JP2004346194A - Acrylic resin film, and molded product and part for vehicle having the film laminated thereon - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare an acrylic resin film for providing a resin molded product having not only a white metallic texture but also a chromatic color-based metallic texture; and to provide a molded product and a part for a vehicle having the film laminated thereon and the metallic texture. <P>SOLUTION: The acrylic resin film having 10-500 μm thickness comprises 100 pts. mass of an acrylic resin, 0.01-30 pts. mass of flaky aluminum oxide coated with a metal oxide. The acrylic resin film preferably has a layer of a photocurable resin composition comprising a thermoplastic resin having a radically polymerizable unsaturated group on a side chain, and a photopolymerization initiator. The acrylic resin film is preferably obtained by applying a print having ≤60 L<SP>*</SP>in a L<SP>*</SP>a<SP>*</SP>b<SP>*</SP>color system, or laminating a resin sheet having ≤60 L<SP>*</SP>in the L<SP>*</SP>a<SP>*</SP>b<SP>*</SP>color system thereon. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（上式中、Ｒ^４およびＲ^５は、それぞれ、エーテル結合、エステル結合またはエポキシ結合を有していてもよい炭素数１〜１０の炭化水素残基を表し、Ｒ^６は水素原子または炭素数１〜１０の炭化水素残基を表し、Ｒ^７は水素原子またはメチル基を表し、Ｒ^８は炭素数１〜３のアルキル基またはフェニル基を表し、ａおよびｂは、それぞれ０〜３の整数であり、ｃは４−ａ−ｂを満足する１〜４の整数であり、ｎは０〜２の整数であり、ｐは１〜６の整数である）
前記構造式（ａ３−２）で表されるシラン化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、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、ジメチルジメトキシシラン、ジフェニルジメトキシシラン、メチルエチルジエトキシシラン、メチルフェニルジメトキシシラン、トリメチルエトキシシラン、メトキシエチルトリエトキシシラン、アセトキシエチルトリエトキシシラン、ジエトキシエチルジメトキシシラン、テトラアセトキシシラン、メチルトリアセトキシシラン、テトラキス（２−メトキシエトキシ）シラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等が挙げられる。
【００８３】
前記構造式（ａ３−３）で表されるシラン化合物としては、例えば、テトラキス（アクリロイルオキシエトキシ）シラン、テトラキス（メタクリロイルオキシエトキシ）シラン、メチルトリス（アクリロイルオキシエトキシ）シラン、メチルトリス（メタクリロイルオキシエトキシ）シラン等が挙げられる。
【００８４】
前記構造式（ａ３−４）で表されるシラン化合物としては、例えば、β−アクリロイルオキシエチルジメトキシメチルシラン、γ−アクリロイルオキシプロピルメトキシジメチルシラン、γ−アクリロイルオキシプロピルトリメトキシシラン、β−メタクリロイルオキシエチルジメトキシメチルシラン、γ−メタクリロイルオキシプロピルトリメトキシシラン等が挙げられる。
【００８５】
前記構造式（ａ３−５）で表されるシラン化合物としては、例えば、ビニルメチルジメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン等が挙げられる。
【００８６】
前記構造式（ａ３−６）で表されるシラン化合物としては、例えば、γ−メルカプトプロピルジメトキシメチルシラン、γ−メルカプトプロピルトリメトキシシラン等が挙げられる。
【００８７】
前記構造式（ａ３−７）で表されるシラン化合物としては、例えばｐ−ビニルフェニルメチルジメトキシシラン、ｐ−ビニルフェニルトリメトキシシラン等が挙げられる。
【００８８】
かかるシラン化合物は、無機微粒子（ａ−３）の固形分１モル部に対して、０〜３モル部の割合で使用することが好ましい。シラン化合物の使用量が３モル部を超える場合には、得られる光硬化性樹脂組成物の層を有するアクリル樹脂フィルムの耐磨耗性が低下することがある。
【００８９】
シラン化合物で表面処理された無機微粒子は、市販品を利用したり、または公知の方法により無機微粒子を表面処理したりすることにより得ることができる。公知の表面処理方法としては、例えば、少量の水の存在下で、シラン化合物と無機微粒子を加熱攪拌することにより、処理することができる。
【００９０】
無機微粒子（ａ−３）を、側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）に添加する方法としては、予め側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）を合成後、無機微粒子を混合しても良いし、また側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）を構成するビニル重合性単量体と無機微粒子を混合した条件下で重合する方法等の任意の方法を選択することができる。
【００９１】
本発明で用いられる光硬化性樹脂組成物（Ａ）においては、必須成分の側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）および光重合開始剤（ａ−２）、さらに、必要に応じて使用することができる前述した無機微粒子（ａ−３）以外に、必要に応じて、増感剤、変性用樹脂、染料、顔料およびレベリング剤やハジキ防止剤、紫外線吸収剤、光安定剤、酸化安定剤等の添加剤を配合することができる。上記の増感剤は、光硬化反応を促進するものであって、その例としてはベンゾフェノン、ベンゾインイソプロピルエーテル、チオキサントン等が挙げられる。
【００９２】
ただし、光硬化性樹脂組成物（Ａ）は、前記側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）以外の架橋性化合物を実質的に含有すべきではない。特に、４０℃において液体状の架橋性モノマー、オリゴマーや、数平均分子量２０００以下の低分子量の架橋性モノマー、オリゴマーは実質的に含有するべきではない。特に、４０℃において液体状の架橋性モノマー、オリゴマーや、数平均分子量２０００以下の低分子量の架橋性モノマー、オリゴマーを含有すると、長期間の保管や加熱成形時において表面粘着性を有するようになり、印刷工程において不具合を生じたり、インサート成形又はインモールド成形時において金型を汚染したりする等の問題を生じることがある。より好ましくは、５０℃において液体状の架橋性モノマー、オリゴマーを実質的に含有するべきではなく、さらに好ましくは６０℃において液体状の架橋性モノマー、オリゴマーを実質的に含有するべきではない。なお、「実質的に含有しない」の表現は、光硬化性樹脂組成物（Ａ）に含まれる、側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）の固形分１００質量部に対して、１質量％以下であることを意味する。
【００９３】
本発明においては、上記の如き光硬化性樹脂組成物（Ａ）を用いるため、光硬化性樹脂組成物の層をアクリル樹脂フィルム上に形成した場合にも、アクリル樹脂フィルムの表面は粘着性がなく、また表面の粘着性が時間と共に変化する等の現象も起こらず、ロール状態での保存安定性が良好となる。
【００９４】
本発明のアクリル樹脂フィルムは、上述したような光硬化性樹脂組成物の層を有することより、光硬化前の優れた成形性や保存安定性と、光硬化後の優れた表面性状（硬度、耐候性、耐磨耗性等）を高次元で両立しているアクリル樹脂フィルムとなる。後述するように、通常、本発明の光硬化性樹脂組成物の層を有するアクリル樹脂フィルムは、有機溶剤等の溶剤に光硬化性樹脂組成物（Ａ）を混合、溶解させた溶液を、あらかじめ作製されたアクリル樹脂フィルム上に各種コート法によりコーティングした後に溶剤除去の為の加熱乾燥を行って製造する。この際、アクリル樹脂フィルム内に溶剤が多量に残存していると、光照射前の光硬化性樹脂組成物（Ａ）の層表面が粘着性を有するようになり、印刷工程における歩留まりの低下や、ロール状態での保存安定性の低下、あるいはインサート成形又はインモールド成形時における金型汚染性の低下等の問題を生じる。また、光硬化性樹脂組成物の層を有するアクリル樹脂フィルムをインサート成形又はインモールド成形することによって得られたインサート成形品又はインモールド成形品を光硬化させても、耐擦傷性、耐薬品性、耐候性等の表面物性が劣ることがある。このような不具合を解決するには、アクリル樹脂フィルム中の溶剤量を出来るだけ少なくすることが好ましい。
【００９５】
光硬化性樹脂組成物（Ａ）の層を有する本発明のアクリル樹脂フィルムの製造方法としては、例えば、側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）と光重合開始剤（ａ−２）と、必要に応じて無機微粒子（ａ−３）を含む光硬化性樹脂組成物（Ａ）を有機溶媒等の溶剤に十分に攪拌溶解させ、グラビア印刷法、スクリーン印刷法、オフセット印刷法等の公知の印刷方法や、フローコート法、スプレーコート法、バーコート法、グラビアコート法、ロールコート法、ブレードコート法、ロッドコート法、ロールドクターコート法、エアナイフコート法、コンマロールコート法、リバースロールコート法、トランスファーロールコート法、キスロールコート法、カーテンコート法、ディッピングコート法等の公知のコート方法によりアクリル樹脂フィルム上にコーティングし、溶剤除去のための加熱乾燥を行う方法がある。
【００９６】
光硬化性樹脂組成物（Ａ）を攪拌溶解させる溶剤としては、光硬化性樹脂組成物（Ａ）の各成分を溶解または均一に分散させ、且つアクリル樹脂フィルムの物性（機械的強度、透明性、等）に実用上甚大な悪影響を及ぼさず、さらにアクリル樹脂フィルムの主たる構成成分である樹脂成分のガラス転移温度より８０℃以上高くない、好ましくは３０℃以上高くない沸点を有している揮発性の溶剤が好ましい。そのような溶剤としては、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、エチレングリコール等のアルコール系溶剤；キシレン、トルエン、ベンゼン等の芳香族系溶剤；ヘキサン、ペンタン等の脂肪族炭化水素系溶剤；クロロホルム、四塩化炭素等のハロゲン化炭化水素系溶剤；フェノール、クレゾール等のフェノール系溶剤；メチルエチルケトン、メチルイソブチルケトン、アセトン等のケトン系溶剤；ジエチルエーテル、メトキシトルエン、１，２−ジメトキシエタン、１，２−ジブトキシエタン、１，１−ジメトキシメタン、１，１−ジメトキシエタン、１，４−ジオキサン、ＴＨＦ等のエーテル系溶剤；ギ酸、酢酸、プロピオン酸等の脂肪酸系溶剤；無水酢酸等の酸無水物系溶剤；酢酸エチル、酢酸ブチル、ギ酸ブチル等のエステル系溶剤；エチルアミン、トルイジン、ジメチルホルムアミド、ジメチルアセトアミド等の窒素含有溶剤；チオフェン、ジメチルスホキシド等の硫黄含有溶剤；ジアセトンアルコール、２−メトキシエタノール（メチルセロソルブ）、２−エトキシエタノール（エチルセロソルブ）、２−ブトキシエタノール（ブチルセロソルブ）、ジエチレングリコール、２−アミノエタノール、アセトシアノヒドリン、ジエタノールアミン、モルホリン等の２種以上の官能基を有する溶剤；あるいは水等、各種公知の溶剤を適宜使用することができる。
【００９７】
ここでアクリル樹脂フィルム内の残存溶剤に起因する不具合を解消し、且つ低コストで生産効率を向上させる目的でより短時間でアクリル樹脂フィルムを製造するためには、溶剤除去のための加熱乾燥条件を強化し乾燥を十分に行う必要がある。しかし、この時にアクリル樹脂フィルムを、アクリル樹脂フィルムの熱変形温度以上の温度で、連続して２０秒間以上加熱乾燥させると、アクリル樹脂フィルムが僅かな張力でも引き伸ばされてしまい、アクリル樹脂フィルムの厚みが薄くなるばかりか、光硬化後の光硬化性樹脂組成物の層の耐擦傷性、表面硬度の低下等を招くことがある。
