JP3859465B2 - Acrylic resin composition, film thereof, and production method thereof - Google Patents

Description

【００３６】
（式中、Ｒはｎ−オクチル基、イソノニル基、２−エチルヘキシル基を表し、ｎは２〜４の整数を表す）で表されるアジピン酸系ポリエステルであることがより好ましい。
【００３７】
本発明のフィルムは、上記の課題を解決するために、上記のアクリル樹脂組成物をカレンダー加工してなることを特徴としている。
【００３８】
上記アクリル樹脂組成物は、柔軟性が高くかつカレンダー加工性の良いものである。このため、上記アクリル樹脂組成物をカレンダー加工することにより、適度な柔軟性、伸び、弾性、強度を有し、加工性、印刷性、および粘着・接着に対する適性が良好なフィルムを提供することができる。
【００３９】
本発明のフィルムの製造方法は、アクリル樹脂組成物を用いてなるフィルムの製造方法において、上記アクリル樹脂組成物をカレンダー成形する工程を含み、かつ、上記アクリル樹脂組成物が、メタクリル酸メチルとアクリル酸アルキルとからなる共重合体Ａと、メタクリル酸メチルとアクリル酸アルキルとスチレンとからなる共重合体Ｂと、からなり、メルトフローレイト（２３０℃、３７．３Ｎ）が１５以下であり、上記アクリル樹脂組成物が、上記共重合体Ａと上記共重合体Ｂとの合計１００重量部に対して５０重量部以下の可塑剤をさらに含み、上記可塑剤が、ポリエステル系可塑剤であることを特徴としている。
【００４０】
上記ポリエステル系可塑剤は、一般式（１）
【００４１】
【化４】

【００４２】
（式中、Ｒはｎ−オクチル基、イソノニル基、２−エチルヘキシル基を表し、ｎは２〜４の整数を表す）
で表されるアジピン酸系ポリエステルであることがより好ましい。
【００４３】
上記カレンダー成形する工程における、上記アクリル樹脂組成物の温度は、１５０℃〜２００℃の範囲内であることが好ましい。
【００４４】
【発明の実施の形態】
本発明のアクリル樹脂組成物は、メタクリル酸メチルとアクリル酸アルキルとからなる共重合体Ａと、メタクリル酸メチルとアクリル酸アルキルとスチレンとからなる共重合体Ｂと、からなり、メルトフローレイト（２３０℃、３７．３Ｎ）が１５以下であるものである。以下に、本発明のアクリル樹脂組成物の好適な実施の形態について説明する。
【００４５】
上記共重合体Ａは、メタクリル酸メチルとアクリル酸アルキルとを共重合させることにより得られるものであり、これらを共重合する方法としては、例えば、懸濁重合、乳化重合、溶液重合、塊状重合等が挙げられる。また、重合の際には、必要に応じて、連鎖移動剤、その他の重合助剤を使用してもよい。連鎖移動剤としては従来より知られている各種のものを使用することができ、特にメルカプタン類が好ましい。
【００４６】
共重合体Ａを構成するアクリル酸アルキルとしては、特に限定されないが、アルキル部分の炭素数が大きいものが好ましく、具体的には、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸ペンチル、アクリル酸ヘキシル、アクリル酸２−エチルヘキシル等を挙げることができ、これらは１種または２種以上を組み合わせて使用することができる。アルキル部分の炭素数が大きいアクリル酸アルキルを用いることにより、上記アクリル樹脂組成物の柔軟性をより良好なものにすることができる。
【００４７】
共重合体Ｂは、メタクリル酸メチルとアクリル酸アルキルとスチレンとを共重合させて得られるものであり、これらを共重合する方法としては、例えば、懸濁重合、乳化重合、溶液重合、塊状重合等が挙げられる。重合の際には、必要に応じて、連鎖移動剤、その他の重合助剤を使用してもよい。連鎖移動剤としては従来より知られている各種のものを使用することができ、特にメルカプタン類が好ましい。
【００４８】
共重合体Ｂを構成するアクリル酸アルキルとしては、上記した共重合体Ａを構成するアクリル酸アルキルと同様のものを用いることができる。
【００４９】
上記アクリル樹脂組成物をポリ塩化ビニル樹脂の代替材料として用いるためには、従来のポリ塩化ビニル樹脂用の設備をそのまま使用して上記アクリル樹脂組成物を加工することができることが好ましい。ここで、ポリ塩化ビニル樹脂は高温においては熱分解による品質の低下が著しいため、ポリ塩化ビニル樹脂用の設備の能力は、一般に２００℃を上限とするものが多い。このため、上記アクリル樹脂組成物のカレンダー加工設備としてポリ塩化ビニル樹脂用のものをそのまま用いるためには、２００℃以下の温度範囲におけるアクリル樹脂組成物のカレンダー加工性が良好であることが必要となる。
【００５０】
また、カレンダー加工においては、カレンダー加工を行う樹脂の溶融状態における粘度が、その混練効率およびバンクの回転に影響する。このため、カレンダー加工によって均質な薄いフィルムを得るためには、アクリル樹脂組成物の粘度が重要となる。
【００５１】
そこで、上記アクリル樹脂組成物は、メルトフローレイト（２３０℃、３７．３Ｎ）を１５以下としている。このため、１５０℃〜２００℃の範囲内における溶融状態のアクリル樹脂組成物の粘度を、混練効率が良くかつバンクの回転を良好なものにすることができる。したがって、ポリ塩化ビニル樹脂用のカレンダー加工設備を用いて上記アクリル樹脂組成物をカレンダー加工することにより、均質な薄いフィルムを得ることができる。
【００５２】
また、上記アクリル樹脂組成物は、メルトフローレイト（２３０℃、３７．３Ｎ）が１〜１５の範囲内であることが好ましい。メルトフローレイトを１以上とすることにより、ポリ塩化ビニル樹脂用のカレンダー加工設備を用いてカレンダー加工をする際に、上記アクリル樹脂組成物の粘度が高すぎることによりカレンダー加工性が低下することを防止できる。
【００５３】
すなわち、本発明のアクリル樹脂組成物は、１５０℃〜２００℃の範囲内における溶融状態の粘度が、混練効率が良くかつバンクの回転を良好にする粘度となるため、ポリ塩化ビニル樹脂用のカレンダー加工設備を用いて、平滑、均質で透明性の高い、かつ折り曲げ時に白化のおきないフィルムを成型することが可能なアクリル樹脂組成物を提供することができる。
【００５４】
また、上記アクリル樹脂組成物は、さらに可塑剤を含むことが好ましい。上記アクリル樹脂組成物に可塑剤を配合することにより、その柔軟性をさらに向上させることができる。これにより、上記アクリル樹脂により成型されたフィルムの耐折り曲げ白化性がより向上する。さらにカレンダー加工時のバンクの回転性、および溶融時の上記アクリル樹脂の伸びが向上するため、表面形状が良好な外観性の良いフィルムを提供することができる。
【００５５】
上記可塑剤の配合量は、上記アクリル樹脂組成物中の共重合体Ａと共重合体Ｂとの合計１００重量部に対して、１〜５０重量部の範囲内であり、５〜３０重量部の範囲内であることが好ましい。上記可塑剤の量を上記の範囲内とすることにより、可塑剤配合による柔軟性向上効果を得ることができ、かつ、上記アクリル樹脂組成物により成型されたフィルムの高温高圧条件下における、耐ブルーム・ブリード性を良好にすることができる。
【００５６】
上記可塑剤としては、環境ホルモンの疑いのないポリエステル系可塑剤またはアクリル系可塑剤を用いることがより好ましい。これにより、より安全性が高く、環境への影響も少ないアクリル樹脂組成物を提供することができる。
【００５７】
上記ポリエステル系可塑剤としては、例えば、アジピン酸、マゼライン酸、セバチン酸、フタル酸等の二塩基性酸と、グリコール、グリセリン類および一塩基酸等とのポリマー等が用いられる。具体的には、ジブチルフタレート、ジペンチルフタレート、ジオクチルフタレート、ジイソデシルフタレート、ブチルラウリルフタレート、ジトリデシルフタレート、ブチルベンジルフタレート、ブチルフタリルブチルグリコレート等が挙げられ、これらは１種または２種以上を組み合わせて使用することができる。
【００５８】
また、上記ポリエステル系可塑剤としては、特に、以下の一般式（１）で表されるアジピン酸系ポリエステルが好ましい。下記の一般式（１）で表されるアジピン酸系ポリエステルはアクリル樹脂組成物との相溶性が良好であるため、アクリル樹脂組成物の柔軟性を効果的に向上させることができる。
【００５９】
【化５】

