JP4641344B2 - Multilayer acrylic resin film for decoration, laminated resin molded product obtained by laminating the same, and method for producing the same - Google Patents

Description

（参考例３）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時間に渡り滴下し、滴下終了後２時間保持を行い、重合を完結させた。得られたラテックスを０．２５％硫酸水溶液に添加し、重合体を酸凝析した後脱水、水洗、乾燥し、粉体状で重合体を回収した。得られた共重合体の還元粘度ηｓｐ／ｃは０．３８Ｌ／ｇであった。
【０１２６】
（参考例４）多層構造重合体（IV）の製造
冷却機付き重合容器内にイオン交換水２５０部、スルホコハク酸のエステルソーダ塩２部、ソヂウムホルムアルデヒドスルホキシレート０．０５部を仕込み、窒素雰囲気下で攪拌後、ＭＭＡ１．６部、ＢＡ８部、１，３ＢＤ０．４部、ＡＭＡ０．１部およびクメンハイドロパーオキサイド０．０４部からなる混合物を仕込んだ。７０℃に昇温後、６０分間反応を断続させ、最内層重合体（Ａ）の重合を完結した。続いて架橋弾性重合体（Ｂ）を形成するＭＭＡ１．５部、ＢＡ２２．５部、１，３ＢＤ１．０部、ＡＭＡ０．２５部からなる単量体混合物を６０分間で添加して重合を行い、２層架橋ゴム弾性体を得た。この際、架橋弾性重合体（Ｂ）を形成する単量体混合物に対して０．０５部のクメンハイドロパーオキサイドを添加した。
【０１２７】
続いて中間層（Ｄ）として、ＭＭＡ５部、ＢＡ５部、およびＡＭＡ０．１部の混合物を反応させ、最後に最外層重合体（Ｃ）としてＭＭＡ５２．２５部、ＢＡ２．７５部からなる単量体混合物を反応させ最外層重合体（Ｃ）を形成し、重合体エマルジョンを得た。
【０１２８】
その後、得られた重合体エマルジョンを、重合体１００部に対して５部の塩化カルシウムを用いて塩析し、洗浄後乾燥し、粉体状で多層構造重合体（IV）を得た。
【０１２９】
（参考例５）水酸基含有重合体（Ｖ）の製造
撹拌機、還流冷却器、窒素ガス導入口等の付いた反応容器に次の混合物を仕込んだ。
【０１３０】

容器内を十分に窒素ガスで置換した後、上記混合物の混合物を撹拌しながら７５℃まで加熱し、窒素ガス気流中で重合を進めた。２時間後に９０℃に昇温してさらに４５分保持して重合を完了し、引き続いて目開き１５０メッシュの条件で篩別を行い、通過したビーズを脱水、乾燥して水酸基含有重合体（Ｖ）を得た。
【０１３１】
（実施例１）多層アクリル樹脂フイルム（ＸＡ−１−１）の製造
参考例１で製造した熱可塑性重合体（Ｉ）８０部、参考例２で製造したゴム含有重合体（II）２０部、参考例３で製造した熱可塑性重合体（III）５部、アルミニウム顔料アルペーストＴＣＲ３１３０（東洋アルミニウム（株）製、形状：鱗片状、粒度：１３μｍ）０．５部、紫外線吸収剤アデカスタブＬＡ−３１ＲＧ（旭電化（株）製）１．４部および、ヒンダードアミン系光安定剤ＬＡ−５７（旭電化（株）製）０．２部をヘンシェルミキサーを用いて混合した。次いで、φ５０ｍｍのスクリュー型単軸押出機を用いてシリンダー温度２３０℃、ダイ温度２３０℃で溶融混練し、アクリル樹脂組成物（Ａ−１）のペレットを得た。
【０１３２】
次に、得られたアクリル樹脂組成物（Ａ−１）を８０℃で一昼夜乾燥し、Ｔダイを取り付けたφ６５ｍｍのノンベントスクリュー型押出機（三菱重工（株）製ＨＭＥ−６５）、１本の冷却ロールおよび巻き取り機を備えた製膜機を用い、シリンダー温度２４０℃、Ｔダイ温度２５０℃、冷却ロール温度７０℃で膜厚７５μｍのアクリル樹脂フイルム（Ａ−１−１）を製膜した。
【０１３３】
一方、参考例１で製造した熱可塑性重合体（Ｉ）８４部、参考例２で製造したゴム含有重合体（II）１６部、参考例３で製造した熱可塑性重合体（III）２部、紫外線吸収剤アデカスタブＬＡ−３１ＲＧ（旭電化（株）製）１．４部および、ヒンダードアミン系光安定剤ＬＡ−５７（旭電化（株）製）０．２部をヘンシェルミキサーを用いて混合した。次いで、φ５０ｍｍのスクリュー型単軸押出機を用いてシリンダー温度２３０℃、ダイ温度２３０℃で溶融混練し、アクリル樹脂組成物（Ｘ−１）のペレットを得た。
【０１３４】
次に、得られたアクリル樹脂組成物（Ｘ−１）を８０℃で一昼夜乾燥し、Ｔダイを取り付けたφ６５ｍｍのノンベントスクリュー型押出機（三菱重工（株）製ＨＭＥ−６５）、１本の冷却ロールおよび巻き取り機を備えた製膜機を用い、シリンダー温度２４０℃、Ｔダイ温度２５０℃、冷却ロール温度７０℃で膜厚５０μｍのアクリル樹脂フイルム（Ｘ−１）を製膜した。
【０１３５】
次に、金属ベルトが並列に位置するベルトプレス装置を用い、加熱領域の温度１５０℃でアクリル樹脂フイルム（Ａ−１−１）と（Ｘ−１）をラミネートし、総厚約１２５μmの多層アクリル樹脂フイルム（ＸＡ−１−１）を製造した。
【０１３６】
得られた多層アクリル樹脂フイルム（ＸＡ−１−１）の全光線透過率を測定し、結果を表１に示した。
【０１３７】
得られたアクリル樹脂フイルム（ＸＡ−１−１）と厚み２mm、長さ３００ｍｍ、幅３００ｍｍの黒色、白色、黄色、青色の各色のＡＢＳ樹脂（三菱レイヨン（株）製ダイヤペットＡＢＳ１００１）板とをプレス成形機を用いて、１４０℃でプレス成形し、黒色、白色、黄色、青色の各色のＡＢＳ板表面にアクリル樹脂フイルム（ＸＡ−１−１）がメタリック層がＡＢＳ樹脂と接するように貼り合わされた積層シートを作製し、このシートを２００ｍｍ×２００ｍｍ×深さ２０ｍｍのキャビティを有する金型を備えた真空成形機を用いてメタリック顔料を含有しない面が外表面になる様に真空成形し、箱形のアクリル樹脂フイルム積層樹脂成形品（ア−１）〜（ア−４）を作製した。
【０１３８】
得られた成形品（ア−１）〜（ア−４）の外観を表１に示した。
【０１３９】
さらに、アクリル樹脂フイルム（ＸＡ−１−１）を型締め力２．２ＭＮの射出成形機に取り付けた投影面積５００ｃｍ^２、絞り深さ１０ｃｍのキャビティを有する真空成形可能な射出成形金型の雌型キャビティ表面にメタリック層側が成形樹脂に接する様にセットし（型開状態）、非接触加熱板によりアクリル樹脂フイルムを加熱した後、真空成形によりキャビティ面に追従させた。次いで金型を閉じてから黒色、白色、黄色、青色の各色のＡＢＳ樹脂（三菱レイヨン（株）製ダイヤペットＡＢＳ１００１）をシリンダー温度２３０℃で射出成形して、アクリル樹脂フイルム積層射出成形品（い −１）〜（い−４）を製造した。
【０１４０】
得られた成形品（い −１）〜（い−４）の外観を表１に示した。
【０１４１】
（実施例２）多層アクリル樹脂フイルム（ＹＡ−１−１）の製造
参考例４で得られた多層構造重合体（IV）１００部、紫外線吸収剤アデカスタブＬＡ−３１ＲＧ（旭電化（株）製）１．４部および、ヒンダードアミン系光安定剤ＬＡ−５７（旭電化（株）製）０．２部をヘンシェルミキサーを用いて混合した。次いで、φ５０ｍｍのスクリュー型単軸押出機を用いてシリンダー温度２３０℃、ダイ温度２３０℃で溶融混練し、アクリル樹脂組成物（Ｙ−１）のペレットを得た。
【０１４２】
次に、得られたアクリル樹脂組成物（Ｙ−１）を８０℃で一昼夜乾燥し、Ｔダイを取り付けたφ６５ｍｍのノンベントスクリュー型押出機（三菱重工（株）製ＨＭＥ−６５）、１本の冷却ロールおよび巻き取り機を備えた製膜機を用い、シリンダー温度２４０℃、Ｔダイ温度２５０℃、冷却ロール温度７０℃で膜厚５０μｍのアクリル樹脂フイルム（Ｙ−１）を製膜した。
【０１４３】
次に、メタリック顔料を含有しないアクリル樹脂層を構成するアクリル樹脂フイルムを（Ｙ−１）に変更した以外は実施例１と同様にしてベルトプレス装置を用い、アクリル樹脂フイルム（Ａ−１−１）と（Ｙ−１）がラミネートされた、総厚約１２５μmの多層フイルム（ＹＡ−１−１）を製造した。
【０１４４】
得られた多層アクリル樹脂フイルム（ＹＡ−１−１）の全光線透過率を測定し、結果を表１に示した。
【０１４５】
次に実施例１で用いた多層アクリル樹脂フイルム（ＸＡ−１−１）を多層アクリル樹脂フイルム（ＹＡ−１−１）に変更する以外は、同様の方法で多層アクリル樹脂フイルム積層樹脂成形品（ア−５）〜（ア−８）を作製した。
【０１４６】
得られた成形品（ア−５）〜（ア−８）の外観を表１に示した。
【０１４７】
さらに、多層アクリル樹脂フイルムを（ＸＡ−１−１）から（ＹＡ−１−１）に変更する以外は、実施例１と同様にして多層アクリル樹脂フイルム積層射出成形品（い −５）〜（い−８）を製造した。
【０１４８】
得られた成形品（い −５）〜（い−８）の外観を表１に示した。
【０１４９】
（実施例３）多層アクリル樹脂フイルム（ＸＡ−１−２）の製造
実施例１で製造したアクリル樹脂組成物（Ａ−１）およびアクリル樹脂組成物（Ｘ−１）とを、４０ｍｍφ一軸押出機、６５ｍｍφ一軸押出機およびフィードブロック型ダイスを用いて押し出し成形し、メタリック層の厚みが１２５μm、メタリック顔料を含有しないアクリル樹脂層の厚みが５０μmの多層アクリル樹脂フイルム（ＸＡ−１−２）を作製した。
【０１５０】
得られた多層アクリル樹脂フイルム（ＸＡ−１−２）の全光線透過率を測定し、結果を表１に示した。
【０１５１】
次に、実施例１と同様にして、得られた多層アクリル樹脂フイルム（ＸＡ−１−２）を用いて多層アクリル樹脂フイルム積層樹脂成形品（イ−１）〜（イ−４）を作製した。
【０１５２】
得られた成形品（イ−１）〜（イ−４）の外観を表１に示した。
【０１５３】
さらに、前述の多層アクリル樹脂フイルム（ＸＡ−１−２）を用い、実施例１と同様にしてアクリル樹脂フイルム積層射出成形品（ろ−１）〜（ろ−４）を製造した。
【０１５４】
得られた成形品（ろ−１）〜（ろ−４）の外観を表１に示した。
【０１５５】
（実施例４）多層アクリル樹脂フイルム（ＹＡ−１−２）の製造
実施例３で用いたアクリル樹脂組成物（Ｘ−１）を（Ｙ−１）に変更した以外は実施例３と同様にして総厚み１７５μmの多層アクリル樹脂フイルム（ＹＡ−１−２）を作製した。
【０１５６】
得られた多層アクリル樹脂フイルム（ＹＡ−１−２）の全光線透過率を測定し、結果を表１に示した。
【０１５７】
次に、実施例１と同様にして、得られた多層アクリル樹脂フイルム（ＹＡ−１−２）を用いて多層アクリル樹脂フイルム積層樹脂成形品（イ−５）〜（イ−８）を作製した。
【０１５８】
得られた成形品（イ−５）〜（イ−８）の外観を表１に示した。
【０１５９】
さらに、前述の多層アクリル樹脂フイルム（ＹＡ−１−２）を用い、実施例１と同様にして多層アクリル樹脂フイルム積層射出成形品（ろ−５）〜（ろ−８）を製造した。
【０１６０】
得られた成形品（ろ−５）〜（ろ−８）の外観を表１に示した。
【０１６１】
（実施例５）多層アクリル樹脂フイルム（ＸＡ−２−１）の製造
実施例１のアクリル樹脂組成物（Ａ−１）の製造に用いたアルミニウム顔料添加量を１．５部に変更した以外は同様の方法でアクリル樹脂組成物（Ａ−２）を作製し、実施例１と同様の方法で、膜厚７５μｍのアクリル樹脂フイルム（Ａ−２−１）を得た。
【０１６２】
次に、実施例で用いたアクリル樹脂フイルム（Ａ−１−１）を（Ａ−２−１）に変更した以外は実施例１と同様にして総厚み１２５μmの多層アクリル樹脂フイルム（ＸＡ−２−１）を作製した。
【０１６３】
得られた多層アクリル樹脂フイルム（ＸＡ−２−１）の全光線透過率を測定し、結果を表１に示した。
【０１６４】
次に、実施例１と同様にして多層アクリル樹脂フイルム（ＸＡ−２−１）を用いて多層アクリル樹脂フイルム積層樹脂成形品（ウ−１）〜（ウ−４）および多層アクリル樹脂フイルム積層射出成形品（は−１）〜（は−４）を製造した。
【０１６５】
得られた成形品（ウ−１）〜（ウ−４）および（は−１）〜（は−４）の外観を表１に示した。
【０１６６】
（実施例６）多層アクリル樹脂フイルム（ＹＡ−２−１）の製造
実施例５で用いたアクリル樹脂フイルム（Ｘ−１）を（Ｙ−１）に変更した以外は実施例１と同様にして同様にして総厚み１２５μmの多層アクリル樹脂フイルム（ＹＡ−２−１）を作製した。
【０１６７】
得られた多層アクリル樹脂フイルム（ＹＡ−２−１）の全光線透過率を測定し、結果を表１に示した。
【０１６８】
次に、実施例１と同様にして多層アクリル樹脂フイルム（ＹＡ−２−１）を用いて多層アクリル樹脂フイルム積層樹脂成形品（ウ−５）〜（ウ−８）および多層アクリル樹脂フイルム積層射出成形品（は−５）〜（は−８）を製造した。
【０１６９】
得られた成形品（ウ−５）〜（ウ−８）および（は−５）〜（は−８）の外観を表１に示した。
【０１７０】
（実施例７）多層アクリル樹脂フイルム（ＸＢ−１）の製造
実施例１のアクリル樹脂組成物（Ａ−１）の製造に用いたアルミニウム顔料をアルペーストＴＣＲ３０４０（東洋アルミニウム（株）製、形状：鱗片状、粒度：１７μｍ）に変更した以外は同様の方法でメタリック層を構成する樹脂組成物（Ｂ−１）を作製し、実施例１と同様の方法で、膜厚７５μｍのアクリル樹脂フイルム（Ｂ−１）を得た。
【０１７１】
次に、実施例１に用いるアクリル樹脂フイルム（Ａ−１）を（Ｂ−１）に変更した以外は実施例１と同様にして総厚み１２５μmの多層アクリル樹脂フイルム（ＸＢ−１）を作製した。
【０１７２】
得られた多層アクリル樹脂フイルム（ＸＢ−１）の全光線透過率を測定し、結果を表１に示した。
【０１７３】
次に、実施例１と同様にして多層アクリル樹脂フイルム（ＸＢ−１）を用いて多層アクリル樹脂フイルム積層樹脂成形品（エ−１）〜（エ−４）および多層アクリル樹脂フイルム積層射出成形品（に−１）〜（に−４）を製造した。
【０１７４】
得られた成形品（エ−１）〜（エ−４）および（に−１）〜（に−４）の外観を表１に示した。
【０１７５】
（実施例８）多層アクリル樹脂フイルム（ＹＢ−１）の製造
実施例７で使用したアクリル樹脂フイルム（Ｘ−１）を（Ｙ−１）に変更した以外は実施例１と同様にして総厚み１２５μmの多層のアクリル樹脂フイルム（ＹＢ−１）を作製した。
【０１７６】
得られた多層アクリル樹脂フイルム（ＹＢ−１）の全光線透過率を測定し、結果を表１に示した。
【０１７７】
次に、実施例１と同様にして多層アクリル樹脂フイルム（ＹＢ−１）を用いて多層アクリル樹脂フイルム積層樹脂成形品（エ−５）〜（エ−８）および多層アクリル樹脂フイルム積層射出成形品（に−５）〜（に−８）を製造した。
【０１７８】
得られた成形品（エ−５）〜（エ−８）および（に−５）〜（に−８）の外観を表１に示した。
【０１７９】
（実施例９）多層アクリル樹脂フイルム（ＸＣ−１）の製造
実施例１のアクリル樹脂組成物（Ａ−１）の製造に用いたアルミニウム顔料をアルペーストＴＣＲ３０１０（東洋アルミニウム（株）製、形状：鱗片状、粒度：３１μｍ）に変更し、添加量を０．２部に変更した以外は実施例１と同様の方法でメタリック層を構成する樹脂組成物（Ｃ−１）を作製し、実施例１と同様にして、膜厚７５μｍのアクリル樹脂フイルム（Ｃ−１）を得た。
【０１８０】
次に、メタリック層を構成するアクリル樹脂フイルムを（Ｃ−１）に変更した以外は実施例１と同様にして総厚み１２５μmの多層アクリル樹脂フイルム（ＸＣ−１）を作製した。
【０１８１】
得られた多層アクリル樹脂フイルム（ＸＣ−１）の全光線透過率を測定し、結果を表２に示した。
【０１８２】
次に、実施例１と同様にして多層アクリル樹脂フイルム（ＸＣ−１）を用いて多層アクリル樹脂フイルム積層樹脂成形品（オ−１）〜（オ−４）および多層アクリル樹脂フイルム積層射出成形品（ほ−１）〜（ほ−４）を製造した。
【０１８３】
得られた成形品（オ−１）〜（オ−４）および（ほ−１）〜（ほ−４）の外観を表２に示した。
【０１８４】
（実施例１０）多層アクリル樹脂フイルム（ＹＣ−１）の製造
実施例９でメタリック顔料を含有しないアクリル樹脂層を構成するアクリル樹脂フイルム（Ｘ−１）を（Ｙ−１）に変更した以外は実施例１と同様にして同様にして総厚み１２５μmの多層アクリル樹脂フイルム（ＹＣ−１）を作製した。
【０１８５】
得られた多層アクリル樹脂フイルム（ＹＣ−１）の全光線透過率を測定し、結果を表２に示した。
【０１８６】
次に、実施例１と同様にして多層アクリル樹脂フイルム（ＹＣ−１）を用いて多層アクリル樹脂フイルム積層樹脂成形品（オ−５）〜（オ−８）および多層アクリル樹脂フイルム積層射出成形品（ほ−５）〜（ほ−８）を製造した。
【０１８７】