【００９８】
光硬化性樹脂組成物の層を有するアクリル樹脂フィルムの加熱乾燥条件は、アクリル樹脂フィルムの熱変形温度を超えない範囲の温度で加熱乾燥させるか、またはアクリル樹脂フィルムの熱変形温度より高い温度で乾燥させる場合には、アクリル樹脂フィルムの熱変形温度＋１５℃以下、好ましくは＋１０℃以下とし、且つその温度での加熱乾燥時間を２０秒以下、好ましくは１０秒以下、さらに好ましくは５秒以下とするとよい。
【００９９】
乾燥機としては、溶剤として可燃性有機溶剤を使用する場合には、安全性の点から蒸気による空気加熱式の熱源を備えたものを用い、乾燥機内の熱風を向流接触せしめる方式及びノズルよりアクリル樹脂フィルムに吹き付ける方式等が用いることができる。乾燥機の形状は、アーチ式、フラット式等、目的に合わせて公知のものを選択して用いることができる。
【０１００】
本発明のアクリル樹脂フィルムは、アクリル樹脂フィルム上に、Ｌ^＊ａ^＊ｂ^＊表色系においてＬ^＊が６０以下である印刷を施すことができる。Ｌ^＊ａ^＊ｂ^＊表色系においてＬ^＊が６０以下である印刷を施すことで、ホワイトメタリック調以外の有彩色系メタリック調の質感を有する外観となる。より好ましくはＬ^＊が３０以下、最も好ましくはＬ^＊が１０以下である印刷が、有彩色系メタリック調の質感を発現させる観点から望ましい。
【０１０１】
このような印刷は公知の方法により行うことができるが、カーボンブラックに代表される黒色着色剤を含有するインキや、赤色、青色、緑色、黄色の顔料、染料を組み合わせたインキを用いて、グラビア印刷で得ることが好ましい。
【０１０２】
また、本発明のアクリル樹脂フィルムは、公知の樹脂シートと貼りあわされた構成とすることもできる。この場合、Ｌ^＊ａ^＊ｂ^＊表色系においてＬ^＊が６０以下である公知の樹脂シートと貼りあわされた構成とすることで、有彩色系メタリック調の質感を有する外観となる。より好ましくはＬ^＊が３０以下、最も好ましくはＬ^＊が１０以下である樹脂シートと貼りあわされた構成とすることが、有彩色系メタリック調発現の観点から望ましい。
【０１０３】
このような樹脂シートと貼りあわされたアクリル樹脂フィルムを得る方法としては、アクリル樹脂フィルムと樹脂シートを加熱し、境界面の熱融着により貼りあわせるラミネーション法、境界面に接着性の層を設けてアクリル樹脂フィルムと樹脂シートを貼りあわせるラミネーション法等の方法、あるいは樹脂シートとなる樹脂を押出成形する時、ダイスから出てきた溶融樹脂にアクリル樹脂フィルムを直接接触させ、境界面の熱融着により貼りあわせる方法等が挙げられる。
【０１０４】
なお、上記の樹脂シートとしては、公知の熱可塑性樹脂を用いた樹脂シートであれば特に限定されないが、シート状とする樹脂にカーボンブラックに代表される黒色着色剤や、赤色、青色、緑色、黄色の顔料、染料を組み合わせたものを含有する樹脂を用いることでＬ^＊が６０以下である樹脂シートが得られる。樹脂の種類としては、例えばアクリル樹脂、ポリカーボネート（以降ＰＣ）樹脂、ＡＢＳ樹脂、ＡＢＳ／ＰＣ樹脂、塩化ビニル（以降ＰＶＣ）樹脂、ポリエステル樹脂、または、これらを主成分とする樹脂が好ましい。ただし、ポリオレフィン樹脂等のアクリル樹脂に熱融着しない樹脂の場合においては、アクリル樹脂フィルムと樹脂シートの境界面に接着性の層を設けることで張りあわせる事が可能である。
【０１０５】
樹脂シートの成形法としては、Ｔダイ法、カレンダー法、インフレーション法等公知の方法が挙げられる。
【０１０６】
樹脂シートの厚みは、用途に応じて替えられるため特に限定されないが、本発明のアクリル樹脂フィルムと貼りあわせられる範囲であり、かつ真空・圧空成形が可能な範囲であることが好ましい。具体的には、１００μｍから２ｍｍ程度のものが成形性の観点から好ましい。
【０１０７】
以上のような本発明のアクリル樹脂フィルムが積層された成形品を製造する方法としては、本発明のアクリル樹脂フィルムの、金属酸化物で表面コートしたフレーク状酸化アルミニウムを含有する層が表面になるように真空・圧空成形することにより成形品を得ることができる。このような成形品は、ホワイトメタリック調や、有彩色系のメタリック調の質感を有する成形品となる。
【０１０８】
また、アクリル樹脂フィルムを予め成形品の形状に真空・圧空成形、突き上げ成形等により加工し、これを射出成形用金型に配置後、基材樹脂を射出成形すると同時に成形品を成形する方法（インサート成形法）；射出成形用金型キャビティー内でアクリル樹脂フィルムを真空・圧空成形した後、金型キャビティー内に基材樹脂を射出成形する方法（インモールド成形法）によっても、成形品を得ることができる。
【０１０９】
なお、成形品を構成する基材樹脂としては、アクリル樹脂フィルムとの接着性に優れるものであれば特に限定されないが、例えばアクリル樹脂、ＰＣ樹脂、ＡＢＳ樹脂、ＡＢＳ／ＰＣ樹脂、ＰＶＣ樹脂、ポリエステル樹脂、または、これらを主成分とする基材樹脂が好ましい。ただし、ポリオレフィン樹脂等のアクリル樹脂に熱融着しない基材樹脂の場合においては、本発明のアクリル樹脂フィルムが基材樹脂と接する面に、接着性の層を設けることで積層する事が可能である。
【０１１０】
なお、Ｌ^＊ａ^＊ｂ^＊表色系においてＬ^＊が６０以下である樹脂を基材樹脂として用いることで、アクリル樹脂フィルム自体にＬ^＊が６０以下の部分を持たなくても、有彩色系メタリック調の質感を有する成形品とすることができる。より好ましくはＬ^＊が３０以下、最も好ましくはＬ^＊が１０以下である基材樹脂が、有彩色系メタリック調の質感を発現する観点から望ましい。
【０１１１】
また、光硬化性樹脂組成物の層を有するアクリル樹脂フィルムを用いた場合は、成形品を金型内より取り出した後、光照射することにより成形品表面の光硬化性樹脂組成物を光硬化させることができる。照射する光としては、電子線、紫外線、γ線等を挙げることができる。照射条件は、光硬化性樹脂組成物（Ａ）の光硬化特性に応じて定められるが、照射量は、通常５００〜１０，０００ｍＪ／ｃｍ^２程度である。これによって、光硬化性樹脂組成物（Ａ）が硬化して硬質の被膜が表面に形成された成形品を得ることができる。このような成形品は耐磨耗性に優れるので自動車外装用途に好適である。
【０１１２】
本発明のアクリル樹脂フィルムが積層された成形品の工業的用途例としては、車輌内装部品（例えばインストルメントパネル、コンソールボックス、メーターカバー、ドアロックペゼル、ステアリングホイール、パワーウィンドウスイッチベース、センタークラスター、ダッシュボード等）、車輌外装部品（例えばウェザーストリップ、バンパー、バンパーガード、サイドマッドガード、ボディーパネル、スポイラー、フロントグリル、ストラットマウント、ホイールキャップ、センターピラー、ドアミラー、センターオーナメント、サイドモール、ドアモール、ウインドモール等、窓、ヘッドランプカバー、テールランプカバー、風防部品等）；窓枠、サッシ等の建材部品；食器、玩具、ゲーム機等の雑貨；掃除機ハウジング、テレビジョンハウジング、エアコンハウジング等の家電部品；インテリア部材；船舶部材；パソコンハウジング、携帯電話ハウジング等の電子通信機等を例示することができる。特に、本発明のアクリル樹脂フィルムが少なくとも表面の一部に配置された上述の車輌内装部品や車輌外装部品等の車輌用部品、特に車輌外装部品は、耐磨耗性に優れており好適である。
【０１１３】
【実施例】
以下、実施例により本発明をさらに詳細に説明するが、本発明は実施例により限定されるものではない。実施例中の「部」は「質量部」を、「％」は「質量％」をそれぞれ表す。また、実施例中の略号は以下のとおりである。
メチルメタクリレート ＭＭＡ
ブチルアクリレート ＢＡ
アリルメタクリレート ＡＭＡ
スチレン Ｓｔ
メチルアクリレート ＭＡ
ｔ−ブチルハイドロパーオキサイド ｔＢＨ
ｎ−オクチルメルカプタン ｎＯＭ。
【０１１４】
熱可塑性重合体（Ｉ）（ＩＩＩ）、ゴム含有重合体（ＩＩ）、およびアクリル樹脂フィルムについては、以下の試験法により諸物性を測定した。
１）熱可塑性重合体（Ｉ）（ＩＩＩ）の還元粘度
重合体０．１ｇをクロロホルム１００ｍＬに溶解し、２５℃で測定した。
２）ゴム含有重合体（ＩＩ）の質量平均粒子径
乳化重合にて得られたゴム含有重合体（ＩＩ）のポリマーラテックスの質量平均粒子径を大塚電子（株）製の光散乱光度計ＤＬＳ−７００を用い、動的光散乱法で測定した。
３）アクリル樹脂フィルムの製膜性
Ｔダイ法にて厚み１２５μｍのアクリル樹脂フィルムを製膜した後、５時間以上フィルムが切れなかったものを良好とした。
４）Ｌ^＊の測定方法
スガ試験機株式会社製、ＳＭ−Ｃを用いてＬ^＊ａ^＊ｂ^＊表色系で測定した。
５）成形品の耐磨耗性
テーバー磨耗試験（片側５００ｇ荷重、ＣＳ−１０Ｆ磨耗輪を用い、回転速度６０ｒｐｍ、試験回数５００回で試験を実施）後の曇価を測定した。そして（試験後の曇価）−（試験前の曇価）で表される数値を耐磨耗性（％）として示した。なお、この数値が２５以下のものは外観変化が少なく耐磨耗性に優れる。
【０１１５】
＜実施例１＞
ａ）ゴム含有重合体（ＩＩ）の製造
反応容器に以下に示す（イ）を仕込み、攪拌を行いながら窒素雰囲気下８０℃で２００分間にわたって以下に示す原料（ロ）（重合体（ＩＩ−Ａ）用単量体原料）を連続的に添加し、その後さらに１２０分間重合を行い、弾性重合体（ＩＩ−Ａ）のラテックスを得た。
【０１１６】
この弾性重合体（ＩＩ−Ａ）のラテックスに、引き続いて以下に示す（ハ）を添加し、攪拌を行いながら窒素雰囲気下８０℃で、以下に示す原料（ニ）（ゴム重合体（ＩＩ−Ｂ）用単量体原料）を１００分間にわたって連続的に添加し、その後さらに８０℃で６０分間連続して重合を行うことにより硬質重合体（ＩＩ−Ｂ）を形成し、ゴム含有重合体（ＩＩ）のラテックスを得た。ゴム含有重合体（ＩＩ）の質量平均粒子径は０．１２μｍであった。
【０１１７】
このゴム含有重合体（ＩＩ）のラテックスに対して、酢酸カルシウムを用いて凝析、凝集、固化反応を行い、ろ過、水洗後乾燥してゴム含有重合体（ＩＩ）を得た。
【０１１８】

【０１１９】
ｂ）熱可塑性重合体（ＩＩＩ）の製造
反応容器に窒素置換したイオン交換水２００部を仕込み、乳化剤オレイン酸カリウム１部、過硫酸カリウム０．３部を仕込んだ。続いてＭＭＡ４０部、ＢＡ１０部、ｎＯＭ０．００５部を仕込み、窒素雰囲気下６５℃にて３時間撹拌し、重合を完結させた。引き続いて、ＭＭＡ４８部、ＢＡ２部からなる単量体混合物を２時間にわたり滴下し、滴下終了後２時間保持を行い、重合を完結させて、熱可塑性重合体（ＩＩＩ）のラテックスを得た。このラテックスを０．２５％硫酸水溶液に添加して重合体を酸凝析した後、脱水、水洗、乾燥し、粉体状の熱可塑性重合体（ＩＩＩ）を回収した。この熱可塑性重合体（ＩＩＩ）の還元粘度ηｓｐ／ｃは０．３８Ｌ／ｇであった。
【０１２０】
ｃ）アクリル樹脂フィルムの製造
上記の如くして得たゴム含有重合体（ＩＩ）１６部および熱可塑性重合体（ＩＩＩ）１部と、熱可塑性重合体（Ｉ）としてのＭＭＡ／ＭＡ共重合体（ＭＭＡ／ＭＡ＝９８／２、還元粘度０．０６Ｌ／ｇ）８３部、チヌビン２３４（商品名、チバスペシャリティケミカルズ製）１．４部、アデカスタブＬＡ６７（商品名、旭電化工業製）０．３部、アデカスタブＡＯ６０（商品名、旭電化工業製、フェノール系抗酸化剤）０．１部と、金属酸化物で表面コートしたフレーク状酸化アルミニウムとしてシラリックＴ６０−１０ＷＮＴＳｂ（商品名、メルク（株）製）３部とをヘンシェルミキサーを用いて混合した。次いで、４０ｍｍφの２軸スクリュー型押出機（Ｌ／Ｄ＝２６）を用いて、シリンダー温度２００℃〜２６０℃、ダイ温度２５０℃で溶融混練しペレット化した。このペレットを８０℃で一昼夜乾燥し、３００ｍｍＴダイを取り付けた４０ｍｍφのノンベントスクリュー型押出機（Ｌ／Ｄ＝２６）を用いて、シリンダー温度２００℃〜２４０℃、Ｔダイ温度２５０℃で、１２５μｍの厚みのアクリル樹脂フィルムを製膜した。製膜性は良好であった。
【０１２１】
得られたアクリル樹脂フィルムを、真空引き機能を持つ金型で真空成形した。その後、成形したアクリル樹脂フィルムを金型に配した状態で、ＡＢＳ樹脂（ＵＭＧ ＡＢＳ（株）製、商品名：ダイヤペットＡＢＳバルクサムＴＭ２５Ｂ 白色）を射出成形しインモールド成形品を得た。
【０１２２】
得られたアクリル樹脂フィルム、及び成形品は、良好なゴールド感を有するホワイトメタリック調の外観を示した。
【０１２３】
＜実施例２＞
金属酸化物で表面コートしたフレーク状酸化アルミニウムとしてシラリックＴ６０−１０ＷＮＴＣ（商品名、メルク（株）製）を用いる以外は実施例１と同様に実施しアクリル樹脂フィルムおよび成形品を得た。製膜性は良好であった。
【０１２４】
得られたアクリル樹脂フィルム、及び成形品は良好なシルバー感を有するホワイトメタリック調の外観を示した。
【０１２５】
＜実施例３＞
金属酸化物で表面コートしたフレーク状酸化アルミニウムとしてシラリックＴ６０−１０ＷＮＴＭ（商品名、メルク（株）製）を用いる以外は実施例１と同様に実施しアクリル樹脂フィルムおよび成形品を得た。製膜性は良好であった。
【０１２６】
得られたアクリル樹脂フィルム、及び成形品は良好なブルー感を有するホワイトメタリック調の外観を示した。
【０１２７】
＜実施例４＞
金属酸化物で表面コートしたフレーク状酸化アルミニウムを用いずに、実施例１と同様の手法で透明なアクリル樹脂フィルムを製膜した。得られた透明なアクリル樹脂フィルムと、実施例１で得られたゴールド感を有するホワイトメタリック調の外観を有するアクリル樹脂フィルムを熱ラミネートした。
