JP4011655B2 - Compatibilizer and method for producing the same - Google Patents

Description

（式中、Ｅは、置換基を有していてもよいアルキレン基、置換基を有していてもよいシクロアルキレン基または置換基を有していてもよいアリーレン基を示し、Ｒ¹，Ｒ²，Ｒ³およびＲ⁴は、同一又は異なって、水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を示す。）
前記式で表されるビスオキサゾリン化合物において、Ｅのアルキレン基としては、例えば、Ｃ_1-10アルキレン基（例えば、メチレン、エチレン、トリメチレン、プロピレン、テトラメチレン、ペンタメチレン、ヘキサメチレン基など）などが挙げられる。シクロアルキレン基には、例えば、Ｃ_5-10シクロアルキレン基（例えば、１，３−シクロペンチレン、１，３−シクロヘキシレン、１，４−シクロヘキシレン基など）などが含まれる。アリーレン基には、Ｃ_6-12アリーレン基（例えば、１，３−フェニレン、１，４−フェニレン、１，５−ナフチレン、２，５−ナフチレン基など）などが含まれる。
前記アルキレン基、シクロアルキレン基やアリーレン基は置換基を有していてもよい。このような置換基としては、例えば、ハロゲン原子（例えば、フッ素、塩素、臭素原子など）、アルキル基（例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチルなどの炭素数１〜６程度のアルキル基など）、アルコキシ基（例えば、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシなどの炭素数１〜６程度のアルコキシ基など）などが挙げられる。
好ましいＥには、置換基を有していてもよいアリール基、特に置換基を有していてもよいフェニレン基（例えば、１，３−フェニレン基または１，４−フェニレン基など）が含まれる。
【００２５】
前記式において、Ｒ¹，Ｒ²，Ｒ³およびＲ⁴で表されるアルキル基には、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチル、ペンチル、ヘキシル基などのＣ_1-10アルキル基が例示される。好ましいアルキル基は、炭素数１〜６程度の低級アルキル基、特に炭素数１〜４の低級アルキル基（例えば、特にメチル基、エチル基、プロピル基、イソプロピル基など）である。
Ｒ¹，Ｒ²，Ｒ³およびＲ⁴で表されるアリール基にはフェニル、１−ナフチル、２−ナフチル基などが含まれる。
前記アルキル基やアリール基は、置換基を有していてもよい。置換基を有するアルキル基には、例えば、ジクロロメチル、トリクロロメチル、トリフルオロメチル、２，２，２−トリクロロエチル、２，２，２−トリフルオロエチル、ペンタフルオロエチルなどのハロゲン化Ｃ_1-4アルキル基などが含まれる。置換基を有するアリール基には、例えば、２−クロロフェニル、３−クロロフェニル、４−クロロフェニル、２，４−ジクロロフェニル、３，５−ジクロロフェニル基などのハロゲン原子を有するフェニル基、２−メチルフェニル、３−メチルフェニル、４−メチルフェニル、２，４−ジメチルフェニル、３，５−ジメチルフェニル、４−エチルフェニル基などのＣ_1-4アルキル−フェニル基、２−メトキシフェニル、３−メトキシフェニル、４−メトキシフェニル、２，４−ジメトキシフェニル、３，５−ジメトキシフェニル、４−エトキシフェニル基などのＣ_1-4アルコキシ−フェニル基などが挙げられる。
特に好ましいビスオキサゾリン化合物は下記式で表すことができる。
【００２６】
【化７】

（式中、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴は、同一又は異なって、水素原子又はＣ_1-4アルキル基を示す。）
特に、Ｒ¹及びＲ²の少くとも一方（特にＲ²）は水素原子、Ｒ³及びＲ⁴の少くとも一方（特にＲ⁴）は水素原子であるのが好ましい。さらに好ましくは、Ｒ¹，Ｒ²，Ｒ³およびＲ⁴はいずれも水素原子である。
【００２７】
前記式で表されるビスオキサゾリン化合物のうち好ましい化合物の具体例としては、例えば、１，６−ビス（１，３−オキサゾリ−２−イル）ヘキサン、１，８−ビス（１，３−オキサゾリ−２−イル）オクタン、１，１０−ビス（１，３−オキサゾリ−２−イル）デカン、１，３−ビス（１，３−オキサゾリ−２−イル）シクロヘキサン、１，４−ビス（１，３−オキサゾリ−２−イル）シクロヘキサン、２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）、２，２′−（１，４−フェニレン）−ビス（２−オキサゾリン）、２，２′−（１，２−フェニレン）−ビス（２−オキサゾリン）、２，２′−（１，３−フェニレン）−ビス（４−メチル−２−オキサゾリン）、２，２′−（１，４−フェニレン）−ビス（４−メチル−２−オキサゾリン）、２，２′−（１，２−フェニレン）−ビス（５−メチル−２−オキサゾリン）、２，２′−（１，３−フェニレン）−ビス（５−メチル−２−オキサゾリン）、２，２′−（１，４−フェニレン）−ビス（５−メチル−２−オキサゾリン）、２，２′−（１，３−フェニレン）−ビス（４−メチルフェニル−２−オキサゾリン）、２，２′−（１，４−フェニレン）−ビス（４−メチルフェニル−２−オキサゾリン）、２，２′−（１，３−フェニレン）−ビス（４−クロロフェニル−２−オキサゾリン）、２，２′−（１，４−フェニレン）−ビス（４−クロロフェニル−２−オキサゾリン）などが挙げられる。
ビスオキサゾリン化合物は一種または二種以上使用できる。
なお、ビスオキサゾリン化合物は、慣用の方法、例えば、脂肪酸又はそのメチルエステルとエタノールアミンとを触媒の存在下で反応させ、複素５員環化合物を生成させる方法（「プラスチック エージ」，114頁，Mar．1995）に準じて、前記式においてＥに対応するジカルボン酸又はその低級アルキルエステルとエタノールアミン又はその誘導体とを反応させ、複素５員環化合物を生成させることにより得ることができる。
【００２８】
カップリング剤としては、加水分解性有機基を有する有機金属化合物、例えば、シランカップリング剤、チタネートカップリング剤、アルミネートカップリング剤などが挙げられる。好ましいカップリング剤には、シランカップリング剤などの有機ケイ素化合物、例えば、ハロゲン原子、ヒドロキシル基、メルカプト基、カルボキシル基、アミノ基、エポキシ基、イソシアネート基、ビニル基、（メタ）アクリロイル基から選択された少くとも一種の官能基と、加水分解性基（アルコキシ基）やシリル基とを有するケイ素化合物が含まれる。有機ケイ素化合物（特にシランカップリング剤）の好ましい反応性基は、ハロゲン原子、ヒドロキシル基、メルカプト基、カルボキシル基、アミノ基、エポキシ基、イソシアネート基（特に、ヒドロキシル基、メルカプト基、カルボキシル基、アミノ基、エポキシ基、イソシアネート基）である。シランカップリング剤は、単独又は二種以上の反応性基を有していてもよい。
【００２９】
ハロゲン原子には、塩素、臭素、ヨウ素原子などが含まれ、エポキシ基は、炭化水素基の不飽和結合（例えば、シクロペンテニル基、シクロへキセニル基などのシクロアルケニル基の不飽和二重結合）の酸化により生成するエポキシ環や、グリシジル基のエポキシ環で構成されていてもよい。アミノ基には１又は２個の低級Ｃ_1-4アルキル基（例えば、メチル、エチル、プロピル、イソプロピル、ブチル基など）が置換していてもよく、（メタ）アクリロイル基は（メタ）アクリロイルオキシ基で構成してもよい。
シランカップリング剤のアルコキシ基には、例えば、メトキシ、エトキシ、フロポキシ、イソプロポキシ、ブトキシ、イソブトキシ、ｓ−ブトキシ、ｔ−ブトキシ基などのＣ_1-4アルコキシ基が含まれる。好ましいアルコキシ基は加水分解性アルコキシ基（特にメトキシ基又はエトキシ基）である。
シランカップリング剤において前記反応性基の数は１〜３（特に１又は２）程度であり、アルコキシ基の数は１〜３（特に２又は３）程度である。
シランカップリング剤の具体例としては、例えば、ハロゲン含有シランカップリング剤（２−クロロエチルトリメトキシシラン，２−クロロエチルトリエトキシシラン，３−クロロプロピルトリメトキシシラン，３−クロロプロピルトリエトキシシランなど）、ヒドロキシル基含有シランカップリング剤（２−ヒドロキシエチルトリメトキシシラン、２−ヒドロキシエチルトリエトキシシラン、３−ヒドロキシプロピルトリメトキシシラン、３−ヒドロキシプロピルトリエトキシシランなど）、メルカプト基含有シランカップリング剤（２−メルカプトエチルトリメトキシシラン、２−メルカプトエチルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシランなど）、カルボキシル基含有シランカップリング剤（カルボキシメチルトリメトキシシラン，カルボキシメチルトリエトキシシラン，２−カルボキシエチルトリメトキシシラン，２−カルボキシエチルトリエトキシシラン，３−カルボキシプロピルトリメトキシシラン，３−カルボキシプロピルトリエトキシシラン）、アミノ基含有シランカップリング剤（２−アミノエチルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、２−［Ｎ−（２−アミノエチル）アミノ］エチルトリメトキシシラン、３−［Ｎ−（２−アミノエチル）アミノ］プロピルトリメトキシシラン、３−（２−アミノエチル）アミノ］プロピルトリエトキシシランなど）、エポキシ基含有シランカップリング剤［２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、３−（３，４−エポキシシクロヘキシル）プロピルトリメトキシシラン、２−グリシジルオキシエチルトリメトキシシラン、２−グリシジルオキシエチルトリエトキシシラン、３−グリシジルオキシプロピルトリメトキシシラン、３−グリシジルオキシプロピルトリエトキシシランなど］、イソシアネート基含有シランカップリング剤（２−イソシアネートエチルトリメトキシシラン，２−イソシアネートエチルトリエトキシシラン，３−イソシアネートプロピルトリメトキシシラン，３−イソシアネートプロピルトリエトキシシランなど）、ビニル基含有シランカップリング剤（ビニルトリメトキシシラン、ビニルトリエトキシシランなど）、（メタ）アクリロイル基含有シランカップリング剤（２−メタクリロイルオキシエチルトリメトキシシラン、２−メタクリロイルオキシエチルトリエトキシシラン、２−アクリロイルオキシエチルトリメトキシシラン、３−メタクリロイルオキシプロピルトリメトキシシラン、３−メタクリロイルオキシプロピルトリエトキシシラン、３−アクリロイルオキシプロピルトリメトキシシランなど）などが例示できる。これらのシランカップリング剤は単独で又は二種以上組合わせて使用できる。
【００３０】
また、担体が金属である場合、少なくとも金属と配位結合可能な官能基を有する化合物（配位性化合物）としては、例えば、メルカプトアルコール（メルカプトエタノールなど）、硫黄又は窒素含有化合物（システィン、ヒスチジンなど）、メルカプト基含有シランカップリング剤（メルカプトプロピルトリメトキシシランなど）などが例示できる。例えば、メルカプトエタノールの場合、メルカプト基が前記例示の金属（金，白金など）と配位結合を形成するので、残余のヒドロキシル基を２官能性化合物（Ｃ）との反応に利用できる。
【００３１】
［２官能性化合物（Ｃ）］
２官能性化合物（Ｃ）としては、２つの官能基のうち少なくとも１つの官能基が前記担体（Ａ）又は表面処理剤（Ｂ）の反応性基に対して反応性を有する種々の化合物が使用でき、２官能性化合物（Ｃ）の官能基は担体（Ａ）又は表面処理剤（Ｂ）の反応性基の種類に応じて選択できる。前記２官能性化合物（Ｃ）の官能基の種類は同一であってもよく異なっていてもよい。
２官能性化合物（Ｃ）の官能基（ｃ）としては、担体（Ａ）又は表面処理剤（Ｂ）の反応性基（ａ）に応じて、例えば、前記の項で例示の担体（Ａ）の反応性基（ａ１）と表面処理剤（Ｂ）との組み合わせと同様にして選択できる。なお、２官能性化合物（Ｃ）としては、通常、カップリング剤や配位性化合物以外の化合物が使用される。
【００３２】
好ましい２官能性化合物（Ｃ）は、極性基（例えば、エステル結合，アミド結合などの分極した結合，ヒドロキシル基，カルボキシル基，酸無水物基，アミノ基、アミド基などの極性基）を有する極性基含有化合物が含まれる。好ましい２官能性化合物（Ｃ）には、ヒドロキシル基，カルボキシル基，エポキシ基，アミノ基に対して反応性の官能基を有する化合物（例えば、カルボキシル基又は酸無水物基含有化合物，アミノ基含有化合物，オキサゾリン基含有化合物）、特にアミノ基含有化合物（ジアミン）やオキサゾリン基含有化合物（ビスオキサゾリン化合物）が含まれる。
【００３３】
［疎水性化合物（Ｄ）］
疎水性化合物（Ｄ）は、前記担体（Ａ）の反応性基又は２官能性化合物（Ｃ）の官能基に対して反応性を有するとともに疎水性鎖を有している。すなわち、疎水性化合物（Ｄ）は、通常、活性水素原子を含む反応性基を有しており、この反応性基は、前記担体（Ａ）の反応性基及び／又は２官能性化合物（Ｃ）の官能基に対して反応可能である。疎水性鎖は化合物（Ｄ）の側鎖を構成してもよいが、通常、主鎖を構成している。
【００３４】
前記疎水性化合物（Ｄ）は疎水性（主）鎖を有する限り、低分子量化合物であってもよく高分子量化合物（ポリマー）であってもよい。なお、高分子量化合物は、分子量が比較的小さなオリゴマー領域の重合体も含む。疎水性化合物の主鎖は、通常、主に炭化水素基、好ましくは脂肪族炭化水素基で構成される場合が多い。炭化水素基は飽和炭化水素基（例えば、メチレン、エチレン、プロピレン単位など）であってもよく、不飽和炭化水素基（例えば、ブタジエン単位など）であってもよい。主鎖に占める炭化水素基の割合は、例えば、５０モル％以上（５０〜１００モル％）、好ましくは７０〜１００モル％、さらに好ましくは８０〜１００モル％程度である。
【００３５】
疎水性化合物において、活性水素原子を含む反応性基としては、例えば、フェノール性であってもよいヒドロキシル基、メルカプト基、カルボキシル基、酸無水物基、アミノ基などが挙げられる。疎水性化合物は、同一の反応性基を有していてもよく、異なる複数の反応性基を有していてもよい。好ましい反応性基には、担体の反応性基及び／又は２官能性化合物の官能基に対する反応性の高い反応性基［（例えば、オキサゾリンに対して活性の高い官能基（例えば、ヒドロキシル基，カルボキシル基及びアミノ基）］、特にカルボキシル基が含まれる。
さらに、主鎖が疎水性である疎水性化合物は、親水性化合物であってもよいが、通常、疎水性であり水不溶性である。
【００３６】
低分子量の疎水性化合物（Ｄ１）
低分子量の疎水性化合物（Ｄ１）としては、常温で液体または固体の低揮発性化合物（例えば、常圧での沸点が１５０℃以上の非揮発性化合物など）を使用する場合が多く、分子量１０００以下（好ましくは１００〜７５０、さらに好ましくは１５０〜７５０程度）の化合物を用いる場合が多い。このような化合物の主鎖は、通常、炭素数６〜３０（好ましくは炭素数８〜２６、さらに好ましくは炭素数１０〜２４）程度の脂肪族炭化水素基で構成されている。