得られた成形品（オ−５）〜（オ−８）および（ほ−５）〜（ほ−８）の外観を表２に示した。
【０１８８】
（実施例１１）多層アクリル樹脂フイルム（ＸＡ−１−３）の製造
実施例１の、メタリック顔料を含有しないアクリル樹脂層を構成するアクリル樹脂組成物（Ｘ−１）の作製時に、参考例５で製造した水酸基含有重合体（Ｖ）を、アクリル樹脂組成物（Ｘ−１）１００部に対し、１０部添加してアクリル樹脂組成物（Ｘ−２）を作製し、これを用いて実施例１と同様にして５０μmのアクリル樹脂フイルム（Ｘ−２）を製造した。
【０１８９】
得られたフイルム（Ｘ−２）と実施例１で作製したフイルム（Ａ−１−１）を用い、実施例１と同様にして総厚約１２５μmの多層フイルム（ＸＡ−１−３）を製造した。
【０１９０】
得られた多層アクリル樹脂フイルム（ＸＡ−１−３）の全光線透過率を測定し、結果を表２に示した。
【０１９１】
次に、実施例１と同様にして多層アクリル樹脂フイルム（ＸＡ−１−３）を用いて多層アクリル樹脂フイルム積層樹脂成形品（カ−１）〜（カ−４）および多層アクリル樹脂フイルム積層射出成形品（ヘ−１）〜（ヘ−４）を製造した。
【０１９２】
得られた成形品（カ−１）〜（カ−４）および（へ−１）〜（へ−４）の色調外観を表２に示す。多層アクリル樹脂フイルム積層成形品（カ−１）〜（カ−４）および（へ−１）〜（へ−４）は、深み感のあるメタリック調に加え、高品質な艶消し外観を示した。
【０１９３】
（実施例１２）多層アクリル樹脂フイルム（ＹＡ−１−３）の製造
実施例１１のアクリル樹脂組成物（Ｘ−１）を（Ｙ−１）に変更した以外は実施例１１と同様にして総厚み約１２５μmの多層アクリル樹脂フイルム（ＹＡ−１−３）を作製した。
【０１９４】
得られた多層アクリル樹脂フイルム（ＹＡ−１−３）の全光線透過率を測定し、結果を表２に示した。
【０１９５】
次に、実施例１と同様にして多層アクリル樹脂フイルム（ＹＡ−１−３）を用いて多層アクリル樹脂フイルム積層樹脂成形品（カ−５）〜（カ−８）および多層アクリル樹脂フイルム積層射出成形品（へ−５）〜（へ−８）を製造した。
【０１９６】
得られた成形品（カ−５）〜（カ−８）および（へ−５）〜（へ−８）の外観を表２に示す。多層アクリル樹脂フイルム積層成形品（カ−５）〜（カ−８）および（へ−５）〜（へ−８）は、深み感のあるメタリック調に加え、高品質な艶消し外観を示した。
【０１９７】
（比較例１）多層アクリル樹脂フイルム（ＸＡ−２−２）の製造
実施例５でメタリック層を構成するアクリル樹脂フイルムの膜厚を２００μmに変更してアクリルフイルム（Ａ−２−２）を得た以外は実施例１と同様にして同様にして総厚み２５０μmの多層アクリル樹脂フイルム（ＸＡ−２−２）を作製した。
【０１９８】
得られたアクリル樹脂フイルム（ＸＡ−２−２）の全光線透過率を測定し、結果を表２に示した。
【０１９９】
次に、実施例１と同様にしてアクリル樹脂フイルム（ＸＡ−２−２）を用いてアクリル樹脂フイルム積層樹脂成形品（キ１）〜（キ４）およびアクリル樹脂フイルム積層射出成形品（と１）〜（と４）を製造した。
【０２００】
得られた成形品（キ１）〜（キ４）および（と１）〜（と４）の外観を表２に示した。
【０２０１】
（比較例２）多層アクリル樹脂フイルム（ＸＥ−１）の製造
実施例９のアクリル樹脂組成物（Ｃ−１）の製造で用いたアルミニウム顔料添加量を０．０１部に変更した以外は実施例１と同様にしてメタリック層を構成する樹脂組成物（Ｅ−１）を作製し、実施例１と同様にして、膜厚５０μｍのアクリル樹脂フイルム（Ｅ−１）を得た。
【０２０２】
次に、メタリック層を構成するアクリル樹脂フイルムを（Ｅ−１）に変更した以外は実施例１と同様にして総厚み約１００μmの多層のアクリル樹脂フイルム（ＸＥ−１）を作製した。
【０２０３】
得られたアクリル樹脂フイルム（ＸＥ−１）の全光線透過率を測定し、結果を表２に示した。
【０２０４】
次に、実施例１と同様にしてアクリル樹脂フイルム（ＸＥ−１）を用いてアクリル樹脂フイルム積層樹脂成形品（ク−１）〜（ク−４）およびアクリル樹脂フイルム積層射出成形品（ち−１）〜（ち−４）を製造した。
【０２０５】
得られた成形品（ク−１）〜（ク−４）および（ち−１）〜（ち−４）の外観を表２に示した。
【０２０６】
（比較例３）単層アクリル樹脂フイルム
実施例１のメタリック層を構成するアクリル樹脂フイルム（Ａ−１−１）の全光線透過率および表面光沢度を表２に示す。
【０２０７】
次に、アクリル樹脂フイルム（Ａ−１−１）を用いて実施例１と同様の方法でプレス成形を行い、アクリル樹脂フイルム積層樹脂成形品（ケ−１）〜（ケ−４）を得た。次に実施例１と同様の方法で、アクリル樹脂フイルム（Ａ−１−１）を用いて射出成形を行い、アクリル樹脂フイルム積層射出成形品（り−１）〜（り−４）を得た。
【０２０８】
得られた成形品（ケ−１）〜（ケ−４）および（り−１）〜（り−４）の外観を表２に示した。
【０２０９】
これより得られた成形品はいずれも基材の色調を反映したメタリック調の質感を発現するものの、メタリック調の深み感はなく、且つ成形品表面の平滑性に劣るものであった。
【０２１０】
以上の実施例および比較例より、次のことが明らかとなった。
【０２１１】
第１に、全光線透過率が１０〜９０％の範囲にある加飾用多層アクリル樹脂フイルムを使用した多層アクリル樹脂フイルム積層樹脂成形品および多層アクリル樹脂フイルム積層射出成形品は各色の基材色を反映した、意匠性の高い外観を示した。
【０２１２】
特に、全光線透過率が６０〜９０％の範囲にある加飾用多層アクリル樹脂フイルムを使用することにより、基材の持つ色相をも反映した良好なメタリック調の質感を示した。
【０２１３】
第２に、比較例１より、全光線透過率が１０％未満の加飾用多層アクリル樹脂フイルムを使用した多層アクリル樹脂フイルム積層樹脂成形品および多層アクリル樹脂フイルム積層射出成形品は、基材色が反映されず、フイルム色のみを示す外観となった。
【０２１４】
第３に、比較例２より、全光線透過率が９０％を超える加飾用多層アクリル樹脂フイルムを使用した多層アクリル樹脂フイルム積層樹脂成形品および多層アクリル樹脂フイルム積層射出成形品は、メタリック外観は得られず、基材のソリッド色のみを示す外観となった。
【０２１５】
第４に、実施例１１、１２の加飾用多層アクリル樹脂フイルムを使用した樹脂成形品は、深み感のあるメタリック調に加え、高品質な艶消し外観を有し、この様に重厚な質感が付与できる加飾用フイルムは工業的価値が極めて高い。
【０２１６】
第５に、比較例３のメタリック顔料を含有しないアクリル樹脂層を表層に有さないアクリル樹脂フイルムを使用したアクリル樹脂フイルム積層樹脂成形品は、深み感のあるメタリック調が得られず、また表面平滑性にも劣るため、加飾用フイルムとしての工業的価値が低い。
【０２１７】
【表１】

【表２】

【０２１８】
【発明の効果】
以上の説明から明らかなように、アクリル樹脂組成物中にメタリック顔料を含有するメタリック層と、メタリック顔料を含有しないアクリル樹脂層とからなり、全光線透過率が１０％〜９０％であることを特徴とする厚み１０〜５００μｍの加飾用多層アクリル樹脂フイルムを用いることにより、フイルム積層樹脂成形品において、基材の有する色相に対応して積層樹脂成形品のメタリック調の質感を変更することができ、用いるメタリック顔料含有フィルムの種類を変えることなく、基材である樹脂成形品の色調を変えるだけで様々な質感のメタリック調を有する、意匠性の高い樹脂成形品を良好な生産性で製造することができるため、工業的利用価値は高い。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a multilayer acrylic resin film suitable for metallic surface decoration on a laminated resin molded article, and a laminated resin molded article having a deep metallic appearance, wherein the multilayer acrylic resin film is laminated, and It relates to the manufacturing method.
[0002]
[Prior art]
In recent years, more sophisticated textures have been demanded for the surface decoration of resin molded products. In particular, the addition of metallic texture to the surface of resin molded products by metallic coating, wet plating, dry plating, etc. 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 such a resin molded product, in addition to the method of directly decorating the surface of the resin molded product, such as printing, plating, metal deposition, etc., the resin molded product is configured. There are a method of kneading high-brightness pigments such as aluminum pigments and pearl pigments in the resin composition to be processed, and a method of laminating a resin film subjected to coating, plating, vapor deposition, etc. In recent years, a method of laminating decorated resin films has been used in various industrial fields due to the wide range of productivity and freedom of work environment.
[0004]
Specifically, in JP-A No. 11-20787, an fluoric resin containing a pearl pigment and a fluoric resin containing an inorganic pigment having a different color tone are fed into an extruder equipped with a feed block die. A multilayer film formed by molding and a method of producing a resin molded product having a metallic texture by laminating the multilayer film on a resin base material have been proposed.
[0005]
Japanese Patent Application Laid-Open No. 11-245261 proposes a method of obtaining a molded product having a metallic texture by insert molding using an insert film obtained by metal deposition on an acrylic film.
[0006]
Japanese Patent Laid-Open No. 2000-33675 discloses a decorative board in which a colored acrylic resin sheet and a transparent acrylic resin sheet having a specific breaking elongation are laminated, and titanium dioxide as a colorant used in the colored acrylic resin sheet. A metallic decorative board using a pearl pigment made of a coated mica foil powder is illustrated.
[0007]
Japanese Patent Application Laid-Open No. 11-123739 proposes a method for obtaining a metallic-like molded product having a sense of depth by insert molding of an aluminum pigment-containing polypropylene resin using a transfer film.
[0008]
Japanese Patent Laid-Open No. 2000-88653 discloses a silver metallic laminated film produced by feeding a resin in which an aluminum paste is mixed into an acrylic resin composition and an acrylic resin through a feed block type multilayer die, and in-mold molding using the same. A method for obtaining a molded article having a metallic texture is described.
[0009]
On the other hand, in the kind of metallic-like texture to be given to resin molded products, silver metallic tone imitating aluminum or black metallic imitating steel depending on the application or user's preference when using resin molded products as industrial members Tones, yellow metallic tone that mimics brass, gold metallic tone that mimics gold or blue metallic tone that combines various chromatic hues in metallic tone, metallic resin tone products with various textures such as red metallic tone Is strongly demanded mainly for vehicle exterior members, interior members or miscellaneous goods.
[0010]
As a method for expressing the metallic tone of these various textures, metal powder such as aluminum powder, iron powder and brass powder, pearl pigment such as natural pearl essence, basic lead carbonate and its titanium dioxide coated pigment, natural mica and synthetic mica In combination with high-brightness pigments such as metal oxide-coated pigments and achromatic pigments such as carbon black and titanium white and / or chromatic pigments or dyes having various hues, a metallic tone with a variety of hues can be obtained. The technology to be developed is widely applied in the field of printing, painting or colorants for resins.
