hydroxybenzoate, heptadecanyl hydroxybenzoate; butoxyphenol, octyloxyphenol, nonyloxyphenol, Long-chain alkyloxyphenols such as decanyloxyphenol, tetradecanyloxyphenol, heptadecanyloxyphenol, and octadecanyloxyphenol Class are exemplified. The addition amount of this molecular weight regulator is 3-70 mol% with respect to all the bisphenols.
[0021]
The copolymerized polycarbonate oligomer synthesized by these reactions is mixed with an aromatic polycarbonate and directly or once pelletized, and is subjected to known molding methods such as extrusion molding, injection molding, blow molding, compression molding, and wet molding. It can be molded.
[0022]
The amount of the general formula (A) used is the total amount of the general formulas (A), (B) and (C) in consideration of the transparency and flame retardancy of the molded product of the aromatic polycarbonate to be mixed. On the other hand, it is 10 to 80% by weight. When the general formula (A) is less than 10% by weight, white turbidity occurs when mixed with an aromatic polycarbonate. If the general formula (A) exceeds 80% by weight, the flame retardancy becomes insufficient.
[0023]
The use amount of the general formula (B) is based on the total amount of the general formulas (A), (B) and (C) in consideration of the transparency and flame retardancy of the molded product of the aromatic polycarbonate to be mixed. 10 to 80% by weight. When the general formula (B) is less than 10% by weight, white turbidity occurs when mixed with an aromatic polycarbonate. If the general formula (B) exceeds 80% by weight, the flame retardancy becomes insufficient.
[0024]
The use amount of the general formula (C) is based on the total amount of the general formulas (A), (B) and (C) in consideration of the transparency and flame retardancy of the molded product of the aromatic polycarbonate to be mixed. 1 to 80% by weight. If the said general formula (C) is less than 1 weight%, when it mixes with an aromatic polycarbonate, remarkable cloudiness will arise. If the general formula (C) exceeds 80% by weight, the flame retardancy becomes insufficient.
[0025]
The intrinsic viscosity of the copolymerized polycarbonate oligomer of the present invention is 0.01 dl / g or more and less than 0.2 dl / g in consideration of dispersibility with respect to the aromatic polycarbonate to be mixed.
[0026]
In addition, the copolymeric polycarbonate oligomer of the present invention can be used in combination with other known flame retardants such as halogen compounds such as bromine compounds, fluorine compounds and chlorine compounds, phosphorus compounds and organic sulfonic acid metal salts. Since the copolymeric polycarbonate oligomer of the present invention has extremely high resistance to dripping flame, it is preferably used in combination with a flame retardant having a high fire extinguishing effect such as a halogen compound and a phosphorus compound. In particular, when used in combination with a carbonate compound of brominated bisphenol A, excellent flame retardancy can be exhibited.
[0027]
The flame retardant of the present invention ensures hindered phenol-based or phosphite-based antioxidants; silicon-based, fatty acid ester-based, fatty acid-based, fatty acid glycerides, as desired, in order to ensure the stability and releasability required during molding. Lubricants and mold release agents such as natural oils and beeswaxes; light stabilizers such as benzotriazoles, benzophenones, dibenzoylmethanes, salicylates; antistatic agents such as polyalkylene glycols and fatty acid glycerides, etc. It's okay.
[0028]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[0029]
Synthesis example 1
Into 49 liters of an 8.8% (w / v) aqueous sodium hydroxide solution, 3.906 kg of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (hereinafter abbreviated as BCFL) and polyorganosiloxane [general formula In (B), R_FiveAnd R₆Is a trimethylene group, and X is a random copolymer comprising 26 dimethylsiloxanes and 13 diphenylsiloxanes on average] 2.604 kg (hereinafter abbreviated as Si monomer), 2,2-bis (4- Hydroxyphenyl) propane 0.490 kg (hereinafter abbreviated as BPA) and hydrosulfite 20 g were added and dissolved. To this was added 36 liters of methylene chloride, and while stirring at 15 ° C., 1.815 kg of phosgene was blown at a rate of 0.12 kg / min.
After completion of the blowing, 123 g of p-tert-butylphenol (hereinafter abbreviated as PTBP) was added, and the mixture was vigorously stirred for 10 minutes. Further, 10 ml of triethylamine was added, and the mixture was stirred for about 1 hour for polymerization.
The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washed with water until the washing liquid had a conductivity of 10 μS / cm or less, to obtain a purified resin liquid. The obtained purified resin solution was slowly dropped into 60 ° C. hot water that was vigorously stirred, and the polymer was solidified while removing the solvent. The solid was filtered and dried to obtain a white powdery polymer.
