JP3559805B2 - High refractive index coating composition and coated article obtained from the composition - Google Patents

Description

ここで、Ｒ⁶は水素原子またはメチル基、ｂは２〜１０の整数、好ましくは４〜６の整数をそれぞれ表す。
【００４１】
上記一般式（Ｄ）で表される化合物は、
例えば、
４−ヒドロキシブチルアクリレート、
４−ヒドロキシブチルメタクリレート、
４−ヒドロキエチルアクリレート、
４−ヒドロキエチルメタクリレート
である。
【００４２】
ＣＨ₂＝ＣＨ-（-ＣＨ₂-）_d-Ｏ-（-ＣＨ₂-）_e-ＯＨ （Ｅ）
ここで、ｄは０または１の整数、ｅは４〜１０の整数をそれぞれ表す。
【００４３】
上記一般式（Ｅ）で表される化合物は、
例えば、
４−ヒドロキシブチルアリルエーテル、
４−ヒドロキシブチルビニルエーテル
である。
【００４４】
ＣＨ₂＝ＣＨ-（-ＣＨ₂-）_d-（-ＯＲ⁷-）_f-ＯＨ （Ｆ）
ここで、Ｒ⁷は−ＣＨ₂ＣＨ₂−または−ＣＨ₂ＣＨ（ＣＨ₃）−であり、ｄは０または１の整数、ｆは２〜９の整数である。
【００４５】
上記一般式（Ｆ）で表される化合物は、
例えば、
ジエチレングリコールモノアリルエーテル、
トリエチレングリコールモノビニルエーテル
である。
【００４６】
上記本発明の第三成分はコーティング組成物中の総固形分中の１〜４５重量％、好ましくは２〜３０重量％で用いられる。第三成分がコーティング組成物中の総固形分中の１重量％未満であると、深染めができなく、また、４５重量％を超えると塗膜の硬度が低下する。
【００４７】
（４）本発明のコーティング組成物は上記第一成分〜第三成分の他に後述の硬化触媒を含み、また有機ケイ素化合物またはその部分加水分解物として次の一般式（Ｇ）を有する化合物を第四成分として必要に応じて含むことができる。一般式（Ｇ）の化合物を添加することで得られる塗膜はその塗膜上にコーティングされる反射防止膜との密着性が向上し、また塗膜の硬さが増す。この化合物（Ｇ）の添加量の調節により得られる塗膜の屈折率の調整も可能となる。
【００４８】
Ｒ ⁸ _hＲ² _aＳｉ（ＯＲ³）_4-h-a （Ｇ）
ここで、Ｒ²とＲ³は一般式（Ａ）で定義したものと同一であり、Ｒ ⁸ は炭素原子数１〜４のアルキル基、ハロゲン化アルキル基、炭素原子数６〜１２のアリール基またはハロゲン化アリール基、炭素原子数５〜８のメタクリロキシアルキル基、炭素原子数２〜１０のウレイドアルキレン基、芳香族ウレイドアルキレン基、ハロゲン化芳香族アルキレン基、メルカプトアルキレン基のいずれかを表し、ａは０、１または２の整数、ｈは０〜３の整数を表す。
【００４９】
一般式（Ｇ）の化合物を添加することで得られる塗膜は、その塗膜上にコーティングされる反射防止膜との密着性が向上し、また、塗膜の硬さが増す。この化合物（Ｇ）の添加量の調整により得られる塗膜の屈折率の調整も可能となる。
【００５０】
上記一般式（Ｇ）で表される有機ケイ素化合物は、
例えば、
トリメチルメトキシシラン、
トリエチルメトキシシラン、
トリメチルエトキシシラン、
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、
ジフェニルメチルメトキシシラン、
フェニルジメチルメトキシシラン、
フェニルジメチルエトキシシラン、
ビニルジメチルメトキシシラン、
ビニルジメチルエトキシシラン、
ビニル（β−メトキシエトキシ）シラン、
【００５１】
γ−アクリロキシプロピルジメチルメトキシシラン、
γ−メタクリロキシプロピルジメチルメトキシシラン、
γ−メルカプトプロピルジメチルメトキシシラン、
γ−メルカプトプロピルジメチルエトキシシラン、
Ｎ−β（アミノエチル）γ−アミノプロピルジメチルメトキシシラン、
γ−アミノプロピルジメチルメトキシシラン、
γ−アミノプロピルジメチルエトキシシラン、
γ−グリシドキシプロピルジメチルメトキシシラン、
γ−グリシドキシプロピルジメトキシエトキシシラン、
β−（３，４−エポキシシクロヘキシル）エチルジメチルメトキシシラン、
ジメチルジメトキシシラン、
ジエチルジメトキシシラン、
ジメチルジエトキシシラン、
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、
フェニルメチルジメトキシシラン、
フェニルメチルジエトキシシラン、
ビニルメチルジメトキシシラン、
ビニルメチルジエトキシシラン、
【００５２】
γ−アクリロキシプロピルメチルジメトキシシラン、
γ−メタクリロキシプロピルジメチルジメトキシシラン、
γ−メルカプトプロピルメチルジメトキシシラン、
γ−メルカプトプロピルメチルジエトキシシラン、
Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、
γ−アミノプロピルメチルジメトキシシラン、
γ−アミノプロピルメチルジエトキシシラン、
γ−グリシドキシプロピルメチルジメトキシシラン、
γ−グリシドキシプロピルメトキシジエトキシシラン、
β−（３，４−エポキシシクロヘキシル）エチルメチルジメトキシシラン、
メチルトリメトキシシラン、
エチルトリメトキシシラン、
メチルトリエトキシシラン、
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、
フェニルトリエトキシシラン、
ビニルトリメトキシシラン、
ビニルトリエトキシシラン、
ビニル（β−メトキシエトキシ）シラン、
【００５３】
γ−アクリロキシプロピルトリメトキシシラン、
γ−メタクリロキシプロピルトリメトキシシラン、
γ−メルカプトプロピルトリメトキシシラン、
γ−メルカプトプロピルトリエトキシシラン、
Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、
γ−アミノプロピルトリメトキシシラン、
γ−アミノプロピルトリエトキシシラン、
γ−グリシドキシプロピルトリメトキシシラン、
β−グリシドキシプロピルトリメトキシシラン、
γ−グリシドキシプロピルトリエトキシシラン、
β−グリシドキシプロピルトリエトキシシラン、
β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、
テトラエチルオルソシリケート、
テトラメチルオルトシリケート
等である。
【００５４】
上記本発明の第四成分はコーティング組成物中の総固形分中の０〜６０重量％、好ましくは２〜４５重量％で用いられる。第四成分がコーティング組成物中の総固形分中の６０重量％を超えると屈折率を高くすることが困難になる。
【００５５】
（５）本発明のコーティング組成物の硬化触媒としては
カルボン酸のアルカリ金属塩およびアンモニウム塩；例えば酢酸ナトリウム、酢酸アンモニウム
アセチルアセトンの金属塩およびアンモニウム塩；例えばアセチルアセトンアルミニウム、アセチルアセトンジルコニウム塩、アセチルアセトンアンモニウム塩
第１〜第３級アミン；例えばブチルアミン、ヒドロキシエチルアミン、ジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン、ジメチルフェニルアミン、ポリアルキレンアミン
過塩素酸の金属塩およびアンモニウム塩；例えば過塩素酸マグネシウム、過塩素酸アンモニウム
エチルアセトアセテートの金属塩
アセチルアセトンとエチルアセトアセテートが配位した金属塩
有機金属塩；例えばナフテン酸亜鉛、オクチル酸錫
ルイス酸；例えばＳｎＣｌ₄、ＴｉＣｌ₄、ＺｎＣｌ₂
等が用いられる。
【００５６】
本発明のコーティング組成物の硬化触媒としては、前記した化合物と有機メルカプタンやメルカプトアルキレンシランを併用することも可能である。前記硬化触媒の添加時期は混合液調合時でも塗布直前でも良い。硬化触媒の前記添加時期の選択は必要に応じて任意に決定する。
また、本発明の硬化触媒はコーティング組成物中の総固形分中の０．００１〜１０重量％用いる。
【００５７】
（６）本発明のコーティング組成物の分散媒としてはアルコール類、エーテル類、芳香族炭化水素、エステル類、ケトン類化合物が用いられる。例えば、メタノール、エタノール、イソプロピルアルコール、ｎ−ブタノール、２−ブタノール、メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ、エチレングリコール、酢酸メチル、酢酸エチル、ジエチルエーテル、テトラヒドロフラン、アセトン、キシレン、Ｎ，Ｎ−ジメチルホルムアミド、メチルエチルケトン、ジクロロエタン、トルエンなどが用いられる。
【００５８】
この希釈用分散媒はコーティング組成物中の総固形分に対して１００〜８００重量％添加して用いる。前記分散媒の添加量が１００重量％未満だと、得られる塗膜の膜厚が厚くなり、クラックが生じやすくなる。また前記添加量が８００重量％を超えると得られる塗膜の膜厚が薄くなり、塗膜硬度が不十分となる。また、これらの分散媒は前記第一成分の分散媒と兼用しても良い。
【００５９】
（７）その他本発明のコーティング組成物にはコーティング時のフロー性を改善するためにレベリング剤を添加することができる。例えばポリオキシアルキレンとポリジメチルシロキサンの共重合体、ポリオキシアルキレンとフルオロカーボンとの共重合体等を用いることができる。上記添加剤はコーティング組成物中の総液重量の０．００１〜５重量％添加して用いる。
この他、必要に応じて、酸化防止剤、耐候性付与剤、着色剤または帯電防止剤も添加可能である。
【００６０】
好ましい膜厚は０．２〜１０μｍであり、膜厚が０．２μｍ未満であると硬度が不足、１０μｍを超えるとクラックが入りやすくなる。また硬化膜の屈折率は１．４８〜１．７０に調整することができる。
【００６１】
本発明のコーティング組成物の基材への塗布方法はディップ法、フロー法、スピンナー法、スプレー法等の方法を採用できる。熱処理条件は５０〜１３０℃、１〜１０時間が好ましいが、基材の耐熱性により変わる。
【００６２】
（８）前記基材は屈折率が１．５０以上の高屈折率樹脂からなる眼鏡用プラスチックレンズ、光学用部材（ガラス製品を含む）、シート、成型物等である。
【００６３】
屈折率が１．５０より高い透明基材としては、例えば、ポリカーボネート（屈折率：１．５８）がある。また、各種眼鏡用プラスチックレンズ／公知の公開特許公報により多くの樹脂が提案されている。
【００６４】
例えば、ポリウレタン樹脂からなるプラスチックレンズ、メタクリル系重合体からなるプラスチックレンズ、アリル系重合体からなるプラスチックレンズあるいはそれらの併用タイプ等が用いられる。
【００６５】
ポリウレタン樹脂からなるレンズの例としては三井東圧化学（株）製モノマーＭＲ−６、改良ＭＲ−６、ＭＲ−７（すべて商標名）を熱硬化してなるレンズ、メタクリル系重合体からなるレンズとしてはトクヤマ（株）製モノマーＴＳ−２６（商標名）をラジカル重合してなるレンズ、ウレタン反応とビニル重合反応を併用したレンズとしては三菱瓦斯化学（株）製モノマーＭＬ−３（商標名）を重合してなるレンズが用いられる。
【００６６】
（９）反射防止膜
ハードコート被膜の上に単層あるいは多層の無機物からなる反射防止膜を設けることにより反射の低減、透過率の向上、耐候性の向上を図ることができる。
【００６７】
無機物としては、ＳｉＯ、ＳｉＯ₂、Ｓｉ₃Ｎ₄、ＴｉＯ₂、ＺｒＯ₂、Ａｌ₂Ｏ₃、ＭｇＦ₂、Ｔａ₂Ｏ₅等を用いて真空蒸着法等によって薄膜を形成する。
【００６８】
ハードコートの付着性を改善するためにあらかじめレンズ基材をアルカリ処理、酸処理、プラズマ処理、コロナ処理、火炎処理等の前処理を行うことが有効である。
【００６９】
【作用】
本発明で得られるコーティング組成物を高屈折率基材に塗布、硬化して得られた被膜は、非常に高い耐擦傷性、耐摩擦性を有する一方、干渉縞の発生が抑えられ、しかも深染め可能である。その理由は第三成分のＯＨ基を有する化合物のＯＨ基が有機ケイ素化合物の縮合体の所々に反応してぶら下がり染料のトラップもしくは通過可能なチャンネルを作ったため、非常に高い耐擦傷性、耐摩擦性を有する一方、深染めが可能となるものと考えられる。
【００７０】
