JP3941300B2 - Olefin resin composition and thermoplastic resin composition containing the same - Google Patents

Description

【０００８】
但し、ヒドロキシフェニル環上のヒドロキシル基に対してオルト位にある置換基Ｒ₁ は炭素原子数１〜１０の直鎖状、分岐状もしくは環状の脂肪族炭化水素基、アルコキシ基、又は芳香族炭化水素基を表し、またＲ₂ 、Ｒ₃ の一方は、α，β−不飽和カルボン酸エステル基を有する基、他方は水素、炭素原子数１〜１０の直鎖状、分岐状、もしくは環状の脂肪族炭化水素基、アルコキシ基、もしくは芳香族炭化水素基、又はハロゲン原子を表す。なおＲ₂ の結合部位はヒドロキシル基に対してメタ位又はパラ位であり、Ｒ₃ の位置は特に限定されない。
また、本発明の要旨は、成分（Ａ）のオレフィン系樹脂がプロピレン系樹脂である上記のオレフィン系樹脂組成物、及び成分（Ａ）〜（Ｃ）を含有する混合物をラジカル発生剤の存在下で溶融混練することにより得られる上述のオレフィン系樹脂組成物にも存している。
【０００９】
更に、本発明のもう一つの要旨は、熱可塑性樹脂と上記のオレフィン系樹脂組成物とを含有する熱可塑性樹脂組成物であって、熱可塑性樹脂とオレフィン系樹脂組成物との合計量を１００重量％とした時に、オレフィン系樹脂組成物の含有量が０．１〜５０重量％である熱可塑性樹脂組成物、及びヒンダードアミン単位の含有量が０. ０１〜５重量％となるようにヒンダードアミン系光安定剤を含有するこの熱可塑性樹脂組成物にも存している。
また、本発明の別の要旨は、上記の熱可塑性樹脂組成物からなるフィルム又はシートにも存している。
【００１０】
【発明の実施の形態】
以下、本発明を詳細に説明する。
（１）オレフィン系樹脂組成物の各成分
成分（Ａ）：オレフィン系樹脂
本発明の組成物の原料として用いるオレフィン系樹脂は、炭素原子数２〜１２、好ましくは２〜８のα−オレフィンの単独重合体又はそれらを主成分とする共重合体である。これらのα−オレフィンの具体例としては、エチレン、プロピレン、１−ブテン、１−ヘキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、３，３−ジメチル−１−ブテン、４，４−ジメチル−１−ペンテン、３−メチル−１−ヘキセン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、５−メチル−１−ヘキセン、アリルシクロペンタン、アリルシクロヘキサン、アリルベンゼン、３−シクロヘキシル−１−ブテン、ビニルシクロプロパン、ビニルシクロヘキサン、２−ビニルビシクロ［２．２．１］−ヘプタンなどを挙げることができる。これらのα−オレフィンは１種類を用いても、また、２種以上を用いても差し支えない。
これらのα−オレフィンのうちで好ましいものとしては、エチレン、プロピレン、１−ブテン、１−ヘキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、３−メチル−１−ヘキセン等であり、エチレン、プロピレン、１−ブテン、３−メチル−１−ブテン又は４−メチル−１−ペンテンが更に好ましい。
【００１１】
上記のようなオレフィン系樹脂の中でもプロピレン系樹脂、即ちプロピレン単独重合体及びプロピレンを主体とする他のα−オレフィンとの共重合体が特に好ましく、具体的にはアイソタクティックポリプロピレン、シンジオタクティックポリプロピレン、プロピレン−エチレン共重合体、プロピレン−ブテン共重合体等が挙げられる。また、これらのプロピレン系樹脂を混合して用いることもできる。
【００１２】
成分（Ｂ）：特定の置換基を特定の位置に有するベンゾトリアゾール系の紫外線吸収基を有するα，β−不飽和カルボン酸エステル
成分（Ｂ）の特定の置換基を特定の位置に有するベンゾトリアゾール系の紫外線吸収基を含有するα，β−不飽和カルボン酸エステルは、下記の式（１）により表される２−（２’−ヒドロキシフェニル）ベンゾトリアゾール誘導体である。
【００１３】
【化３】

【００１４】
上記の式（１）において置換基Ｒ₁ は炭素原子数１〜１０の直鎖状、分岐状もしくは環状の脂肪族炭化水素基、アルコキシ基、又は芳香族炭化水素基を表す。このＲ₁ のヒドロキシフェニル環に結合する炭素の構造は基本的にはどのような構造でもよいが、好ましくは２級炭素であり、更に好ましくは３級炭素、最も好ましいのは４級炭素である。好ましい構造例としては、ｔ−ブチル基、ｔ−アミル基、１，１，３，３−テトラメチルブチル基、α，α−ジメチルベンジル基等が挙げられる。なお、Ｒ₁ の結合部位はヒドロキシル基に対してオルト位であることが必要である。Ｒ₁ をオルト位に有していない場合は、本発明の特有の効果は得られない。
【００１５】
またＲ₂ 及びＲ₃ はいずれか一方がα，β−不飽和カルボン酸エステル基を有する置換基であり、他方は水素、炭素原子数１〜１０の直鎖状、分岐状もしくは環状の脂肪族炭化水素基、アルコキシ基、もしくは芳香族炭化水素基、又はハロゲン原子である。Ｒ₂ の結合部位は、ヒドロキシル基に対してメタ位、パラ位のいずれでもよく、また置換基Ｒ₃ の位置も特に限定はされない。
α，β−不飽和カルボン酸残基の代表的な例としては例えば、アクリル酸、メタクリル酸等のモノカルボン酸の残基やマレイン酸、フマル酸等のジカルボン酸の残基が挙げられ、中でもアクリル酸又はメタクリル酸の残基が好ましい。なおジカルボン酸の残基の場合、そのエステル結合の数はモノエステル及びジエステルのどちらでもよい。
このような このような特定の置換基を特定の位置に有するベンゾトリアゾール系の紫外線吸収基を含有するα，β−不飽和カルボン酸エステルの具体例としては、次のような構造式で表されるものが挙げられる。
【００１６】
【化４】

