JP4485717B2 - Thermoplastic material composition and optical component comprising the same - Google Patents

Description

【００１５】
（但し化学式（１）において、Ｘは１〜４の整数であり、Ｒ１及びＲ２は、それぞれ独立に、化学式群（２）（化２）のいずれかから選ばれる１価の結合基を表す。なお、化学式（２）において、Ｙは１〜３０の整数、Ｚは０〜５の整数である。）
【００１６】
［２］ 熱可塑性樹脂が、溶融成形可能な熱可塑性樹脂であり、熱可塑性材料組成物が、溶融成形可能な熱可塑性材料組成物である、［１］記載の熱可塑性材料組成物。
【００１７】
［３］ 熱可塑性樹脂が、アクリル樹脂、環状オレフィン樹脂、環状脂肪族鎖を有するポリカーボネート樹脂、環状脂肪族鎖を有するポリエステル樹脂、環状脂肪族鎖を有するポリエーテル樹脂、環状脂肪族鎖を有するポリアミド樹脂、または環状脂肪族鎖を有するポリイミド樹脂である［１］〜［２］記載の熱可塑性材料組成物。
【００１８】
［４］ ［１］〜［３］記載の熱可塑性材料組成物を含んで構成される光学部品。
【００１９】
［５］ 光学部品が、レンズであることを特徴とする［４］記載の光学部品。
【００２０】
［６］ レンズが、眼鏡レンズ、光学機器用レンズ、オプトエレクトロニクス用レンズ、レーザー用レンズ、ＣＤピックアップ用レンズ、自動車用ランプレンズまたはＯＨＰ用レンズであることを特徴とする［５］記載のレンズ。
【００２１】
［７］ 光学部品が、光ファイバーであることを特徴とする［４］記載の光学部品。
【００２２】
［８］ 光学部品が、光導波路であることを特徴とする［４］記載の光学部品。
【００２３】
［９］ 光学部品が、光フィルターであることを特徴とする［４］記載の光学部品。
【００２４】
［１０］ 光学部品が、光学用接着剤であることを特徴とする［４］記載の光学部品。
【００２５】
【発明の実施の形態】
本発明の熱可塑性材料組成物は、数式（Ａ）及び（Ｂ）で示される屈折率ｎ₁及びアッベ数ν₁を有する熱可塑性樹脂１００重量部と、平均粒子直径ｄ_iが数式（Ｃ）で示され、化学式（１）で示される化合物により表面修飾が施された、表面修飾チタン酸化物微粒子１〜２００重量部とから構成される、数式（Ｄ）、（Ｅ）及び（Ｆ）で示される屈折率ｎ₂及びアッベ数ν₂を有し、かつ数式（Ｇ）で示される黄色度Ｙを有する熱可塑性材料組成物である。
【００２６】
１．４５≦ｎ₁≦１．６５ （Ａ）
ν₁≧１９５−１００ｎ₁ （Ｂ）
１ｎｍ≦ｄ_i≦２００ｎｍ （Ｃ）
１．４５＜ｎ₂≦１．８０ （Ｄ）
ν₂≧２００−１００ｎ₂ （Ｅ）
ｎ₂≧ｎ₁＋０．０１ （Ｆ）
−３≦Ｙ≦１０ （Ｇ）
Ｓｉ（ＯＲ₁）_X（Ｒ₂）_4-X （１）
【００２７】
【化３】

【００２８】
（但し化学式（１）において、Ｘは１〜４の整数であり、Ｒ１及びＲ２は、それぞれ独立に、化学式群（２）（化３）のいずれかから選ばれる１価の結合基を表す。なお、化学式（２）において、Ｙは１〜３０の整数、Ｚは０〜５の整数である。）
【００２９】
本発明において用いる熱可塑性樹脂は、数式（Ａ）及び（Ｂ）で示される屈折率ｎ₁及びアッベ数ν₁を有する熱可塑性樹脂である。屈折率ｎ₁及びアッベ数ν₁が、数式（Ａ）及び（Ｂ）で示される範囲を外れると、得られる熱可塑性材料組成物の屈折率ｎ₂及びアッベ数ν₂が、数式（Ｄ）、（Ｅ）及び（Ｆ）で示される範囲を外れる恐れがある。
【００３０】
本発明における屈折率（ｎ、ｎ₁、ｎ₂）とは、「季刊化学総説Ｎｏ．３９ 透明ポリマーの屈折率制御 日本化学会編、学会出版センター」に記載されているとおり、５８８ｎｍの波長における屈折率を示す。また本発明におけるアッベ数（ν、ν₁、ν₂）とは、「季刊化学総説Ｎｏ．３９ 透明ポリマーの屈折率制御日本化学会編、学会出版センター」に記載されているとおり、数式（Ｋ）で示される値である。但し数式（Ｋ）において、ｎｄ、ｎｆ、ｎｃはそれぞれ、５８８ｎｍ、４８６ｎｍ、６５６ｎｍにおける屈折率を示す。
【００３１】
ν＝（ｎｄ−１）／（ｎｆ−ｎｃ） （Ｋ）
【００３２】
本発明において用いる熱可塑性樹脂は、ガラス転移温度が８０℃以上４００℃以下であることが好ましく、１００℃以上３００℃以下であることがより好ましい。ガラス転移温度が８０℃未満であると、十分な耐熱性が得られない恐れがあり、またガラス転移温度が４００℃を超えると、成形加工する際に高温が必要となり、プロセス的に不利となるばかりでなく、材料が変色する等の問題が生じる恐れがある。
【００３３】
本発明において用いる熱可塑性樹脂は、光線透過率が７０％以上であることが好ましく、８０％以上であることがより好ましい。光線透過率が７０％未満であると、得られる熱可塑性材料組成物の光線透過率が７０％未満となる恐れがある。なお本発明における光線透過率とは、樹脂を加熱成形して厚さ３．２ｍｍの基板を作成し、ＡＳＴＭ Ｄ１００３に従って得られる値である。
【００３４】
本発明において用いる熱可塑性樹脂は、密度が２．０ｇ／ｃｍ³以下であることが好ましく、１．５ｇ／ｃｍ³以下であることがより好ましい。密度が２．０ｇ／ｃｍ³を超えると、得られる熱可塑性材料組成物の密度が２．０ｇ／ｃｍ³を超える恐れがある。
【００３５】
本発明において用いる熱可塑性樹脂として、溶融成形が可能な熱可塑性樹脂を用いることにより、本発明の熱可塑性材料組成物として、溶融成形が可能な熱可塑性材料組成物を得ることができる。
【００３６】
本発明における熱可塑性樹脂とは、ある温度範囲で加熱により軟化し、その軟化した状態で成形や押し出し等により製品加工ができることを示す。具体的には、例えば、加熱状態でプレスすることにより、０．１〜５０００μｍ程度の厚さを有するフィルムを成形できる性能を有する。また、本発明における溶融成形が可能な熱可塑性樹脂とは、熱的に安定な温度域で溶融成形が可能な溶融粘度を有しており、押し出しや射出等により成形加工ができることを示す。具体的には、例えば、空気中において加熱により樹脂の５重量％が減少する温度、すなわち５％重量減少温度に比べ、１〜１００パスカル・秒程度の溶融粘度を有する温度が３０℃以上、好ましくは５０℃以上低いことをいう。溶融成形性を有することにより、押し出し成形、射出成形、真空成形、ブロー成形、圧縮成型、ブロー成形、カレンダー成形、積層成形等が可能となり、ディスク、ファイバー等の様々な成形体を得ることができる。
【００３７】
本発明において用いる熱可塑性樹脂は、上述の光学特性（屈折率及びアッベ数）を満たすものであり、より好ましくはさらに、上述のガラス転移温度、光線透過率、密度、及び樹脂加工性（熱可塑性及び／または溶融成形性）をも満たす樹脂である。例えば、アクリル樹脂、環状脂肪族鎖を有するポリカーボネート樹脂、環状脂肪族鎖を有するポリエステル樹脂、環状脂肪族鎖を有するポリエーテル樹脂、環状脂肪族鎖を有するポリアミド樹脂、または環状脂肪族鎖を有するポリイミド樹脂等が挙げられる。より具体的には、例えば、第１表（表１）記載の化学式（３）〜（１６）で示される構造骨格を有する樹脂を挙げることができるが、これらに限定されるものではない。
【００３８】
【表１】

【００３９】
また、環状脂肪族鎖の一部を芳香環に置き換えた共重合体を用いることもでき、硫黄を結合鎖などに一部含んだチオカーボネートやチオエステル、チオエーテル等も好適に用いることができる。なお、芳香環や硫黄はアッベ数の低減を伴うことがあるので、本発明で提示している熱可塑性樹脂の光学特性を外れない範囲で選択することが重要である。
【００４０】
本発明において用いる熱可塑性樹脂の製造方法は、特に限定されるものではなく、公知のいずれの方法を用いることもできる。また樹脂に含まれる不純物の種類及び量についても、特に制限されるものではないが、用途によっては不純物が本発明の効果を損なう恐れがあるので、総不純物量は１重量％以下、特にナトリウムや塩素などのイオン性不純物は０．５重量％以下であることが望ましい。
【００４１】
本発明において用いる熱可塑性樹脂の分子量は、特に限定されるものではなく、用途や加工方法に応じ、任意の分子量とすることができるが、成形加工性を勘案すると、樹脂を０．５ｇ／１００ミリリットルの濃度で溶解可能な溶剤に溶解した後の３５℃で測定した対数粘度の値が、０．１〜３．０デシリットル／ｇであることが好ましい。
【００４２】
また、着色の抑制や溶融成形における流動性の改善などを目的として、メタノールやエタノールなどのモノアルコール類、フェノールやターシャリーブチルフェノールといった芳香族モノヒドロキシ化合物などの末端封止用化合物を併用してもよい。
【００４３】
本発明の熱可塑性樹脂は、構成単位の繰り返しに特に制限はなく、交互構造、ランダム構造、ブロック構造等のいずれの場合でも良い。また、通常用いられる分子形状は線状であるが、分岐している形状を用いても良い。また、グラフト状でも良い。
【００４４】
本発明において用いる表面修飾チタン酸化物微粒子は、化学式（１）で示される化合物により表面修飾が施されたチタン酸化物微粒子である。
【００４５】
Ｓｉ（ＯＲ₁）_X（Ｒ₂）_4-X （１）
【００４６】
【化４】