これに対して、従来の本発明類似のコーティング組成物は、染色可能な有機成分を架橋剤として用いているため有機ケイ素のみによる被膜に比べると相対的に強度が低下する。
【００７１】
【実施例】
本発明の実施例を説明する。
実施例１
ＴｉＯ₂−Ｆｅ₂Ｏ₃−ＳｉＯ₂からなる複合金属酸化物ゾル（固形分３０％、メタノール分散ゾル、触媒化成工業（株）製、商標名オプトレイク１１３０Ｆ−２（Ａ−８））３０３ｇをフラスコに計り取る。そこへ、蒸留水１７０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシランを１９１ｇとメチルトリメトキシシラン６９ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００７２】
その後、混合液を撹拌しながら、イソプロピルアルコールを２２０ｇ添加し、次に一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステル（日本油脂（株）製、商標名ブレンマーＰＥ２００）を４０ｇ添加した。さらに、硬化触媒として過塩素酸アンモニウムを３ｇ、フローコントロール剤としてシリコーン界面活性剤（日本ユニカー（株）製、商標名Ｌ−７００１）を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。
【００７３】
屈折率１．５９４のウレタン樹脂からなるプラスチックレンズ（三井東圧化学（株）製モノマーである商標名ＭＲ−６を熱重合してなるレンズ）に上記混合液を塗布し、１２０℃で１時間熱硬化した。得られた塗膜の外見は無色透明であった。付着性は１００／１００、硬化膜の屈折率は１．５８であり、干渉縞はほとんど目立たなかった。また膜厚は１．５〜２．０μｍで、ＳＷ硬度は４であった。また、５分間染色で透過率が３２％になった。
【００７４】
実施例２
実施例１のＴｉＯ₂−Ｆｅ₂Ｏ₃−ＳｉＯ₂からなる複合金属酸化物ゾルをＴｉＯ₂−ＣｅＯ₂−ＳｉＯ₂からなる複合金属酸化物ゾル（固形分３０％、メタノール分散ゾル、触媒化成工業（株）製、商標名オプトレイク１１３０Ａ（Ａ−８））に代える以外は同じ方法を用いた。結果は表１に示した。
【００７５】
実施例３
実施例１のＴｉＯ₂−Ｆｅ₂Ｏ₃−ＳｉＯ₂からなる複合金属酸化物ゾルをＴｉＯ₂−ＳｉＯ₂からなる複合金属酸化物ゾル（固形分３０％、メタノール分散ゾル、触媒化成工業（株）製、ＴｉＯ₂／ＳｉＯ₂＝８５／１５）に代える以外は同じ方法を用いた。結果は表１に示した。
【００７６】
実施例４
ＴｉＯ₂−ＣｅＯ₂からなる複合金属酸化物ゾル（固形分２０％、メタノール分散ゾル、触媒化成工業（株）製、ＴｉＯ₂／ＣｅＯ₂＝８／２）４５５ｇをフラスコに計り取る。そこへ、蒸留水１４２ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシランを１９１ｇとメチルトリメトキシシラン６９ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００７７】
その後、混合液を撹拌しながらイソプロピルアルコールを１００ｇ添加し、次にブレンマーＰＥ２００を４０ｇ添加した。さらに、硬化触媒として過塩素酸アンモニウムを３ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００７８】
実施例５
実施例１のＴｉＯ₂−Ｆｅ₂Ｏ₃−ＳｉＯ₂からなる複合金属酸化物ゾルをＳｂ₂Ｏ₅からなる金属酸化物ゾル（固形分３０％、メタノール分散ゾル、日産化学工業（株）製、商標名サンコロイド_RＡＭＴ−１３０）に代える以外は同じ方法を用いた。結果は表１に示した。
【００７９】
実施例６
ＣｅＯ₂からなる金属酸化物ゾル（固形分１５％、水分散ゾル、多木化学（株）製、商標名ニードラルＵ−１５）４６７ｇをフラスコに計り取る。次にγ−グリシドキシプロピルトリメトキシシラン１８４ｇを徐々に添加し、加水分解を行った。添加終了後さらに１時間撹拌した。
【００８０】
その後、混合液を撹拌しながら、イソプロピルアルコールを３１６ｇ添加し、次にブレンマーＰＥ２００を３０ｇ添加した。さらに、硬化触媒として過塩素酸アンモニウムを３ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００８１】
実施例７
オプトレイク１１３０Ｆ−２（Ａ−８）３０３ｇをフラスコに計り取る。そこへ、蒸留水１７０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン２３９ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００８２】
その後、混合液を撹拌しながらメタノールを２４１ｇ添加し、次にブレンマーＰＥ２００を４０ｇ添加した。さらに、硬化触媒としてアセチルアセトン金属塩の変性体（ホープ製薬（株）、商標名アセトープ−Ａｌ（ＭＸ））１５ｇ、フローコントロール剤としてシリコーン界面活性剤（ダウコーニングアジア（株）製、商標名ペインタッド_R３２）を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００８３】
実施例８
オプトレイク１１３０Ｆ−２（Ａ−８）３４０ｇをフラスコに計り取る。そこへ、蒸留水１２２ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン１３４ｇとメチルトリメトキシシラン１２８ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００８４】
その後、混合液を撹拌しながらエタノールを２２９ｇ添加し、次にブレンマーＰＥ２００を４０ｇ添加した。さらに、硬化触媒として過塩素酸アンモニウムを３ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００８５】
実施例９
オプトレイク１１３０Ｆ−２（Ａ−８）３１２ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン８３ｇとメチルトリメトキシシラン１７８ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００８６】
その後、混合液を撹拌しながらエタノールを２３４ｇ添加し、次にブレンマーＰＥ２００を６０ｇ添加した。さらに、硬化触媒としてアセルチルアセトンアルミニウム９ｇ、フローコントロール剤としてシリコーン界面活性剤（ダウコーニングアジア（株）製、商標名ペインタッド_R５７）を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００８７】
実施例１０
オプトレイク１１３０Ｆ−２（Ａ−８）３１０ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン１８９ｇとメチルトリメトキシシラン３４ｇ、さらにジメチルジメトキシシラン２７ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００８８】
その後、混合液を撹拌しながらメタノールを２７７ｇ添加し、次に一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝２のポリエチレングリコールモノメタクリル酸エステル（日本油脂（株）製、商標名ブレンマーＰＥ９０）を３０ｇ添加した。さらに、硬化触媒としてアセルチルアセトンアルミニウム９ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００８９】
実施例１１
オプトレイク１１３０Ｆ−２（Ａ−８）３１０ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン２１２ｇとテトラエチルオルソシリケート５８ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００９０】
その後、混合液を撹拌しながらメタノールを２５７ｇ添加し、次にブレンマーＰＥ２００を３０ｇ添加した。さらに、硬化触媒としてアセルチルアセトンアルミニウム９ｇ、フローコントロール剤としてペインタッド_R３２を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００９１】
実施例１２
オプトレイク１１３０Ｆ−２（Ａ−８）２４７ｇをフラスコに計り取る。そこへ、蒸留水１５０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン２１０ｇとフェニルトリメトキシシラン５７ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００９２】
その後、混合液を撹拌しながらメタノールを３０３ｇ添加し、次にブレンマーＰＥ２００を２０ｇ添加した。さらに、硬化触媒としてアセトープ−Ａｌ（ＭＸ）１５ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００９３】
実施例１３
オプトレイク１１３０Ｆ−２（Ａ−８）３１０ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン２１１ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００９４】
その後、混合液を撹拌しながらエタノールを３２６ｇ添加し、次にブレンマーＰＥ９０を２０ｇ添加した。さらに、硬化触媒としてアセチルアセトンアルミニウムを９ｇ、フローコントロール剤としてペインタッド_R５７を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００９５】
実施例１４
オプトレイク１１３０Ｆ−２（Ａ−８）３１０ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン１６９ｇとメチルトリメトキシシラン６８ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００９６】
その後、混合液を撹拌しながらＩＰＡを２８０ｇ添加し、次にブレンマーＰＥ２００を２０ｇ添加した。さらに、硬化触媒として過塩素酸アンモニウムを３ｇ、フローコントロール剤としてペインタッド_R５７を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００９７】
実施例１５
オプトレイク１１３０Ｆ−２（Ａ−８）３１０ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン２７８ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【００９８】
その後、混合液を撹拌しながらＩＰＡを２７０ｇ添加し、次にブレンマーＰＥ２００を８ｇ添加した。さらに、硬化触媒としてアセチルアセトンアルミニウム９ｇ、フローコントロール剤としてペインタッド_R３２を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【００９９】
実施例１６
実施例１の一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステルを一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨＣＨ₃ＣＨ₂ＣＨ₂、ｃ＝５のポリプロピレングリコールモノメタクリル酸エステル（日本油脂（株）製、商標名ブレンマーＰＰ１０００）に代える以外は同じ方法を用いた。結果は表１に示した。
【０１００】
実施例１７
オプトレイク１１３０Ｆ−２（Ａ−８）３１０ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン１７９ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【０１０１】
その後、混合液を撹拌しながらＩＰＡを２８０ｇ添加し、次にブレンマーＰＥ９０を１００ｇ添加した。さらに、硬化触媒としてアセチルアセトンアルミニウム９ｇ、フローコントロール剤としてペインタッド_R３２を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示した。
