JP2004256632A - Coating composition and resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a transparent coating composition which has improved adhesivity between resin layers, excellent weather resistance, abrasion resistance, impact resistance, heat resistance and water resistance and a resin laminate using the same. <P>SOLUTION: The coating composition [(A)+(B)+(C)+(D)+(E)] for a resin is obtained by mixing an organotrialkoxysilane (A) with colloidal silica (B) containing silicic anhydride and having 4-20 nm particle diameters, an acrylic organic copolymer (C), an amine carboxylate and/or ammonium carboxylate (D) and a silicone-containing polymer ultraviolet light absorbent (E) in a specific ratio. The resin laminate (J) comprises a cured layer (I) obtained by coating at least one side of a polycarbonate resin base (F) with an acrylic resin layer (H) containing an ultraviolet light absorbent (G), coating the acrylic resin layer (H) with the coating composition [(A)+(B)+(C)+(D)+(E)] and curing the coating film. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

（式中、Ｒ^１１は水素原子、炭素数１〜６のアルキル基、又は炭素数１〜６のアルコキシル基を示す。Ｒ^１２は炭素数１〜１０のアルキレン基、又は炭素数１〜１０のオキシアルキレン基を示し、ｍ^１は０又は１を示す。Ｒ^１３は水素原子、又は低級アルキル基を示す。Ｘ^１はエステル結合、アミド結合、エーテル結合、又はウレタン結合を示す。）
【００２４】
【化２】

（式中、Ｒ^２１は水素原子、ハロゲン原子、又はメチル基を示す。Ｒ^２２は水素原子、又は炭素数１〜６の炭化水素基を示す。Ｒ^２３は炭素数１〜１０のアルキレン基、又は炭素数１〜１０のオキシアルキレン基を示し、ｍ^２１は０又は１を示す。Ｒ^２４は炭素数１〜８のアルキレン基、アミノ基を有する炭素数１〜８のアルキレン基、又はヒドロキシル基を有する炭素数１〜８のアルキレン基を示し、ｍ^２２は０又は１を示す。Ｒ^２５は水素原子、又は低級アルキル基を示す。Ｘ^２はエステル結合、アミド結合、エーテル結合、又はウレタン結合を示す。）
【００２５】
【化３】

（式中、Ｒ^３１は水素原子、又はメチル基を示す。Ｒ^３２は炭素数１〜６のアルキレン基、又は炭素数１〜６のオキシアルキレン基を示し、ｍ^３１は０又は１を示す。Ｒ^３３は炭素数１〜６のアルキレン基、アミノ基を有する炭素数１〜６のアルキレン基、又はヒドロキシル基を有する炭素数１〜６のアルキレン基を示し、ｍ^３２は０又は１を示す。ｎは１〜２００の整数を示し、Ｘ^３はエステル結合又はアミド結合を示す。）
【００２６】
シリコーン含有紫外線吸収剤（Ｅ）を構成する前記各成分の比率は、（ｅ１＋ｅ２）／ｅ３／ｅ４／ｅ５＝５〜５０／５〜６０／５０〜８０／５〜２０（重量％）である。また、シリコーンマクロマー（ｅ３）の重量平均分子量は２００〜１０，０００であることが好ましい。シリコーン含有紫外線吸収剤（Ｅ）は、アルコキシシラン（Ａ）、コロイダルシリカ（Ｂ）、アルコキシシリル基を含有する有機共重合体（Ｃ）、アミンカルボキシレート及び／又は第４級アンモニウムカルボキシレート（Ｄ）の合計１００重量部に対し、０．５〜３５重量部配合される。シリコーン含有紫外線吸収剤（Ｅ）の配合量が０．５重量部より少ないと、樹脂用コーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］の耐候性に対する改良効果が小さく、３５重量部より多いと樹脂用コーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］を硬化した硬化層の線膨張係数が大きくなり好ましくない。
【００２７】
樹脂用コーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］の分散溶媒は、本発明の効果を損なわない範囲で使用することができ、分散溶媒としてはゾルの安定性や入手のし易さの観点から、水、或いは低級アルコールであるメタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ケトン類であるメチルエチルケトン、ジアセチルアセトンなどを用いることが好ましい。又、本発明において前記溶媒効果を発現させるためには、組成物中の水分含有量が１５％以下とすることが好ましい。１５％を超えると水がシラノール基に選択的に配位するため、シラノール基の安定性が損なわれる。
【００２８】
本発明の樹脂用コーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］の保存温度は、通常２５℃以下、好ましくは１５℃以下、更に好ましくは５℃以下である。２５℃を超えると、保存期間が長い場合、加水分解・縮合反応が徐々に進行するので好ましくない。
本発明のポリオルガノシロキサンを含む組成物を用いて硬化被膜を形成させる際、硬化被膜の硬度や耐擦傷性の向上、又は高屈折率化などの光学的機能性を付与させるために、公知の硬化触媒や金属酸化物及びその他の添加物を適宜加えても良い。
【００２９】
硬化触媒の具体例としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、酢酸ナトリウム、酢酸カリウム、蟻酸ナトリウム、蟻酸カリウム、ｎ−ヘキシルアミン、プロピオン酸カリウム、トリブチルアミン、ジアザビシクロウンデセンのごとき塩基性化合物、テトライソプロピルチタネート、テトラブチルチタネート、アルミニウムトリイソブトキシド、アルミニウムトリイソプロポキシド、γ−アミノプロピルトリメトキシシラン、アルミニウムアセチルアセトナート、過塩素酸アルミニウム、塩化アルミニウム、コバルトオクチレート、コバルトアセチルアセトナート、鉄アセチルアセトナート、錫アセチルアセトナート、ジブトキシ錫オクチレートの如き金属化合物類、ｐ−トルエンスルホン酸、トリクロル酢酸の如き酸性化合物類が挙げられる。硬化触媒の添加量は、本発明の樹脂用コーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］１００重量部に対して０．０１〜１０重量部であることが好ましい。
【００３０】
金属酸化物の具体例としては、シリカ、アルミナ、酸化チタン、酸化セリウム酸化錫、酸化ジルコニウム、酸化アンチモン、酸化鉄などが挙げられる。特に、耐擦傷性を目的とした硬化剤とする場合には、コロイダルシリカ（シリカゾル）が好適である。硬化剤として使用する場合の金属酸化物の添加量は、本発明のコーティング組成物１００重量部に対して５〜５００重量部、特に１０〜２００重量部であることが好ましい。これらの金属酸化物の存在下に縮合反応を行っても良く、また縮合反応後に加えても良い。
【００３１】
本発明の樹脂用コーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］をアクリル樹脂層（Ｈ）上に塗装する方法は、塗装される成形品の形状や塗装目的に応じて、刷毛、ロール、ディッピング、流し塗り、スプレー、ロールコーター、フローコーター、遠心コーター、スクリーンプロセス等がある。
【００３２】
ポリカーボネート樹脂基材（Ｆ）となるポリカーボネート樹脂は、芳香族ポリカーボネート、脂肪族ポリカーボネート、芳香族−脂肪族ポリカーボネートを用いることができるが、芳香族ポリカーボネートが好ましい。本発明における芳香族ポリカーボネート樹脂としては、芳香族ジヒドロキシ化合物、またはこれと少量のポリヒドロキシ化合物をホスゲンまたは炭酸のジエステルと反応させることによって作られる、分岐していてもよい熱可塑性芳香族ポリカーボネート重合体または共重合体である。製造方法については、特に限定されるものでは無く、ホスゲン法（界面重合法）あるいは、溶融法（エステル交換法）等公知の方法で製造することができる。さらに、溶融法で製造され末端ＯＨ基量を調整した芳香族ポリカーボネート樹脂も使用することができる。このようにして製造されたポリカーボネート樹脂のうち、本発明に使用されるポリカーボネート樹脂は、ポリスチレン換算重量平均分子量が４５，０００〜７０，０００のものである。
【００３３】
次に、ポリカーボネート樹脂基材（Ｆ）とポリオルガノシロキサンを含む組成物の硬化層（Ｉ）との中間に位置するアクリル樹脂層（Ｈ）について具体的に述べる。アクリル樹脂層（Ｈ）におけるアクリル樹脂は、メチルメタクリレートの構成単位のモノマー量が全構成単位の総モノマー量に対して８０モル％以上で、好ましくは８０〜９９モル％で、ポリスチレン換算重量平均分子量が７０，０００〜１５０，０００であることが好ましい。アクリル樹脂がメチルメタクリレート単重合体では、熱安定性が劣る。またアクリル樹脂の荷重撓み温度は９０℃以上が良く、好ましくは９５℃以上、更に好ましくは１００℃以上である。