[0011]
Conventionally, when a metallic tone of various textures is imparted to the surface of a resin molded product using the above-described decorative film, for example, a method of laminating and using a metallic tone printing film is different depending on the target texture. It is necessary to prepare a printing film, which is unsuitable for production of poor productivity, particularly for production of a wide variety of products, and its industrial utility value is low.
[0012]
Further, in the case of using a film having a metal vapor deposition layer as in the example of Japanese Patent Application Laid-Open No. 11-245261, it is difficult to express a metallic tone with a different texture unless the type of metal to be vapor deposited is substantially changed. Also, when using a metal vapor-deposited film, cracks are likely to occur in the metal vapor-deposited layer due to the stretching process such as laminating or in-mold molding for laminating the resin-deposited product. There is a drawback that there is a limitation on the shape of the.
[0013]
In addition, in the method of kneading a metallic pigment into a molding resin as disclosed in JP-A-11-123739, it is necessary to change the type of the metallic pigment used in the molding resin in order to impart a metallic tone with a different texture. In this case, the mechanical properties and moldability of the resin molded product as the base material are likely to be lowered, and the industrial value is low. In addition, when a metallic pigment is added to a resin molded product, a relatively large amount of pigment is required, which is not preferable from the viewpoint of economy.
[0014]
On the other hand, in the method of laminating a colored film containing a metallic pigment described in JP-A No. 2000-33675, JP-A No. 11-208787 and JP-A No. 2000-86853, a metallic material of the colored film to be used is laminated. By changing the tone texture, a metallic tone resin molded product can be obtained without impairing the properties of the substrate. However, in any method, the texture of the resin molded product in which the films are laminated is determined by the texture of the metallic film to be used. For example, when changing the texture by changing the hue of the metallic tone, Therefore, it is not suitable for the production of poor productivity, especially for the production of a wide variety of products, and its industrial utility value is low.
[0015]
Specifically, Japanese Patent Application Laid-Open No. 2000-33675 describes that a colored acrylic resin-based sheet containing a pearl pigment is laminated on a decorative sheet surface constituting a molded product, and a transparent acrylic resin-based sheet is laminated on the surface. However, there is no specific description about the kind and addition amount of the pearl pigment and the light transmittance of the colored acrylic resin-based sheet, and when this laminated sheet is used, it can be obtained even if the type of the base material is changed. There is no change in the metallic texture of the laminated resin molded product, and the metallic decoration method that does not give variations to the metallic texture in this way has low industrial utility value.
[0016]
Moreover, although it is described using the multilayer film produced by adding a pearl pigment to the fluorine resin of Unexamined-Japanese-Patent No. 11-20787, it does not mention the light transmittance of the multilayer film to be used, but this When a multilayer film is used, even if the type of base material is changed, there is no change in the metallic texture that can be obtained. The utility value is low.
[0017]
Moreover, although the Example of Unexamined-Japanese-Patent No. 2000-86853 describes using the multilayer film which consists of the colored layer which added the aluminum pigment to the acrylic composition, and the transparent acrylic resin layer as a laminated resin molded product. , There is no description about the thickness of each multilayer film, there is no specific description about the light transmittance as a multilayer film, and even if this laminate sheet is used, even if the type of substrate is changed There is no change in the metallic texture of the resulting laminated resin molded product, and the metallic decoration method that does not give variations to the metallic texture in this way has low industrial utility value.
[0018]
As described above, conventionally, in a resin molded product having a metallic texture, the types of films on which various metallic resin molded products having different textures are laminated without impairing the characteristics of the resin molded product as a base material. No method has been found for efficient production without changing the process, and there has been a strong demand for the development of a technology for realizing this.
[0019]
[Problems to be solved by the invention]
An object of the present invention is to provide a film containing a metallic pigment for obtaining a resin molded article having a metallic tone and a resin molded article obtained by laminating the film.
[0020]
[Means for Solving the Problems]
That is, the gist of the present invention is that at least one acrylic resin metallic layer containing a metallic pigment and at least one acrylic resin layer not containing a metallic pigment each have a total light transmittance of 10 to 90%. It exists in the multilayer acrylic resin film for decorating of thickness 10-500 micrometers, the laminated resin molded product which laminated | stacked it, and its manufacturing method.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described.
[0022]
Although it does not specifically limit to the acrylic resin metallic layer and acrylic resin layer of the multilayer acrylic resin film of this invention, Usually, a well-known acrylic resin composition can be used. For example, it is preferable to use an acrylic resin composition disclosed in Japanese Patent Publication No. 62-19309, Japanese Patent Laid-Open No. 63-77963, Japanese Patent Laid-Open No. 8-323934, and the like.
[0023]
As a first specific example of the acrylic resin composition used for the acrylic resin metallic layer and the acrylic resin layer of the multilayer acrylic resin film of the present invention,
The acrylic resin composition preferably contains 75 to 94.5% by mass of the following thermoplastic polymer (I) and 5.5 to 25% by mass of the following rubber-containing polymer (II).
[0024]
The thermoplastic polymer (I) comprises a vinyl monomer copolymerizable with 50% by mass or more of methacrylic acid alkyl ester, less than 50% by mass of acrylic acid alkyl ester, and at least one of methacrylic acid alkyl ester and acrylic acid alkyl ester. It is a thermoplastic polymer obtained by polymerizing the monomer mixture (I) comprising 49% by mass or less of one or more of the monomers.