【０１０２】
実施例１８
実施例１の一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステルを一般式ＤでＲ⁶＝水素原子、ｂ＝４の４−ヒドロキシブチルアクリレート（大阪有機工業（株）製、商標名４−ＨＢＡ）に代える以外は同じ方法を用いた。結果は表１に示した。
【０１０３】
実施例１９
実施例１の一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステルを一般式Ｅでｄ＝０、ｂ＝４の４−ヒドロキシブチルビニルエーテル（アイエスエスピー・ジャパン（株）製、商標名ラピキュアー_RＨＢＶＥ）に代える以外は同じ方法を用いた。結果は表１に示した。
【０１０４】
実施例２０
実施例１の一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステルを一般式Ｅでｄ＝１、ｂ＝２のエチレングリコールモノアリルエーテル（東京化成工業（株）製）に代える以外は同じ方法を用いた。結果は表１に示した。
【０１０５】
実施例２１
実施例１の一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステルを一般式Ｆでｄ＝１、ｆ＝３〜４のアリル化ポリエーテル（日本油脂（株）製、商標名ユニオックスＰＫＡ−５００１）に代える以外は同じ方法を用いた。結果は表１に示した。
【０１０６】
実施例２２
実施例１の一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステルを２−ヒドロキシ−３−フェノキシプロピルアクリレート（新中村化学工業（株）製、商標名ＮＫエステル７０２Ａ）に代える以外は同じ方法を用いた。結果は表１に示した。
【０１０７】
実施例２３
実施例１の一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステルを２−ヒドロキシ−１，３−ジメタクリロキシプロパン（新中村化学工業（株）製、商標名ＮＫエステル７０１）に代える以外は同じ方法を用いた。結果は表１に示した。
【０１０８】
実施例２４
実施例１の一般式ＣでＲ⁶＝メチル基、Ｒ⁷＝ＣＨ₂ＣＨ₂、ｃ＝４のポリエチレングリコールモノメタクリル酸エステルをペンタエリスリトールトリアクリレート（東亜合成化学（株）製、商標名アロニックスＭ−３０５）に代える以外は同じ方法を用いた。結果は表１に示した。
【０１０９】
実施例２５
実施例１の混合液を屈折率１．５９４のウレタン樹脂からなるプラスチックレンズ（三井東圧化学（株）製モノマー改良ＭＲ−６を熱重合してなるレンズ）に塗布し、１２０℃で１時間熱硬化した。得られたレンズの干渉縞はほとんど目立たなかった。その他は実施例１と同様に評価した。結果は表１に示した。
【０１１０】
実施例２６
実施例１の混合液を屈折率１．５９のメタクリル系重合体からなるプラスチックレンズ（トクヤマ（株）製モノマーＴＳ−２６を熱重合してなるレンズ）に塗布し、１２０℃で１時間熱硬化した。得られたレンズの干渉縞はほとんど目立たなかった。その他は実施例１と同様に評価した。結果は表１に示した。
【０１１１】
実施例２７
実施例１の混合液を屈折率１．５９のウレタン反応とラジカル重合を併用した重合体からなるプラスチックレンズ（三菱瓦斯化学（株）製モノマーＭＬ−３を熱重合してなるレンズ）に塗布し、１２０℃で１時間熱硬化した。得られたレンズの干渉縞はほとんど目立たなかった。その他は実施例１と同様に評価した。結果は表１に示した。
【０１１２】
実施例２８
実施例１の混合液を屈折率１．６０のトリアジン環を主成分とするプラスチックレンズＫ−２５（クレハレンテック（株）製）に塗布し、１２０℃で１時間熱硬化した。得られたレンズの干渉縞はほとんど目立たなかった。その他は実施例１と同様に評価した。結果は表１に示した。
【０１１３】
実施例２９
オプトレイク１１３０Ｆ−２（Ａ−８）４３３ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン１８４ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【０１１４】
その後、混合液を撹拌しながらＩＰＡを２１０ｇ添加し、次にユニオックスＰＫＡ−５００１を４０ｇ添加した。さらに、硬化触媒としてアセチルアセトンアルミニウム３ｇ、フローコントロール剤としてペインタッド_R５７を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。
【０１１５】
屈折率１．６６のポリウレタン樹脂からなるプラスチックレンズ（三井東圧化学（株）製モノマーである商標名ＭＲ−７を熱重合してなるレンズ）に上記混合液を塗布し、１２０℃で１時間熱硬化した。得られた塗膜の屈折率は１．６４であり、レンズの干渉縞はほとんど目立たなかった。また膜厚は１．５〜２．０μｍであった。その他は実施例１と同様に評価した。結果は表１に示した。
【０１１６】
実施例３０
オプトレイク１１３０Ｆ−２（Ａ−８）４６８ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシラン１３５ｇ、さらに、フェニルトリメトキシシラン３７ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【０１１７】
その後、混合液を撹拌しながらエタノールを１８８ｇ添加し、次にブレンマーＰＥ４００を４０ｇ添加した。さらに、硬化触媒としてアセトープ−Ａｌ（ＭＸ）１５ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。上記混合液を用いて実施例２９と同様に評価した。結果は表１に示した。
【０１１８】
実施例３１
オプトレイク１１３０Ｆ−２（Ａ−８）２０８ｇをフラスコに計り取る。そこへ、蒸留水１２０ｇを撹拌しながら添加した。次にγ−グリシドキシプロピルトリメトキシシランを２２３ｇとメチルトリメトキシシラン８０ｇを徐々に添加する。添加終了後さらに２時間撹拌した。
【０１１９】
その後、混合液を撹拌しながらイソプロピルアルコールを３１５ｇ添加し、次にブレンマーＰＥ２００を４０ｇ添加した。さらに、硬化触媒として過塩素酸アンモニウム３ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で４８時間熟成した。
【０１２０】
屈折率１．５６のジアリルフタレート重合体を主成分とするプラスチックレンズに上記混合液を塗布し、１２０℃で１時間熱硬化した。得られた塗膜の外観は無色透明であった。付着性は１００／１００であり、硬化膜の屈折率は１．５４であり、干渉縞はほとんど目立たなかった。また膜厚は１．７〜２．２μｍであった。その他は実施例１と同様に評価した。結果は表１に示した。
【０１２１】
実施例３２
実施例１の混合液を屈折率１．５６のトリアジン環を主成分とするプラスチックレンズＫ−２３（クレハレンテック（株）製）に塗布し、１２０℃で１時間熱硬化した。得られたレンズの干渉縞はほとんど目立たなかった。その他は実施例１と同様に評価した。結果は表１に示した。
【０１２２】
上記実施例１〜３２で得られたプラスチックレンズ基材上に真空蒸着法によりハードコート側からＺｒＯ₂、ＳｉＯ₂、ＺｒＯ₂、ＳｉＯ₂の４層の反射防止膜を形成した。形成された反射防止膜の光学的膜厚は順に約λ／１２、λ／１２、λ／２、λ／４である。なおλは光の波長５２０ｎｍである。得られたレンズの評価結果は表２に示した。
【０１２３】
比較例１
グリシドキシプロピルトリメトキシシラン２７５ｇをフラスコに計り取り、液温を１０℃以下に保持し、撹拌を行いながら０．０１規定の塩酸水溶液を６３ｇ徐々に添加し、γ−グリシドキシプロピルトリメトキシシランの加水分解を行った。次に、メタノール２９８ｇを加えてさらに１時間撹拌した。次にこの溶液にオプトレイク１１３０Ｆ−２（Ａ−８）３５０ｇを添加した。添加終了後さらに１時間撹拌した。さらに硬化触媒として過塩素酸アンモニウムを３ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で２４時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示す。
【０１２４】
比較例２
比較例１のＴｉＯ₂−Ｆｅ₂Ｏ₃−ＳｉＯ₂からなる複合金属酸化物ゾルをＴｉＯ₂−ＣｅＯ₂−ＳｉＯ₂からなる複合金属酸化物ゾルに代える以外は同じ方法を用いた。結果は表１に示す。
【０１２５】
比較例３
比較例１のＴｉＯ₂−Ｆｅ₂Ｏ₃−ＳｉＯ₂からなる複合金属酸化物ゾルをＳｂ₂Ｏ₅からなる金属酸化物ゾルに代える以外は同じ方法を用いた。結果は表１に示す。
【０１２６】
比較例４
コロイダルシリカ（固形分３０％、水分散ゾル、日産化学（株）製、商標名スノーテックスＯ−４０）３００ｇをフラスコに計り取り、冷却撹拌しながらγ−グリシドキシプロピルトリメトキシシラン２０４ｇを徐々に添加する。添加終了後さらに１時間撹拌した。途中、混合液の昇温がなくなった時点で冷却を止めた。
【０１２７】
その後、混合液を撹拌しながら、イソプロパノールを４５１ｇ添加し、次にＰＥ９０を３８ｇ添加した。さらに、過塩素酸アンモニウムを１．５ｇ、フローコントロール剤としてＬ−７００１を０．４ｇ添加し、１時間撹拌した。上記混合液を室温で２４時間熟成した。上記混合液を用いて実施例１と同様に評価した。結果は表１に示す。
【０１２８】
【表１】

【０１２９】
上記実施例と比較例に示すように、本発明の第三成分のない比較例１〜３のコーティング組成物は染色がほとんどできず、また比較例４の場合は低屈折率のハードコート層が得られ、干渉縞が生じる。
このように本発明の上記実施例のコーティング組成物から得られる塗膜は干渉縞がなく、深染が可能である。
【０１３０】
上記実施例と比較例でのコーティング液の塗布方法は次の通りである。
（１）レンズ基材を８％のＮａＯＨ水溶液に３０分間浸漬し、十分に水洗した後、乾燥させた。
（２）各コーティング液を１５ｃｍ／分の引き上げ速度でディッピングを行った。
（３）約５分室温乾燥後、１２０℃で１時間加熱硬化した。
【０１３１】
また、実施例と比較例で得られた塗膜の試験方法は次の通りである。
（１）クロスハッチ試験（ゴバン目試験ＪＩＳＫ５４００に準拠した）
（２）スチールウール試験
スチールウール＃００００を用い１ｋｇ荷重でこすり、傷の付きぐあいを以下の基準に基づき相対比較した。
５：全く傷が付かない、 ４：若干の傷が付く、
３：傷が付く、 ２：ひどい傷が付く、
１：基材まで傷が付く
（３）染色性
Ｂｒａｉｎ Ｐｏｗｅｒ Ｉｎｃ（ＵＳＡ）のＢＰＩ ＧＲＡＹを蒸留水で９％に希釈したものを９０℃に加熱し、この水溶液に各コート液を塗布したレンズを５分間浸漬し、その後レンズを取りだし、水洗した。染色後の全光線透過率を測定し、染色性を比較した。
（４）干渉縞
ＭＩＤＷＥＳＴ ＳＣＩＥＮＴＩＦＩＣ ＣＯ．（ＵＳＡ）の単色ランプ ＵＮＩＬＡＭＰを用いてコート後のレンズの干渉縞を目視観察した。
（５）耐候性コート後のレンズの耐候性試験をキャノンアークウェザオメータで行った。
この試験は６８±３℃のブラックパネル温度で１６分／２時間のサイクルで水をスプレーしながら２４８時間照射し、その後のクロスハッチテストおよび外観を表２に示す。
【０１３２】
【表２】

【発明の効果】
本発明により、コーティング組成物を高屈折率の基材に塗布硬化して得られた被膜は、非常に高い耐擦傷性、耐摩擦性を有する一方、干渉縞の発生が抑えられ、しかも深染め可能である。
こうして、上記優れた性質を有する被覆物品が得られる。[0001]
[Industrial applications]
The present invention relates to a coating composition capable of obtaining a hard coat film having a high refractive index and excellent hardness, and a coated article obtained by coating the composition.