【００３４】
アクリル樹脂の製造方法は一般的に乳化重合法、懸濁重合法、連続重合法とに大別されるが、本発明に使用されるアクリル樹脂は連続重合法により製造されたアクリル樹脂が好ましい。さらに、連続製造法には連続塊状重合法と連続溶液重合法とに分けることができるが、本発明においてはどちらかの製法で得られたアクリル樹脂を用いることができる。
【００３５】
アクリル樹脂層（Ｈ）中には、耐候性を長期間保持する目的のために紫外線吸収剤（Ｇ）を０．１〜５．０重量％含有するのがよい。好ましくは０．２〜３．５重量％含有し、さらに好ましい含有率は０．５〜３．０重量％である。紫外線吸収剤の含有率が０．１重量％未満の場合、十分な耐候性を示さない。また、５．０重量％を超えて配合してもさらなる耐候性向上は期待できないばかりでなく、これら添加剤がブリードアウトを起こし、白化の原因になったり、密着性の低下、また機械的性能、特に耐衝撃性を損ねることが多い。
【００３６】
これらのアクリル樹脂層（Ｈ）に添加される紫外線吸収剤（Ｇ）の例としては、アクリル樹脂層の透明性を維持するためベンゾトリアゾール系、ベンゾフェノン系、サリチル酸フェニルエステル系、トリアジン系の紫外線吸収剤が挙げられる。
【００３７】
ベンゾトリアゾール系紫外線吸収剤としては、２−（５−メチル−２−ヒドロキシフェニル）ベンゾトリアゾール、２−［２−ヒドロキシ−３，５−ビス（α，α−ジメチルベンジル）フェニル］−２Ｈ−ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔ−オクチルフェニル）ベンゾトリアゾール、２，２−メチレンビス［４−（１，１，３，３−テトラメチレンブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール］等を例示することができる。
【００３８】
ベンゾフェノン系紫外線吸収剤としては、２−ヒドロキシ−４−オクトキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−４’−クロルベンゾフェノン、２，２−ジヒドロキシ−４−メトキシベンゾフェノン、２，２−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン等を例示することができる。
【００３９】
サリチル酸フェニルエステル系紫外線吸収剤としては、ｐ−ｔ−ブチルフェニルサリチル酸エステル等が例示できる。
【００４０】
トリアジン系紫外線吸収剤としては、２，４−ジフェニル−６−（２−ヒドロキシ−４−メトキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−エトキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−（２−ヒドロキシ−４−プロポキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−（２−ヒドロキシ−４−ブトキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ブトキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ヘキシルオキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−オクチルオキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ドデシルオキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ベンジルオキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ブトキシエトキシ）−１，３，５−トリアジン等を挙げることができる。
【００４１】
さらに、アクリル樹脂層（Ｈ）には一般的に入手可能な酸化防止剤及び着色防止剤等の添加剤が含まれる。これらアクリル樹脂層（Ｈ）に添加される酸化防止剤、着色防止剤としては、チバ・スペシャルティ・ケミカルズ（株）、住友化学工業（株）、旭電化工業（株）等のカタログに記載の各種の酸化防止剤、着色防止剤の使用が可能である。
【００４２】
酸化防止剤の例として、２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔ−フェノール）、３，３’，３”，５，５’，５”−ヘキサ−ｔ−ブチル−α，α’，α”−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾール、エチレンビス（オキシエチレン）ビス［３−（５−ｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート］、ヘキサメチレンビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、２，６−ジ−ｔ−ブチル−４−［４，６−ビス（オクチルチオ）−１，３，５−トリアジン−２−イルアミノ］フェノール、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ’−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニルプロピオナミド）、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，３，５−トリス［（４−ｔ−ブチル−３−ヒドロキシ−２，６−キシリル）メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）トリオン、ジアリル−３，３’−チオジプロピオネート、ペンタエリスリチルテトラキス（３−ラウリルチオプロピオネート）、トリス（ノニルフェニル）フォスファイト、トリス（ジノニルフェニル）フォスファイト、４，４’−チオビス（３−６−ｔ−ブチルフェノール）、チオジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、トリスノリルフェニルフォスファイト、トリフェニルフォスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト等がある。さらに、旭電化工業（株）カタログに記載のＰＥＰ４Ｃ、ＰＥＰ８、ＰＥＰ２４Ｇ、ＰＥＰ３６、ＨＰ−１０等も使用可能であるが、これらに限定されるものではない。
【００４３】
ポリカーボネート樹脂基材（Ｆ）の少なくとも片面に紫外線吸収剤（Ｇ）を含有するアクリル樹脂層（Ｈ）を設けた成形品を製造するための方法については、特に制限はい。例えば、ポリカーボネート樹脂基材（Ｆ）及びアクリル樹脂層（Ｈ）の原料樹脂を同時に溶融押出して成形する共押出法や、ポリカーボネート樹脂基材（Ｆ）をシート状に押出成形する際に同時にアクリル樹脂層（Ｈ）を溶融押出してラミネートする方法、予めフィルム状に成形されたアクリル樹脂層（Ｈ）をポリカーボネート樹脂基材（Ｆ）の押出成形時に連続的に熱ラミネートする方法、シート状或いはフィルム状に成形されたポリカーボネート樹脂基材（Ｆ）及びアクリル樹脂層（Ｈ）をプレス機にて熱圧着する方法等が用いられるが、安価に大量に生産する場合は共押出法が好適である。
【００４４】
共押出法で用いられる押出装置としては、ポリカーボネート樹脂基材（Ｆ）を押出すメイン押出機と、被覆層となる紫外線吸収剤（Ｇ）を含有するアクリル樹脂層（Ｈ）を押出す１又は２以上のサブ押出機により構成され、通常サブ押出機はメイン押出機より小型のものが採用される。メイン押出機の温度条件は、通常２３０℃〜２９０℃、好ましくは２４０℃〜２８０℃であり、サブ押出機の温度条件は、通常２２０℃〜２７０℃、好ましくは２３０℃〜２６０℃である。２種以上の溶融樹脂を被覆する方法としては、フィードブロック方式、マルチマニホールド方式等の公知の方法を用いることが出来る。この場合、フィードブロックで積層された溶融樹脂はＴダイなどのシート成形ダイに導かれ、シート状に成形された後、表面を鏡面処理された成形ロール（ポリッシングロール）に流入して、バンクを形成する。
このシート状成形物は、成形ロール通過中に鏡面仕上げと冷却が行われ、積層板が形成される。マルチマニホールドダイの場合は、該ダイ内で積層された溶融樹脂は同様にダイ内部でシート状に成形された後、成形ロールにて鏡面仕上げ及び冷却が行われ、積層板が形成される。ダイの温度としては、通常２４０℃〜３００℃、好ましくは２５０℃〜２９０℃であり、成形ロール温度としては、通常１００〜１９０℃、好ましくは１１０〜１８０℃である。ロールは縦型ロールまたは、横型ロールを適宜使用できる。
【００４５】
該ポリカーボネート樹脂層（Ｆ）と該アクリル樹脂層（Ｈ）とを共押出しする際、フィードブロック、Ｔダイでの成形性、及びポリッシングロールでの巻き付き防止のために添加される滑剤は、アクリル樹脂に対して０．０１〜１重量％であり、好ましくは０．０２〜０．８重量％、更に好ましくは０．０２〜０．７重量％である。滑剤添加量が０．０１％未満の場合、ロールとの密着性改善には寄与することがなく、十分な効果を示さない。また、１％を超えて添加してもさらなる成形性改善効果は見られず、これら滑剤がブリードアウトを起こし、埃付着、次工程での塗料等の密着性不全など積層体の表面特性を低下させる原因となる場合も起こり得る。アクリル樹脂に添加される滑剤は、花王（株）、日本油脂（株）、旭電化工業（株）、共栄社化学（株）などのカタログに記載の各種の滑剤の使用が可能である。これらの例として、エステル類としてブチルステアレート、アルコール類としてステアリルアルコール、グリセリンエステルとしてステアリン酸モノグリセライド、ソルビタンエステルとしてソルビタンモノパルミチテート、ソルビタンモノステアレート、多価アルコールとしてマンニトール、脂肪酸としてステアリン酸、油脂系ワックスとして硬化ひまし油、モノアマイドとしてのステアリン酸アマイド、オレイン酸アマイド、ビスアマイドとしてエチレンビスステアリン酸アマイド、及び複合滑剤などを例示することができるがこれらだけに限定されるものではない。