【００３７】
ヒドロキシル基を有する低分子量の疎水性化合物としては、例えば、炭素数１０〜３０程度の脂肪族アルコール（例えば、ラウリルアルコール、テトラデシルアルコール、セチルアルコール、オクタデシルアルコール、アラキルアルコール、セリルアルコール、メリシルアルコール、オレイルアルコールなど）、炭素数４〜１０程度の脂肪族ジオール（１，４−ブタンジオール、１，６−ヘキサンジオールなど）、フェノール性ヒドロキシル基を有する化合物［例えば、フェノール、アルキルフェノール（例えば、アルキル部分の炭素数が４〜２０、好ましくは炭素数８〜１４程度のアルキルフェノール）など］などが挙げられる。好ましい疎水性低分子化合物には、Ｃ_10-26脂肪族アルコール（特にＣ_12-24脂肪族アルコール）、フェノール性ヒドロキシル基を有する化合物（例えば、前記アルキルフェノールなど）が含まれる。
メルカプト基を有する低分子量の疎水性化合物としては、例えば、前記脂肪族アルコールに対応するチオアルコールが例示できる。
【００３８】
カルボキシル基または酸無水物基を有する低分子量の疎水性化合物としては、例えば、炭素数６以上のカルボン酸、例えば、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスミチン酸、パルミチン酸、ステアリン酸、ジオキシステアリン酸、ベヘン酸、モンタン酸などのＣ_6-30飽和脂肪酸、リンデル酸、パルミトオレイン酸、オレイン酸、エライジン酸、リノール酸、リノレン酸、エレオステアリン酸、アラキドン酸、エルカ酸などのＣ_10-24不飽和脂肪酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、アゼライン酸、セバシン酸などの炭素数４〜４０程度の飽和多価カルボン酸、マレイン酸、無水マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸などの不飽和多価カルボン酸、ダイマー酸などや、これらに対応する酸無水物が例示される。これらのカルボン酸または酸無水物は一種または二種以上使用できる。
これらのカルボン酸又は酸無水物のうち、炭素数が６以上のカルボン酸、特に脂肪族モノカルボン酸、中でも高級脂肪酸を使用する場合が多い。高級脂肪酸の炭素数は、例えば、炭素数１０〜２６程度、中でも炭素数１２〜２４程度であるのが好ましい。高級脂肪酸は、不飽和高級脂肪酸であってもよいが、飽和高級脂肪酸が有利に使用される。
【００３９】
アミノ基を有する低分子量の疎水性化合物としては、例えば、カプリルアミン、ラウリルアミン、ミリスチルアミン、パルミチルアミン、ステアリルアミン、オレイルアミンなどの第１級アミン、ジデシルアミン、ジドデシルアミン、ジテトラデシルアミン、ジヘキサデシルアミン、ジオクタデシルアミンなどの第２級アミン、ヘキサメチレンジアミンなどのジアミンなどが例示できる。好ましいアミン化合物には、炭素数１０〜２６、好ましくは炭素数１２〜２４（例えば、炭素数１２〜１８）程度の高級アミン、特に第１級アミンが含まれる。これらのアミン化合物も一種または二種以上使用できる。
【００４０】
さらには、低分子量の疎水性化合物には、異種の反応性を有する化合物、例えば、カルボキシル基とアミノ基とを有する化合物、カルボキシル基とヒドロキシル基とを有する化合物なども含まれる。このような化合物には、例えば、アミノカプロン酸、アミノウンデカン酸などの炭素数６〜１８程度のアミノカルボン酸や対応するラクタム、オキシヘキサン酸，オキシオクタン酸，オキシデカン酸，オキシドデカン酸，オキシオクタデカン酸などの炭素数６〜１８程度のオキシカルボン酸や対応するラクトン（γ−カプロラクトン，γ−ラウロラクトン，γ−パルミトラクトン，γ−ステアロラクトン，δ−バレロラクトン，δ−カプロラクトンなど）などが挙げられる。
これらの低分子量の疎水性化合物（Ｄ１）は種類の異なる複数の化合物を組み合わせて使用してもよい。
【００４１】
高分子量の疎水性化合物（ポリマー）（Ｄ２）
高分子量の疎水性化合物（疎水性高分子）（Ｄ２）は、直鎖状または分岐鎖状であってもよい。疎水性（主）鎖を有するポリマーの種類は特に制限されないが、オレフィン系ポリマー、スチレン系ポリマー、アクリル系ポリマーなどが挙げられる。好ましいポリマーはオレフィン系ポリマー及びスチレン系ポリマーである。
オレフィン系ポリマーは、例えば、エチレン、プロピレン、１−ブテン、イソブテン、１−ペンテン、４−メチル−１−ペンテンなどのオレフィン；１，３−ブタジエン、イソプレンなどのジエンなどの重合性単量体により得ることができる。スチレン系ポリマーは、スチレン、α−メチルスチレンなどのスチレン系単量体などの重合性単量体により得ることができる。
【００４２】
前記疎水性高分子は、前記重合性単量体の単独または共重合体に限らず、前記重合性単量体と、共重合可能な単量体との共重合体であってもよい。共重合体の重合形態は特に制限されず、ランダム重合体、ブロック共重合体、グラフト共重合体などのいずれであってもよい。共重合可能な単量体としては、例えば、アクリル酸エステル、メタクリル酸エステル、アクリロニトリルなどのアクリル系単量体；酢酸ビニル、プロピオン酸ビニルなどのビニルエステル単量体などが挙げられる。共重合可能な単量体は１種または２種以上使用できる。
【００４３】
前記疎水性（主）鎖を有するポリマーとしては、例えば、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−プロピレン−ジエン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エチル共重合体、ポリブテン、ポリブタジエン、アクリロニトリル−ブタジエン共重合体、ポリイソブチレン、ポリイソプレン、ポリメチルペンテンなどのオレフィン系ポリマー；ポリスチレン、スチレン−ブタジエン共重合体、スチレン−アクリロニトリル共重合体、スチレン−アクリロニトル−ブタジエン共重合体などのスチレン系ポリマー、これらの水素添加物などが挙げられる。
【００４４】
疎水性高分子の分子量は特に制限されないが、少量の添加でアロイ化したり、変性効率を高めるためには、比較的低分子量であるのが有利である。このような低分子量ポリマーには、低分子量ポリエチレン、低分子量ポリプロピレン、液状ポリプロピレン、液状ポリブダシエン、ポリブテン、液状ポリイソブチレン、液状ブチルゴムなどの低分子量又は液状ポリオレフィン；低分子量スチレン系ポリマー；これらの水素添加物が含まれる。特に好ましいポリマーには、ポリエチレンなどのオレフィン系ポリマーが含まれる。
【００４５】
このような疎水性高分子は、前記低分子量の化合物と同様に、活性水素原子を含む反応性基、例えば、ヒドロキシル基、メルカプト基、カルボキシル基、アミノ基などを有している。このような反応性基は、前記重合性単量体、必要に応じて前記共重合性単量体とともに、ヒドロキシル基、メルカプト基、カルボキシル基やアミノ基を有する単量体を共重合することにより前記疎水性（主）鎖を有するポリマーに導入できる。また、反応性基は、前記疎水性高分子の高分子反応により導入することもできる。
【００４６】
ヒドロキシル基を有する単量体には、例えば、アリルアルコール、ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレートなどが含まれる。メルカプト基を有する単量体には、上記ヒドロキシル基を有する単量体に対応する化合物が含まれる。カルボキシル基又は酸無水物基を有する単量体には、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、クロトン酸、１０−ウンデシレン酸、ビニル安息香酸、５−ノルボルネン−２−カルボン酸、無水マレイン酸などのエチレン性不飽和カルボン酸とその無水物などが含まれる。アミノ基を有する単量体には、アミノスチレン、ビニルアミン、アリルアミンなどが含まれる。好ましい単量体には、カルボキシル基やアミノ基、特にカルボキシル基を有する単量体が含まれる。
【００４７】
共重合反応によりカルボキシル基又は酸無水物基が導入されたポリマーとしては、変性ポリオレフィン、例えば、エチレン−（メタ）アクリル酸共重合体、プロピレン−（メタ）アクリル酸共重合体、エチレン−無水マレイン酸共重合体（無水マレイン酸変性ポリエチレン）、プロピレン−無水マレイン酸共重合体（無水マレイン酸変性ポリプロピレン）、エチレン−（メタ）アクリル酸−無水マレイン酸共重合体などが挙げられる。
【００４８】
高分子反応によりヒドロキシル基、カルボキシル基、アミノ基を導入する方法としては慣用の方法が採用できる。例えば、ヒドロキシル基は、酢酸ビニルやエチレンカルボナートの共重合と加水分解反応、オレフィン系ポリマーなどの酸化反応により生成したカルボニル基やカルボキシル基の還元反応などにより導入でき、ポリマーが不飽和結合を有する場合にはフリーデルクラフツ反応によるフェノール基の導入やフリーデルクラフツ反応による酢酸基の導入と加水分解反応により導入できる。カルボキシル基は、酸化反応や熱分解反応、過酸化物を用いた加熱処理、ポリマーが不飽和結合を有する場合には過酸化物の存在下での無水マレイン酸との反応により導入できる。アミノ基は、Ｎ−ビニルホルムアミドの共重合と加水分解反応により導入できると共に、カルボキシル基を有するポリマーを酸クロライドとし、ｐ−フェニレンジアミンなどのジアミンと反応させることによっても生成させることができる。
【００４９】
疎水性（主）鎖を有するポリマーの分子量は特に制限されないが、例えば、重量平均分子量５００〜２５００００、好ましくは７００〜１０００００、さらに好ましくは１０００〜２５０００程度である。特に好ましいポリマーには、分子量１０００〜２５０００程度（例えば、分子量１０００〜１００００、好ましくは１０００〜５０００程度）の比較的低分子量のポリマーが含まれる。
【００５０】
［相溶化剤組成物及びその製造方法］
本発明の相溶化剤組成物は、必要に応じて前記表面処理剤（Ｂ）とともに、少なくとも、前記担体（Ａ），２官能性化合物（Ｃ）及び疎水性化合物（Ｄ）で構成されており、前記相溶化剤組成物は、前記各成分の混合により調製でき、一部の成分は予め反応させていてもよい。各成分の好ましい組み合わせは次の通りである。
（１）表面処理剤で処理することなく反応性基を固有に備えた担体（Ａ）（特に有機物質やカーボンブラックなどの無機物質で構成された担体）と、担体（Ａ）の反応性基に対して反応可能な官能基を有する２官能性化合物（Ｃ）と、この２官能性化合物の官能基又は担体（Ａ）の反応性基に対して反応性を有する疏水性化合物（Ｄ）との組み合わせ
（２）２官能性化合物（Ｃ）に対して不活性な担体（特に無機物質で構成された担体）と、この担体に対して反応性基を導入して反応性基を有する担体（Ａ）を生成するための表面処理剤（Ｂ）と、この表面処理剤の反応性基に対し反応可能な官能基を有する２官能性化合物（Ｃ）と、この２官能性化合物の官能基又は担体（Ａ）の反応性基に対して反応性を有する疎水性化合物（Ｄ）との組み合わせ
（３）表面処理剤（Ｂ）で表面処理され、反応性基が導入された担体（特に無機物質で構成された担体）（Ａ）と、担体（Ａ）の反応性基に対して反応可能な官能基を有する２官能性化合物（Ｃ）と、この２官能性化合物の官能基又は担体（Ａ）の反応性基に対して反応性を有する疎水性化合物（Ｄ）との組み合わせ
（４）表面処理剤（Ｂ）で表面処理され、かつ２官能性化合物（Ｃ）と反応させた担体（特に無機物質で構成された担体）（Ａ）と、この２官能性化合物（Ｃ）の官能基又は担体（Ａ）の反応性基に対して反応性を有する疎水性化合物（Ｄ）との組み合わせ
（５）表面処理剤（Ｂ）で表面処理され、反応性基が導入された担体（特に無機物質で構成された担体）（Ａ）と、２官能性化合物（Ｃ）と疎水性化合物（Ｄ）との反応生成物であって、前記担体の反応性基に対して反応性を有するとともに疎水性鎖を有する反応生成物との組み合わせ
高い補強性を付与するためには、担体が有機物質（特に粉粒状又は繊維状有機物質）である場合、前記（１）の組み合わせが有用であり、担体が無機物質である場合、少くとも表面処理剤（Ｂ）の処理又は反応により反応性基が導入された担体（Ａ）を含む組み合わせ、すなわち前記（３），（４）及び（５）の組み合わせが有用である。
相溶化剤組成物は、前記成分の組み合わせにより構成されていればよく、均一又は不均一な混合物であってもよい。
なお、２以上の成分の反応方法には、後述する［相溶化剤の製造方法］の項に記載の種々の方法が採用できる。
【００５１】
相溶化剤組成物を構成する各成分の割合は、複数のポリマーで構成されたポリマー組成物に相溶性および補強性を付与できる範囲で選択できる。前記表面処理剤（Ｂ）の使用量は、担体（Ａ）の種類や表面積および２官能性化合物（Ｃ）の種類に応じて選択でき、例えば、反応性基を有さない担体又は担体（Ａ）１００重量部に対して０〜２５０重量部（例えば、０．１〜２５０重量部）、好ましくは０〜２００重量部（１〜２００重量部）、さらに好ましくは０〜１５０重量部（例えば、１〜１５０重量部）程度の範囲から選択できる。
２官能性化合物（Ｃ）の使用量は、例えば、前記担体（Ａ）１００重量部に対して０．１〜１５０重量部（例えば、０．１〜１２０重量部）、好ましくは０．１〜１００重量部（例えば、１〜７５重量部）程度である。
疎水性化合物（Ｄ）の割合は、例えば、担体（Ａ）１００重量部に対して０．０１〜１５０重量部、好ましくは０．０１〜１００重量部、さらに好ましくは０．１〜７０重量部程度である。
【００５２】
このような相溶化剤組成物を用いると、各成分を反応させることなく、互いに非相溶の複数のポリマーを含む組成物に各成分を単に添加し、溶融混合するという簡単な操作で前記非相溶のポリマーをアロイ化できる。なお、複数のポリマーの相溶化は、前記溶融混合過程で生じるものと思われる。そのため、互いに非相溶のポリマーの組み合わせに応じて各成分を反応させて相溶化剤の組成を調整する必要がなく、相溶化剤の設計の自由度、材料の選択幅が大きくなるとともに、相溶化剤を効率よく設計できる。また、担体、特に粉粒状又は繊維状担体の分散により相分離構造を微細化できるとともに、補強性を付与できる。
【００５３】
［相溶化剤］
本発明において、必要により表面処理剤（Ｂ）で処理した前記担体（Ａ），２官能性化合物（Ｃ）および疎水性化合物（Ｄ）とを反応させ、反応生成物を相溶化剤として使用してもよい。このような相溶化剤は、下記式（Ｉ）又は（ＩＩ）で表すことができる。
Ａ−［（Ｂ１）_m−Ｃ−Ｄ］_n （Ｉ）
［Ｄ−（Ｂ２）_r］_s−Ａ−［（Ｂ１）_p−Ｃ］_q （ＩＩ）
（式中、Ａは担体、Ｂ１およびＢ２は、担体Ａと、遊離の官能基を有する２官能性化合物Ｃ又は疎水性鎖を有する化合物Ｄとを連結する有機基、ｍ，ｐおよびｒは０又は１、ｎ，ｑ及びｓは１以上の整数を示す。ｍ，ｐおよびｒは、それぞれ、ｎ，ｑ及びｓにより異なっていてもよい）
すなわち、式中、Ａは反応性基を有さない担体又は担体（Ａ）、Ｂ１およびＢ２は担体（Ａ）に対して結合し、かつ遊離の官能基を有する化合物（Ｂ）の単位，Ｃは担体（Ａ）又は化合物（Ｂ）の官能基に対して反応し、かつ遊離の官能基を有する２官能性化合物（Ｃ）の単位、Ｄは化合物（Ｂ）又は２官能性化合物（Ｃ）の官能基に対して反応し、かつ疎水性鎖を有する化合物（Ｄ）の単位を示す。