【０１２８】
得られたアクリル樹脂フィルムを用いて、透明なアクリル樹脂フィルムの層が表面となるように、実施例１と同様にして成形品を得た。
【０１２９】
得られた成形品は深み感を有し、且つゴールド感を有するホワイトメタリック調の外観を示した。
＜実施例５〜７＞
それぞれ実施例１〜３で得られたアクリル樹脂フィルムに、カーボンブラックを含有するインキを用いて黒色のグラビア印刷を施した。なお、印刷面のＬ^＊は５であった。その後、それぞれ実施例１〜３と同様の手法で成形品を得た。
【０１３０】
得られた、印刷が施されたそれぞれのアクリル樹脂フィルム、及びそれぞれの成形品は、良好なゴールドメタリック調、シルバーメタリック調、ブルーメタリック調の外観を示した。
【０１３１】
＜実施例８＞
＜側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）の製造＞
窒素導入口、攪拌機、コンデンサーおよび温度計を備えた１Ｌの４つ口フラスコに、メチルエチルケトン５０部を入れ、８０℃に昇温した。窒素雰囲気下でメチルメタクリレート７９．９部、グリシジルメタクリレート２０．１部およびアゾビスイソブチロニトリル０．５部の混合物を３時間かけて滴下した。その後、メチルエチルケトン（沸点７９．６℃）８０部とアゾビスイソブチロニトリル０．２部の混合物を加え、重合させた。４時間後、メチルエチルケトン７４．４部、ハイドロキノンモノメチルエーテル０．５部、トリフェニルホスフィン２．５部およびアクリル酸１０．１部を加え、空気を吹き込みながら８０℃で３０時間攪拌した。その後、冷却した後、反応物をフラスコより取り出し、側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）の溶液を得た。
【０１３２】
側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）における単量体の重合率は９９．５％以上であり、ポリマー固形分量は約３５質量％、数平均分子量は約３万、ガラス転移温度は約１０５℃、二重結合当量は平均７８８ｇ／ｍｏｌであった。
＜コロイダルシリカ（無機微粒子（ａ−３））の製造＞
攪拌機、コンデンサーおよび温度計を備えたフラスコに、固形分換算のモル部でＩＰＡ−ＳＴ（商品名、イソプロパノール分散コロイダルシリカゾル（日産化学工業（株）製），シリカ粒子径＝１５ｎｍ）を１部、ＫＢＭ５０３（商品名、γ−メタクリロイルオキシプロピルトリメトキシシラン（信越化学工業（株）製），分子量＝２４８）を０．１部、水を０．３部入れ、攪拌しながら湯浴の温度を７５℃に上げ、その温度で２時間反応させることにより、イソプロパノール中に分散され、表面がシラン化合物で処理されたコロイダルシリカを得た。続いて、イソプロパノールを留去した後にトルエン（沸点１１０．６℃）を添加することを繰り返し、完全にイソプロパノールをトルエンに置換することにより、トルエン中に分散され、表面がシラン化合物で処理されたコロイダルシリカを得た。＜光硬化性樹脂組成物の製造＞
固形分換算の質量部で、上記の側鎖にラジカル重合性不飽和基を有する熱可塑性樹脂（ａ−１）１００部、１−ヒドロキシシクロヘキシルフェニルケトン（光重合開始剤（ａ−２））３部、上記のコロイダルシリカ（無機微粒子（ａ−３））６６部からなる光硬化性樹脂組成物を、プロペラ型ミキサーで攪拌して調製した。
＜光硬化性樹脂組成物の層を有するアクリル樹脂フィルム、成形品の製造＞
実施例１で得られたアクリル樹脂フィルム上に光硬化性樹脂組成物をコンマロールコーターにて塗工幅２５０ｍｍで塗工を行った。引き続いて、下記表１の温度条件に設定したトンネル型乾燥炉（巾８００ｍｍ，高さ１００ｍｍ，長さ８ｍ，４つの乾燥ゾーン（１ゾーンの長さ２ｍ）に分割，シートの動きに対して向流になるように熱風を送り込む方式）の中を、１０ｍ／分の速度で通過させて溶剤を揮発させ、厚さ８μｍの光硬化性樹脂層を形成した。この時の各乾燥ゾーンの滞在時間を下記表１に示す。
【０１３３】
【表１】

続いて、幅２００ｍｍにスリットして２０ｍの長さにＡＢＳ製コアにロール状に巻き取った。
【０１３４】
この光硬化性樹脂組成物の層を有するアクリル樹脂フィルムを、光硬化性樹脂組成物の層が金型の内壁面に向き合うように金型内に配置し、次いで赤外線ヒーターにより温度３５０℃で１０秒間予備加熱した後、さらに加熱を行いながら真空吸引することにより金型形状にアクリル樹脂フィルムを追従させた。
【０１３５】
次に、成形温度２８０〜３００℃、金型温度４０〜６０℃の条件において、ポリカーボネート樹脂を基材樹脂として用いてインサート成形を行い、光硬化性樹脂組成物の層を有するアクリル樹脂フィルムが成形品表面に密着したインサート成形品を得た。
【０１３６】
次いで、紫外線照射装置を用いて、約７００ｍＪ／ｃｍ^２の紫外線を照射して、光硬化性樹脂組成物を硬化させ、インサート成形品を得た。
【０１３７】
得られた成形品は深み感を有し、且つゴールド感を有するホワイトメタリック調の外観を示した。また、耐磨耗性に優れたものであった。
【０１３８】
＜実施例９〜１１＞
実施例１〜３で得られたアクリル樹脂フィルムを用い、成形品の基材樹脂としてＡＢＳ樹脂（ＵＭＧ ＡＢＳ（株）製、商品名：ダイヤペットＡＢＳバルクサムＴＭ２５Ｂ 白色）のかわりにＡＢＳ樹脂（ＵＭＧ ＡＢＳ（株）製、商品名：ダイヤペットＡＢＳバルクサムＴＭ２５Ｂ 黒色）を用いて、実施例１〜３と同様に実施し成形品を得た。なお、上記の黒色のＡＢＳ樹脂を用いて、実施例１記載の射出成形法に従って、金型にフィルムを配さずに成形して得られた成形品のＬ^＊は９であった。
【０１３９】
得られたそれぞれの成形品は、良好なゴールドメタリック調、シルバーメタリック調、ブルーメタリック調の外観を示した。
【０１４０】
＜実施例１２＞
実施例４で得られたアクリル樹脂フィルムと、Ｔダイ法で１ｍｍ厚に成形したＡＢＳシート（「ダイヤペットＡＢＳ ＳＷ７ 黒色」（三菱レイヨン社製；商品名）を用いてシート化したもの、シートのＬ^＊は８）を、ゴールド感を有するホワイトメタリック調の外観を有するアクリル樹脂フィルム面がＡＢＳシートに接するように熱ラミネートして、ゴールドメタリック調のアクリル樹脂フィルムを得た。このアクリル樹脂フィルムを用いて真空成形を行った。続いて不要部分を取り除いた後、アクリル樹脂フィルムを射出成形金型に装着して、ＡＢＳ樹脂（ＵＭＧ ＡＢＳ（株）製、商品名：ダイヤペットＡＢＳバルクサムＴＭ２５Ｂ白色）を射出成形しインサート成形品を得た。
【０１４１】
得られたインサート成形品は深み感を有するゴールドメタリック調の外観を示した。
【０１４２】
＜実施例１３〜１５＞
金属酸化物で表面コートしたフレーク状酸化アルミニウムの添加量を６質量部とする以外は、実施例９〜１１と同様にそれぞれ実施しアクリル樹脂フィルムおよび成形品を得た。製膜性は良好であった。
【０１４３】
得られたアクリル樹脂フィルム、及び成形品は、それぞれ実施例９〜１１で得られたアクリル樹脂フィルム、及び成形品と比較して、輝度が高いメタリック外観を示した。
【０１４４】
＜実施例１６＞
実施例８で得られた光硬化性樹脂組成物の層を有するアクリル樹脂フィルムのゴールド感を有するホワイトメタリック調の外観を有する面に、カーボンブラックを含有するインキを用いて黒色のグラビア印刷を施す以外は実施例８と同様に実施し成形品を得た。なお、印刷面のＬ^＊は５であった。
【０１４５】
得られた成形品は深み感を有するゴールドメタリック調の外観を示した。また、耐磨耗性に優れたものであった。
【０１４６】
＜実施例１７＞
実施例３で得られたアクリル樹脂フィルムを用い、実施例８と同様の手法で光硬化性樹脂組成物の層を有するアクリル樹脂フィルムを得た。
【０１４７】
この光硬化性樹脂組成物の層を有するアクリル樹脂フィルムと、Ｔダイ法で１ｍｍ厚に成形したＡＢＳシート（「ダイヤペットＡＢＳ ＳＷ７ 黒色」（三菱レイヨン社製；商品名））を用いてシート化したもの、シートのＬ^＊は８）を、ブルー感を有するホワイトメタリック調の外観を有するアクリル樹脂フィルム面がＡＢＳシートに接するように熱ラミネートして、ブルーメタリック調のアクリル樹脂フィルムを得た。このアクリル樹脂フィルムを用いて、成形温度２８０〜３００℃、金型温度４０〜６０℃の条件において、ポリカーボネート樹脂を基材樹脂として用いてインサート成形を行い、光硬化性樹脂組成物の層を有するアクリル樹脂フィルムが成形品表面に密着したインサート成形品を得た。
【０１４８】
次いで、紫外線照射装置を用いて、約７００ｍＪ／ｃｍ^２の紫外線を照射して、光硬化性樹脂組成物を硬化させ、インサート成形品を得た。
【０１４９】
得られた成形品は深み感を有するブルーメタリック調の外観を示した。また、耐磨耗性に優れたものであった。
【０１５０】
＜比較例１〜６＞
金属酸化物で表面コートしたフレーク状酸化アルミニウムを用いない以外は実施例１〜３、９〜１１と同様に実施しアクリル樹脂フィルムおよび成形品を得た。製膜性は良好であった。
【０１５１】
得られたアクリル樹脂フィルム、及び成形品はいずれもメタリック調の外観を示さなかった。
【０１５２】
＜比較例７〜９＞
金属酸化物で表面コートしたフレーク状酸化アルミニウムの添加量を３５質量部とする以外は実施例１〜３と同様に実施した。頻繁にフィルム切れが発生したためアクリル樹脂フィルムが得られなかった。
【０１５３】
＜比較例１０＞
金属酸化物で表面コートしたフレーク状酸化アルミニウムを用いない以外は実施例８と同様に実施し光硬化性樹脂組成物の層を有するアクリル樹脂フィルムおよび成形品を得た。製膜性は良好であった。
【０１５４】
得られたアクリル樹脂フィルム、及び成形品はメタリック調の外観を示さなかった。
【０１５５】
【発明の効果】
以上説明したとおり、本発明のアクリル樹脂フィルムを用いることで種々のメタリック調の質感を有する成形品を提供することができる。これらの成形品は良好なメタリック感を有し、車輌内装部品あるいは車輌外装部品として特に有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to an acrylic resin film suitable for metallic surface decoration of a molded product, and a molded product having a metallic appearance and a vehicle component in which the acrylic resin film is laminated.
[0002]
[Prior art]
In recent years, more sophisticated textures have been required for surface decoration of resin molded products, and in particular, metallic coating, wet plating, dry plating, etc., have been applied to the surface of resin molded products with metallic textures. It is applied to various industrial uses such as parts, home appliances, OA equipment and miscellaneous goods.
[0003]
Conventionally, as a method of imparting a metallic texture to the surface of a resin molded product, in addition to directly applying a surface decoration such as printing, plating, or metal deposition to the surface of the resin molded product, a method of forming a resin molded product is described. There is a method of kneading a high-brightness pigment such as an aluminum pigment or a pearl pigment into a resin composition to be coated, and a method of laminating a resin film having been subjected to painting, plating, vapor deposition, etc. on the surface of a resin molded product. 2. Description of the Related Art A method of laminating a decorated resin film has been used in various industrial fields in recent years due to productivity and a wide degree of freedom of a working environment.