【００４６】
共押出により製造されたアクリル樹脂層（Ｈ）の膜厚は、１〜１００μｍが良く、好ましくは３〜８０μｍ、さらに好ましくは５〜５０μｍである。１μｍ未満ではその効果が発揮されず、１００μｍを超えると樹脂積層体（Ｊ）の耐衝撃性を著しく低下させ、さらには経済性においても不利である。
また、アクリル樹脂層（Ｈ）上にコーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］を塗布し、硬化することによって形成される硬化層（Ｉ）の厚みは１〜１０μｍであり、好ましくは２〜８μｍ、さらに好ましくは３〜７μｍである。硬化層（Ｉ）の厚みが１μｍ未満では耐候性が劣り、１０μｍを越えると硬化時にクラックが発生するので好ましくない。
【００４７】
【実施例】
以下に本発明を実施例によってさらに詳述するが、本発明はこれによって限定されるものではない。また、特に断らない限り、以下に記す「部」及び「％」はそれぞれ「重量部」及び「重量％」を意味する。
【００４８】
本実施例で用いた評価、試験方法を以下に示す。
（１）密着性：ＪＩＳ Ｋ５４００に準拠し、サンプルをカミソリの刃で２ｍｍ間隔に６本ずつ切れ目をいれて２５個の碁盤目をつくり、市販のセロテープ（登録商標）をよく密着させた後、９０°手前方向に急激に剥がした時、塗膜が全く剥離しないものを○で表示した。
（２）耐煮沸性：評価サンプルを１００℃の沸騰水に２時間浸漬した後の外観変化、密着性を評価し、変化のないものを○とした。
（３）耐候性：ＪＩＳ Ｋ５４００に準拠し、カーボンアーク式サンシャインウェザーメーターにて促進試験を行い密着性で剥離する迄の時間を求めた。
【００４９】
製造例１（ポリカーボネート樹脂とアクリル樹脂被覆層からなる共押出シートの製造）
基板層にポリカーボネート樹脂（Ｅ−２０００Ｕ、三菱ガス化学社製、ポリスチレン換算重量平均分子量；６３，０００）を用い、ポリカーボネートを押し出す押出機として、バレル直径６５ｍｍ、スクリュウのＬ／Ｄ＝３５、シリンダー温度２７０℃とした。
また、被覆層を形成するアクリル樹脂を押し出す押出機は、バレル直径３２ｍｍ、スクリュウのＬ／Ｄ＝３２、シリンダー温度２５０℃に設定した。２種類の樹脂を同時に溶融押出し、積層する際には、フィードブロックを使用し、ポリカーボネート樹脂の片面にアクリル樹脂を積層した。ダイヘッド内温度は２７０℃とし、ダイ内で積層一体化された樹脂は、鏡面仕上げされた３本のポリッシングロールに導かれ、１番ロール温度１１０℃、２番ロール温度１３０℃、３番ロール温度１８０℃に設定した。最初に流入するロール間隔にて、バンクを形成した後、２番、３番ロールを通過させた。引き取り速度は１．２ｍ／分、引き取り用ピンチロール速度１．６ｍ／分とした。
得られたシートは、厚さ０．５ｍｍ、アクリル樹脂被覆層は２０μｍで、外観の優れたのもであった。
【００５０】
ここで使用したアクリル樹脂は、連続重合法で製造された三菱ガス化学社製ＭＧＣ−１０（特開平７−１３３３０３号公報記載の方法）に紫外線吸収剤としてチヌビン１５７７（チバ・スペシャルティ・ケミカル社製）２％と、酸化防止剤としてスミライザーＢＨＴ（住友化学工業社製）０．１％及びアデガスタブＰＥＰ−３６（旭電化工業社製）０．０５％及び滑剤として、ステアリルアルコール０．４％を添加した樹脂を用いた。
【００５１】
合成例１（有機共重合体（Ｃ−１）の合成）
γ−メタクリロキシプロピルトリメトキシシラン２０重量部に、これと共重合可能な単量体としてメチルメタクリレート６０重量部、エチルアクリレート５重量部、酢酸ビニル５重量部、グリシジルメタクリレート１０重量部、エチレングリコール・ジメタクリレート０．２重量部及び重合触媒としてのアゾビスイソブチロニトリル０．５重量部、ジアセトンアルコール１００重量部を配合し、窒素気流下に８０〜９０℃で５時間加熱撹拌し、粘度４２，４００ｃｐｓで、アルコキシシリル基２０重量％を含有する単量体含有量の有機共重合体（Ｃ−１）を得た。
【００５２】
合成例２（有機共重合体（Ｃ−２）の合成）
メチルメタクリレート６０重量部、エチルアクリレート５重量部、酢酸ビニル５重量部、グリシジルメタクリレート３０重量部、エチレングリコール・ジメタクリレート０．２重量部及び重合触媒としてのアゾビスイソブチロニトリル０．５重量部、ジアセトンアルコール１００重量部を配合し、窒素気流下に８０〜９０℃で５時間加熱撹拌し、粘度５０，５００ｃｐｓで、アルコキシシリル基を含有しない有機共重合体（Ｃ−２）を得た。
【００５３】
実施例１〜６
表１に示すようにメチルトリメトキシシラン（Ａ）１００重量部と酢酸１部を混合した後、氷浴で冷却し攪拌を行いながら温度を０〜１０℃に保持し、次いでスノーテックス３０（商品名：日産化学工業（株）製コロイダルシリカＳｉＯ２３０ｗｔ％平均粒径１０〜２０ｎｍ）８４部を滴下した。滴下後温度を１０℃に保持し４時間攪拌を行った後、更にスノーテックスＩＢＡ−ＳＴ（商品名：日産化学工業（株）製コロイダルシリカ２５〜２６ｗｔ％平均粒子径１０〜２０ｎｍ）８４部を滴下し、２０℃で１２時間攪拌を行い熟成を行った。その後、上記合成例１〜２の有機共重合体（Ｃ−１）及び有機共重合体（Ｃ−２）を、表１〜表２に示した比率で配合し、次に、酢酸セロソルブ４５部、イソブチルアルコール５０部及びＫＰ−３４１（商品名：信越化学工業（株）製ポリオキシアルキレングリコールジメチルシロキサン共重合体）０．０２部を滴下混合し、更に硬化触媒としてテトラメチルアンモニウムアセテートを０．０２部滴下し混合し塗料を調製した。調製後、高分子タイプの紫外線吸収剤（一方社油脂工業（株）製ＸＬ−１８３ ５０ｗｔ％）を塗料中の樹脂分１００部に対して１０部添加し塗料を完成させた。
製造例１の共押シートのアクリル樹脂被覆面上に、前記塗料を塗布し、熱風乾燥機にて１３０℃で１時間硬化させ、厚さ４μｍの硬化層を積層した。得られた樹脂積層体の評価結果を表１〜２に示した。
【００５４】
比較例１〜３
有機共重合体（Ｃ−１）、又は有機共重合体（Ｃ−２）の配合率を表１〜表２のように変えた以外は、実施例１〜６と全く同一条件で樹脂積層体を製造し、評価結果を表１〜２に示した。
【００５５】
【表１】

【００５６】
【表２】

【００５７】
比較例４
メチルトリメトキシシラン（Ａ）１００重量部に、酢酸１部を混合した後、氷浴で冷却し攪拌を行いながら温度を０〜１０℃に保持し、次いでスノーテックス３０（商品名日産化学工業（株）製コロイダルシリカＳｉＯ２３０ｗｔ％平均粒径１０〜２０ｎｍ）８４部を滴下した。滴下後温度を１０℃に保持し４時間攪拌を行った後、更にスノーテックスＩＢＡ−ＳＴ（商品名：日産化学工業（株）製コロイダルシリカ２５〜２６ｗｔ％平均粒子径１０〜２０ｎｍ）８４部を滴下し、２０℃で５０時間攪拌を行い熟成を行った。
次に、酢酸セロソルブ４５部、イソブチルアルコール５０部及びＫＰ−３４１（商品名：信越化学工業（株）製ポリオキシアルキレングリコールジメチルシロキサン共重合体）０．０２部を滴下混合し、更に硬化触媒としてテトラメチルアンモニウムアセテートを０．０２部滴下し混合し塗料を調製した。調製後、紫外線吸収剤として２，４−ジヒドロキシベンゾフェノンを塗料中の樹脂分１００部に対して１０部添加し塗料を完成させた。
製造例１の共押シートのアクリル樹脂被覆面上に、前記塗料を塗布し、熱風乾燥機にて１３０℃で１時間硬化させ、厚さ４μｍの硬化層を積層した。得られた樹脂積層体を実施例１と同一条件で評価した結果、耐煮沸性は○、４％、耐候性処理後の密着性は２６００時間であった。
【００５８】
上記の実施例から明らかなように、本発明の樹脂積層体は、特に耐煮沸密着性、耐候性処理後の密着性に優れているが、比較例の樹脂積層体は耐候性処理後の密着性が非常に劣り、実用性の低いものであった。
【００５９】
【発明の効果】
本発明の樹脂用コーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］は、透明性、耐摩耗性、耐熱性及び耐水性のみならず、耐候性にも著しく優れている。また、ポリカーボネート樹脂基材（Ｆ）の少なくとも一方の面を紫外線吸収剤（Ｇ）含有のアクリル樹脂層（Ｈ）で被覆し、該アクリル樹脂層（Ｈ）を前記樹脂用コーティング組成物［（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＋（Ｅ）］でコーティングし、硬化させた硬化層（Ｉ）からなる樹脂積層体（Ｊ）は、各樹脂層間の密着性が良好で、透明性、耐候性、耐摩耗性、耐衝撃性、耐熱性及び耐水性に優れ、得られた塗膜は高光沢で鮮映感のある仕上がりの良いものが得られるので幅広い分野で使用できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin coating composition and a resin laminate obtained by applying the composition to a resin surface and curing the resin composition. More specifically, a coating composition for a resin having excellent weather resistance, abrasion resistance, impact resistance, heat resistance and water resistance, and a polycarbonate resin substrate, and an ultraviolet absorber on at least one surface of the substrate. The present invention relates to a resin laminate comprising a cured layer obtained by laminating an acrylic resin layer containing, and applying and curing the coating composition on the acrylic resin layer.