【００６０】
（式中、Ｒはｎ−オクチル基、イソノニル基、２−エチルヘキシル基を表し、ｎは２〜４の整数を表す）。
【００６１】
上記アクリル系可塑剤とは、アクリル化合物のうち可塑剤として用いられるものをいう。また、アクリル系可塑剤は、１種または２種以上を組み合わせて使用することができる。
【００６２】
上記アクリル樹脂組成物は、上記した共重合体Ａと共重合体Ｂとを含有してなり、必要に応じてさらに可塑剤を含んでなるものであるが、必要に応じてさらに、一般的な配合剤、例えば、安定剤、滑剤、加工助剤、耐衝撃助剤、発泡剤、充填剤、着色剤、紫外線吸収剤、抗菌剤、艶消し剤等を配合することができる。
【００６３】
本発明のフィルムは、上記アクリル樹脂組成物をカレンダー加工することにより得られるものである。上記カレンダー加工に用いられるカレンダー形式は、特に限定されないが、例えば、逆Ｌ型、Ｚ型、直立２本型、Ｌ型、傾斜３本型等が挙げられる。
【００６４】
上記アクリル樹脂組成物は、上記したようにその柔軟性およびカレンダー加工性が良好であるため、該アクリル樹脂をカレンダー加工することにより、ポリ塩化ビニル樹脂のような柔軟な風合いをもち、平滑、均質で透明性の高い、かつ折り曲げ時に白化のおきないフィルムを成型することができる。さらに、該フィルムは、焼却時にダイオキシンが発生せず、かつ適度な柔軟性、伸び、弾性、強度を有し、２次加工時における加工性、印刷性、および粘着・接着に対する適性が良好なものである。
【００６５】
また、カレンダー加工における上記アクリル樹脂組成物の温度は、１５０℃〜２００℃の範囲内であることが好ましく、１７０℃〜１９５℃の範囲内であることがより好ましい。カレンダー加工における上記アクリル樹脂組成物の温度を上記範囲内とすることにより、カレンダー加工時における、上記アクリル樹脂組成物の混練効率およびバンクの回転を良好にすることが可能となる。このため、均質なフィルムが得られ、また、一般にその上限温度が２００℃であるポリ塩化ビニル樹脂用のカレンダー加工設備を用いてカレンダー加工を行うことができる。
【００６６】
すなわち、上記フィルムはポリ塩化ビニル樹脂製フィルムの代替品に要求される性質を満足するものであり、屋内外用の合板、鋼板、壁紙等の化粧材、ステッカー、マーキングフィルム、粘着テープ、看板装飾用印刷ベースフィルム、およびこれらのトップ保護フィルムとしての用途等に非常に有用である。
【００６７】
【実施例】
以下に実施例および比較例を掲げて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
【００６８】
〔実施例１〕共重合体Ａ（メタクリル酸メチル・アクリル酸アルキル共重合体）として、クラレ（株）製パラペットＨＲ−Ａ（商品名）９０重量部、および共重合体Ｂ（メタクリル酸メチル・アクリル酸アルキル・スチレン共重合体）として、三菱レイヨン（株）製メタブレンＷ３４１（商品名）１０重量部を有してなるアクリル樹脂組成物（ＭＦＲ（２３０℃、３７．３Ｎ）＝１）に、酸化防止剤１重量部（日本油脂（株）製アンチオクス１０（商品名））、安定剤０．４重量部（堺化学（株）製Ｃａ−ＳＴ（商品名）０．２重量部、堺化学（株）製Ｚｎ−ＳＴ（商品名）０．２重量部）、滑剤１重量部（旭電化（株）製ＬＳ−５（商品名））、紫外線吸収剤０．５重量部（住友化学（株）製バイオソープ５８３（商品名））を加えてバンバリーミキサーで溶融混練後、カレンダー加工設備本体の各ロールを通し、厚みが０．０８ｍｍのフィルムを作製した。このとき上記成分よりなるアクリル樹脂組成物の温度（材料温度）が１５０℃から２００℃の範囲内となるように、カレンダー加工設備本体の各ロールの温度を設定した。その際に、カレンダー加工の状態、およびカレンダー加工により得られたフィルムを、下記の評価方法・基準により評価した。このカレンダー加工性の評価、およびフィルムの評価により、アクリル樹脂組成物のポリ塩化ビニル樹脂の代替材料としての可能性について判断した。
【００６９】
〔評価方法・評価基準〕アクリル樹脂組成物のカレンダー加工性および得られたフィルムの評価方法、基準について以下に説明する。
【００７０】
〔滑性（ロールヘの樹脂の密着性）〕ロールに樹脂がべたつかずに綺麗に剥がれてフィルム化可能なものを○と評価し、べたついて引き剥がしが困難なものを×と評価した。
【００７１】
〔バンクの回転性〕カレンダーロール間にある樹脂のバンクが、ロールの回転にあわせて綺麗に回るものを○と評価し、バンクが綺麗に回らずスリップや凸凹が発生するものを×と評価した。
【００７２】
〔ロールヘのプレートアウト〕カレンダーロールに溶融樹脂から可塑剤や添加剤が噴出して（プレートアウト）ロール表面が曇るものを×と評価し、プレートアウトがおきないものを○と評価した。
【００７３】
〔溶融フィルムの延伸性（カレンダーロールからテイクオフロール間）〕１００〜３００％の延伸を行うことにより、フィルム全体が均一になりネッキングがおきないものを○と評価し、フィルムの厚みが均一にならないものや、溶融した樹脂の張力が低すぎてドローダウンしたものや、ネッキングの起きたものを×と評価した。
【００７４】
〔フィルムの表面性〕フィルムの表面が平滑でフローマークの発生がないかどうかを目視により判断し、表面が平滑で良好なものを○と評価し、表面が荒れたりフローマークが発生したものを×と評価した。
【００７５】
〔巻き取り時のフィルムの割れ〕フィルム巻き取りの際に割れるものを×と評価し、割れずに巻き取ることができるものを○と評価した。
【００７６】
〔カレンダー加工性〕カレンダー加工性を総合的に判断し、カレンダー加工性が良好なものを○と評価し、良好でないものを×と評価した。具体的には、上記滑性、バンクの回転性、ロールヘのプレートアウト、溶融フィルムの延伸性、フィルムの表面性および巻き取り時のフィルムの割れの全てについて○と評価されたものをカレンダー加工性が良好と評価し、これらのうちいずれかひとつでも×と評価されたものをカレンダー加工性が良好でないと評価した。
【００７７】
〔フィルムの耐折曲げ性〕カレンダー加工により得られたフィルムを、１８０°折り曲げた際のフィルムの白化を目視により判断し、白化しないものを○と評価し、白化するものを×と評価した。
【００７８】
〔フィルムの耐ブルーム・ブリード性〕得られたフィルムを温度７０℃、湿度９５％ＲＨの高温高湿槽中に１週間放置した後における、フィルム表面のブルーム、ブリードの発生の有無を目視により判断し、これらが発生しないものを○、発生するものを×と評価した。
【００７９】
〔実施例２〕実施例１のアクリル樹脂組成物を、共重合体Ａと共重合体Ｂとのブレンド（ＭＦＲ（２３０℃、３７．３Ｎ）＝４）である住友化学（株）製スミペックスＨＴ０３Ｙ（商品名）１００重量部とし、ポリエステル系可塑剤として大日本インキ化学工業（株）製ポリサイザーＷ−１０４０−ＥＬ（商品名）５重量部をさらに配合したこと以外は実施例１と同様にして行った。
【００８０】
〔実施例３〕実施例１のアクリル樹脂組成物を、共重合体Ａと共重合体Ｂとのブレンド（ＭＦＲ（２３０℃、３７．３Ｎ）＝１４）である住友化学（株）製スミペックスＨＴ５０Ｙ（商品名）１００重量部とし、ポリエステル系可塑剤として大日本インキ化学工業（株）製ポリサイザーＷ−２３００−ＥＬ（商品名）２０重量部をさらに配合したこと以外は実施例１と同様にして行った。
【００８１】
〔実施例４〕実施例１のアクリル樹脂組成物を、共重合体Ａとして住友化学（株）製スミペックスＬＧ２（商品名）９０重量部と、共重合体Ｂとして三菱レイヨン（株）製メタブレンＷ３４１（商品名）１０重量部とを配合してなるアクリル樹脂組成物（ＭＦＲ（２３０℃、３７．３Ｎ）＝１４）とし、ポリエステル系可塑剤として大日本インキ化学工業（株）製ポリサイザーＷ−４０１０−ＥＬ（商品名）５０重量部をさらに配合したこと以外は実施例１と同様にして行った。
【００８２】
〔実施例５〕実施例１のアクリル樹脂組成物を、共重合体Ａと共重合体Ｂとのブレンド（ＭＦＲ（２３０℃、３７．３Ｎ）＝４）である住友化学（株）製スミペックスＨＴ５３Ｘ（商品名）１００重量部とし、アクリル系可塑剤として東亜合成（株）製ＡＲＵＦＯＮ ＵＰ−１０００（商品名）１０重量部をさらに配合したこと以外は実施例１と同様にして行った。
【００８３】
〔実施例６〕実施例１のアクリル樹脂組成物を、共重合体Ａと共重合体Ｂとのブレンド（ＭＦＲ（２３０℃、３７．３Ｎ）＝１．２）であるクラレ（株）製パラペットＧＲ−Ｆ（商品名）１００重量部とし、アクリル系可塑剤として東亜合成（株）製ＡＲＵＦＯＮ ＵＰｌ０００（商品名）５０重量部をさらに配合したこと以外は実施例１と同様にして行った。
【００８４】
〔比較例１〕実施例１のアクリル樹脂組成物を、共重合体Ａ（ＭＦＲ（２３０℃、３７．３Ｎ）＝２）である住友化学（株）製スミペックスＭＨ（商品名）１００重量部としたこと、および耐ブルーム・ブリード性を評価するためのシートを２００℃で電熱プレスにより作製したこと以外は実施例１と同様にして行った。
【００８５】
なお、比較例２〜４はいずれもカレンダー加工によりシートを成型することができなかったため、比較例１と同様にシートの作製は２００℃で電熱プレスにより行った。
【００８６】
〔比較例２〕実施例１のアクリル樹脂組成物を、共重合体Ａと共重合体Ｂとのブレンド（ＭＦＲ（２３０℃、３７．３Ｎ）＝２４）である住友化学（株）製スミペックスＨＴ２０Ｙ（商品名）１００重量部としたこと以外は実施例１と同様にして行った。
【００８７】
〔比較例３〕実施例１のアクリル樹脂組成物を、共重合体Ａ（ＭＦＲ（２３０℃、３７．３Ｎ）＝２１）である住友化学（株）製スミペックスＬＧ２１（商品名）１００重量部としたこと以外は実施例１と同様にして行った。
【００８８】
〔比較例４〕実施例１のアクリル樹脂組成物を、共重合体Ａとしての住友化学（株）製スミペックスＬＧ２１（商品名）９０重量部と、共重合体Ｂとしての三菱レイヨン（株）製メタブレンＷ３４１（商品名）１０重量部とからなるアクリル樹脂組成物（ＭＦＲ（２３０℃、３７．３Ｎ）＝１９）とし、ポリエステル系可塑剤として大日本インキ化学工業（株）製ポリサイザーＷ−１０４０−ＥＬ（商品名）１０重量部をさらに用いたこと以外は実施例１と同様にして行った。
【００８９】
実施例および比較例について評価した結果を、それぞれ表１、表２に示す。
【００９０】
【表１】