【００５４】
前記式（Ｉ）で表される相溶化剤は、直接又は前記表面処理剤（Ｂ）を介して、前記担体（Ａ）に前記２官能性化合物（Ｃ）を反応させ、次いで２官能性化合物の残存する官能基に前記疎水性化合物（Ｄ）を反応させた反応生成物に対応する。前記式（ＩＩ）で表される相溶化剤は、直接又は表面処理剤（Ｂ）を介して、前記担体（Ａ）に２官能性化合物（Ｃ）と疎水性化合物（Ｄ）とを順次反応させた反応生成物に対応する。
【００５５】
前記式（Ｉ）（ＩＩ）において、Ｂ１，Ｂ２は、前記担体（Ａ）との反応により生成する結合基（例えば、酸素原子、硫黄原子、ＣＯＯ基、ＮＨ基、ＮＨＣＯ基、−ＣＨ（ＯＨ）−ＣＨ₂−，−ＳｉＯ−など）を含む表面処理剤（Ｂ）の残基に相当する。好ましいＢ１，Ｂ２には、結合基（酸素原子、ＣＯＯ基、ＮＨ基、ＮＨＣＯ基、−ＣＨ（ＯＨ）−ＣＨ₂−，−ＳｉＯ−など）を含むカップリング剤残基（特にシランカップリング剤残基）含まれる。
また、担体（Ａ）の反応性基又は表面処理剤（Ｂ）に残存する反応性基は、結合基（例えば、酸素原子、硫黄原子、ＣＯＯ基、ＮＨ基、ＮＨＣＯ基、−ＣＨ（ＯＨ）−ＣＨ₂−など）を介して、２官能性化合物（Ｃ）と結合している。
【００５６】
ｍ，ｐおよびｒは、表面処理剤（Ｂ）の有無に対応する０又は１，ｎ，ｑ及びｓは２官能性化合物（Ｃ）や疎水性化合物（Ｄ）の導入量に対応する１以上の整数であり、ｍ，ｐおよびｒは、ｎ，ｑ及びｓに応じて異なっていてもよい。
【００５７】
前記式（Ｉ）（ＩＩ）において、疎水性化合物（Ｄ）の単位は相溶化剤の末端及び／又は側鎖を構成する。好ましい疎水性化合物（Ｄ）の単位は、低分子量の疎水性化合物（Ｄ１）では少くとも末端に結合し、高分子量の疎水性化合物（Ｄ２）では少なくとも側鎖に結合している場合が多い。
【００５８】
好ましい相溶化剤は、下記式（ｉ）又は（ｉｉ）で表すことができる。
【００５９】
【化８】

（式中、Ｒ¹，Ｒ²，Ｒ³およびＲ⁴は、同一又は異なって、水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を示す。Ａ，Ｂ１，Ｂ２，Ｄ，Ｅ，ｍ，ｎ，ｐ，ｑ，ｒ，ｓは前記に同じ。）
この式（ｉ）又は（ｉｉ）で表される相溶化剤は、２官能性化合物としてビスオキサゾリン化合物を用いた相溶化剤に相当する。
前記式（ｉ）及び式（ｉｉ）において、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴は前記に通りである。好ましいＲ¹，Ｒ²，Ｒ³及びＲ⁴は、水素原子又はＣ_1-4アルキル基であり、アルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチル基が挙げられる。さらに好ましいアルキル基には、メチル、エチル基、特にメチル基が含まれる。特に好ましいＲ¹及びＲ³は水素原子またはＣ_1-4アルキル基（特にメチル基）であり、好ましいＲ²及びＲ⁴は水素原子である。
式（ｉ）及び（ｉｉ）において、疎水性化合物（Ｄ）は、前記オキサゾリン基又は表面処理剤（Ｃ）の残存する反応性基との反応により生成する結合基（酸素原子、硫黄原子、ＣＯＯ基、ＮＨ基など）を介して、オキサゾリン環の開環ユニットや表面処理剤（Ｃ）と結合している。好ましい結合基には、通常、酸素原子、ＣＯＯ基およびＮＨ基、特にＣＯＯ基が含まれる。
【００６０】
さらに、前記式（ｉ）及び式（ｉｉ）で表される相溶化剤は、疎水性化合物（Ｄ）として低分子量の疎水性化合物（Ｄ１）を用いた相溶化剤と、高分子量の疎水性化合物（Ｄ２）を用いた相溶化剤とに大別できる。
低分子量の疎水性化合物（Ｄ１）を用いた相溶化剤は下記式（ｉａ）及び（ｉｉａ）で表すことができる。
【００６１】
【化９】

（式中、Ｄ１は炭素数６〜３０の脂肪族炭化水素基を示し、Ｒ¹，Ｒ²，Ｒ³およびＲ⁴は、水素原子又はＣ_1-4アルキル基を示し、Ｒ¹及びＲ²の少くとも一方は水素原子、Ｒ³及びＲ⁴の少くとも一方は水素原子である。Ａ，Ｂ１，Ｂ２，ｍ，ｎ，ｐ，ｑ，ｒ，ｓは前記に同じ）
高分子量の疎水性化合物（Ｄ２）を用いた相溶化剤は下記式（ｉｂ）及び（ｉｉｂ）で表すことができる。
【００６２】
【化１０】

（式中、Ｙ及びＺはそれぞれポリマーの主鎖を構成する炭化水素基を示し、Ｚは不飽和結合を有していてもよく、ａ／（ａ＋ｂ）＝０．１〜２０モル％である。Ｒ¹，Ｒ²，Ｒ³及びＲ⁴は水素原子又はＣ_1-4アルキル基を示し、Ｒ¹及びＲ²の少くとも一方は水素原子、Ｒ³及びＲ⁴の少くとも一方は水素原子である。Ａ，Ｂ１，Ｂ２，ｍ，ｎ，ｐ，ｑ，ｒ，ｓは前記に同じ）
前記式（ｉｂ）及び（ｉｉｂ）で表される化合物において、ポリマーの主鎖がオレフィン系ポリマーで構成されている場合、前記ＹはＣ_nＨ_2n-1（ｎは１〜４の整数を示す）で表され、ＺはＣ_nＨ_2n又はＣ_nＨ_2n-2（ｎは前記に同じ）で表される。前記式（ｉｂ）及び（ｉｉｂ）で表される高分子量の相溶化剤において、好ましいａ／（ａ＋ｂ）は０．５〜１０モル％、特に０．５〜７モル％程度である。
【００６３】
このような相溶化剤（Ｉ）及び（ＩＩ）を、互いに非相溶の複数のポリマー組成物に添加すると、互いに非相溶のポリマーを有効に相溶化できる。例えば、相溶化剤（ｉａ）（ｉｂ）及び（ｉｉａ）（ｉｉｂ）を互いに非相溶の複数のポリマー組成物に添加すると、疎水性鎖と、残存するオキサゾリン基またはアミド結合とを利用して、マトリックスポリマー中にポリマーを相分散させ有効に相溶化できる。さらに、担体、特に粉粒状又は繊維状担体の分散効果により相分離構造を微細化できるとともに、補強性を有効に付与できる。
【００６４】
［相溶化剤の製造方法］
前記相溶化剤は、必要に応じて表面処理剤（Ｂ）で処理又は反応させた反応性基を有する担体（Ａ）と、この担体の反応性基に対して反応可能な官能基を有する２官能性化合物（Ｃ）と、この２官能性化合物（Ｃ）の官能基又は前記担体（Ａ）の反応性基に対する反応性基を有する疎水性合物（Ｄ）とを反応させることにより得ることができる。
【００６５】
担体（Ａ）と表面処理剤（Ｂ）との反応には、担体の種類、担体及び表面処理剤の反応性基の種類などに応じて、通常の有機合成反応が利用できる。例えば、前記（ａ１−１）ハロゲン原子を有する担体では脱ハロゲン化水素反応が利用でき、（ａ１−２）ヒドロキシル基及びメルカプト基を有する担体では、エステル化、ウレタン化反応、オキサゾリン基の開環反応、カップリング剤の縮合反応が利用できる。（ａ１−３）カルボキシル基及び酸無水物基を有する担体では、エステル化、アミド化反応、エポキシ開環反応、イソシアネート基に対する付加反応（アミド結合生成反応）、オキサゾリン基の開環反応、カップリング剤の縮合反応などが利用できる。（ａ１−４）アミノ基を有する担体では、アミド化反応、エポキシ開環反応、イソシアネート基に対する付加反応（尿素結合生成反応）、オキサゾリン基開環反応、カップリング剤の縮合反応などが利用できる。（ａ１−５）エポキシ基を有する担体では、エポキシ環の開環反応が利用でき、（ａ１−６）イソシアネート基を有する担体では、イソシアネート基に対する付加反応（ウレタン結合生成反応，尿素結合生成反応，アミド結合生成反応など）が利用でき、（ａ１−７）ビニル基及び（メタ）アクリロイル基を有する担体では、付加（重合）反応を利用できる。
【００６６】
各成分の反応割合は担体の種類や表面積など応じて広い範囲から選択できる。表面処理剤（Ｂ）の割合は、例えば、担体（Ａ）１００重量部に対して０〜１０００重量部（例えば、０．１〜１０００重量部）、好ましくは０〜５００重量部（例えば、０．１〜５００重量部）、さらに好ましくは０．２〜２００重量部（例えば、０．２〜１５０重量部）程度の範囲から選択できる。反応は、触媒の存在下又は非存在下で行ってもよく、有機溶媒の存在下又は非存在下で行うことができ、有機溶媒としては担体を可溶化しない貧溶媒を用いる場合が多い。反応温度は、担体や表面処理剤の種類に応じて、例えば、２０〜１５０℃程度の範囲から選択できる。粒子状反応生成物は、濾別などにより分離し、適当な溶媒で洗浄し、後続する反応に供してもよい。
より具体的には、有機又は無機担体とシランカップリング剤との反応は、例えば、アルコール類（メタノール、エタノール、イソプロパノールなど）などの反応に不活性な有機溶媒中、分散させた担体とシランカップリング剤とを反応させることにより行うことができる。反応温度は、例えば、３０℃〜溶媒の還流温度の範囲から選択できる。
【００６７】
担体（Ａ）の反応性基（又は表面処理剤（Ｂ）により導入された担体（Ａ）の反応性基）と、２官能性化合物（Ｃ）との反応も、担体，表面処理剤や２官能性化合物の種類に応じて、前記担体と表面処理剤との反応と同様に行うことができる。２官能性化合物（Ｃ）の割合は、通常、担体（Ａ）の反応性基に対して過剰量であり、例えば、担体（Ａ）の反応性基１モルに対して２官能性化合物（Ｃ）０．５〜５モル、好ましくは０．７〜３モル、さらに好ましくは０．８〜２モル程度である。２官能性化合物（Ｃ）の重量割合は、分子量に依存するので一概に断定できないが、反応性基を有する担体（Ａ）１００重量部に対して０．１〜２００重量部、好ましくは０．１〜１５０重量部、さらに好ましくは０．１〜１００重量部程度の範囲から選択できる。この反応も触媒の存在下又は非存在下で行ってもよい。また、反応に不活性な溶媒の存在下、懸濁乃至分散系で行なってもよい。溶媒としては、例えば、メタノール、エタノール、イソプロパノールなどのアルコール類；ペンタン、ヘキサン、オクタンなどの脂肪族炭化水素；シクロヘキサン、メチルシクロヘキサンなどの脂環族炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素；塩化メチル、塩化メチレン、クロロホルム、トリクロロエチレンなどのハロゲン化炭化水素；酢酸エチルなどのエステル類；アセトン、メチルエチルケトンなどのケトン類；ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフランなどのエーテル類；Ｎ−メチルピロリドン、アセトニトリル、ジメチルホルムアミドなどの含窒素化合物；およびこれらの混合溶媒が挙げられる。有機溶媒は、前記担体に対する貧溶媒である場合が多い。反応温度は、例えば、２０〜２５０℃程度の範囲から選択できる。
【００６８】
担体（Ａ）の反応性基又は２官能性化合物（Ｃ）の官能基と、疎水性化合物（Ｄ）との反応は、前記担体（Ａ）の反応性基と２官能性化合物（Ｃ）の官能基との反応と同様にして行うことができる。なお、低分子量の疎水性化合物（Ｄ１）を用いると、反応効率、反応操作性を向上させることができるので有利である。疎水性化合物（Ｄ）の使用量は、担体（Ａ）の反応性基又は２官能性化合物（Ｃ）の残存する官能基１モルに対して、例えば、疎水性化合物（Ｄ）の反応性基０．５〜５モル、好ましくは０．７〜３モル、さらに好ましくは１〜２モル程度となる範囲から選択できる。疎水性化合物（Ｄ）の重量割合は、分子量に依存するので一概に断定できないが、例えば、担体（Ａ）１００重量部に対して０．０１〜２００重量部、好ましくは０．０２〜１５０重量部、さらに好ましくは０．０５〜１００重量部程度である。
【００６９】
なお、前記各反応は、通常、窒素、ヘリウム、アルゴンなどの不活性雰囲気中、攪拌しながら行なうことができる。反応終了後、必要に応じて、濾過，濃縮，乾固、溶剤分別法などの慣用の方法により相溶化剤を得ることができる。
【００７０】
このような方法により、前記式（Ｉ）に対応する下記（１）の相溶化剤、前記式（ＩＩ）に対応する下記（２）の相溶化剤、さらにはこれらの化合物（１）（２）の混合物で構成された相溶化剤を得ることができる。
（１）２官能性化合物（Ｃ）の残基を介して、担体（Ａ）に疎水性鎖を有する化合物（Ｄ）の残基が結合している相溶化剤
（２）担体（Ａ）に、２官能性化合物（Ｃ）の残基および疎水性鎖を有する化合物（Ｄ）の残基が結合している相溶化剤
［ポリマーアロイの製造方法（ポリマー組成物の改質方法）］
前記相溶化剤組成物及び相溶化剤は、広い範囲のポリマーの相溶化に利用でき、互いに非相溶のポリマー組成物に添加混合して相分離構造の微細化とともに相溶化し、補強されたポリマーアロイを得る上で有用である。特に、非極性ポリマーと（例えば、オレフィン系ポリマー）、このポリマーに対して非相溶の極性ポリマー（例えば、エステル，アミド，エーテルなどの酸素原子，チッ素原子，硫黄原子を含むポリマー）とを含むポリマー組成物に添加してポリマーアロイを得る上で有用である。
【００７１】
前記ポリマーとしては、例えば、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、ポリ（４−メチル−ペンテン−１）などのオレフィン系ポリマー；ポリメタクリル酸メチルなどのアクリル系ポリマー；ポリスチレン、スチレン−メタクリル酸メチル共重合体、アクリロニトリル−スチレン共重合体、アクリロニトリル−ブタシエン−スチレンブロック共重合体などのスチレン系ポリマー；ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのポリエステルやポリアリレート；ナイロン６、ナイロン６６、ナイロン６１０などのポリアミド；ポリアセタール；ポリカーボネート；ポリフェニレンオキシド；ポリフェニレンスルフィド；ポリサルホン；ポリエーテルサルホン；ポリエーテルエーテルケトン；ポリオキシベンジレン；ポリアミドイミドなどが挙げられる。なお、ポリマーアロイ化に際しては、熱可塑性エラストマー、熱硬化性樹脂などの他の成分を併用してもよい。
前記相溶化剤組成物や相溶化剤は、エンジニアリングプラスチックのポリマーアロイ化、例えば、ポリプロピレンなどのオレフィン系ポリマーと、ポリエステルやポリアミドなどとのポリマーアロイ化にも利用できる。
【００７２】
本発明の相溶化剤組成物または相溶化剤は、少量の添加量で複数のポリマーを相溶化できるだけでなく、ポリマー組成物に高い補強性を付与できるという特色がある。そのため、相溶化剤組成物及び相溶化剤の添加量は、ポリマーの種類、所望する特性などに応じて広い範囲から選択でき、例えば、ポリマー組成物１００重量部に対して０．０１〜１００重量部、好ましくは０．１〜５０重量部、さらに好ましくは２〜３０重量部程度の範囲から選択できる。
【００７３】
ポリマーアロイは、互いに非相溶の前記複数のポリマーと相溶化剤組成物又は相溶化剤とを、溶融混練などの慣用の方法によりポリマーブレンドすることにより調製できる。アロイ化したポリマー組成物は、通常、慣用の成形法、例えば、射出成形法、押出し成形法などにより所定の形状に成形される。
【００７４】
なお、本発明のポリマーアロイの製造方法は、互いに非相溶の複数のポリマーを含むポリマー組成物に前記相溶化剤組成物又は相溶化剤を添加混合し、加熱溶融することにより前記複数のポリマーを相溶化できるため、ポリマー組成物の相溶化方法、又はポリマー組成物の改質方法と言うこともできる。
【００７５】
【発明の効果】