[0025]
The rubber-containing polymer (II) has a multilayer structure composed of two or more layers including an elastic inner layer and a hard outer layer, and the elastic inner layer is obtained by polymerizing an alkyl acrylate mainly. It has one or more layers made of coalescence, and the hard outer layer has one or more layers made of hard polymer obtained mainly by graft polymerization of alkyl methacrylate in the presence of the elastic (co) polymer. It is a rubber-containing polymer.
[0026]
Although the methacrylic acid alkyl ester and acrylic acid alkyl ester used by thermoplastic polymer (I) are not specifically limited, The methacrylic acid alkyl ester and acrylic acid alkyl ester which have a C1-C4 alkyl group are preferable.
[0027]
Examples of such alkyl methacrylate esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like, and methyl methacrylate is preferable. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate and the like.
[0028]
The content of the acrylic acid alkyl ester used in the thermoplastic polymer (I) is preferably 50% by mass or less, and more preferably 0.1 to 40% by mass.
[0029]
As the copolymerizable vinyl monomer used in the thermoplastic polymer (I), a known monomer can be used. Specific examples thereof include aromatic alkenyl such as styrene and cyanation such as acrylonitrile. A vinyl compound is mentioned.
[0030]
The reduced viscosity of the thermoplastic polymer (I) (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) realizes an appropriate elongation of the acrylic resin composition upon melting and good film-forming properties. Therefore, 0.1 L / g or less is preferable. Moreover, in order to realize sufficient flexibility of the acrylic resin film and to suppress film breakage during film formation and subsequent secondary processing, it is preferably 0.05 L / g or more.
[0031]
The polymerization method of the thermoplastic polymer (I) is not particularly limited, but can be performed by a usual method such as suspension polymerization, emulsion polymerization, bulk polymerization and the like. In addition, in order to make a viscosity into a preferable range, a chain transfer agent may be required. As the chain transfer agent, known ones can be used, but mercaptans are preferred. The amount of the chain transfer agent can be appropriately determined depending on the type and composition of the monomer.
[0032]
Examples of the rubber-containing polymer (II) include 50 to 99.9% by mass of an acrylic acid alkyl ester, 49.9% by mass or less of another copolymerizable vinyl monomer, and a copolymerizable crosslinkable monomer. After polymerizing a monomer mixture comprising 0.1 to 10% by mass of an elastomer to obtain an elastic (co) polymer, in the presence of 100 parts by mass of the obtained elastic (co) polymer, 10 to 400 parts by weight (100 parts by weight of an elastic (co) polymer) of a monomer mixture comprising 50% by weight or more of a methacrylic acid ester and less than 50% by weight of a vinyl monomer copolymerizable therewith Is preferably produced by polymerizing at least one stage.
[0033]
In order to suppress the resulting acrylic resin film from becoming brittle, the content of the elastic (co) polymer in the rubber-containing polymer (II) is the same as that of the thermoplastic polymer (I) and the rubber-containing polymer. 5 mass% or more is preferable in 100 mass% of total amounts of (II), and 8 mass% or more is more preferable. On the other hand, in order to improve the transparency of the resulting acrylic resin film, the content is preferably 18% by mass or less, and more preferably 15% by mass or less.
[0034]
In particular, the following rubber-containing polymer (II) having a semi-hard core structure can also be used. That is, the rubber-containing polymer (II) having a semi-hard core structure is an elastic (co) polymer ((II-A) comprising an innermost layer polymer (II-A) and an intermediate layer rubber polymer (II-B). ) + (II-B)) and a hard polymer (II-C) in the outermost layer, and the polymer (II-A) in which the innermost layer is composed mainly of methacrylic acid alkyl ester and acrylic acid alkyl ester, intermediate From a rubber polymer (II-B) whose layer has a glass transition temperature of less than 0 ° C. whose main component is an alkyl acrylate ester, and a hard polymer (II-C) whose outermost layer is a main component of an alkyl methacrylate ester Has a three-layer structure.
[0035]
In view of moldability, the polymer (II-A) in the elastic (co) polymer is preferably 20% by mass or more, and more preferably 30% by mass or more. For the same reason, the rubber polymer (II-B) in the elastic (co) polymer is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 80% by mass or less.
[0036]
Further, the glass transition temperature of the innermost layer polymer (II-A) is preferably 0 ° C. or higher, more preferably 15 ° C. or higher, and preferably lower than 25 ° C. If the glass transition temperature is 0 ° C. or higher, the plasticizer whitening resistance of the resulting acrylic resin layer is improved, and if it is less than 25 ° C., the moldability at the time of vacuum forming of the obtained acrylic resin layer is improved. is there.
[0037]
As the alkyl acrylate ester used in the production of the above elastic (co) polymer, those having an alkyl group having 1 to 8 carbon atoms are preferable, and among them, butyl acrylate, 2-ethylhexyl acrylate, etc. Is preferred. As the copolymerizable vinyl monomer used for obtaining the elastic (co) polymer, methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate and cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable.
[0038]
Furthermore, in the production of an elastic (co) polymer, it is preferable to use a copolymerizable crosslinkable monomer. The crosslinkable monomer to be used is not particularly limited, but preferably ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, Examples include diallyl maleate, trimethylol triacrylate, and allyl cinnamate, and these can be used alone or in combination of two or more.
[0039]
Examples of the methacrylic acid ester grafted on the elastic (co) polymer include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like.
[0040]
Examples of the vinyl monomer to be grafted onto the elastic (co) polymer include alkyl acrylates such as methyl acrylate, butyl acrylate and cyclohexyl acrylate, styrene, acrylonitrile and the like. In addition, in order to suppress aggregation of the elastic (co) polymer, the mixture of monomers to be grafted is preferably 10 parts by mass or more, and 20 parts by mass or more with respect to 100 parts by mass of the elastic (co) polymer. More preferably, 400 parts by mass or less is preferable, and 200 parts by mass or less is more preferable.
[0041]
The weight average particle diameter of the rubber-containing polymer (II) described above is preferably 0.2 μm or more, and more preferably 0.25 μm or more in order to realize sufficient film forming properties of the resulting acrylic resin film. Moreover, in order to implement | achieve sufficient transparency of an acrylic resin film, 0.4 micrometer or less is preferable and 0.35 micrometer or less is more preferable.
[0042]
The rubber-containing polymer (II) can be produced by a known emulsion polymerization method. The polymerization temperature varies depending on the type and amount of the polymerization initiator used, but is preferably 40 ° C or higher, more preferably 60 ° C or higher, preferably 95 ° C or lower, and more preferably 120 ° C or lower.
[0043]
As the polymerization initiator, a known one can be used, and the addition method can be a method of adding to one or both of the aqueous phase and the monomer phase.
[0044]
As the emulsifier, an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used, and an anionic surfactant is particularly preferable. Anionic surfactants include potassium oleate, sodium stearate, sodium myristate, sodium N-lauroylsarcosate, alkenyl succinate dipotassium salt, sulfate ester salt such as sodium lauryl sulfate, dioctyl sulfosuccinate sodium Sulfonic acid salts such as sodium dodecylbenzenesulfonate and sodium alkyldiphenyl ether disulfonate, and phosphoric acid ester salts such as sodium polyoxyethylene alkylphenyl ether phosphate.
[0045]
The latex obtained by the emulsion polymerization method is coagulated by a known coagulation method such as an acid coagulation method, a salt coagulation method, a freeze coagulation method, or a spray drying method. As the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. As the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium sulfate, acetic acid Organic salts such as calcium and magnesium acetate can be used. The solidified polymer is further washed, dehydrated and dried.
[0046]
In addition, when an acrylic resin film is formed using the above composition, 50 methyl methacrylate is added to the above composition in order to improve the film forming property by controlling the film thickness and the film forming speed with high accuracy. A thermoplastic polymer (III) obtained by polymerizing a monomer mixture (III) comprising at least 50% by mass and at least one vinyl monomer copolymerizable with methyl methacrylate and less than 50% by mass. ) Is preferably added.
[0047]
In addition, the content of the thermoplastic polymer (III) relative to 100 parts by mass of the total amount of the thermoplastic polymer (I) and the rubber-containing polymer (II) is 0.1 to sufficiently improve the film forming property. 10 parts by mass or less is preferable.
[0048]
The reduced viscosity of the thermoplastic polymer (III) (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is set to 0.00% in order to obtain an acrylic resin film (layer) with good thickness accuracy. Those exceeding 2 L / g are preferred, 2 L / g or less is preferred, and 1.2 L / g or less is more preferred.
[0049]
Further, in order to suppress the resulting acrylic resin film from becoming brittle, the ratio of the elastic (co) polymer in the rubber-containing polymer (II) is determined by the thermoplastic polymer (I), the rubber-containing polymer ( II) and 5% by mass or more of 100% by mass of the total amount of the thermoplastic polymer (III) are preferable, and 18% by mass or less is preferable in order to improve the transparency of the resulting acrylic resin film.
[0050]
Examples of vinyl monomers copolymerizable with methyl methacrylate used in the production of thermoplastic polymer (III) include acrylic acid alkyl esters, methacrylic acid alkyl esters, aromatic vinyl compounds, and vinylcyan compounds. It is done. The polymerization is preferably carried out by an emulsion polymerization method, and it is produced by separating and collecting a polymer latex produced by a known emulsion polymerization method using various coagulants or separating and collecting a solid content by spray drying.
[0051]
Moreover, as a 2nd specific example of the acrylic resin composition which comprises the metallic layer and acrylic resin layer of a multilayer acrylic resin film, it is preferable to use the following resin compositions.
[0052]
Copolymerized with an alkyl acrylate having an alkyl group of 1 to 8 carbon atoms and / or an alkyl methacrylate (A1) having an alkyl group of 1 to 4 carbon atoms and a component of 0 to 20 mass% (A1). Total amount of other possible double-bonded monomer (A2) and 0-10% by weight of polyfunctional monomer (A3) ((A1) + (A2) + (A3) = 100% by weight ) Innermost layer polymer (A) comprising a composition of 0.1 to 5 parts by mass of graft crossing agent with respect to 100 parts by mass,
Alkyl acrylate (B1) having 80 to 100% by mass of an alkyl group having 1 to 8 carbon atoms, monomer (B2) having another double bond copolymerizable with component (B1) of 0 to 20% by mass And 0 to 10% by mass of the polyfunctional monomer (B3) in a total amount ((B1) + (B2) + (B3) = 100% by mass) of 0.1 to 5 parts by mass of the graft A cross-linked elastic polymer (B) comprising a composition of a crossover agent,
A glass transition temperature of at least 60 ° C. comprising a composition of 51 to 100% by mass of an alkyl methacrylate having 1 to 4 carbon atoms (C1) and 0 to 49% by mass of a monomer (C2) having a copolymerizable double bond. Outermost layer polymer (C)
Is an alkyl acrylate (D1) having 10 to 90% by mass of an alkyl group having 1 to 8 carbon atoms as an intermediate layer (D) between the polymer (B) layer and the polymer (C) layer, 90% by weight of alkyl methacrylate having 1 to 4 carbon atoms (D2), 0 to 20% by weight of (D1) and other monomers having double bonds copolymerizable with (D2) component ( 0.1 to 100 parts by mass of D3) and 0 to 10% by mass of the polyfunctional monomer (D4) (D1) + (D2) + (D3) + (D4) = 100% by mass) The intermediate layer (D) comprising a composition of ˜5 parts by mass of the grafting agent, wherein the amount of alkyl acrylate in the intermediate layer (D) monotonously decreases from the crosslinked elastic polymer (B) toward the outermost layer polymer (C). ) At least one layer and a gel containing a multilayer structure polymer There at least 50%, the resin composition remaining metal content is 500ppm or less.
[0053]
The alkyl acrylate having an alkyl group having 1 to 8 carbon atoms constituting the innermost layer polymer (A) may be linear or branched, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl. Acrylate, 2-octyl acrylate and the like can be used alone or in combination, but those having a low glass transition temperature are more preferred.
[0054]
The alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms may be linear or branched, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate or the like can be used alone or in combination. .
[0055]
These alkyl (meth) acrylates (A1) are preferably used in the range of 80 to 100% by mass.
[0056]
Further, these alkyl (meth) acrylates are most preferably used in a unified manner for all the multistage layers thereafter, but two or more types of monomers may be mixed or different types of acrylates may be used depending on the final purpose.