[0004]
Japanese Patent Application Laid-Open No. H11-245261 (Patent Document 1) describes a method for obtaining a molded product having a metallic texture by insert molding using an insert film obtained by metal-depositing an acrylic resin film.
[0005]
Further, Japanese Patent Application Laid-Open No. 2000-86853 (Patent Document 2) discloses a silver metallic laminate film produced by passing a resin obtained by mixing an aluminum paste into an acrylic resin composition and an acrylic resin through a feed block type multilayer die, and A method for obtaining a molded article having a metallic texture by in-mold molding using the same is described.
[0006]
JP-A-2002-146054 (Patent Document 3) describes a decorative acrylic resin film containing a metallic pigment and having a specific total light transmittance, and a laminated resin molded product using the same. .
[0007]
On the other hand, in the type of texture particularly metallic to be imparted to the resin molded product, according to the use or the user's preference when using the resin molded product as an industrial member, a white metallic tone imitating pearl, imitating aluminum Silver metallic tone, black metallic tone that imitates steel, yellow metallic tone that imitates brass, gold metallic tone that imitates gold, or blue metallic tone that combines various chromatic hues in metallic tone, red metallic tone, etc. There is a strong demand for a metallic-like resin molded product having a high texture, especially for vehicle exterior members, interior members, and miscellaneous goods.
[0008]
Metallic powders such as aluminum powder, iron powder and brass powder, pearl pigments such as natural pearl essence, basic lead carbonate and its titanium dioxide coated pigment, natural mica, synthetic mica And a combination of a high-brightness pigment such as a metal oxide-coated pigment and an achromatic pigment such as carbon black and titanium white and / or a chromatic pigment or dye having various hues to obtain a metallic tone having various hues. The techniques to be developed are widely applied in the fields of printing, painting and coloring agents for resins. For example, with respect to the white metallic tone, a film having a white metallic tone can be obtained relatively easily only by adding a pearl pigment or the like, but gold metallic, blue metallic, yellow metallic, silver metallic, etc. are chromatic colors together with metal powder. Since it is necessary to use a combination of the above pigments or dyes, skill is required for toning and shaping.
[0009]
Conventionally, when giving a metallic texture of various textures to the surface of a resin molded product using the above-described film, for example, in a method of using a metallic print film laminated and used, different printing adapted to the intended texture. The film must be applied, and the strength of the film tends to decrease due to the effect of the solvent after printing, and the handleability tends to decrease.
[0010]
In the case of using an acrylic resin film having a metal deposition layer as in the example of JP-A-11-245261 (Patent Document 1), a metallic tone with a different texture is exhibited unless the type of metal to be deposited is substantially changed. It is difficult to use a metal-deposited film, and when a metal-deposited film is used, cracks are likely to occur in the metal-deposited layer by a stretching process such as a lamination method or an in-mold molding method for laminating the film on a resin molded product. For this reason, there is a disadvantage that the shape of the substrate molded product is limited.
[0011]
In the examples of JP-A-2000-86853 (Patent Document 2), a multilayer film composed of a colored layer obtained by adding an aluminum pigment to an acrylic composition and a transparent acrylic resin layer is used as a laminated resin molded product. Although specifically described, it specifically discloses a silver metallic tone film to which an aluminum paste is added, and does not disclose a method for obtaining a film of white metallic, blue metallic, yellow metallic or the like.
[0012]
Japanese Patent Application Laid-Open No. 2002-146054 (Patent Document 3) discloses various methods by changing the hue of a resin serving as a base material using an acrylic resin film having a specific total light transmittance having a metallic pigment. It is disclosed that a metallic molded product of a color tone can be obtained, but in order to obtain a metallic molded product of various colors, it was necessary to stock various resins as a base material. Further, since the total light transmittance of the acrylic resin film is limited, it is difficult to obtain a molded article having a strong metallic appearance, and thus its industrial utility value is low.
[0013]
As described above, conventionally, no method has been found for producing a metallic-tone resin molded article having a different texture covered with an acrylic resin film having various metallic appearances, and a technique for realizing this has not been found. There was a strong demand for the development of.
[0014]
[Patent Document 1]
JP-A-11-245261
[Patent Document 2]
JP-A-2000-86853
[Patent Document 3]
JP-A-2002-146054
[Patent Document 4]
JP-B-62-19309
[Patent Document 5]
JP-A-63-77663
[Patent Document 6]
JP-A-8-323934
[Patent Document 7]
JP-A-7-149994
[0015]
[Problems to be solved by the invention]
An object of the present invention is to provide an acrylic resin film for obtaining a molded product having a chromatic metallic texture as well as a white metallic tone, and a molded product having a metallic texture obtained by laminating the acrylic resin film and a vehicle component. To provide.
[0016]
[Means for Solving the Problems]
The present invention relates to an acrylic resin film having a thickness of 10 to 500 μm, containing an acrylic resin and 0.01 to 30 parts by mass of a flake-like aluminum oxide surface-coated with a metal oxide with respect to 100 parts by mass of the acrylic resin. is there. Such an acrylic resin film is suitable for giving a metallic texture to a molded product.
[0017]
Further, on the acrylic resin film, a photocurable resin composition containing a thermoplastic resin (a-1) having a radical polymerizable unsaturated group in a side chain and a photopolymerization initiator (a-2) ( An acrylic resin film having the layer (A) is preferred. Further, the photocurable resin composition (A) preferably contains inorganic fine particles (a-3). With such a configuration, it is possible to impart excellent surface properties (hardness, weather resistance, abrasion resistance, etc.) to the molded product.
[0018]
In addition, on the acrylic resin film, L^*a^*b^*L in the color system^*Acrylic resin film on which is printed is 60 or less, or L^*a^*b^*L in the color system^*Acrylic resin film bonded with a resin sheet having a value of 60 or less is preferable. Such an acrylic resin film can impart a chromatic metallic texture to a molded product.
[0019]
Further, the present invention is a molded product in which the above-mentioned acrylic resin film is laminated on a base resin. Such a molded article has a metallic texture. Furthermore, L^*a^*b^*L in the color system^*Is less than 60, the acrylic resin film itself has L^*Even if the molded article does not have a portion of 60 or less, the molded article has a chromatic metallic texture. In particular, it is preferable that the above-mentioned acrylic resin film is used as a vehicle component arranged on at least a part of the surface.
[0020]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described.
[0021]
The acrylic resin film of the present invention can be obtained from a known acrylic resin composition. The acrylic resin composition is not particularly limited. For example, JP-B-62-19309 (Patent Document 4), JP-A-63-77963 (Patent Document 5), and JP-A-8-323934. Acrylic resin compositions and the like described in the claims and examples of (Patent Document 6) can be used.
[0022]
A preferred example of the acrylic resin composition used in the present invention is an acrylic resin composition containing a thermoplastic polymer (I) and a rubber-containing polymer (II).
[0023]
The thermoplastic polymer (I) contains 50 to 100% by mass of an alkyl methacrylate, 0 to 50% by mass of an alkyl acrylate if necessary, and at least one of other copolymerizable vinyl monomers if necessary. It is obtained by polymerizing a resin composition containing a monomer material consisting of 0 to 49% by mass of a seed, and has a reduced viscosity (0.1 g of a polymer dissolved in 100 mL of chloroform and measured at 25 ° C). It is less than 0.1 L / g.
[0024]
When the reduced viscosity of the thermoplastic polymer (I) is 0.1 L / g or less, the raw material composition for producing an acrylic resin film has an appropriate melt viscosity and has good film-forming properties. Further, the reduced viscosity of the thermoplastic polymer (I) is preferably at least 0.05 L / g. When it is higher than 0.05 L / g, sufficient toughness can be exhibited to suppress breakage of the acrylic resin film during film formation and printing.
[0025]
As the alkyl methacrylate contained in the monomer material for obtaining the thermoplastic polymer (I), methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like can be used, but methyl methacrylate is most preferred.
[0026]
Methyl acrylate, ethyl acrylate, butyl acrylate, and the like can be used as the alkyl acrylate optionally contained in the monomer material for obtaining the thermoplastic polymer (I). The proportion of the alkyl acrylate in the monomer raw material is in the range of 0 to 50% by mass, and preferably in the range of 0.1 to 40% by mass.
[0027]
Known monomers can be used as other copolymerizable vinyl monomers contained as necessary in the monomer raw material for obtaining the thermoplastic polymer (I). Specifically, alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, acrylic monomers such as methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, and the like are preferable, and one or more of these are used. Can be used in combination.
[0028]
The method of polymerizing the resin composition containing the monomer raw material for obtaining the thermoplastic polymer (I) is not particularly limited, but may be a usual method such as suspension polymerization, emulsion polymerization, or bulk polymerization. In order to adjust the viscosity to the above range, a chain transfer agent is usually used. Known chain transfer agents can be used, but mercaptans are preferred. The amount of the chain transfer agent may be appropriately determined depending on the type and composition of the monomer contained in the above monomer raw material.
[0029]
The rubber-containing polymer (II) is an elastic copolymer having a structure of one layer or two or more layers obtained by polymerizing a resin composition containing a monomer material mainly composed of an alkyl acrylate as an inner layer ( II-A) and a hard polymer (II-B) having a structure of one layer or two or more layers obtained by graft-polymerizing a resin composition containing a monomer material mainly composed of an alkyl methacrylate ester as an outer layer. Is a rubber-containing polymer having a multilayer structure of two or more layers. In addition, the main component means the component most contained in the components contained in the monomer raw material.
[0030]
As the alkyl acrylate which is the main component of the monomer raw material for obtaining the elastic copolymer (II-A), known ones can be used, and among them, butyl acrylate and 2-ethylhexyl acrylate Are preferred.
[0031]
Further, the monomer raw material for obtaining the elastic copolymer (II-A) may contain other copolymerizable vinyl monomers. As other copolymerizable vinyl monomers, methyl methacrylate, butyl methacrylate, alkyl methacrylates such as cyclohexyl methacrylate, styrene, acrylonitrile, and the like are preferable, and these are used alone or in combination of two or more. be able to.
[0032]
The ratio with the other vinyl monomers copolymerizable with the alkyl acrylate is 35 to 100% by mass of the alkyl acrylate and 0 to 65% by mass of the other vinyl monomer copolymerizable. . When the content of the alkyl acrylate is 35% by mass or more, the molding whitening resistance is improved. A more preferred use range is 50% by mass or more.
[0033]
The monomer material for obtaining the elastic copolymer (II-A) further contains a crosslinkable monomer. The crosslinkable monomer is not particularly limited, but is preferably ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanate. Nurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, allyl cinnamate and the like can be mentioned, and these can be used alone or in combination. The crosslinkable monomer is used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the above-mentioned alkyl acrylate and another copolymerizable vinyl monomer. It is preferable to use 0.1 parts by mass or more, particularly 0.3 parts by mass or more, from the viewpoint of molding whitening resistance. With respect to the use of the crosslinkable monomer in an amount of more than 10 parts by mass, there is no particular problem in the properties of the elastic copolymer. However, when the amount is more than 10 parts by mass, the effect on the amount added is small.
[0034]
The elastic copolymer (II-A) can have a structure of one layer or two or more layers. In the case of a structure having two or more layers, the compounding ratio of each component as described above may be such that it satisfies the entire monomer raw material for forming each layer of the elastic copolymer (II-A). . That is, when the elastic copolymer (II-A) has a two-layer structure in order to form a hard core structure, it may be copolymerizable with the alkyl acrylate of the monomer material forming the first layer. Can be adjusted so that the alkyl acrylate is 35% by mass or less. For example, a multilayer polymer having a hard core structure having a particle diameter of 0.2 μm or less as disclosed in JP-A-7-149994 (Patent Document 7) can be used.
[0035]
As the outer layer, the alkyl methacrylate, which is the main component of the monomer material for obtaining the hard polymer (II-B), which is grafted onto the elastic copolymer (II-A), is contained in the monomer material in an amount of 50%. % By mass, and specifically, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and the like can be used.
[0036]
Further, the monomer raw material for forming the hard polymer (II-B) may contain 50% by mass or less of at least one other copolymerizable vinyl monomer. Other copolymerizable vinyl monomers are not particularly limited, but specifically include methyl acrylate, butyl acrylate, alkyl acrylates such as cyclohexyl acrylate, styrene, acrylonitrile, and the like. One type or a combination of two or more types can be used.
[0037]
The hard polymer (II-B) is graft-polymerized so as to be 10 to 400 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the elastic copolymer (II-A). The polymerization may be performed in two or more stages. In particular, when the amount of the hard polymer (II-B) is less than 10 parts by mass with respect to 100 parts by mass of the elastic copolymer (II-A), the transparency deteriorates due to aggregation of the elastic copolymer (II-A). Occurs and is not preferred.
[0038]
The preferred mass average particle diameter of the rubber-containing polymer (II) as described above is 0.05 to 0.4 μm. The rubber-containing polymer (II) can be obtained by ordinary emulsion polymerization. When the mass average particle diameter is 0.4 μm or less, more preferably 0.25 μm or less, and still more preferably 0.18 μm or less, transparency is improved. The particle diameter is preferably 0.05 μm or more from the viewpoint of film forming properties.