This polymer had an intrinsic viscosity [η] at a temperature of 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent was 0.13 dl / g.
As a result of analyzing the obtained polymer from an infrared absorption spectrum, 1770 cm.^-1Absorption by carbonyl group at nearby position, 1240cm^-1Absorption by an ether bond was observed at a nearby position, and it was confirmed to have a carbonate bond. Moreover, 3650-3200cm^-1Absorption due to a hydroxyl group was hardly observed at the position.
When the monomer in this polycarbonate was measured by GPC analysis, all the monomers were 20 ppm or less.
As a result of combining these, the ratio of BCFL, Si monomer and BPA of this polycarbonate was almost the same as the charging ratio.
[0030]
Synthesis example 2
The same operation as in Synthesis Example 1 was conducted except that PTBP was changed to 100 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Example 1 except for the intrinsic viscosity. It was.
[0031]
Synthesis example 3
The same procedure as in Synthesis Example 1 was conducted except that BCFL was changed to 4.130 kg, Si monomer was changed to 2.800 kg, phosgene was changed to 1.637 kg, and PTBP was changed to 91 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio. It was.
[0032]
Synthesis example 4
The same procedure as in Synthesis Example 1 was conducted except that BCFL was changed to 0.840 kg, Si monomer was changed to 0.560 kg, BPA was changed to 5.600 kg, phosgene was changed to 3.461 kg, and PTBP was changed to 448 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio. It was.
[0033]
Synthesis example 5
The same procedure as in Synthesis Example 1 was conducted except that BCFL was changed to 5.180 kg, Si monomer was changed to 1.330 kg, phosgene was changed to 2.235 kg, and PTBP was changed to 124 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio. It was.
[0034]
Synthesis Example 6
The same procedure as in Synthesis Example 1 was conducted except that BCFL was changed to 1.330 kg, Si monomer was changed to 5.180 kg, phosgene was changed to 0.934 kg, and PTBP was changed to 52 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio. It was.
[0035]
Synthesis example 7
The same procedure as in Synthesis Example 1 was conducted except that BCFL was changed to 0.420 kg, Si monomer was changed to 0.280 kg, phosgene was changed to 3.421 kg, and PTBP was changed to 576 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio. It was.
[0036]
Synthesis Example 8
The same procedure as in Synthesis Example 1 was performed except that BC179 was changed to 4.179 kg, Si monomer was 2.786 kg, BPA was 0.035 kg, phosgene was changed to 1.633 kg, and PTBP was changed to 91 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio. It was.
[0037]
Synthesis Example 9
The same procedure as in Synthesis Example 1 was conducted except that BCFL was changed to 5.880 kg, Si monomer was changed to 0.630 kg, phosgene was changed to 2.472 kg, and PTBP was changed to 137 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio. It was.
[0038]
Synthesis Example 10
The procedure was the same as in Synthesis Example 1 except that BCFL was changed to 0.630 kg, Si monomer was changed to 5.880 kg, phosgene was changed to 0.689 kg, and PTBP was changed to 39 g.
The obtained polymer had an intrinsic viscosity [η] of 0.19 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio. It was.
[0039]
Synthesis Example 11
A 1 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with 450 g of water and 143 g of toluene, and heated to an internal temperature of 80 ° C. in an oil bath. A dropping funnel was charged with 148 g of phenyltrichlorosilane, 23 g of diphenyldichlorosilane, 21 g of methylphenyldichlorosilane, and 17 g of tetrachlorosilane. The mixture was added dropwise to the flask with stirring for 1 hour. Matured for hours. The water phase that had been separated by leaving to stand while cooling to room temperature was removed, followed by mixing with a 10% aqueous solution of sodium sulfate, stirring for 10 minutes, and then leaving to stand for 30 minutes to remove the separated water tank. The reaction was stopped repeatedly until the phase was neutral. An ester adapter was attached, and the toluene phase containing the organopolysiloxane was heated to reflux to remove water from the toluene phase. After the internal temperature reached 110 ° C., the mixture was further continued for 1 hour, and then cooled to room temperature. The obtained polyorganosiloxane solution was filtered to remove unnecessary substances, and then toluene was removed by distillation under reduced pressure to obtain 110 g of solid polyorganosiloxane.
[0040]
[Table 1]