【００１７】
【化５】

【００１８】
成分（Ｃ）：芳香族ビニル化合物
本発明の組成物において成分（Ｃ）として用いられる芳香族ビニル化合物としては、例えば、スチレン、α−メチルスチレン、α−メトキシスチレン、メチルスチレン、ジメチルスチレン、２，４，６−トリメチルスチレン、クロロスチレン、ジクロロスチレン、ブロモスチレン、ニトロスチレン、クロロメチルスチレン、シアノスチレン、ｔ−ブチルスチレン、ビニルナフタレン等が挙げられ、中でもスチレン、α−メチルスチレン、メチルスチレンが好ましい。これらの芳香族ビニル化合物は単独で又は２種以上を併用して用いることができる。
【００１９】
（２）オレフィン系樹脂組成物の組成
本発明のオレフィン系樹脂組成物の原料となる混合物中の各成分の配合量としては、成分（Ａ）のオレフィン系樹脂の使用量を１００重量部としたとき、成分（Ｂ）の特定の置換基を特定の位置に有するベンゾトリアゾール系の紫外線吸収基を含有するα，β−不飽和カルボン酸エステルの配合量は、０．１〜２０重量部、好ましくは０．５〜１５重量部の範囲であり、成分（Ｃ）の芳香族ビニル化合物の配合量は、０．１〜５０重量部、好ましくは０．５〜３０重量部の範囲である。
【００２０】
成分（Ｂ）の配合量が０．１重量部未満の場合は、添加の目的である紫外線吸収性が不足する。一方、配合量が２０重量部を超えても、量の増加に見合う効果の向上は見られず、逆にこれらがブリード等の原因となる可能性が大きくなり好ましくない。
成分（Ｃ）の配合量が０．１重量部未満では、成分（Ｂ）の成分（Ａ）との反応性が低下してしまい、未反応体の残留が起きやすくなり、得られた組成物等を成形加工する際に、ロールが汚れたり、ブリードアウトによって成形品の外観が悪化することがある。一方、成分（Ｃ）を５０重量部を超えて使用すると、オレフィン系樹脂の柔軟性が阻害されたり、得られる組成物の透明性が悪化することがあるので、やはり好ましくない。
なお、成分（Ｂ）の特定の置換基を特定の位置に有するベンゾトリアゾール系の紫外線吸収基を含有するα，β−不飽和カルボン酸エステルの配合量に対する成分（Ｃ）の芳香族ビニル化合物の配合量の比率（重量比）は、１／９９〜９９／１の範囲、好ましくは１０／９０〜９０／１０の範囲である。
【００２１】
（３）ラジカル発生剤
上述の各成分を含有する混合物をラジカル反応条件下で反応させて本発明のオレフィン系樹脂組成物を得ることができる。このラジカル反応を行わせるために用いるラジカル発生剤としては、例えばｔ−ブチルヒドロパーオキシド、クメンヒドロパーオキシド、２，５−ジメチルヘキサン−２，５−ジヒドロパーオキシド、ｔ−ブチルパーオキシベンゾエート、ベンゾイルパーオキシド、ジクミルパーオキシド、１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、ジブチルパーオキシド、メチルエチルケトンパーオキシド、過酸化カリウム、過酸化水素等の有機及び無機過酸化物、２，２′−アゾビスイソブチロニトリル、２，２′−アゾビス（イソブチルアミド）ジハライド、２，２′−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］、アゾジ−ｔ−ブタン等のアゾ化合物、及びジクミル等の炭素ラジカル発生剤等が例示できる。これらのラジカル発生剤は、（Ｂ）成分の特定の置換基を特定の位置に有するベンゾトリアゾール系の紫外線吸収基を有するα，β−不飽和カルボン酸エステルの種類や反応条件に応じて適宜選択すればよく、また２種以上を併用してもよい。このラジカル発生剤は有機溶剤等に溶解して用いることもできる。
ラジカル発生剤の使用量としては、成分（Ａ）のオレフィン系樹脂１００重量部に対して０．０１〜３０重量部、好ましくは０．０５〜１０重量部の範囲とするのがよい。ラジカル発生剤の使用量が０．０１重量部未満では、成分（Ｂ）の成分（Ａ）への付加量が低下してしまい、未反応体の残留が起きやすくなり好ましくない。一方、３０重量部を超えて使用すると、例えばポリプロピレン系樹脂では主鎖切断による劣化が進行し、ポリエチレン系樹脂ではゲル化が著しくなるなど、オレフィン系樹脂が本来有する特性を著しく損なうため好ましくない。
【００２２】
（４）オレフィン系樹脂組成物の調製
本発明のオレフィン系樹脂組成物は、上述の各成分をラジカル反応条件下で反応させて調製されるが、その調製に際しては、溶融混練法、溶液法、及び懸濁法等の方法が特に限定することなく使用できるが、溶融混練法を用いるのが好ましい。
溶融混練法に用いる混練機としては、ラボプラストミル、一軸または二軸押出機等の押出機、横型二軸多円板装置、横型二軸表面更新機等の横型二軸撹拌機、ダブルヘリカルリボン撹拌機等の縦型二軸撹拌機等が挙げられる。
溶融混練の温度は、ラジカル発生剤からラジカルが生成し、かつ用いるオレフィン系樹脂が溶融状態になる温度であれば特に限定されないが、オレフィン系樹脂の劣化防止を考慮すれば３００℃以下が好ましい。混練時間は、０．１〜１０分、好ましくは０．５〜５分の範囲とするのがよい。
【００２３】
各配合成分及びラジカル発生剤の添加方法としては、予め成分（Ａ）のオレフィン系樹脂とその他の成分を一括混練してドライブレンドとする方法、成分（Ｂ）、（Ｃ）又はラジカル発生剤のいずれかと成分（Ａ）のオレフィン系樹脂とをドライブレンドしておいて、これを溶融混練する途中で残る成分を添加する方法、あるいは溶融状態となった成分（Ａ）のオレフィン系樹脂にその他の配合成分とラジカル発生剤とを添加混合する方法等がある。
【００２４】
なお、混練時の粘度調節や反応効率向上を目的としてキシレン等の有機溶剤を、例えばオレフィン系樹脂１００重量部に対して０．１〜５重量部程度添加してもよい。また未反応物や添加した溶剤等を除去するために、前記の混練機や撹拌機の内部を１０〜１５００Ｐａ程度の減圧にしてもよい。
また溶液法においては、沸点が１００℃以上のハロゲン置換または非置換の芳香族炭化水素系の溶剤、例えばクロロベンゼン、キシレン等に各成分を溶解し、通常８０〜１２０℃程度の温度で、２〜８時間程度反応させる方法を用いることができる。
【００２５】
（５）熱可塑性樹脂組成物
上記のようにして調製されるオレフィン系樹脂組成物は、その紫外線吸収能を活かして、他の熱可塑性樹脂に添加して組成物として用いることができる。
使用できる熱可塑性樹脂としては、オレフィン系樹脂、スチレン系樹脂、塩化ビニル系樹脂等が挙げられる。中でも、オレフィン系樹脂が好ましく、特にポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−ブテン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体が好ましい。
熱可塑性樹脂組成物中の本発明のオレフィン系樹脂組成物の含有量は、熱可塑性樹脂と本発明のオレフィン系樹脂組成物との合計量を１００重量％とした時に、０．１〜５０重量％であるのが好ましく、０．５〜３０重量％であるのが更に好ましい。
【００２６】
本発明の熱可塑性樹脂組成物には、ヒンダードアミン系光安定剤を含有させることが好ましい。熱可塑性樹脂組成物中におけるヒンダードアミン系光安定剤の好ましい含有量は、含まれるヒンダードアミン単位の量が、０．０１〜５重量％、より好ましくは０．０２〜４重量％となる範囲である。
またこの熱可塑性樹脂組成物には、上記の成分に加えて、目的に応じて各種の添加剤、例えば酸化防止剤、中和剤、増核剤、滑剤、流動性改良剤、離型剤、充填剤、無機フィラー、着色剤等を、本発明の効果を損なわない範囲で添加してもよい。
【００２７】
上記の熱可塑性樹脂組成物は、熱可塑性樹脂の成形に通常用いられる成形方法、即ち押出成形法、射出成形法、圧縮成形法、カレンダー加工法などにより所望の形状に成形できる。また、この組成物をＴダイ成形、インフレーション成形等して得られるフィルム又はシートは、耐候性、紫外線吸収性、表面外観が良好であるので、農業用フィルム、建材、包装袋等の長期間の耐候性が要求される用途に用いるのに特に好適である。
【００２８】
【実施例】
以下、本発明を実施例を用いて更に具体的に説明するが、本発明はその要旨を越えない限り以下の実施例によって限定されるものではない。
なお、以下の実施例・比較例においては「部、％」は特記するものを除き重量基準の値を示す。
（１）オレフィン系樹脂組成物の製造
＜製造例１＞
成分（Ａ）の粉末状ポリプロピレン（日本ポリケム株式会社製、商品名「ＴＡ８」、ＭＦＲ＝０．８ｇ／１０分）を１００重量部、成分（Ｂ）として下記式（３）で表される特定の置換基を特定の位置に有するベンゾトリアゾール系の紫外線吸収基を含有するα，β−不飽和カルボン酸エステル（大塚化学株式会社製、「ｔ−Ｂｕ ＲＵＶＡ」）５重量部、及び成分（Ｃ）の芳香族ビニル単量体としてスチレン５重量部を、ラジカル発生剤のα, α'-ビス( ｔ- ブチルパーオキシ) ジイソプロピルベンゼン（日本油脂株式会社製、商品名「パーブチルＰ」、以下「パーブチルＰ」と略記することがある）１重量部とともにドライブレンドした後、二軸混練機（株式会社日本製鋼所製、型番「ＴＥＸ−３０」）にて、１８０℃、回転数２５０ｒｐｍ、吐出量１０ｋｇ／時間の条件で混練し、本発明のオレフィン系樹脂組成物を製造した 。
【００２９】
【化６】