【００９１】
【表２】

【００９２】
表１に示すように、共重合体Ａと共重合体Ｂとからなり、メルトフローレイト（２３０℃、３７．３Ｎ）が１５以下である実施例１〜６のアクリル樹脂組成物は、いずれもカレンダー加工性が良好であった。また、実施例１〜６のアクリル樹脂組成物をカレンダー加工して得られたフィルムは、耐折り曲げ白化性、および耐ブルーム・ブリード性に優れるものであった。すなわち、本実施例１〜６のアクリル樹脂組成物は、いずれもカレンダー加工に適しており、かつカレンダー加工により、ポリ塩化ビニル樹脂製フィルムの代替品として好適な、品質が良好なフィルムを成型できることが分かる。
【００９３】
これに対し、表２に示すように、比較例１〜４のアクリル樹脂組成物は、いずれもカレンダー加工性が悪く、カレンダー加工によるフィルムの成型ができないものであった。
【００９４】
比較例１より、メルトフローレイトが１５以下であっても、アクリル樹脂組成物が共重合体Ａのみからなる場合は巻き取り時に割れが生じるため、カレンダー加工によりフィルムを成型できないことが分かる。さらに、比較例２〜４より、メルトフローレイトが１５よりも大きいアクリル樹脂組成物は、共重合体Ａのみからなるものであるか共重合体Ａと共重合体Ｂとからなるものであるかに関わらず、カレンダー加工によってフィルムを成型することはできないことが分かる。
【００９５】
また、上記アクリル樹脂組成物は、その温度が１５０℃〜２００℃の範囲内でカレンダー加工することができるため、ポリ塩化ビニル樹脂用のカレンダー加工設備をそのまま用いることができるものである。
【００９６】
以上より、共重合体Ａと共重合体Ｂとからなり、かつメルトフローレイトが１５以下のアクリル樹脂組成物はカレンダー加工性が良好であり、かつ、カレンダー加工によって良好な品質のフィルムが得られることが分かる。すなわち、上記構成のアクリル樹脂組成物は、ポリ塩化ビニル樹脂の代替材料として好適な材料であり、該アクリル系樹脂組成物をカレンダー加工することにより、ポリ塩化ビニル樹脂製フィルムの代替品に要求される性質を満足するフィルムを提供することができる。
【００９７】
【発明の効果】
本発明のアクリル樹脂組成物は、以上のように、メタクリル酸メチルとアクリル酸アルキルとからなる共重合体Ａと、メタクリル酸メチルとアクリル酸アルキルとスチレンとからなる共重合体Ｂと、からなり、メルトフローレイト（２３０℃、３７．３Ｎ）が１５以下である構成である。
【００９８】
それゆえ、従来のポリ塩化ビニル樹脂用のカレンダー加工設備を用いたカレンダー加工により、折り曲げ時の白化が抑えられた、外観の良い、薄いフィルムを成型できる、ポリ塩化ビニルの代替材料として優れた性質を有するアクリル樹脂組成物を提供できるという効果を奏する。
【００９９】
上記アクリル樹脂組成物は、上記共重合体Ａと上記共重合体Ｂとの合計１００重量部に対して５０重量部以下の可塑剤をさらに含むことがより好ましい。
【０１００】
これにより、アクリル樹脂組成物の柔軟性が更に向上するため、その風合いをポリ塩化ビニル樹脂により近づけることができる。したがって、さらに外観の良いフィルムを成型することが可能であるアクリル樹脂組成物を提供できるという効果を奏する。
【０１０１】
また、上記可塑剤はポリエステル系可塑剤またはアクリル系可塑剤であることがさらに好ましい。
【０１０２】
上記ポリエステル系可塑剤およびアクリル系可塑剤は、いずれも環境ホルモンの疑いの無い可塑剤であるため、可塑剤の配合による環境への影響を確実に防止することができるという効果を奏する。
【０１０３】
また、上記ポリエステルの可塑剤が、一般式（１）
【０１０４】
【化６】