[0002]
[Prior art]
Compared to glass lenses, plastic lenses, which are a type of transparent molded body, are superior in safety, workability, fashionability, lightness, etc. In addition, development of hard coating technology and anti-reflection technology for this lens Has spread rapidly in recent years. Silica-based hard coat films applied to plastic lenses have attracted attention because of their high hardness and abrasion resistance.However, plastic lenses with a high refractive index have been developed and have become widely used. There is a phenomenon that the refractive index difference is large and interference fringes occur due to the difference in film thickness.
[0003]
In addition, instead of silica, a high refractive index hard coat film using a high refractive index metal oxide such as antimony oxide, zirconium oxide, titanium oxide, tin oxide, etc. is formed on plastic lenses and other transparent molded products. Has also been done.
[0004]
Japanese Patent Publication No. 63-37142 discloses a hard coat film composed of antimony oxide and epoxysilane, and JP-A-5-2102 discloses a hard coat film composed of fine particles composed of titanium oxide, iron oxide and silicon dioxide and epoxysilane. Japanese Unexamined Patent Publication No. Hei 5-164902 discloses a hard coat film composed of fine particles composed of titanium oxide, cerium oxide and silicon dioxide, and epoxysilane and a tetrafunctional silane compound.
[0005]
[Problems to be solved by the invention]
However, the conventional high-refractive-index hard coat film on a transparent substrate could hardly be dyed after coating, or could not be deeply dyed even if it could be slightly dyed. In order to perform deep dyeing, it was necessary to lower the hardness of the hard coat film.
[0006]
Accordingly, an object of the present invention is to provide a coating composition that can suppress the occurrence of interference fringes when applied to a high refractive index substrate.
[0007]
Another object of the present invention is to provide a coating composition which can be dyed after coating and which can be deeply dyed and which can provide a hard coat film having extremely excellent hardness.
[0008]
Further, it is an object of the present invention to provide a coating composition that provides an optically transparent cured film.
[0009]
Another object of the present invention is to provide a coated article obtained by applying the coating composition to a substrate such as a plastic lens.
[0010]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following configuration.
That is, (1) specific oxide fine particles containing at least one of silica, iron oxide, titanium oxide, cerium oxide, zirconium oxide, antimony oxide, zinc oxide and tin oxide, or a mixture thereof, or fine particles comprising a composite oxide thereof. 10 to 70% by weight, and (2) 5 to 90% by weight of an epoxy group-containing silicon compound or a partial hydrolyzate thereof.
(3)Compounds having only one OH group in the molecule and represented by the general formulas (C) to (F)
CH _Two = C (R ⁶ ) CO - ( - OR ⁷ - ) _c OH (C)
CH _Two = C (R ⁶ ) COO - ( - CH _Two - ) _b OH (D)
CH _Two = CH - ( - CH _Two - ) _d - O - ( - CH _Two - ) _e - OH (E)
CH _Two = CH - ( - CH _Two - ) _d - ( - OR ⁷ - ) _f - OH (F)
( Where R ⁶ Is a hydrogen atom or a methyl group, R ⁷ Is -CH _Two CH _Two -Or -CH _Two CH (CH _Three B is an integer of 2 to 10, preferably 4 to 6, c is an integer of 1 to 9, preferably 2 to 4, d is an integer of 0 or 1, and e is 4 An integer of 10 to 10, and f represents an integer of 2 to 9, respectively. )
Consisting of at least one compound selected from the group consisting of
1 to 45% by weight of an organic compound soluble in water or a lower alcohol having 4 or less carbon atoms,
(4) It contains a curing catalyst for an epoxy group-containing silicon compound or a partial hydrolyzate thereof.ThermosettingHigh refractive index coating composition, or
SaidThermosettingA coated article obtained by applying and curing a high refractive index coating composition on a high refractive index substrate.
[0011]
The components contained in the coating composition of the present invention will be described.
(1) The first component of the present invention is a sol in which the fine particles of the specific oxide are dispersed alone in a dispersion solvent or a sol compound thereof, preferably at least two types of the specific oxide, or a mixture of the specific oxide and silicon dioxide. Alternatively, a sol in which fine particles composed of a composite metal oxide in a physically bonded state are dispersed in a dispersion solvent can be used. These composite metal oxide fine particles are used for further improving the performance of each metal oxide single fine particle.
[0012]
Examples of the composite oxide fine particles containing titanium oxide include composite metal oxide fine particles composed of titanium oxide, iron oxide and silicon dioxide, and composite metal oxide fine particles composed of titanium oxide, cerium oxide and silicon dioxide. It is known that fine particles of titanium oxide alone are inferior in weather resistance, and it has been pointed out that a problem of weather resistance also occurs when a coating film is formed. Since iron oxide or cerium oxide has a longer absorption wavelength range than titanium oxide, it has the function of improving the weather resistance of titanium oxide, and silicon dioxide has the function of increasing the stability of composite fine particles. I have.
[0013]
For example, TiO_TwoIn the case of an iron oxide component, a titanium oxide component and a silica component as an example of a composite metal oxide containing_TwoO_ThreeAnd the titanium oxide component is converted to TiO_TwoAnd convert the silica component to SiO_TwoWeight ratio Fe when converted to_TwoO_Three/ TiO_Two= 0.005 to 1.0, and by including the weight ratio of 0.005 or more, the weather resistance of the coating film is further improved. On the other hand, when the weight ratio exceeds 1.0, the coating film turns yellow and transparency decreases.
[0014]
Also, the weight ratio SiO_Two/ (Fe_TwoO_Three+ TiO_Two) Is preferably in the range of 0.001 to 1.0, and when the weight ratio is 0.001 or more, the dispersion stability of the sol is improved. When the weight ratio exceeds 1.0, the effect of increasing the refractive index is reduced.
[0015]
When the composite metal oxide is composed of, for example, a cerium oxide component, a titanium oxide component, and a silica component, the amount of the cerium oxide component is CeO._TwoAnd the titanium oxide component is converted to TiO_TwoAnd convert the silica component to SiO_TwoWeight ratio when converted to CeO_Two/ TiO_TwoIs in the range of 0.1 to 1.0, and the weight ratio SiO_Two/ (CeO_Two+ TiO_Two) Is preferably in the range of 0.05 to 0.5, and the weight ratio CeO_Two/ TiO_TwoIs 0.1 or more, the weather resistance of the coating film is further improved, and if it exceeds 1.0, the yellow color of the coating film is increased. Also, weight ratio SiO_Two/ (CeO_Two+ TiO_Two) Is 0.05 or more, the dispersion stability of the sol is improved._TwoAnd TiO_TwoDispersion stability is reduced.
[0016]
Further, it is desirable that the average particle diameter of the particles of each substance of the specific oxide, a mixture thereof, or a composite metal oxide thereof is in a range of 1 to 100 nm. When the average particle diameter is less than 1 nm, the particles cannot be substantially produced, and when the average particle diameter exceeds 100 nm, the transparency of the coating film decreases.
[0017]
Further, the specific oxide, a mixture thereof, or a composite oxide thereof is improved in reactivity and affinity between the specific oxide and the like and the matrix by surface modification with an organosilicon compound, and the specific oxide and the like are improved. And the solvent have improved affinity. At this time, as the organosilicon compound used,
[0018]
For example
R_ThreeA monofunctional silane represented by SiX (R is an organic group having an alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a mercapto group, an amino group, an epoxy group, and X is a hydrolyzable group);
For example,
Trimethylmethoxysilane,
Triethylmethoxysilane,
Trimethylethoxysilane,
Triethylethoxysilane,
Triphenylmethoxysilane,
Diphenylmethylmethoxysilane,
Phenyldimethylmethoxysilane,
Phenyldimethylethoxysilane,
Vinyldimethylmethoxysilane,
Vinyldimethylethoxysilane,
[0019]
γ-acryloxypropyldimethylmethoxysilane,
γ-methacryloxypropyldimethylmethoxysilane,
γ-mercaptopropyldimethylmethoxysilane,
γ-mercaptopropyldimethylethoxysilane,
N-β (aminoethyl) γ-aminopropyldimethylmethoxysilane,
γ-aminopropyldimethylmethoxysilane,
γ-aminopropyldimethylethoxysilane,
γ-glycidoxypropyldimethylmethoxysilane,
γ-glycidoxypropyldimethoxyethoxysilane,
β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane
Etc.,
[0020]
Or R_TwoSix_TwoA bifunctional silane represented by
For example,
Dimethyldimethoxysilane,
Diethyldimethoxysilane,
Dimethyldiethoxysilane,
Diethyldiethoxysilane,
Diphenyldimethoxysilane,
Phenylmethyldimethoxysilane,
Phenylmethyldiethoxysilane,
Vinylmethyldimethoxysilane,
Vinylmethyldiethoxysilane,
[0021]
γ-acryloxypropylmethyldimethoxysilane,
γ-methacryloxypropyldimethyldimethoxysilane,
γ-mercaptopropylmethyldimethoxysilane,
γ-mercaptopropylmethyldiethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane,
γ-aminopropylmethyldimethoxysilane,
γ-aminopropylmethyldiethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane,
γ-glycidoxypropylmethyldiethoxysilane,
β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane
Etc.,
[0022]
Or RSix_ThreeA trifunctional silane represented by
For example,
Methyltrimethoxysilane,
Ethyltrimethoxysilane,
Methyltriethoxysilane,
Ethyltriethoxysilane,
Phenyltrimethoxysilane,
Phenyltriethoxysilane,
Vinyltrimethoxysilane,
Vinyltriethoxysilane,
Vinyl (β-methoxyethoxy) silane,
γ-acryloxypropyltrimethoxysilane,
γ-methacryloxypropyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane,
[0023]
N-β (aminoethyl) γ-aminopropyltrimethoxysilane,
γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane,
β-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane,
β-glycidoxypropyltriethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
Etc., and also SiX_FourA tetrafunctional silane represented by
For example,
Tetraethyl orthosilicate,
Tetramethyl orthosilicate
And so on.