【００３０】
＜製造例２＞
製造例１において、成分（Ｃ）のスチレンを添加しなかったこと以外は同様にして本発明の範囲外のオレフィン系樹脂組成物を製造した。
【００３１】
＜製造例３＞
製造例１において成分（Ｂ）の特定の置換基を特定の位置に含有するベンゾトリアゾール系のα，β−不飽和カルボン酸エステル（大塚化学株式会社製、「ｔ−Ｂｕ ＲＵＶＡ」）に代えて、下式（７）で示される構造のフェノール性水酸基のオルト位に置換基がない反応性紫外線吸収剤（大塚化学株式会社製「ＲＵＶＡ９３」）を５重量部用いたこと以外は同様にして本発明の範囲外のオレフィン系樹脂組成物を製造した。
【００３２】
【化７】

【００３３】
＜製造例４＞
成分（Ａ）として粉末状ポリプロピレン（日本ポリケム株式会社製、商品名「ＴＡ３」、ＭＦＲ＝１０ｇ／１０分）を１００重量部を用い、成分（Ｂ）に代えて、下式（８）で示されるフェノール性水酸基に対してオルト位に嵩高い置換基を有する２−（２’−ヒドロキシフェニル）ベンゾトリアゾール誘導体ではあるが、反応性基であるα, β−不飽和カルボン酸エステル基を有していない紫外線吸収剤（チバスペシャリティーケミカルズ株式会社製、「チヌビン２３４」）５重量部とをドライブレンドした後、製造例１と同様にして混練を行って本発明の範囲外のオレフィン系樹脂組成物を製造した。
【００３４】
【化８】