[0041]
[Explanation of Table 1]
BCFL copolymerization ratio: BCFL copolymerization ratio (% by weight) with respect to the total amount of BCFL, Si monomer, and BPA
Si monomer copolymerization ratio: Copolymerization ratio of Si monomer to the total amount of BCFL, Si monomer, and BPA (% by weight)
BPA copolymerization ratio: BPA copolymerization ratio (% by weight) with respect to the total amount of BCFL, Si monomer and BPA
Intrinsic viscosity: The intrinsic viscosity [η] (dl / g) of a 0.5 g / 100 cc dichloromethane resin solution was determined at 20 ° C. and a Huggins constant of 0.45.
[0042]
Example 1
Commercially available BPA-type polycarbonate (E-1000 manufactured by Mitsubishi Gas Chemical Co., Inc., [η] = 0.64 dl / g, hereinafter abbreviated as E-1000) 4.95 kg with 0.05 kg of the flame retardant obtained in Synthesis Example 1 The mixture was added and melt pelletized at 300 ° C. in a vented 20 mm extruder. Using the obtained pellet with a 0.4 mm thickness spacer, molding temperature 300 ° C., press pressure 100 kgf / cm²30 plate-shaped pieces of 200 mm × 200 mm × 0.4 mm thickness were compression molded. A 0.4 mm thick combustion test piece was punched out of the plate-like piece using a power press machine, and the one suitable for the UL 94-1993 combustion test piece was selected. The selected combustion test piece was subjected to a combustion test according to the method of UL94-1993. However, in order to accurately evaluate the anti-dripping flame resistance of a test piece, the test piece is ignited only once, and the test is performed until the burning test piece dripped and the absorbent cotton placed under the test piece burns up. Continued flame contact on one piece. And the time from the start of flame contact to the absorbent cotton burning was measured. A total of 10 measurements were taken and the average value was taken as the time to dripping flame. The time to dripping flame was 6 seconds. In addition, 10 test pieces each having a size of 50 mm × 50 mm × thickness 0.4 mm (± 0.002 mm) were punched out from the plate-like piece using a power press. The total light transmittance and haze of the 10 test specimens obtained were measured using HM-100 manufactured by Murakami Color Research Laboratory, and the average value of 10 measurements was taken as the total light transmittance and haze, respectively. The total light transmittance was 91.0%, and the haze was 0.9%.
[0043]
However, the relationship between the total light transmittance and haze is as follows._t, The parallel light transmittance T_p, T_dWhen Haze is H, the following relationship is established.
T_p= T_t-T_d
H = (T_d/ T_t) × 100
[0044]
Example 2
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 2. The time to dripping flame was 7 seconds, the total light transmittance was 91.0%, and the haze was 0.8%.
[0045]
Example 3
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 3. The time to dripping flame was 7 seconds, the total light transmittance was 91.0%, and the haze was 1.0%.
[0046]
Example 4
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 4. The time to dripping flame was 5 seconds, the total light transmittance was 91.2%, and the haze was 0.5%.
[0047]
Example 5
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 5. The time to dripping flame was 5 seconds, the total light transmittance was 91.3%, and the haze was 0.5%.
[0048]
Example 6
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 6. The time to dripping flame was 12 seconds, the total light transmittance was 90.0%, and the haze was 1.5%.
[0049]
Example 7
E-1000 (Mitsubishi Gas Chemical Co., Ltd.) 3.95 kg, Tetrabromobisphenol A type polycarbonate oligomer (Mitsubishi Gas Chemical Co., Ltd. FR-53, hereinafter abbreviated as FR-53) 1 kg (20 wt%) and synthesis example The flame retardant 0.05 kg obtained in 1 was added, and melt pelletization was performed at 300 ° C. in a vented 20 mm extruder. Using the obtained pellet with a 0.4 mm thickness spacer, molding temperature 300 ° C., press pressure 100 kgf / cm²30 sheets of 200 mm × 200 mm × 0.4 mm thick plate-like pieces were compression molded. A 0.4 mm thick combustion test piece was punched out of the plate-like piece using a power press machine, and the one suitable for the UL 94-1993 combustion test piece was selected. The selected combustion test piece was subjected to a combustion test according to the method of UL94-1993. The flame retardancy in UL94-1993 was V-0. Further, ten test pieces each having a size of 50 mm × 50 mm × thickness 0.4 mm (± 0.002 mm) were punched out from the plate-like piece using a power press. The total light transmittance and haze of the 10 test specimens obtained were measured using HM-100 manufactured by Murakami Color Research Laboratory, and the average value of 10 measurements was taken as the total light transmittance and haze, respectively. The total light transmittance was 91.0%, and the haze was 0.7%.
[0050]
Example 8
The same test as in Example 7 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 2. The flame retardancy in UL94-1993 was V-0, the total light transmittance was 91.0%, and the haze was 0.8%.
[0051]
Example 9
Test similar to Example 7 except that E-1000 is changed to 4.25 kg, FR-53 is changed to 0.5 kg (10 wt%), and the flame retardant obtained in Synthesis Example 1 is changed to 0.25 kg (5 wt%). Went. The flame retardancy in UL94-1993 was V-0, the total light transmittance was 91.0%, and the haze was 1.0%.
[0052]
Example 10
The same test as in Example 9 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 2. The flame retardancy in UL94-1993 was V-0, the total light transmittance was 91.2%, and the haze was 1.0%.
[0053]
Comparative Example 1
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was not used. The time to dripping flame was 3 seconds, the total light transmittance was 91.3%, and the haze was 0.6%.
[0054]
Comparative Example 2
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 7. The time to dripping flame was 3 seconds, the total light transmittance was 91.7%, and the haze was 1.0%.
[0055]
Comparative Example 3
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 8. The time to dripping flame was 7 seconds, the total light transmittance was 89.0%, and the haze was 70.0%.
[0056]
Comparative Example 4
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 9. The time to dripping flame was 4 seconds, the total light transmittance was 91.2%, and the haze was 0.7%.
[0057]
Comparative Example 5
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 10. The time to dripping flame was 12 seconds, the total light transmittance was 90.0%, and the haze was 13.1%.
[0058]
Comparative Example 6
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the Si monomer used in Synthesis Example 1. The time to dripping flame was 4 seconds, the total light transmittance was 88.9%, and the haze was 76.5%.
[0059]
Comparative Example 7
The same test as in Example 1 was performed except that the flame retardant obtained in Synthesis Example 1 was changed to the flame retardant obtained in Synthesis Example 11. The time to dripping flame was 4 seconds, the total light transmittance was 89.0%, and the haze was 70.0%.
[0060]
Comparative Example 8
Same as Example 7 except that E-1000 was changed to 4.00 kg (80 wt%), FR-53 was changed to 1.00 kg (20 wt%), and the flame retardant obtained in Synthesis Example 1 was changed to 0 kg (0 wt%). The test was conducted. The flame retardancy in UL94-1993 was V-2, the total light transmittance was 91.3%, and the haze was 0.6%.
[0061]
Comparative Example 9
E-1000 is 3.50 kg (70 wt%), FR-53 is 1.00 kg (20 wt%), the flame retardant obtained in Synthesis Example 1 is 0.5 kg (10 wt%) the flame retardant obtained in Synthesis Example 7 The same test as in Example 7 was performed except that the change was made. The flame retardancy in UL94-1993 was V-2, the total light transmittance was 91.7%, and the haze was 1.0%.
[0062]
Comparative Example 10
E-1000 is 3.50 kg (70 wt%), FR-53 is 1.00 kg (20 wt%), the flame retardant obtained in Synthesis Example 1 is 0.5 kg (10 wt%) the flame retardant obtained in Synthesis Example 9 The same test as in Example 7 was performed except that the change was made. The flame retardancy in UL94-1993 was V-2, the total light transmittance was 91.2%, and the haze was 0.7%.
[0063]
[Table 2]