[0039]
The above acrylic resin composition can contain a thermoplastic polymer (III) as needed. The thermoplastic polymer (III) contains 50 to 100% by mass of methyl methacrylate and, if necessary, a monomer comprising at least one other vinyl monomer copolymerizable therewith with 0 to 50% by mass. A thermoplastic polymer having a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of more than 0.15 L / g. is there.
[0040]
The use of the thermoplastic polymer (III) improves film-forming properties, and is particularly effective when a high level of thickness accuracy and film-forming speed are required. When the reduced viscosity of the thermoplastic polymer (III) is in a range exceeding 0.15 L / g, an acrylic resin film having good thickness accuracy is obtained. The reduced viscosity of the thermoplastic polymer (III) used is usually more than 0.15 L / g and 2 L / g or less, preferably 1.2 L / g or less.
[0041]
Examples of the vinyl monomer copolymerizable with methyl methacrylate optionally contained in a monomer material for forming the thermoplastic polymer (III) used in the present invention include alkyl acrylate and alkyl methacrylate. Esters, aromatic vinyl compounds, vinyl cyanide compounds and the like can be used. The polymerization is preferably carried out by an emulsion polymerization method, and the polymer can be recovered in a powder form by a usual emulsion polymerization method and a post-treatment method.
[0042]
The acrylic resin composition which can be used in the present invention comprises 20 to 94.5 parts by mass of the thermoplastic polymer (I) and 5.5 to 80 parts by mass of the rubber-containing polymer (II) as described above. The total of (I) and component (II) is 100 parts by mass. However, when the thermoplastic polymer (III) is used in combination, 10 to 94.4 parts by mass of the thermoplastic polymer (I), 5.5 to 80 parts by mass of the rubber-containing polymer (II), and the thermoplastic polymer ( III) 0.1 to 10 parts by mass, and the total of the components (I), (II) and (III) is 100 parts by mass. When the component (III) is contained, the effect of improving the film forming property is exhibited by setting the content to 0.1 part by mass or more, and the viscosity of the acrylic resin composition becomes moderate by setting the content to 10 parts by mass or less. It is preferable from the viewpoint of film forming property and transparency.
[0043]
The rubber-containing polymer (II) is used in a range of 5.5 to 80 parts by mass. In particular, the ratio of the elastic copolymer (II-A) in the rubber-containing polymer (II) is determined by the component (I) ) And component (II), or 5 to 72% by mass of the total of component (I), component (II) and component (III). The proportion of the elastic copolymer (II-A) is preferably 5% by mass or more from the viewpoint of whitening resistance to molding and film-forming properties, more preferably 10% by mass or more, and even more preferably 20% by mass or more. . Further, it is preferable that the proportion of the elastic copolymer is 72% by mass or less from the viewpoint of transparency and film forming property.
[0044]
The acrylic resin film of the present invention contains a flake-like aluminum oxide surface-coated with a metal oxide. Examples of the metal oxide coated on the flake-like aluminum oxide include titanium oxide and iron oxide. Depending on the type of the metal oxide and the thickness of the coating, an acrylic resin film having a pearl or metallic texture having various colors can be obtained. The mass average particle diameter of the flake-like aluminum oxide surface-coated with such a metal oxide is preferably in the range of 5 to 30 μm. When it is 5 μm or more, the handleability is good, and when it is 30 μm or less, the mechanical strength of the acrylic resin film tends to be maintained. As the flake-shaped aluminum oxide surface-coated with such a metal oxide, for example, Silalic (registered trademark) manufactured by Merck Ltd. can be used.
[0045]
The content of the flake-shaped aluminum oxide surface-coated with the metal oxide in the acrylic resin film is 0.01 mass with respect to 100 parts by mass of the acrylic resin in consideration of the metallic tone imparting property and mechanical strength of the acrylic resin film. Parts or more and 30 parts by mass or less. Preferably it is 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass. When the amount is 0.01 parts by mass or more, a sufficient metallic texture can be obtained, and on the other hand, when the amount is 30 parts by mass or less, the acrylic resin film has a toughness that can be formed.
[0046]
The thickness of such an acrylic resin film is 10 μm or more. If it is 10 μm or more, a strength applicable to secondary processing can be obtained. It is more preferably at least 50 μm, even more preferably at least 70 μm. In addition, the thickness of the acrylic resin film of the present invention is 500 μm or less. When the thickness is 500 μm or less, good film-forming properties can be realized, stable production can be performed, and the rigidity of the obtained acrylic resin film can be kept low, so that good secondary workability such as laminating properties can be realized. In addition, the mass per unit area can be reduced, which is economically preferable. From the above viewpoint, the thickness is more preferably 300 μm or less.
[0047]
In the acrylic resin film of the present invention, if necessary, general compounding agents, for example, stabilizers, lubricants, processing aids, plasticizers, impact-resistant aids, ultraviolet absorbers, light stabilizers, foaming agents, coloring Agents and matting agents can be added.
[0048]
In particular, in order to impart weather resistance, it is preferable to add an ultraviolet absorber in a range of 0.1 to 5% by mass. The molecular weight of the ultraviolet absorber used is preferably 300 or more, and particularly preferably 400 or more. By using an ultraviolet absorber having a molecular weight of 300 or more, it is possible to prevent the ultraviolet absorber from volatilizing and contaminating the mold when performing vacuum / pressure molding in the injection mold.
[0049]
The type of the ultraviolet absorber is not particularly limited, but a benzotriazole-based compound having a molecular weight of 400 or more or a triazine-based compound having a molecular weight of 400 or more can be particularly preferably used. A specific example of the former is Tinuvin 234 (product of Ciba Specialty Chemicals) Adecastab LA-31 (trade name) of Asahi Denka Kogyo Co., Ltd., and specific examples of the latter include Tinuvin 1577 (trade name) of Ciba Specialty Chemicals Co., Ltd. As a hindered amine light stabilizer (HALS), ADK STAB LA-57 and LA67 (trade names) of Asahi Denka Kogyo KK can also be used.
[0050]
The acrylic resin film of the present invention can be produced by a melt extrusion method such as a melt casting method, a T-die method or an inflation method; a method such as a calendering method. It is preferable to produce by a melt extrusion method using an extrusion film forming machine equipped with a winding machine. The T-die used is not particularly limited, but a coat hanger type T-die is preferable from the viewpoint of stabilizing the flowability of the molten resin in the T-die.
[0051]
The acrylic resin composition melt-extruded from the T-die is formed into a film by a take-off machine having a cooling roll. The method of cooling the molten resin is not particularly limited, but a method of forming a film by contacting with one metal roll; forming a film by sandwiching a plurality of rolls or belts selected from a metal roll, a non-metal roll and a metal belt. The method can be illustrated.
[0052]
Among these, in order to obtain the mirror surface of the acrylic resin film surface and a sense of depth, a method of forming a film by sandwiching it with a plurality of rolls or belts selected from a metal roll, a non-metal roll and a metal belt is preferable. In the case where the acrylic resin film is sandwiched by a plurality of rolls, the film is formed so that at least the effective surface side of the acrylic resin film is in contact with the metal roll. When printing is performed on the acrylic resin film, printing omissions can be significantly reduced by printing on the effective surface. Here, the effective surface is a surface on which printing is performed.
[0053]
The acrylic resin film of the present invention as described above results in an acrylic resin film having a white metallic tone. Furthermore, a configuration in which a layer to be described later is formed on the above-described acrylic resin film, or a configuration in which printing is performed on the above-described acrylic resin film can also be employed.
[0054]
The acrylic resin film of the present invention may have a structure in which a transparent acrylic resin film or sheet containing no pigment is attached to one side of the acrylic resin film as described above. Such an acrylic resin film has a deeper metallic appearance.
[0055]
Examples of a method of attaching a transparent acrylic resin film or sheet to the acrylic resin film include a method of laminating by dry lamination, wet lamination, hot melt lamination, or the like. Moreover, it can also be performed by a heat press lamination method.
[0056]
Also, a method of simultaneously laminating the acrylic resin composition with the transparent acrylic resin film or sheet while melt-extruding the above-described acrylic resin composition, and a method of simultaneously laminating with the acrylic resin film while melt-extruding the composition for forming the transparent acrylic resin film or sheet Examples thereof include an extrusion lamination method using a T-die or the like. Further, as a method of laminating while simultaneously melt-extruding the acrylic resin composition and a composition for forming a transparent acrylic resin film or sheet, a method of bonding in a die by a feed block method or a multi-manifold method, Examples include a method by co-extrusion molding, such as a method in which a plurality of die lips are provided on one die and bonded outside the die.
[0057]
Further, the acrylic resin film of the present invention may have a structure having a layer of the photocurable resin composition (A). The photocurable resin composition (A) contains a thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain and a photopolymerization initiator (a-2), and is other than the above (a-1). Is substantially free of the crosslinkable compound. In the photocurable resin composition (A) of the present invention, since a component having a radical polymerizable unsaturated group in the polymer side chain is introduced, a cross-linking reaction proceeds between the polymer side chains. Good photo-curable acrylic with good abrasion resistance and abrasion resistance, no need to contain low molecular weight cross-linkable compound having reactive vinyl group, therefore no surface tackiness and excellent storage stability This has the advantage that a resin film can be obtained.
[0058]
Examples of the thermoplastic resin (a-1) having a radical polymerizable unsaturated group in a side chain include a polymer having a glass transition temperature of 25 to 175 ° C., preferably 30 to 150 ° C. And the like. Specifically, a compound obtained by polymerizing or copolymerizing the following compounds (1) to (7) and having a radically polymerizable unsaturated group introduced by a method (a) to (f) described below is used. Can be. In addition, "(meth) acrylate" represents acrylate or methacrylate, "(meth) acrylic acid" represents acrylic acid or methacrylic acid, "(meth) acrylamide" represents acrylamide or methacrylamide, and "( "Meth) acryloyloxy" refers to acryloyloxy or methacryloyloxy.
(1) Monomers having a hydroxyl group: N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meth) acrylate
(2) Carboxyl-containing monomer: (meth) acrylic acid, acryloyloxyethyl monosuccinate, etc.
(3) Monomers having an epoxy group: glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc.
(4) Monomers having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, etc.
(5) Amino group-containing monomer: (meth) acrylamide, diacetone acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.
(6) Monomer having a sulfone group: 2-acrylamido-2-methylpropanesulfonic acid and the like
(7) Isocyanate group-containing monomer: an addition product of a diisocyanate and a radical polymerizable monomer having active hydrogen, such as an equimolar addition product of 2,4-toluene diisocyanate and 2-hydroxyethyl acrylate, Isocyanate ethyl (meth) acrylate and the like.
[0059]
Further, in order to adjust the glass transition temperature of the polymer or copolymer of the above compound, or to harmonize the physical properties of the photocurable acrylic resin film, a monomer copolymerizable with the above compound and It can also be copolymerized. Examples of such a copolymerizable monomer include (meth) acrylates such as methyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and isobornyl (meth) acrylate, N-phenylmaleimide, and cyclohexylmaleimide. And imide derivatives such as N-butylmaleimide, olefinic monomers such as butadiene, and aromatic vinyl compounds such as styrene and α-methylstyrene.
[0060]
A radically polymerizable unsaturated group can be introduced into the above-mentioned polymer or copolymer by the following methods (a) to (f).
(A) In the case of a polymer or copolymer of the monomer (1) having a hydroxyl group, a monomer (2) having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.
(B) In the case of a polymer or copolymer of a monomer (2) having a carboxyl group and a monomer (6) having a sulfone group, a condensation reaction is carried out with the monomer (1) having a hydroxyl group. .
(C) In the case of a polymer or copolymer of a monomer (3) having an epoxy group, a monomer (7) having an isocyanate group, or a monomer (4) having an aziridinyl group, a hydroxyl group is used. The monomer (1) having a carboxyl group or the monomer (2) having a carboxyl group is subjected to an addition reaction.
(D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer (3) having an epoxy group or a monomer (4) having an aziridinyl group, or an isocyanate group is used. The monomer (7) or an equimolar addition product of a diisocyanate compound and a hydroxyl group-containing acrylate monomer is subjected to an addition reaction.
(E) In the case of a polymer or copolymer of the monomer (5) having an amino group, the monomer (2) having a carboxyl group is subjected to a condensation reaction.
(F) In the case of a polymer or copolymer of the monomer (5) having an amino group, the monomer (3) having an epoxy group or the monomer having an acetoacetoxy group is subjected to an addition reaction.
[0061]
The above reaction is preferably carried out while adding a trace amount of a polymerization inhibitor such as hydroquinone and sending dry air.
[0062]
The amount of the radically polymerizable unsaturated group in the side chain of the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in the side chain is double bond equivalent (per one side chain radically polymerizable unsaturated group). It is preferable from the viewpoint of improving scratch resistance and abrasion resistance that the number average molecular weight) is 3,000 g / mol or less on average as calculated from the charged value. The more preferable range of the double bond equivalent is 1200 g / mol or less on average, and the still more preferable range is 800 g / mol or less on average.