Since the resin laminate of the present invention is excellent in transparency, weather resistance, abrasion resistance, impact resistance, heat resistance and water resistance, transparent roofs such as window glasses for automobiles and vehicles, sun roofs, lamp covers, greenhouses, etc. And lighting windows, road noise barriers, signboards, vending machine front panels, optical components such as carports, spectacle lenses, camera lenses, etc., protective sheets for LCD and EL displays, diaphragms to block oxygen and moisture, etc. Available for the field.
[0002]
[Prior art]
Organic transparent plastic materials, especially polycarbonate resins, have excellent impact strength and high load deflection temperature, and are excellent in dimensional stability, workability, and self-extinguishing properties, so they are used in many fields including optical materials. I have. However, since the surface hardness is low and the abrasion resistance and weather resistance are inferior, there is a problem that the most important transparency as a transparent material is impaired.
In addition, other plastic materials, such as polymethyl methacrylate, polystyrene and polyvinyl chloride, are used for various applications because of their excellent transparency, light weight, and easy workability. Molded articles also have problems that impact resistance, abrasion resistance, and solvent resistance are lower than those of other materials, and the surface is easily damaged.
[0003]
In order to solve these problems, after treating a plastic substrate with a composition comprising a silicone-based primer and 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, a colloidal silica-containing organopolysiloxane is treated. A method of applying a composition and curing the coating film is disclosed (Patent Document 1), but the weather resistance is insufficient, and furthermore, it is necessary to apply a primer and a cured film (two coats). There was a major drawback of reduced sex. It has also been proposed to laminate a three-layer structure composed of a specific layer on the surface of a plastic substrate (Patent Document 2). Further, a surface-hardened layer or a primer layer, and then a surface-hardened layer is formed on a polycarbonate resin plate containing an ultraviolet absorbent. A surface-hardened plate that is sequentially laminated is also disclosed (Patent Document 3), but in each case, the productivity is extremely low due to the two-coat method.
[0004]
In order to improve the productivity of the above two-coat system, the ionizing radiation is applied on the acrylic resin layer of the co-extruded sheet in which the thickness of the acrylic resin layer is 1/10 or less of the polycarbonate layer as a one-coat system. A laminated body in which a curable resin, a thermosetting resin, and a silicone-based curable resin are laminated is disclosed (Patent Document 4). Further, a polycarbonate resin base material / a resin layer containing an ultraviolet absorber / a surface hardness layer is disclosed. UV curable resin paint, a polyorganosiloxane, in which a photopolymerization initiator is added as a curing catalyst to a resin composition composed of one or more monofunctional or polyfunctional acrylate monomers or oligomers as a surface cured layer of a laminated body Patent Document 5 discloses a laminated body obtained by applying and curing a thermosetting, acryl or melamine thermosetting resin paint. Adhesiveness cases, crack resistance was insufficient in weather resistance.
[0005]
As described above, the two-coat system of the primer and the cured film has a problem that the production efficiency is particularly low. Further, when a one-coat type transparent resin laminate obtained by applying and curing a polyorganosiloxane-based thermosetting resin paint or the like without a primer is used outdoors, for example, a transparent resin such as a window or a lamp cover of a car or a vehicle, a greenhouse, etc. Coating agents and resin laminates that are capable of withstanding outdoor environments with severe temperature differences between sunlight, rain, humidity, high and low temperatures, such as roofs, daylight windows, eyeglass lenses, and camera lenses, are not yet sufficient. In the situation.
[0006]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2-182768 [Patent Document 2]
Japanese Patent Application Laid-Open No. 9-11405 [Patent Document 3]
Japanese Patent Application Laid-Open No. 9-174784 [Patent Document 4]
JP-A-8-25589 [Patent Document 5]
JP-A-8-230127
[Problems to be solved by the invention]
An object of the present invention is to solve the problems of the prior art, has good adhesion between resin layers, has excellent weather resistance, abrasion resistance, impact resistance, heat resistance, and water resistance. It is an object of the present invention to provide a highly transparent coating composition and a resin laminate using the same.
[0008]
[Means for Solving the Problems]
Means for Solving the Problems The present inventors diligently studied in order to solve the above-mentioned problems of the prior art, and obtained a highly productive one-coat resin coating composition [(A) + (B) + ( C) + (D) + (E)]. That is, the highly productive one-coat resin coating composition of the present invention contains an organotrialkoxysilane (A), colloidal silica (B) containing silicic anhydride and having a particle size of 4 to 20 nm, and an acrylic organic copolymer. The polymer (C), the amine carboxylate and / or ammonium carboxylate (D), and the silicone-containing polymer ultraviolet absorber (E) are blended in a specific ratio. Even a composition [(A) + (B) + (D) + (E)] composed of the compounds (A), (B), (D) and (E) as a resin coating composition has a certain degree of weather resistance. , Abrasion resistance, impact resistance, heat resistance, and water resistance. The composition [(A) + (B) + (D) + (E)] further includes an acrylic organic copolymer (C). The added resin coating composition of the present invention [(A) + (B) + (C) + (D) + (E)] has the following properties: adhesion, weather resistance and abrasion resistance between the coating film and the base resin. It has a great feature that heat resistance and water resistance are remarkably excellent.
[0009]
When the coating composition for a resin [(A) + (B) + (C) + (D) + (E)] of the present invention is directly coated on a polycarbonate resin substrate and cured, the coating composition [( A) + (B) + (C) + (D) + (E)] and the adhesion to the polycarbonate resin substrate is insufficient. Also, a coating composition [(A) + (B) + (C) + (D) + (E)] is applied to the acrylic resin using an acrylic resin containing an ultraviolet absorber instead of the polycarbonate resin base material. When cured by curing, there is no problem of adhesion, but the impact strength of the obtained resin laminate is extremely low, and the object of the present invention cannot be achieved. On the other hand, at least one surface of the polycarbonate resin substrate (F) is coated with an acrylic resin layer (H) containing an ultraviolet absorber (G), and the acrylic resin layer (H) is coated with the coating composition [(A ) + (B) + (C) + (D) + (E)], and the resin laminate (J) composed of the cured layer (I) coated and cured has no such problems at all. They have found that they have excellent adhesion between layers, transparency, weather resistance, abrasion resistance, impact resistance, heat resistance and water resistance, and have completed the second invention.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The coating composition of the present invention [(A) + (B) + (C) + (D) + (E)]
(1) 100 parts by weight of an organotrialkoxysilane (A) represented by the following formula (1):
(2) 100 parts by weight of a composition [(A) + (B)] comprising 50 to 200 parts by weight of colloidal silica (B) having a silicic acid content of 10 to 50% by weight and a particle size of 4 to 20 nm On the other hand,
(3) An acrylic organic copolymer (C) of an acrylic and / or vinyl monomer containing 50% by weight or less of an alkoxysilyl group and another monomer copolymerizable with the monomer. For 100 parts by weight of a composition [(A) + (B) + (C)] containing 3 to 20 parts by weight,
{Circle around (4)} Composition [(A) + (B) + (C) + (D)] containing 1.0 to 5.0 parts by weight of amine carboxylate and / or quaternary ammonium carboxylate (D) 100 For parts by weight,
{Circle around (5)} A silicone-containing polymer ultraviolet absorber (E) is blended in an amount of 0.5 to 35 parts by weight.