【００３５】
（２）熱可塑性樹脂組成物及びフィルム／シート
＜実施例１＞
ポリプロピレン樹脂（日本ポリケム株式会社製、商品名「ＦＸ３」、ＭＦＲ＝７ｇ／１０分）８１重量％、製造例１のオレフィン系樹脂組成物１５重量％、及びエチレン／４−アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン共重合体（日本ポリケム株式会社製「ＫＯＫＡＮＯＸ ＸＪ１００Ｈ」（商品名）、４−アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン含量５重量％（ヒンダードアミン単位として３．３重量％）、ＭＦＲ３ｇ／１０分（１９０℃，荷重２１．１８Ｎ（２．１６ｋｇｆ）））４重量％をドライブレンドした後、株式会社プラコー製３５φＴダイ小型フィルム成形機を用いて、成形温度２６０℃、押出機の回転数９０ｒｐｍ、ロール温度３０℃、引取速度７．５ｍ／分の条件で成形して厚さ８０μｍのフィルムを作成した。
【００３６】
＜比較例１＞
上記実施例１において、製造例１のオレフィン系樹脂組成物に代えて製造例２のオレフィン系樹脂組成物を使用したこと以外は同様にしてフィルムを作成した。
＜比較例２＞
上記実施例１において、製造例１のオレフィン系樹脂組成物に代えて製造例３のオレフィン系樹脂組成物を使用したこと以外は同様にしてフィルムを作成した。
＜比較例３＞
上記実施例１において、製造例１のオレフィン系樹脂組成物に代えて製造例４のオレフィン系樹脂組成物を使用したこと以外は同様にしてフィルムを作成した。
【００３７】
（３）評価方法
＜オレフィン系樹脂組成物の評価＞
上記の製造例において得られたオレフィン系樹脂組成物中の、成分（Ｂ）の紫外線吸収能を有するα，β−不飽和カルボン酸エステル（以下「変性剤」と記す）の付加量及び該組成物のメルトフローレート（ＭＦＲ）を以下のようにして測定した。結果を表１に示す。
【００３８】
ｉ）変性剤付加量
変性剤（反応性紫外線吸収剤）のオレフィン系樹脂への付加量は、得られたオレフィン系樹脂組成物０．３ｇを１４０℃で２０ミリリットルのキシレンに溶解し、このキシレン溶液をテトラヒドロフラン２００ミリリットル中に注加して得られる沈殿物（精製樹脂）をプレス成形して得られたフィルムの赤外線吸収スペクトルにおける１７２５ｃｍ^-1付近のカルボニル基の吸収から、別途作成した検量線を用いて求めた。
ii）メルトフローレート（ＭＦＲ）
ＪＩＳ Ｋ７２１０に従って、株式会社東洋精機製作所製メルトインデクサを用いて温度２３０℃、荷重２１．１８Ｎ（２．１６ｋｇｆ）にて測定した。なお、ＭＦＲが１００ｇ／１０分を越えるものに関しては、１８０℃においてＭＦＲ測定を行い、別途作成した換算式を用いて２３０℃における値に換算した。
【００３９】
＜熱可塑性樹脂組成物の評価＞
上記の実施例及び比較例で作成したフィルムについて、以下の方法により成形性、耐候性、紫外線吸収性、及び成形品外観を評価した。結果を表２にまとめて示す。
ｉ）成形性（ロール汚れ）
Ｔダイ小型フィルム成形機によりフィルムの製造を１０分間行った後の、巻き取りロールの汚れの付着状況を観察し、下記の基準により評価した。
○：ロール汚れが認められない
△：ロール汚れが若干認められる
×：ロール汚れが著しい
ii）耐候性
得られた成形フィルムをＭＤ方向に１４．５ｃｍ×３．５ｃｍの大きさに切り出し、スガ試験機株式会社製「デューパネル光コントロールウェザーメーター」（ブラックパネル温度：６３℃、紫外線照射：８時間、蒸気噴霧：４時間）中で暴露試験を行い、フィルム表面に微細なヒビが発生したこと又はフィルムを折り曲げた際にクラックが発生することが目視により確認できる状態に至るまでの紫外線照射時間を測定した。
iii ）紫外線吸収能保持率
得られたフィルムの、３４０ｎｍ付近で最大吸収を示す波長における紫外線吸光度を株式会社島津製作所製「紫外可視分光光度計ＵＶ−２２００」を用いて測定し、下記指標により評価した。
【００４０】
【数１】
１００×（耐候性試験２００時間経過後の吸光度）／（初期吸光度）
【００４１】
iv）成形品外観（透明性とブリード特性）
得られた成形フィルムのヘーズを、初期及び４０℃熱風オーブン中に２週間放置した後にＪＩＳ Ｋ７１０５に従って測定した。また、４０℃熱風オーブン中に２週間放置した後の粉ふきの状態も観察した。
粉ふき○：粉ふき認められず。
粉ふき×：粉ふき顕著。
【００４２】
【表１】
表１