[0063]
In this way, by introducing a plurality of radically polymerizable unsaturated groups involved in crosslinking into the thermoplastic resin, there is no need to use a low molecular weight crosslinking compound, and during long-term storage and heat molding described below. However, it is possible to efficiently improve cured physical properties without having surface tackiness.
[0064]
The number average molecular weight of the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain is preferably in the range of 5,000 to 2,500,000, and in the range of 10,000 to 1,000,000. Is more preferred. When insert or in-mold molding of an acrylic resin film having a layer of the photo-curable resin composition, the mold releasability is improved, and the surface hardness of the insert or in-mold molded article after photo-curing is improved. In view of this, the number average molecular weight is preferably 5,000 or more. On the other hand, the number average molecular weight is preferably 2,500,000 or less from the viewpoint of easiness of synthesis and appearance, and from the viewpoint of expressing adhesion to the acrylic resin film.
[0065]
In addition, the glass transition temperature of the thermoplastic resin (a-1) having a radical polymerizable unsaturated group in the side chain is preferably adjusted to 25 to 175 ° C, and is preferably adjusted to 30 to 150 ° C. More preferred. From the viewpoint that the mold releasability of the acrylic resin film having the layer of the photocurable resin composition at the time of insert or in-mold molding becomes good, and the surface hardness of the insert or in-mold molded product after photocuring is improved. The glass transition temperature is preferably 25 ° C. or higher. On the other hand, the glass transition temperature is preferably 175 ° C. or lower from the viewpoint of the handleability of the acrylic resin film having the photocurable resin composition layer.
[0066]
In consideration of the glass transition temperature of the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in the obtained side chain, a vinyl polymerizable monomer having a high glass transition temperature as a homopolymer is used. It is preferred to use. Further, from the viewpoint of improving the weather resistance of the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain, it is preferable to use (meth) acrylates as a vinyl polymerizable monomer as a main component. .
[0067]
Further, as described later, when the inorganic fine particles (a-3) are added to the photocurable resin composition (A), the functional groups (hydroxyl group, carboxyl group, silanol group) on the surface of the inorganic fine particles (a-3) are added. And the like), for example, a vinyl polymerizable monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated silyl group and an alkoxysilyl group in the molecule. Since the resulting photocurable resin composition works to further improve physical properties such as rigidity, toughness, and heat resistance, such a functional group is contained as a part of a radically polymerizable vinyl polymerizable monomer component. May be.
[0068]
Examples of the vinyl polymerizable monomer containing such a reactive group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, vinyl trichlorosilane, Vinyl trimethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane and the like can be mentioned.
[0069]
Examples of the photopolymerization initiator (a-2) include a photoradical polymerization initiator that generates a radical by light irradiation.
[0070]
As the photo-radical polymerization initiator (a-2), known compounds can be used, and there is no particular limitation. However, in consideration of yellowing during curing and deterioration during weathering, acetophenone-based, benzophenone-based, and acylphosphine-based compounds can be used. A photo-radical polymerization initiator that does not contain an amino group in the molecule, such as an oxide type, is preferred. For example, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Phosphine oxide is preferred. Among these, depending on the molding method, the temperature may temporarily be higher than the boiling point of the compound, so that it may be appropriately selected according to the molding method. In order to increase the surface hardness of the molded article, an additive such as n-methyldiethanolamine that suppresses the inhibition of polymerization and curing by oxygen may be added.
[0071]
In addition to these photopolymerization initiators, various peroxides may be added in consideration of curing using heat during molding. When a peroxide is contained in the photocurable resin composition (A), it is necessary to cure the composition at 150 ° C. for about 30 seconds. Therefore, a peroxide having a low critical temperature, for example, lauroyl peroxide, t -Butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like are preferably used.
[0072]
The amount of the photo-radical polymerization initiator to be added is preferably 5% by mass or less based on the compound having a radically polymerizable unsaturated group in the side chain, particularly because the residual amount after curing affects the weather resistance. The amount of the amino radical photopolymerization initiator related to the change is preferably 1% by mass or less.
[0073]
To the photocurable resin composition (A), inorganic fine particles (a-3) can be added for the purpose of further improving scratch resistance and abrasion resistance. The type, particle diameter, and form of the inorganic fine particles (a-3) are not particularly limited as long as the obtained layer of the photocurable resin composition becomes transparent. Examples of the inorganic fine particles (a-3) include colloidal silica, alumina, and titanium oxide. These may be used alone or in combination of two or more. Among them, colloidal silica is particularly preferable from the viewpoints of availability, price, and transparency and abrasion resistance of the obtained photocurable resin composition layer.
[0074]
Colloidal silica can be used in the form of a normal aqueous dispersion or in the form of being dispersed in an organic solvent, but can be used together with a thermoplastic resin having a radical polymerizable unsaturated group in the side chain as the component (a-1). For uniform and stable dispersion, it is preferable to use colloidal silica dispersed in an organic solvent.
[0075]
Examples of such an organic solvent include methanol, isopropyl alcohol, n-butanol, ethylene glycol, xylene / butanol, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, and toluene. Among them, it is preferable to select an organic solvent that can dissolve the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain. Further, as described later, when producing an acrylic resin film having a layer of the photocurable resin composition of the present invention, these organic solvents are heated and dried to volatilize, and thus are the main constituent components of the acrylic resin film. An organic solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C. than the glass transition temperature of the resin component is preferable because it hardly remains in the acrylic resin film.
[0076]
As the colloidal silica dispersed in an organic solvent, commercially available products dispersed in a dispersion medium, for example, methanol silica sol MA-ST, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene glycol silica sol EG -ST, xylene / butanol silica sol XBA-ST, ethyl cellosolve silica sol ETC-ST, butyl cellosolve silica sol BTC-ST, dimethylformamide silica sol DBF-ST, dimethylacetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK- ST (the trade name, manufactured by Nissan Chemical Industries, Ltd.) or the like can be used.
[0077]
The particle diameter of the inorganic fine particles (a-3) is usually 200 nm or less from the viewpoint of the transparency of the obtained layer of the photocurable resin composition. It is more preferably 100 nm or less, and further preferably 50 nm or less.
[0078]
The amount of the inorganic fine particles (a-3) to be added is 5 to 400 parts by mass of the inorganic fine particles with respect to 100 parts by mass of the solid content of the thermoplastic resin (a-1) having a radical polymerizable unsaturated group in the side chain. Parts is preferred, and a range of 10 to 200 parts by mass is particularly preferred. When the addition amount of the inorganic fine particles (a-3) is less than 5 parts by mass, the effect of improving the abrasion resistance may not be observed, and when the addition amount exceeds 400 parts by mass, the photocuring property may not be obtained. Not only does the storage stability of the resin composition (A) decrease, but also the moldability of the resulting acrylic resin film having a layer of the photocurable composition may decrease.
[0079]
Further, as the inorganic fine particles (a-3) used in the present invention, those whose surface has been previously treated with a silane compound represented by the following structural formula (a3-1) may be used. The use of the surface-treated inorganic fine particles further improves the storage stability of the photocurable resin composition (A), and the surface hardness and weather resistance of the resulting acrylic resin film having a layer of the photocurable resin composition. Is also preferable.
[0080]
SiR¹ _aR² _b(OR³)_c                                (A3-1)
(In the above formula, R¹And R²Represents a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond or a carbon-carbon double bond,³Represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond or a carbon-carbon double bond, and a and b are each an integer of 0 to 3 And c is an integer of 1 to 4 that satisfies 4-ab)
Among the silane compounds represented by the structural formula (a3-1), silane compounds represented by the following structural formulas (a3-2) to (a3-7) are preferable.
[0081]
SiR⁴ _aR⁵ _b(OR⁶)_c                                (A3-2)
SiR⁴ _n(OCH₂CH₂OCO (R⁷) C = CH₂)_4-n      (A3-3)
CH₂= C (R⁷) COO (CH₂)_pSiR⁸ _n(OR⁶)_3-n  (A3-4)
CH₂= CHSiR⁸ _n(OR⁶)_3-n                        (A3-5)
HS (CH₂)_pSiR⁸ _n(OR⁶)_3-n                    (A3-6)
[0082]
Embedded image

(In the above formula, R⁴And R⁵Represents a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond or an epoxy bond,⁶Represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms;⁷Represents a hydrogen atom or a methyl group;⁸Represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, a and b are each an integer of 0 to 3, c is an integer of 1 to 4 that satisfies 4-ab, and n is 0 And p is an integer of 1 to 6.
Examples of the silane compound represented by the structural formula (a3-2) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, Diethoxyethyldimethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ-glycidoxy Trimethoxysilane, .gamma.-glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
[0083]
Examples of the silane compound represented by the structural formula (a3-3) include tetrakis (acryloyloxyethoxy) silane, tetrakis (methacryloyloxyethoxy) silane, methyltris (acryloyloxyethoxy) silane, and methyltris (methacryloyloxyethoxy) silane And the like.
[0084]
Examples of the silane compound represented by the structural formula (a3-4) include β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane, and β-methacryloyloxy. Ethyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and the like.
[0085]
Examples of the silane compound represented by the structural formula (a3-5) include vinyl methyl dimethoxy silane, vinyl trimethoxy silane, and vinyl triethoxy silane.
[0086]
Examples of the silane compound represented by the structural formula (a3-6) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, and the like.
[0087]
Examples of the silane compound represented by the structural formula (a3-7) include p-vinylphenylmethyldimethoxysilane, p-vinylphenyltrimethoxysilane, and the like.
[0088]
It is preferable to use such a silane compound in an amount of 0 to 3 mol parts per 1 mol part of the solid content of the inorganic fine particles (a-3). If the amount of the silane compound exceeds 3 mole parts, the abrasion resistance of the resulting acrylic resin film having a layer of the photocurable resin composition may decrease.
[0089]
The inorganic fine particles surface-treated with a silane compound can be obtained by using a commercially available product or by subjecting the inorganic fine particles to a surface treatment by a known method. As a known surface treatment method, for example, the treatment can be performed by heating and stirring the silane compound and the inorganic fine particles in the presence of a small amount of water.
[0090]
As a method of adding the inorganic fine particles (a-3) to the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain, a thermoplastic resin having a radically polymerizable unsaturated group in a side chain in advance can be used. After synthesizing (a-1), inorganic fine particles may be mixed, or a vinyl polymerizable monomer constituting a thermoplastic resin (a-1) having a radical polymerizable unsaturated group in a side chain may be mixed with an inorganic fine particle. Any method such as a method of polymerizing under the condition that the fine particles are mixed can be selected.
[0091]
In the photocurable resin composition (A) used in the present invention, a thermoplastic resin (a-1) having a radical polymerizable unsaturated group in a side chain of an essential component, a photopolymerization initiator (a-2), Further, in addition to the above-mentioned inorganic fine particles (a-3) which can be used as required, a sensitizer, a denaturing resin, a dye, a pigment, a leveling agent, a repelling inhibitor, an ultraviolet absorber, if necessary. And additives such as light stabilizers and oxidation stabilizers. The sensitizer promotes the photocuring reaction, and examples thereof include benzophenone, benzoin isopropyl ether, and thioxanthone.
[0092]
However, the photocurable resin composition (A) should not substantially contain a crosslinkable compound other than the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in the side chain. In particular, a crosslinkable monomer or oligomer which is liquid at 40 ° C. or a low molecular weight crosslinkable monomer or oligomer having a number average molecular weight of 2000 or less should not be substantially contained. In particular, when a liquid crosslinkable monomer or oligomer at 40 ° C. or a low molecular weight crosslinkable monomer or oligomer having a number average molecular weight of 2000 or less is contained, it becomes surface tacky during long-term storage or heat molding. In some cases, problems may occur in the printing process, or the mold may be contaminated during insert molding or in-mold molding. More preferably, it should not substantially contain a liquid crosslinkable monomer or oligomer at 50 ° C, and even more preferably should not substantially contain a liquid crosslinkable monomer or oligomer at 60 ° C. The expression “substantially not contained” refers to a solid content of 100% by mass of the thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain contained in the photocurable resin composition (A). Parts by weight means 1% by mass or less.
[0093]
In the present invention, since the photocurable resin composition (A) as described above is used, even when a layer of the photocurable resin composition is formed on an acrylic resin film, the surface of the acrylic resin film has tackiness. Further, the phenomenon that the surface tackiness changes with time does not occur, and the storage stability in a roll state is improved.
[0094]
Since the acrylic resin film of the present invention has a layer of the photocurable resin composition as described above, excellent moldability and storage stability before photocuring, and excellent surface properties (hardness, The resulting acrylic resin film has both high levels of weather resistance and abrasion resistance. As will be described later, usually, an acrylic resin film having a layer of the photocurable resin composition of the present invention is prepared by mixing a solution obtained by mixing and dissolving the photocurable resin composition (A) in a solvent such as an organic solvent in advance. After coating on the produced acrylic resin film by various coating methods, it is heated and dried to remove the solvent, thereby producing the film. At this time, if a large amount of solvent remains in the acrylic resin film, the surface of the layer of the photocurable resin composition (A) before light irradiation becomes tacky, and the yield in the printing process may be reduced. This causes problems such as a decrease in storage stability in a roll state and a decrease in mold contamination during insert molding or in-mold molding. Further, even when an insert molded product or an in-mold molded product obtained by insert molding or in-mold molding of an acrylic resin film having a layer of the photocurable resin composition is photocured, scratch resistance, chemical resistance And physical properties such as weather resistance may be inferior. In order to solve such a problem, it is preferable to reduce the amount of the solvent in the acrylic resin film as much as possible.