【００４７】
（但し化学式（１）において、Ｘは１〜４の整数であり、Ｒ１及びＲ２は、それぞれ独立に、化学式群（２）（化４）のいずれかから選ばれる１価の結合基を表す。なお、化学式（２）において、Ｙは１〜３０の整数、Ｚは０〜５の整数である。）
【００４８】
本発明において用いる表面修飾チタン酸化物微粒子の合成方法は、特に限定されるものではなく、公知のいずれの方法も用いることができるが、チタン酸化物微粒子を合成した後に、化学式（１）で示される化合物を用いて、その表面を修飾する方法が好適に用いられる。チタン酸化物微粒子の合成方法は、特に限定されるものではなく、公知のいずれの方法も用いることができる。例えば、ハロゲン化チタンやアルコキシチタンを原料に用い、水を含有する反応系において加水分解することにより、所望のチタン酸化物微粒子を得ることができる。この際、微粒子の安定化のために有機酸や有機アミンなどを併用する方法も用いられる。より具体的には、例えば、ジャーナル・オブ・ケミカルエンジニアリング・オブ・ジャパン第１巻１号２１−２８頁（１９９８年）に記載された公知の方法を用いることができる。これらの方法に従えば、例えば、平均粒子直径５ｎｍの酸化チタンはチタニウムテトライソプロポキサイドや四塩化チタンを原料として、適当な溶媒中で加水分解させる際に適当な添加剤を共存させることにより容易に製造することができる。また、ハロゲン化チタンやアルコキシチタンなどのチタン化合物を、火炎中で酸化分解させてチタン酸化物微粒子を得る方法も用いることができる。チタン酸化物の構造も特に限定されるものではなく、ルチル型結晶構造、アナターゼ型結晶構造、また非結晶構造（アモルファス）などのいずれをも用いることができる。なお、本発明の効果を効率よく発現させるためには、ルチル型結晶構造、アナターゼ型結晶構造、またはその混合構造を用いることが好ましい。チタン酸化物微粒子を化学式（１）で示される化合物を用いて表面修飾する方法は、特に限定されるものではなく、公知のいずれの方法も用いることができる。例えば、水が存在する条件下で、化学式（１）で示される化合物を加水分解させ、チタン酸化物微粒子の表面に修飾する方法が挙げられる。この方法では、酸またはアルカリなどの触媒が好適に用いられ、チタン酸化物微粒子表面の水酸基と、化学式（１）で示される化合物が加水分解して生じる水酸基とが、脱水して結合を形成することが一般に考えられている。
【００４９】
本発明において用いる表面修飾チタン酸化物微粒子は、上述の化学式（１）で示される化合物により表面修飾が施される。
具体的には、例えば、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトラフェノキシシラン、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、メチルトリエトキシシラン、メチルトリフェノキシシラン、エチルトリエトキシシラン、フェニルトリメトキシシラン、３−メチルフェニルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジフェノキシシラン、トリメチルメトキシシラン、トリエチルエトキシシラン、トリフェニルメトキシシラン、トリフェニルフェノキシシランなどが挙げられる。
【００５０】
これらの化合物は、反応速度などの特性が異なり、表面修飾の条件などに適した化合物を用いることができる。また、１種類のみを用いても、複数種類を併用してもよい。さらに、用いる化合物によって得られる表面修飾チタン酸化物微粒子の性状は異なることがあり、材料組成物を得るにあたって用いる熱可塑性樹脂との親和性を、表面修飾する際に用いる化合物を選ぶことによって図ることも可能である。表面修飾の割合は特に限定されるものではないが、表面修飾後の微粒子に対して、チタン酸化物の割合が３０〜９９重量％であることが好ましく、６０〜９８重量％であることがより好ましい。
【００５１】
本発明において用いる表面修飾チタン酸化物微粒子の平均粒子直径ｄ_iは、数式（Ｃ）で示される平均粒子直径ｄ_iである。平均粒子直径ｄ_iが１ｎｍ未満であると、得られる熱可塑性材料組成物の屈折率ｎ₂及びアッベ数ν₂が、数式（Ｄ）、（Ｅ）及び（Ｆ）で示される範囲を外れる恐れがある。また平均粒子直径ｄ_iが２００ｎｍを超えると、得られる熱可塑性材料組成物が濁るなどして透明性が低下し、光線透過率が７０％未満となる恐れがある。
【００５２】
１ｎｍ≦ｄ_i≦２００ｎｍ （Ｃ）
１．４５＜ｎ₂≦１．８０ （Ｄ）
ν₂≧２００−１００ｎ₂ （Ｅ）
ｎ₂≧ｎ₁＋０．０１ （Ｆ）
【００５３】
本発明において用いる表面修飾チタン酸化物微粒子の形状は、特に限定されるものではないが、好適には球状の微粒子が用いられる。また、粒子径の分布に関しても特に制限されるものではないが、本発明の効果をより効率よく発現させるためには、広範な分布を有するものよりも、比較的狭い分布を持つものが好適に用いられる。
【００５４】
本発明において、前述の化学式（１）で示される化合物を用いて表面修飾が施された、表面修飾チタン酸化物微粒子を用いることが重要である。表面修飾が施されていないチタン酸化物微粒子を用いると、材料組成物の無色性が低減し、黄色度Ｙが数式（Ｇ）で示される範囲を外れる恐れがある。なお、本発明における黄色度とは、厚さ３．２ｍｍの基板をＪＩＳ Ｋ７１０３に従って透過法にて測定した値を示す。
【００５５】
−３≦Ｙ≦１０ （Ｇ）
【００５６】
本発明における熱可塑性材料組成物は、数式（Ａ）及び（Ｂ）で示される屈折率ｎ₁及びアッベ数ν₁を有する熱可塑性樹脂１００重量部と、平均粒子直径ｄ_iが数式（Ｃ）で示され、化学式（１）で示される化合物により表面修飾が施された、表面修飾チタン酸化物微粒子１〜２００重量部とから成り、より好適には、熱可塑性樹脂１００重量部と表面修飾チタン酸化物微粒子５〜１５０重量部から成る。
【００５７】
但し化学式（１）において、Ｘは１〜４の整数であり、Ｒ１及びＲ２は、それぞれ独立に、化学式群（２）（化５）のいずれかから選ばれる１価の結合基を表す。なお、化学式（２）において、Ｙは１〜３０の整数、Ｚは０〜５の整数である。
熱可塑性樹脂１００重量部に対して表面修飾チタン酸化物微粒子が１重量部未満であると、得られる熱可塑性材料組成物の屈折率ｎ₂及びアッベ数ν₂が、数式（Ｄ）、（Ｅ）及び（Ｆ）で示される範囲を外れる恐れがある。また、表面修飾チタン酸化物微粒子が２００重量部を超えると、得られる熱可塑性材料組成物の屈折率ｎ₂及びアッベ数ν₂が、数式（Ｄ）、（Ｅ）及び（Ｆ）で示される範囲を外れる恐れがあるばかりでなく、材料組成物の熱可塑性という特性が損なわれる恐れがある。
【００５８】
１．４５≦ｎ₁≦１．６５ （Ａ）
ν₁≧１９５−１００ｎ₁ （Ｂ）
１ｎｍ≦ｄ_i≦２００ｎｍ （Ｃ）
１．４５＜ｎ₂≦１．８０ （Ｄ）
ν₂≧２００−１００ｎ₂ （Ｅ）
ｎ₂≧ｎ₁＋０．０１ （Ｆ）
Ｓｉ（ＯＲ₁）_X（Ｒ₂）_4-X （１）
【００５９】
【化５】