本発明の相溶化剤組成物及び相溶化剤は、前記成分で構成されているため、相溶性に乏しい広い範囲のポリマーに適用でき、添加量が少量であっても複数のポリマーの特性が有効に発現するポリマーアロイを得ることができるだけでなく、相分離構造を微細化できるとともに、ポリマーアロイに高い補強性を付与できる。相溶化剤組成物は、反応させることなくポリマー組成物に添加するだけで、ポリマー組成物を経済的に有利に改質でき、互いに非相溶の複数のポリマーを簡便かつ効率よく相溶化でき、相溶化剤組成物の選択幅及び自由度が大きい。
本発明の方法では、前記相溶化剤組成物や相溶化剤を、混合や３成分又は４成分の反応という簡単な方法で得ることができる。
さらに、本発明の製造方法では、互いに非相溶の複数のポリマーを含むポリマー組成物に相溶化剤組成物又は相溶化剤を添加するだけでポリマー組成物を改質でき、ポリマーアロイを効率よく製造できる。
【００７６】
【実施例】
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。
実施例１
二酸化ケイ素の粉体［（株）ナカライテスク製，平均粒子径５μｍ］１００ｇをエチルアルコール［（株）ナカライテスク製］１０００ｍｌに撹拌分散し、分散液にカルボキシメチルトリエトキシシラン［チッソ（株）製，ＳＩＣ２２６４．５］０．２５５ｇを添加し、還流下で８時間反応させた。反応混合液を冷却した後、粉体粒子を濾別し、テトラヒドロフランで十分に洗浄し、減圧乾燥した。乾燥した処理粉体に対して２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ）０．１３１ｇを添加し、２００℃で３０分間反応させた後、ラウリン酸（日本油脂（株）製，ＮＡＡ−１２２）０．０６ｇを添加し、２００℃で３０分間反応させることにより、表面にオキサゾリン基と長鎖アルキル基とを有する粉末状相溶化剤を得た。なお、ラウリン酸との上記反応をＦＴ−ＩＲ（日本分光（株）製）により追跡したところ、オキサゾリン環の１６５０ｃｍ^-1近傍の吸収とカルボン酸の１７２０ｃｍ^-1近傍の吸収が減少し、両者の反応によるアミド基の１５５０ｃｍ^-1近傍の吸収が増加した。
【００７７】
ポリプロピレン（東燃化学（株）製，Ｊ２０５）４０重量部とポリアミド−６（東洋紡（株）製，Ｔ−８００）６０重量部、および上記粉末状相溶化剤１０重量部との混合物を２軸スクリュー押出し機により２００〜２６０℃で溶融混練し、成形することによりポリマーアロイを得た。得られた成形体の断面を電子顕微鏡で観察したところ、図１に示されるようにミクロ層がマトリックス中に均一に分散しており、相溶性の高い微細な相が観察された。また、無機粉体の分散効果により相分離構造が微細化した。また、ＪＩＳ Ｋ−７１１３に準拠して引張り試験に供したところ、成形品の引張り強度および引張り弾性率の向上が認められ、補強効果が認められた。
【００７８】
比較例１
ポリプロピレン（東燃化学（株）製，Ｊ２０５）４０重量部とポリアミド−６（東洋紡（株）製，Ｔ−８００）６０重量部、および二酸化ケイ素粉体［（株）ナカライテスク製，平均粒子径５μｍ］１０重量部との混合物を２軸スクリュー押出し機により２００〜２６０℃で溶融混練し、成形することによりポリマーアロイを得た。得られた成形体の断面を電子顕微鏡で観察したところ、図２に示されるように相分離が認められた。
【００７９】
実施例２
二酸化ケイ素微粒子（日本アエロジル（株）製，平均粒子径１２ｎｍ）１０ｇをエチルアルコール［（株）ナカライテスク製］１０００ｍｌに撹拌分散し、分散液にγ−グリシドキシプロピルトリメトキシシラン［東レ・ダウコーニング・シリコーン（株）製，ＳＨ６０４０］１２．１ｇを添加し、還流下で８時間反応させた。反応混合液を冷却した後、粒子を遠心分離し、テトラヒドロフランで十分に洗浄し減圧乾燥した。乾燥した処理粉体に対して１，１０−ジアミノデカン［アルドリッチＡｌｄｒｉｃｈ社製］５．４ｇを添加し、２００℃で３０分間反応させた後、無水マレイン酸変性ポリプロピレン［三洋化成（株）製，ユーメックス１０１０］５．４ｇを添加し、２００℃で３０分間反応させることにより、微粒子状相溶化剤を得た。
【００８０】
ポリプロピレン（東燃化学（株）製，Ｊ２０５）４０重量部とポリブチレンテレフタレート（日本ジーイープラスチックス（株）製，バロックス３１０）６０重量部、および上記微粒子状相溶化剤５重量部との混合物を、二軸スクリュー押出し機により２００〜２６０℃で溶融混練し、成形することによりポリマーアロイを得た。
得られた成形品の断面を電子顕微鏡で観察したところ、図３に示されるように、ミクロ相がマトリックス中に均一に分散しており、相溶性の高い微細な相が観察された。また、無機粉体の分散効果により相分離構造が微細化した。
【００８１】
実施例３
カーボンブラック粒子（三菱化学（株）製，平均粒子径１８ｎｍ）１０ｇをエチルアルコール［（株）ナカライテスク製］１０００ｍｌに撹拌分散し、分散液に２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ）４．６ｇを添加し、還流下で８時間反応させた。反応混合液を冷却した後、粒子を遠心分離し、テトラヒドロフランで十分に洗浄し、減圧乾燥した。乾燥した処理粉体に対しパルミチン酸（日本油脂（株）製，ＮＡＡ−１６０）２．１ｇを添加し、２００℃で３０分間反応させることにより、微粒子状相溶化剤を得た。
【００８２】
ポリプロピレン（東燃化学（株）製，Ｊ２０５）４０重量部とポリアミド−６（東洋紡（株）製，Ｔ−８００）６０重量部、および上記微粒子状相溶化剤１０重量部との混合物を２軸スクリュー押出し機により２００〜２６０℃で溶融混練し、成形することによりポリマーアロイを得た。得られた成形体の断面を電子顕微鏡で観察したところ、図４に示されるようにミクロ層がマトリックス中に均一に分散しており、相溶性の高い微細な相が観察された。また、無機粉体の分散効果により相分離構造が微細化した。
【００８３】
実施例４
二酸化ケイ素の粉体［（株）ナカライテスク製，平均粒子径５μｍ］１００ｇをエチルアルコール［（株）ナカライテスク製］１０００ｍｌに撹拌分散し、分散液にカルボキシメチルトリエトキシシラン［チッソ（株）製，ＳＩＣ２２６４．５］０．２５５ｇを添加し、還流下で８時間反応させた。反応混合液を冷却した後、粉体粒子を濾別し、テトラヒドロフランで十分に洗浄し、減圧乾燥することにより、表面にカルボキシル基を有する粉体粒子を得た。
ポリプロピレン（東燃化学（株）製，Ｊ２０５）３０重量部、ポリアミド−６（東洋紡（株）製，Ｔ−８００）７０重量部、乾燥した処理粉体１０重量部、２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ）０．１３１重量部、およびラウリン酸（日本油脂（株）製，ＮＡＡ−１２２）０．０６重量部の混合物を２軸スクリュー押出し機により２００〜２６０℃で溶融混練し、成形することによりポリマーアロイを得た。得られた成形体の断面を電子顕微鏡で観察したところ、図５に示されるようにミクロ層がマトリックス中に均一に分散しており、相溶性の高い微細な相が観察された。
【００８４】
比較例２
ポリプロピレン（東燃化学（株）製，Ｊ２０５）３０重量部、ポリアミド−６（東洋紡（株）製，Ｔ−８００）７０重量部、および相溶化剤としての無水マレイン酸変性ポリプロピレン（三洋化成（株）製，ユーメックス１０１０）１０重量部の混合物を２軸スクリュー押出し機により２００〜２６０℃で溶融混練し、成形することによりポリマーアロイを得た。
得られた成形体の断面を電子顕微鏡で観察したところ、図６に示されるようにミクロ層がマトリックス中に均一に分散していたが、高い相溶性を得るためには１０重量部という多量の相溶化剤が必要であった。
【００８５】
そして、下記の成形品について、ＪＩＳ Ｋ−７１１３に準拠して引張り強度および引張り弾性率を測定した。結果を表に示す。
（ i ）ポリプロピレン（東燃化学（株）製，Ｊ２０５）の成形品
（ ii ）ポリアミド−６（東洋紡（株）製，Ｔ−８００）の成形品
（ iii ）ポリプロピレン（東燃化学（株）製，Ｊ２０５）３０重量部およびポリアミド−６（東洋紡（株）製，Ｔ−８００）７０重量部の混合物の成形品
（ iv ）比較例２の成形品
（ v ）実施例４の成形品
【００８６】
【表１】

実施例５
ラウリン酸（日本油脂（株）製，ＮＡＡ−１２２，分子量２００．３）０．４８重量部と２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ，分子量２１６．２）０．４２重量部とを、窒素ガス雰囲気下、溶媒を使用することなく１５０℃で撹拌しながら反応させ、末端にオキサゾリン基が導入されたアミド結合を有する反応生成物を得た。
【００８７】
ポリプロピレン（東燃化学（株）製，Ｊ２０５）５０重量部とポリブチレンテレフタレート（日本ジーイープラスチックス（株）製，バロックス３１０）５０重量部との混合物に、実施例２と同様にしてγ−グリシドキシプロピルトリメトキシシランで処理した二酸化ケイ素微粒子５重量部、上記反応生成物０．９重量部を添加し、実施例２と同様にして成形品を得た。そして、成形品の断面を電子顕微鏡で観察したところ、図３と同様にミクロ相が微細化されて均一であり、相溶化していることが認められた。
【００８８】
実施例６
ポリプロピレン（東燃化学（株）製，Ｊ２０５）５０重量部とポリブチレンテレフタレート（日本ジーイープラスチックス（株）製，バロックス３１０）５０重量部との混合物に、実施例２と同様にしてγ−グリシドキシプロピルトリメトキシシランで処理した二酸化ケイ素微粒子５重量部、ミリスチン酸（日本油脂（株）製，ＮＡＡ−１４２）０．５１重量部、および２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ，分子量２１６．２）０．４９重量部を添加し、実施例２と同様に成形することによりポリマーアロイを得た。
得られた成形品の断面を電子顕微鏡で観察したところ、図３と同様にミクロ相が微細化されて均一であり、ポリマー成分が相溶化していた。
【００８９】
実施例７
ポリプロピレン（東燃化学（株）製，Ｊ２０５）５０重量部とポリブチレンテレフタレート（日本ジーイープラスチックス（株）製，バロックス３１０）５０重量部との混合物に、実施例２と同様にしてγ−グリシドキシプロピルトリメトキシシランで処理した二酸化ケイ素微粒子５重量部、パルミチン酸（日本油脂（株）製，ＮＡＡ−１６０，分子量２５６．４）０．５４重量部、および２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ，分子量２１６．２）０．４６重量部を添加し、実施例２と同様に成形することによりポリマーアロイを得た。
得られた成形品の断面を電子顕微鏡で観察したところ、図３と同様にミクロ相が微細化されて均一であり、ポリマー成分が相溶化していた。
【００９０】
実施例８
ポリプロピレン（東燃化学（株）製，Ｊ２０５）５０重量部とポリブチレンテレフタレート（日本ジーイープラスチックス（株）製，バロックス３１０）５０重量部との混合物に、実施例２と同様にしてγ−グリシドキシプロピルトリメトキシシランで処理した二酸化ケイ素微粒子５重量部、ステアリン酸（日本油脂（株）製，ＮＡＡ−１８０，分子量２８４．５）０．５７重量部、および２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ，分子量２１６．２）０．４３重量部を添加し、実施例２と同様に成形することによりポリマーアロイを得た。
得られた成形品の断面を電子顕微鏡で観察したところ、図３と同様に、ミクロ相が微細化して均一であり、ポリマー成分が相溶化していた。
【００９１】
実施例９
ポリプロピレン（東燃化学（株）製，Ｊ２０５）５０重量部とポリブチレンテレフタレート（日本ジーイープラスチックス（株）製，バロックス３１０）５０重量部との混合物に、実施例２と同様にしてγ−グリシドキシプロピルトリメトキシシランで処理した二酸化ケイ素微粒子５重量部、酸化型低密度ワックス［三洋化成（株）製、サンワックスＥ−３１０、平均分子量２０００、酸価２２（ＣＯＯＨ基濃度：２９×１０^-5モル／ｇ）］０．９４重量部、および２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ，分子量２１６．２）０．０５８重量部を添加し、実施例２と同様に成形することによりポリマーアロイを得た。
得られた成形品の断面を電子顕微鏡で観察したところ、図３と同様に、ミクロ相が微細化して均一に分散し、ポリマー成分が相溶化していた。
【００９２】
実施例１０
酸化型低密度ワックス［三洋化成（株）製、サンワックスＥ−３１０、平均分子量２０００、酸価２２（ＣＯＯＨ基濃度：２９×１０^-5モル／ｇ）］０．９４重量部と、２，２′−（１，３−フェニレン）−ビス（２−オキサゾリン）（武田薬品工業（株）製，１，３−ＢＰＯ，分子量２１６．２）０．０５８重量部とを、窒素ガス雰囲気下、１５０℃で撹拌しながら反応させることにより、末端にオキサゾリン基が残存するアミド結合を有する化合物が得られた。このような化合物が生成していることは、ＦＴ−ＩＲにより、オキサゾリン環に起因する１６５０ｃｍ^-1近傍の吸収とカルボン酸に起因する１７２０ｃｍ^-1近傍の吸収が減少し、アミド基に起因する１５５０ｃｍ^-1近傍の吸収が増加することから確認された。
【００９３】
そして、ポリプロピレン（東燃化学（株）製，Ｊ２０５）５０重量部とポリブチレンテレフタレート（日本ジーイープラスチックス（株）製，バロックス３１０）５０重量部との混合物に、実施例２と同様にしてγ−グリシドキシプロピルトリメトキシシランで処理した二酸化ケイ素微粒子５重量部、上記反応生成物１．０重量部を添加し、実施例２と同様に成形することによりポリマーアロイを得た。
得られた成形品の断面を電子顕微鏡で観察したところ、図３と同様に均一な相が認められ、ミクロ相がマトリックス中に均一に分散した相溶性が良好なポリマーアロイが得られた。
【図面の簡単な説明】
【図１】 図１は実施例１で得られた成形品の断面を示す電子顕微鏡写真（図面代用写真）である。
【図２】 図２は比較例１で得られた成形品の断面を示す電子顕微鏡写真（図面代用写真）である。
【図３】 図３は実施例２で得られた成形品の断面を示す電子顕微鏡写真（図面代用写真）である。
【図４】 図４は実施例３で得られた成形品の断面を示す電子顕微鏡写真（図面代用写真）である。
【図５】 図５は実施例４で得られた成形品の断面を示す電子顕微鏡写真（図面代用写真）である。
【図６】 図６は比較例２で得られた成形品の断面を示す電子顕微鏡写真（図面代用写真）である。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a compatibilizer composition or compatibilizer useful for compatibilizing a plurality of polymers to obtain a polymer alloy, a method for producing the compatibilizer, and the compatibilizer composition or compatibilizer. The present invention relates to a method for producing a polymer alloy using.