[0095]
The method for producing the acrylic resin film of the present invention having a layer of the photocurable resin composition (A) includes, for example, a thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain and photopolymerization initiation. The agent (a-2) and, if necessary, the photocurable resin composition (A) containing the inorganic fine particles (a-3) are sufficiently stirred and dissolved in a solvent such as an organic solvent, and the gravure printing method and the screen printing method are used. , Known printing methods such as offset printing, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, rod coating, roll doctor coating, air knife coating, comma Known coating methods such as roll coating, reverse roll coating, transfer roll coating, kiss roll coating, curtain coating, and dipping coating More coatings on the acrylic resin film, a method of performing heating and drying for solvent removal.
[0096]
As a solvent for stirring and dissolving the photocurable resin composition (A), the components of the photocurable resin composition (A) are dissolved or uniformly dispersed, and the physical properties (mechanical strength, transparency, etc.) of the acrylic resin film are used. , Etc.) do not have a serious adverse effect on practical use, and have a boiling point not higher than 80 ° C., preferably not higher than 30 ° C. than the glass transition temperature of the resin component which is a main component of the acrylic resin film. Solvents are preferred. Examples of such a solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, and ethylene glycol; aromatic solvents such as xylene, toluene, and benzene; aliphatic hydrocarbon solvents such as hexane and pentane; Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; phenol solvents such as phenol and cresol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and acetone; diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1 Ether-based solvents such as 2,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane, and THF; fatty acid-based solvents such as formic acid, acetic acid, and propionic acid; Acid anhydride solvents: ethyl acetate, butyl acetate, Ester solvents such as butyl acid; nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide; sulfur-containing solvents such as thiophene and dimethylsulfoxide; diacetone alcohol, 2-methoxyethanol (methylcellosolve), and 2-ethoxy. A solvent having two or more functional groups such as ethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, and morpholine; or a known solvent such as water is appropriately used. can do.
[0097]
Here, in order to eliminate the problems caused by the residual solvent in the acrylic resin film and to produce the acrylic resin film in a shorter time for the purpose of improving production efficiency at low cost, heat drying conditions for removing the solvent are required. And drying must be performed sufficiently. However, if the acrylic resin film is heated and dried continuously for 20 seconds or more at a temperature equal to or higher than the thermal deformation temperature of the acrylic resin film at this time, the acrylic resin film is stretched even with a slight tension, and the thickness of the acrylic resin film is reduced. Not only may be reduced, but also the photo-curable resin composition layer after photo-curing may have a reduced scratch resistance and a lower surface hardness.
[0098]
The heating and drying conditions of the acrylic resin film having the layer of the photocurable resin composition are heat-dried at a temperature not exceeding the heat deformation temperature of the acrylic resin film, or at a temperature higher than the heat deformation temperature of the acrylic resin film. When drying, the heat deformation temperature of the acrylic resin film is set to + 15 ° C. or lower, preferably + 10 ° C. or lower, and the heating and drying time at that temperature is set to 20 seconds or lower, preferably 10 seconds or lower, and more preferably 5 seconds or lower. Good to do.
[0099]
If a flammable organic solvent is used as the solvent, use a device equipped with an air-heated heat source using steam from the viewpoint of safety. A method of spraying on an acrylic resin film or the like can be used. The shape of the dryer can be selected and used according to the purpose, such as an arch type or a flat type.
[0100]
The acrylic resin film of the present invention is obtained by forming L on the acrylic resin film.^*a^*b^*L in the color system^*Is 60 or less. L^*a^*b^*L in the color system^*Is 60 or less, an appearance having a chromatic metallic tone other than white metallic tone is obtained. More preferably, L^*Is 30 or less, most preferably L^*Is preferably 10 or less from the viewpoint of developing the texture of the chromatic metallic tone.
[0101]
Such printing can be performed by a known method, and gravure using an ink containing a black colorant represented by carbon black or an ink combining red, blue, green, and yellow pigments and dyes. Preferably, it is obtained by printing.
[0102]
Further, the acrylic resin film of the present invention may be configured to be bonded to a known resin sheet. In this case, L^*a^*b^*L in the color system^*Is 60 or less, and thereby has a chromatic metallic metallic appearance. More preferably, L^*Is 30 or less, most preferably L^*From the viewpoint of developing a chromatic metallic tone.
[0103]
As a method of obtaining such an acrylic resin film bonded to a resin sheet, a lamination method in which the acrylic resin film and the resin sheet are heated and bonded by heat fusion at the boundary surface, and an adhesive layer is provided at the boundary surface When laminating the acrylic resin film and the resin sheet by lamination method, or when extruding the resin to become the resin sheet, the acrylic resin film is brought into direct contact with the molten resin coming out of the die, and the thermal fusion of the boundary surface is performed. And the like.
[0104]
The above-mentioned resin sheet is not particularly limited as long as it is a resin sheet using a known thermoplastic resin, and a black colorant represented by carbon black in the resin in the form of a sheet, red, blue, green, By using a resin containing a combination of yellow pigments and dyes, L^*Is 60 or less. As the type of the resin, for example, an acrylic resin, a polycarbonate (hereinafter, PC) resin, an ABS resin, an ABS / PC resin, a vinyl chloride (hereinafter, PVC) resin, a polyester resin, or a resin containing these as a main component is preferable. However, in the case of a resin which is not heat-fused to an acrylic resin such as a polyolefin resin, it is possible to bond the resin by providing an adhesive layer on the boundary surface between the acrylic resin film and the resin sheet.
[0105]
Examples of the method for forming the resin sheet include known methods such as a T-die method, a calendar method, and an inflation method.
[0106]
The thickness of the resin sheet is not particularly limited because it varies depending on the application, but is preferably in a range in which the resin sheet can be bonded to the acrylic resin film of the present invention and in a range in which vacuum / pressure forming can be performed. Specifically, those having a thickness of about 100 μm to about 2 mm are preferable from the viewpoint of moldability.
[0107]
As a method for producing a molded article in which the acrylic resin film of the present invention is laminated as described above, the layer containing the flake-like aluminum oxide surface-coated with a metal oxide of the acrylic resin film of the present invention becomes a surface. Thus, a molded article can be obtained by vacuum / pressure molding. Such a molded article has a white metallic tone or a chromatic metallic metallic texture.
[0108]
Also, a method in which an acrylic resin film is preliminarily processed into the shape of a molded article by vacuum / pressure molding, push-up molding, and the like, and is arranged in an injection mold, followed by injection molding of the base resin and molding of the molded article at the same time ( Insert molding method); A molded product can also be formed by vacuum / pressure forming an acrylic resin film in the mold cavity for injection molding, and then injecting the base resin into the mold cavity (in-mold molding method). Can be obtained.
[0109]
The base resin constituting the molded product is not particularly limited as long as it has excellent adhesiveness to the acrylic resin film. For example, acrylic resin, PC resin, ABS resin, ABS / PC resin, PVC resin, polyester A resin or a base resin containing these as a main component is preferable. However, in the case of a base resin that is not thermally fused to an acrylic resin such as a polyolefin resin, the acrylic resin film of the present invention can be laminated by providing an adhesive layer on a surface in contact with the base resin. is there.
[0110]
Note that L^*a^*b^*L in the color system^*Is 60 or less as the base resin, so that the acrylic resin film itself has L^*Can be a molded article having a chromatic metallic metallic texture even if it does not have a portion of 60 or less. More preferably, L^*Is 30 or less, most preferably L^*Is preferred from the viewpoint of exhibiting a chromatic metallic metallic texture.
[0111]
When an acrylic resin film having a layer of the photocurable resin composition is used, the molded article is taken out of the mold and irradiated with light to cure the photocurable resin composition on the molded article surface. Can be done. Examples of the light to be irradiated include an electron beam, ultraviolet light, and γ-ray. The irradiation conditions are determined according to the photocuring characteristics of the photocurable resin composition (A), and the irradiation amount is usually 500 to 10,000 mJ / cm.²It is about. Thereby, the photocurable resin composition (A) can be cured to obtain a molded article having a hard film formed on the surface. Such a molded article is excellent in abrasion resistance, and thus is suitable for automotive exterior use.
[0112]
Examples of industrial applications of the molded article on which the acrylic resin film of the present invention is laminated include vehicle interior parts (for example, instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards) Etc.), vehicle exterior parts (for example, weather strip, bumper, bumper guard, side mud guard, body panel, spoiler, front grill, strut mount, wheel cap, center pillar, door mirror, center ornament, side molding, door molding, wind molding, etc. Windows, headlamp covers, tail lamp covers, windshield parts, etc.); building materials such as window frames and sashes; miscellaneous goods such as tableware, toys, game machines, etc .; Interior member; housing, appliance parts such as air conditioner housing ship member; computer housing, can be exemplified an electronic communication device such as a cellular phone housing. In particular, vehicle parts such as the above-described vehicle interior parts and vehicle exterior parts, in which the acrylic resin film of the present invention is disposed on at least a part of the surface, and especially vehicle exterior parts, are excellent in wear resistance and are suitable. .
[0113]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the examples, “parts” represents “parts by mass”, and “%” represents “% by mass”. Abbreviations in the examples are as follows.
Methyl methacrylate MMA
Butyl acrylate BA
Allyl methacrylate AMA
Styrene St
Methyl acrylate MA
t-butyl hydroperoxide tBH
n-octyl mercaptan nOM.
[0114]
The physical properties of the thermoplastic polymers (I) and (III), the rubber-containing polymer (II), and the acrylic resin film were measured by the following test methods.
1) Reduced viscosity of thermoplastic polymers (I) and (III)
0.1 g of the polymer was dissolved in 100 mL of chloroform and measured at 25 ° C.
2) Mass average particle diameter of rubber-containing polymer (II)
The mass average particle diameter of the polymer latex of the rubber-containing polymer (II) obtained by the emulsion polymerization was measured by a dynamic light scattering method using a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd.
3) Film forming properties of acrylic resin film
After forming an acrylic resin film having a thickness of 125 μm by a T-die method, a film in which the film did not break for 5 hours or more was evaluated as good.
4) L^*How to measure
L using SM-C manufactured by Suga Test Machine Co., Ltd.^*a^*b^*It was measured in a color system.
5) Abrasion resistance of molded products
The haze value was measured after a Taber abrasion test (500 g load on one side, using a CS-10F abrasion wheel, the rotation speed was 60 rpm, and the test was performed 500 times). The numerical value represented by (haze value after test)-(haze value before test) was shown as abrasion resistance (%). Those having a numerical value of 25 or less have little change in appearance and are excellent in abrasion resistance.
[0115]
<Example 1>
a) Production of rubber-containing polymer (II)
The following raw material (b) (monomer raw material for polymer (II-A)) shown below was charged into a reaction vessel over a period of 200 minutes at 80 ° C. under a nitrogen atmosphere with stirring. After the addition, polymerization was further performed for 120 minutes to obtain a latex of the elastic polymer (II-A).
[0116]
To the latex of the elastic polymer (II-A), (c) shown below was added, and the raw material (d) (rubber polymer (II- B) for 100 minutes, followed by continuous polymerization at 80 ° C. for 60 minutes to form a hard polymer (II-B) and a rubber-containing polymer (II-B). A latex of II) was obtained. The mass average particle diameter of the rubber-containing polymer (II) was 0.12 μm.
[0117]
The latex of the rubber-containing polymer (II) was subjected to coagulation, coagulation, and solidification reactions using calcium acetate, followed by filtration, washing with water and drying to obtain a rubber-containing polymer (II).
[0118]

[0119]
b) Production of thermoplastic polymer (III)
A reaction vessel was charged with 200 parts of nitrogen-exchanged ion-exchanged water, 1 part of emulsifier potassium oleate and 0.3 part of potassium persulfate. Subsequently, 40 parts of MMA, 10 parts of BA, and 0.005 part of nOM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture composed of 48 parts of MMA and 2 parts of BA was added dropwise over 2 hours, and after completion of the addition, the mixture was maintained for 2 hours to complete the polymerization, thereby obtaining a latex of a thermoplastic polymer (III). The latex was added to a 0.25% sulfuric acid aqueous solution to acid coagulate the polymer, followed by dehydration, washing with water and drying to recover a powdery thermoplastic polymer (III). The reduced viscosity ηsp / c of this thermoplastic polymer (III) was 0.38 L / g.