[0024]
The surface modification with the organosilicon compound of the first component may be performed without hydrolyzing the hydrolyzable groups of the organosilicon compound, or may be performed after the hydrolysis.
[0025]
The amount of the organosilicon compound is 0.01 to 0.15 times the weight of the fine particles of the first component, depending on the amount of hydroxyl groups present on the surface of the oxide or composite oxide.
[0026]
Next, as a dispersion medium of the first component, water, a hydrocarbon, a halogenated hydrocarbon, an ester, a ketone, an alcohol, a cellosolve, an amine, an organic carboxylic acid, or the like is used. Further, two or more kinds of the dispersion media may be mixed.
[0027]
For example, methanol, ethanol, isopropyl alcohol, n-butanol, 2-butanol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran, acetone, xylene, N, N-dimethyl Formamide, methyl ethyl ketone, dichloroethane, toluene and the like.
[0028]
The dispersion sol of the first component is, for example, Opto-lake 1130F-2 (A-8) (iron oxide-titanium oxide-silica composite particles (particle diameter: 10 nm, compounding ratio: TiO) manufactured by Catalyst Chemical Industry Co., Ltd.)_Two: Fe_TwoO_Three: SiO_Two= 80: 0.7: 19.3), solid content 30%, methanol dispersion), Optrake 1130A (A-8) (cerium oxide-titanium oxide-silica composite particles (particle diameter 10 nm, compounding ratio TiO)_Two: CeO: SiO_Two= 68:17:15), solid content 30%, methanol dispersion) and the like.
[0029]
Fine particles of the first component are used to increase the refractive index of the coating film. It is known that when the refractive index of the coating film falls within the range of the refractive index of the substrate ± 0.03, preferably ± 0.020, the occurrence of interference fringes can be suppressed. That is, it is necessary to adjust the addition amount of the fine particle sol according to the refractive index of the transparent substrate to be applied. On the other hand, the addition amount of the fine particle sol is also restricted in order to improve other coating film properties.
[0030]
Therefore, the fine particles of the first component are used at 10 to 70% by weight, preferably 15 to 60% by weight, based on the total solids in the coating composition. If the amount of the fine particles of the first component is less than 10% by weight of the total solid content in the coating composition, the effect of increasing the refractive index will be small, and if it exceeds 70% by weight, cracks will occur in the coating film.
[0031]
(2) The epoxy group-containing silicon compound or its partial hydrolyzate as the second component of the present invention is an epoxy group-containing silicon compound represented by the following general formula (A) or its partial hydrolyzate.
[0032]
R¹R^Two _aSi (OR^Three)_3-a                    (A)
Where R¹Is a group containing an epoxy group having 2 to 12 carbon atoms, R^TwoIs an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group, R^ThreeRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an acyl group, or an alkylacyl group, and a represents 0, 1 or 2.
[0033]
The epoxy group-containing silicon compound represented by the general formula (A) is
For example,
γ-glycidoxypropyltrimethoxysilane,
β-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane,
β-glycidoxypropyltriethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane,
γ-glycidoxypropylmethyldiethoxysilane,
β- (3.4-epoxycyclohexyl) ethyltrimethoxysilane,
γ- (β-glycidoxyethoxy) propyltrimethoxysilane,
β- (3.4-epoxycyclohexyl) ethyltriethoxysilane,
γ-glycidoxypropylphenyldimethoxysilane,
γ-glycidoxypropylphenyldiethoxysilane
It is.
[0034]
The second component of the present invention is used in an amount of 5 to 90% by weight, preferably 10 to 85% by weight based on the total solid content in the coating composition. If the second component is less than 5% by weight of the total solids in the coating composition, the dyeability of the coating film will be reduced, and if it exceeds 90% by weight, the added amount of the composite oxide sol will be small and the refractive index will be high. No.
[0035]
(3) The third component of the present invention has only one OH group or SH group in the molecule, and further has a functional group represented by the following structural formula in the molecular main chain: -O-, -CO-O A compound containing at least one of-, -S-, -CO-S- or -CS-S- and soluble in water or a lower alcohol having 4 or less carbon atoms is represented by the following general formula (B). be able to.
[0038]
Preferred compounds of the third component of the present invention are compounds represented by the following general formulas (C) to (F).
CH _Two = C (R ⁶ ) CO-(-OR ⁷ −) _c OH (C)
Where R⁶Is a hydrogen atom or a methyl group, R⁷Is-CH _Two CH _Two -Or -CH _Two CH (CH _Three )-c is an integer of 1 to 9, preferably 2 to 4.
[0039]
The compound represented by the general formula (C) is
For example,
Diethylene glycol monoacrylate,
Tetraethylene glycol monoacrylate,
Polyethylene glycol monoacrylate,
Tripropylene glycol monoacrylate,
Polypropylene glycol monoacrylate,
Diethylene glycol monomethacrylate,
Tetraethylene glycol monomethacrylate,
Polyethylene glycol monomethacrylate,
Tripropylene glycol monomethacrylate,
Polypropylene glycol monomethacrylate
And so on.
[0040]
Embedded image

Where R⁶Represents a hydrogen atom or a methyl group, and b represents an integer of 2 to 10, preferably 4 to 6.
[0041]
The compound represented by the general formula (D) is
For example,
4-hydroxybutyl acrylate,
4-hydroxybutyl methacrylate,
4-hydroxyethyl acrylate,
4-hydroxyethyl methacrylate
It is.
[0042]
CH_Two= CH-(-CH_Two-)_d-O-(-CH_Two-)_e-OH (E)
Here, d represents an integer of 0 or 1, and e represents an integer of 4 to 10, respectively.
[0043]
The compound represented by the general formula (E) is
For example,
4-hydroxybutyl allyl ether,
4-hydroxybutyl vinyl ether
It is.
[0044]
CH_Two= CH-(-CH_Two-)_d-(-OR⁷-)_f-OH (F)
Where R⁷Is -CH_TwoCH_Two-Or -CH_TwoCH (CH_Three)-, D is an integer of 0 or 1, and f is an integer of 2-9.
[0045]
The compound represented by the general formula (F) is
For example,
Diethylene glycol monoallyl ether,
Triethylene glycol monovinyl ether
It is.
[0046]
The third component of the present invention is used in an amount of 1 to 45% by weight, preferably 2 to 30% by weight based on the total solid content in the coating composition. If the third component is less than 1% by weight of the total solid content in the coating composition, deep dyeing cannot be performed, and if it exceeds 45% by weight, the hardness of the coating film decreases.
[0047]
(4) The coating composition of the present invention contains, in addition to the first to third components, a curing catalyst described below, and a compound having the following general formula (G) as an organosilicon compound or a partial hydrolyzate thereof. It can be included as necessary as a fourth component. A coating film obtained by adding the compound of the general formula (G) has improved adhesion to an antireflection film coated on the coating film, and increases hardness of the coating film. By adjusting the amount of the compound (G), the refractive index of the coating film obtained can be adjusted.
[0048]
R ⁸ _hR^Two _aSi (OR^Three)_4-ha (G)
Where R^TwoAnd R^ThreeIs the same as defined in formula (A), ⁸ Is an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group, an aryl group or a halogenated aryl group having 6 to 12 carbon atoms, a methacryloxyalkyl group having 5 to 8 carbon atoms, It represents any of a ureidoalkylene group, an aromatic ureidoalkylene group, a halogenated aromatic alkylene group, and a mercaptoalkylene group, a represents an integer of 0, 1 or 2, and h represents an integer of 0 to 3.
[0049]
A coating film obtained by adding the compound of the general formula (G) has improved adhesion to an antireflection film coated on the coating film, and has an increased hardness. It is also possible to adjust the refractive index of the coating film obtained by adjusting the amount of the compound (G) added.
[0050]
The organosilicon compound represented by the general formula (G) is
For example,
Trimethylmethoxysilane,
Triethylmethoxysilane,
Trimethylethoxysilane,
Triethylethoxysilane,
Triphenylmethoxysilane,
Diphenylmethylmethoxysilane,
Phenyldimethylmethoxysilane,
Phenyldimethylethoxysilane,
Vinyldimethylmethoxysilane,
Vinyldimethylethoxysilane,
Vinyl (β-methoxyethoxy) silane,
[0051]
γ-acryloxypropyldimethylmethoxysilane,
γ-methacryloxypropyldimethylmethoxysilane,
γ-mercaptopropyldimethylmethoxysilane,
γ-mercaptopropyldimethylethoxysilane,
N-β (aminoethyl) γ-aminopropyldimethylmethoxysilane,
γ-aminopropyldimethylmethoxysilane,
γ-aminopropyldimethylethoxysilane,
γ-glycidoxypropyldimethylmethoxysilane,
γ-glycidoxypropyldimethoxyethoxysilane,
β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane,
Dimethyldimethoxysilane,
Diethyldimethoxysilane,
Dimethyldiethoxysilane,
Diethyldiethoxysilane,
Diphenyldimethoxysilane,
Phenylmethyldimethoxysilane,
Phenylmethyldiethoxysilane,
Vinylmethyldimethoxysilane,
Vinylmethyldiethoxysilane,
[0052]
γ-acryloxypropylmethyldimethoxysilane,
γ-methacryloxypropyldimethyldimethoxysilane,
γ-mercaptopropylmethyldimethoxysilane,
γ-mercaptopropylmethyldiethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane,
γ-aminopropylmethyldimethoxysilane,
γ-aminopropylmethyldiethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane,
γ-glycidoxypropylmethoxydiethoxysilane,
β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane,
Methyltrimethoxysilane,
Ethyltrimethoxysilane,
Methyltriethoxysilane,
Ethyltriethoxysilane,
Phenyltrimethoxysilane,
Phenyltriethoxysilane,
Vinyltrimethoxysilane,
Vinyltriethoxysilane,
Vinyl (β-methoxyethoxy) silane,
[0053]
γ-acryloxypropyltrimethoxysilane,
γ-methacryloxypropyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane,
N-β (aminoethyl) γ-aminopropyltrimethoxysilane,
γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane,
β-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane,
β-glycidoxypropyltriethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
Tetraethyl orthosilicate,
Tetramethyl orthosilicate
And so on.