[0057]
The monomer (A2) having another double bond copolymerizable with the component (A1) includes acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid and methacrylic acid, styrene , Alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used, and it is preferably used in the range of 0 to 20% by mass.
[0058]
Furthermore, as the polyfunctional monomer (A3), alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, 1,4 butylene glycol dimethacrylate, and propylene glycol dimethacrylate are preferable. Polyvinylbenzene such as trivinylbenzene and alkylene glycol diacrylate can also be used.
[0059]
These monomers effectively act to bridge the layer in which they are contained, and do not act on bonding between layers with other layers. Even if the polyfunctional monomer (A3) is not used at all, if a graft crossing agent is present, a fairly stable multi-layer structure can be obtained. It is arbitrarily used depending on the purpose of addition, and the use range is preferably 0 to 10% by mass.
[0060]
On the other hand, examples of the graft crossing agent include acrylic, methacrylic or crotyl esters of copolymerizable α / β-unsaturated carboxylic acid or dicarboxylic acid, preferably allyl esters of acrylic acid, methacrylic acid, maleic acid and fumaric acid. In particular, allyl methacrylate is preferred. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also preferable.
[0061]
The amount of the grafting agent used is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the total amount of the components (A1) to (A3). If the amount is less than 0.1 parts by mass, the effective amount of graft bonding is small, and if it exceeds 5 parts by mass, the amount of reaction with the crosslinked elastic polymer (B) polymerized in the second stage becomes large. The elastic modulus of the resulting two-layer crosslinked rubber elastic body is reduced.
[0062]
The content of the innermost layer polymer (A) in the multilayer structure polymer constituting the acrylic resin composition is preferably 5 to 35% by mass, more preferably 5 to 15% by mass, and the crosslinked elastic polymer (B). It is preferable that it is lower than the content of.
[0063]
Examples of the alkyl acrylate (B1) having an alkyl group having 1 to 8 carbon atoms used for the crosslinked elastic polymer (B) include the same as those used for the innermost layer polymer (A). The other monomer (B2) having a double bond copolymerizable with the component (B1) is the same as the alkyl methacrylate similar to that used in the innermost layer polymer (A) or the component (A2). These monomers can be used, and can be used alone or in a mixture. Further, the same polyfunctional monomer (B3) and graft crossing agent as those used in the innermost layer polymer (A) can be used.
[0064]
The monomers constituting these crosslinked elastic polymers (B) are in the range of 80 to 100% by mass for the (B1) component, 0 to 20% by mass for the (B2) component, and 0 to 10% by mass for the (B3) component. It is preferable that the amount of the graft crossing agent used is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of (B1) to (B3).
[0065]
The glass transition temperature of the crosslinked elastic polymer (B) alone is preferably 0 ° C. or less, more preferably −30 ° C. or less, and good physical properties are obtained.
[0066]
The content of the cross-linked elastic polymer (B) in the multilayer structure polymer is preferably in the range of 10 to 45% by mass, and is preferably higher than the content of the innermost layer polymer (A).
[0067]
As C1-C4 alkyl methacrylate (C1) used for outermost layer polymer (C), the thing similar to what is used for innermost layer polymer (A) is mentioned, Moreover, (C1) component and Examples of the monomer (C2) having another double bond capable of copolymerization include the same alkyl acrylate as that used for the innermost layer polymer (A) and the same monomer as the component (A2). Can be used alone or in a mixture.
[0068]
The monomer constituting the outermost layer polymer (C) is preferably used in the range of 51 to 100% by mass of (C1) and 0 to 49% by mass of the component (C2).
[0069]
The glass transition temperature of the outermost layer polymer (C) alone is preferably 60 ° C. or higher, more preferably 80 ° C. or higher in order to obtain excellent solvent resistance and water whitening resistance. If the glass transition temperature of the outermost layer polymer (C) alone is less than 60 ° C., the solvent resistance and water whitening resistance of the final polymer described later are not excellent.
[0070]
The content of the outermost layer polymer (C) in the multilayer structure polymer is preferably 10 to 80% by mass, more preferably 40 to 60% by mass.
[0071]
The components (D1) to (D4) constituting the intermediate layer (D) and the graft crossing agent are the same as those used for the innermost layer polymer (A). The graft crossing agent used for the intermediate layer (D) is essential for tightly bonding the polymer layers and obtaining excellent physical properties.
[0072]
The content of the intermediate layer (D) in the multilayer structure polymer is preferably 5 to 35% by mass. If it is less than 5% by mass, the function as an intermediate layer cannot be expressed, and if it exceeds 35% by mass, the balance of the final polymer may be lost.
[0073]
In producing the multilayer structure polymer, the emulsion particle diameter of the final polymer is not particularly limited, but a range of about 800 to 2000 mm is most preferable because a balanced structure can be obtained. The surfactant and catalyst used in the production are not particularly limited, and can be subjected to salting-out treatment by adding additives such as an antioxidant and a lubricant as necessary.
[0074]
Moreover, when producing a multilayer structure polymer, when carrying out the salting-out process using a metal salt, it is preferable to make residual metal content in a final product into 500 ppm or less. In particular, when using a metal salt having a strong affinity for water such as magnesium and sodium as a salting-out agent, if the residual metal content is not reduced as much as possible, a whitening phenomenon occurs when the final polymer is immersed in boiling water, It may become a practical problem.
[0075]
As the method for producing the multilayer structure polymer, the sequential multi-stage polymerization method by emulsion polymerization is most preferable, but it is not particularly limited to this method. For example, after emulsion polymerization, suspension polymerization is performed during the polymerization of the outermost layer polymer (C). It can also be carried out by an emulsion suspension polymerization method for conversion into a system.
[0076]
The thermal deformation temperature of the acrylic resin composition used for the acrylic resin metallic layer and the acrylic resin layer of the multilayer acrylic resin film of the present invention is preferably 60 ° C to 110 ° C. As an example of the resin composition when a heat deformation temperature in the range of 60 ° C. to 70 ° C. is necessary, the resin composition shown in the second specific example is preferable, and heat exceeding 70 ° C. and 110 ° C. or less is preferable. As an example of the resin composition when the deformation temperature is required, the resin composition shown in the first specific example is preferable. Although the heat distortion temperature of the resin composition shown in the first specific example varies depending on the amount of the rubber-containing polymer (II) used, the heat distortion temperature of the thermoplastic polymer (I) is mainly dominant. . The heat distortion temperature of the thermoplastic polymer (I) can be controlled by adjusting the monomer composition of the thermoplastic polymer (I) by a known method. For example, when methyl acrylate is used as a copolymerization component, the methyl methacrylate content in the thermoplastic polymer (I) is 88% by mass when the heat distortion temperature is 80 ° C. or higher. When the heat distortion temperature is 100 ° C. or higher, the methyl methacrylate content in the thermoplastic polymer (I) can be adjusted to 95% by mass or higher. In the case where the heat distortion temperature is 110 ° C. or higher, maleimides such as maleic anhydride and phenylmaleimide may be copolymerized in the thermoplastic polymer (I). Even when the heat distortion temperature is 80 ° C. or higher and 100 ° C. or higher, maleimides such as maleic anhydride and phenylmaleimide can be copolymerized. In this case, if the content of methyl methacrylate is reduced good.
[0077]
In addition, the resin composition shown in the first specific example is preferably used when the resin molded product containing the multilayer acrylic resin film is used for an application requiring particularly high surface hardness and heat resistance. When used for applications that require stretchability of the acrylic resin film, secondary workability such as bending, and moldability during vacuum forming, it is preferable to use the resin composition shown in the second specific example.
[0078]
In the present invention, the acrylic resin layer has a function of imparting surface gloss and depth to the base resin molded product in addition to the good metallic tone texture of the metallic layer.
[0079]
There are no particular limitations on the metallic pigment used in the decorative multilayer acrylic resin film of the present invention, aluminum pigment; natural pearl essence, basic lead carbonate, bismuth acid chloride and bismuth acid chloride coated mica, titanium dioxide Coated mica, titanium dioxide and / or various metal oxide coated mica, titanium dioxide coated basic lead carbonate, titanium dioxide and / or various metal oxide coated basic lead carbonate, titanium dioxide coated barium sulfate, titanium dioxide and / or various Metal oxide-coated barium sulfate or the like can be used. The various metal oxides mentioned here include chromium oxide, copper oxide, tin oxide, cobalt oxide, aluminum oxide, zinc oxide, iron oxide; natural mica, synthetic mica and the like.
[0080]
Considering the coloring performance and cost, it is preferable to use a scaly aluminum pigment, and the particle size of the scaly aluminum is not particularly limited, and it is preferably 5 to 60 μm.
[0081]
The total light transmittance of the decorative multilayer acrylic resin film of the present invention must be 10 to 90%.
[0082]
When the total light transmittance is less than 10%, the color tone of the laminated resin molded product obtained by laminating the film has an appearance in which only the metallic pigment color dominates, so the laminated resin molded product corresponds to the hue of the base material. The metallic texture of the product cannot be changed. On the other hand, when the total light transmittance exceeds 90%, it becomes difficult to apply the metallic light base material which is the object of the present invention.
[0083]
On the other hand, if the total light transmittance is 10% or more, the color of the base material is reflected, and by changing the base material color, the metallic texture of the laminated resin molded product corresponding to the hue of the base material is changed. Can be changed.
[0084]
Further, the total light transmittance of the decorative acrylic resin film is preferably 60 to 90% because a metallic texture that effectively reflects the base material color can be obtained, and more preferable total light rays. The transmittance range is 60 to 85%.
[0085]
Here, effectively reflecting the base color is not limited to the metallic texture that reflects only the shade of the base color, for example, when the surface of the black resin base is decorated with a silver metallic tone The appearance is not a silver metallic color that depends only on the surface metallic layer, but a blackish black iron color reflecting the black of the base material, or a yellow base material like a brass when using a yellow base material It shows that a pearl white-like appearance can be imparted to a resin molded product by using an external appearance or a white base material.
[0086]
In addition, when changing the color tone of the decorative film itself on the surface in order to give various metallic color appearances as described above, it is necessary to prepare a decoration medium for each color, resulting in low productivity and poor economic efficiency. Become. However, by laminating a decorative multilayer acrylic resin film having a total light transmittance of 10 to 90% on the base resin molded product, the metallic tone of the multilayer resin molded product corresponding to the hue of the base material is obtained. The texture can be changed, and without changing the type of metallic pigment-containing film used, it is possible to obtain resin molded products having various metallic textures by simply changing the color tone of the resin molded product as the base material. it can.
[0087]
The thickness of the multi-layer acrylic resin film for decoration of the present invention is 10 μm or more. If the film thickness is 10 μm or more, the film strength applicable to the secondary processing can be reproduced. Moreover, in order to improve the film forming property and the deep transparency of the resin molded product in which the acrylic resin film is laminated, the thickness is more preferably 50 μm or more, and further preferably 70 μm or more.
[0088]
Further, the thickness of the decorative multilayer acrylic resin film of the present invention is 500 μm or less. If the film is 500 μm or less, good film formation can be realized, stable production becomes possible, and the rigidity of the resulting acrylic resin film can be kept small, so that secondary workability such as good laminating properties is realized. it can. In addition, it is economically preferable because the mass per unit area can be reduced. From the above viewpoint, 300 μm or less is more preferable.
[0089]
The ratio of the thickness of the metallic layer containing the metallic pigment of the decorative multilayer acrylic resin film of the present invention and the thickness of the acrylic resin layer not containing the metallic pigment is not particularly limited, but the multilayer acrylic resin film In consideration of the surface gloss and the metallic depth of the resin molded product, the thickness of the acrylic resin layer not containing the metallic pigment is preferably 5% or more of the thickness of the multilayer acrylic resin film, more preferably 10% or more. .
[0090]
Factors that determine the total light transmittance of the decorative multi-layer acrylic resin film of the present invention are the addition amount of the metallic pigment and the film thickness. By changing these, the total light transmittance of the film can be changed. it can.
[0091]
The content of the metallic pigment is not particularly limited as long as the total light transmittance of the resulting multilayer film is in the range of 10 to 90%. However, in consideration of the metallic tone imparting property and mechanical strength of the film, the acrylic pigment is not limited. It is preferably 0.01% by weight or more and 10% by weight or less in the resin metallic layer, more preferably 0.01% by weight or more and 2% by weight or less, and further preferably 0.01% by weight or more and 1% by weight or less. . If it is less than 0.01% by weight, it is difficult to obtain a sufficient metallic appearance. On the other hand, if it exceeds 10% by weight, the film becomes brittle and film formation may be difficult.