[0002]
[Prior art]
  In recent years, in order to effectively express the characteristics of a plurality of polymers, it has been studied to mix and alloy polymers having different characteristics. In this polymer alloy, a plurality of incompatible polymers are usually used, and the obtained polymer alloy constitutes a heterogeneous polymer system.
  On the other hand, a heterogeneous polymer composed of a plurality of polymers generally has poor mechanical properties such as impact resistance and toughness. Therefore, in a polymer alloy, a polymer containing a unit that is the same as or similar to a structural unit of a plurality of polymers is conventionally added. For example, JP-A-3-76743 discloses a composition containing a specific engineering plastic and a rubber-reinforced styrene resin, an oxazoline-modified copolymer of a vinyl oxazoline, an aromatic vinyl monomer, and another vinyl monomer. A thermoplastic resin composition containing a coalescence is disclosed. JP-A-3-172347 discloses a thermoplastic resin comprising polyester, an aromatic vinyl polymer having a reactive group obtained by copolymerizing a monomer having a vinyloxazoline or glycidyl group and styrene, and a polycarbonate. A composition is disclosed. Furthermore, JP-A-2-255857 discloses an aromatic carbonate composition containing an aromatic carbonate resin and a functional elastic polymer. The functional elastic polymer includes a reaction product of an ethylene elastomer having a reactive group and polystyrene functionalized with oxazoline. The oxazoline-modified copolymers described in these prior documents are useful for alloying specific polymers. However, when an oxazoline-modified copolymer is used, not only the application range of the polymer that can be alloyed is narrow, but it is difficult to alloy with a small amount of addition. Furthermore, it is difficult to impart reinforcement to the polymer alloy and improve the mechanical strength.
[0003]
  In JP-A-6-184224, a polymer having a functional group containing an active hydrogen atom such as a carboxyl group at the end or side chain of a hydrophobic main chain (for example, a modified olefin polymer) is reacted with oxazoline. Discloses a method for producing a compatibilizer. The compatibilizer obtained by this method is useful for obtaining a polymer alloy by adding a small amount to a mutually incompatible polymer composition. However, in order to obtain a compatibilizing agent, it is necessary to react a polymer having a functional group containing an active hydrogen atom in advance with oxazoline, so that the selection range of the polymer and oxazoline is narrowed when designing the compatibilizing agent. It is possible and economically advantageous to make it difficult to easily compatibilize mutually incompatible polymer compositions. Furthermore, even if the compatibilizing agent described in this document is used, the mechanical strength of the polymer alloy depends on the constituent resin of the polymer alloy, so that it is difficult to impart high reinforcement to the polymer alloy.
[0004]
  Utilizing the fact that a high molecular weight polymer is produced by the ester amide bond between the oxazoline group of bis-2-oxazoline and two or more terminal carboxyl groups of the molecular chain, the molecular weight is decreased due to aging and hydrolysis, It has also been proposed that scrap resins (polyester, polyamide, etc.) that are incompatible with each other are converted into block copolymers by reacting with bis-2-oxazoline and reused as a compatible system ("Plastic Age"). 114-118, Mar. 1995). In British Patent No. 1426409, bisoxazoline is added to a high molecular weight polyester having a carboxyl group in order to prevent the polyester from being decomposed or the molecular weight being lowered in the melt extrusion process for spinning. It has been proposed to denature. However, these documents do not describe a method of using a bis-2-oxazoline compound as a compatibilizing agent. Further, since the resin has a high molecular weight, it is difficult to alloy a plurality of incompatible polymers with each other by adding a small amount of the reaction product. Furthermore, it is difficult to impart reinforcement to the resin composition.
[0005]
[Problems to be solved by the invention]
  Therefore, the object of the present invention is a compatibilizing agent composition that can be applied to a wide range of polymers with poor compatibility, and can obtain a polymer alloy that effectively exhibits the characteristics of a plurality of polymers even when the addition amount is small. Or it is providing the compatibilizing agent and its manufacturing method.
  Another object of the present invention is to provide a compatibilizing agent composition, a compatibilizing agent and a method for producing the compatibilizing agent that can not only effectively express the properties of a plurality of incompatible polymers but also can effectively impart reinforcing properties to the polymer alloy. It is to provide.
  Still another object of the present invention is to provide a method for producing a polymer alloy that can efficiently modify a polymer composition containing a plurality of incompatible polymers with each other by adding a small amount.
  Another object of the present invention is to provide a method for producing a polymer alloy that is economically advantageous and can be easily and efficiently alloyed with a small amount of a plurality of incompatible polymers, and to which reinforcing properties are imparted. There is to do.
[0006]
[Means for Solving the Problems]
  As a result of intensive studies to achieve the above object, the present inventors have added (1) a carrier having a reactive group and a bifunctional compound such as bisoxazoline to a resin composition containing a plurality of incompatible polymers. A compound and a hydrophobic polymer or hydrophobic compound having a reactive functional group, or (2) a hydrophobic polymer or hydrophobic compound having a reactive functional group and a carrier having a reactive group. It has been found that the addition of a reaction product obtained by reacting a functional compound with a compound can modify and alloy a composition containing a plurality of polymers, and can provide reinforcement.
[0007]
  That is, the compatibilizer composition of the present invention comprises a carrier (A) having a reactive group, and a bifunctional compound (C) having a functional group capable of reacting with the reactive group of the carrier (A). A compound (D) having a hydrophobic group and a functional group containing an active hydrogen atom reactive to the functional group of the bifunctional compound (C) or the reactive group of the carrier (A). (I) the reactive group is, HiDroxyl group, mercapto group, carboxyl group, acid anhydride group, amino group,OrEpoxyOn the basisYes,(Ii) The carrier constituting the carrier (A) having a reactive group is an inorganic substance, and (iii)The bifunctional compound (C) is, An amino group-containing compound or an oxazoline group-containing compound, and (iv) Compound (D) is a higher fatty acid having 10 to 26 carbon atoms, or a polyolefin into which a carboxyl group or an acid anhydride group has been introduced by a copolymerization reaction. (V) The proportion of the bifunctional compound (C) is 0.1 to 150 parts by weight and the proportion of the compound (D) having a hydrophobic main chain is 0.01 to 100 parts by weight with respect to 100 parts by weight of the carrier (A). 150 parts by weight. In this composition, in order to impart reinforcement, the carrier constituting the carrier (A) having a reactive group is in the form of powder or fiber.NoIt is useful to be an organic material. This carrier (A) is a carrier (A) that has been treated with a surface treatment agent (B) having a reactive group for the bifunctional compound (C), for example, a silane coupling agent, and the like, and a reactive group has been introduced. There may be. Examples of the bifunctional compound (C) include a bisoxazoline compound.Ru.
  The compatibilizing agent of the present invention is a reaction product of the above components and can be represented by the following formula (I) or (II).
[0008]
              A-[(B1)_m-C-D]_n                  (I)
        [D- (B2)_r]_s-A-[(B1)_p-C]_q      (II)
(Where AIs antiCarrier (A) having a reactive group, C is the frontWritingA unit of a bifunctional compound (C) having a functional group capable of reacting with a reactive group of the body (A), D is a unit of a compound (D) having a hydrophobic chain, B1 and B2 are A, An organic group linking C or D, m, p and r are 0 or 1, and n, q and s are integers of 1 or more. m, p and r may be different depending on n, q and s, respectively)
  In the method of the present invention, a carrier (A) having a reactive group, a bifunctional compound (C) having a functional group capable of reacting with the reactive group of the carrier, and a functional group of the bifunctional compound Alternatively, the compatibilizer composition is produced by mixing the compound (D) having reactivity with the reactive group of the carrier and having a hydrophobic main chain.
  In another method of the present invention, a carrier (A) having a reactive group, a bifunctional compound (C) having a functional group capable of reacting with the reactive group of the carrier, and the bifunctional compound ( The compatibilizing agent is obtained by reacting the compound (D) having a functional group of C) or a reactive group with respect to the reactive group of the carrier (A) and having a hydrophobic chain.
[0009]
  Further, in the method of the present invention, the compatibilizer composition is added to a polymer composition that is incompatible with each other (for example, a polymer composition that includes a nonpolar polymer and a polar polymer that is incompatible with the polymer). Alternatively, a method for producing a polymer alloy by adding a compatibilizing agent is also included.
[0010]
  In this specification, “bifunctional compound” means( i )Not limited to compounds having the same or different two functional groups,( ii )A compound having the above two functional groups in addition to a functional group not involved in the reaction (for example, secondary hydroxyl group, imino group, etc.),( iii )A compound having a single functional group that is reactive to a reactive group of the carrier and that generates a functional group by reaction with the reactive group and substantially functions as a bifunctional compound (for example, The term also includes an acid anhydride that generates a carboxyl group by reaction, an epoxy compound that generates a hydroxyl group by reaction, and the like.
  “Bond” is used to mean including a covalent bond, an ionic bond, and a hydrogen bond.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
  [Compatibilizer composition]
  The compatibilizing agent composition comprises a carrier (A) having a reactive group, a bifunctional compound (C) having a reactive functional group with respect to the reactive group of the carrier, and a function of the bifunctional compound (C). And reactive to the reactive group of the group or the carrier (A)HydrophobicIt is comprised with the compound (D) (Hereafter, it may only be called a hydrophobic compound (D).) Which has a property chain. Hydrophobic compound (D) isHydrophobicMay be present in the side chain, but at least in the main chain in many cases.
  [Carrier (A) having a reactive group]
  Consists of a carrier (A) having a reactive groupBurdenTo the bodyAny of organic substances (thermoplastic resins and thermosetting resins) and inorganic substances can be used. Among organic substances, thermoplastic resins include, for example, olefin resins (polyethylene, polypropylene, ethylene-propylene copolymer, polyethylene oxide, polypropylene oxide, maleic anhydride modified polyolefin, glycidyl (meth) acrylate modified polyolefin, (meth) Acrylic acid-modified polyolefin, ethylene-vinyl acetate copolymer, etc.), vinyl acetate resin (polyvinyl acetate, vinyl acetate-vinyl chloride copolymer, etc.), vinyl alcohol resin (eg, polyvinyl alcohol, ethylene-vinyl alcohol copolymer) Polymers), polyvinyl formal (polyvinyl acetal, etc.), rayon, chlorine-containing resins (polyvinyl chloride, vinylidene chloride resins, etc.), fluororesins, acrylic resins (polymethyl methacrylate, methacrylate methacrylate) Ru- (meth) acrylic acid copolymer), styrene resin (polystyrene, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, styrene- Acrylonitrile copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), maleic anhydride modified AS resin, maleic anhydride modified ABS resin, etc.), styrene-acrylic monomer copolymer, polyester (Polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalate such as polyethylene naphthalate, polyarylate, etc.), polyamide (polyamide 6, polyamide 6-6, polyamide 6-10, polyamide 11, polyamide 1) , Aromatic polyamide, etc.), thermoplastic polyurethane resin, polycarbonate resin (bisphenol A type polycarbonate, etc.), polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, liquid crystalline polymer, cellulose ester, etc. It is.
  Examples of thermosetting resins include phenolic resins, amino resins (urea resins, melamine resins, etc.), unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, epoxy resins, polyurethane resins, silicon resins, polyimides, and thermosetting resins. A crosslinked or cured product of a functional resin is also included.
[0012]
  Examples of inorganic substances include carbon, silica sand, silica, silicon dioxide, glass, mica, talc, clay, diatomaceous earth, carbonate (calcium carbonate, magnesium carbonate, etc.), metal sulfate (barium sulfate, etc.), metal oxidation (Silicon oxide, Aluminum oxide (alumina), Titanium oxide, Copper oxide, Silver oxide, Fe oxide)₂O_Three, Fe_ThreeO_Four, Zinc oxide, zirconium oxide, magnesium oxide, etc.), metal hydroxides (such as aluminum hydroxide), metal sulfides (such as cadmium sulfide, zinc sulfide), non-oxide ceramics (carbides such as silicon carbide and boron carbide, Nitride such as titanium nitride, boron nitride, aluminum nitride, silicon nitride, silicide, boride), potassium titanate, aluminum borate, molybdenum disulfide, metal (aluminum, copper, nickel, tungsten, gold, silver, Platinum, cadmium, zinc, lead, etc.).
[0013]
  Burdenthe body'sThe shape is not particularly limited, but it is advantageous that the carrier is in the form of powder or fiber in order to impart high reinforcement. Specific examples of such a carrier include organic particles (crosslinked polymethyl methacrylate, crosslinked polystyrene, etc.), inorganic particles (silica, silica sand, silicon dioxide, calcium carbonate, titanium oxide, aluminum oxide, carbon black). Etc.), organic fiber (polypropylene fiber, polyester fiber, polyamide fiber, vinylon fiber, polyacrylonitrile fiber, etc.), inorganic fiber (glass fiber, carbon fiber, rock wool, silica fiber, alumina fiber, potassium titanate fiber, silicon carbide fiber) , Whisker, etc.).
  The average particle diameter of the granular material is, for example, 1 nm to 50 μm, preferably 5 nm to 30 μm, particularly about 10 nm to 20 μm. The average fiber diameter is, for example, 0.1 to 150 μm, preferably 1 to 100 μm, particularly about 5 to 50 μm, and the average fiber length is, for example, 10 μm to 5 mm, preferably 50 μm to 3 mm, particularly about 100 μm to 2 mm. You can choose from.
[0014]
  [Reactive group and surface treatment agent (B)]
  As long as the carrier (A) has a reactive group (a1) with respect to the functional group of the bifunctional compound (C), the carrier (A1) itself has a reactive group (A1) (for example, an organic polar polymer or carbon black). The surface treatment agent (B) or the reactive group (b2) having a reactive functional group (b1) for the carrier (A) and a reactive group (b2) for the bifunctional compound (C) may be generated. The carrier (A2) into which the reactive group (b2) has been introduced by treating with the surface treating agent (B) to be used may be used. The surface treatment agent (B) can also be referred to as a surface modifier. In addition, even if it is the support | carrier (A1) which has a reactive group itself, you may introduce | transduce a reactive group (b2) further by the said surface treating agent (B) or a surface modifier. The surface treatment agent (B) is usually at leastCarrier orA reactive agent having a reactive functional group (b1) for the carrier (A) and a reactive group (b2) for the bifunctional compound (B) can be used. The reactive functional group (b1) and the reactive group (b2) May be the same or different.
  The reactive groups (a1) and (b2) of the carrier (A) or the surface treatment agent (B) for the bifunctional compound (C) can be selected according to the type of the bifunctional compound (C), and are generally halogenated. Atoms, hydroxyl groups, mercapto groups, carboxyl groups (including active ester groups such as N-succinimidyloxycarbonyl and cyclohexylaminocarbonyl groups), acid anhydride groups, amino groups, epoxy groups (or glycidyl groups) , Isocyanate groups, polymerizable groups (such as vinyl groups and (meth) acryloyl groups), and hydrolyzable organic groups (such as alkoxy groups) of coupling agents such as alcoholates. Preferred reactive groups are usually carboxyl groups (including active ester groups), acid anhydride groups, amino groups, and epoxy groups (or glycidyl groups). In addition, in an organic substance, the monomer which has the said reactive group (For example, carboxyl group containing monomers, such as (meth) acrylic acid and maleic acid, acid anhydride group monomers, such as maleic anhydride, glycidyl (Epoxy group-containing monomers such as (meth) acrylates) and reactive groups may be introduced by copolymerization of oligomers or polymers having reactive groups, and by various reactions such as oxidation, reduction, and halogenation reactions. A reactive group may be introduced into the organic substance. Furthermore, a reactive group may be introduced into an organic substance by a reaction with a reagent having the reactive group or generating a reactive group using a polymer reaction.