【００６０】
本発明における熱可塑性材料組成物は、熱可塑性樹脂と表面修飾チタン酸化物微粒子から成るが、その作成方法は特に限定されるものではない。すなわち、熱可塑性樹脂と表面修飾チタン酸化物微粒子をそれぞれ独立して作成し、その後に両者を混合させる方法、予め作成した表面修飾チタン酸化物微粒子が存在する条件で熱可塑性樹脂を作成する方法、予め作成した熱可塑性樹脂が存在する条件で表面修飾チタン酸化物微粒子を作成する方法、熱可塑性樹脂と表面修飾チタン酸化物微粒子の両者を同時に作成させる方法など、いずれの方法をも採用できる。具体的には、例えば、熱可塑性樹脂が溶解した溶液と、表面修飾チタン酸化物微粒子が均一に分散した分散液の二液を均一に混合し、熱可塑性樹脂に対して溶解性が乏しい溶液中に打ち合わせることにより、目的とする材料組成物を得る方法を好適に挙げることができるが、これに限定されるものではない。
【００６１】
本発明における熱可塑性材料組成物において、熱可塑性樹脂と表面修飾チタン酸化物微粒子の混合の程度は特に限定されるものではないが、本発明の効果をより効率よく発現させるためには、均一に混合していることが望ましい。混合の程度が不十分の場合には、特に屈折率やアッベ数、光線透過率などの光学特性に影響を及ぼすことが懸念され、また熱可塑性や溶融成形性などの樹脂加工性にも悪影響する恐れがある。混合の程度は、その作成方法に影響されることが考えられ、用いる熱可塑性樹脂及び表面修飾チタン酸化物微粒子の特性を十分に勘案して、方法を選択することが重要である。熱可塑性樹脂と表面修飾チタン酸化物微粒子の両者がより均一に混合するために、熱可塑性樹脂と表面修飾チタン酸化物微粒子を直接結合させる方法等も、本発明において好適に用いることができる。
【００６２】
本発明の熱可塑性材料組成物は、数式（Ｄ）、（Ｅ）及び（Ｆ）で示される屈折率ｎ₂及びアッベ数ν₂を有し、かつ数式（Ｇ）で示される黄色度Ｙを有する光学的に優れた材料組成物であり、さらには熱可塑性及び／または射出成形性を有するために、成形加工性に非常に優れた材料組成物である。この優れた光学特性と成形加工性を併せ持った材料は、これまでに開示されている材料では達成することができなかった特性であり、特定の熱可塑性樹脂と特定のチタン酸化物微粒子から成ることが、この特性に寄与していることが考えられる。
【００６３】
１．４５＜ｎ₂≦１．８０ （Ｄ）
ν₂≧２００−１００ｎ₂ （Ｅ）
ｎ₂≧ｎ₁＋０．０１ （Ｆ）
−３≦Ｙ≦１０ （Ｇ）
【００６４】
本発明の熱可塑性材料組成物は、▲１▼数式（Ｈ）及び（Ｊ）で表される屈折率ｎおよびアッベ数νを有する優れた光学特性、▲２▼黄色度１０以下、▲３▼ガラス転移温度８０℃以上の耐熱性、▲４▼光線透過率７０％以上の透明性、▲５▼密度２．０ｇ／ｃｍ³以下の軽量性、及び▲６▼熱可塑性及び／または溶融成形性を併せ持ち、これらの優れた性能を損なうことなく、さらに屈折率ｎを数式（Ｈ）で表されるの範囲で任意に調節ができる。屈折率の調節は、用いる熱可塑性樹脂とチタン酸化物微粒子の構成比を調節すること等により、精度よく調節することができる。
【００６５】
１．４５＜ｎ≦１．８０ （Ｈ）
ν≧２００−１００ｎ （Ｊ）
【００６６】
本発明の熱可塑性材料組成物は、高屈折性、低分散性（高いアッベ数）、耐熱性、光線透過性、軽量性、成形加工性を併せ持ち、さらには屈折率を任意に調節できる、光学特性に優れた熱可塑性材料組成物であり、光学用部品に好適に使用できる。
【００６７】
本発明の熱可塑性材料組成物を含んで構成される光学部品に特に制限はなく、例えば、部品の一部あるいは全部に使用することができ、高屈折性と低分散性が必要とされる部品、高い透明性を必要とされる部品、あるいは透明性と高屈折性を必要とされる部品等が挙げられる。また、任意に屈折率を調節できるため、例えば光ファイバーや光導波路、一部のレンズのように、異なる屈折率を併用したり、屈折率に分布を必要とする光学用部品にも好適に用いることができる。より具体的には、例えば、レンズ（例えば、眼鏡レンズ、光学機器用レンズ、オプトエレクトロニクス用レンズ、レーザー用レンズ、ＣＤピックアップ用レンズ、自動車用ランプレンズ、ＯＨＰ用レンズ等）、光ファイバー、光導波路、光フィルター、光学用接着剤、光ディスク基盤、ディスプレー基盤、コーティング材、プリズム等が挙げられる。
【００６８】
本発明の熱可塑性材料組成物は、原料に溶融成形可能な熱可塑性樹脂を用いることにより、溶融成形性を有するようになるため、従来用いられている熱硬化性樹脂に比べ、これら上述の光学部品を効率よく製造することができる。
【００６９】
【実施例】
以下、本発明を実施例により詳細に説明する。尚、実施例中の熱可塑性樹脂、チタン酸化物微粒子、熱可塑性材料組成物等の物性及び光学特性は以下の方法により測定した。
▲１▼対数粘度η：熱可塑性樹脂を、その樹脂が溶解可能な溶媒（例えばクロロホルム、１−メチル−２−ピロリドン、ジメチルホルムアミド、オルト−ジクロロベンゼン、クレゾール等）に、０．５ｇ／１００ミリリットルの濃度で溶解した後、３５℃において測定した。
▲２▼屈折率ｎ及びアッベ数ν：通常の熱プレス機を用いて厚さ約０．１〜１ｍｍの板上サンプルを作成し、アッベ屈折計（アタゴ社ＤＲ−Ｍ２）により測定した。
▲３▼ガラス転移温度Ｔｇ：ＤＳＣ（島津ＤＴ−４０シリーズ，ＤＳＣ−４１Ｍ）により測定した。
▲４▼光線透過率：材料組成物を加熱成形して厚さ３．２ｍｍの基板を作成し、ＡＳＴＭ Ｄ１００３に従って測定した。
▲５▼５％重量減少温度Ｔｄ₅：空気中でＤＴＡ−ＴＧ（島津ＤＴ−４０シリーズ、ＤＴＧ−４０Ｍ）により測定した。
▲６▼溶融粘度：高化式フローテスター（島津ＣＦＴ−５００）で直径０．１ｃｍ、長さ１ｃｍのオリフィスを用いて溶融粘度を測定した。所定の温度で５分間保った後、１０万ヘクトパスカルの圧力で押し出した。
▲７▼黄色度：材料組成物を加熱成形して厚さ３．２ｍｍの基板を作成し、ＪＩＳ Ｋ７１０３に従って透過法にて測定した。
【００７０】
【合成例１】
第２表（表２）に示した化学式（１７）の繰り返し構造単位を有するポリカーボネート樹脂を溶液重合法にて合成した。窒素導入ライン、攪拌機、温度計を備えた重合容器に、４，４’−ビシクロヘキサノール１９．８ｇ（０．１ｍｏｌ）、及びピリジン２００ｇを仕込み、撹拌して完全に溶解させた。溶液を温水浴で４０℃に保ち、溶液を激しく撹拌させながら、ホスゲンを約０．２５ｇ／分の速度で吹き込んだ。約２５分後にピリジン塩酸塩が析出し始め、さらに約１５分後、溶液の粘性が徐々に増し始めた。さらに１０分ホスゲンを吹き込んだ後に供給を止め、そのまま１時間激しく撹拌を続けた。その後、その状態で上部よりメタノール２００ｇとイオン交換水１００ｇの混合液３００ｇを５分かけて導入し、析出したポリカーボネート樹脂を濾別した。ピリジン塩酸塩などの残留物を除くため、得られたポリカーボネート樹脂をメタノール６００ｇとイオン交換水３００ｇの混合液９００ｇに懸濁させ、ホモミキサーを用いて激しく撹拌し、再度濾別した。この操作を３回繰り返した後、メタノール９００ｇで洗浄し、８０℃で２時間真空乾燥させて樹脂２２．０ｇを得た。
得られたポリカーボネート樹脂について、Ｃ、Ｈの元素分析を行ったところ、その含有量はそれぞれ７０．１ｗｔ％、８．８ｗｔ％であり、それぞれの理論値６９．６ｗｔ％、８．９ｗｔ％とほぼ同等であり、化学式（１７）の繰り返し構造単位を有するポリカーボネート樹脂であることを確認した。
得られたポリカーボネート樹脂について、上記の方法に従って対数粘度η、屈折率ｎ、アッベ数ν、ガラス転移温度Ｔｇ、及び光線透過率、密度ρ、５％重量減少温度Ｔｄ₅、及び溶融粘度の評価を行い、結果を表２に示した。この樹脂は、５％重量減少温度に比べて５０℃以上の十分に低い１８０℃において、９パスカル・秒という、溶融成形を行うのに適した溶融粘度を有しており、溶融成形が可能な熱可塑性樹脂であることがわかる。結果からわかるように、このポリカーボネート樹脂は、数式（Ａ）及び（Ｂ）で示される屈折率ｎ₁及びアッベ数ν₁を有する溶融成形可能な熱可塑性樹脂であり、本発明の条件に適した樹脂である。
【００７１】
１．４５≦ｎ₁≦１．６５ （Ａ）
ν₁≧１９５−１００ｎ₁ （Ｂ）
【００７２】
【合成例２】
４，４’−ビシクロヘキサノール１９．８ｇ（０．１ｍｏｌ）の代わりに２，２−ビス（４−ヒドロキシシクロヘキシル）プロパン２４．０ｇ（０．１ｍｏｌ）に変えた以外は、合成例１と同様にして、表２に示した化学式（１８）の繰り返し構造単位を有するポリカーボネート樹脂を溶液重合法にて合成し、樹脂２６．２ｇを得た。得られた樹脂のＣ、Ｈの元素分析から、化学式（１８）の繰り返し構造単位を有するポリカーボネート樹脂であることを確認した。
合成例１と同様にして各特性の評価を行い、結果を第２表（表２）に示した。結果からわかるように、このポリカーボネート樹脂は本発明の条件に適した樹脂である。
【００７３】
【合成例３】
第２表（表２）に示した化学式（１９）の繰り返し構造単位を有するポリエステル樹脂を、酸クロリド法にて合成した。窒素導入ライン、攪拌機、温度計を備えた重合容器に、４，４’−ビシクロヘキサノール１９．８ｇ（０．１ｍｏｌ）、１，４−シクロヘキサンジカルボン酸クロリド２０．９ｇ（０．１ｍｏｌ）、及びニトロベンゼン１００ｇを仕込んだ。窒素雰囲気下で撹拌しながらゆっくり加熱し、２時間で１４５℃まで昇温した。この温度で６時間保持して重合させた後、ニトロベンゼンを減圧下で留去した。残ったポリマーを更にこの温度にて減圧下で２時間乾燥させ、樹脂３２．４ｇを得た。得られた樹脂のＣ、Ｈの元素分析から、化学式（１９）の繰り返し構造単位を有するポリエステル樹脂であることを確認した。
合成例１と同様にして各特性の評価を行い、結果を第２表（表２）に示した。結果からわかるように、このポリエステル樹脂は本発明の条件に適した樹脂である。
【００７４】
【合成例４】
４，４’−ビシクロヘキサノール１９．８ｇ（０．１ｍｏｌ）の代わりに２，２−ビス（４−ヒドロキシシクロヘキシル）プロパン２４．０ｇ（０．１ｍｏｌ）に変えた以外は、合成例３と同様にして、第２表（表２）に示した化学式（２０）の繰り返し構造単位を有するポリエステル樹脂を酸クロリド法にて合成し、樹脂３６．４ｇを得た。得られた樹脂のＣ、Ｈの元素分析から、化学式（２０）の繰り返し構造単位を有するポリエステル樹脂であることを確認した。
合成例１と同様にして各特性の評価を行い、結果を第２表（表２）に示した。結果からわかるように、このポリエステル樹脂は本発明の条件に適した樹脂である。
【００７５】
【合成例５】
第２表（表２）に示した化学式（２１）の繰り返し構造単位を有するポリエーテル樹脂を、ポリマー・マテリアル・サイエンス・エンジニアリング第６０巻１７０頁（１９８９年）に従って合成した。得られた樹脂のＣ、Ｈの元素分析から、化学式（２１）の繰り返し構造単位を有するポリエーテル樹脂であることを確認した。
合成例１と同様にして各特性の評価を行い、結果を第２表（表２）に示した。結果からわかるように、このポリエーテル樹脂は本発明の条件に適した樹脂である。
【００７６】
【合成例６】
第２表（表２）に示した化学式（２２）の繰り返し構造単位を有するポリアミド樹脂を、酸クロリド法にて合成した。窒素導入ライン、攪拌機、温度計を備えた重合容器に、１，４−シクロヘキサンジアミン１１．４ｇ（０．１ｍｏｌ）及びＮ，Ｎ−ジメチルアセトアミド２００ｇを仕込み、氷冷しながら撹拌した。１，４−シクロヘキサンジアミンが溶解した後、１，４−シクロヘキサンジカルボン酸クロリド２０．９ｇ（０．１ｍｏｌ）を徐々に加え、その後３時間撹拌を続けた。その後、その状態で上部よりメタノール２００ｇとイオン交換水１００ｇの混合液３００ｇを５分かけて導入し、析出した樹脂を濾別した。ピリジン塩酸塩などの残留物を除くため、得られた樹脂をメタノール６００ｇとイオン交換水３００ｇの混合液９００ｇに懸濁させ、ホモミキサーを用いて激しく撹拌し、再度濾別した。この操作を３回繰り返した後、メタノール９００ｇで洗浄し、８０℃で２時間真空乾燥させて樹脂２４．０ｇを得た。得られた樹脂のＣ、Ｈの元素分析から、化学式（２２）の繰り返し構造単位を有するポリアミド樹脂であることを確認した。
合成例１と同様にして各特性の評価を行い、結果を第２表（表２）に示した。結果からわかるように、このポリアミド樹脂は本発明の条件に適した樹脂である。
【００７７】
【合成例７】
４，４’−ビシクロヘキサノール１９．８ｇ（０．１ｍｏｌ）の代わりに２，２−ビス（４−ヒドロキシシクロヘキシル）プロパン１２．０ｇ（０．０５ｍｏｌ）とビスフェノールＡ１１．４ｇ（０．０５ｍｏｌ）に変えた以外は、合成例１と同様にして、第２表（表２）に示した化学式（２５）の繰り返し構造単位を有するポリカーボネート樹脂を溶液重合法にて合成し、樹脂２３．２ｇを得た。得られた樹脂のＣ、Ｈの元素分析から、化学式（２５）の繰り返し構造単位を有するポリカーボネート樹脂であることを確認した。
合成例１と同様にして各特性の評価を行い、結果を第２表（表２）に示した。結果からわかるように、このポリカーボネート樹脂は本発明の条件に適していない樹脂である。
【００７８】
【合成例８】
４，４’−ビシクロヘキサノール１９．８ｇ（０．１ｍｏｌ）の代わりに１，４−シクロヘキサンジオール１１．６ｇ（０．１ｍｏｌ）、１，４−シクロヘキサンジカルボン酸クロリド２０．９ｇ（０．１ｍｏｌ）の代わりにテレフタル酸クロリド２０．３ｇ（０．１ｍｏｌ）に変えた以外は、合成例３と同様にして、第２表（表２）に示した化学式（２６）の繰り返し構造単位を有するポリエステル樹脂を酸クロリド法にて合成し、樹脂２３．８ｇを得た。
得られた樹脂のＣ、Ｈの元素分析から、化学式（２６）の繰り返し構造単位を有するポリエステル樹脂であることを確認した。
合成例１と同様にして各特性の評価を行い、結果を第２表（表２）に示した。結果からわかるように、このポリエステル樹脂は本発明の条件に適していない樹脂である。
【００７９】
【表２】

【００８０】
【合成例９】
四塩化チタンを原料に、チタン酸化物微粒子の合成を行った。まず、ジャパニーズ・ジャーナル・オブ・アプライド・フィジクス第３７巻４６０３−４６０８頁（１９９８年）に記載の方法に準じて、中間物であるＴｉＯＣｌ₂の合成を行った。四塩化チタン２５．０ｇ（０．１３２ｍｏｌ）を窒素ボックス内で三口フラスコに装入し、メタノール・氷浴で−５℃程度に冷却した。撹拌を行いながら、ここに蒸留水１４．３ｇ（０．７９２ｍｏｌ）を、３０分かけてゆっくり滴下した。最終的に黄色い透明な粘性のある液体が得られた。この液体を１２５ｇの蒸留水で希釈し、ＴｉＯＣｌ₂の水溶液を得た。次いで、蒸留水１４５０ｇ、エタノール１６５０ｇ及びプロピオン酸５．３１ｇ（０．０７２ｍｏｌ）から成り、５０℃に維持された混合液に、ＴｉＯＣｌ₂水溶液を撹拌しながら一気に投入した。さらに５０℃にて撹拌を続けると、数十分で薄く白濁し始めた。この条件で６時間熟成した後、１００００ｒｐｍで２分間遠心分離を行い、得られた白色のゲル状物を酢酸エチルに懸濁させ、さらに同条件で遠心分離を行い、白色の微粒粉末１０．０ｇを得た。この微粒粉末１０ｇを１−ブタノール２００ｇに白濁させ、超音波処理を３０分間行った後、１００℃において３０分間加熱した。得られた白濁液を、蒸留水２０００ｇ、メタノール２０００ｇおよび３５重量％塩酸水溶液２１ｇからなる混合液に添加し、透明な分散液を得た。この透明な分散液を５０℃で撹拌しながら、メタノール１００ｇにジメチルジメトキシシラン６ｇ添加した混合液を、６０分間かけて滴下し、その後同条件で２時間熟成した。得られた透明な分散液を、１００００ｒｐｍで２分間遠心分離を行い、得られた白色のゲル状物を酢酸エチルに懸濁させ、さらに同条件で遠心分離を行い、白色の微粒粉末１１．５ｇを得た。元素分析から、チタン酸化物の含有量は８７重量％であることを確認した。この粒子を電子顕微鏡観察し、粒子はほぼ真球状であり、平均粒子直径が５ｎｍであることを確認した。また赤外分光分析から、メチル基のＣ−Ｈ結合に起因する吸収ピークが見られ、表面修飾が施されていることが確認された。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この酸化物微粒子は本発明の条件に適した微粒子である。
【００８１】
【合成例１０】
ジメチルジメトキシシラン６ｇの代わりにトリメチルメトキシシラン６ｇを用いた以外は、合成例９と同様にして白色の微粒粉末１１．８ｇを得た。元素分析からチタン酸化物の含有量は８５重量％、電子顕微鏡観察から粒子はほぼ真球状で平均粒子直径が５ｎｍであること、赤外分光分析からメチル基のＣ−Ｈ結合に起因する吸収ピークが見られ、表面修飾が施されていることが確認された。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この酸化物微粒子は本発明の条件に適した微粒子である。
【００８２】
【合成例１１】
ジメチルジメトキシシラン６ｇの代わりにメチルメトリトキシシラン６ｇを用いた以外は、合成例９と同様にして白色の微粒粉末１１．０ｇを得た。元素分析からチタン酸化物の含有量は８９重量％、電子顕微鏡観察から粒子はほぼ真球状で平均粒子直径が５ｎｍであること、赤外分光分析からメチル基のＣ−Ｈ結合に起因する吸収ピークが見られ、表面修飾が施されていることが確認された。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この酸化物微粒子は本発明の条件に適した微粒子である。
【００８３】
【合成例１２】
ジメチルジメトキシシラン６ｇの代わりにジフェニルジメトキシシラン６ｇを用いた以外は、合成例９と同様にして白色の微粒粉末１１．９ｇを得た。元素分析からチタン酸化物の含有量は８５重量％、電子顕微鏡観察から粒子はほぼ真球状で平均粒子直径が５ｎｍであること、赤外分光分析から芳香環のＣ−Ｈ結合に起因する吸収ピークが見られ、表面修飾が施されていることが確認された。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この酸化物微粒子は本発明の条件に適した微粒子である。
【００８４】
【合成例１３】
合成例９と同様にしてチタン酸化物微粒子が得られた後、表面修飾を施さなかった。元素分析からチタン酸化物の含有量は９９．５重量％、電子顕微鏡観察から粒子はほぼ真球状で平均粒子直径が５ｎｍであることを確認した。また赤外分光分析から、いずれのＣ−Ｈ結合に起因する吸収ピークも見られないことが確認された。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この酸化物微粒子は本発明の条件に適していない微粒子である。
【００８５】
【合成例１４】
用いるプロピオン酸の量を、５．３１ｇ（０．０７２ｍｏｌ）から２６．６ｇ（０．３６ｍｏｌ）に変えた以外は、合成例９と同様にして合成を行い、白色の微粒粉末１１．９ｇを得た。元素分析からチタン酸化物の含有量は８５重量％、電子顕微鏡観察から粒子はほぼ真球状で平均粒子直径が２ｎｍであること、赤外分光分析からメチル基のＣ−Ｈ結合に起因する吸収ピークが見られ、表面修飾が施されていることが確認された。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この酸化物微粒子は本発明の条件に適した微粒子である。
【００８６】
【合成例１５】
用いるプロピオン酸の量を、５．３１ｇ（０．０７２ｍｏｌ）から０．０５３１ｇ（０．０００７２ｍｏｌ）に変えた以外は、合成例９と同様にして合成を行い、白色の微粒粉末１０．６ｇを得た。元素分析からチタン酸化物の含有量は８５重量％、電子顕微鏡観察から粒子はほぼ真球状で平均粒子直径が１５０ｎｍであること、赤外分光分析からメチル基のＣ−Ｈ結合に起因する吸収ピークが見られ、表面修飾が施されていることが確認された。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この酸化物微粒子は本発明の条件に適した微粒子である。
【００８７】
【合成例１６】
用いるプロピオン酸の量を、５．３１ｇ（０．０７２ｍｏｌ）から１０６．２ｇ（１．４４ｍｏｌ）に変えた以外は、合成例９と同様にして合成を行い、白色の微粒粉末１０．６ｇを得た。電子顕微鏡観察から粒子はほぼ真球状であるが、平均粒子直径が０．８ｎｍであることを確認した。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この二酸化チタン微粒子は本発明の条件に適していない無機微粒子である。
【００８８】
【合成例１７】
用いるプロピオン酸の量を、５．３１ｇ（０．０７２ｍｏｌ）から０．００５３１ｇ（０．００００７２ｍｏｌ）に変えた以外は、合成例９と同様にして合成を行い、白色の微粒粉末９．２ｇを得た。電子顕微鏡観察から粒子はほぼ真球状であるが、平均粒子直径が２５０ｎｍであることを確認した。微粒子の評価結果を第３表（表３）に示す。結果からわかるように、この二酸化チタン微粒子は本発明の条件に適していない無機微粒子である。
【００８９】
【表３】