【００４３】
【表２】
表２

【００４４】
（４）結果の評価
上記の実施例及び比較例から次の点が明らかである。
・成分（Ｃ）を含まない場合（製造例２→比較例１）では、反応性を有する紫外線吸収剤を使用しても、その反応が進まず、付加量が少ないため、対応する実施例（実施例１）と比べて、紫外線吸収能の保持率は不十分で、またロール汚れや粉ふきも著しい。
・本発明の特定構造の成分（Ｂ）とは異なる構造の反応性紫外線吸収剤を用いた場合（製造例３→比較例２）は、ロール汚れや粉ふき等は良好であるが、耐候性が本発明のものと比べて劣っている。
・反応性の基を持たない紫外線吸収剤を用いた場合（製造例４→比較例３）は、ロール汚れや粉ふきが劣り、また経時的なヘーズの悪化が起こる。
【００４５】
【発明の効果】
上述した通り、本発明のオレフィン系樹脂組成物、これに基づく熱可塑性樹脂組成物、及びフィルム又はシートはブリードやプレートアウト( ロール汚れ) がなく、また耐候性（紫外線吸収能の保持率）や透明性も良好であるので、特に耐候性が要求される農業用、建材用、包装用に好適に使用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention reacts an olefin resin with an α, β-unsaturated carboxylic acid ester containing a benzotriazole-based ultraviolet absorbing group having a specific substituent at a specific position and an aromatic vinyl compound under radical reaction conditions. It is related with the olefin resin composition containing the modified olefin polymer obtained by making it carry out.
The present invention also contains the above-mentioned olefin resin composition, has good moldability, weather resistance, ultraviolet absorption, and surface appearance, and requires long-term weather resistance of agricultural films, building materials, packaging bags and the like. In particular, the present invention relates to a thermoplastic resin composition that is particularly useful in applications.
[0002]
[Prior art]
As materials for exterior building materials, building material decorative sheets, agricultural films, food packaging films, etc., vinyl chloride resins that have a balance of performance such as transparency, secondary processability, whitening resistance, and weather resistance have been conventionally used. Widely used. However, vinyl chloride resins generate hydrogen chloride and other gases during incineration, which may cause damage to furnace materials depending on the incinerator. Examples of using olefin resins as an alternative are It can be seen.
Olefin-based resins are low in cost, excellent in mechanical strength, heat resistance, oil resistance, etc., and also have excellent appearance such as transparency, so they are molded by various molding methods, such as films, fibers, molded products, etc. In fields where long-term weather resistance is required, such as for building materials, agricultural sheets or films, in addition to olefinic resins, various types such as UV absorbers and light stabilizers are used. The additives are used.
[0003]
However, the molecular weight of such additives is relatively small compared to the base olefin resin, and many of them have insufficient compatibility with the resin. There were problems such as insufficient weather resistance improvement effects, processing equipment due to bleed and plate-out, particularly defective product appearance due to contamination of the roll and transfer of the contamination.
In particular, in applications such as decorative sheets for building materials that are assumed to be used for a long period of time, a large amount of an ultraviolet absorber is blended for the purpose of protecting the printed layer of the base, so it is important to solve these problems.
[0004]
In order to solve this problem, in Japanese Patent Laid-Open No. 63-227575, an ultraviolet absorber having a polymerizable unsaturated group in the molecule is added during the production of the resin to form a copolymer, whereby the resin skeleton absorbs ultraviolet rays. A method of introducing an agent has been proposed. However, this method is effective for acrylic resins and methacrylic resins. However, in the case of an olefin resin produced using a so-called coordination anion catalyst such as a Ziegler-Natta catalyst, the ultraviolet absorber itself is used. Since it acts as a catalyst poison for such a catalyst, there is a problem that the polymerization reaction does not proceed, and it is difficult to apply this method.
Therefore, for olefin resins, a method has been proposed in which an ultraviolet absorber having an unsaturated group in the molecule is melt kneaded with a polypropylene resin under radical reaction conditions and the ultraviolet absorber is introduced into the resin (special feature). (Kaihei 8-208765). However, the weather resistance may be insufficient even by this method, especially when blended with a hindered amine light stabilizer often used in polyolefin resin, not only the improvement effect is not seen for the plate-out, There was also a problem that the effect of improving the weather resistance was insufficient, and in particular, the ultraviolet absorption ability significantly decreased with time due to ultraviolet irradiation.
[0005]
[Problems to be solved by the invention]
The present invention provides an olefin-based resin composition excellent in moldability, bleed, plate-out (roll dirt), weather resistance, UV-absorbing property against UV-ray stability, and transparency without the above-mentioned problems. An object of the present invention is to provide a thermoplastic resin composition having good weather resistance based on the above.
[0006]
[Means for Solving the Problems]
The gist of the present invention resides in an olefin-based resin composition obtained by reacting a mixture containing the following components (A) to (C) under radical reaction conditions.
(A) 100 parts by weight of an olefin resin (B) 0.1 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester containing a 2- (2′-hydroxyphenyl) benzotriazole group represented by the chemical formula (1) (C) Aromatic vinyl compound 0.1-50 parts by weight
[Chemical 2]

[0008]
However, the substituent R _{1 in the} ortho position with respect to the hydroxyl group on the hydroxyphenyl ring is a linear, branched or cyclic aliphatic hydrocarbon group, alkoxy group or aromatic carbon atom having 1 to 10 carbon atoms. Represents a hydrogen group, and one of R ₂ and R ₃ is a group having an α, β-unsaturated carboxylic acid ester group, and the other is hydrogen, a linear, branched or cyclic group having 1 to 10 carbon atoms. It represents an aliphatic hydrocarbon group, an alkoxy group, an aromatic hydrocarbon group, or a halogen atom. The binding site of R ₂ is meta or para to the hydroxyl group, and the position of R ₃ is not particularly limited.
The gist of the present invention is that the olefin resin of component (A) is a propylene resin, and a mixture containing components (A) to (C) in the presence of a radical generator. It exists also in the above-mentioned olefin resin composition obtained by melt-kneading.
[0009]
Furthermore, another gist of the present invention is a thermoplastic resin composition containing a thermoplastic resin and the olefin resin composition, wherein the total amount of the thermoplastic resin and the olefin resin composition is 100. A thermoplastic resin composition having an olefin resin composition content of 0.1 to 50% by weight and a hindered amine system so that the content of hindered amine units is 0.01 to 5% by weight. This thermoplastic resin composition containing a light stabilizer is also present.
Another gist of the present invention resides in a film or sheet comprising the thermoplastic resin composition.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
(1) Each component of the olefin resin composition
Component (A): Olefin resin The olefin resin used as a raw material for the composition of the present invention is a homopolymer of an α-olefin having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, or a main polymer thereof. It is a copolymer as a component. Specific examples of these α-olefins include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3, 3 -Dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene , Allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2.2.1] -heptane, and the like. These α-olefins may be used alone or in combination of two or more.
Among these α-olefins, preferred are ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3 -Methyl-1-hexene and the like, more preferably ethylene, propylene, 1-butene, 3-methyl-1-butene or 4-methyl-1-pentene.
[0011]
Among the olefin resins as described above, propylene resins, that is, propylene homopolymers and copolymers with other α-olefins mainly composed of propylene are particularly preferable. Specifically, isotactic polypropylene and syndiotactic are used. Examples include polypropylene, propylene-ethylene copolymer, and propylene-butene copolymer. Moreover, these propylene-type resins can also be mixed and used.
[0012]
Component (B): α, β-unsaturated carboxylic acid ester having a benzotriazole-based UV-absorbing group having a specific substituent at a specific position A specific substituent of component (B) at a specific position The α, β-unsaturated carboxylic acid ester containing a benzotriazole-based UV-absorbing group is a 2- (2′-hydroxyphenyl) benzotriazole derivative represented by the following formula (1).
[0013]
[Chemical 3]