【０１０５】
（式中、Ｒはｎ−オクチル基、イソノニル基、２−エチルヘキシル基を表し、ｎは２〜４の整数を表す）で表されるアジピン酸系ポリエステルであることがより好ましい。
【０１０６】
本発明のフィルムの製造方法は、上記アクリル樹脂組成物をカレンダー成形する工程を含む構成である。
【０１０７】
それゆえ、適度な柔軟性、伸び、弾性、強度を有し、加工性、印刷性、および粘着・接着に対する適性が良好な、ポリ塩化ビニル樹脂フィルムの代替品として有用なフィルムを提供できるという効果を奏する。[0001]
BACKGROUND OF THE INVENTION
  The present invention provides a calender for a polyvinyl chloride (PVC) resin having an unprecedented soft texture, no problem of dioxin generation during incineration, and no suspected substance as an environmental hormone. Acrylic resin composition that can be calendered using processing equipment as it is, and does not whiten when bent, flexibly follows a curved surface, weather resistance, impact resistance, transparency, coloring, printability, adhesiveness It is related with the film of an acrylic resin composition which can be used by the use and method similar to a polyvinyl chloride resin film, and its manufacturing method.
[0002]
[Prior art]
  In recent years, from the viewpoint of environmental protection, an alternative from polyvinyl chloride resin to non-chlorinated materials has been demanded. As alternative materials, polyolefin resins such as polyethylene, polypropylene, and olefin thermoplastic elastomer (TPO) are considered promising particularly in consideration of economy and safety. However, since this polyolefin resin does not reach the polyvinyl chloride resin in terms of transparency and weather resistance of the film, the performance as a substitute material for the polyvinyl chloride resin is not sufficient.
[0003]
  Thus, an acrylic resin is an example of a material excellent in transparency and weather resistance required for a substitute material for the polyvinyl chloride resin. This acrylic resin has excellent mechanical properties and chemical properties, and has been used as organic glass for a long time in various fields such as lighting covers and outdoor signboards due to its transparency, weather resistance and high hardness. Has been. Acrylic resin is a highly safe material that does not contain substances that adversely affect the human body, and is therefore widely used as a medical instrument.
[0004]
  As described above, since the polyvinyl chloride resin is being repelled for the reason that dioxin may be generated during incineration, the acrylic resin has recently attracted attention as an alternative material for the hard polyvinyl chloride resin.
[0005]
  However, the acrylic resin itself is very hard and suitable as an alternative material for the hard polyvinyl chloride resin, but there is a problem that it is easy to crack and has little elongation when processed into a film. For this reason, some products have acrylic resin containing a rubber component for thick sheets, but when processed into a film having a thickness of 0.2 mm (200 μm) or less, it becomes white and lacks flexibility. There is no acrylic resin film having a texture like soft polyvinyl chloride resin.
[0006]
  Here, as a general molding method of acrylic resin, there are injection molding, extrusion molding, pressure molding and the like, and cast molding or extrusion molding using a T-die has been conventionally used as a sheet molding method. Yes. This extrusion molding is excellent in terms of cost performance because the quality is stable when one product is continuously produced, and is a molding method suitable for mass production.
[0007]
  However, since extrusion molding requires a long time until it reaches a steady state where the product can be taken stably, there is a problem that the loss of materials and time until the steady state is reached is very large. Therefore, for example, there is a strict requirement for color reproducibility, such as in the field of products that produce small quantities of many varieties that need to be changed frequently, and for adjusting the operating conditions while watching the finish. In the field of products, it becomes a non-economic and resource-consuming manufacturing method.
[0008]
  On the other hand, as a sheet molding method other than extrusion molding using a T-die, there is a calendar process in which a sheet is formed by rolling a resin with a hot roll. Compared to other molding methods such as extrusion laminating, extrusion stretching, and inflation processing, this calendering process has the advantage of easy setup change, less material loss, and relatively easy change of conditions during operation. There is.
[0009]
  In other words, calendering is a manufacturing method with high utility value when it is necessary to produce products (molded products) that require a large number of products in small quantities and color variations that require strict color tone reproducibility in a short time. . For this reason, conventionally, in the fields of building materials and marking films made of polyvinyl chloride resin, a molding method using calendar processing has been used.
[0010]
  Under these circumstances, in recent trends in which an alternative material for polyvinyl chloride resin is required, an alternative material for polyvinyl chloride resin that can be calendered is required as one major requirement. Furthermore, from the viewpoint of effective use of existing equipment, it is desired to be able to use the currently used vinyl chloride resin calendering equipment as it is.
[0011]
  Here, in general, a polyvinyl chloride resin is markedly deteriorated in quality due to thermal decomposition at a high temperature, and therefore the calendering temperature is usually 200 ° C. or lower. Therefore, the upper limit of the capacity of the calendering equipment for polyvinyl chloride resin is often 200 ° C. For this reason, in order to use the calendering equipment for polychlorinated resin as it is, the alternative material needs to be capable of calendering at 200 ° C. or lower.
[0012]
  In particular, in recent years, high-performance indoor and outdoor plywood, steel sheets, wallpaper, and other decorative materials, stickers, marking films, adhesive tapes, and signboard printing base films that are molded from a substitute material for polyvinyl chloride resin. , And these top protective films are desired. The film used for such applications usually needs to have a thickness of 0.5 mm or less, and is further required to have appropriate flexibility, elongation, elasticity, and strength. Further, like the polyvinyl chloride resin film, it is also necessary that the processability, printability, and suitability for adhesion and adhesion during the secondary processing of the film are good.
[0013]
  As a film comprising an acrylic resin, JP-A 2000-154263 discloses an acrylic resin film for laminating, in which an acrylic resin composition comprising a thermoplastic polymer and a rubber-containing polymer is formed into a film by calendering. Yes.
[0014]
[Problems to be solved by the invention]
  However, by molding a conventional acrylic resin by calendering, only thick and highly rigid sheets can be produced, so it has moderate flexibility, elongation, elasticity, strength, processability, printability, and adhesion. -There is a problem that a film having a thickness suitable for adhesion of 0.5 mm or less cannot be molded.
[0015]
  Furthermore, at a temperature in the range of 150 to 200 ° C., the viscosity of the melted acrylic resin (melt viscosity) is generally too high, so the acrylic resin melted by the calender roll cannot be sufficiently kneaded, and the bank rotation However, there is a problem that a flow mark is generated in the film and a uniform thin film cannot be obtained.