[0011]
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, and R ² represents an alkyl group.)
[0012]
R ¹ in the organotrialkoxysilane (A) represented by the above formula (1) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, and n Alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, n-hexyl group, n-heptyl group, and other γ-chloropropyl groups, vinyl groups, 3,3,3-tri Examples thereof include a fluoropropyl group, a γ-glycidoxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopropyl group, a phenyl group, and a 3,4-epoxycyclohexylethyl group. R ² in the organotrialkoxysilane (A) is an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, a sec-butyl. Group, tert-butyl group and the like.
[0013]
Specific examples of these organotrialkoxysilanes (A) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3 , 3-Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxy Propyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, Examples thereof include di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like, preferably tetramethoxysilane, tetraethoxysilane. Methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyl diethoxy silane. These organosilanes can be used alone or in combination of two or more.
[0014]
The hydrolysis of the organotrialkoxysilane (A) for obtaining the polyorganosiloxane used in the present invention is carried out by a known method, for example, by adding water to a lower alcohol solution of the alkoxysilane (A) in the presence of an acid catalyst. Is Examples of the lower alcohol include methanol, ethanol, isopropanol and butanol. In addition, an aqueous dispersion of colloidal silica may be added together with an acid catalyst during the hydrolysis. The polyorganosiloxane obtained in this way is substantially free of a 1-dimer component, 65% by weight or more of hexamers or more, and has a number average polymerization degree of 8-30. preferable.
[0015]
In the coating composition [(A) + (B) + (C) + (D) + (E)] of the present invention, the colloidal silica (B) constituting the composition contains 10 to 50 silicic anhydrides. % By weight, and the colloidal silica has a particle size of 4 to 20 nm. Such a dispersant for colloidal silica (B) may be water or an organic solvent, or a hydrophilic organic solvent (for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol, and the like). A mixed solvent of water and at least one of ethylene glycol derivatives such as glycol monobutyl ether and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; diacetone alcohol and the like can be used.
Among these aqueous solvents, water or a mixed solvent of water and methanol is preferable in terms of dispersion stability and drying property of the dispersion medium after coating.
[0016]
As a product in which colloidal silica is dispersed in a basic aqueous solution, as a product in which Nissan Chemical Industry Co., Ltd. Snowtex 30, Snowtex 40, Catalyst Kasei Kogyo Co., Ltd., Cataroid S30, Cataloid S40, and an acidic aqueous solution are dispersed. Nissan Chemical Industries, Ltd. Snowtex O, Nissan Chemical Industries, Ltd. MA-ST, IPA-ST, NBA-ST, IBA-ST, EG-ST, XBA-ST, as products dispersed in organic solvents. There are NPC-ST and DMAC-ST.
In the present invention, in order to obtain a dispersion having excellent stability and to obtain a coating composition [(A) + (B) + (C) + (D)] which is particularly excellent in weather resistance, the particle size is 4 to 10%. Use colloidal silica in the range of 20 nm.
The colloidal silica (B) is preferably used in a range of 50 to 200 parts by weight based on 100 parts by weight of the organotrialkoxysilane (A).
[0017]
The coating composition [(A) + (B) + (C) + (D) + (E)] of the present invention comprises an acrylic and / or vinyl monomer containing 50% by weight or less of an alkoxysilyl group. Organic copolymer (C) of a monomer and another monomer copolymerizable with these monomers is coated with an alkoxysilyl group to form a coating composition [(A) + (B) + (C) + (D) + (E)] and the resin substrate (F), and the heat resistance and durability are also improved. However, when the content of the monomer containing an alkoxysilyl group exceeds 50% by weight, the adhesiveness decreases.
[0018]
Examples of the acrylic monomer having an alkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltributoxysilane, and 3-methacryloxypropyltriisopropyl. Penoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltributoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltributoxy Silane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethyltributoxysilane, 3-methacryloxypropylmethyldimethoxysila , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldibutoxysilane, methacryloxymethylmethyldimethoxymethoxy, methacryloxymethylmethyldiethoxysilane, methacryloxymethylmethyldibutoxysilane, 3-acryloxypropyl There are methyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldibutoxysilane, acryloxymethylmethyldimethoxysilane, acryloxymethylmethyldiethoxysilane, acryloxymethylmethyldibutoxysilane, and the like. From the viewpoints of workability, reactivity, and crosslinkability, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane are preferred.
[0019]
Examples of the vinyl monomer containing an alkoxysilyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane. , Vinylmethyldibutoxysilane, vinylmethylbis (2-methoxyethoxy) silane, 3-vinyloxypropyltrimethoxysilane, 3-vinyloxypropyltriethoxysilane, 3-vinyloxypropylmethyldimethoxysilane, 3-vinyloxypropyl There are methyldiethoxysilane and the like, and vinyltrimethoxysilane, vinyltriethoxysilane, and 3-vinyloxypropyltrimethoxysilane are preferable from the viewpoint of workability and reactivity.
Other monomers copolymerizable with alkoxysilane, methyl methacrylate, butyl methacrylate, alkyl methacrylate such as 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, alkyl acrylate such as butyl acrylate, glycidyl methacrylate, acrylamide, acrylonitrile, Vinyl ethers such as vinyl acetate, ethyl vinyl ether, butyl vinyl ether, and hexyl vinyl ether; ethylene glycol; dimethacrylate;
[0020]
The organic copolymer (C) is a copolymer of the above-mentioned monomer containing 50% by weight or less of an alkoxysilyl group and another monomer copolymerizable therewith. Benzoyl peroxide, a radical polymerization catalyst selected from azo compounds such as azobisisobutyronitrile and peroxides such as benzoyl peroxide and dicumyl peroxide to a solution containing the monomer, and heated and reacted. can get.
The organic copolymer (C) is blended in an amount of 3 to 20 parts by weight based on 100 parts by weight of the composition [(A) + (B)] composed of the organotrialkoxysilane (A) and the colloidal silica (B). . If the amount of the organic copolymer (C) is less than 3 parts by weight, the adhesion in the weather resistance test is poor. If the amount exceeds 20 parts by weight, the appearance becomes white in the boiling resistance test, resulting in poor adhesion. In addition, whitening occurs in a weather resistance test.
[0021]
As amine carboxylate and / or quaternary ammonium carboxylate (D) constituting the coating composition [(A) + (B) + (C) + (D) + (E)] of the present invention, dimethylamine acetate is used. And ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, trimethylbenzylammonium acetate, tetramethylammonium acetate, tetra-n-butylammonium acetate, tetraethylammonium acetate, 2-hydroxyethyltrimethylammonium acetate, and the like.
This amine carboxylate and / or quaternary ammonium carboxylate (D) is a composition comprising an alkoxysilane (A), colloidal silica (B) and an organic copolymer (C) [(A) + (B) + (C)] It is used in the range of 1.0 to 5.0 parts by weight based on 100 parts by weight. When the amount of the amine carboxylate and / or the quaternary ammonium carboxylate (D) is less than 1.0 part by weight, the abrasion resistance of the film is low, and when it exceeds 5.0 parts by weight, the transparency of the film is reduced. Is not preferred.