  Preferred for inorganic materialsCarrier orThe carrier (A) is often treated with the surface treatment agent (B) or the surface modifier.
[0015]
  Surface treatment agent (B)Carrier orIt can be selected according to the kind of the carrier (A) and the kind of the functional group of the bifunctional compound (C),Carrier orCombinations of the carrier (A) and the surface treatment agent (B) having a reactive functional group (b1) are as follows, for example.
[0016]
  1. BurdenBody isWhen having the following reactive group (a1)
  BurdenBody isIn the case of having the reactive group (a1), the reactive group may be further generated by treating or reacting the carrier (A) with the surface treatment agent (B). In this case, the surface treatment agent (B) can be used in place of the bifunctional compound (C). Therefore, when the carrier (A) having a reactive group is treated or reacted with the surface treatment agent (B), the bifunctional compound (C) is not necessarily required.
[0017]
  (A1-1) Halogen atom:
    (B) an amino group-containing compound, a hydroxyl group-containing compound,
        Mercapto group-containing compound
  (A1-2) Hydroxyl group and mercapto group:
    (B) a carboxyl group-containing compound, an acid anhydride group-containing compound,
        Isocyanate group-containing compounds, oxazoline group-containing compounds,
        Coupling agent
  (A1-3) Carboxyl group and acid anhydride group:
    (B) a hydroxyl group-containing compound, a mercapto group-containing compound,
        Amino group-containing compounds, epoxy group-containing compounds,
        Isocyanate group-containing compounds, oxazoline group-containing compounds,
        Coupling agent
  (A1-4) Amino group:
    (B) a carboxyl group-containing compound, an acid anhydride group-containing compound,
        Epoxy group-containing compounds, isocyanate group-containing compounds,
        Oxazoline group-containing compound, coupling agent
  (A1-5) Epoxy group:
    (B) a carboxyl group-containing compound, an acid anhydride group-containing compound,
        Amino group-containing compounds
  (A1-6) Isocyanate group:
    (B) a hydroxyl group-containing compound, a mercapto group-containing compound,
        Carboxyl group-containing compound, amino group-containing compound
  (A1-7) Vinyl group and (meth) acryloyl group:
    (B) Vinyl group-containing compound, (meth) acryloyl group-containing compound
  2. BurdenBody isWhen it is an inorganic substance (metal oxide, ceramics, etc.)
    (B) Coupling agent
  3. BurdenBody isIf it is metal
    (B) Coupling agent, coordination compound
  Examples of the hydroxyl group-containing compound include diols such as aliphatic diols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, and hexanediol, glycerin, Examples include aliphatic polyhydric alcohols such as trimethylolpropane, alicyclic diols such as 1,4-cyclohexanediol and hydrogenated bisphenol A, and aromatic diols such as alkylene oxide adducts of bisphenol A and bisphenol A. Examples of the mercapto group-containing compound include dithiols corresponding to the diols.
[0018]
  Examples of compounds containing a carboxyl group or an acid anhydride group include dicarboxylic acids (saturated fats such as oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Unsaturated aliphatic dicarboxylic acid such as aliphatic dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic acid, highmic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, etc. Alicyclic dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and other aromatic dicarboxylic acids) or acid anhydrides or derivatives thereof (for example, lower alkyl esters such as methyl esters, carboxylic acids) Halide, active ester, etc.).
  The carboxyl group-containing compound may have a hydroxyl group. Examples of the compound having a hydroxyl group and a carboxyl group include aliphatic oxycarboxylic acids (for example, glycolic acid, lactic acid, oxypropionic acid, daltonic acid, malic acid, tartaric acid, citric acid, pantothenic acid, etc.), aromatic oxycarboxylic acids (P-hydroxybenzoic acid, salicylic acid, etc.) and the like are included. Examples of the compound having a hydroxyl group and a carboxyl group include oxycarboxylic acids having about 6 to 18 carbon atoms such as oxyhexanoic acid, oxyoctanoic acid, oxydecanoic acid, oxidodecanoic acid, and oxyoctadecanoic acid, and corresponding lactones (γ-caprolactone). , Γ-laurolactone, γ-palmilactone, γ-stearolactone, δ-valerolactone, δ-caprolactone, etc.).
[0019]
  Examples of the amino group-containing compound include aliphatic diamines (for example, ethylenediamine, γ- (methylamino) propylamine, diaminopropane, tetramethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 1, 10-diaminodecane, α, ω-C_11-12Alkylenediamine, alkylenediamine such as 1,12-diaminododecane, heptacamethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, polyetherdiamine, etc.), alicyclic diamine (isophoronediamine, bis (aminomethyl) cyclohexane, Bis (4-amino-3-methylcyclohexyl) methane), aromatic diamine (m- or p-phenylenediamine, diaminotoluene, xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone and the like).
  The amino group-containing compound may have a hydroxyl group or a carboxyl group. Examples of the compound having an amino group and a hydroxyl group include amino alcohol (2-aminoethanol, diethanolamine, 2-aminoisopropanol, etc.), aminophenol and the like.
  Examples of the compound having an amino group and a carboxyl group include amino acids (glycine, alanine, valine, leucine, isoleucine, lysine, serine, threonine, phenylalanine, aspartic acid, glutamic acid, methionine, arginine, tryptophan, histidine, proline, oxy Examples thereof include proline and cystine) or active esters thereof, aliphatic aminocarboxylic acids (aminocaproic acid, aminoundecanoic acid) or corresponding lactams, aromatic aminocarboxylic acids (aminobenzoic acid and the like), and the like.
[0020]
  Examples of the epoxy group-containing compound include alkylene oxide (ethylene oxide, propylene oxide, etc.), epichlorohydrin, glycidyl ether (bisphenol A type epoxy compound, alkylene glycol diglycidyl ether, polyoxyalkylene glycol diglycidyl ether, 1,4-cyclohexane. Dimethanol diglycidyl ether), glycidyl ester (diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimer acid diglycidyl ester, etc.), glycidyl amine (diglycidyl aniline, diglycidyl toluidine, N, N-diglycidyl) -4-glycidyloxyaniline and the like).
[0021]
  Examples of the isocyanate group-containing compound include aromatic diisocyanates (tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, etc.), alicyclic diisocyanates (isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), Methylcyclohexane diisocyanate), aliphatic diisocyanate (hexamethylene diisocyanate, lysine diisocyanate, etc.) and the like.
[0022]
    Examples of the vinyl group or (meth) acryloyl group-containing compound include compounds having a hydroxyl group (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, etc.)._2-10Alkylene glycol mono (meth) acrylate, polyoxy C_2-4Alkylene glycol mono (meth) acrylate, allyl alcohol, etc.), compounds having carboxyl groups or acid anhydride groups ((meth) acrylic acid, itaconic acid, maleic anhydride, etc.), compounds having amino groups (aminostyrene, vinylamine, Examples thereof include allylamine and the like, compounds having an epoxy group (such as allyl glycidyl ether and glycidyl (meth) acrylate), and compounds having an isocyanate group (such as vinyl isocyanate).
[0023]
  The oxazoline group-containing compound includes a bisoxazoline compound represented by the following formula.
[0024]
[Chemical 6]

(In the formula, E represents an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, or an arylene group which may have a substituent;¹, R², R^ThreeAnd R^FourAre the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. )
  In the bisoxazoline compound represented by the above formula, examples of the alkylene group for E include C_1-10An alkylene group (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene group, etc.) and the like can be mentioned. Cycloalkylene groups include, for example, C_5-10A cycloalkylene group (for example, 1,3-cyclopentylene, 1,3-cyclohexylene, 1,4-cyclohexylene group, etc.) and the like are included. The arylene group includes C_6-12Arylene groups (for example, 1,3-phenylene, 1,4-phenylene, 1,5-naphthylene, 2,5-naphthylene group, etc.) are included.
  The alkylene group, cycloalkylene group and arylene group may have a substituent. Examples of such substituents include halogen atoms (eg, fluorine, chlorine, bromine atoms), alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, etc.). And an alkoxy group (for example, an alkoxy group having about 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.).
  Preferred E includes an aryl group which may have a substituent, particularly a phenylene group which may have a substituent (for example, a 1,3-phenylene group or a 1,4-phenylene group). .
[0025]
  In the above formula, R¹, R², R^ThreeAnd R^FourExamples of the alkyl group represented by C include, for example, C such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups._1-10An alkyl group is exemplified. A preferable alkyl group is a lower alkyl group having about 1 to 6 carbon atoms, particularly a lower alkyl group having 1 to 4 carbon atoms (for example, particularly a methyl group, an ethyl group, a propyl group, an isopropyl group, etc.).
  R¹, R², R^ThreeAnd R^FourThe aryl group represented by the formula includes phenyl, 1-naphthyl, 2-naphthyl group and the like.
  The alkyl group or aryl group may have a substituent. Examples of the alkyl group having a substituent include halogenated C such as dichloromethyl, trichloromethyl, trifluoromethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl._1-4Alkyl groups and the like are included. Examples of the aryl group having a substituent include a phenyl group having a halogen atom such as 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, and 3,5-dichlorophenyl group, 2-methylphenyl, 3 -C such as methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 4-ethylphenyl group_1-4C such as alkyl-phenyl group, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, 4-ethoxyphenyl group_1-4An alkoxy-phenyl group etc. are mentioned.
  A particularly preferred bisoxazoline compound can be represented by the following formula.
[0026]
[Chemical 7]

(Wherein R¹, R², R^ThreeAnd R^FourAre the same or different and are a hydrogen atom or C_1-4An alkyl group is shown. )
  In particular, R¹And R²At least one (especially R²) Is a hydrogen atom, R^ThreeAnd R^FourAt least one (especially R^Four) Is preferably a hydrogen atom. More preferably, R¹, R², R^ThreeAnd R^FourAre all hydrogen atoms.
[0027]
  Specific examples of preferable compounds among the bisoxazoline compounds represented by the above formula include, for example, 1,6-bis (1,3-oxazolid-2-yl) hexane, 1,8-bis (1,3-oxazoli). -2-yl) octane, 1,10-bis (1,3-oxazol-2-yl) decane, 1,3-bis (1,3-oxazoli-2-yl) cyclohexane, 1,4-bis (1 , 3-Oxazolin-2-yl) cyclohexane, 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,4-phenylene) -bis (2-oxazoline) 2,2 '-(1,2-phenylene) -bis (2-oxazoline), 2,2'-(1,3-phenylene) -bis (4-methyl-2-oxazoline), 2,2'- (1,4-Phenylene) -bis (4-methyl) -2-oxazoline), 2,2 '-(1,2-phenylene) -bis (5-methyl-2-oxazoline), 2,2'-(1,3-phenylene) -bis (5-methyl-2) -Oxazoline), 2,2 '-(1,4-phenylene) -bis (5-methyl-2-oxazoline), 2,2'-(1,3-phenylene) -bis (4-methylphenyl-2-) Oxazoline), 2,2 '-(1,4-phenylene) -bis (4-methylphenyl-2-oxazoline), 2,2'-(1,3-phenylene) -bis (4-chlorophenyl-2-oxazoline) ), 2,2 '-(1,4-phenylene) -bis (4-chlorophenyl-2-oxazoline), and the like.
  One or two or more bisoxazoline compounds can be used.
  The bisoxazoline compound can be prepared by a conventional method, for example, a method in which a fatty acid or its methyl ester and ethanolamine are reacted in the presence of a catalyst to form a heterocyclic 5-membered ring compound (“Plastic Age”, page 114, Mar. .1995) can be obtained by reacting a dicarboxylic acid corresponding to E in the above formula or a lower alkyl ester thereof with ethanolamine or a derivative thereof to form a heterocyclic 5-membered ring compound.
[0028]
  Examples of the coupling agent include organometallic compounds having a hydrolyzable organic group, such as a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. Preferred coupling agents are selected from organic silicon compounds such as silane coupling agents such as halogen atoms, hydroxyl groups, mercapto groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups, vinyl groups, and (meth) acryloyl groups. And silicon compounds having at least one functional group and a hydrolyzable group (alkoxy group) or silyl group. Preferred reactive groups of organosilicon compounds (particularly silane coupling agents) are halogen atoms, hydroxyl groups, mercapto groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups (particularly hydroxyl groups, mercapto groups, carboxyl groups, amino groups). Group, epoxy group, isocyanate group). The silane coupling agent may have one or two or more reactive groups.
[0029]
  Halogen atoms include chlorine, bromine, iodine atoms, etc., and an epoxy group is an unsaturated bond of a hydrocarbon group (for example, an unsaturated double bond of a cycloalkenyl group such as a cyclopentenyl group or a cyclohexenyl group). It may be composed of an epoxy ring produced by oxidation of glycidyl or an epoxy ring of a glycidyl group. The amino group contains 1 or 2 lower C_1-4An alkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl group, etc.) may be substituted, and the (meth) acryloyl group may be composed of a (meth) acryloyloxy group.
  Examples of the alkoxy group of the silane coupling agent include C, such as methoxy, ethoxy, furopoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, and t-butoxy groups._1-4An alkoxy group is included. Preferred alkoxy groups are hydrolyzable alkoxy groups (particularly methoxy groups or ethoxy groups).
  In the silane coupling agent, the number of reactive groups is about 1 to 3 (particularly 1 or 2), and the number of alkoxy groups is about 1 to 3 (particularly 2 or 3).
  Specific examples of the silane coupling agent include halogen-containing silane coupling agents (2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane). Hydroxyl group-containing silane coupling agent (2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, etc.), mercapto group-containing silane cup Ring agent (2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc.), carboxyl group Silane coupling agent (carboxymethyltrimethoxysilane, carboxymethyltriethoxysilane, 2-carboxyethyltrimethoxysilane, 2-carboxyethyltriethoxysilane, 3-carboxypropyltrimethoxysilane, 3-carboxypropyltriethoxysilane) Amino group-containing silane coupling agents (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysilane) 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- (2-aminoethyl) amino] propyltriethoxysilane, etc.), epoxy group-containing silane coupling agent [2- (3,4) -Epoxy Rohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxy Ethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, etc.], isocyanate group-containing silane coupling agent (2-isocyanatoethyltrimethoxysilane, 2-isocyanatoethyltriethoxysilane, 3 -Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents (vinyltrimethoxysilane, vinyltriethoxy) Silane etc.), (meth) acryloyl group-containing silane coupling agent (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane , 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc.). These silane coupling agents can be used alone or in combination of two or more.
[0030]
  Also, bearBody isWhen it is a metal, examples of the compound (coordinating compound) having at least a functional group capable of coordinating with the metal include a mercapto alcohol (mercaptoethanol, etc.), a sulfur or nitrogen-containing compound (cystine, histidine, etc.) Examples thereof include a group-containing silane coupling agent (such as mercaptopropyltrimethoxysilane). For example, in the case of mercaptoethanol, the mercapto group forms a coordinate bond with the above exemplified metals (gold, platinum, etc.), so that the remaining hydroxyl group can be used for the reaction with the bifunctional compound (C).
[0031]
  [Bifunctional compound (C)]
  As the bifunctional compound (C), various compounds in which at least one of the two functional groups is reactive with the reactive group of the carrier (A) or the surface treatment agent (B) are used. The functional group of the bifunctional compound (C) can be selected according to the type of the reactive group of the carrier (A) or the surface treatment agent (B). The kind of the functional group of the bifunctional compound (C) may be the same or different.