【００９０】
【実施例１】
第３表（表３）記載の番号（Ｕ１）の酸化物微粒子０．３ｇを１−ブタノール１０ｇに懸濁させ、超音波処理を３０分行った後、１００℃にて３０分加熱した。得られる白濁液を、表２記載の番号（Ｐ１）の樹脂が１０重量％で溶解したクロロホルム溶液１０ｇに、撹拌しながら常温で５分かけて滴下した。得られた混合液は、ほんのり青白がかった無色透明な液であった。この液を、ホモジナイザーを用いてメタノールと蒸留水の等容量混合液中に析出させ、無機微粒子が樹脂中に混合した材料組成物を得た。この組成物を加熱成形して、厚さ３．２ｍｍの基板を作成したところ、この基板は無色透明であった。電子顕微鏡観察を行ったところ、無機微粒子が樹脂中に均一に分散していることを確認した。この材料組成物について、屈折率、アッベ数、ガラス転移温度、光線透過率、密度、５％重量減少温度、溶融粘度、及び黄色度を測定し、その結果を第４表（表４）に示した。結果からわかるように、この材料組成物は、数式（Ｄ）、（Ｅ）及び（Ｆ）で示される屈折率ｎ₂及びアッベ数ν₂を有し、かつ数式（Ｇ）で示される黄色度Ｙを有する溶融成形可能な可塑性材料組成物、すなわち光学特性および成形加工性に優れた材料組成物であり、さらにはガラス転移温度８０℃以上の耐熱性、光線透過率７０％以上の透明性、密度２．０ｇ／ｃｍ³以下の軽量性をも併せ持つものであることがわかる。従って、このような特性が要求される光学部品に適した材料組成物である。
【００９１】
１．４５＜ｎ₂≦１．８０ （Ｄ）
ν₂≧２００−１００ｎ₂ （Ｅ）
ｎ₂≧ｎ₁＋０．０１ （Ｆ）
−３≦Ｙ≦１０ （Ｇ）
【００９２】
【実施例２〜８】
用いる樹脂を、第２表（表２）記載の番号（Ｐ２）〜（Ｐ８）の樹脂に代えた以外は、実施例１と同様にして材料組成物を作成し、その物性測定結果を第４表（表４）に記した。いずれの実施例においても、得られる材料組成物は実施例１の材料組成物と同様な優れた特性を有しており、光学部品に適した材料組成物であることがわかる。
【００９３】
【比較例１〜２】
用いる樹脂を、第２表（表２）記載の番号（Ｐ９）〜（Ｐ１０）の樹脂に代えた以外は、実施例１と同様にして材料組成物を作成し、その物性測定結果を第４表（表４）に記した。本発明の条件範囲の樹脂を用いているため、得られた材料組成物は、数式（Ｅ）、（Ｆ）及び（Ｇ）で示される屈折率ｎ₂及びアッベ数ν₂を満たさない。
【００９４】
【実施例９〜１１】
用いる樹脂を、第２表（表２）記載の番号（Ｐ３）の樹脂に、また用いる酸化物微粒子を、第３表（表３）記載の番号（Ｕ２）〜（Ｕ４）代えた以外は、実施例１と同様にして材料組成物を作成し、その物性測定結果を第４表（表４）に記した。いずれの実施例においても、得られる材料組成物は実施例１の材料組成物と同様な優れた特性を有しており、光学部品に適した材料組成物であることがわかる。
【００９５】
【比較例３】
用いる樹脂を、第２表（表２）記載の番号（Ｐ３）の樹脂に、また用いる酸化物微粒子を、第３表（表３）記載の番号（Ｕ５）代えた以外は、実施例１と同様にして材料組成物を作成した。得られた組成物から作成された基板はうすく黄色く着色した透明な基板であり、黄色度が１２．０であった。
【００９６】
【実施例１２〜１３】
用いる樹脂を、第２表（表２）記載の番号（Ｐ３）の樹脂に代え、また用いる酸化物微粒子の量を代えた以外は、実施例１と同様にして材料組成物を作成し、その物性測定結果を第４表（表４）に記した。いずれの実施例においても、得られる材料組成物は実施例１の材料組成物と同様な優れた特性を有しており、光学部品に適した材料組成物であることがわかる。
【００９７】
【比較例４】
用いる樹脂を、第２表（表２）記載の番号（Ｐ３）の樹脂に代え、また用いる酸化物微粒子の量を代えた以外は、実施例１と同様にして材料組成物を作成し、その物性測定結果を表４に記した。酸化物微粒子の使用量が本発明の条件の範囲外であるため、光学特性の向上は図ることができず、得られた材料組成物は、数式（Ｇ）で示される屈折率ｎ₂を満たすものではない。
【００９８】
ｎ₂≧ｎ₁＋０．０１ （Ｇ）
【００９９】
【比較例５】
用いる樹脂を、第２表（表２）記載の番号（Ｐ３）の樹脂に代え、また用いる酸化物微粒子の量を代えた以外は、実施例１と同様にして材料組成物を作成した。しかし、得られた材料組成物は非常に脆く、熱プレス等でフィルムを作成することができなかった。すなわち、熱可塑性を有していない材料組成物であった。
【０１００】
【実施例１４〜１５】
用いる樹脂を、第２表（表２）記載の番号（Ｐ３）の樹脂に代え、また用いる酸化物微粒子を、第３表（表３）記載の番号（Ｕ６）〜（Ｕ７）代えた以外は、実施例１と同様にして材料組成物を作成し、その物性測定結果を第４表（表４）に記した。いずれの実施例においても、得られる材料組成物は実施例１の材料組成物と同様な優れた特性を有しており、光学部品に適した材料組成物であることがわかる。
【０１０１】
【比較例６】
用いる樹脂を、第２表（表２）記載の番号（Ｐ３）の樹脂に、また用いる無機微粒子を、第３表（表３）記載の番号（Ｕ８）代えた以外は、実施例１と同様にして材料組成物を作成した。得られた組成物から作成された基板は白濁しており、光線透過率が低いために屈折率及びアッベ数の測定ができなかった。電子顕微鏡観察から、無機微粒子が凝集した状態であった。
【０１０２】
【比較例７】
用いる樹脂を、第２表（表２）記載の番号（Ｐ３）の樹脂に、また用いる無機微粒子を、第３表（表３）記載の番号（Ｕ９）代えた以外は、実施例１と同様にして材料組成物を作成した。得られた組成物から作成された基板は白濁しており、光線透過率が低いために屈折率及びアッベ数の測定ができなかった。電子顕微鏡観察から、無機微粒子が凝集していることは観察されなかった。
【０１０３】
【表４】