[0014]
In the above formula (1), the substituent R ₁ represents a linear, branched or cyclic aliphatic hydrocarbon group, alkoxy group or aromatic hydrocarbon group having 1 to 10 carbon atoms. The structure of the carbon bonded to the hydroxyphenyl ring of R ₁ may be basically any structure, but is preferably a secondary carbon, more preferably a tertiary carbon, and most preferably a quaternary carbon. . Examples of preferred structures include t-butyl group, t-amyl group, 1,1,3,3-tetramethylbutyl group, α, α-dimethylbenzyl group and the like. The binding site of R ₁ needs to be in the ortho position with respect to the hydroxyl group. When R ₁ is not in the ortho position, the specific effect of the present invention cannot be obtained.
[0015]
One of R ₂ and R ₃ is a substituent having an α, β-unsaturated carboxylic acid ester group, and the other is hydrogen, a linear, branched or cyclic aliphatic group having 1 to 10 carbon atoms. It is a hydrocarbon group, an alkoxy group, an aromatic hydrocarbon group, or a halogen atom. The bonding site of R ₂ may be in the meta position or para position with respect to the hydroxyl group, and the position of the substituent R ₃ is not particularly limited.
Representative examples of α, β-unsaturated carboxylic acid residues include residues of monocarboxylic acids such as acrylic acid and methacrylic acid, and residues of dicarboxylic acids such as maleic acid and fumaric acid. Acrylic acid or methacrylic acid residues are preferred. In the case of a dicarboxylic acid residue, the number of ester bonds may be either a monoester or a diester.
Specific examples of such α, β-unsaturated carboxylic acid esters containing a benzotriazole-based UV-absorbing group having a specific substituent at a specific position are represented by the following structural formula. Can be mentioned.
[0016]
[Formula 4]

[0017]
[Chemical formula 5]

[0018]
Component (C): aromatic vinyl compound Examples of the aromatic vinyl compound used as the component (C) in the composition of the present invention include styrene, α-methylstyrene, α-methoxystyrene, methylstyrene, Examples include dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, and vinylnaphthalene. Among them, styrene, α-methylstyrene Methylstyrene is preferred. These aromatic vinyl compounds can be used alone or in combination of two or more.
[0019]
(2) Composition of Olefin Resin Composition As a blending amount of each component in the mixture that is a raw material of the olefin resin composition of the present invention, the amount of the olefin resin used as the component (A) is 100 parts by weight. The blending amount of the α, β-unsaturated carboxylic acid ester containing a benzotriazole-based UV-absorbing group having a specific substituent of the component (B) at a specific position is preferably 0.1 to 20 parts by weight, Is in the range of 0.5 to 15 parts by weight, and the compounding amount of the aromatic vinyl compound of component (C) is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight.
[0020]
When the compounding amount of the component (B) is less than 0.1 parts by weight, the ultraviolet absorptivity as the purpose of addition is insufficient. On the other hand, even if the blending amount exceeds 20 parts by weight, the improvement in the effect commensurate with the increase in the amount is not seen, and conversely, the possibility that these cause bleed or the like increases is not preferable.
When the blending amount of component (C) is less than 0.1 parts by weight, the reactivity of component (B) with component (A) decreases, and unreacted substances are likely to remain, resulting in a composition obtained. When molding such as, the roll may become dirty or the appearance of the molded product may deteriorate due to bleeding out. On the other hand, if the component (C) is used in an amount exceeding 50 parts by weight, the flexibility of the olefin-based resin may be hindered or the transparency of the resulting composition may be deteriorated.
In addition, the aromatic vinyl compound of the component (C) with respect to the blending amount of the α, β-unsaturated carboxylic acid ester containing a benzotriazole-based ultraviolet absorbing group having a specific substituent of the component (B) at a specific position. The ratio (weight ratio) of the blending amounts is in the range of 1/99 to 99/1, preferably in the range of 10/90 to 90/10.
[0021]
(3) Radical generator The olefin resin composition of the present invention can be obtained by reacting a mixture containing the above-described components under radical reaction conditions. Examples of the radical generator used for causing the radical reaction include t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, t-butyl peroxybenzoate, Organic and inorganic peroxides such as benzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, 2'-azobisisobutyronitrile, 2,2'-azobis (isobutyramide) dihalide, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], azodi-t-butane Examples of azo compounds such as dioctyl and carbon radical generators such as dicumyl It can be. These radical generators are appropriately selected according to the type of α, β-unsaturated carboxylic acid ester having a benzotriazole-based ultraviolet absorbing group having a specific substituent of the component (B) at a specific position and reaction conditions. What is necessary is just to use 2 types or more together. This radical generator can also be used by dissolving in an organic solvent or the like.
The amount of the radical generator used is 0.01 to 30 parts by weight, preferably 0.05 to 10 parts by weight based on 100 parts by weight of the olefin resin of component (A). If the amount of radical generator used is less than 0.01 parts by weight, the amount of component (B) added to component (A) decreases, and unreacted substances are likely to remain, which is not preferable. On the other hand, if the amount exceeds 30 parts by weight, for example, deterioration due to main chain cleavage proceeds in polypropylene resins, and gelation becomes remarkable in polyethylene resins, which is not preferable because the properties inherent in olefin resins are significantly impaired.
[0022]
(4) Preparation of olefin-based resin composition The olefin-based resin composition of the present invention is prepared by reacting the above-described components under radical reaction conditions. In the preparation, a melt-kneading method, a solution method, In addition, a method such as a suspension method can be used without any particular limitation, but a melt-kneading method is preferably used.
As a kneading machine used for the melt kneading method, a laboplast mill, an extruder such as a uniaxial or biaxial extruder, a horizontal biaxial multi-disk apparatus, a horizontal biaxial agitator such as a horizontal biaxial surface renewal machine, a double helical ribbon Examples thereof include a vertical biaxial stirrer such as a stirrer.
The temperature of the melt kneading is not particularly limited as long as radicals are generated from the radical generator and the olefin resin used is in a molten state, but is preferably 300 ° C. or less in consideration of prevention of deterioration of the olefin resin. The kneading time is 0.1 to 10 minutes, preferably 0.5 to 5 minutes.
[0023]
As a method for adding each compounding component and the radical generator, a method in which the olefin resin of component (A) and other components are kneaded in advance to form a dry blend, component (B), (C) or radical generator Either one of the components (A) and the olefin resin of component (A) is dry blended, and the component remaining during the melt kneading is added, or other components are added to the component (A) olefin resin in the molten state. There is a method of adding and mixing a blending component and a radical generator.
[0024]
For example, an organic solvent such as xylene may be added in an amount of about 0.1 to 5 parts by weight with respect to 100 parts by weight of the olefin resin for the purpose of adjusting the viscosity during kneading and improving the reaction efficiency. In order to remove unreacted substances, added solvent, and the like, the inside of the kneader or stirrer may be depressurized to about 10 to 1500 Pa.
In the solution method, each component is dissolved in a halogen-substituted or unsubstituted aromatic hydrocarbon solvent having a boiling point of 100 ° C. or higher, for example, chlorobenzene, xylene, etc., and usually at a temperature of about 80 to 120 ° C., A method of reacting for about 8 hours can be used.
[0025]
(5) Thermoplastic resin composition The olefin-based resin composition prepared as described above can be used as a composition by adding to other thermoplastic resins by making use of its ultraviolet absorbing ability.
Examples of the thermoplastic resin that can be used include olefin resins, styrene resins, and vinyl chloride resins. Of these, olefin-based resins are preferable, and polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer are particularly preferable.
The content of the olefinic resin composition of the present invention in the thermoplastic resin composition is 0.1 to 50% by weight when the total amount of the thermoplastic resin and the olefinic resin composition of the present invention is 100% by weight. %, And more preferably 0.5 to 30% by weight.
[0026]
The thermoplastic resin composition of the present invention preferably contains a hindered amine light stabilizer. The preferred content of the hindered amine light stabilizer in the thermoplastic resin composition is such that the amount of hindered amine units contained is 0.01 to 5% by weight, more preferably 0.02 to 4% by weight.
In addition to the above components, the thermoplastic resin composition includes various additives depending on the purpose, such as antioxidants, neutralizers, nucleating agents, lubricants, fluidity improvers, mold release agents, You may add a filler, an inorganic filler, a coloring agent, etc. in the range which does not impair the effect of this invention.
[0027]
The thermoplastic resin composition can be molded into a desired shape by a molding method usually used for molding a thermoplastic resin, that is, an extrusion molding method, an injection molding method, a compression molding method, a calendering method, or the like. In addition, a film or sheet obtained by T-die molding, inflation molding or the like of this composition has good weather resistance, ultraviolet absorption, and surface appearance, so that it can be used for a long time such as agricultural films, building materials, packaging bags, etc. It is particularly suitable for use in applications requiring weather resistance.
[0028]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the following examples and comparative examples, “parts,%” indicates a value based on weight, unless otherwise specified.
(1) Production of Olefin Resin Composition <Production Example 1>
Component (A) powdered polypropylene (trade name “TA8”, manufactured by Nippon Polychem Co., Ltd., MFR = 0.8 g / 10 min) is 100 parts by weight, and the component (B) is represented by the following formula (3) 5 parts by weight of an α, β-unsaturated carboxylic acid ester (“t-Bu RUVA” manufactured by Otsuka Chemical Co., Ltd.) containing a benzotriazole-based ultraviolet absorbing group having a substituent of ) 5 parts by weight of styrene as an aromatic vinyl monomer, α, α'-bis (t-butylperoxy) diisopropylbenzene (trade name “Perbutyl P”, manufactured by NOF Corporation), hereinafter “ After dry blending together with 1 part by weight (sometimes abbreviated as “perbutyl P”), 180 ° C., 250 rpm rotation speed, discharge using a twin-screw kneader (manufactured by Nippon Steel Works, model number “TEX-30”) The olefin resin composition of the present invention was produced by kneading under the condition of an output amount of 10 kg / hour.
[0029]
[Chemical 6]