[0092]
Also, since the total light transmittance can be changed depending on the particle size of the metallic pigment, when using a large particle size pigment, even if the addition amount and the thickness of the metallic layer are the same, when using a small particle size pigment The total light transmittance tends to be larger than that.
[0093]
In the acrylic resin composition used for the metallic layer and / or the acrylic resin layer constituting the multilayer acrylic resin film of the present invention, a general compounding agent such as a stabilizer, a lubricant, a processing aid, A plasticizer, an impact aid, and an ultraviolet absorber can be added, and a foaming agent, a coloring agent, and a matting agent can be added within a range where the total light transmittance satisfies the present invention. Particularly in terms of protecting the substrate, it is preferable to add an ultraviolet absorber in the range of 0.1 to 5% by weight in order to provide weather resistance. The molecular weight of the ultraviolet absorber used is preferably 300 or more, particularly preferably 400 or more. By using an ultraviolet absorber having a molecular weight of 300 or more, it is possible to suppress the ultraviolet absorber from volatilizing and contaminating the mold when vacuum / pressure forming is performed in an injection mold.
[0094]
The type of the UV absorber is not particularly limited, but a benzotriazole type having a molecular weight of 400 or more or a triazine type having a molecular weight of 400 or more can be particularly preferably used. Specific examples of Adeka Stab LA-31 from the company, and Tinuvin 1577 from Ciba Geigy are listed as specific examples of the latter. In addition, as a hindered amine light stabilizer (HALS),
Adeka Stub LA-57 manufactured by Asahi Denka Kogyo Co., Ltd. can also be used.
[0095]
As a method of adding a matte appearance to the metallic tone, there are a method of adding a matting agent to the acrylic resin film of the metallic layer alone and a method of performing mat processing by surface transfer on the acrylic resin film surface of the metallic layer alone. Since these methods cannot provide a deep surface design, it is preferable to add a matting agent to the acrylic resin layer not containing the metallic pigment of the acrylic resin film of the present invention.
[0096]
In particular, in order to give a high-quality matte state as a surface appearance, a known matting agent is added to the resin composition constituting the acrylic resin layer not containing the metallic pigment of the acrylic resin film of the present invention. However, it is possible to use a polymer matting agent as disclosed in JP-A-7-238202, that is, an acrylic acid hydroxyalkyl ester or / and a methacrylic acid hydroxyalkyl ester 1 having an alkyl group having 1 to 8 carbon atoms. -80% by weight, 10 to 99% by weight of methacrylic acid alkyl ester having 1 to 13 carbon atoms, 0 to 79% by weight of acrylic acid alkyl ester having 1 to 8 carbon atoms, and copolymerizable Using a linear polymer having a hydroxyl group obtained by polymerizing 0 to 50% by weight of at least one other vinyl monomer It is preferable.
[0097]
The multi-layer acrylic resin film for decoration of the present invention can be produced by combining two or more layers at the time of film formation or by separately forming films for forming each layer and laminating these films separately. It is preferable to produce it.
[0098]
For example, a multi-manifold method and a merging apparatus are used in which a plurality of extrusion molding machines are used to form a plurality of resin layers into a film shape and then the resin is bonded in a molten state. Examples include a feed block method in which a plurality of resins used are joined and bonded into a film shape, and an inflation method using a round die.
[0099]
As a method of separately forming a film for forming each layer in advance and laminating these films separately, a method for manufacturing a film for forming each layer in advance includes, for example, a melt casting method, a T-die method, an inflation method, etc. Examples of the melt extrusion method; calendering method, etc., but from the viewpoint of economy, it is preferable to produce by an extrusion film forming machine equipped with a T die, a cooling roll and a winder, and the T die to be used is particularly Although not limited, a coat hanger type T die is preferable from the viewpoint of stabilizing the fluidity of the molten resin in the T die.
[0100]
The acrylic resin composition melt-extruded from the T-die is formed into a film by a take-up machine equipped with a cooling roll. Although it does not specifically limit as a cooling method of molten resin, The method of forming into a film by contacting one metal roll; The method of forming into a film by pinching | interposing to a some metal roll, a nonmetallic roll, and / or a metal belt is illustrated. be able to.
[0101]
As a method of laminating the film forming each layer, for example, a dry laminating method in which an adhesive layer is provided between films and bonded through a laminating roll, a plurality of films are preheated and then made of two metals and / or non-metals. Examples thereof include a roll press laminating method in which a plurality of films are preliminarily heated and sandwiched between a plurality of metal belts and adhered to each other by a roll press laminating method.
[0102]
As a method for producing a laminated resin molded product in which the decorative multi-layer acrylic resin film of the present invention is laminated, for example, the acrylic resin film is used as a base material on the thermoplastic resin sheet so that the metallic layer is on the base material side. Laminate method that is set and bonded by heating and pressurization, lamination method using adhesive, or thermoplastic resin sheet extrusion molding, the acrylic resin film is melted into the molten resin coming out of the die A method of obtaining a laminated resin molded product of an acrylic resin film by preparing a laminated sheet by a method such as directly laminating so as to be on the resin side, and vacuum-compressing the laminated sheet.
[0103]
As a method of laminating the decorative multilayer acrylic resin film of the present invention on the surface of an injection-molded product to produce an acrylic resin film laminate-molded product, for example, the acrylic resin film is placed on the surface of the injection-molded product so that the metallic layer is on the inside. (Lamination molding method): Acrylic resin film is processed into the shape of the injection-molded product in advance by vacuum / pressure molding, push molding, etc. so that the acrylic resin layer not containing the metallic pigment becomes the outer surface. A method of molding a laminated injection molded product at the same time as injection molding (insert molding method) by performing injection molding after placing the resin in the injection molding mold; using acrylic resin film and metallic pigment in the injection mold cavity Set so that the layer that does not contain is on the mold wall side, vacuum and pressure molding, and then mold in the mold cavity How to injection molding fat (in-mold method).
[0104]
As described above, the decorative multilayer acrylic resin film of the present invention has a total light transmittance of 10 to 90%, so that the metallic tone of the laminated resin molded product corresponds to the hue of the substrate. Highly designable resin molding that can change the texture and has various metallic textures just by changing the color tone of the resin molded product that is the base material without changing the type of decorative acrylic resin film to be used The product can be manufactured with good productivity.
[0105]
In addition, since the decorative multilayer acrylic resin film of the present invention has an acrylic resin layer that does not contain a metallic pigment on the surface, the surface gloss and depth that can never be obtained with an acrylic resin film with a single metallic layer is a resin molded product. Can be granted.
[0106]
Industrial application examples of the acrylic resin film laminated resin molded product including the decorative multilayer acrylic resin film of the present invention include vehicle parts such as vehicle interiors and exteriors; building parts such as window frames and sashes; tableware, toys, Miscellaneous goods such as game machines; home appliance parts such as vacuum cleaner housings, television housings, and air conditioner housings; interior members; ship members; electronic communication devices such as personal computer housings and mobile phone housings.
[0107]
【Example】
The present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention. Unless otherwise specified, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, and commercially available high-purity products were used.
[0108]
The following abbreviations may also be used:
Methyl methacrylate MMA,
Methyl acrylate MA,
Butyl acrylate BA,
Styrene St,
Allyl methacrylate AMA,
1,3-butylene glycol dimethacrylate 1,3BD,
t-butyl hydroperoxide tBH,
t-hexyl hydroperoxide tHH,
n-octyl mercaptan nOM.
[0109]
(Evaluation methods)
Each characteristic of the obtained thermoplastic polymer (I), rubber-containing polymer (II), thermoplastic polymer (III) and acrylic resin film was measured as follows.
[0110]
(A) Reduced viscosity (L / g) of thermoplastic polymers (I) and (III): 0.1 g of polymer sample was dissolved in 100 mL of chloroform at 25 ° C., and AVL-2C automatic viscometer manufactured by Sun Electronics Co., Ltd. It measured using.
[0111]
(A) Weight average particle diameter (μm) of rubber-containing polymer (II): The final particle diameter of the polymer latex of rubber-containing polymer (II) obtained by emulsion polymerization is the light from Otsuka Electronics Co., Ltd. Measurement was performed by a dynamic light scattering method using a scattering photometer DLS-700.
[0112]
(C) Total light transmittance (%) of acrylic resin film: Measured with an HR100 reflection / transmittance meter manufactured by Murakami Color Research Laboratory in accordance with JIS K6714.
[0113]
(D) Surface glossiness (%) of acrylic resin film: Surface gloss at 60 ° was measured using a gloss meter (GM-26D type manufactured by Murakami Color Research Laboratory).
[0114]
(E) Evaluation of laminated resin molded products and laminated injection molded products:
The surface appearance is evaluated by changing the color tone of the resin as the base material.
[0115]
A: Metallic appearance with a metallic view centered on the base color.
[0116]
○: Metallic color that allows you to check the base color on the background of metallic appearance
Toned appearance.
[0117]
△: Only the shade of the base color can be confirmed on the background of metallic appearance
Metallic appearance.
[0118]
×: The color of the base material is not reflected and the metallic tone of the film
appearance.
[0119]
XX: No metallic appearance, surface appearance of base color only
[0120]
(Reference Example 1) Production of thermoplastic polymer (I)
As the thermoplastic polymer (I), an MMA / MA copolymer (MMA / MA = 98/2, reduced viscosity 0.06 L / g) was produced.
[0121]
(Reference Example 2) Production of rubber-containing polymer (II)
Under a nitrogen atmosphere, 244 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, the temperature was raised to 80 ° C., (i) shown below was added, and then the polymer (II-A) shown below was added while stirring. 1/15 of the monomer mixture (ii) was charged and held for 15 minutes. Thereafter, the remainder of (b) was continuously added so that the increase rate per hour of the monomer mixture with respect to water was 8%. And it hold | maintained for 1 hour and the latex which consists of a polymer (II-A) was obtained.
[0122]
Next, 0.6 parts of sodium formaldehyde sulfoxylate was added to the obtained latex, and then held for 15 minutes. While stirring at 80 ° C. in a nitrogen atmosphere, the monomer mixture was mixed with water for 1 hour. The monomer mixture (C) of polymer (II-B) shown below was continuously added so that the increase rate per unit was 4%. Thereafter, the rubber polymer (II-B) was polymerized by holding for 2 hours to obtain an elastic polymer latex.
[0123]
Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the obtained elastic polymer latex, and then kept for 15 minutes. While stirring at 80 ° C. in a nitrogen atmosphere, the monomer mixture was mixed with water. as the growth rate per hour is 10%, it was added outermost polymer below the monomer mixture (II-C) and (d) successively. Thereafter, the outermost layer polymer (II-C) was polymerized by holding for 1 hour to obtain a latex of the rubber-containing polymer (II). The rubber-containing polymer (II) obtained had an average particle size of 0.28 μm.
[0124]
Thereafter, the latex of the rubber-containing polymer (II) was subjected to coagulation, aggregation and solidification using calcium acetate, filtered, washed with water and dried to obtain a rubber-containing polymer (II).
[0125]

(Reference Example 3) Production of thermoplastic polymer (III)
A reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and 1 part of an emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. 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 under a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of MMA and 2 parts of BA was added dropwise over 2 hours, and kept for 2 hours after completion of the addition to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, the polymer was acid coagulated, then dehydrated, washed with water and dried, and the polymer was recovered in powder form. The obtained copolymer had a reduced viscosity ηsp / c of 0.38 L / g.
[0126]
(Reference Example 4) Production of multilayer structure polymer (IV)
In a polymerization vessel equipped with a cooler, 250 parts of ion-exchanged water, 2 parts of an ester soda salt of sulfosuccinic acid, 0.05 part of sodium formaldehyde sulfoxylate were charged and stirred in a nitrogen atmosphere. 1.6 parts of MMA and 8 parts of BA , 1,3BD 0.4 part, AMA 0.1 part and cumene hydroperoxide 0.04 part. After raising the temperature to 70 ° C, the reaction was interrupted for 60 minutes to complete the polymerization of the innermost layer polymer (A). Subsequently, a monomer mixture composed of 1.5 parts of MMA, 22.5 parts of BA, 1.0 part of 1,3BD, and 0.25 part of AMA forming the crosslinked elastic polymer (B) is added for 60 minutes for polymerization, A two-layer crosslinked rubber elastic body was obtained. At this time, 0.05 part of cumene hydroperoxide was added to the monomer mixture forming the crosslinked elastic polymer (B).