  As the functional group (c) of the bifunctional compound (C), depending on the reactive group (a) of the carrier (A) or the surface treatment agent (B), for example, the above-mentioned itemsoIt can be selected in the same manner as the combination of the reactive group (a1) of the exemplified carrier (A) and the surface treatment agent (B). In addition, as a bifunctional compound (C), compounds other than a coupling agent and a coordination compound are used normally.
[0032]
  Preferred difunctional compounds (C) are polar having polar groups (for example, polar bonds such as ester bonds and amide bonds, polar groups such as hydroxyl groups, carboxyl groups, acid anhydride groups, amino groups and amide groups). Group-containing compounds are included. Preferred bifunctional compounds (C) include compounds having functional groups reactive with hydroxyl groups, carboxyl groups, epoxy groups, and amino groups (for example, carboxyl group or acid anhydride group-containing compounds, amino group-containing compounds). , Oxazoline group-containing compounds), particularly amino group-containing compounds (diamines) and oxazoline group-containing compounds (bisoxazoline compounds).
[0033]
  [Hydrophobic compound (D)]
  The hydrophobic compound (D) is reactive to the reactive group of the carrier (A) or the functional group of the bifunctional compound (C).HydrophobicHas a sex chain. That is, the hydrophobic compound (D) usually has a reactive group containing an active hydrogen atom, and this reactive group is a reactive group and / or a bifunctional compound (C) of the carrier (A). ). The hydrophobic chain may constitute the side chain of the compound (D), but usually constitutes the main chain.
[0034]
  The hydrophobic compound (D) may be a low molecular weight compound or a high molecular weight compound (polymer) as long as it has a hydrophobic (main) chain. The high molecular weight compound includes an oligomer region polymer having a relatively small molecular weight. The main chain of the hydrophobic compound is usually composed mainly of hydrocarbon groups, preferably aliphatic hydrocarbon groups. The hydrocarbon group may be a saturated hydrocarbon group (for example, methylene, ethylene, propylene unit, etc.) or an unsaturated hydrocarbon group (for example, butadiene unit, etc.). The ratio of the hydrocarbon group in the main chain is, for example, about 50 mol% or more (50 to 100 mol%), preferably about 70 to 100 mol%, and more preferably about 80 to 100 mol%.
[0035]
  In the hydrophobic compound, examples of the reactive group containing an active hydrogen atom include a hydroxyl group, a mercapto group, a carboxyl group, an acid anhydride group, and an amino group, which may be phenolic. The hydrophobic compounds may have the same reactive group or may have a plurality of different reactive groups. Preferred reactive groups include reactive groups that are highly reactive with the reactive group of the carrier and / or the functional group of the bifunctional compound (for example, functional groups that are highly active towards oxazolines (eg, hydroxyl groups, carboxyls Groups and amino groups)], in particular carboxyl groups.
  Furthermore, the hydrophobic compound having a hydrophobic main chain may be a hydrophilic compound, but is usually hydrophobic and insoluble in water.
[0036]
  Low molecular weight hydrophobic compound (D1)
  As the low molecular weight hydrophobic compound (D1), a low-volatile compound that is liquid or solid at room temperature (for example, a non-volatile compound having a boiling point of 150 ° C. or higher at normal pressure) is often used, and a molecular weight of 1000 The following (preferably 100 to 750, more preferably about 150 to 750) compounds are often used. The main chain of such a compound is usually composed of an aliphatic hydrocarbon group having about 6 to 30 carbon atoms (preferably 8 to 26 carbon atoms, more preferably 10 to 24 carbon atoms).
[0037]
  Examples of the low molecular weight hydrophobic compound having a hydroxyl group include aliphatic alcohols having about 10 to 30 carbon atoms (for example, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, octadecyl alcohol, aralkyl alcohol, ceryl alcohol, melylyl). Alcohol, oleyl alcohol, etc.), aliphatic diols having about 4 to 10 carbon atoms (1,4-butanediol, 1,6-hexanediol, etc.), compounds having a phenolic hydroxyl group [eg, phenol, alkylphenol (eg, Alkyl group having 4 to 20 carbon atoms, preferably about 8 to 14 carbon atoms), and the like. Preferred hydrophobic low molecular weight compounds include C_10-26Fatty alcohols (especially C_12-24Aliphatic alcohol), and a compound having a phenolic hydroxyl group (for example, the alkylphenol and the like).
  Examples of the low molecular weight hydrophobic compound having a mercapto group include thioalcohols corresponding to the aliphatic alcohols.
[0038]
  Examples of the low molecular weight hydrophobic compound having a carboxyl group or an acid anhydride group include carboxylic acids having 6 or more carbon atoms such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid. , Dioxystearic acid, behenic acid, montanic acid, etc._6-30C such as saturated fatty acid, Linderic acid, palmitooleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, erucic acid_10-24Saturated polycarboxylic acid having about 4 to 40 carbon atoms such as unsaturated fatty acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, maleic acid, maleic anhydride, fumaric acid, citracone Examples thereof include unsaturated polyvalent carboxylic acids such as acid, itaconic acid and glutaconic acid, dimer acid, and acid anhydrides corresponding thereto. These carboxylic acids or acid anhydrides can be used singly or in combination.
  Of these carboxylic acids or acid anhydrides, carboxylic acids having 6 or more carbon atoms, particularly aliphatic monocarboxylic acids, especially higher fatty acids are often used. The carbon number of the higher fatty acid is, for example, preferably about 10 to 26 carbon atoms, and more preferably about 12 to 24 carbon atoms. The higher fatty acid may be an unsaturated higher fatty acid, but a saturated higher fatty acid is advantageously used.
[0039]
  Examples of the low molecular weight hydrophobic compound having an amino group include primary amines such as caprylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, didecylamine, didodecylamine, ditetradecylamine, Examples include secondary amines such as dihexadecylamine and dioctadecylamine, and diamines such as hexamethylenediamine. Preferred amine compounds include higher amines having about 10 to 26 carbon atoms, preferably about 12 to 24 carbon atoms (for example, 12 to 18 carbon atoms), especially primary amines. These amine compounds can also be used singly or in combination.
[0040]
  Furthermore, the low molecular weight hydrophobic compound includes compounds having different reactivity, for example, a compound having a carboxyl group and an amino group, a compound having a carboxyl group and a hydroxyl group, and the like. Examples of such compounds include aminocarboxylic acids having about 6 to 18 carbon atoms such as aminocaproic acid and aminoundecanoic acid, and corresponding lactams, oxyhexanoic acid, oxyoctanoic acid, oxydecanoic acid, oxide decanoic acid, and oxyoctadecanoic acid. Such as oxycarboxylic acids having about 6 to 18 carbon atoms and corresponding lactones (γ-caprolactone, γ-laurolactone, γ-palmilactone, γ-stearolactone, δ-valerolactone, δ-caprolactone, etc.) Can be mentioned.
  These low molecular weight hydrophobic compounds (D1) may be used in combination of a plurality of different types of compounds.
[0041]
  High molecular weight hydrophobic compound (polymer) (D2)
  The high molecular weight hydrophobic compound (hydrophobic polymer) (D2) may be linear or branched. The type of polymer having a hydrophobic (main) chain is not particularly limited, and examples thereof include olefin polymers, styrene polymers, acrylic polymers, and the like. Preferred polymers are olefin polymers and styrene polymers.
  The olefin polymer is, for example, an olefin such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene; a polymerizable monomer such as a diene such as 1,3-butadiene and isoprene. Obtainable. The styrenic polymer can be obtained from a polymerizable monomer such as a styrene monomer such as styrene or α-methylstyrene.
[0042]
  The hydrophobic polymer is not limited to the polymerizable monomer alone or a copolymer, but may be a copolymer of the polymerizable monomer and a copolymerizable monomer. The polymerization form of the copolymer is not particularly limited, and may be any of a random polymer, a block copolymer, a graft copolymer, and the like. Examples of the copolymerizable monomer include acrylic monomers such as acrylic acid esters, methacrylic acid esters, and acrylonitrile; vinyl ester monomers such as vinyl acetate and vinyl propionate. One or two or more copolymerizable monomers can be used.
[0043]
  Examples of the polymer having a hydrophobic (main) chain include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer. Olefinic polymer such as polymer, polybutene, polybutadiene, acrylonitrile-butadiene copolymer, polyisobutylene, polyisoprene, polymethylpentene; polystyrene, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer Examples thereof include styrenic polymers such as polymers and hydrogenated products thereof.
[0044]
  The molecular weight of the hydrophobic polymer is not particularly limited, but a relatively low molecular weight is advantageous in order to alloy with a small amount of addition or to improve the modification efficiency. Such low molecular weight polymers include low molecular weight polyethylene, low molecular weight polypropylene, liquid polypropylene, liquid polybutadiene, polybutene, liquid polyisobutylene, liquid butyl rubber and other low molecular weight or liquid polyolefins; low molecular weight styrenic polymers; Is included. Particularly preferred polymers include olefinic polymers such as polyethylene.
[0045]
  Such a hydrophobic polymer has a reactive group containing an active hydrogen atom, for example, a hydroxyl group, a mercapto group, a carboxyl group, an amino group, and the like, like the low molecular weight compound. Such a reactive group is obtained by copolymerizing a monomer having a hydroxyl group, a mercapto group, a carboxyl group or an amino group together with the polymerizable monomer, and optionally the copolymerizable monomer. It can be introduced into the polymer having the hydrophobic (main) chain. The reactive group can also be introduced by a polymer reaction of the hydrophobic polymer.
[0046]
  Examples of the monomer having a hydroxyl group include allyl alcohol, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like. The monomer having a mercapto group includes a compound corresponding to the monomer having a hydroxyl group. Examples of the monomer having a carboxyl group or an acid anhydride group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, 10-undecylene acid, vinylbenzoic acid, 5-norbornene-2-carboxylic acid, Ethylenically unsaturated carboxylic acids such as maleic anhydride and anhydrides thereof are included. Monomers having an amino group include aminostyrene, vinylamine, allylamine and the like. Preferred monomers include monomers having a carboxyl group or amino group, particularly a carboxyl group.
[0047]
  Examples of the polymer having a carboxyl group or an acid anhydride group introduced by a copolymerization reaction include modified polyolefins such as ethylene- (meth) acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, and ethylene-maleic anhydride. Examples include acid copolymers (maleic anhydride-modified polyethylene), propylene-maleic anhydride copolymers (maleic anhydride-modified polypropylene), and ethylene- (meth) acrylic acid-maleic anhydride copolymers.
[0048]
  As a method for introducing a hydroxyl group, a carboxyl group, or an amino group by a polymer reaction, a conventional method can be employed. For example, a hydroxyl group can be introduced by copolymerization and hydrolysis reaction of vinyl acetate or ethylene carbonate, reduction reaction of carbonyl group or carboxyl group generated by oxidation reaction of olefin polymer, etc., and the polymer has an unsaturated bond. In some cases phenol by Friedel-Crafts reactionBaseAcetic acid by the introduction of and Friedel-Crafts reactionBaseCan be introduced by hydrolysis reaction. The carboxyl group can be introduced by oxidation reaction, thermal decomposition reaction, heat treatment using peroxide, or reaction with maleic anhydride in the presence of peroxide when the polymer has an unsaturated bond. The amino group can be introduced by copolymerization and hydrolysis reaction of N-vinylformamide, and can also be generated by reacting a polymer having a carboxyl group with an acid chloride and a diamine such as p-phenylenediamine.
[0049]
  Although the molecular weight of the polymer having a hydrophobic (main) chain is not particularly limited, for example, the weight average molecular weight is 500 to 250,000, preferably 700 to 100,000, and more preferably about 1,000 to 25,000. Particularly preferred polymers include relatively low molecular weight polymers having a molecular weight of about 1000 to 25000 (eg, molecular weight of 1000 to 10,000, preferably about 1000 to 5000).
[0050]
  [Compatibilizer composition and production method thereof]
  The compatibilizing agent composition of the present invention comprises at least the carrier (A), the bifunctional compound (C) and the hydrophobic compound (D) together with the surface treatment agent (B) as necessary. The compatibilizer composition can be prepared by mixing the components, and some of the components may be reacted in advance. Preferred combinations of the components are as follows.
  (1) Carrier (A) (in particular, a carrier composed of an inorganic substance such as an organic substance or carbon black) having a reactive group inherently without being treated with a surface treatment agent, and a carrier(A)Bifunctional compound (C) having a functional group capable of reacting with the reactive group, and a hydrophobic compound having reactivity with the functional group of the bifunctional compound or the reactive group of the carrier (A) Combination with (D)
  (2) Inactive carrier for the bifunctional compound (C)body(In particular, a carrier composed of an inorganic substance) and a reactive group introduced to this carrierTo produce a carrier (A) having a reactive groupA surface treatment agent (B), a bifunctional compound (C) having a functional group capable of reacting with a reactive group of the surface treatment agent, and a functional group or carrier (A) of the bifunctional compound Combination with a hydrophobic compound (D) having reactivity to the reactive group of
  (3) Surface treatment with the surface treatment agent (B), and a reactive group introducedbody(Especially carriers composed of inorganic substances)(A)And carrier(A)The bifunctional compound (C) having a functional group capable of reacting with the reactive group, and the reactive group of the bifunctional compound or the reactive group of the carrier (A).HydrophobicCombination with the active compound (D)
  (4) The surface treated with the surface treatment agent (B) and reacted with the bifunctional compound (C)body(Especially carriers composed of inorganic substances)(A)And reactive to the functional group of this bifunctional compound (C) or the reactive group of the carrier (A)HydrophobicCombination with the active compound (D)
  (5) The surface treatment agent (B) is surface-treated and the reactive group is introduced.body(Especially carriers composed of inorganic substances)(A)And a bifunctional compound (C)HydrophobicA reaction product with a reactive compound (D), which is reactive with the reactive group of the carrier and has a hydrophobic chain
  In order to impart high reinforcing properties, the combination of (1) is useful when the support is an organic substance (particularly a powdered or fibrous organic substance), and at least the surface when the support is an inorganic substance. A combination containing the carrier (A) having a reactive group introduced by treatment or reaction of the treatment agent (B), that is, a combination of the above (3), (4) and (5) is useful.
  The compatibilizer composition may be composed of a combination of the above components, and may be a uniform or non-uniform mixture.
  In addition, as a reaction method of two or more components, various methods described in the section of “Method for producing compatibilizer” described later can be employed.
[0051]
  The ratio of each component which comprises a compatibilizer composition can be selected in the range which can provide compatibility and reinforcement to the polymer composition comprised by the some polymer. The amount of the surface treatment agent (B) used can be selected according to the type and surface area of the carrier (A) and the type of the bifunctional compound (C).A carrier having no reactive group or0 to 250 parts by weight (for example, 0.1 to 250 parts by weight), preferably 0 to 200 parts by weight (1 to 200 parts by weight), more preferably 0 to 150 parts by weight with respect to 100 parts by weight of the carrier (A). It can be selected from a range of about (for example, 1 to 150 parts by weight).
  The amount of the bifunctional compound (C) used is, for example, 0.1 to 150 parts by weight (for example, 0.1 to 120 parts by weight), preferably 0.1 to 120 parts by weight with respect to 100 parts by weight of the carrier (A). It is about 100 parts by weight (for example, 1 to 75 parts by weight).
  The proportion of the hydrophobic compound (D) is, for example, 0.01 to 150 parts by weight, preferably 0.01 to 100 parts by weight, and more preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the carrier (A). Degree.
[0052]
  When such a compatibilizing agent composition is used, each component is simply added to a composition containing a plurality of incompatible polymers without causing the components to react with each other, and the above non-compatibility composition is melted and mixed. Compatible polymers can be alloyed. In addition, it is considered that the compatibilization of a plurality of polymers occurs in the melt mixing process. Therefore, it is not necessary to adjust the composition of the compatibilizer by reacting each component according to the combination of incompatible polymers with each other, and the degree of freedom in designing the compatibilizer and the choice of materials are increased. The solubilizer can be designed efficiently. Further, the phase separation structure can be refined and the reinforcing property can be imparted by the dispersion of the carrier, particularly the granular or fibrous carrier.