[0054]
The fourth component of the present invention is used in an amount of 0 to 60% by weight, preferably 2 to 45% by weight, based on the total solid content in the coating composition. If the fourth component exceeds 60% by weight of the total solids in the coating composition, it will be difficult to increase the refractive index.
[0055]
(5) As a curing catalyst for the coating composition of the present invention,
Alkali metal and ammonium salts of carboxylic acids; eg sodium acetate, ammonium acetate
Metal salts and ammonium salts of acetylacetone; for example, aluminum acetylacetone, zirconium acetylacetone, ammonium acetylacetone
Primary to tertiary amines; for example, butylamine, hydroxyethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, dimethylphenylamine, polyalkyleneamine
Metal and ammonium salts of perchloric acid; eg, magnesium perchlorate, ammonium perchlorate
Metal salt of ethyl acetoacetate
Metal salt coordinated by acetylacetone and ethyl acetoacetate
Organic metal salts; for example, zinc naphthenate, tin octylate
Lewis acid; for example, SnCl_Four, TiCl_Four, ZnCl_Two
Are used.
[0056]
As the curing catalyst for the coating composition of the present invention, the above-mentioned compound can be used in combination with an organic mercaptan or a mercaptoalkylenesilane. The curing catalyst may be added at the time of preparing the mixed solution or immediately before coating. The selection of the time of addition of the curing catalyst is arbitrarily determined as needed.
The curing catalyst of the present invention is used in an amount of 0.001 to 10% by weight based on the total solid content in the coating composition.
[0057]
(6) Alcohols, ethers, aromatic hydrocarbons, esters, and ketone compounds are used as the dispersion medium of the coating composition of the present invention. For example, methanol, ethanol, isopropyl alcohol, n-butanol, 2-butanol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran, acetone, xylene, N, N- Dimethylformamide, methyl ethyl ketone, dichloroethane, toluene and the like are used.
[0058]
The diluting dispersion medium is used by adding 100 to 800% by weight based on the total solid content in the coating composition. When the addition amount of the dispersion medium is less than 100% by weight, the thickness of the obtained coating film becomes large, and cracks are easily generated. On the other hand, when the amount exceeds 800% by weight, the thickness of the obtained coating film becomes thin, and the coating film hardness becomes insufficient. Further, these dispersion media may also be used as the dispersion media of the first component.
[0059]
(7) Others A leveling agent can be added to the coating composition of the present invention in order to improve flowability during coating. For example, a copolymer of polyoxyalkylene and polydimethylsiloxane, a copolymer of polyoxyalkylene and fluorocarbon, and the like can be used. The above additives are used in an amount of 0.001 to 5% by weight based on the total liquid weight in the coating composition.
In addition, if necessary, an antioxidant, a weathering agent, a coloring agent or an antistatic agent can be added.
[0060]
The preferred film thickness is 0.2 to 10 μm, and if the film thickness is less than 0.2 μm, the hardness is insufficient, and if it exceeds 10 μm, cracks are easily formed. The refractive index of the cured film can be adjusted to 1.48 to 1.70.
[0061]
As a method for applying the coating composition of the present invention to a substrate, a dip method, a flow method, a spinner method, a spray method, or the like can be employed. The heat treatment conditions are preferably 50 to 130 ° C. and 1 to 10 hours, but vary depending on the heat resistance of the substrate.
[0062]
(8) The base material is a plastic lens for glasses made of a high refractive index resin having a refractive index of 1.50 or more, an optical member (including a glass product), a sheet, a molded product, or the like.
[0063]
Examples of the transparent substrate having a refractive index higher than 1.50 include polycarbonate (refractive index: 1.58). In addition, various resins have been proposed in various kinds of plastic lenses for spectacles / known patent publications.
[0064]
For example, a plastic lens made of a polyurethane resin, a plastic lens made of a methacrylic polymer, a plastic lens made of an allyl polymer, or a combination type thereof are used.
[0065]
Examples of a lens made of a polyurethane resin include a lens obtained by thermally curing a monomer MR-6 manufactured by Mitsui Toatsu Chemicals Co., Ltd., modified MR-6, and MR-7 (all trade names), and a lens made of a methacrylic polymer. As a lens obtained by radical polymerization of a monomer TS-26 (trade name) manufactured by Tokuyama Corporation, and as a lens combining a urethane reaction and a vinyl polymerization reaction, a monomer ML-3 (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd. Is used.
[0066]
(9) Anti-reflection film
By providing a single-layer or multilayer anti-reflection film on the hard coat film, reflection can be reduced, transmittance can be improved, and weather resistance can be improved.
[0067]
As the inorganic substance, SiO, SiO_Two, Si_ThreeN_Four, TiO_Two, ZrO_Two, Al_TwoO_Three, MgF_Two, Ta_TwoO_FiveA thin film is formed by a vacuum deposition method or the like.
[0068]
In order to improve the adhesion of the hard coat, it is effective to perform pretreatment such as alkali treatment, acid treatment, plasma treatment, corona treatment, and flame treatment on the lens substrate in advance.
[0069]
[Action]
A coating obtained by applying and curing the coating composition obtained by the present invention on a high refractive index substrate has extremely high scratch resistance and rub resistance, while suppressing the occurrence of interference fringes, and Dyeable. The reason is that the OH group of the compound having an OH group of the third component reacts with the condensate of the organosilicon compound and hangs to create a trap or a channel through which the dye can pass. It is thought that deep dyeing is possible while having the property.
[0070]
On the other hand, a conventional coating composition similar to the present invention uses a dyeable organic component as a cross-linking agent, so that its strength is relatively lower than that of a coating made of only organosilicon.
[0071]
【Example】
An embodiment of the present invention will be described.
Example 1
TiO_Two-Fe_TwoO_Three-SiO_TwoOf a composite metal oxide sol (solid content: 30%, methanol dispersed sol, manufactured by Catalyst Chemicals, Inc., trade name: Optrake 1130F-2 (A-8)) is weighed into a flask. Thereto, 170 g of distilled water was added with stirring. Next, 191 g of γ-glycidoxypropyltrimethoxysilane and 69 g of methyltrimethoxysilane are gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0072]
Then, while stirring the mixture, 220 g of isopropyl alcohol was added.⁶= Methyl group, R⁷= CH_TwoCH_Two, 40 g of polyethylene glycol monomethacrylate (c = 4, manufactured by NOF CORPORATION, trade name: Blenmer PE200). Further, 3 g of ammonium perchlorate as a curing catalyst and 0.4 g of a silicone surfactant (trade name L-7001, manufactured by Nippon Unicar Co., Ltd.) were added as a flow control agent, and the mixture was stirred for 1 hour. The mixture was aged at room temperature for 48 hours.
[0073]
A plastic lens made of urethane resin having a refractive index of 1.594 (a lens obtained by thermally polymerizing a trade name of MR-6, a monomer manufactured by Mitsui Toatsu Chemicals, Inc.) is coated with the above mixed solution, and the mixture is applied at 120 ° C. for 1 hour. Heat cured. The appearance of the obtained coating film was colorless and transparent. The adhesion was 100/100, the refractive index of the cured film was 1.58, and interference fringes were hardly noticeable. The film thickness was 1.5 to 2.0 μm, and the SW hardness was 4. In addition, the transmittance became 32% after 5 minutes of staining.
[0074]
Example 2
TiO of Example 1_Two-Fe_TwoO_Three-SiO_TwoComposite oxide sol consisting of TiO_Two-CeO_Two-SiO_Two(A solid content of 30%, methanol-dispersed sol, manufactured by Sekiyu Kasei Kogyo Co., Ltd., trade name Optrake 1130A (A-8)). The results are shown in Table 1.
[0075]
Example 3
TiO of Example 1_Two-Fe_TwoO_Three-SiO_TwoComposite oxide sol consisting of TiO_Two-SiO_TwoMetal oxide sol (solid content 30%, methanol dispersion sol, manufactured by Catalyst Chemical Industry Co., Ltd., TiO_Two/ SiO_Two= 85/15) except that the same method was used. The results are shown in Table 1.
[0076]
Example 4
TiO_Two-CeO_TwoComposite metal oxide sol (solid content 20%, methanol dispersed sol, manufactured by Catalyst Chemical Industry Co., Ltd., TiO_Two/ CeO_Two= 8/2) Weigh 455 g into flask. Thereto, 142 g of distilled water was added with stirring. Next, 191 g of γ-glycidoxypropyltrimethoxysilane and 69 g of methyltrimethoxysilane are gradually added. After completion of the addition, the mixture was further stirred for 2 hours.
[0077]
Thereafter, 100 g of isopropyl alcohol was added while stirring the mixture, and then 40 g of Blemmer PE200 was added. Further, 3 g of ammonium perchlorate as a curing catalyst and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0078]
Example 5
TiO of Example 1_Two-Fe_TwoO_Three-SiO_TwoThe composite metal oxide sol consisting of Sb_TwoO_FiveMetal oxide sol (solid content 30%, methanol dispersion sol, manufactured by Nissan Chemical Industries, Ltd., trade name: Sun Colloid)_RAMT-130) was used in place of AMT-130). The results are shown in Table 1.
[0079]
Example 6
CeO_Two467 g of a metal oxide sol (solid content 15%, aqueous dispersion sol, trade name: Needal U-15, manufactured by Taki Kagaku Co., Ltd.) is measured in a flask. Next, 184 g of γ-glycidoxypropyltrimethoxysilane was gradually added to carry out hydrolysis. After completion of the addition, the mixture was further stirred for 1 hour.
[0080]
Thereafter, while stirring the mixture, 316 g of isopropyl alcohol was added, and then 30 g of Blemmer PE200 was added. Further, 3 g of ammonium perchlorate as a curing catalyst and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0081]
Example 7
303 g of Optrake 1130F-2 (A-8) is weighed into a flask. Thereto, 170 g of distilled water was added with stirring. Next, 239 g of γ-glycidoxypropyltrimethoxysilane is gradually added. After completion of the addition, the mixture was further stirred for 2 hours.
[0082]
Thereafter, 241 g of methanol was added while stirring the mixture, and then 40 g of Blemmer PE200 was added. Furthermore, 15 g of a modified acetylacetone metal salt (Hope Pharmaceutical Co., Ltd., trade name: Acetop-Al (MX)) as a curing catalyst, and a silicone surfactant (Dow Corning Asia Co., Ltd., trade name: Paintad) as a flow control agent_R32) was added and stirred for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0083]
Example 8
Weigh 340 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 122 g of distilled water was added with stirring. Next, 134 g of γ-glycidoxypropyltrimethoxysilane and 128 g of methyltrimethoxysilane are gradually added. After completion of the addition, the mixture was further stirred for 2 hours.