【０１０４】
【発明の効果】
本発明の熱可塑性材料組成物、及びそれを含んで構成される光学部品は、▲１▼数式（Ｈ）及び（Ｊ）で表される屈折率ｎおよびアッベ数νを有する優れた光学特性、▲２▼黄色度１０以下、▲３▼ガラス転移温度８０℃以上の耐熱性、▲４▼光線透過率７０％以上の透明性、▲５▼密度２．０ｇ／ｃｍ³以下の軽量性、及び▲６▼熱可塑性及び／または溶融成形性を併せ持つ材料組成物、及びそれを含んで構成される光学部品であり、例えば、レンズ（例えば、眼鏡レンズ、光学機器用レンズ、オプトエレクトロニクス用レンズ、レーザー用レンズ、ＣＤピックアップ用レンズ、自動車用ランプレンズ、ＯＨＰ用レンズ等）、光ファイバー、光導波路、光フィルター、光学用接着剤、光ディスク基盤、ディスプレー基盤、コーティング材、プリズム等の用途に好適である。
１．４５＜ｎ≦１．８０ （Ｈ）
ν≧２００−１００ｎ （Ｊ）[0001]
[Industrial application fields]
The present invention relates to a thermoplastic material composition and an optical component comprising the same, and more specifically, is excellent in high refraction, low dispersibility (high Abbe number), heat resistance, transparency, and lightness. , Thermoplastic material compositions, and optical components comprising the same (for example, lenses (for example, spectacle lenses, optical instrument lenses, optoelectronic lenses, laser lenses, CD pickup lenses, automobiles) Lamp lenses, OHP lenses, etc.), optical fibers, optical waveguides, optical filters, optical adhesives, optical disk substrates, display substrates, coating materials, prisms, and the like.
[0002]
[Prior art]
In recent years, research on optoelectronics toward an advanced information society has been vigorously conducted, and research on optical materials has been actively conducted to realize this. The following properties are required as optical materials that support various developments in optoelectronics, such as optical communication, optical recording, optical processing, optical measurement, and optical computation. That is, high refractive properties, low dispersibility (that is, high Abbe number), heat resistance, transparency, colorlessness, cleanness, easy moldability, light weight, chemical resistance, solvent resistance, and the like.
[0003]
Until now, inorganic materials such as quartz and optical glass have been mainly used as optical materials. Although these inorganic materials have excellent optical characteristics and heat resistance, they have problems such as processability, cost, and high density. For example, the density of an optical glass having a refractive index of 1.70 is about 3.0 g / cm. ^Three And very big. In recent years, in order to meet these requirements, development of materials having excellent optical characteristics, workability, lightness, and the like has been promoted, and expectations for organic optical materials, particularly resin materials having thermoplasticity, are increasing. Thermoplastic resin material has many features such as light weight, excellent flexibility, no electrical induction, easy molding, etc. Optical fiber, optical waveguide, optical disk substrate, optical filter, lens Development for applications such as optical adhesives is being made.
[0004]
A typical thermoplastic resin material is polycarbonate resin, which is made from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) as a raw material, which is superior in transparency and lighter than glass. It is applied as an optical component in many fields because of its features such as excellent impact resistance and melt molding, which facilitates mass production. However, although the refractive index has a relatively high value of about 1.58, the Abbe number representing the degree of dispersibility of the refractive index is as low as 30, and the balance between the refractive index and the dispersion characteristics is poor. The present situation is that the use of resin is limited. For example, it is known that a spectacle lens, which is a representative example of optical components, should have an Abbe number of 40 or more in view of visual functions (Quarterly Chemical Review No. 39 Refractive Index Control of Transparent Polymers The Chemical Society of Japan Ed., Academic Publishing Center, etc.), it is difficult to obtain desired characteristics even if a polycarbonate resin made from bisphenol A is used as it is.
[0005]
Many attempts have been made so far to solve these problems. Polycarbonate resins (Japanese Patent Laid-Open No. 10-251500, etc.) having a specific structure comprising an oxygen-containing ring, aromatic and aliphatic resins have been introduced. Copolymerized polycarbonate resins (JP 2000-230044, etc.), polycarbonate resins having a specific aliphatic structure (JP 2000-63506, etc.) have been proposed. However, for example, when applied to a spectacle lens, there are few resins having an Abbe number of 40 or more, which is necessary for visual function, and most are about 30 to 38. Several resins having an Abbe number of 40 or more have been proposed, but the refractive index is at most about 1.56 and cannot be applied to applications where a high refractive index and a high Abbe number are desired. For example, in the case of a spectacle lens, a resin having a refractive index of 1.58 or more and an Abbe number of 40 or more is desired.
[0006]
Furthermore, there is a demand for the development of a material that uses a plurality of materials having different refractive indexes, such as an optical fiber, an optical waveguide, and some lenses, or has a distribution in the refractive index. In order to cope with these materials, it is indispensable to arbitrarily adjust the refractive index.
[0007]
On the other hand, development of thermosetting resins especially for eyeglass lenses has been actively conducted. Many resins have been put on the market so far, and many of them have very excellent optical properties with a high refractive index of 1.60 or more and an Abbe number of 40 or more. It has the feature that it is lighter than that (Quarterly Chemistry Review No. 39 Controlling the refractive index of transparent polymers, The Chemical Society of Japan, Japan Society for Publication Press, etc.). However, since all of these are thermoplastic resins, it generally takes a complicated process and a large amount of time of several tens of hours or more, which is a very big problem in terms of production efficiency. .
[0008]
Therefore, a material having high refractive property, low dispersibility (high Abbe number), colorlessness (low yellowness), heat resistance, transparency, and light weight, and further having thermoplasticity capable of arbitrarily controlling the refractive index, An optical component including the same has not yet been found, and its development has been eagerly desired.
[0009]
[Problems to be solved by the present invention]
In view of the above-mentioned problems of the prior art, the object of the present invention is: (1) excellent optical characteristics having a refractive index n and an Abbe number ν represented by the formulas (H) and (J), and (2) yellowness of 10 (3) Heat resistance of glass transition temperature of 80 ° C. or higher, (4) Transparency of light transmittance of 70% or higher, (5) Density of 2.0 g / cm ^Three An object of the present invention is to provide a material composition having the following light weight and (6) thermoplasticity and / or melt moldability, and an optical component comprising the material composition.
[0010]
1.45 <n ≦ 1.80 (H)
ν ≧ 200-100n (J)
[0011]
[Means for Solving the Problems]
As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have obtained from a thermoplastic resin having specific optical properties and titanium oxide fine particles having a specific average particle diameter subjected to surface modification. The resulting material composition has high refractive index, low dispersibility (high Abbe number), colorlessness (low yellowness), heat resistance, transparency, and light weight, and thermoplasticity that can arbitrarily control the refractive index. The optical component comprising the material composition has high refractive index, low dispersibility (high Abbe number), colorlessness (low yellowness), heat resistance, transparency, and lightness. The present invention was completed by finding out that it has excellent workability and moldability.
[0012]
That is, this invention is specified by the matter described in the following [1]-[10].
[1] Refractive index n expressed by mathematical formulas (A) and (B) ₁ And Abbe number ν ₁ 100 parts by weight of a thermoplastic resin having an average particle diameter d _i Is represented by Formula (C), and is composed of 1 to 200 parts by weight of surface-modified titanium oxide fine particles that have been surface-modified by the compound represented by Chemical Formula (1), Formulas (D) and (E) And the refractive index n shown in (F) ₂ And Abbe number ν ₂ And a thermoplastic material composition having a yellowness Y represented by the formula (G).
[0013]
1.45 ≦ n ₁ ≦ 1.65 (A)
ν ₁ ≧ 195-100n ₁ (B)
1 nm ≦ d _i ≦ 200nm (C)
1.45 <n ₂ ≦ 1.80 (D)
ν ₂ ≧ 200-100n ₂ (E)
n ₂ ≧ n ₁ +0.01 (F)
−3 ≦ Y ≦ 10 (G)
Si (OR ₁ ) _X (R ₂ ) _4-X (1)
[0014]
[Chemical formula 2]

[0015]
(However, in the chemical formula (1), X is an integer of 1 to 4, and R1 and R2 each independently represent a monovalent linking group selected from any one of the chemical formula group (2) and chemical formula 2). In chemical formula (2), Y is an integer of 1 to 30, and Z is an integer of 0 to 5.)
[0016]
[2] The thermoplastic material composition according to [1], wherein the thermoplastic resin is a melt-moldable thermoplastic resin, and the thermoplastic material composition is a melt-moldable thermoplastic material composition.
[0017]
[3] The thermoplastic resin is an acrylic resin, a cyclic olefin resin, a polycarbonate resin having a cyclic aliphatic chain, a polyester resin having a cyclic aliphatic chain, a polyether resin having a cyclic aliphatic chain, and a polyamide having a cyclic aliphatic chain. The thermoplastic material composition according to [1] to [2], which is a resin or a polyimide resin having a cyclic aliphatic chain.
[0018]
[4] An optical component comprising the thermoplastic material composition according to [1] to [3].
[0019]
[5] The optical component according to [4], wherein the optical component is a lens.
[0020]
[6] The lens according to [5], wherein the lens is a spectacle lens, an optical device lens, an optoelectronic lens, a laser lens, a CD pickup lens, an automobile lamp lens, or an OHP lens.
[0021]
[7] The optical component according to [4], wherein the optical component is an optical fiber.
[0022]
[8] The optical component according to [4], wherein the optical component is an optical waveguide.
[0023]
[9] The optical component according to [4], wherein the optical component is an optical filter.
[0024]
[10] The optical component according to [4], wherein the optical component is an optical adhesive.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The thermoplastic material composition of the present invention has a refractive index n represented by formulas (A) and (B). ₁ And Abbe number ν ₁ 100 parts by weight of a thermoplastic resin having an average particle diameter d _i Is represented by Formula (C), and is composed of 1 to 200 parts by weight of surface-modified titanium oxide fine particles that have been surface-modified by the compound represented by Chemical Formula (1), Formulas (D) and (E) And the refractive index n shown in (F) ₂ And Abbe number ν ₂ And a thermoplastic material composition having a yellowness Y represented by the formula (G).
[0026]
1.45 ≦ n ₁ ≦ 1.65 (A)
ν ₁ ≧ 195-100n ₁ (B)
1 nm ≦ d _i ≦ 200nm (C)
1.45 <n ₂ ≦ 1.80 (D)
ν ₂ ≧ 200-100n ₂ (E)
n ₂ ≧ n ₁ +0.01 (F)
−3 ≦ Y ≦ 10 (G)
Si (OR ₁ ) _X (R ₂ ) _4-X (1)
[0027]
[Chemical 3]

[0028]
(In the chemical formula (1), X is an integer of 1 to 4, and R1 and R2 each independently represent a monovalent linking group selected from any one of the chemical formula group (2) and chemical formula 3). In chemical formula (2), Y is an integer of 1 to 30, and Z is an integer of 0 to 5.)
[0029]
The thermoplastic resin used in the present invention has a refractive index n represented by the mathematical formulas (A) and (B). ₁ And Abbe number ν ₁ Is a thermoplastic resin. Refractive index n ₁ And Abbe number ν ₁ Is out of the range represented by the mathematical formulas (A) and (B), the refractive index n of the resulting thermoplastic material composition ₂ And Abbe number ν ₂ However, there is a risk of deviating from the range indicated by the mathematical formulas (D), (E), and (F).
[0030]
Refractive index (n, n ₁ , N ₂ ) Indicates the refractive index at a wavelength of 588 nm, as described in “Quarterly Chemical Review No. 39, Control of Refractive Index of Transparent Polymer, Edited by Chemical Society of Japan, Society Press”. The Abbe numbers (ν, ν) ₁ , Ν ₂ ) Is a value represented by the mathematical formula (K), as described in “Quarterly Chemical Review No. 39, Control of Refractive Index of Transparent Polymer, Edited by Chemical Society of Japan, Society Publishing Center”. However, in the formula (K), nd, nf, and nc indicate refractive indexes at 588 nm, 486 nm, and 656 nm, respectively.
[0031]
v = (nd-1) / (nf-nc) (K)
[0032]
The thermoplastic resin used in the present invention preferably has a glass transition temperature of 80 ° C. or higher and 400 ° C. or lower, and more preferably 100 ° C. or higher and 300 ° C. or lower. If the glass transition temperature is less than 80 ° C, sufficient heat resistance may not be obtained, and if the glass transition temperature exceeds 400 ° C, a high temperature is required for molding, which is disadvantageous in terms of process. In addition to this, problems such as discoloration of the material may occur.
[0033]
The thermoplastic resin used in the present invention preferably has a light transmittance of 70% or more, and more preferably 80% or more. If the light transmittance is less than 70%, the resulting thermoplastic material composition may have a light transmittance of less than 70%. The light transmittance in the present invention is a value obtained in accordance with ASTM D1003 by forming a substrate having a thickness of 3.2 mm by thermoforming a resin.
[0034]
The thermoplastic resin used in the present invention has a density of 2.0 g / cm. ^Three Or less, preferably 1.5 g / cm ^Three The following is more preferable. Density is 2.0g / cm ^Three Exceeds the density of the resulting thermoplastic material composition is 2.0 g / cm ^Three There is a risk of exceeding.
[0035]
By using a thermoplastic resin capable of melt molding as the thermoplastic resin used in the present invention, a thermoplastic material composition capable of melt molding can be obtained as the thermoplastic material composition of the present invention.
[0036]
The thermoplastic resin in the present invention indicates that it can be softened by heating in a certain temperature range, and product processing can be performed by molding or extrusion in the softened state. Specifically, for example, it has a performance capable of forming a film having a thickness of about 0.1 to 5000 μm by pressing in a heated state. In addition, the thermoplastic resin capable of melt molding in the present invention has a melt viscosity capable of melt molding in a thermally stable temperature range, and indicates that molding can be performed by extrusion or injection. Specifically, for example, the temperature at which 5% by weight of the resin is reduced by heating in air, that is, the temperature having a melt viscosity of about 1 to 100 Pascal / second is 30 ° C. or higher, preferably 5% by weight. Means lower by 50 ° C. or more. By having melt moldability, extrusion molding, injection molding, vacuum molding, blow molding, compression molding, blow molding, calendar molding, laminate molding, etc. are possible, and various molded products such as disks and fibers can be obtained. .
[0037]
The thermoplastic resin used in the present invention satisfies the above-mentioned optical characteristics (refractive index and Abbe number), and more preferably, the above-mentioned glass transition temperature, light transmittance, density, and resin processability (thermoplasticity). And / or melt moldability). For example, an acrylic resin, a polycarbonate resin having a cyclic aliphatic chain, a polyester resin having a cyclic aliphatic chain, a polyether resin having a cyclic aliphatic chain, a polyamide resin having a cyclic aliphatic chain, or a polyimide having a cyclic aliphatic chain Examples thereof include resins. More specifically, for example, resins having a structural skeleton represented by chemical formulas (3) to (16) described in Table 1 (Table 1) can be given, but the present invention is not limited thereto.
[0038]
[Table 1]

[0039]
Further, a copolymer in which a part of the cyclic aliphatic chain is replaced with an aromatic ring can be used, and a thiocarbonate, a thioester, a thioether, or the like partially containing sulfur in the bond chain can also be suitably used. In addition, since an aromatic ring and sulfur may be accompanied by a reduction in the Abbe number, it is important to select within a range that does not deviate from the optical properties of the thermoplastic resin presented in the present invention.
[0040]
The method for producing the thermoplastic resin used in the present invention is not particularly limited, and any known method can be used. Also, the type and amount of impurities contained in the resin are not particularly limited, but depending on the use, impurities may impair the effects of the present invention, so the total impurity amount is 1% by weight or less, particularly sodium or It is desirable that ionic impurities such as chlorine be 0.5% by weight or less.
[0041]
The molecular weight of the thermoplastic resin used in the present invention is not particularly limited, and can be set to an arbitrary molecular weight depending on the application and processing method. However, in consideration of molding processability, the resin is 0.5 g / 100. It is preferable that the value of the logarithmic viscosity measured at 35 ° C. after being dissolved in a solvent capable of being dissolved at a concentration of milliliter is 0.1 to 3.0 deciliter / g.
[0042]
Also, end-capping compounds such as monoalcohols such as methanol and ethanol, and aromatic monohydroxy compounds such as phenol and tertiary butylphenol may be used in combination for the purpose of suppressing coloration and improving fluidity in melt molding. Good.
[0043]
In the thermoplastic resin of the present invention, the repeating of the structural unit is not particularly limited, and may be any of an alternating structure, a random structure, a block structure, and the like. Moreover, although the molecular shape used normally is linear, you may use the shape branched. Also, it may be grafted.
[0044]
The surface-modified titanium oxide fine particles used in the present invention are titanium oxide fine particles that have been surface-modified with a compound represented by the chemical formula (1).
[0045]
Si (OR ₁ ) _X (R ₂ ) _4-X (1)
[0046]
[Formula 4]