[0030]
<Production Example 2>
In Production Example 1, an olefin resin composition outside the scope of the present invention was produced in the same manner except that the component (C) styrene was not added.
[0031]
<Production Example 3>
Instead of the benzotriazole-based α, β-unsaturated carboxylic acid ester (manufactured by Otsuka Chemical Co., Ltd., “t-Bu RUVA”) containing the specific substituent of component (B) in a specific position in Production Example 1 The present invention is the same except that 5 parts by weight of a reactive ultraviolet absorber having no substituent at the ortho position of the phenolic hydroxyl group having the structure represented by the following formula (7) (“RUVA93” manufactured by Otsuka Chemical Co., Ltd.) is used. An olefin resin composition outside the scope of the invention was produced.
[0032]
[Chemical 7]

[0033]
<Production Example 4>
100 parts by weight of powdery polypropylene (manufactured by Nippon Polychem Co., Ltd., trade name “TA3”, MFR = 10 g / 10 min) is used as component (A) instead of component (B). 2- (2′-hydroxyphenyl) benzotriazole derivative having a bulky substituent at the ortho position with respect to the phenolic hydroxyl group, but having a reactive α, β-unsaturated carboxylic acid ester group Olefin resin composition outside the scope of the present invention was dry blended with 5 parts by weight of a non-ultraviolet absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., “Tinubin 234”) and then kneaded in the same manner as in Production Example 1. The thing was manufactured.
[0034]
[Chemical 8]