[0016]
  Here, as described above, the calendering equipment for polyvinyl chloride resin generally has an upper limit of 200 ° C. Within this temperature range, the viscosity of the melted acrylic resin, the tension at the time of melting, and the elongation (stretchability) ) Is not suitable for calendar processing. For this reason, there also exists a problem that an acrylic resin cannot be processed using the calendar processing equipment for polyvinyl chloride resins.
[0017]
  As described above, although the viscosity of the resin greatly affects the calendar processability, the above publication does not describe the viscosity of the acrylic resin composition. For this reason, this acrylic resin composition cannot be calendered to form a uniform thin film.
[0018]
  As described above, there is no acrylic resin with excellent calendar workability that can form a film using a calendar processing apparatus for polyvinyl chloride resin, and a flexible texture like polyvinyl chloride resin. In addition, there is no acrylic resin film that is smooth, homogeneous, highly transparent, and does not whiten when bent.
[0019]
  The present invention has been made to solve the above-mentioned problems, and its purpose is to use a calendering equipment for polyvinyl chloride resin that satisfies the performance required for an alternative material for polyvinyl chloride resin. Providing an acrylic resin composition that can be calendered, and having a soft texture such as a vinyl chloride resin made of this acrylic resin composition, in smoothness, homogeneity, transparency, and resistance to bending whitening It is providing the film which is excellent, and its manufacturing method.
[0020]
[Means for Solving the Problems]
  In order to solve the above problems, the acrylic resin composition of the present invention comprises a copolymer A comprising methyl methacrylate and alkyl acrylate, and a copolymer B comprising methyl methacrylate, alkyl acrylate and styrene. The melt flow rate (230 ° C., 37.3 N) is 15 or less.
[0021]
  According to the above invention, an acrylic resin composition that can be used as an alternative material for the polyvinyl chloride resin can be provided. That is, the present invention provides an acrylic resin composition capable of forming a film having a soft texture like polyvinyl chloride resin and excellent in transparency and resistance to whitening by using a calendar processing facility for polyvinyl chloride resin. It becomes possible.
[0022]
  Conventionally, if the film is molded using only the copolymer A of methyl methacrylate and alkyl acrylate, the film is not stretched because its hardness is too high, and it is very easy to break. There was a problem of cracking during take-up due to low elongation during melting.
[0023]
  In contrast, the acrylic resin composition of the present invention is a rubber component of an acrylic resin composed of methyl methacrylate, alkyl acrylate, and styrene to copolymer A having a high hardness composed of methyl methacrylate and alkyl acrylate. The melt flow rate (230 degreeC, 37.3N) formed by mix | blending a certain copolymer B is 15 or less.
[0024]
  That is, the acrylic resin composition of the present invention has a high hardness copolymer A (methyl methacrylate / alkyl acrylate copolymer) and copolymer B (methyl methacrylate / alkyl acrylate) which is a rubber component of an acrylic resin.・ Since styrene copolymer) is blended (blended), its flexibility is improved. Thereby, since the elongation of the acrylic resin composition at the time of melting is improved, workability at the time of molding is improved, and as a result, the appearance of the film is improved. In addition, since the acrylic resin composition has good flexibility, the film molded from the composition has suppressed whitening when the film is bent.
[0025]
  Moreover, in order to shape | mold a film by calendering, it is necessary to make the viscosity of an acrylic resin composition suitable for calendering. Accordingly, the acrylic resin composition of the present invention has a melt flow rate (230 ° C., 37.3 N) of 15 or less. Thereby, the viscosity of the acrylic resin composition in 150 to 200 degreeC which is the range of the capability of the conventional calendering equipment for polyvinyl chloride resin can be made into the viscosity suitable for calendering. That is, when the melt flow rate (230 ° C., 37.3 N) of the acrylic resin composition is set to 15 or less, the acrylic resin composition is used when calendering is performed using the calendering equipment for polyvinyl chloride resin. It is possible to prevent a situation where the viscosity of the product is too low and the molten film is drawn down, making it impossible to take the film from the calendar roll.
[0026]
  Thereby, the acrylic resin composition which can use the calendar processing equipment for conventional polyvinyl chloride resin as it is can be provided. Therefore, an acrylic resin composition having excellent properties that can be used as a substitute material for polyvinyl chloride, that is, smooth, homogeneous and transparent by calendering using conventional calendering equipment for polyvinyl chloride resin. It is possible to provide an acrylic resin composition that can form a high-quality film that is high and suppressed in whitening during bending.
[0027]
  Here, melt flow rate (MFR) is a thermoplastic material that is extruded within a certain period of time under specific test conditions in accordance with the measurement method specified in JIS (JISK6370-4-2). The amount of. In the present invention, the melt flow rate was measured under the conditions of 230 ° C. and 37.7 N.
[0028]
  More preferably, the acrylic resin composition further comprises 50 parts by weight or less of a plasticizer with respect to 100 parts by weight as a total of the copolymer A and the copolymer B.
[0029]
  Thereby, since the softness | flexibility of an acrylic resin composition improves, the texture can be brought closer to a polyvinyl chloride resin. That is, in forming the film by calendering, the rotation of the bank and the elongation at the time of melting of the acrylic resin composition are improved, so that the appearance of the obtained film is improved.
[0030]
  When the film is stored under high-temperature and high-humidity conditions by setting the blending amount of the plasticizer to 50 parts by weight or less with respect to a total of 100 parts by weight of the copolymer A and the copolymer B In this case, since bloom and bleed are prevented from occurring on the film surface, a surface having a good appearance can be maintained.
[0031]
  Therefore, it is possible to provide an acrylic resin composition that is used as a film material that has a better appearance and does not change even under high temperature and high humidity conditions.
[0032]
  Also,The plasticizer is a polyester plasticizerMore preferably.
[0033]
  The polyester plasticizer isIn any case, there is no suspicion of environmental hormones, and therefore, it is possible to reliably prevent the influence on the environment by adding a plasticizer.
[0034]
  Further, the plasticizer for the polyester is represented by the general formula (1).
[0035]
[Chemical3]