[0127]
Subsequently, as an intermediate layer (D), a mixture of 5 parts of MMA, 5 parts of BA, and 0.1 part of AMA is reacted, and finally a monomer composed of 52.25 parts of MMA and 2.75 parts of BA as the outermost layer polymer (C). The mixture was reacted to form the outermost layer polymer (C) to obtain a polymer emulsion.
[0128]
Thereafter, the obtained polymer emulsion was salted out using 5 parts of calcium chloride with respect to 100 parts of the polymer, washed and dried to obtain a multilayered polymer (IV) in a powder form.
[0129]
Reference Example 5 Production of hydroxyl group-containing polymer (V)
The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.
[0130]

After sufficiently replacing the inside of the container with nitrogen gas, the mixture was heated to 75 ° C. while stirring, and polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C. and held for another 45 minutes to complete the polymerization, followed by sieving under the condition of 150 mesh openings, and the passed beads were dehydrated and dried to obtain a hydroxyl group-containing polymer (V )
[0131]
(Example 1) Production of multilayer acrylic resin film (XA-1-1)
80 parts of the thermoplastic polymer (I) produced in Reference Example 1, 20 parts of the rubber-containing polymer (II) produced in Reference Example 2, 5 parts of the thermoplastic polymer (III) produced in Reference Example 3, and an aluminum pigment Alpaste TCR3130 (manufactured by Toyo Aluminum Co., Ltd., shape: scaly, particle size: 13 μm), 0.5 part of UV absorber Adekastab LA-31RG (manufactured by Asahi Denka Co., Ltd.), and hindered amine light stability 0.2 parts of agent LA-57 (Asahi Denka Co., Ltd.) was mixed using a Henschel mixer. Next, the mixture was melt-kneaded at a cylinder temperature of 230 ° C. and a die temperature of 230 ° C. using a φ50 mm screw type single screw extruder to obtain pellets of the acrylic resin composition (A-1).
[0132]
Next, the obtained acrylic resin composition (A-1) was dried at 80 ° C. all day and night, and a φ65 mm non-vent screw type extruder (HME-65 manufactured by Mitsubishi Heavy Industries, Ltd.) equipped with a T die, 1 piece A film forming machine equipped with a cooling roll and a winder is used to form an acrylic resin film (A-1-1) with a cylinder temperature of 240 ° C., a T die temperature of 250 ° C., a cooling roll temperature of 70 ° C. and a film thickness of 75 μm did.
[0133]
On the other hand, 84 parts of the thermoplastic polymer (I) produced in Reference Example 1, 16 parts of the rubber-containing polymer (II) produced in Reference Example 2, 2 parts of the thermoplastic polymer (III) produced in Reference Example 3, Ultraviolet absorber Adekastab LA-31RG (Asahi Denka Co., Ltd.) 1.4 parts and hindered amine light stabilizer LA-57 (Asahi Denka Co., Ltd.) 0.2 parts were mixed using a Henschel mixer. Next, the mixture was melt-kneaded at a cylinder temperature of 230 ° C. and a die temperature of 230 ° C. using a φ50 mm screw type single screw extruder to obtain pellets of the acrylic resin composition (X-1).
[0134]
Next, the obtained acrylic resin composition (X-1) was dried at 80 ° C. all day and night, and a φ65 mm non-vent screw type extruder (HME-65 manufactured by Mitsubishi Heavy Industries, Ltd.) with a T-die attached. An acrylic resin film (X-1) having a film thickness of 50 μm was formed at a cylinder temperature of 240 ° C., a T die temperature of 250 ° C., and a cooling roll temperature of 70 ° C. using a film forming machine equipped with a cooling roll and a winder.
[0135]
Next, using a belt press apparatus in which metal belts are arranged in parallel, the acrylic resin films (A-1-1) and (X-1) are laminated at a heating region temperature of 150 ° C., and a multilayer acrylic having a total thickness of about 125 μm. A resin film (XA-1-1) was produced.
[0136]
The total light transmittance of the obtained multilayer acrylic resin film (XA-1-1) was measured, and the results are shown in Table 1.
[0137]
The obtained acrylic resin film (XA-1-1) and a 2 mm thick, 300 mm long, 300 mm wide black, white, yellow, and blue color ABS resin (Diapet ABS1001 manufactured by Mitsubishi Rayon Co., Ltd.) plate Using a press molding machine, press molding is performed at 140 ° C., and an acrylic resin film (XA-1-1) is bonded to the surface of the ABS plate in black, white, yellow, and blue so that the metallic layer is in contact with the ABS resin. The laminated sheet was prepared, and this sheet was vacuum-formed using a vacuum forming machine equipped with a mold having a cavity of 200 mm × 200 mm × depth 20 mm so that the surface not containing the metallic pigment becomes the outer surface, Shaped acrylic resin film laminated resin molded articles (A-1) to (A-4) were produced.
[0138]
The appearances of the obtained molded products (A-1) to (A-4) are shown in Table 1.
[0139]
Furthermore, a projection area of 500 cm is obtained by attaching an acrylic resin film (XA-1-1) to an injection molding machine having a clamping force of 2.2 MN. ² Set the metallic mold side to the surface of the female cavity of a vacuum moldable injection mold having a cavity with a drawing depth of 10 cm (mold open state), and heat the acrylic resin film with a non-contact heating plate After that, the cavity surface was followed by vacuum forming. Next, after closing the mold, ABS resin of black, white, yellow, and blue colors (Diapet ABS1001 manufactured by Mitsubishi Rayon Co., Ltd.) is injection molded at a cylinder temperature of 230 ° C., and an acrylic resin film laminated injection molded product (I -1) to (I-4) were produced.
[0140]
Appearances of the obtained molded products (I-1) to (I-4) are shown in Table 1.
[0141]
(Example 2) Production of multilayer acrylic resin film (YA-1-1)
100 parts of the multilayer polymer (IV) obtained in Reference Example 4, 1.4 parts of the ultraviolet absorber ADK STAB LA-31RG (manufactured by Asahi Denka Co., Ltd.) and hindered amine light stabilizer LA-57 (Asahi Denka ( 0.2 part) was mixed using a Henschel mixer. Next, the mixture was melt-kneaded at a cylinder temperature of 230 ° C. and a die temperature of 230 ° C. using a φ50 mm screw-type single-screw extruder to obtain pellets of an acrylic resin composition (Y-1).
[0142]
Next, the obtained acrylic resin composition (Y-1) was dried at 80 ° C. all day and night, and a φ65 mm non-vent screw type extruder (HME-65 manufactured by Mitsubishi Heavy Industries, Ltd.) equipped with a T die, 1 piece An acrylic resin film (Y-1) having a film thickness of 50 μm was formed at a cylinder temperature of 240 ° C., a T die temperature of 250 ° C., and a cooling roll temperature of 70 ° C. using a film forming machine equipped with a cooling roll and a winder.
[0143]
Next, an acrylic resin film (A-1-1) was used in the same manner as in Example 1 except that the acrylic resin film constituting the acrylic resin layer containing no metallic pigment was changed to (Y-1). ) And (Y-1) were laminated to produce a multilayer film (YA-1-1) having a total thickness of about 125 μm.
[0144]
The total light transmittance of the obtained multilayer acrylic resin film (YA-1-1) was measured, and the results are shown in Table 1.
[0145]
Next, a multilayer acrylic resin film laminated resin molded product (with the same method) except that the multilayer acrylic resin film (XA-1-1) used in Example 1 is changed to a multilayer acrylic resin film (YA-1-1) ( A-5) to (A-8) were prepared.
[0146]
Appearances of the obtained molded products (A-5) to (A-8) are shown in Table 1.
[0147]
Furthermore, except for changing the multilayer acrylic resin film from (XA-1-1) to (YA-1-1), a multilayer acrylic resin film laminated injection molded product (I-5) to (I-5) to ( I-8) was produced.
[0148]
Appearances of the obtained molded products (I-5) to (I-8) are shown in Table 1.
[0149]
(Example 3) Production of multilayer acrylic resin film (XA-1-2)
The acrylic resin composition (A-1) and acrylic resin composition (X-1) produced in Example 1 were extruded using a 40 mmφ single screw extruder, a 65 mmφ single screw extruder and a feed block die, and metallic. A multilayer acrylic resin film (XA-1-2) having a layer thickness of 125 μm and an acrylic resin layer containing no metallic pigment having a thickness of 50 μm was produced.
[0150]
The total light transmittance of the obtained multilayer acrylic resin film (XA-1-2) was measured, and the results are shown in Table 1.
[0151]
Next, in the same manner as in Example 1, multilayer acrylic resin film laminated resin molded articles (I-1) to (I-4) were produced using the obtained multilayer acrylic resin film (XA-1-2). .
[0152]
Table 1 shows the appearance of the obtained molded products (A-1) to (A-4).
[0153]
Furthermore, using the multilayer acrylic resin film (XA-1-2) described above, acrylic resin film laminated injection molded articles (Fro-1) to (Fro-4) were produced in the same manner as in Example 1.
[0154]
Table 1 shows the appearances of the obtained molded products (RO-1) to (RO-4).
[0155]
(Example 4) Production of multilayer acrylic resin film (YA-1-2)
A multilayer acrylic resin film (YA-1-2) having a total thickness of 175 μm was prepared in the same manner as in Example 3 except that the acrylic resin composition (X-1) used in Example 3 was changed to (Y-1). did.
[0156]
The total light transmittance of the obtained multilayer acrylic resin film (YA-1-2) was measured, and the results are shown in Table 1.
[0157]
Next, in the same manner as in Example 1, multilayer acrylic resin film laminated resin molded articles (I-5) to (I-8) were produced using the obtained multilayer acrylic resin film (YA-1-2). .
[0158]
Appearances of the obtained molded products (A-5) to (A-8) are shown in Table 1.
[0159]
Furthermore, multilayer acrylic resin film laminated injection molded articles (Fro-5) to (Fro-8) were produced in the same manner as in Example 1 using the aforementioned multilayer acrylic resin film (YA-1-2).
[0160]
Table 1 shows the appearances of the obtained molded products (Ro-5) to (Ro-8).
[0161]
(Example 5) Production of multilayer acrylic resin film (XA-2-1)
An acrylic resin composition (A-2) was prepared in the same manner except that the aluminum pigment addition amount used in the production of the acrylic resin composition (A-1) of Example 1 was changed to 1.5 parts. An acrylic resin film (A-2-1) having a film thickness of 75 μm was obtained in the same manner as in Example 1.
[0162]
Next, a multilayer acrylic resin film (XA-2) having a total thickness of 125 μm was obtained in the same manner as in Example 1 except that the acrylic resin film (A-1-1) used in the example was changed to (A-2-1). -1) was produced.
[0163]
The total light transmittance of the obtained multilayer acrylic resin film (XA-2-1) was measured, and the results are shown in Table 1.
[0164]
Next, in the same manner as in Example 1, using the multilayer acrylic resin film (XA-2-1), multilayer acrylic resin film laminated resin molded articles (U-1) to (U-4) and multilayer acrylic resin film laminated injection Molded articles (ha-1) to (ha-4) were produced.
[0165]
Appearances of the obtained molded products (U-1) to (U-4) and (ha-1) to (ha-4) are shown in Table 1.
[0166]
(Example 6) Production of multilayer acrylic resin film (YA-2-1)
A multilayer acrylic resin film (YA-2-1) having a total thickness of 125 μm in the same manner as in Example 1, except that the acrylic resin film (X-1) used in Example 5 was changed to (Y-1). Was made.
[0167]
The total light transmittance of the obtained multilayer acrylic resin film (YA-2-1) was measured, and the results are shown in Table 1.
[0168]
Next, in the same manner as in Example 1, using the multilayer acrylic resin film (YA-2-1), multilayer acrylic resin film laminated resin molded articles (U-5) to (W-8) and multilayer acrylic resin film laminated injection Molded articles (ha-5) to (ha-8) were produced.