[0022]
The silicone-containing polymer ultraviolet absorber (E) constituting the resin coating composition [(A) + (B) + (C) + (D) + (E)] of the present invention is disclosed in JP-A-2001-139924. It is an ultraviolet absorber disclosed in the publication, that is, at least one selected from a benzophenone-based ultraviolet-absorbing monomer (e1) represented by the following formula (2) and a benzotriazole-based ultraviolet-absorbing monomer (e2) represented by the following formula (3) A kind of ultraviolet absorbing monomer (e1 + e2), a silicone macromer (e3) represented by the following formula (4), a functional group-containing copolymerizable vinyl monomer (e4), and a functional group-free copolymerizable vinyl compound (e5) Is a polymer having a weight average molecular weight of 10,000 to 100,000.
[0023]
Embedded image

(Wherein, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms. R ¹² represents an alkylene group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Represents an oxyalkylene group, m ¹ represents 0 or 1. R ¹³ represents a hydrogen atom or a lower alkyl group. X ¹ represents an ester bond, an amide bond, an ether bond, or a urethane bond.
[0024]
Embedded image

(In the formula, R ²¹ represents a hydrogen atom, a halogen atom, or a methyl group. R ²² represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ²³ represents an alkylene group having 1 to 10 carbon atoms, Or an oxyalkylene group having 1 to 10 carbon atoms, m ²¹ represents 0 or 1. R ²⁴ is an alkylene group having 1 to 8 carbon atoms, an alkylene group having 1 to 8 carbon atoms having an amino group, or a hydroxyl group. represents an alkylene group having 1 to 8 carbon atoms ^{having, m 22} is ^{.R 25} indicating 0 or 1 .X ² represents a hydrogen atom, or a lower alkyl group is an ester bond, an amide bond, an ether bond, or urethane bond Is shown.)
[0025]
Embedded image

(In the formula, R ³¹ represents a hydrogen atom or a methyl group. R ³² represents an alkylene group having 1 to 6 carbon atoms or an oxyalkylene group having 1 to 6 carbon atoms, and m ³¹ represents 0 or 1. R ³³ represents an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 6 carbon atoms having an amino group, or an alkylene group having 1 to 6 carbon atoms having a hydroxyl group, and m ³² represents 0 or 1. n represents an integer of 1 to 200, and X ³ represents an ester bond or an amide bond.
[0026]
The ratio of each of the components constituting the silicone-containing ultraviolet absorber (E) is (e1 + e2) / e3 / e4 / e5 = 5 to 50/5 to 60/50 to 80/5 to 20 (% by weight). Further, the weight average molecular weight of the silicone macromer (e3) is preferably from 200 to 10,000. The silicone-containing ultraviolet absorber (E) includes alkoxysilane (A), colloidal silica (B), organic copolymer containing alkoxysilyl group (C), amine carboxylate and / or quaternary ammonium carboxylate (D ) Is added in an amount of 0.5 to 35 parts by weight based on 100 parts by weight in total. When the blending amount of the silicone-containing ultraviolet absorber (E) is less than 0.5 part by weight, the weather resistance of the resin coating composition [(A) + (B) + (C) + (D) + (E)] Is less than 35 parts by weight, the coefficient of linear expansion of the cured layer obtained by curing the resin coating composition [(A) + (B) + (C) + (D) + (E)] increases. Not preferred.
[0027]
The dispersion solvent of the resin coating composition [(A) + (B) + (C) + (D) + (E)] can be used as long as the effects of the present invention are not impaired. From the viewpoint of sol stability and availability, it is preferable to use water or lower alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, and ketones such as methyl ethyl ketone and diacetylacetone. In order to exert the above-mentioned solvent effect in the present invention, the water content in the composition is preferably 15% or less. If it exceeds 15%, water is selectively coordinated to the silanol group, so that the stability of the silanol group is impaired.
[0028]
The storage temperature of the resin coating composition [(A) + (B) + (C) + (D) + (E)] of the present invention is usually 25 ° C. or lower, preferably 15 ° C. or lower, more preferably 5 ° C. or lower. It is as follows. If the temperature exceeds 25 ° C., if the storage period is long, the hydrolysis / condensation reaction gradually proceeds, which is not preferable.
When forming a cured film using the composition containing the polyorganosiloxane of the present invention, to improve the hardness and scratch resistance of the cured film, or to impart optical functionality such as a high refractive index, a known A curing catalyst, a metal oxide, and other additives may be appropriately added.
[0029]
Specific examples of the curing catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, potassium acetate, sodium formate, potassium formate, n-hexylamine, potassium propionate, tributylamine, and diazaamine. Basic compounds such as bicycloundecene, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, γ-aminopropyltrimethoxysilane, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt Metal compounds such as octylate, cobalt acetylacetonate, iron acetylacetonate, tin acetylacetonate, dibutoxytin octylate, p-toluenesulfonic acid, Such acidic compounds of the chloroacetic acid and the like. The addition amount of the curing catalyst is 0.01 to 10 parts by weight based on 100 parts by weight of the resin coating composition [(A) + (B) + (C) + (D) + (E)] of the present invention. Preferably, there is.
[0030]
Specific examples of the metal oxide include silica, alumina, titanium oxide, cerium oxide, tin oxide, zirconium oxide, antimony oxide, and iron oxide. In particular, colloidal silica (silica sol) is preferable when the curing agent is used for the purpose of abrasion resistance. When used as a curing agent, the amount of the metal oxide to be added is preferably 5 to 500 parts by weight, particularly preferably 10 to 200 parts by weight, based on 100 parts by weight of the coating composition of the present invention. The condensation reaction may be performed in the presence of these metal oxides, or may be added after the condensation reaction.
[0031]
The method for coating the resin coating composition [(A) + (B) + (C) + (D) + (E)] of the present invention on the acrylic resin layer (H) is based on the shape of the molded article to be coated. There are a brush, a roll, a dipping, a flow coating, a spray, a roll coater, a flow coater, a centrifugal coater, a screen process, and the like, depending on the purpose of the coating.
[0032]
As the polycarbonate resin serving as the polycarbonate resin substrate (F), an aromatic polycarbonate, an aliphatic polycarbonate, or an aromatic-aliphatic polycarbonate can be used, but an aromatic polycarbonate is preferable. As the aromatic polycarbonate resin in the present invention, an aromatic dihydroxy compound or an optionally branched thermoplastic aromatic polycarbonate polymer produced by reacting a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester Or it is a copolymer. The production method is not particularly limited, and it can be produced by a known method such as a phosgene method (interfacial polymerization method) or a melting method (ester exchange method). Further, an aromatic polycarbonate resin produced by a melting method and having a terminal OH group content adjusted can also be used. Among the polycarbonate resins thus produced, the polycarbonate resin used in the present invention has a weight average molecular weight in terms of polystyrene of 45,000 to 70,000.
[0033]
Next, the acrylic resin layer (H) located between the polycarbonate resin substrate (F) and the cured layer (I) of the composition containing the polyorganosiloxane will be specifically described. The acrylic resin in the acrylic resin layer (H) has a monomer amount of methyl methacrylate of 80 mol% or more, preferably 80 to 99 mol%, based on the total monomer amount of all the constitutional units, and a weight average molecular weight in terms of polystyrene. Is preferably from 70,000 to 150,000. When the acrylic resin is a methyl methacrylate homopolymer, the thermal stability is poor. The load deflection temperature of the acrylic resin is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, and further preferably 100 ° C. or higher.
[0034]
The method for producing an acrylic resin is generally roughly classified into an emulsion polymerization method, a suspension polymerization method, and a continuous polymerization method. The acrylic resin used in the present invention is preferably an acrylic resin produced by a continuous polymerization method. Further, the continuous production method can be divided into a continuous bulk polymerization method and a continuous solution polymerization method. In the present invention, an acrylic resin obtained by either method can be used.
[0035]
The acrylic resin layer (H) preferably contains 0.1 to 5.0% by weight of an ultraviolet absorber (G) for the purpose of maintaining weather resistance for a long period of time. The content is preferably 0.2 to 3.5% by weight, and more preferably 0.5 to 3.0% by weight. When the content of the ultraviolet absorber is less than 0.1% by weight, sufficient weather resistance is not exhibited. Further, even if the content exceeds 5.0% by weight, further improvement in weather resistance cannot be expected, and furthermore, these additives cause bleed out and cause whitening, decrease in adhesion, and mechanical performance. In particular, the impact resistance is often impaired.
[0036]
Examples of the ultraviolet absorber (G) added to these acrylic resin layers (H) include benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, and triazine-based ultraviolet absorbers for maintaining the transparency of the acrylic resin layer. Agents.