[0036]
  (Wherein, R represents an n-octyl group, isononyl group, 2-ethylhexyl group, and n represents an integer of 2 to 4).
[0037]
  In order to solve the above-mentioned problems, the film of the present invention is characterized by calendering the above acrylic resin composition.
[0038]
  The acrylic resin composition has high flexibility and good calendar workability. Therefore, by calendering the acrylic resin composition, it is possible to provide a film having moderate flexibility, elongation, elasticity, strength, and good workability, printability, and adhesion / adhesion suitability. it can.
[0039]
  The method for producing a film of the present invention includes a step of calendering the acrylic resin composition in a method for producing a film using the acrylic resin composition, and the acrylic resin composition comprises methyl methacrylate and acrylic. A copolymer A composed of an alkyl acid, and a copolymer B composed of methyl methacrylate, an alkyl acrylate, and styrene, and the melt flow rate (230 ° C., 37.3 N) is 15 or less.The acrylic resin composition further includes a plasticizer of 50 parts by weight or less based on a total of 100 parts by weight of the copolymer A and the copolymer B, and the plasticizer is a polyester plasticizer. is thereIt is characterized by that.
[0040]
  The polyester plasticizer has the general formula (1)
[0041]
[Formula 4]

[0042]
(In the formula, R represents n-octyl group, isononyl group, 2-ethylhexyl group, and n represents an integer of 2-4)
It is more preferable that it is adipic acid type | system | group polyester represented by these.
[0043]
  The temperature of the acrylic resin composition in the calender molding step is preferably in the range of 150 ° C to 200 ° C.
[0044]
DETAILED DESCRIPTION OF THE INVENTION
  The acrylic resin composition of the present invention comprises a copolymer A composed of methyl methacrylate and alkyl acrylate, and a copolymer B composed of methyl methacrylate, alkyl acrylate and styrene, and has a melt flow rate ( 230 ° C., 37.3 N) is 15 or less. Below, suitable embodiment of the acrylic resin composition of this invention is described.
[0045]
  The copolymer A is obtained by copolymerizing methyl methacrylate and alkyl acrylate. Examples of the copolymerization method include suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. Etc. Moreover, in the case of superposition | polymerization, you may use a chain transfer agent and another polymerization adjuvant as needed. Various conventionally known chain transfer agents can be used, and mercaptans are particularly preferred.
[0046]
  The alkyl acrylate constituting the copolymer A is not particularly limited, but those having a large number of carbon atoms in the alkyl portion are preferred. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Examples thereof include pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate and the like, and these can be used alone or in combination of two or more. By using an alkyl acrylate having a large number of carbon atoms in the alkyl moiety, the flexibility of the acrylic resin composition can be further improved.
[0047]
  The copolymer B is obtained by copolymerizing methyl methacrylate, alkyl acrylate, and styrene. Examples of the copolymerization method include suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. Etc. In the polymerization, a chain transfer agent and other polymerization aids may be used as necessary. Various conventionally known chain transfer agents can be used, and mercaptans are particularly preferred.
[0048]
  As the alkyl acrylate constituting the copolymer B, the same alkyl acrylate as constituting the copolymer A can be used.
[0049]
  In order to use the acrylic resin composition as an alternative material for the polyvinyl chloride resin, it is preferable that the acrylic resin composition can be processed using conventional equipment for polyvinyl chloride resin as it is. Here, since the quality of polyvinyl chloride resin is significantly deteriorated due to thermal decomposition at high temperatures, the capacity of equipment for polyvinyl chloride resin generally has an upper limit of 200 ° C. in many cases. For this reason, in order to use the thing for polyvinyl chloride resin as it is as the calendering equipment of the said acrylic resin composition, it is necessary for the calendering property of the acrylic resin composition in the temperature range of 200 degrees C or less to be favorable. Become.
[0050]
  In calendar processing, the viscosity of the resin subjected to calendar processing in the molten state affects the kneading efficiency and the rotation of the bank. For this reason, in order to obtain a uniform thin film by calendering, the viscosity of the acrylic resin composition is important.
[0051]
  Therefore, the acrylic resin composition has a melt flow rate (230 ° C., 37.3 N) of 15 or less. For this reason, the viscosity of the molten acrylic resin composition in the range of 150 ° C. to 200 ° C. can be made with good kneading efficiency and good rotation of the bank. Therefore, a uniform thin film can be obtained by calendering the acrylic resin composition using a calendering equipment for polyvinyl chloride resin.
[0052]
  Moreover, it is preferable that the said acrylic resin composition has a melt flow rate (230 degreeC, 37.3N) in the range of 1-15. When the melt flow rate is set to 1 or more, when calendering is performed using a calendering equipment for polyvinyl chloride resin, the viscosity of the acrylic resin composition is too high, so that the calenderability is lowered. Can be prevented.
[0053]
  That is, in the acrylic resin composition of the present invention, the viscosity in the molten state within the range of 150 ° C. to 200 ° C. is a viscosity that provides good kneading efficiency and good bank rotation. An acrylic resin composition capable of forming a smooth, homogeneous, highly transparent film that does not whiten when bent can be provided using a processing facility.
[0054]
  Moreover, it is preferable that the said acrylic resin composition contains a plasticizer further. The softness | flexibility can further be improved by mix | blending a plasticizer with the said acrylic resin composition. Thereby, the bending whitening resistance of the film shape | molded by the said acrylic resin improves more. Furthermore, since the rotational property of the bank at the time of calendar processing and the elongation of the acrylic resin at the time of melting are improved, a film having a good surface shape and good appearance can be provided.
[0055]
  The blending amount of the plasticizer is in the range of 1 to 50 parts by weight and 5 to 30 parts by weight with respect to 100 parts by weight in total of the copolymer A and the copolymer B in the acrylic resin composition. It is preferable to be within the range. By making the amount of the plasticizer within the above range, it is possible to obtain the effect of improving the flexibility by blending the plasticizer, and bloom resistance under high temperature and high pressure conditions of the film molded by the acrylic resin composition・ Bleedability can be improved.
[0056]
  As the plasticizer, it is more preferable to use a polyester plasticizer or an acrylic plasticizer with no doubt of environmental hormones. Thereby, it is possible to provide an acrylic resin composition with higher safety and less influence on the environment.
[0057]
  Examples of the polyester plasticizer include polymers of dibasic acids such as adipic acid, mazeline acid, sebacic acid, and phthalic acid, and glycols, glycerols, and monobasic acids. Specific examples include dibutyl phthalate, dipentyl phthalate, dioctyl phthalate, diisodecyl phthalate, butyl lauryl phthalate, ditridecyl phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, and the like. These are one or a combination of two or more. Can be used.
[0058]
  The polyester plasticizer is particularly preferably an adipic acid-based polyester represented by the following general formula (1). Since the adipic acid-based polyester represented by the following general formula (1) has good compatibility with the acrylic resin composition, the flexibility of the acrylic resin composition can be effectively improved.
[0059]
[Chemical5]