[0084]
Thereafter, 229 g of ethanol was added while stirring the mixture, and then 40 g of Blemmer PE200 was added. Further, 3 g of ammonium perchlorate as a curing catalyst and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0085]
Example 9
Weigh 312 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 83 g of γ-glycidoxypropyltrimethoxysilane and 178 g of methyltrimethoxysilane are gradually added. After completion of the addition, the mixture was further stirred for 2 hours.
[0086]
Thereafter, 234 g of ethanol was added while stirring the mixture, and then 60 g of Blemmer PE200 was added. Furthermore, 9 g of aluminum acetylacetone as a curing catalyst, and a silicone surfactant as a flow control agent (Paintad, trade name, manufactured by Dow Corning Asia Co., Ltd.)_R57) was added and stirred for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0087]
Example 10
Weigh 310 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 189 g of γ-glycidoxypropyltrimethoxysilane, 34 g of methyltrimethoxysilane, and 27 g of dimethyldimethoxysilane are gradually added. After completion of the addition, the mixture was further stirred for 2 hours.
[0088]
Thereafter, while stirring the mixture, 277 g of methanol was added.⁶= Methyl group, R⁷= CH_TwoCH_TwoAnd 30 g of polyethylene glycol monomethacrylate (c = 2, manufactured by NOF CORPORATION, trade name: Blenmer PE90). Further, 9 g of aluminum acetylacetone as a curing catalyst and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0089]
Example 11
Weigh 310 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 212 g of γ-glycidoxypropyltrimethoxysilane and 58 g of tetraethyl orthosilicate are gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0090]
Thereafter, while stirring the mixture, 257 g of methanol was added, and then 30 g of Blemmer PE200 was added. Further, 9 g of aluminum acetylacetone was used as a curing catalyst, and Paintad was used as a flow control agent._R32 was added and stirred for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0091]
Example 12
Weigh 247 g of Opt Lake 1130F-2 (A-8) into a flask. Thereto, 150 g of distilled water was added with stirring. Next, 210 g of γ-glycidoxypropyltrimethoxysilane and 57 g of phenyltrimethoxysilane are gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0092]
Thereafter, 303 g of methanol was added while stirring the mixture, and then 20 g of Blemmer PE200 was added. Further, 15 g of acetop-Al (MX) as a curing catalyst and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0093]
Example 13
Weigh 310 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 211 g of γ-glycidoxypropyltrimethoxysilane is gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0094]
Thereafter, 326 g of ethanol was added while stirring the mixture, and then 20 g of Blenmer PE90 was added. Further, 9 g of aluminum acetylacetone was used as a curing catalyst, and Paintad was used as a flow control agent._R57g was added and stirred for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0095]
Example 14
Weigh 310 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 169 g of γ-glycidoxypropyltrimethoxysilane and 68 g of methyltrimethoxysilane are gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0096]
Thereafter, while stirring the mixture, 280 g of IPA was added, and then 20 g of Blemmer PE200 was added. Further, 3 g of ammonium perchlorate was used as a curing catalyst, and Paintad was used as a flow control agent._R57g was added and stirred for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0097]
Example 15
Weigh 310 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 278 g of γ-glycidoxypropyltrimethoxysilane is gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0098]
Thereafter, 270 g of IPA was added while stirring the mixture, and then 8 g of Blemmer PE200 was added. Further, 9 g of aluminum acetylacetone was used as a curing catalyst, and Paintad was used as a flow control agent._R32 was added and stirred for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0099]
Example 16
In the general formula C of Example 1, R⁶= Methyl group, R⁷= CH_TwoCH_Two, C = 4, a polyethylene glycol monomethacrylate having the general formula C⁶= Methyl group, R⁷= CH_TwoCHCH_ThreeCH_TwoCH_Two, C = 5, except that polypropylene glycol monomethacrylate (trade name: Blemmer PP1000, manufactured by NOF Corporation) was used. The results are shown in Table 1.
[0100]
Example 17
Weigh 310 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 179 g of γ-glycidoxypropyltrimethoxysilane is gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0101]
Thereafter, while stirring the mixture, 280 g of IPA was added, and then 100 g of Blemmer PE90 was added. Further, 9 g of aluminum acetylacetone was used as a curing catalyst, and Paintad was used as a flow control agent._R32 was added and stirred for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0102]
Example 18
In the general formula C of Example 1, R⁶= Methyl group, R⁷= CH_TwoCH_Two, C = 4, a polyethylene glycol monomethacrylate having the general formula D⁶= Hydrogen atom, b = 4 The same method was used except that 4-hydroxybutyl acrylate (trade name: 4-HBA, manufactured by Osaka Organic Industry Co., Ltd.) was used. The results are shown in Table 1.
[0103]
Example 19
In the general formula C of Example 1, R⁶= Methyl group, R⁷= CH_TwoCH_Two, C = 4, a polyethylene glycol monomethacrylate ester of the general formula E, d = 0, b = 4, 4-hydroxybutyl vinyl ether (manufactured by ISSP Japan Co., Ltd., trade name rapicure)_RHBVE), but the same method was used. The results are shown in Table 1.
[0104]
Example 20
In the general formula C of Example 1, R⁶= Methyl group, R⁷= CH_TwoCH_TwoThe same method was used except that polyethylene glycol monomethacrylate having c = 4 was replaced by ethylene glycol monoallyl ether having d = 1 and b = 2 (manufactured by Tokyo Chemical Industry Co., Ltd.) in the general formula E. The results are shown in Table 1.
[0105]
Example 21
In the general formula C of Example 1, R⁶= Methyl group, R⁷= CH_TwoCH_Two, And c = 4, except that the polyethylene glycol monomethacrylate ester of general formula F is replaced with an allylated polyether of d = 1 and f = 3 to 4 (manufactured by NOF CORPORATION, trade name UNIOX PKA-5001). The same method was used. The results are shown in Table 1.
[0106]
Example 22
In the general formula C of Example 1, R⁶= Methyl group, R⁷= CH_TwoCH_Two, C = 4, except that polyethylene glycol monomethacrylate was replaced with 2-hydroxy-3-phenoxypropyl acrylate (trade name: NK ester 702A, manufactured by Shin-Nakamura Chemical Co., Ltd.). The results are shown in Table 1.
[0107]
Example 23
In the general formula C of Example 1, R⁶= Methyl group, R⁷= CH_TwoCH_Two, C = 4, except that the polyethylene glycol monomethacrylate was replaced by 2-hydroxy-1,3-dimethacryloxypropane (trade name: NK ester 701, manufactured by Shin-Nakamura Chemical Co., Ltd.). The results are shown in Table 1.
[0108]
Example 24
In the general formula C of Example 1, R⁶= Methyl group, R⁷= CH_TwoCH_Two, C = 4, except that polyethylene glycol monomethacrylate was replaced with pentaerythritol triacrylate (trade name ARONIX M-305, manufactured by Toagosei Chemical Co., Ltd.). The results are shown in Table 1.
[0109]
Example 25
The mixture of Example 1 was applied to a plastic lens made of a urethane resin having a refractive index of 1.594 (a lens obtained by thermally polymerizing a monomer-modified MR-6 manufactured by Mitsui Toatsu Chemicals, Inc.), and then heated at 120 ° C. for 1 hour. Heat cured. The interference fringes of the obtained lens were almost inconspicuous. Others were evaluated similarly to Example 1. The results are shown in Table 1.
[0110]
Example 26
The liquid mixture of Example 1 was applied to a plastic lens made of a methacrylic polymer having a refractive index of 1.59 (a lens obtained by thermally polymerizing a monomer TS-26 manufactured by Tokuyama Corporation), and heat-cured at 120 ° C. for 1 hour. did. The interference fringes of the obtained lens were almost inconspicuous. Others were evaluated similarly to Example 1. The results are shown in Table 1.
[0111]
Example 27
The mixed solution of Example 1 was applied to a plastic lens (a lens obtained by thermally polymerizing a monomer ML-3 manufactured by Mitsubishi Gas Chemical Co., Ltd.) made of a polymer obtained by using both a urethane reaction and a radical polymerization having a refractive index of 1.59. At 120 ° C. for 1 hour. The interference fringes of the obtained lens were almost inconspicuous. Others were evaluated similarly to Example 1. The results are shown in Table 1.
[0112]
Example 28
The mixture of Example 1 was applied to a plastic lens K-25 (manufactured by Kureharen Tech Co., Ltd.) having a triazine ring having a refractive index of 1.60 as a main component, and heat-cured at 120 ° C. for 1 hour. The interference fringes of the obtained lens were almost inconspicuous. Others were evaluated similarly to Example 1. The results are shown in Table 1.
[0113]
Example 29
Weigh 433 g of Optrake 1130F-2 (A-8) in a flask. Thereto, 120 g of distilled water was added with stirring. Next, 184 g of γ-glycidoxypropyltrimethoxysilane is gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0114]
Thereafter, 210 g of IPA was added while stirring the mixture, and then 40 g of UNIOX PKA-5001 was added. Further, 3 g of aluminum acetylacetone was used as a curing catalyst, and Paintad was used as a flow control agent._R57g was added and stirred for 1 hour. The mixture was aged at room temperature for 48 hours.
[0115]
The above-mentioned mixture is applied to a plastic lens (a lens obtained by thermally polymerizing a brand name of MR-7, a monomer manufactured by Mitsui Toatsu Chemicals, Inc.) having a refractive index of 1.66, and the mixture is applied at 120 ° C. for 1 hour. Heat cured. The refractive index of the obtained coating film was 1.64, and interference fringes of the lens were almost inconspicuous. The thickness was 1.5 to 2.0 μm. Others were evaluated similarly to Example 1. The results are shown in Table 1.
[0116]
Example 30
Weigh 468 g of Optrake 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 135 g of γ-glycidoxypropyltrimethoxysilane and 37 g of phenyltrimethoxysilane are gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0117]
Thereafter, while stirring the mixture, 188 g of ethanol was added, and then 40 g of Blenmer PE400 was added. Further, 15 g of acetop-Al (MX) as a curing catalyst and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 48 hours. Evaluation was performed in the same manner as in Example 29 using the above mixed liquid. The results are shown in Table 1.
[0118]
Example 31
Weigh 208 g of Optics 1130F-2 (A-8) into a flask. Thereto, 120 g of distilled water was added with stirring. Next, 223 g of γ-glycidoxypropyltrimethoxysilane and 80 g of methyltrimethoxysilane are gradually added. After the addition was completed, the mixture was stirred for 2 hours.
[0119]
Thereafter, while stirring the mixture, 315 g of isopropyl alcohol was added, and then 40 g of Blemmer PE200 was added. Further, 3 g of ammonium perchlorate as a curing catalyst and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 48 hours.