[0064]
[Explanation of Table 2]
Molding machine (plate-shaped product): manufactured by Shinto Metal Industry Co., Ltd. Use 37.
Time until dripping flame: The time from the start of flame contact until the absorbent cotton flames up when the test piece is ignited using UL94-1993 equipment or the like.
Total light transmittance: The total light transmittance of 10 test pieces having a thickness of 0.4 mm was measured with 19 mmφ transmitted light using HM-100 manufactured by Murakami Color Research Laboratory, and the average value was defined as the total light transmittance. .
Haze: The haze of 10 test pieces having a thickness of 0.4 mm was measured with 19 mmφ transmitted light using HM-100 manufactured by Murakami Color Research Laboratory, and the average value was defined as haze.
[0065]
[Table 3]

[0066]
[Explanation of Table 3]
Flame retardant addition rate: E-1000, weight ratio of the flame retardant to the total amount of flame retardants of Synthesis Examples 1-10 and FR-53 (wt%)
Molding machine (plate-shaped product): manufactured by Shinto Metal Industry Co., Ltd. Use 37.
UL94 flame retardancy: The flame retardance of a 0.4 mm thick test piece was evaluated by the method of UL94-1993.
Total light transmittance: The total light transmittance of 10 test pieces having a thickness of 0.4 mm was measured with 19 mmφ transmitted light using HM-100 manufactured by Murakami Color Research Laboratory, and the average value was defined as the total light transmittance. .
Haze: The haze of 10 test pieces having a thickness of 0.4 mm was measured with 19 mmφ transmitted light using HM-100 manufactured by Murakami Color Research Laboratory, and the average value was defined as haze.
[0067]
【The invention's effect】
By adding the copolymer polycarbonate oligomer of the present invention to an aromatic polycarbonate, the transparency of the aromatic polycarbonate is not impaired, and dripping flame resistance particularly in a thin wall can be remarkably improved.