[0047]
(In the chemical formula (1), X is an integer of 1 to 4, and R1 and R2 each independently represents a monovalent linking group selected from any one of the chemical formula group (2) and chemical formula 4). In chemical formula (2), Y is an integer of 1 to 30, and Z is an integer of 0 to 5.)
[0048]
The method of synthesizing the surface-modified titanium oxide fine particles used in the present invention is not particularly limited, and any known method can be used, but after synthesizing the titanium oxide fine particles, it is represented by the chemical formula (1). A method of modifying the surface with a compound to be used is preferably used. The method for synthesizing the titanium oxide fine particles is not particularly limited, and any known method can be used. For example, desired titanium oxide fine particles can be obtained by using titanium halide or alkoxy titanium as a raw material and hydrolyzing in a reaction system containing water. At this time, a method of using an organic acid, an organic amine or the like in combination is also used for stabilizing the fine particles. More specifically, for example, a known method described in Journal of Chemical Engineering of Japan Vol. 1, No. 1, pages 21-28 (1998) can be used. According to these methods, for example, titanium oxide having an average particle diameter of 5 nm can be easily obtained by using titanium tetraisopropoxide or titanium tetrachloride as a raw material and coexisting appropriate additives when hydrolyzed in an appropriate solvent. Can be manufactured. A method of obtaining titanium oxide fine particles by oxidizing and decomposing a titanium compound such as titanium halide or alkoxy titanium in a flame can also be used. The structure of the titanium oxide is not particularly limited, and any of a rutile type crystal structure, an anatase type crystal structure, and an amorphous structure (amorphous) can be used. In order to efficiently express the effects of the present invention, it is preferable to use a rutile type crystal structure, an anatase type crystal structure, or a mixed structure thereof. The method for surface modification of the titanium oxide fine particles with the compound represented by the chemical formula (1) is not particularly limited, and any known method can be used. For example, a method of hydrolyzing the compound represented by the chemical formula (1) under conditions where water is present to modify the surface of the titanium oxide fine particles can be mentioned. In this method, a catalyst such as acid or alkali is preferably used, and the hydroxyl group on the surface of the titanium oxide fine particles and the hydroxyl group generated by hydrolysis of the compound represented by the chemical formula (1) are dehydrated to form a bond. It is generally considered.
[0049]
The surface-modified titanium oxide fine particles used in the present invention are surface-modified with the compound represented by the above chemical formula (1).
Specifically, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyl Triethoxysilane, phenyltrimethoxysilane, 3-methylphenyltrimethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiphenoxysilane, trimethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenyl Examples include phenoxysilane.
[0050]
These compounds have different characteristics such as reaction rate, and compounds suitable for surface modification conditions can be used. Further, only one type may be used or a plurality of types may be used in combination. Furthermore, the properties of the surface-modified titanium oxide fine particles obtained may vary depending on the compound used, and the affinity with the thermoplastic resin used to obtain the material composition should be determined by selecting the compound used for the surface modification. Is also possible. The ratio of the surface modification is not particularly limited, but the ratio of the titanium oxide is preferably 30 to 99% by weight and more preferably 60 to 98% by weight with respect to the fine particles after the surface modification. preferable.
[0051]
Average particle diameter d of surface-modified titanium oxide fine particles used in the present invention _i Is the average particle diameter d given by equation (C) _i It is. Average particle diameter d _i Is less than 1 nm, the refractive index n of the resulting thermoplastic material composition ₂ And Abbe number ν ₂ However, there is a risk of deviating from the range indicated by the mathematical formulas (D), (E), and (F). The average particle diameter d _i If the thickness exceeds 200 nm, the resulting thermoplastic material composition may become turbid, resulting in a decrease in transparency and a light transmittance of less than 70%.
[0052]
1 nm ≦ d _i ≦ 200nm (C)
1.45 <n ₂ ≦ 1.80 (D)
ν ₂ ≧ 200-100n ₂ (E)
n ₂ ≧ n ₁ +0.01 (F)
[0053]
The shape of the surface-modified titanium oxide fine particles used in the present invention is not particularly limited, but preferably spherical fine particles are used. Further, the particle size distribution is not particularly limited, but in order to achieve the effect of the present invention more efficiently, a particle having a relatively narrow distribution is preferably used rather than a particle having a wide distribution. Used.
[0054]
In the present invention, it is important to use surface-modified titanium oxide fine particles that have been surface-modified using the compound represented by the chemical formula (1). When titanium oxide fine particles not subjected to surface modification are used, the colorlessness of the material composition is reduced, and the yellowness Y may be out of the range represented by the formula (G). In addition, the yellowness in this invention shows the value which measured the board | substrate of thickness 3.2mm with the permeation | transmission method according to JISK7103.
[0055]
−3 ≦ Y ≦ 10 (G)
[0056]
The thermoplastic material composition of the present invention has a refractive index n represented by the mathematical formulas (A) and (B). ₁ And Abbe number ν ₁ 100 parts by weight of a thermoplastic resin having an average particle diameter d _i Is represented by the formula (C), and is composed of 1 to 200 parts by weight of surface-modified titanium oxide fine particles that have been surface-modified by the compound represented by the chemical formula (1), and more preferably 100 weights of the thermoplastic resin. Part and surface modified titanium oxide fine particles 5 to 150 parts by weight.
[0057]
However, in the chemical formula (1), X is an integer of 1 to 4, and R1 and R2 each independently represent a monovalent linking group selected from any one of the chemical formula group (2) (chemical formula 5). In chemical formula (2), Y is an integer of 1 to 30, and Z is an integer of 0 to 5.
When the surface-modified titanium oxide fine particles are less than 1 part by weight relative to 100 parts by weight of the thermoplastic resin, the refractive index n of the resulting thermoplastic material composition ₂ And Abbe number ν ₂ However, there is a risk of deviating from the range indicated by the mathematical formulas (D), (E), and (F). Further, when the surface-modified titanium oxide fine particles exceed 200 parts by weight, the refractive index n of the resulting thermoplastic material composition ₂ And Abbe number ν ₂ However, there is a possibility that not only the range shown by the mathematical formulas (D), (E) and (F) may be deviated, but also the thermoplastic property of the material composition may be impaired.
[0058]
1.45 ≦ n ₁ ≦ 1.65 (A)
ν ₁ ≧ 195-100n ₁ (B)
1 nm ≦ d _i ≦ 200nm (C)
1.45 <n ₂ ≦ 1.80 (D)
ν ₂ ≧ 200-100n ₂ (E)
n ₂ ≧ n ₁ +0.01 (F)
Si (OR ₁ ) _X (R ₂ ) _4-X (1)
[0059]
[Chemical formula 5]