[0120]
c) Manufacture of acrylic resin film
16 parts of the rubber-containing polymer (II) and 1 part of the thermoplastic polymer (III) obtained as described above, and an MMA / MA copolymer (MMA / MA = 98 /) as the thermoplastic polymer (I) 2, reduced viscosity 0.06 L / g) 83 parts, Tinuvin 234 (trade name, manufactured by Ciba Specialty Chemicals) 1.4 parts, ADK STAB LA67 (trade name, manufactured by Asahi Denka Kogyo) 0.3 part, ADK STAB AO60 (trade name) Phenolic antioxidant, manufactured by Asahi Denka Kogyo Co., Ltd.) and 3 parts of Silicalic T60-10WNTSb (trade name, manufactured by Merck Co., Ltd.) as flaky aluminum oxide surface-coated with a metal oxide. And mixed. Next, using a 40 mmφ twin screw extruder (L / D = 26), the mixture was melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C. to form pellets. The pellets were dried at 80 ° C. all day and night and 125 μm at a cylinder temperature of 200 ° C. to 240 ° C. and a T die temperature of 250 ° C. using a 40 mm φ non-vent screw type extruder (L / D = 26) equipped with a 300 mm T die. An acrylic resin film having a thickness of 1 was formed. The film forming property was good.
[0121]
The obtained acrylic resin film was vacuum formed by a mold having a vacuuming function. Thereafter, an ABS resin (trade name: Diapet ABS Bulk Sum TM25B, white, manufactured by UMG ABS Co., Ltd.) was injection-molded in a state where the formed acrylic resin film was placed in a mold to obtain an in-mold molded product.
[0122]
The obtained acrylic resin film and molded article had a white metallic appearance having a good gold appearance.
[0123]
<Example 2>
An acrylic resin film and a molded product were obtained in the same manner as in Example 1, except that Silicalic T60-10W NTC (trade name, manufactured by Merck Ltd.) was used as flake-form aluminum oxide whose surface was coated with a metal oxide. The film forming property was good.
[0124]
The obtained acrylic resin film and molded product exhibited a white metallic tone appearance having a good silver feeling.
[0125]
<Example 3>
An acrylic resin film and a molded product were obtained in the same manner as in Example 1 except that Silalic T60-10WNTM (trade name, manufactured by Merck Ltd.) was used as the flake aluminum oxide surface-coated with a metal oxide. The film forming property was good.
[0126]
The obtained acrylic resin film and molded product exhibited a white metallic appearance having a good blue feeling.
[0127]
<Example 4>
A transparent acrylic resin film was formed in the same manner as in Example 1 without using the flaky aluminum oxide surface-coated with a metal oxide. The obtained transparent acrylic resin film and the acrylic resin film having a white metallic appearance having a gold appearance obtained in Example 1 were thermally laminated.
[0128]
Using the obtained acrylic resin film, a molded article was obtained in the same manner as in Example 1 so that the layer of the transparent acrylic resin film became the surface.
[0129]
The obtained molded product had a deep metallic appearance and a white metallic appearance having a golden appearance.
<Examples 5 to 7>
Each of the acrylic resin films obtained in Examples 1 to 3 was subjected to black gravure printing using an ink containing carbon black. In addition, L of the printing surface^*Was 5. Thereafter, molded articles were obtained in the same manner as in Examples 1 to 3, respectively.
[0130]
The resulting printed acrylic resin films and the respective molded articles exhibited good gold metallic tone, silver metallic tone, and blue metallic tone appearance.
[0131]
Example 8
<Production of thermoplastic resin (a-1) having radically polymerizable unsaturated group in side chain>
50 parts of methyl ethyl ketone was placed in a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature was raised to 80 ° C. Under a nitrogen atmosphere, a mixture of 79.9 parts of methyl methacrylate, 20.1 parts of glycidyl methacrylate and 0.5 part of azobisisobutyronitrile was added dropwise over 3 hours. Thereafter, a mixture of 80 parts of methyl ethyl ketone (boiling point: 79.6 ° C.) and 0.2 parts of azobisisobutyronitrile was added and polymerized. After 4 hours, 74.4 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 10.1 parts of acrylic acid were added, and the mixture was stirred at 80 ° C for 30 hours while blowing air. Then, after cooling, the reaction product was taken out of the flask to obtain a solution of a thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain.
[0132]
The polymerization rate of the monomer in the thermoplastic resin (a-1) having a radical polymerizable unsaturated group in the side chain is 99.5% or more, the polymer solid content is about 35% by mass, and the number average molecular weight is about 3%. The glass transition temperature was about 105 ° C., and the double bond equivalent was 788 g / mol on average.
<Production of colloidal silica (inorganic fine particles (a-3))>
In a flask equipped with a stirrer, a condenser and a thermometer, 1 part of IPA-ST (trade name, isopropanol-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd., silica particle diameter = 15 nm) in terms of solids content; 0.1 parts of KBM503 (trade name, γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), molecular weight = 248) and 0.3 parts of water are added. C. and reacted at that temperature for 2 hours to obtain colloidal silica dispersed in isopropanol and having a surface treated with a silane compound. Subsequently, repeating the addition of toluene (boiling point: 110.6 ° C.) after distilling off isopropanol, completely replacing the isopropanol with toluene, dispersing in toluene, and colloidal having a surface treated with a silane compound. Silica was obtained. <Production of photocurable resin composition>
100 parts by mass of the above-mentioned thermoplastic resin (a-1) having a radical polymerizable unsaturated group in the side chain, and 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator (a-2)) And a photocurable resin composition comprising 66 parts of the above colloidal silica (inorganic fine particles (a-3)) by stirring with a propeller mixer.
<Production of an acrylic resin film having a layer of a photocurable resin composition and a molded article>
The photocurable resin composition was applied on the acrylic resin film obtained in Example 1 with a coating width of 250 mm using a comma roll coater. Subsequently, a tunnel-type drying furnace (width 800 mm, height 100 mm, length 8 m, divided into four drying zones (length of one zone 2 m)) set to the temperature conditions shown in Table 1 below is suitable for sheet movement. (A method in which hot air is sent so as to flow) at a speed of 10 m / min to evaporate the solvent, thereby forming a photocurable resin layer having a thickness of 8 μm. The stay time in each drying zone at this time is shown in Table 1 below.
[0133]
[Table 1]

Subsequently, it was slit into a width of 200 mm and wound up in a roll shape on a core made of ABS to a length of 20 m.
[0134]
The acrylic resin film having the layer of the photocurable resin composition is placed in a mold so that the layer of the photocurable resin composition faces the inner wall surface of the mold. After preheating for 2 seconds, the acrylic resin film was made to follow the mold shape by vacuum suction while further heating.
[0135]
Next, under conditions of a molding temperature of 280 to 300 ° C. and a mold temperature of 40 to 60 ° C., insert molding is performed using a polycarbonate resin as a base resin to form an acrylic resin film having a layer of a photocurable resin composition. An insert molded product closely contacting the product surface was obtained.
[0136]
Then, using an ultraviolet irradiation device, about 700 mJ / cm²Was irradiated to cure the photocurable resin composition to obtain an insert molded product.
[0137]
The obtained molded product had a deep metallic appearance and a white metallic appearance having a golden appearance. Further, it was excellent in abrasion resistance.
[0138]
<Examples 9 to 11>
Using the acrylic resin films obtained in Examples 1 to 3, instead of ABS resin (trade name: Diapet ABS Bulk Sum TM25B white, manufactured by UMG ABS Co., Ltd.) as a base resin for molded articles, an ABS resin (UMG ABS) A molded product was obtained in the same manner as in Examples 1 to 3 using a trade name: Diapet ABS Bulk Sum TM25B (trade name, manufactured by Co., Ltd.). In addition, using the above-mentioned black ABS resin, according to the injection molding method described in Example 1, the L of a molded product obtained by molding without disposing a film in a mold was used.^*Was 9.
[0139]
Each of the obtained molded products showed good appearance of gold metallic tone, silver metallic tone, and blue metallic tone.
[0140]
<Example 12>
The acrylic resin film obtained in Example 4, and an ABS sheet ("Diapet ABS SW7 Black" (manufactured by Mitsubishi Rayon Co., Ltd .; trade name)) formed into a 1 mm thick sheet by the T-die method, L^*8) was heat-laminated such that the surface of an acrylic resin film having a white metallic tone appearance having a gold feeling was in contact with the ABS sheet to obtain a gold metallic tone acrylic resin film. Vacuum molding was performed using this acrylic resin film. Subsequently, after removing unnecessary portions, an acrylic resin film is mounted on an injection mold, and an ABS resin (trade name: Diapet ABS Bulk Sum TM25B, white, manufactured by UMG ABS Co., Ltd.) is injection molded to form an insert molded product. Obtained.
[0141]
The obtained insert molded product had a gold metallic tone appearance having a sense of depth.
[0142]
<Examples 13 to 15>
Except that the addition amount of the flaky aluminum oxide surface-coated with the metal oxide was 6 parts by mass, each was carried out in the same manner as in Examples 9 to 11, to obtain an acrylic resin film and a molded product. The film forming property was good.
[0143]
The obtained acrylic resin film and molded article exhibited a metallic appearance having higher luminance than the acrylic resin films and molded articles obtained in Examples 9 to 11, respectively.
[0144]
<Example 16>
The surface of the acrylic resin film having a layer of the photocurable resin composition obtained in Example 8 having a white metallic appearance having a gold appearance is subjected to black gravure printing using an ink containing carbon black. A molding was obtained in the same manner as in Example 8 except for the above. In addition, L of the printing surface^*Was 5.
[0145]
The obtained molded product had a gold metallic tone appearance having a deep feeling. Further, it was excellent in abrasion resistance.
[0146]
<Example 17>
Using the acrylic resin film obtained in Example 3, an acrylic resin film having a layer of the photocurable resin composition was obtained in the same manner as in Example 8.
[0147]
An acrylic resin film having a layer of the photocurable resin composition and an ABS sheet ("Diapet ABS SW7 Black" (manufactured by Mitsubishi Rayon Co., Ltd .; trade name)) formed to a thickness of 1 mm by a T-die method are formed into sheets. , L of the sheet^*8) was heat-laminated so that the acrylic resin film surface having a white metallic appearance having a blue appearance was in contact with the ABS sheet to obtain a blue metallic acrylic film. Using this acrylic resin film, under a condition of a molding temperature of 280 to 300 ° C. and a mold temperature of 40 to 60 ° C., insert molding is performed using a polycarbonate resin as a base resin, and has a layer of a photocurable resin composition. An insert molded product in which the acrylic resin film was in close contact with the molded product surface was obtained.
[0148]
Then, using an ultraviolet irradiation device, about 700 mJ / cm²Was irradiated to cure the photocurable resin composition to obtain an insert molded product.
[0149]
The resulting molded article had a deep blue metallic appearance. Further, it was excellent in abrasion resistance.
[0150]
<Comparative Examples 1 to 6>
Except not using the flaky aluminum oxide surface-coated with the metal oxide, it carried out similarly to Examples 1-3 and 9-11, and obtained the acrylic resin film and the molded article. The film forming property was good.
[0151]
Neither the obtained acrylic resin film nor the molded product showed a metallic appearance.
[0152]
<Comparative Examples 7 to 9>
The procedure was performed in the same manner as in Examples 1 to 3, except that the amount of the flaky aluminum oxide surface-coated with the metal oxide was changed to 35 parts by mass. An acrylic resin film could not be obtained due to frequent film breakage.
[0153]
<Comparative Example 10>
An acrylic resin film having a layer of the photocurable resin composition and a molded product were obtained in the same manner as in Example 8, except that the flaky aluminum oxide surface-coated with a metal oxide was not used. The film forming property was good.
[0154]
The obtained acrylic resin film and molded product did not show a metallic appearance.
[0155]
【The invention's effect】
As explained above, molded articles having various metallic textures can be provided by using the acrylic resin film of the present invention. These molded articles have a good metallic feeling and are particularly useful as vehicle interior parts or vehicle exterior parts.

Claims (10)

An acrylic resin film having a thickness of 10 to 500 µm, comprising an acrylic resin and 0.01 to 30 parts by mass of flake aluminum oxide surface-coated with a metal oxide based on 100 parts by mass of the acrylic resin. A photocurable resin composition comprising, on the acrylic resin film according to claim 1, a thermoplastic resin (a-1) having a radical polymerizable unsaturated group in a side chain, and a photopolymerization initiator (a-2). An acrylic resin film having a layer of the product (A). The acrylic resin film according to claim 2, wherein the photocurable resin composition (A) contains inorganic fine particles (a-3). An acrylic resin film, wherein the acrylic resin film according to claim 1 is printed with L ^* of 60 or less in the L ^* a ^* b ^* color system. An acrylic resin film comprising the acrylic resin film according to claim 1 and a resin sheet having an L ^* a ^* b ^* color system in which L ^* is 60 or less. A photocurable composition comprising, on the acrylic resin film according to claim 4 or 5, a thermoplastic resin (a-1) having a radically polymerizable unsaturated group in a side chain and a photopolymerization initiator (a-2). An acrylic resin film having a layer of the resin composition (A). The acrylic resin film according to claim 6, wherein the photocurable resin composition (A) contains inorganic fine particles (a-3). A molded product in which the acrylic resin film according to any one of claims 1 to 7 is laminated on a base resin. A molded product obtained by laminating the acrylic resin film according to any one of claims 1 to 3 on a base resin having L ^* of 60 or less in an L ^* a ^* b ^* color system. A vehicle component having the acrylic resin film according to any one of claims 1 to 7 disposed on at least a part of its surface.