[0037]
Examples of the benzotriazole-based ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzo. Triazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl) -6- (2H-benzotriazole -2-yl) phenol] and the like.
[0038]
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4′-chlorobenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can be exemplified.
[0039]
Examples of the salicylic acid phenyl ester-based ultraviolet absorber include pt-butylphenylsalicylate.
[0040]
Examples of triazine-based ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-4-. Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4- (Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- (Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazi , 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1 , 3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine and the like.
[0041]
Further, the acrylic resin layer (H) contains generally available additives such as an antioxidant and an anti-coloring agent. Examples of the antioxidant and anticolorant added to the acrylic resin layer (H) include various types described in catalogs such as Ciba Specialty Chemicals Co., Ltd., Sumitomo Chemical Co., Ltd. and Asahi Denka Kogyo Co., Ltd. It is possible to use antioxidants and coloring inhibitors.
[0042]
Examples of antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol), and 2,2′-methylenebis (4-ethyl -6-t-phenol), 3,3 ', 3 ", 5,5', 5" -hexa-t-butyl-α, α ', α "-(mesitylene-2,4,6-triyl) tri -P-cresol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], 2,6-di-t-butyl-4- [4,6-bis (octylthio) -1,3,5-triazin-2-ylamino] phenol, pentaerythritol tetrakis [3- (3,5-di- -Butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), 1,3,5 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [ (4-t-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione, diallyl-3,3′-thio Dipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, 4,4′-thiobis (3-6-t-butyl) Phenol), thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], trisnolylphenylphosphite, triphenylphosphite, tris (2,4-di-t-butyl) Further, PEP4C, PEP8, PEP24G, PEP36, HP-10, etc. described in the catalog of Asahi Denka Kogyo Co., Ltd. can also be used, but the present invention is not limited thereto.
[0043]
There is no particular limitation on the method for producing a molded article in which the acrylic resin layer (H) containing the ultraviolet absorbent (G) is provided on at least one surface of the polycarbonate resin substrate (F). For example, a co-extrusion method in which the raw material resins of the polycarbonate resin base material (F) and the acrylic resin layer (H) are simultaneously melt-extruded and formed, or an acrylic resin is simultaneously formed when the polycarbonate resin base material (F) is extruded into a sheet shape. A method in which the layer (H) is melt-extruded and laminated, a method in which the acrylic resin layer (H) previously formed into a film is continuously heat-laminated during the extrusion molding of the polycarbonate resin substrate (F), a sheet or a film For example, a method of thermocompression bonding the polycarbonate resin base material (F) and the acrylic resin layer (H) molded by a press machine is used, but a coextrusion method is suitable for mass production at low cost.
[0044]
The extruder used in the co-extrusion method includes a main extruder that extrudes a polycarbonate resin base material (F), and an extruder that extrudes an acrylic resin layer (H) containing an ultraviolet absorber (G) to be a coating layer. It is composed of two or more sub-extruders, and the sub-extruder is usually smaller than the main extruder. The temperature condition of the main extruder is usually 230 ° C to 290 ° C, preferably 240 ° C to 280 ° C, and the temperature condition of the sub extruder is usually 220 ° C to 270 ° C, preferably 230 ° C to 260 ° C. As a method of coating two or more types of molten resins, a known method such as a feed block method or a multi-manifold method can be used. In this case, the molten resin laminated by the feed block is guided to a sheet forming die such as a T die, formed into a sheet shape, and then flows into a forming roll (polishing roll) having a mirror-finished surface, thereby forming a bank. Form.
The sheet-like molded product is mirror-finished and cooled while passing through a molding roll, and a laminated plate is formed. In the case of a multi-manifold die, the molten resin laminated in the die is similarly formed into a sheet inside the die, and then mirror-finished and cooled by a forming roll to form a laminated plate. The temperature of the die is usually from 240 to 300 ° C, preferably from 250 to 290 ° C, and the temperature of the forming roll is usually from 100 to 190 ° C, preferably from 110 to 180 ° C. As the roll, a vertical roll or a horizontal roll can be appropriately used.
[0045]
When the polycarbonate resin layer (F) and the acrylic resin layer (H) are co-extruded, a lubricant added for the formability of a feed block, a T-die, and the prevention of winding around a polishing roll is an acrylic resin. 0.01 to 1% by weight, preferably 0.02 to 0.8% by weight, more preferably 0.02 to 0.7% by weight. When the amount of the lubricant added is less than 0.01%, it does not contribute to the improvement of the adhesion to the roll and does not show a sufficient effect. Further, even if added in excess of 1%, no further improvement in moldability is observed, and these lubricants cause bleed-out, deteriorating the surface properties of the laminate, such as dust adhesion and poor adhesion of paints in the next step. In some cases, this can cause the problem. As the lubricant to be added to the acrylic resin, various lubricants described in catalogs such as Kao Corporation, Nippon Oil & Fats Co., Ltd., Asahi Denka Kogyo Co., Ltd., and Kyoeisha Chemical Co., Ltd. can be used. Examples of these, butyl stearate as esters, stearyl alcohol as alcohols, monoglyceride stearate as glycerin ester, sorbitan monopalmititate, sorbitan monostearate as sorbitan ester, mannitol as polyhydric alcohol, stearic acid as fatty acid, Examples of the oil-based wax include hardened castor oil, stearic acid amide, oleic acid amide as monoamide, ethylene bisstearic acid amide as bisamide, and composite lubricant, but are not limited thereto.
[0046]
The thickness of the acrylic resin layer (H) produced by coextrusion is preferably 1 to 100 μm, preferably 3 to 80 μm, and more preferably 5 to 50 μm. When the thickness is less than 1 μm, the effect is not exhibited. When the thickness exceeds 100 μm, the impact resistance of the resin laminate (J) is remarkably reduced, and further, it is disadvantageous in economy.
A cured layer (I) formed by applying and curing a coating composition [(A) + (B) + (C) + (D) + (E)] on the acrylic resin layer (H). Has a thickness of 1 to 10 μm, preferably 2 to 8 μm, and more preferably 3 to 7 μm. If the thickness of the cured layer (I) is less than 1 μm, the weather resistance is poor, and if it exceeds 10 μm, cracks occur during curing, which is not preferable.
[0047]
【Example】
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” and “%” described below mean “parts by weight” and “% by weight”, respectively.
[0048]
The evaluation and test methods used in this example are shown below.
(1) Adhesion: According to JIS K5400, the sample was cut with a razor blade at intervals of 6 mm at intervals of 2 mm to form 25 grids, and a commercial cellotape (registered trademark) was closely adhered. When the coating film was not peeled off at all when the film was suddenly peeled in the forward direction by 90 °, the circle was marked with ○.
(2) Boiling resistance: Changes in appearance and adhesion after the evaluation sample was immersed in boiling water at 100 ° C. for 2 hours were evaluated.
(3) Weather resistance: According to JIS K5400, an acceleration test was performed using a carbon arc type sunshine weather meter, and the time required for peeling with adhesion was determined.
[0049]
Production Example 1 (Production of co-extruded sheet composed of polycarbonate resin and acrylic resin coating layer)
A polycarbonate resin (E-2000U, manufactured by Mitsubishi Gas Chemical Company, weight average molecular weight in terms of polystyrene; 63,000) was used for the substrate layer. As an extruder for extruding polycarbonate, a barrel diameter of 65 mm, screw L / D = 35, cylinder temperature were used. 270 ° C.
The extruder for extruding the acrylic resin forming the coating layer was set to a barrel diameter of 32 mm, screw L / D = 32, and a cylinder temperature of 250 ° C. When two types of resins were simultaneously melt-extruded and laminated, an acrylic resin was laminated on one surface of a polycarbonate resin using a feed block. The temperature inside the die head is 270 ° C, and the resin laminated and integrated in the die is guided to three mirror-finished polishing rolls, and the first roll temperature is 110 ° C, the second roll temperature is 130 ° C, and the third roll temperature is The temperature was set at 180 ° C. After the bank was formed at the first roll interval, the roll was passed through the second and third rolls. The take-up speed was 1.2 m / min, and the take-out pinch roll speed was 1.6 m / min.
The obtained sheet had a thickness of 0.5 mm and an acrylic resin coating layer of 20 μm, and was excellent in appearance.