[0060]
The thermoplastic material composition in the present invention is composed of a thermoplastic resin and surface-modified titanium oxide fine particles, but the production method is not particularly limited. That is, a thermoplastic resin and surface-modified titanium oxide fine particles are created independently, and then a method of mixing both, a method of creating a thermoplastic resin under conditions in which pre-made surface-modified titanium oxide fine particles exist, Any method such as a method of producing surface-modified titanium oxide fine particles under conditions where a thermoplastic resin prepared in advance is present, and a method of simultaneously producing both a thermoplastic resin and surface-modified titanium oxide fine particles can be employed. Specifically, for example, two solutions of a solution in which a thermoplastic resin is dissolved and a dispersion in which surface-modified titanium oxide fine particles are uniformly dispersed are uniformly mixed in a solution having poor solubility in the thermoplastic resin. A method for obtaining a target material composition can be suitably exemplified by meeting with, but is not limited thereto.
[0061]
In the thermoplastic material composition of the present invention, the degree of mixing of the thermoplastic resin and the surface-modified titanium oxide fine particles is not particularly limited, but in order to achieve the effect of the present invention more efficiently, it should be uniform. It is desirable that they are mixed. If the degree of mixing is insufficient, there is a concern that it may affect the optical properties such as refractive index, Abbe number, and light transmittance, and it will also adversely affect resin processability such as thermoplasticity and melt moldability. There is a fear. The degree of mixing is considered to be affected by the preparation method, and it is important to select a method in consideration of the characteristics of the thermoplastic resin and surface-modified titanium oxide fine particles used. In order to mix both the thermoplastic resin and the surface-modified titanium oxide fine particles more uniformly, a method of directly bonding the thermoplastic resin and the surface-modified titanium oxide fine particles can be suitably used in the present invention.
[0062]
The thermoplastic material composition of the present invention has a refractive index n represented by formulas (D), (E) and (F). ₂ And Abbe number ν ₂ And is an optically excellent material composition having a yellowness Y represented by the formula (G), and further has excellent thermoplasticity and / or injection moldability, and therefore has excellent molding processability. Material composition. This material having both excellent optical properties and moldability is a property that has not been achieved with the materials disclosed so far, and consists of a specific thermoplastic resin and specific titanium oxide fine particles. However, it is thought that this contributes to this characteristic.
[0063]
1.45 <n ₂ ≦ 1.80 (D)
ν ₂ ≧ 200-100n ₂ (E)
n ₂ ≧ n ₁ +0.01 (F)
−3 ≦ Y ≦ 10 (G)
[0064]
The thermoplastic material composition of the present invention comprises: (1) excellent optical properties having a refractive index n and an Abbe number ν represented by formulas (H) and (J), (2) a yellowness of 10 or less, (3) Heat resistance of glass transition temperature of 80 ° C. or higher, (4) transparency of light transmittance of 70% or higher, and (5) density of 2.0 g / cm ^Three It has the following light weight and (6) thermoplasticity and / or melt moldability, and without any loss of these excellent performances, the refractive index n can be arbitrarily adjusted within the range represented by the formula (H). it can. The refractive index can be adjusted with high accuracy by adjusting the composition ratio of the thermoplastic resin to be used and the titanium oxide fine particles.
[0065]
1.45 <n ≦ 1.80 (H)
ν ≧ 200-100n (J)
[0066]
The thermoplastic material composition of the present invention has high refractive properties, low dispersibility (high Abbe number), heat resistance, light transmittance, light weight, and moldability, and can further adjust the refractive index arbitrarily. It is a thermoplastic material composition having excellent characteristics and can be suitably used for optical parts.
[0067]
There are no particular limitations on the optical component comprising the thermoplastic material composition of the present invention. For example, a component that can be used for a part or all of the component and requires high refraction and low dispersibility. And parts that require high transparency or parts that require transparency and high refraction. In addition, since the refractive index can be adjusted arbitrarily, for example, it is also suitable for optical components that require different refractive indexes, such as optical fibers, optical waveguides, and some lenses, or that require a distribution in the refractive index. Can do. More specifically, for example, lenses (for example, eyeglass lenses, optical equipment lenses, optoelectronic lenses, laser lenses, CD pickup lenses, automotive lamp lenses, OHP lenses, etc.), optical fibers, optical waveguides, Examples include an optical filter, an optical adhesive, an optical disk substrate, a display substrate, a coating material, and a prism.
[0068]
The thermoplastic material composition of the present invention has melt moldability by using a thermoplastic resin that can be melt-molded as a raw material. Therefore, the above-mentioned optical materials are used in comparison with conventionally used thermosetting resins. Parts can be manufactured efficiently.
[0069]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. The physical properties and optical properties of the thermoplastic resin, titanium oxide fine particles, thermoplastic material composition, etc. in the examples were measured by the following methods.
(1) Logarithmic viscosity η: 0.5 g / 100 ml of a thermoplastic resin in a solvent in which the resin can be dissolved (for example, chloroform, 1-methyl-2-pyrrolidone, dimethylformamide, ortho-dichlorobenzene, cresol, etc.) After dissolving at a concentration of 1, the measurement was performed at 35 ° C.
{Circle around (2)} Refractive index n and Abbe number ν: A sample on a plate having a thickness of about 0.1 to 1 mm was prepared using a normal hot press machine, and measured by an Abbe refractometer (Atago DR-M2).
(3) Glass transition temperature Tg: measured by DSC (Shimadzu DT-40 series, DSC-41M).
(4) Light transmittance: A substrate having a thickness of 3.2 mm was prepared by thermoforming the material composition, and measured according to ASTM D1003.
(5) 5% weight loss temperature Td _Five : Measured with DTA-TG (Shimadzu DT-40 series, DTG-40M) in air.
(6) Melt viscosity: Melt viscosity was measured with an elevated flow tester (Shimadzu CFT-500) using an orifice having a diameter of 0.1 cm and a length of 1 cm. After maintaining at a predetermined temperature for 5 minutes, the mixture was extruded at a pressure of 100,000 hectopascals.
(7) Yellowness: A substrate having a thickness of 3.2 mm was prepared by thermoforming the material composition and measured by a transmission method in accordance with JIS K7103.
[0070]
[Synthesis Example 1]
A polycarbonate resin having a repeating structural unit represented by the chemical formula (17) shown in Table 2 (Table 2) was synthesized by a solution polymerization method. Into a polymerization vessel equipped with a nitrogen introduction line, a stirrer and a thermometer, 19.8 g (0.1 mol) of 4,4′-bicyclohexanol and 200 g of pyridine were charged and stirred to completely dissolve. The solution was kept at 40 ° C. in a warm water bath and phosgene was blown at a rate of about 0.25 g / min while the solution was vigorously stirred. After about 25 minutes, pyridine hydrochloride began to precipitate, and after about 15 minutes, the viscosity of the solution began to gradually increase. Further, after supplying phosgene for 10 minutes, the supply was stopped, and stirring was continued vigorously for 1 hour. Thereafter, in that state, 300 g of a mixed solution of 200 g of methanol and 100 g of ion-exchanged water was introduced from the upper portion over 5 minutes, and the precipitated polycarbonate resin was separated by filtration. In order to remove residues such as pyridine hydrochloride, the obtained polycarbonate resin was suspended in 900 g of a mixture of 600 g of methanol and 300 g of ion-exchanged water, vigorously stirred using a homomixer, and filtered again. This operation was repeated three times, then washed with 900 g of methanol and vacuum dried at 80 ° C. for 2 hours to obtain 22.0 g of resin.
When the obtained polycarbonate resin was subjected to elemental analysis of C and H, the contents thereof were 70.1 wt% and 8.8 wt%, respectively, and the theoretical values were 69.6 wt% and 8.9 wt%, respectively. It was confirmed that the polycarbonate resins were equivalent and had a repeating structural unit represented by the chemical formula (17).
About the obtained polycarbonate resin, logarithmic viscosity η, refractive index n, Abbe number ν, glass transition temperature Tg, and light transmittance, density ρ, 5% weight reduction temperature Td according to the above method. _Five The melt viscosity was evaluated and the results are shown in Table 2. This resin has a melt viscosity suitable for melt molding of 9 Pascal / second at 180 ° C., which is sufficiently lower than 50 ° C. compared to the 5% weight loss temperature, and can be melt-molded. It turns out that it is a thermoplastic resin. As can be seen from the results, this polycarbonate resin has a refractive index n expressed by the formulas (A) and (B). ₁ And Abbe number ν ₁ Is a melt-moldable thermoplastic resin suitable for the conditions of the present invention.
[0071]
1.45 ≦ n ₁ ≦ 1.65 (A)
ν ₁ ≧ 195-100n ₁ (B)
[0072]
[Synthesis Example 2]
In the same manner as in Synthesis Example 1, except that 19.8 g (0.1 mol) of 4,4′-bicyclohexanol was changed to 24.0 g (0.1 mol) of 2,2-bis (4-hydroxycyclohexyl) propane. Then, a polycarbonate resin having a repeating structural unit represented by the chemical formula (18) shown in Table 2 was synthesized by a solution polymerization method to obtain 26.2 g of a resin. From the elemental analysis of C and H of the obtained resin, it was confirmed to be a polycarbonate resin having a repeating structural unit represented by the chemical formula (18).
Each characteristic was evaluated in the same manner as in Synthesis Example 1, and the results are shown in Table 2 (Table 2). As can be seen from the results, this polycarbonate resin is a resin suitable for the conditions of the present invention.
[0073]
[Synthesis Example 3]
A polyester resin having a repeating structural unit represented by the chemical formula (19) shown in Table 2 (Table 2) was synthesized by the acid chloride method. In a polymerization vessel equipped with a nitrogen introduction line, a stirrer and a thermometer, 19.8 g (0.1 mol) of 4,4′-bicyclohexanol, 20.9 g (0.1 mol) of 1,4-cyclohexanedicarboxylic acid chloride, and nitrobenzene 100 g was charged. The mixture was slowly heated with stirring under a nitrogen atmosphere, and the temperature was raised to 145 ° C. in 2 hours. After polymerization at this temperature for 6 hours, nitrobenzene was distilled off under reduced pressure. The remaining polymer was further dried at this temperature under reduced pressure for 2 hours to obtain 32.4 g of a resin. From the elemental analysis of C and H of the obtained resin, it was confirmed that it was a polyester resin having a repeating structural unit of the chemical formula (19).
Each characteristic was evaluated in the same manner as in Synthesis Example 1, and the results are shown in Table 2 (Table 2). As can be seen from the results, this polyester resin is a resin suitable for the conditions of the present invention.
[0074]
[Synthesis Example 4]
In the same manner as in Synthesis Example 3, except that 19.8 g (0.1 mol) of 4,4′-bicyclohexanol was changed to 24.0 g (0.1 mol) of 2,2-bis (4-hydroxycyclohexyl) propane. Then, a polyester resin having a repeating structural unit of the chemical formula (20) shown in Table 2 (Table 2) was synthesized by the acid chloride method to obtain 36.4 g of a resin. From the elemental analysis of C and H of the obtained resin, it was confirmed that it was a polyester resin having a repeating structural unit of the chemical formula (20).
Each characteristic was evaluated in the same manner as in Synthesis Example 1, and the results are shown in Table 2 (Table 2). As can be seen from the results, this polyester resin is a resin suitable for the conditions of the present invention.
[0075]
[Synthesis Example 5]
A polyether resin having a repeating structural unit represented by the chemical formula (21) shown in Table 2 (Table 2) was synthesized according to Polymer Material Science Engineering Vol. 60, page 170 (1989). From the elemental analysis of C and H of the obtained resin, it was confirmed to be a polyether resin having a repeating structural unit represented by the chemical formula (21).
Each characteristic was evaluated in the same manner as in Synthesis Example 1, and the results are shown in Table 2 (Table 2). As can be seen from the results, this polyether resin is a resin suitable for the conditions of the present invention.
[0076]
[Synthesis Example 6]
A polyamide resin having a repeating structural unit represented by the chemical formula (22) shown in Table 2 (Table 2) was synthesized by the acid chloride method. A polymerization vessel equipped with a nitrogen introduction line, a stirrer, and a thermometer was charged with 11.4 g (0.1 mol) of 1,4-cyclohexanediamine and 200 g of N, N-dimethylacetamide and stirred while cooling with ice. After 1,4-cyclohexanediamine was dissolved, 20.9 g (0.1 mol) of 1,4-cyclohexanedicarboxylic acid chloride was gradually added, and then the stirring was continued for 3 hours. Thereafter, in that state, 300 g of a mixed solution of 200 g of methanol and 100 g of ion-exchanged water was introduced from the upper portion over 5 minutes, and the precipitated resin was separated by filtration. In order to remove residues such as pyridine hydrochloride, the obtained resin was suspended in 900 g of a mixture of 600 g of methanol and 300 g of ion-exchanged water, vigorously stirred using a homomixer, and filtered again. This operation was repeated three times, then washed with 900 g of methanol and vacuum dried at 80 ° C. for 2 hours to obtain 24.0 g of a resin. From the elemental analysis of C and H of the obtained resin, it was confirmed that it was a polyamide resin having a repeating structural unit of the chemical formula (22).
Each characteristic was evaluated in the same manner as in Synthesis Example 1, and the results are shown in Table 2 (Table 2). As can be seen from the results, this polyamide resin is a resin suitable for the conditions of the present invention.
[0077]
[Synthesis Example 7]
Instead of 19.8 g (0.1 mol) of 4,4′-bicyclohexanol, it was changed to 12.0 g (0.05 mol) of 2,2-bis (4-hydroxycyclohexyl) propane and 11.4 g (0.05 mol) of bisphenol A. In the same manner as in Synthesis Example 1, a polycarbonate resin having a repeating structural unit represented by the chemical formula (25) shown in Table 2 (Table 2) was synthesized by a solution polymerization method to obtain 23.2 g of a resin. . From the elemental analysis of C and H of the obtained resin, it was confirmed to be a polycarbonate resin having a repeating structural unit represented by the chemical formula (25).
Each characteristic was evaluated in the same manner as in Synthesis Example 1, and the results are shown in Table 2 (Table 2). As can be seen from the results, this polycarbonate resin is not suitable for the conditions of the present invention.
[0078]
[Synthesis Example 8]
In place of 19.8 g (0.1 mol) of 4,4′-bicyclohexanol, 11.6 g (0.1 mol) of 1,4-cyclohexanediol and 20.9 g (0.1 mol) of 1,4-cyclohexanedicarboxylic acid chloride A polyester resin having a repeating structural unit represented by the chemical formula (26) shown in Table 2 (Table 2) was prepared in the same manner as in Synthesis Example 3 except that 20.3 g (0.1 mol) of terephthalic acid chloride was used instead. Synthesis by the acid chloride method gave 23.8 g of resin.
From the elemental analysis of C and H of the obtained resin, it was confirmed that it was a polyester resin having a repeating structural unit represented by the chemical formula (26).
Each characteristic was evaluated in the same manner as in Synthesis Example 1, and the results are shown in Table 2 (Table 2). As can be seen from the results, this polyester resin is not suitable for the conditions of the present invention.
[0079]
[Table 2]