[0035]
(2) Thermoplastic resin composition and film / sheet <Example 1>
Polypropylene resin (manufactured by Nippon Polychem Co., Ltd., trade name “FX3”, MFR = 7 g / 10 min) 81% by weight, olefinic resin composition of Production Example 1 15% by weight, and ethylene-4-acryloyloxy-2,2 , 6,6-tetramethylpiperidine copolymer ("KOKANOX XJ100H" (trade name) manufactured by Nippon Polychem Co., Ltd.), 4-acryloyloxy-2,2,6,6-tetramethylpiperidine content 5% by weight (as hindered amine units) 3.3 wt%), MFR 3 g / 10 min (190 ° C., load 21.18 N (2.16 kgf))) 4 wt% is dry blended and then molded using a Placo 35φT die small film molding machine. Molded under conditions of temperature 260 ° C, extruder rotation speed 90rpm, roll temperature 30 ° C, take-up speed 7.5m / min You create a 80μm of film.
[0036]
<Comparative Example 1>
A film was prepared in the same manner as in Example 1 except that the olefin resin composition of Production Example 2 was used instead of the olefin resin composition of Production Example 1.
<Comparative example 2>
A film was prepared in the same manner as in Example 1 except that the olefin resin composition of Production Example 3 was used instead of the olefin resin composition of Production Example 1.
<Comparative Example 3>
A film was prepared in the same manner as in Example 1 except that the olefin resin composition of Production Example 4 was used instead of the olefin resin composition of Production Example 1.
[0037]
(3) Evaluation method <Evaluation of olefin resin composition>
Addition amount and composition of α, β-unsaturated carboxylic acid ester (hereinafter referred to as “modifier”) having ultraviolet absorbing ability of component (B) in the olefin resin composition obtained in the above production example and the composition The melt flow rate (MFR) of the product was measured as follows. The results are shown in Table 1.
[0038]
i) Amount of modifying agent added The amount of modifying agent (reactive ultraviolet absorber) added to the olefin resin was obtained by dissolving 0.3 g of the obtained olefin resin composition in 20 ml of xylene at 140 ° C. A separately prepared calibration curve was obtained from absorption of a carbonyl group near 1725 cm ⁻¹ in an infrared absorption spectrum of a film obtained by press-molding a precipitate (purified resin) obtained by pouring the solution into 200 ml of tetrahydrofuran. Obtained using.
ii) Melt flow rate (MFR)
In accordance with JIS K7210, measurement was performed at a temperature of 230 ° C. and a load of 21.18 N (2.16 kgf) using a melt indexer manufactured by Toyo Seiki Seisakusho. In addition, about what MFR exceeds 100 g / 10min, MFR measurement was performed at 180 degreeC and it converted into the value in 230 degreeC using the conversion formula created separately.
[0039]
<Evaluation of thermoplastic resin composition>
About the film created by said Example and comparative example, the moldability, the weather resistance, the ultraviolet absorptivity, and the molded article external appearance were evaluated with the following method. The results are summarized in Table 2.
i) Formability (roll dirt)
After the film was produced for 10 minutes by a T-die small film molding machine, the state of dirt on the take-up roll was observed and evaluated according to the following criteria.
○: Roll stain is not recognized Δ: Roll stain is slightly observed ×: Roll stain is remarkable
ii) Weather resistance The obtained molded film was cut into a size of 14.5 cm × 3.5 cm in the MD direction, “Due Panel Light Control Weather Meter” manufactured by Suga Test Instruments Co., Ltd. (black panel temperature: 63 ° C., UV irradiation) : 8 hours, vapor spraying: 4 hours), UV exposure until it is possible to visually confirm that fine cracks have occurred on the film surface or that cracks have occurred when the film is folded The irradiation time was measured.
iii) UV absorption capacity retention rate The UV absorbance of the obtained film at a wavelength exhibiting the maximum absorption at around 340 nm was measured using “UV-visible spectrophotometer UV-2200” manufactured by Shimadzu Corporation, and evaluated according to the following index. did.
[0040]
[Expression 1]
100 × (absorbance after 200 hours of weather resistance test) / (initial absorbance)
[0041]
iv) Molded product appearance (transparency and bleed characteristics)
The haze of the obtained molded film was measured in accordance with JIS K7105 after being left in an initial stage and a 40 ° C. hot air oven for 2 weeks. Further, the state of dusting after being left in a hot air oven at 40 ° C. for 2 weeks was also observed.
Powder cleaning ○: Powder cleaning is not recognized.
Powder wiping ×: powder wiping remarkable.
[0042]
[Table 1]
Table 1

[0043]
[Table 2]
Table 2

[0044]
(4) Evaluation of results The following points are clear from the above Examples and Comparative Examples.
In the case where the component (C) is not included (Production Example 2 → Comparative Example 1), even if a reactive ultraviolet absorber is used, the reaction does not proceed and the added amount is small. Compared with Example 1), the retention rate of ultraviolet absorbing ability is insufficient, and roll dirt and dusting are also remarkable.
-When a reactive ultraviolet absorber having a structure different from the component (B) having a specific structure of the present invention is used (Production Example 3 → Comparative Example 2), the roll dirt and dusting are good, but the weather resistance is good. Is inferior to that of the present invention.
When using an ultraviolet absorber having no reactive group (Production Example 4 → Comparative Example 3), roll dirt and dusting are inferior, and haze deterioration with time occurs.
[0045]
【The invention's effect】
As described above, the olefin-based resin composition of the present invention, the thermoplastic resin composition based thereon, and the film or sheet are free from bleeding and plate-out (roll dirt), and weather resistance (retention rate of ultraviolet absorption ability) Since transparency is also good, it can be suitably used for agriculture, building materials, and packaging, which require weather resistance.

Claims (6)

An olefin resin composition obtained by reacting a mixture containing the following components (A) to (C) under radical reaction conditions.
(A) 100 parts by weight of an olefin resin (B) 0.1 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester containing a 2- (2′-hydroxyphenyl) benzotriazole group represented by the chemical formula (1) (C) Aromatic vinyl compound 0.1-50 parts by weight

However, the substituent R _{1 in the} ortho position with respect to the hydroxyl group on the hydroxyphenyl ring is a linear, branched or cyclic aliphatic hydrocarbon group, alkoxy group or aromatic carbon atom having 1 to 10 carbon atoms. Represents a hydrogen group, and one of R ₂ and R ₃ is a group having an α, β-unsaturated carboxylic acid ester group, and the other is hydrogen, a linear, branched or cyclic group having 1 to 10 carbon atoms. It represents an aliphatic hydrocarbon group, an alkoxy group, an aromatic hydrocarbon group, or a halogen atom. The binding site of R ₂ is meta or para to the hydroxyl group, and the position of R ₃ is not particularly limited. The olefin resin composition according to claim 1, wherein the olefin resin of component (A) is a propylene resin. The olefin resin composition according to claim 1 or 2, which is obtained by melt-kneading a mixture containing components (A) to (C) in the presence of a radical generator. A thermoplastic resin composition comprising a thermoplastic resin and the olefin resin composition according to any one of claims 1 to 3, wherein the total amount of the thermoplastic resin and the olefin resin composition is 100. A thermoplastic resin composition in which the content of the olefin-based resin composition is 0.1 to 50% by weight when the weight is set. The thermoplastic resin composition according to claim 4, further comprising a hindered amine light stabilizer so that the content of the hindered amine unit is 0.01 to 5% by weight. A film or sheet comprising the thermoplastic resin composition according to claim 4 or 5.