Claims (10)

A polycarbonate derived from the general formulas (A), (B) and (C), wherein the general formula (A) is 10 to 80% by weight and the general formula (B) is 10 to 80% by weight. The general formula (C) is 1 to 80% by weight, the total amount [general formula (A) + general formula (B) + general formula (C)] is 100% by weight, and the intrinsic viscosity is 0. A polycarbonate oligomer characterized by being at least 0.01 dl / g and less than 0.2 dl / g.

(Wherein R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms. An alkoxy group or an aralkyl group having 7 to 17 carbon atoms.)

(Wherein R ₅ and R ₆ represent an aliphatic group having 1 to 6 carbon atoms, and X 1 represents at least two random copolymers selected from dimethylsiloxane, methylphenylsiloxane and diphenylsiloxane. The degree of polymerization represents 2 to 200.)

Wherein R _{7 to} R ₁₀ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. An alkoxy group or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or carbon It can also have an alkoxy group of 1 to 5. Y is

Wherein R ₁₁ and R ₁₂ are each hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Or a group in which R ₁₁ and R ₁₂ are bonded together to form an aliphatic ring or a heterocyclic ring. When these groups have a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. a represents an integer of 0 to 20. )     A resin composition containing the polycarbonate oligomer of claim 1. 2. The polycarbonate oligomer according to claim 1, which is a flame retardant for resin. A flame retardant resin composition comprising the polycarbonate oligomer of claim 1. The general formula (A) is 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2- The polycarbonate oligomer according to claim 1, which is at least one member selected from the group of (methylphenyl) fluorene. The polycarbonate oligomer according to claim 1, wherein the general formula (C) is 2,2-bis (4-hydroxyphenyl) propane. The polycarbonate oligomer according to claim 1, obtained by reacting the general formulas (A), (B) and (C) with phosgene. The resin composition according to claim 2, wherein the 0.4 mm-thick molded article has a total light transmittance of 90% or more. The resin composition according to claim 2, wherein the haze of the molded article having a thickness of 0.4 mm is 10% or less. The resin composition according to claim 4, wherein the flame retardancy in a 20 mm vertical combustion test (UL94-1993) is V-0 at a thickness of 0.4 mm.