[0060]
(In the formula, R represents an n-octyl group, isononyl group, and 2-ethylhexyl group, and n represents an integer of 2 to 4).
[0061]
  The said acrylic plasticizer means what is used as a plasticizer among acrylic compounds. Moreover, an acrylic plasticizer can be used 1 type or in combination of 2 or more types.
[0062]
  The acrylic resin composition contains the above-described copolymer A and copolymer B, and further contains a plasticizer as necessary. Compounding agents such as stabilizers, lubricants, processing aids, impact resistance aids, foaming agents, fillers, colorants, ultraviolet absorbers, antibacterial agents, matting agents and the like can be blended.
[0063]
  The film of the present invention is obtained by calendering the acrylic resin composition. The calendar format used for the calendar processing is not particularly limited, and examples thereof include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape.
[0064]
  Since the acrylic resin composition has good flexibility and calendar workability as described above, the acrylic resin composition has a soft texture like a polyvinyl chloride resin by calendering, and is smooth and homogeneous. It is possible to form a film that is highly transparent and does not whiten when bent. Furthermore, the film does not generate dioxin during incineration, has appropriate flexibility, elongation, elasticity, strength, and has good workability during secondary processing, printability, and suitability for adhesion and adhesion It is.
[0065]
  Moreover, it is preferable that the temperature of the said acrylic resin composition in a calendar process exists in the range of 150 to 200 degreeC, and it is more preferable that it exists in the range of 170 to 195 degreeC. By setting the temperature of the acrylic resin composition in the calendering within the above range, the kneading efficiency of the acrylic resin composition and the rotation of the bank during the calendering can be improved. For this reason, a homogeneous film can be obtained and calendering can be performed using a calendering equipment for polyvinyl chloride resin, which generally has an upper limit temperature of 200 ° C.
[0066]
  That is, the above film satisfies the properties required for a substitute for a film made of polyvinyl chloride resin. For indoor and outdoor plywood, steel sheets, wallpaper and other decorative materials, stickers, marking films, adhesive tapes, signboard decorations It is very useful for printing base films and their use as top protective films.
[0067]
【Example】
  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
[0068]
  [Example 1] As copolymer A (methyl methacrylate / alkyl acrylate copolymer), 90 parts by weight of Parapet HR-A (trade name) manufactured by Kuraray Co., Ltd., and copolymer B (methyl methacrylate. As an alkyl acrylate / styrene copolymer), an acrylic resin composition (MFR (230 ° C., 37.3 N) = 1) having 10 parts by weight of METABRENE W341 (trade name) manufactured by Mitsubishi Rayon Co., Ltd., 1 part by weight of antioxidant (Antifox 10 (trade name) manufactured by NOF Corporation), 0.4 part by weight of stabilizer (0.2 parts by weight of Ca-ST (trade name) manufactured by Sakai Chemical Co., Ltd.) Zn-ST (trade name) 0.2 parts by weight), 1 part by weight of lubricant (LS-5 (trade name) by Asahi Denka Co., Ltd.), 0.5 parts by weight of UV absorber (Sumitomo Chemical ( Biosoap 583 (trade name)) and van After melt-kneaded at mixer, through each roll calendering equipment body, thickness to form a film of 0.08 mm. At this time, the temperature of each roll of the calendering equipment body was set so that the temperature (material temperature) of the acrylic resin composition comprising the above components was within the range of 150 ° C to 200 ° C. At that time, the state of calendering and the film obtained by calendering were evaluated by the following evaluation methods and standards. The evaluation of the calendar processability and the evaluation of the film were used to determine the possibility of the acrylic resin composition as an alternative material for the polyvinyl chloride resin.
[0069]
  [Evaluation Method / Evaluation Criteria] The calendar processability of the acrylic resin composition and the evaluation method and criteria of the obtained film will be described below.
[0070]
  [Lubricity (Adhesiveness of Resin to Roll)] A resin that did not stick to the roll and could be peeled off and formed into a film was evaluated as ○, and a film that was sticky and difficult to peel was evaluated as ×.
[0071]
  [Bank Rotation] The resin bank between the calendar rolls evaluated as ○ when the bank rotates beautifully according to the rotation of the roll, and evaluated as × when the bank does not rotate cleanly and slips or irregularities occur. .
[0072]
  [Plate-out to roll] When the plasticizer or additive was ejected from the molten resin to the calendar roll (plate-out), the roll surface was cloudy, and the case where the plate-out did not occur was evaluated as x.
[0073]
  [Stretchability of melted film (between calender roll and take-off roll)] When the film is stretched 100 to 300%, the whole film becomes uniform and no necking occurs, and the film thickness is not uniform. The thing which pulled down because the tension | tensile_strength of molten resin was too low, and the thing which necking generate | occur | produced were evaluated as x.
[0074]
  [Film surface properties] Visually determine whether the surface of the film is smooth and free of flow marks, evaluate that the surface is smooth and good, and that the surface is rough or has flow marks. X was evaluated.
[0075]
  [Crack of film during winding] A film that was broken during film winding was evaluated as x, and a film that could be wound without cracking was evaluated as ◯.
[0076]
  [Calendar workability] The calendar workability was comprehensively judged, and those having good calendar workability were evaluated as “good”, and those having poor calendar workability were evaluated as “poor”. Specifically, the above-mentioned slipperiness, bank rotation, roll-out plate out, melt film stretchability, film surface property, and film cracking during winding are all evaluated as ○. Was evaluated as good, and any one of these evaluated as x was evaluated as having poor calendar workability.
[0077]
  [Folding resistance of the film] When the film obtained by calendering was bent 180 °, the whitening of the film was judged by visual observation. The film that did not whiten was evaluated as ◯, and the film that was whitened was evaluated as x.
[0078]
  [Blood resistance / bleeding resistance of film] After the obtained film is left in a high-temperature and high-humidity tank at a temperature of 70 ° C. and a humidity of 95% RH for one week, it is judged visually whether or not the film has bloom or bleed. The case where these did not occur was evaluated as ◯, and the case where they occurred was evaluated as ×.
[0079]
  Example 2 The acrylic resin composition of Example 1 is a blend of copolymer A and copolymer B (MFR (230 ° C., 37.3N) = 4), Sumipex HT03Y manufactured by Sumitomo Chemical Co., Ltd. (Trade name) 100 parts by weight, and the same procedure as in Example 1 except that 5 parts by weight of Polycizer W-1040-EL (trade name) manufactured by Dainippon Ink & Chemicals, Inc. was further blended as a polyester plasticizer. went.
[0080]
  [Example 3] Sumipex HT50Y manufactured by Sumitomo Chemical Co., Ltd., which is a blend of copolymer A and copolymer B (MFR (230 ° C., 37.3 N) = 14). (Trade name) 100 parts by weight, and in the same manner as in Example 1 except that 20 parts by weight of Polysizer W-2300-EL (trade name) manufactured by Dainippon Ink & Chemicals, Inc. was further blended as a polyester plasticizer. went.
[0081]
  [Example 4] The acrylic resin composition of Example 1 was prepared by using 90 parts by weight of Sumipex LG2 (trade name) manufactured by Sumitomo Chemical Co., Ltd. as copolymer A, and Metabrene W341 manufactured by Mitsubishi Rayon Co., Ltd. as copolymer B. (Trade name) An acrylic resin composition (MFR (230 ° C., 37.3 N) = 14) blended with 10 parts by weight, and a polyester plasticizer Polysizer W-4010 manufactured by Dainippon Ink & Chemicals, Inc. -Performed in the same manner as in Example 1 except that 50 parts by weight of EL (trade name) was further blended.
[0082]
  [Example 5] Sumipex HT53X manufactured by Sumitomo Chemical Co., Ltd., which is a blend of copolymer A and copolymer B (MFR (230 ° C., 37.3 N) = 4). (Trade name) 100 parts by weight, and the same procedure as in Example 1 except that 10 parts by weight of ARUFON UP-1000 (trade name) manufactured by Toa Gosei Co., Ltd. was further blended as an acrylic plasticizer.
[0083]
  [Example 6] A parapet manufactured by Kuraray Co., Ltd. which is a blend of copolymer A and copolymer B (MFR (230 ° C, 37.3N) = 1.2). It was carried out in the same manner as in Example 1 except that 100 parts by weight of GR-F (trade name) and 50 parts by weight of ARUFON UP1000 (trade name) manufactured by Toa Gosei Co., Ltd. were further blended as an acrylic plasticizer.
[0084]
  [Comparative Example 1] 100 parts by weight of Sumipex MH (trade name) manufactured by Sumitomo Chemical Co., Ltd., which is copolymer A (MFR (230 ° C., 37.3 N) = 2), is used as the acrylic resin composition of Example 1. This was carried out in the same manner as in Example 1 except that a sheet for evaluating bloom resistance and bleed resistance was produced at 200 ° C. by electrothermal pressing.
[0085]
  Since Comparative Examples 2 to 4 could not form a sheet by calendering, the sheet was produced by an electric heating press at 200 ° C. as in Comparative Example 1.
[0086]
  [Comparative Example 2] Sumitex HT20Y manufactured by Sumitomo Chemical Co., Ltd., which is a blend of copolymer A and copolymer B (MFR (230 ° C., 37.3 N) = 24). (Product name) The same procedure as in Example 1 was performed except that the amount was 100 parts by weight.
[0087]
  [Comparative Example 3] 100 parts by weight of Sumipex LG21 (trade name) manufactured by Sumitomo Chemical Co., Ltd., which is copolymer A (MFR (230 ° C., 37.3 N) = 21), is used as the acrylic resin composition of Example 1. Except that, the same procedure as in Example 1 was performed.
[0088]
  [Comparative Example 4] The acrylic resin composition of Example 1 was manufactured by Sumitomo Chemical Co., Ltd. 90 Sumipex LG21 (trade name) as copolymer A, and Mitsubishi Rayon Co., Ltd. as copolymer B. An acrylic resin composition (MFR (230 ° C., 37.3 N) = 19) composed of 10 parts by weight of Metablen W341 (trade name), and a polyester plasticizer, Polycizer W-1040 manufactured by Dainippon Ink & Chemicals, Inc. The same procedure as in Example 1 was performed except that 10 parts by weight of EL (trade name) was further used.
[0089]
  The results evaluated for the examples and comparative examples are shown in Table 1 and Table 2, respectively.
[0090]
[Table 1]