[0080]
[Synthesis Example 9]
Using titanium tetrachloride as a raw material, titanium oxide fine particles were synthesized. First, in accordance with the method described in Japanese Journal of Applied Physics, Volume 37, pages 4603-4608 (1998), TiOCl, which is an intermediate, is used. ₂ Was synthesized. Titanium tetrachloride (25.0 g, 0.132 mol) was charged into a three-necked flask in a nitrogen box and cooled to about −5 ° C. in a methanol / ice bath. While stirring, 14.3 g (0.792 mol) of distilled water was slowly added dropwise over 30 minutes. Finally a yellow transparent viscous liquid was obtained. Dilute this liquid with 125 g of distilled water and add TiOCl. ₂ An aqueous solution of was obtained. Next, a mixture of 1450 g of distilled water, 1650 g of ethanol and 5.31 g (0.072 mol) of propionic acid and maintained at 50 ° C. was mixed with TiOCl. ₂ The aqueous solution was added all at once with stirring. When stirring was further continued at 50 ° C., it started to become cloudy for several tens of minutes. After aging for 6 hours under these conditions, the mixture was centrifuged at 10,000 rpm for 2 minutes, and the resulting white gel was suspended in ethyl acetate and further centrifuged under the same conditions to produce 10.0 g of white fine powder. Got. 10 g of this fine powder was clouded in 200 g of 1-butanol, subjected to ultrasonic treatment for 30 minutes, and then heated at 100 ° C. for 30 minutes. The obtained cloudy liquid was added to a mixed liquid composed of 2000 g of distilled water, 2000 g of methanol, and 21 g of 35 wt% hydrochloric acid aqueous solution to obtain a transparent dispersion. While stirring this transparent dispersion at 50 ° C., a mixed solution obtained by adding 6 g of dimethyldimethoxysilane to 100 g of methanol was dropped over 60 minutes, and then aged for 2 hours under the same conditions. The obtained transparent dispersion was centrifuged at 10,000 rpm for 2 minutes, and the resulting white gel was suspended in ethyl acetate and further centrifuged under the same conditions to obtain 11.5 g of a white fine powder. Got. Elemental analysis confirmed that the titanium oxide content was 87% by weight. The particles were observed with an electron microscope, and it was confirmed that the particles were almost spherical and the average particle diameter was 5 nm. Further, from the infrared spectroscopic analysis, an absorption peak due to the C—H bond of the methyl group was observed, and it was confirmed that the surface modification was performed. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the oxide fine particles are fine particles suitable for the conditions of the present invention.
[0081]
[Synthesis Example 10]
11.8 g of white fine powder was obtained in the same manner as in Synthesis Example 9 except that 6 g of trimethylmethoxysilane was used instead of 6 g of dimethyldimethoxysilane. From elemental analysis, the content of titanium oxide is 85% by weight. From observation by electron microscope, the particles are almost spherical and the average particle diameter is 5 nm. From infrared spectroscopic analysis, absorption peak due to C—H bond of methyl group. It was confirmed that the surface was modified. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the oxide fine particles are fine particles suitable for the conditions of the present invention.
[0082]
[Synthesis Example 11]
11.0 g of white fine powder was obtained in the same manner as in Synthesis Example 9 except that 6 g of methylmethoxysilane was used instead of 6 g of dimethyldimethoxysilane. From elemental analysis, the content of titanium oxide is 89% by weight, from electron microscopy, the particles are almost spherical and the average particle diameter is 5 nm, and from infrared spectroscopy, absorption peaks due to C—H bonds of methyl groups It was confirmed that the surface was modified. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the oxide fine particles are fine particles suitable for the conditions of the present invention.
[0083]
[Synthesis Example 12]
11.9 g of white fine powder was obtained in the same manner as in Synthesis Example 9 except that 6 g of diphenyldimethoxysilane was used instead of 6 g of dimethyldimethoxysilane. From the elemental analysis, the content of titanium oxide is 85% by weight. From the electron microscope observation, the particles are almost spherical and the average particle diameter is 5 nm. It was confirmed that the surface was modified. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the oxide fine particles are fine particles suitable for the conditions of the present invention.
[0084]
[Synthesis Example 13]
After the titanium oxide fine particles were obtained in the same manner as in Synthesis Example 9, no surface modification was performed. Elemental analysis confirmed that the titanium oxide content was 99.5% by weight, and electron microscopic observation confirmed that the particles were almost spherical and the average particle diameter was 5 nm. In addition, infrared spectroscopic analysis confirmed that no absorption peak due to any C—H bond was observed. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the fine oxide particles are fine particles not suitable for the conditions of the present invention.
[0085]
[Synthesis Example 14]
Synthesis was carried out in the same manner as in Synthesis Example 9 except that the amount of propionic acid used was changed from 5.31 g (0.072 mol) to 26.6 g (0.36 mol) to obtain 11.9 g of a white fine powder. It was. From elemental analysis, the content of titanium oxide is 85% by weight. From observation by an electron microscope, the particles are almost spherical and the average particle diameter is 2 nm. From infrared spectroscopic analysis, absorption peak due to C—H bond of methyl group. It was confirmed that the surface was modified. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the oxide fine particles are fine particles suitable for the conditions of the present invention.
[0086]
[Synthesis Example 15]
Synthesis was carried out in the same manner as in Synthesis Example 9 except that the amount of propionic acid used was changed from 5.31 g (0.072 mol) to 0.0531 g (0.00072 mol) to obtain 10.6 g of white fine powder. It was. From the elemental analysis, the titanium oxide content is 85% by weight, from the electron microscope observation, the particles are almost spherical and the average particle diameter is 150 nm, and from the infrared spectroscopic analysis, the absorption peak due to the C—H bond of the methyl group It was confirmed that the surface was modified. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the oxide fine particles are fine particles suitable for the conditions of the present invention.
[0087]
[Synthesis Example 16]
Synthesis was carried out in the same manner as in Synthesis Example 9 except that the amount of propionic acid used was changed from 5.31 g (0.072 mol) to 106.2 g (1.44 mol) to obtain 10.6 g of white fine powder. It was. From observation with an electron microscope, it was confirmed that the particles were almost spherical but the average particle diameter was 0.8 nm. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the titanium dioxide fine particles are inorganic fine particles not suitable for the conditions of the present invention.
[0088]
[Synthesis Example 17]
Synthesis was carried out in the same manner as in Synthesis Example 9 except that the amount of propionic acid used was changed from 5.31 g (0.072 mol) to 0.00531 g (0.000072 mol) to obtain 9.2 g of white fine powder. It was. From observation with an electron microscope, it was confirmed that the particles were almost spherical but the average particle diameter was 250 nm. The evaluation results of the fine particles are shown in Table 3 (Table 3). As can be seen from the results, the titanium dioxide fine particles are inorganic fine particles not suitable for the conditions of the present invention.
[0089]
[Table 3]

[0090]
[Example 1]
After suspending 0.3 g of oxide fine particles having the number (U1) described in Table 3 (Table 3) in 10 g of 1-butanol and performing ultrasonic treatment for 30 minutes, they were heated at 100 ° C. for 30 minutes. The resulting cloudy liquid was added dropwise over 5 minutes at room temperature with stirring to 10 g of a chloroform solution in which the resin of number (P1) shown in Table 2 was dissolved at 10% by weight. The resulting mixed liquid was a clear and colorless liquid with a slight bluish tinge. This liquid was deposited in an equal volume mixture of methanol and distilled water using a homogenizer to obtain a material composition in which inorganic fine particles were mixed in the resin. This composition was thermoformed to produce a substrate having a thickness of 3.2 mm. The substrate was colorless and transparent. Observation with an electron microscope confirmed that the inorganic fine particles were uniformly dispersed in the resin. The refractive index, Abbe number, glass transition temperature, light transmittance, density, 5% weight loss temperature, melt viscosity, and yellowness of this material composition were measured, and the results are shown in Table 4 (Table 4). It was. As can be seen from the results, this material composition has a refractive index n expressed by the mathematical formulas (D), (E) and (F). ₂ And Abbe number ν ₂ A melt-moldable plastic material composition having a yellowness Y represented by the formula (G), that is, a material composition excellent in optical characteristics and moldability, and further having a glass transition temperature of 80 ° C. or higher Heat resistance, transparency of light transmittance of 70% or more, density 2.0 g / cm ^Three It turns out that it also has the following lightness. Therefore, it is a material composition suitable for an optical component that requires such characteristics.
[0091]
1.45 <n ₂ ≦ 1.80 (D)
ν ₂ ≧ 200-100n ₂ (E)
n ₂ ≧ n ₁ +0.01 (F)
−3 ≦ Y ≦ 10 (G)
[0092]
[Examples 2 to 8]
A material composition was prepared in the same manner as in Example 1 except that the resin to be used was replaced with the resins of numbers (P2) to (P8) described in Table 2 (Table 2). It was described in the table (Table 4). In any of the examples, the obtained material composition has excellent characteristics similar to those of the material composition of Example 1, and it can be seen that the material composition is suitable for optical components.
[0093]
[Comparative Examples 1-2]
A material composition was prepared in the same manner as in Example 1 except that the resin to be used was replaced with the resins of numbers (P9) to (P10) described in Table 2 (Table 2). It was described in the table (Table 4). Since the resin in the condition range of the present invention is used, the obtained material composition has a refractive index n represented by mathematical formulas (E), (F), and (G). ₂ And Abbe number ν ₂ Does not meet.
[0094]
Examples 9 to 11
Except that the resin used was replaced with the resin of number (P3) described in Table 2 (Table 2), and the oxide fine particles used were replaced with the numbers (U2) to (U4) described in Table 3 (Table 3), A material composition was prepared in the same manner as in Example 1, and the physical property measurement results are shown in Table 4 (Table 4). In any of the examples, the obtained material composition has excellent characteristics similar to those of the material composition of Example 1, and it can be seen that the material composition is suitable for optical components.
[0095]
[Comparative Example 3]
Example 1 except that the resin used was replaced with the resin of number (P3) described in Table 2 (Table 2) and the oxide fine particles used were replaced with the number (U5) described in Table 3 (Table 3). A material composition was prepared in the same manner. The board | substrate created from the obtained composition was a transparent board | substrate colored lightly yellow, and yellowness was 12.0.
[0096]
Examples 12 to 13
A material composition was prepared in the same manner as in Example 1 except that the resin used was replaced with the resin of number (P3) described in Table 2 (Table 2) and the amount of oxide fine particles used was changed. The physical property measurement results are shown in Table 4 (Table 4). In any of the examples, the obtained material composition has excellent characteristics similar to those of the material composition of Example 1, and it can be seen that the material composition is suitable for optical components.
[0097]
[Comparative Example 4]
A material composition was prepared in the same manner as in Example 1 except that the resin used was replaced with the resin of number (P3) described in Table 2 (Table 2) and the amount of oxide fine particles used was changed. The physical property measurement results are shown in Table 4. Since the amount of the oxide fine particles used is outside the range of the conditions of the present invention, the optical properties cannot be improved, and the obtained material composition has a refractive index n represented by the formula (G). ₂ It does not satisfy.
[0098]
n ₂ ≧ n ₁ +0.01 (G)
[0099]
[Comparative Example 5]
A material composition was prepared in the same manner as in Example 1 except that the resin used was replaced with the resin of number (P3) described in Table 2 (Table 2) and the amount of oxide fine particles used was changed. However, the obtained material composition was very brittle, and a film could not be formed by hot pressing or the like. That is, the material composition did not have thermoplasticity.
[0100]
Examples 14 to 15
The resin used is replaced with the resin of number (P3) described in Table 2 (Table 2), and the oxide fine particles used are replaced with the numbers (U6) to (U7) described in Table 3 (Table 3). A material composition was prepared in the same manner as in Example 1, and the physical property measurement results are shown in Table 4 (Table 4). In any of the examples, the obtained material composition has excellent characteristics similar to those of the material composition of Example 1, and it can be seen that the material composition is suitable for optical components.
[0101]
[Comparative Example 6]
Example 1 except that the resin used was replaced with the resin of number (P3) described in Table 2 (Table 2), and the inorganic fine particles used were replaced with the number (U8) described in Table 3 (Table 3). Thus, a material composition was prepared. The substrate made from the obtained composition was cloudy, and the refractive index and Abbe number could not be measured due to low light transmittance. From observation with an electron microscope, the inorganic fine particles were in an aggregated state.
[0102]
[Comparative Example 7]
Example 1 except that the resin used was replaced with the resin of number (P3) described in Table 2 (Table 2) and the inorganic fine particles used were replaced with the number (U9) described in Table 3 (Table 3). Thus, a material composition was prepared. The substrate made from the obtained composition was cloudy, and the refractive index and Abbe number could not be measured due to low light transmittance. From observation with an electron microscope, it was not observed that the inorganic fine particles were aggregated.
[0103]
[Table 4]

[0104]
【The invention's effect】
The thermoplastic material composition of the present invention and an optical component comprising the same are: (1) excellent optical properties having a refractive index n and an Abbe number ν represented by the formulas (H) and (J), (2) Yellowness of 10 or less, (3) Glass transition temperature of 80 ° C. or more, (4) Light transmittance of 70% or more, (5) Density of 2.0 g / cm ^Three A material composition having the following light weight and (6) thermoplasticity and / or melt moldability, and an optical component comprising the same, such as a lens (for example, a spectacle lens, a lens for an optical instrument, (Optoelectronic lenses, laser lenses, CD pickup lenses, automotive lamp lenses, OHP lenses, etc.), optical fibers, optical waveguides, optical filters, optical adhesives, optical disk substrates, display substrates, coating materials, prisms, etc. Suitable for use.
1.45 <n ≦ 1.80 (H)
ν ≧ 200-100n (J)

Claims (8)

Acrylic resin, cyclic olefin resin, polycarbonate resin having cyclic aliphatic chain, polyester resin having cyclic aliphatic chain, cyclic fat having refractive index n ₁ and Abbe number ν _{1 represented} by formulas (A) and (B) 100 parts by weight of a thermoplastic resin selected from a polyether resin having an aliphatic chain, a polyamide resin having a cyclic aliphatic chain, or a polyimide resin having a cyclic aliphatic chain, and an average particle diameter d _i is represented by the formula (C) And represented by formulas (D), (E), and (F) composed of 1 to 200 parts by weight of surface-modified titanium oxide fine particles that have been surface-modified with a compound represented by chemical formula (1). A thermoplastic material composition having a refractive index n ₂ and an Abbe number ν ₂ and a yellowness Y represented by the formula (G).
1.45 ≦ n ₁ ≦ 1.65 (A)
ν ₁ ≧ 195-100n ₁ (B)
1 nm ≦ d _i ≦ 200 nm (C)
1.45 <n ₂ ≦ 1.80 (D)
ν ₂ ≧ 200-100n ₂ (E)
n ₂ ≧ n ₁ +0.01 (F)
−3 ≦ Y ≦ 10 (G)
Si (OR ₁ ) _x (R ₂ ) _{4- x} (1)

(In the chemical formula (1), x is an integer of 1 to 4, and R ₁ and R ₂ each independently represents a monovalent linking group selected from any one of the chemical formula group (2) (Chemical Formula 1)). In the chemical formula (2), y is an integer of 1 to 30, and z is an integer of 0 to 5.) An optical component comprising the thermoplastic material composition according to claim 1 . The optical component according to claim 2 , wherein the optical component is a lens. 4. The optical component according to claim 3 , wherein the lens is a spectacle lens, an optical device lens, an optoelectronic lens, a laser lens, a CD pickup lens, an automobile lamp lens, or an OHP lens. The optical component according to claim 2 , wherein the optical component is an optical fiber. The optical component according to claim 2 , wherein the optical component is an optical waveguide. The optical component according to claim 2 , wherein the optical component is an optical filter. The optical component according to claim 2 , wherein the optical component is an optical adhesive.