[0120]
The above mixed solution was applied to a plastic lens containing a diallyl phthalate polymer having a refractive index of 1.56 as a main component, and thermally cured at 120 ° C. for 1 hour. The appearance of the obtained coating film was colorless and transparent. The adhesion was 100/100, the refractive index of the cured film was 1.54, and the interference fringes were hardly noticeable. The film thickness was 1.7 to 2.2 μm. Others were evaluated similarly to Example 1. The results are shown in Table 1.
[0121]
Example 32
The mixture of Example 1 was applied to a plastic lens K-23 (manufactured by Kureharen Tech Co., Ltd.) having a triazine ring as a main component and having a refractive index of 1.56, and was thermally cured at 120 ° C. for 1 hour. The interference fringes of the obtained lens were almost inconspicuous. Others were evaluated similarly to Example 1. The results are shown in Table 1.
[0122]
ZrO was formed on the plastic lens substrate obtained in Examples 1 to 32 from the hard coat side by vacuum evaporation._Two, SiO_Two, ZrO_Two, SiO_TwoOf four layers were formed. The optical film thickness of the formed antireflection film is about λ / 12, λ / 12, λ / 2, λ / 4 in order. Here, λ is the light wavelength of 520 nm. Table 2 shows the evaluation results of the obtained lenses.
[0123]
Comparative Example 1
275 g of glycidoxypropyltrimethoxysilane is weighed and placed in a flask, and while maintaining the liquid temperature at 10 ° C. or lower, 63 g of a 0.01 N hydrochloric acid aqueous solution is gradually added while stirring, and γ-glycidoxypropyltrimethoxysilane is added. The silane was hydrolyzed. Next, 298 g of methanol was added, and the mixture was further stirred for 1 hour. Next, 350 g of Optrake 1130F-2 (A-8) was added to this solution. After completion of the addition, the mixture was further stirred for 1 hour. Further, 3 g of ammonium perchlorate as a curing catalyst and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 24 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0124]
Comparative Example 2
TiO of Comparative Example 1_Two-Fe_TwoO_Three-SiO_TwoComposite oxide sol consisting of TiO_Two-CeO_Two-SiO_TwoThe same method was used except that a composite metal oxide sol consisting of The results are shown in Table 1.
[0125]
Comparative Example 3
TiO of Comparative Example 1_Two-Fe_TwoO_Three-SiO_TwoThe composite metal oxide sol consisting of Sb_TwoO_FiveThe same method was used except that a metal oxide sol consisting of The results are shown in Table 1.
[0126]
Comparative Example 4
300 g of colloidal silica (solid content: 30%, aqueous dispersion sol, manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex O-40) is weighed into a flask, and while cooling and stirring, 204 g of γ-glycidoxypropyltrimethoxysilane is gradually added. To be added. After completion of the addition, the mixture was further stirred for 1 hour. On the way, when the temperature of the mixed solution stopped rising, the cooling was stopped.
[0127]
Thereafter, while stirring the mixture, 451 g of isopropanol was added, and then 38 g of PE90 was added. Further, 1.5 g of ammonium perchlorate and 0.4 g of L-7001 as a flow control agent were added, followed by stirring for 1 hour. The mixture was aged at room temperature for 24 hours. Evaluation was performed in the same manner as in Example 1 using the above mixed liquid. The results are shown in Table 1.
[0128]
[Table 1]

[0129]
As shown in the above Examples and Comparative Examples, the coating compositions of Comparative Examples 1 to 3 without the third component of the present invention could hardly be dyed, and in the case of Comparative Example 4, a low refractive index hard coat layer was formed. Resulting in interference fringes.
As described above, the coating film obtained from the coating composition of the above embodiment of the present invention has no interference fringes and can be deep-dyeed.
[0130]
The method of applying the coating liquid in the above Examples and Comparative Examples is as follows.
(1) The lens substrate was immersed in an 8% aqueous NaOH solution for 30 minutes, washed sufficiently with water, and dried.
(2) Each coating solution was dipped at a lifting speed of 15 cm / min.
(3) After drying at room temperature for about 5 minutes, it was heated and cured at 120 ° C. for 1 hour.
[0131]
The test methods for the coating films obtained in Examples and Comparative Examples are as follows.
(1) Cross hatch test (based on Goban test JIS K5400)
(2) Steel wool test
The steel wool # 0000 was rubbed with a load of 1 kg, and the degree of scratching was relatively compared based on the following criteria.
5: No damage at all, 4: Slight damage,
3: Scratch, 2: Severe scratch,
1: The substrate is damaged
(3) Dyeability
A BPI GRAY of Brain Power Inc (USA) diluted to 9% with distilled water was heated to 90 ° C., and the lens coated with each coating solution was immersed in this aqueous solution for 5 minutes, and then the lens was taken out and washed with water. The total light transmittance after dyeing was measured and the dyeability was compared.
(4) Interference fringes
MIDWEST SCIENTIFIC CO. The interference fringes of the coated lens were visually observed using a (USA) monochromatic lamp UNILAMP.
(5) Weather resistance A weather resistance test of the lens after the coating was performed with a Canon Arc Weatherometer.
In this test, irradiation was performed for 248 hours while spraying water at a cycle of 16 minutes / 2 hours at a black panel temperature of 68 ± 3 ° C., and the subsequent cross hatch test and appearance are shown in Table 2.
[0132]
[Table 2]

【The invention's effect】
According to the present invention, a coating obtained by applying and curing a coating composition on a substrate having a high refractive index has extremely high scratch resistance and friction resistance, while suppressing the occurrence of interference fringes and deep dyeing. It is possible.
Thus, a coated article having the above excellent properties is obtained.

Claims (14)

(1) Fine particles of a specific oxide containing at least one of silica, iron oxide, titanium oxide, cerium oxide, zirconium oxide, antimony oxide, zinc oxide and tin oxide, or a mixture thereof, or fine particles made of a composite oxide thereof, (2) 5 to 90% by weight of the epoxy group-containing silicon compound or its partial hydrolyzate and (3) only one OH group in the molecule; Compounds shown in
_{^{CH 2 = C (R 6)}} CO - (- OR 7 -) c OH (C)
_{^{CH 2 = C (R 6)}} COO - (- CH 2 -) b OH (D)
_{CH 2 = CH - (- CH} 2 -) d - O - (- CH 2 -) e - OH (E)
_{CH 2 = CH - (- CH} 2 -) d - (- OR 7 -) f - OH (F)
( Where R ⁶ is a hydrogen atom or a methyl group, R ⁷ is —CH ₂ CH ₂ — or —CH ₂ CH (CH ₃ ) —, and b is an integer of 2 to 10, preferably 4 to 6 , C is an integer of 1 to 9, preferably 2 to 4, d is an integer of 0 or 1, e is an integer of 4 to 10, and f is an integer of 2 to 9 ) .
Consisting of at least one compound selected from the group consisting of
It comprises 1 to 45% by weight of an organic compound soluble in water or a lower alcohol having 4 or less carbon atoms, and (4) a curing catalyst for an epoxy group-containing silicon compound or a partial hydrolyzate thereof. Thermosetting high refractive index coating composition. The thermosetting high refractive index coating composition according to claim 1, wherein the oxide comprises at least one oxide of titanium oxide, iron oxide and silica. When the titanium oxide component is converted to TiO ₂ , the iron oxide component is converted to Fe ₂ O ₃ , and the silica component is converted to SiO ₂ , the weight ratio Fe ₂ O ₃ / TiO ₂ is 0.005 to 1.0. _{3. The} thermosetting high refractive index coating composition according to claim _{2, wherein the} weight ratio SiO ₂ / (Fe ₂ O ₃ + TiO ₂ ) is in the range of 0.001 to 1.0. . The thermosetting high refractive index coating composition according to claim 1, wherein the oxide comprises at least one oxide of titanium oxide, cerium oxide and silica. When the titanium oxide component is converted to TiO ₂ , the cerium oxide component is converted to CeO ₂ , and the silica component is converted to SiO ₂ , the weight ratio CeO ₂ / TiO ₂ is 0.1. 1 to 1.0 range and that the weight ratio SiO ₂ / in the high refractive index of the thermosetting of (CeO ₂ + TiO ₂₎ is according to claim 4, wherein a is in the range of 0.05 to 0.5 Coating composition. 2. The thermosetting high refractive index according to claim 1, wherein the fine particles of each of the specific oxide, the mixture thereof, and the composite metal oxide thereof have an average particle diameter in a range of 1 to 100 nm. Coating composition. 2. The thermosetting high refractive index according to claim 1, wherein the fine particles of each of the specific oxide, the mixture thereof, and the composite metal oxide thereof have their surfaces modified with an organosilicon compound. Coating composition. The epoxy group-containing silicon compound or its partial hydrolyzate is represented by the following general formula (A)
R ¹ R ² _a Si (OR ³ ) _3-a (A)
( Where R1 is a group containing an epoxy group having 2 to 12 carbon atoms, R2 is an alkyl group, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group having 1 to 6 carbon atoms, R3 is represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an acyl group, an alkyl acyl group, respectively, a is to display the 0, 1 or 2)
2. The thermosetting high refractive index coating composition according to claim 1, which is an epoxy group-containing silicon compound represented by the formula or a partial hydrolyzate thereof. As an organosilicon compound or a partial hydrolyzate thereof, a compound represented by the general formula (G)
_{^{R 8 h R 2 a Si (}} OR 3) 4-ha (G)
( Where R ² and R ³ are the same as defined in the general formula (A), and R ⁸ is an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group, an aryl having 6 to 12 carbon atoms. Group or a halogenated aryl group, a methacryloxyalkyl group having 5 to 8 carbon atoms, a ureidoalkylene group having 2 to 10 carbon atoms, an aromatic ureidoalkylene group, a halogenated aromatic alkylene group, or a mercaptoalkylene group. A represents an integer of 0, 1 or 2, and h represents an integer of 0 to 3. )
The thermosetting high refractive index coating composition according to claim 1, wherein the compound represented by the formula (1) is contained in an amount of 0 to 60% by weight based on the total solid weight in the coating composition. Epoxy group-containing silicon compound or a high thermoset claim 1, wherein the containing 0.001 to 10 wt% of a curing catalyst, based on the total solid weight of the coating composition of a partial hydrolyzate thereof Refractive index coating composition. A coated article comprising a transparent substrate having a refractive index of 1.50 or more and a cured film obtained from the high refractive index coating composition according to claim 1 formed on the substrate. The coated article of claim 11, further comprising an antireflection film made of an inorganic compound formed on the cured film. Substrate is a plastic lens having 1.50 or more refractive index, fine acid titanium as particles - according to use fine particles selected from the group consisting of metal oxides of silica - iron oxide - silica, titanium - cerium A coated article according to claim 11, which is a cured film formed from the coating composition according to claim 1 . 14. The coated article according to claim 13, wherein the antireflection film is formed on the cured film.