[0091]
[Table 2]

[0092]
  As shown in Table 1, each of the acrylic resin compositions of Examples 1 to 6 consisting of copolymer A and copolymer B and having a melt flow rate (230 ° C., 37.3 N) of 15 or less is used. The calendar workability was good. Moreover, the film obtained by calendering the acrylic resin composition of Examples 1-6 was excellent in bending whitening resistance and bloom-bleed resistance. That is, the acrylic resin compositions of Examples 1 to 6 are all suitable for calendering, and can be used to mold a film with good quality suitable as an alternative to a polyvinyl chloride resin film by calendering. I understand.
[0093]
  On the other hand, as shown in Table 2, the acrylic resin compositions of Comparative Examples 1 to 4 were all poor in calendar processability and could not be formed into a film by calendar processing.
[0094]
  From Comparative Example 1, it can be seen that even when the melt flow rate is 15 or less, when the acrylic resin composition is composed only of the copolymer A, cracking occurs at the time of winding, so that the film cannot be molded by calendering. Furthermore, from Comparative Examples 2 to 4, is the acrylic resin composition having a melt flow rate greater than 15 composed of only copolymer A or composed of copolymer A and copolymer B? Regardless, it can be seen that the film cannot be formed by calendering.
[0095]
  Moreover, since the said acrylic resin composition can be calendered within the range of the temperature of 150 to 200 degreeC, the calendering equipment for polyvinyl chloride resin can be used as it is.
[0096]
  From the above, the acrylic resin composition comprising the copolymer A and the copolymer B and having a melt flow rate of 15 or less has good calendering properties, and a film of good quality can be obtained by calendering. I understand that. That is, the acrylic resin composition having the above structure is a suitable material as an alternative material for the polyvinyl chloride resin, and is required as an alternative to the polyvinyl chloride resin film by calendering the acrylic resin composition. It is possible to provide a film satisfying the properties.
[0097]
【The invention's effect】
  As described above, the acrylic resin composition of the present invention comprises the copolymer A composed of methyl methacrylate and alkyl acrylate, and the copolymer B composed of methyl methacrylate, alkyl acrylate and styrene. The melt flow rate (230 ° C., 37.3 N) is 15 or less.
[0098]
  Therefore, it has excellent appearance as a substitute material for polyvinyl chloride, which can be formed into a thin film with good appearance and reduced whitening when bent by calendering using conventional calendering equipment for polyvinyl chloride resin. There exists an effect that the acrylic resin composition which has can be provided.
[0099]
  More preferably, the acrylic resin composition further comprises 50 parts by weight or less of a plasticizer with respect to 100 parts by weight as a total of the copolymer A and the copolymer B.
[0100]
  Thereby, since the softness | flexibility of an acrylic resin composition improves further, the texture can be closely approached to a polyvinyl chloride resin. Therefore, there is an effect that it is possible to provide an acrylic resin composition capable of forming a film having a better appearance.
[0101]
  The plasticizer is more preferably a polyester plasticizer or an acrylic plasticizer.
[0102]
  Since both the polyester plasticizer and the acrylic plasticizer are plasticizers that are not suspected of being an environmental hormone, there is an effect that the influence on the environment due to the blending of the plasticizer can be surely prevented.
[0103]
  Further, the plasticizer for the polyester is represented by the general formula (1).
[0104]
[Chemical6]

[0105]
(Wherein, R represents an n-octyl group, isononyl group, 2-ethylhexyl group, and n represents an integer of 2 to 4).
[0106]
  The manufacturing method of the film of this invention is a structure including the process of carrying out the calendar molding of the said acrylic resin composition.
[0107]
  Therefore, it is possible to provide a film useful as an alternative to a polyvinyl chloride resin film, which has appropriate flexibility, elongation, elasticity, strength, processability, printability, and good suitability for adhesion and adhesion. Play.

Claims (4)

It consists of copolymer A consisting of methyl methacrylate and alkyl acrylate, and copolymer B consisting of methyl methacrylate, alkyl acrylate and styrene, and has a melt flow rate (230 ° C., 37.3 N) of 15 And
Further comprising 50 parts by weight or less of a plasticizer with respect to 100 parts by weight as a total of the copolymer A and the copolymer B,
The plasticizer is a polyester plasticizer,
The polyester plasticizer is represented by the general formula (1).

(In the formula, R represents n-octyl group, isononyl group, 2-ethylhexyl group, and n represents an integer of 2-4)
An acrylic resin composition characterized by being an adipic acid-based polyester represented by the formula:   A film obtained by calendering the acrylic resin composition according to claim 1. In the method for producing a film using the acrylic resin composition,
Including a step of calender molding the acrylic resin composition, and
The acrylic resin composition comprises a copolymer A composed of methyl methacrylate and an alkyl acrylate, and a copolymer B composed of methyl methacrylate, an alkyl acrylate and styrene, and a melt flow rate (230 ° C. 37.3N) is 15 or less,
The acrylic resin composition further includes 50 parts by weight or less of a plasticizer with respect to a total of 100 parts by weight of the copolymer A and the copolymer B,
The plasticizer is a polyester plasticizer ,
The polyester plasticizer is represented by the general formula (1).

(In the formula, R represents n-octyl group, isononyl group, 2-ethylhexyl group, and n represents an integer of 2-4)
A method for producing a film, which is an adipic acid-based polyester represented by the formula : The method for producing a film according to claim 3 , wherein the temperature of the acrylic resin composition in the calender molding step is in the range of 150 ° C to 200 ° C.