[0050]
The acrylic resin used here was added to MGC-10 manufactured by Mitsubishi Gas Chemical Company (method described in JP-A-7-133303) manufactured by a continuous polymerization method and tinuvin 1577 (manufactured by Ciba Specialty Chemical Co., Ltd.) as an ultraviolet absorber. 2), 0.1% of Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.) as an antioxidant, 0.05% of Adegastab PEP-36 (manufactured by Asahi Denka Kogyo) and 0.4% of stearyl alcohol as a lubricant. The used resin was used.
[0051]
Synthesis Example 1 (Synthesis of Organic Copolymer (C-1))
20 parts by weight of γ-methacryloxypropyltrimethoxysilane, 60 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate, 5 parts by weight of vinyl acetate, 10 parts by weight of glycidyl methacrylate, 10 parts by weight of ethylene glycol A mixture of 0.2 parts by weight of dimethacrylate, 0.5 parts by weight of azobisisobutyronitrile as a polymerization catalyst, and 100 parts by weight of diacetone alcohol was heated and stirred at 80 to 90 ° C. for 5 hours under a nitrogen stream, and the viscosity was lowered. At 42,400 cps, an organic copolymer (C-1) having a monomer content containing 20% by weight of an alkoxysilyl group was obtained.
[0052]
Synthesis Example 2 (Synthesis of Organic Copolymer (C-2))
60 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate, 5 parts by weight of vinyl acetate, 30 parts by weight of glycidyl methacrylate, 0.2 parts by weight of ethylene glycol dimethacrylate, and 0.5 parts by weight of azobisisobutyronitrile as a polymerization catalyst And 100 parts by weight of diacetone alcohol, and heated and stirred at 80 to 90 ° C. for 5 hours under a nitrogen stream to obtain an organic copolymer (C-2) having a viscosity of 50,500 cps and containing no alkoxysilyl group. .
[0053]
Examples 1 to 6
As shown in Table 1, after mixing 100 parts by weight of methyltrimethoxysilane (A) and 1 part of acetic acid, the mixture was cooled in an ice bath and maintained at a temperature of 0 to 10 ° C. with stirring, and then Snowtex 30 (product) 84 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., 230 wt% average particle diameter: 10 to 20 nm) were added dropwise. After the dropwise addition, the temperature was maintained at 10 ° C., and the mixture was stirred for 4 hours. Then, 84 parts of Snowtex IBA-ST (trade name: colloidal silica manufactured by Nissan Chemical Industries, Ltd., 25 to 26 wt% average particle diameter: 10 to 20 nm) was further added. The mixture was added dropwise and stirred at 20 ° C. for 12 hours for aging. Thereafter, the organic copolymer (C-1) and the organic copolymer (C-2) of the above Synthesis Examples 1 and 2 were blended in the ratio shown in Tables 1 and 2, and then 45 parts of cellosolve acetate were added. , 50 parts of isobutyl alcohol and 0.02 part of KP-341 (trade name: polyoxyalkylene glycol dimethyl siloxane copolymer manufactured by Shin-Etsu Chemical Co., Ltd.) were added dropwise, and tetramethylammonium acetate was added as a curing catalyst in 0.1 ml. 02 parts were dropped and mixed to prepare a paint. After the preparation, 10 parts of a polymer type ultraviolet absorber (50% by weight of XL-183 manufactured by YAS Corporation) was added to 100 parts of the resin in the paint to complete the paint.
The coating material was applied onto the acrylic resin-coated surface of the co-pressed sheet of Production Example 1, and cured at 130 ° C. for 1 hour with a hot air drier to form a cured layer having a thickness of 4 μm. Tables 1 and 2 show the evaluation results of the obtained resin laminate.
[0054]
Comparative Examples 1-3
Except that the blending ratio of the organic copolymer (C-1) or the organic copolymer (C-2) was changed as shown in Tables 1 and 2, the resin laminate was manufactured under the exact same conditions as in Examples 1 to 6. Was produced, and the evaluation results are shown in Tables 1 and 2.
[0055]
[Table 1]

[0056]
[Table 2]

[0057]
Comparative Example 4
After mixing 1 part of acetic acid with 100 parts by weight of methyltrimethoxysilane (A), the temperature is maintained at 0 to 10 ° C. while cooling in an ice bath and stirring, and then Snowtex 30 (trade name Nissan Chemical Industries, Ltd. 84 parts of colloidal silica (SiO 230 wt%, average particle diameter 10 to 20 nm, manufactured by Co., Ltd.) was added dropwise. After the dropwise addition, the temperature was maintained at 10 ° C., and the mixture was stirred for 4 hours. The mixture was added dropwise and stirred at 20 ° C. for 50 hours for aging.
Next, 45 parts of cellosolve acetate, 50 parts of isobutyl alcohol and 0.02 part of KP-341 (trade name: polyoxyalkylene glycol dimethyl siloxane copolymer manufactured by Shin-Etsu Chemical Co., Ltd.) were dropped and mixed, and further as a curing catalyst. 0.02 parts of tetramethylammonium acetate was dropped and mixed to prepare a coating material. After the preparation, 10 parts of 2,4-dihydroxybenzophenone as an ultraviolet absorber was added to 100 parts of the resin in the paint to complete the paint.
The coating material was applied onto the acrylic resin-coated surface of the co-pressed sheet of Production Example 1, and cured at 130 ° C. for 1 hour with a hot air drier to form a cured layer having a thickness of 4 μm. As a result of evaluating the obtained resin laminate under the same conditions as in Example 1, the boiling resistance was ○, 4%, and the adhesion after the weather resistance treatment was 2,600 hours.
[0058]
As is clear from the above Examples, the resin laminate of the present invention is particularly excellent in boiling adhesion and adhesion after weathering treatment, whereas the resin laminate of Comparative Example has adhesion after weathering treatment. The properties were very poor and the practicality was low.
[0059]
【The invention's effect】
The resin coating composition [(A) + (B) + (C) + (D) + (E)] of the present invention has not only transparency, abrasion resistance, heat resistance and water resistance but also weather resistance. Is also significantly better. Further, at least one surface of the polycarbonate resin substrate (F) is coated with an acrylic resin layer (H) containing an ultraviolet absorber (G), and the acrylic resin layer (H) is coated with the resin coating composition [(A ) + (B) + (C) + (D) + (E)], and the resin laminate (J) composed of the cured layer (I), which has good adhesion between the resin layers, It is excellent in transparency, weather resistance, abrasion resistance, impact resistance, heat resistance, and water resistance. The obtained coating film can be used in a wide range of fields because it provides a high-gloss, clear image and good finish.

Claims (5)

(1) 100 parts by weight of an organotrialkoxysilane (A) represented by the following formula (1):
R ¹ Si (OR ² ) ₃ (1)
(In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, and R ² represents an alkyl group.)
(2) 100 parts by weight of a composition [(A) + (B)] comprising 50 to 200 parts by weight of colloidal silica (B) having a silicic acid content of 10 to 50% by weight and a particle size of 4 to 20 nm On the other hand,
{Circle around (3)} 100 parts by weight of a composition [(A) + (B) + (C)] containing 3 to 20 parts by weight of an acrylic organic copolymer (C) containing 50% by weight or less of an alkoxysilyl group. ,
{Circle around (4)} A composition [(A) + (B) + (C) + (D)] containing 1.0 to 5.0 parts by weight of an amine carboxylate and / or a quaternary ammonium carboxylate (D) 100 For parts by weight,
{Circle around (5)} A coating composition [(A) + (B) + (C) + (D) + (E)] containing 0.5 to 35 parts by weight of a silicone-containing polymer ultraviolet absorber (E). A polycarbonate resin base material (F) and an acrylic resin layer (H) containing an ultraviolet absorber (G) are laminated on at least one surface of the base material (F), and a layer is formed on the acrylic resin layer (H). A resin laminate (J) comprising a cured layer (I) cured by applying the coating composition [(A) + (B) + (C) + (D) + (E)] according to item 1. The transparent resin laminate (J) according to claim 2, wherein the one composed of the polycarbonate resin substrate (F) / acrylic resin layer (H) / cured layer (I) is a film, sheet or board. The ultraviolet absorbent (G) in the acrylic resin layer (H) is at least one ultraviolet absorbent selected from the group consisting of benzotriazole, benzophenone, phenyl salicylate and triazine, and contains the ultraviolet absorbent. The transparent resin laminate (J) according to claim 2, wherein the amount is 0.1 to 5% by weight. The transparent resin laminate (J) according to claim 2, wherein the thickness of the acrylic resin layer (H) is 10 to 100 m, and the thickness of the cured layer (I) is 1 to 10 m.