[0169]
The appearances of the obtained molded products (U-5) to (U-8) and (ha-5) to (ha-8) are shown in Table 1.
[0170]
(Example 7) Production of multilayer acrylic resin film (XB-1)
The aluminum pigment used for the production of the acrylic resin composition (A-1) of Example 1 was changed in the same manner except that it was changed to Alpaste TCR3040 (manufactured by Toyo Aluminum Co., Ltd., shape: scale-like, particle size: 17 μm). A resin composition (B-1) constituting the metallic layer was prepared, and an acrylic resin film (B-1) having a film thickness of 75 μm was obtained in the same manner as in Example 1.
[0171]
Next, a multilayer acrylic resin film (XB-1) having a total thickness of 125 μm was produced in the same manner as in Example 1 except that the acrylic resin film (A-1) used in Example 1 was changed to (B-1). .
[0172]
The total light transmittance of the obtained multilayer acrylic resin film (XB-1) was measured, and the results are shown in Table 1.
[0173]
Next, in the same manner as in Example 1, using the multilayer acrylic resin film (XB-1), multilayer acrylic resin film laminated resin molded articles (D-1) to (D-4) and multilayer acrylic resin film laminated injection molded articles (Ni-1) to (Ni-4) were produced.
[0174]
Appearances of the obtained molded articles (D-1) to (D-4) and (NI-1) to (NI-4) are shown in Table 1.
[0175]
(Example 8) Production of multilayer acrylic resin film (YB-1)
A multilayer acrylic resin film (YB-1) having a total thickness of 125 μm was prepared in the same manner as in Example 1 except that the acrylic resin film (X-1) used in Example 7 was changed to (Y-1).
[0176]
The total light transmittance of the obtained multilayer acrylic resin film (YB-1) was measured, and the results are shown in Table 1.
[0177]
Next, in the same manner as in Example 1, using the multilayer acrylic resin film (YB-1), multilayer acrylic resin film laminated resin molded articles (E-5) to (E-8) and multilayer acrylic resin film laminated injection molded articles (Ni-5) to (Ni-8) were produced.
[0178]
Appearances of the obtained molded products (D-5) to (D-8) and (NI-5) to (NI-8) are shown in Table 1.
[0179]
(Example 9) Manufacture of multilayer acrylic resin film (XC-1)
The aluminum pigment used in the production of the acrylic resin composition (A-1) of Example 1 was changed to Alpaste TCR3010 (manufactured by Toyo Aluminum Co., Ltd., shape: scale-like, particle size: 31 μm), and the addition amount was set to 0.00. A resin composition (C-1) constituting the metallic layer was produced in the same manner as in Example 1 except that the content was changed to 2 parts, and in the same manner as in Example 1, an acrylic resin film (C- 1) was obtained.
[0180]
Next, a multilayer acrylic resin film (XC-1) having a total thickness of 125 μm was produced in the same manner as in Example 1 except that the acrylic resin film constituting the metallic layer was changed to (C-1).
[0181]
The total light transmittance of the obtained multilayer acrylic resin film (XC-1) was measured, and the results are shown in Table 2.
[0182]
Next, in the same manner as in Example 1, using the multilayer acrylic resin film (XC-1), multilayer acrylic resin film laminated resin molded articles (O-1) to (O-4) and multilayer acrylic resin film laminated injection molded articles (Ho-1) to (ho-4) were produced.
[0183]
Table 2 shows the appearances of the obtained molded products (e-1) to (e-4) and (e-1) to (e-4).
[0184]
(Example 10) Manufacture of multilayer acrylic resin film (YC-1)
A multilayer acrylic having a total thickness of 125 μm in the same manner as in Example 1 except that the acrylic resin film (X-1) constituting the acrylic resin layer containing no metallic pigment in Example 9 was changed to (Y-1). A resin film (YC-1) was produced.
[0185]
The total light transmittance of the obtained multilayer acrylic resin film (YC-1) was measured, and the results are shown in Table 2.
[0186]
Next, in the same manner as in Example 1, using the multilayer acrylic resin film (YC-1), the multilayer acrylic resin film laminated resin molded products (O-5) to (O-8) and the multilayer acrylic resin film laminated injection molded products (H-5) to (H-8) were produced.
[0187]
The appearances of the obtained molded products (O-5) to (O-8) and (E-5) to (E-8) are shown in Table 2.
[0188]
(Example 11) Manufacture of multilayer acrylic resin film (XA-1-3)
When the acrylic resin composition (X-1) constituting the acrylic resin layer containing no metallic pigment in Example 1 was prepared, the hydroxyl group-containing polymer (V) produced in Reference Example 5 was treated with the acrylic resin composition (X -1) An acrylic resin composition (X-2) was prepared by adding 10 parts to 100 parts, and a 50 μm acrylic resin film (X-2) was produced in the same manner as in Example 1 using this. .
[0189]
Using the obtained film (X-2) and the film (A-1-1) produced in Example 1, a multilayer film (XA-1-3) having a total thickness of about 125 μm is produced in the same manner as in Example 1. did.
[0190]
The total light transmittance of the obtained multilayer acrylic resin film (XA-1-3) was measured, and the results are shown in Table 2.
[0191]
Next, in the same manner as in Example 1, using the multilayer acrylic resin film (XA-1-3), multilayer acrylic resin film laminated resin molded articles (K-1) to (K-4) and multilayer acrylic resin film laminated injection Molded articles (f-1) to (f-4) were produced.
[0192]
Table 2 shows the color appearance of the obtained molded products (K-1) to (K-4) and (H-1) to (H-4). Multi-layer acrylic resin film laminate molded products (K-1) to (K-4) and (H-1) to (H-4) showed a high-quality matte appearance in addition to a metallic feel with a deep feeling. .
[0193]
(Example 12) Production of multilayer acrylic resin film (YA-1-3)
A multilayer acrylic resin film (YA-1-3) having a total thickness of about 125 μm was produced in the same manner as in Example 11 except that the acrylic resin composition (X-1) in Example 11 was changed to (Y-1). .
[0194]
The total light transmittance of the obtained multilayer acrylic resin film (YA-1-3) was measured, and the results are shown in Table 2.
[0195]
Next, in the same manner as in Example 1, using the multilayer acrylic resin film (YA-1-3), multilayer acrylic resin film laminated resin molded products (Car-5) to (Car-8) and multilayer acrylic resin film multilayer injection Molded articles (f-5) to (f-8) were produced.
[0196]
Table 2 shows the appearances of the obtained molded products (K-5) to (K-8) and (H-5) to (H-8). Multi-layer acrylic resin film laminated molded products (K-5) to (K-8) and (H-5) to (H-8) showed a high-quality matte appearance in addition to a deep metallic tone. .
[0197]
(Comparative example 1) Manufacture of multilayer acrylic resin film (XA-2-2)
In the same manner as in Example 1 except that the acrylic film (A-2-2) was obtained by changing the film thickness of the acrylic resin film constituting the metallic layer to 200 μm in Example 5, a multilayer having a total thickness of 250 μm An acrylic resin film (XA-2-2) was produced.
[0198]
The total light transmittance of the obtained acrylic resin film (XA-2-2) was measured, and the results are shown in Table 2.
[0199]
Next, using the acrylic resin film (XA-2-2) in the same manner as in Example 1, the acrylic resin film laminated resin molded products (ki 1) to (ki 4) and the acrylic resin film laminated injection molded products (and 1 ) To (and 4) were produced.
[0200]
Table 2 shows the appearances of the obtained molded products (ki 1) to (ki 4) and (and 1) to (and 4).
[0201]
(Comparative Example 2) Production of multilayer acrylic resin film (XE-1)
Resin composition (E-) constituting the metallic layer in the same manner as in Example 1 except that the amount of the aluminum pigment used in the production of the acrylic resin composition (C-1) in Example 9 was changed to 0.01 parts. 1) was produced, and an acrylic resin film (E-1) having a thickness of 50 μm was obtained in the same manner as in Example 1.
[0202]
Next, a multilayer acrylic resin film (XE-1) having a total thickness of about 100 μm was produced in the same manner as in Example 1 except that the acrylic resin film constituting the metallic layer was changed to (E-1).
[0203]
The total light transmittance of the obtained acrylic resin film (XE-1) was measured, and the results are shown in Table 2.
[0204]
Next, using the acrylic resin film (XE-1) in the same manner as in Example 1, the acrylic resin film laminated resin molded products (K-1) to (K-4) and the acrylic resin film laminated injection molded product (Chi- 1) to (chi-4) were produced.
[0205]
Table 2 shows the appearance of the obtained molded products (ku-1) to (ku-4) and (chi-1) to (chi-4).
[0206]
(Comparative Example 3) Single layer acrylic resin film
Table 2 shows the total light transmittance and surface glossiness of the acrylic resin film (A-1-1) constituting the metallic layer of Example 1.
[0207]
Next, press molding was performed in the same manner as in Example 1 using the acrylic resin film (A-1-1) to obtain acrylic resin film laminated resin molded products (K-1) to (K-4). . Next, injection molding was performed using the acrylic resin film (A-1-1) in the same manner as in Example 1, and acrylic resin film laminated injection molded articles (Ri-1) to (Ri-4) were obtained. .
[0208]
The appearances of the obtained molded products (K-1) to (K-4) and (Ri-1) to (Ri-4) are shown in Table 2.
[0209]
All of the molded products obtained from this exhibited a metallic texture reflecting the color tone of the base material, but there was no metallic depth, and the surface of the molded product was inferior in smoothness.
[0210]
From the above examples and comparative examples, the following has become clear.
[0211]
First, a multilayer acrylic resin film laminated resin molded product and a multilayer acrylic resin film laminated injection molded product using a decorative multilayer acrylic resin film having a total light transmittance in the range of 10 to 90% are each base color. Appearance with high design reflecting the above.
[0212]
In particular, by using a decorative multilayer acrylic resin film having a total light transmittance of 60 to 90%, a good metallic texture reflecting the hue of the substrate was exhibited.
[0213]
Secondly, from Comparative Example 1, a multilayer acrylic resin film laminated resin molded product and a multilayer acrylic resin film laminated injection molded product using a decorative multilayer acrylic resin film having a total light transmittance of less than 10% are based on the base color. Is not reflected, and it has an appearance showing only a film color.
[0214]
Third, from Comparative Example 2, the multilayer acrylic resin film laminated resin molded product and the multilayer acrylic resin film laminated injection molded product using the decorative multilayer acrylic resin film having a total light transmittance of more than 90% are It was not obtained and it became the external appearance which shows only the solid color of a base material.
[0215]
Fourthly, the resin molded product using the decorative multi-layer acrylic resin film of Examples 11 and 12 has a high-quality matte appearance in addition to a metallic feeling with a deep feeling. The decorative film to which can be imparted has an extremely high industrial value.
[0216]
Fifth, the acrylic resin film laminated resin molded article using the acrylic resin film that does not have the acrylic resin layer that does not contain the metallic pigment of Comparative Example 3 as the surface layer does not have a deep metallic tone, and the surface Since it is also inferior in smoothness, its industrial value as a decorative film is low.
[0217]
[Table 1]

[Table 2]

[0218]
【The invention's effect】
As is clear from the above description, the acrylic resin composition comprises a metallic layer containing a metallic pigment and an acrylic resin layer not containing a metallic pigment, and the total light transmittance is 10% to 90%. By using a decorative multi-layer acrylic resin film having a thickness of 10 to 500 μm, it is possible to change the metallic texture of the laminated resin molded product in accordance with the hue of the substrate in the film laminated resin molded product. It is possible to produce highly-designed resin molded products with good design and various metallic textures by changing the color tone of the base resin molded product without changing the type of metallic pigment-containing film used. Therefore, industrial utility value is high.

Claims (1)

A laminated resin molded product in which a decorative multilayer acrylic resin film is laminated on a colored substrate, the decorative multilayer acrylic resin film containing an acrylic resin metallic layer containing a metallic pigment, and an acrylic resin layer containing no metallic pigment A multilayer acrylic resin film for decoration having a thickness of 50 to 500 μm and a total light transmittance of 10 to 90%, wherein the acrylic resin metallic layer melt-extends the acrylic resin composition. A laminated resin molded product that is formed by the above process .