[0053]
  [Compatibilizer]
  In the present invention, if necessary, the carrier (A), the bifunctional compound (C) and the hydrophobic compound (D) treated with the surface treatment agent (B) are reacted, and the reaction product is used as a compatibilizing agent. May be. Such a compatibilizing agent can be represented by the following formula (I) or (II).
            A-[(B1)_m-C-D]_n                (I)
    [D- (B2)_r]_s-A-[(B1)_p-C]_q      (II)
Wherein A is a carrier, B1 and B2 are a carrier A and a bifunctional compound C having a free functional group orHydrophobicAn organic group for linking the compound D having a sex chain, m, p and r are 0 or 1, and n, q and s are integers of 1 or more. m, p and r may be different depending on n, q and s, respectively)
  That is, in the formula, A isA carrier having no reactive group orThe carrier (A), B1 and B2 are bonded to the carrier (A) and have a free functional group unit of the compound (B), and C is the functional group of the carrier (A) or the compound (B). A unit of the bifunctional compound (C) that reacts and has a free functional group, D reacts to the functional group of the compound (B) or the bifunctional compound (C), andHydrophobicThe unit of the compound (D) having a sex chain is shown.
[0054]
  The compatibilizing agent represented by the formula (I) is obtained by reacting the carrier (A) with the bifunctional compound (C) directly or via the surface treatment agent (B), and then bifunctional compound. It corresponds to the reaction product obtained by reacting the hydrophobic compound (D) with the remaining functional group. The compatibilizer represented by the formula (II) reacts the bifunctional compound (C) and the hydrophobic compound (D) sequentially with the carrier (A) directly or via the surface treatment agent (B). Corresponding to the reaction product.
[0055]
  In the formulas (I) and (II), B1 and B2 are linking groups (for example, oxygen atom, sulfur atom, COO group, NH group, NHCO group, —CH (OH) generated by reaction with the carrier (A). ) -CH₂It corresponds to the residue of the surface treatment agent (B) containing-, -SiO- and the like. Preferred B1 and B2 include a bonding group (oxygen atom, COO group, NH group, NHCO group, —CH (OH) —CH₂-, -SiO- and the like) coupling agent residues (particularly silane coupling agent residues).
  The reactive group of the carrier (A) or the reactive group remaining in the surface treatment agent (B) is a bonding group (for example, an oxygen atom, a sulfur atom, a COO group, an NH group, an NHCO group, —CH (OH) -CH₂-Etc.) and is bound to the bifunctional compound (C).
[0056]
  m, p, and r are 0 or 1, corresponding to the presence or absence of the surface treatment agent (B), and n, q, and s are 1 or more corresponding to the introduction amount of the bifunctional compound (C) or the hydrophobic compound (D). And m, p and r may be different depending on n, q and s.
[0057]
  In the formulas (I) and (II), the unit of the hydrophobic compound (D) constitutes the terminal and / or side chain of the compatibilizing agent. The unit of the preferred hydrophobic compound (D) is often bonded to at least the terminal in the low molecular weight hydrophobic compound (D1), and is bonded to at least the side chain in the high molecular weight hydrophobic compound (D2).
[0058]
  A preferable compatibilizer can be represented by the following formula (i) or (ii).
[0059]
[Chemical 8]

(Wherein R¹, R², R^ThreeAnd R^FourAre the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A, B1, B2, D, E, m, n, p, q, r, and s are the same as described above. )
  The compatibilizer represented by the formula (i) or (ii) corresponds to a compatibilizer using a bisoxazoline compound as a bifunctional compound.
  In the formula (i) and formula (ii), R¹, R², R^ThreeAnd R^FourIs as described above. Preferred R¹, R², R^ThreeAnd R^FourIs a hydrogen atom or C_1-4It is an alkyl group, and examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, and t-butyl groups. Further preferred alkyl groups include methyl, ethyl groups, especially methyl groups. Particularly preferred R¹And R^ThreeIs a hydrogen atom or C_1-4An alkyl group (especially a methyl group), preferably R²And R^FourIs a hydrogen atom.
  In the formulas (i) and (ii), the hydrophobic compound (D) is a linking group (oxygen atom, sulfur atom, COO) formed by the reaction with the remaining reactive group of the oxazoline group or the surface treating agent (C). And a surface treatment agent (C) via an oxazoline ring-opening unit. Preferred linking groups usually include oxygen atoms, COO groups and NH groups, especially COO groups.
[0060]
  Furthermore, the compatibilizer represented by the formula (i) and the formula (ii) includes a compatibilizer using a low molecular weight hydrophobic compound (D1) as the hydrophobic compound (D), and a high molecular weight hydrophobic agent. It can be roughly classified into a compatibilizing agent using the compound (D2).
  The compatibilizing agent using the low molecular weight hydrophobic compound (D1) can be represented by the following formulas (ia) and (ia).
[0061]
[Chemical 9]

(In the formula, D1 represents an aliphatic hydrocarbon group having 6 to 30 carbon atoms;¹, R², R^ThreeAnd R^FourIs a hydrogen atom or C_1-4Represents an alkyl group, R¹And R²At least one of them is a hydrogen atom, R^ThreeAnd R^FourAt least one of these is a hydrogen atom. A, B1, B2, m, n, p, q, r, and s are the same as above)
  The compatibilizer using the high molecular weight hydrophobic compound (D2) can be represented by the following formulas (ib) and (iib).
[0062]
[Chemical Formula 10]

(In the formula, Y and Z each represent a hydrocarbon group constituting the main chain of the polymer, Z may have an unsaturated bond, and a / (a + b) = 0.1 to 20 mol%. R¹, R², R^ThreeAnd R^FourIs a hydrogen atom or C_1-4Represents an alkyl group, R¹And R²At least one of them is a hydrogen atom, R^ThreeAnd R^FourAt least one of these is a hydrogen atom. A, B1, B2, m, n, p, q, r, and s are the same as above)
  In the compounds represented by the formulas (ib) and (iib), when the main chain of the polymer is composed of an olefin polymer, the Y is C_nH_2n-1(N represents an integer of 1 to 4), and Z is C_nH_2nOr C_nH_2n-2(N is the same as above). In the high molecular weight compatibilizing agent represented by the formulas (ib) and (iib), a / (a + b) is preferably about 0.5 to 10 mol%, particularly about 0.5 to 7 mol%.
[0063]
  When such compatibilizers (I) and (II) are added to a plurality of incompatible polymer compositions, the incompatible polymers can be effectively compatibilized. For example, when the compatibilizers (ia) (ib) and (ia) (iib) are added to a plurality of incompatible polymer compositions, the hydrophobic chains and the remaining oxazoline groups or amide bonds are utilized. The polymer can be phase-dispersed in the matrix polymer and effectively compatibilized. Furthermore, the phase separation structure can be refined by the dispersion effect of the carrier, particularly the granular or fibrous carrier, and reinforcement can be effectively imparted.
[0064]
  [Method for producing compatibilizer]
  The compatibilizing agent has a carrier (A) having a reactive group treated or reacted with the surface treating agent (B) as necessary, and a functional group capable of reacting with the reactive group of the carrier. It has a functional group (C) and a functional group of the bifunctional compound (C) or a reactive group for the reactive group of the carrier (A).HydrophobicIt can be obtained by reacting the compound (D).
[0065]
  For the reaction between the carrier (A) and the surface treatment agent (B), an ordinary organic synthesis reaction can be used depending on the kind of the carrier and the kind of the reactive group of the carrier and the surface treatment agent. For example, dehydrohalogenation reaction can be used for the carrier having (a1-1) halogen atom, and esterification, urethanization reaction, ring opening of oxazoline group can be used for carrier having (a1-2) hydroxyl group and mercapto group. Reactions and condensation reactions of coupling agents can be used. (A1-3) For a carrier having a carboxyl group and an acid anhydride group, esterification, amidation reaction, epoxy ring-opening reaction, addition reaction to isocyanate group (amide bond formation reaction), ring-opening reaction of oxazoline group, coupling A condensation reaction of the agent can be used. (A1-4) For a carrier having an amino group, an amidation reaction, an epoxy ring-opening reaction, an addition reaction to an isocyanate group (urea bond formation reaction), an oxazoline group ring-opening reaction, a coupling agent condensation reaction, and the like can be used. (A1-5) Epoxy ring-opening reaction can be used for a carrier having an epoxy group, and (a1-6) an addition reaction for an isocyanate group (urethane bond formation reaction, urea bond formation reaction, Amide bond formation reaction etc.) can be used, and (a1-7) a carrier having a vinyl group and a (meth) acryloyl group can use an addition (polymerization) reaction.
[0066]
  The reaction ratio of each component can be selected from a wide range according to the type of the carrier and the surface area. The ratio of the surface treatment agent (B) is, for example, 0 to 1000 parts by weight (for example, 0.1 to 1000 parts by weight), preferably 0 to 500 parts by weight (for example, 0 to 100 parts by weight of the carrier (A)). 0.1 to 500 parts by weight), more preferably 0.2 to 200 parts by weight (for example, 0.2 to 150 parts by weight). The reaction may be carried out in the presence or absence of a catalyst, and can be carried out in the presence or absence of an organic solvent. As the organic solvent, a poor solvent that does not solubilize the carrier is often used. The reaction temperature can be selected from the range of about 20 to 150 ° C., for example, depending on the type of the carrier and the surface treatment agent. The particulate reaction product may be separated by filtration or the like, washed with an appropriate solvent, and used for the subsequent reaction.
  More specifically, the reaction between the organic or inorganic carrier and the silane coupling agent is performed by, for example, dispersing the carrier and the silane cup in an organic solvent inert to the reaction such as alcohols (methanol, ethanol, isopropanol, etc.). It can be performed by reacting with a ring agent. The reaction temperature can be selected from the range of 30 ° C. to the reflux temperature of the solvent, for example.
[0067]
  The reaction between the reactive group of the carrier (A) (or the reactive group of the carrier (A) introduced by the surface treatment agent (B)) and the bifunctional compound (C) is also carried out by the reaction between the carrier, the surface treatment agent and 2 Depending on the type of functional compound, the reaction can be carried out in the same manner as the reaction between the carrier and the surface treatment agent. The ratio of the bifunctional compound (C) is usually an excess amount with respect to the reactive group of the carrier (A). For example, the bifunctional compound (C) is used with respect to 1 mol of the reactive group of the carrier (A). ) 0.5-5 mol, preferably 0.7-3 mol, more preferably about 0.8-2 mol. Since the weight ratio of the bifunctional compound (C) depends on the molecular weight, it cannot be determined unconditionally, but it is 0.1 to 200 parts by weight, preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the carrier (A) having a reactive group. It can be selected from the range of about 1 to 150 parts by weight, more preferably about 0.1 to 100 parts by weight. This reaction may also be performed in the presence or absence of a catalyst. Alternatively, the reaction may be performed in a suspension or dispersion in the presence of a solvent inert to the reaction. Examples of the solvent include alcohols such as methanol, ethanol and isopropanol; aliphatic hydrocarbons such as pentane, hexane and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic carbons such as benzene, toluene and xylene. Hydrogen; halogenated hydrocarbons such as methyl chloride, methylene chloride, chloroform and trichloroethylene; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; N-methyl And nitrogen-containing compounds such as pyrrolidone, acetonitrile and dimethylformamide; and mixed solvents thereof. The organic solvent is often a poor solvent for the carrier. The reaction temperature can be selected, for example, from a range of about 20 to 250 ° C.
[0068]
  The reaction between the reactive group of the carrier (A) or the functional group of the bifunctional compound (C) and the hydrophobic compound (D) is carried out by reacting the reactive group of the carrier (A) with the bifunctional compound (C). The reaction can be performed in the same manner as the reaction with the functional group. Use of the low molecular weight hydrophobic compound (D1) is advantageous because the reaction efficiency and reaction operability can be improved. The amount of the hydrophobic compound (D) used is, for example, the reactive group of the hydrophobic compound (D) with respect to 1 mol of the functional group of the carrier (A) or the remaining functional group of the bifunctional compound (C). It can be selected from a range of 0.5 to 5 mol, preferably 0.7 to 3 mol, more preferably about 1 to 2 mol. Since the weight ratio of the hydrophobic compound (D) depends on the molecular weight, it cannot be determined unconditionally. For example, 0.01 to 200 parts by weight, preferably 0.02 to 150 parts by weight with respect to 100 parts by weight of the carrier (A). Parts, more preferably about 0.05 to 100 parts by weight.
[0069]
  In addition, each said reaction can be normally performed, stirring in inert atmosphere, such as nitrogen, helium, and argon. After completion of the reaction, the compatibilizing agent can be obtained by a conventional method such as filtration, concentration, drying and solvent fractionation, if necessary.
[0070]
  By such a method, the compatibilizer of the following (1) corresponding to the formula (I), the compatibilizer of the following (2) corresponding to the formula (II), and further these compounds (1) (2 A compatibilizer composed of a mixture of
  (1) To the carrier (A) through the residue of the bifunctional compound (C)HydrophobicCompatibilizing agent to which the residue of compound (D) having a functional chain is bound
  (2) The residue of the bifunctional compound (C) on the carrier (A) andHydrophobicCompatibilizing agent to which the residue of compound (D) having a functional chain is bound
  [Production method of polymer alloy (modification method of polymer composition)]
  The compatibilizer composition and the compatibilizer can be used for compatibilization of a wide range of polymers. The compatibilizer composition and the compatibilizer are added to and mixed with an incompatible polymer composition, and are compatibilized and reinforced with refinement of the phase separation structure. This is useful in obtaining a polymer alloy. In particular, a nonpolar polymer (for example, an olefin-based polymer) and a polar polymer incompatible with the polymer (for example, a polymer containing oxygen atoms, nitrogen atoms, sulfur atoms such as esters, amides, and ethers). It is useful when added to a polymer composition containing it to obtain a polymer alloy.
[0071]
  Examples of the polymer include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-pentene-1); acrylic polymers such as polymethyl methacrylate; polystyrene, styrene-methacrylic acid. Styrenic polymers such as methyl copolymers, acrylonitrile-styrene copolymers, acrylonitrile-butacien-styrene block copolymers; polyesters and polyarylates such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, nylon 610, etc. Polyamide; Polyacetal; Polycarbonate; Polyphenylene oxide; Polyphenylene sulfide; Polysulfone; Polyethersulfone; Polyetheretherketone; Poly Kishibenjiren; polyamide imide. In the polymer alloying, other components such as a thermoplastic elastomer and a thermosetting resin may be used in combination.
  The compatibilizer composition and the compatibilizer can also be used for polymer alloying of engineering plastics, for example, polymer alloying of olefinic polymers such as polypropylene with polyesters and polyamides.
[0072]
  The compatibilizing agent composition or the compatibilizing agent of the present invention is characterized in that it can not only compatibilize a plurality of polymers with a small amount of addition, but also can impart high reinforcing properties to the polymer composition. Therefore, the addition amount of the compatibilizing agent composition and the compatibilizing agent can be selected from a wide range according to the kind of polymer, desired characteristics, etc., for example, 0.01 to 100 weights with respect to 100 parts by weight of the polymer composition Part, preferably 0.1 to 50 parts by weight, more preferably about 2 to 30 parts by weight.
[0073]
  The polymer alloy can be prepared by polymer blending the plurality of incompatible polymers with the compatibilizer composition or the compatibilizer by a conventional method such as melt kneading. The alloyed polymer composition is usually molded into a predetermined shape by a conventional molding method such as an injection molding method or an extrusion molding method.
[0074]
  The method for producing a polymer alloy of the present invention includes adding the above-described compatibilizer composition or compatibilizer to a polymer composition containing a plurality of incompatible polymers, and heating and melting the plurality of polymers. Can be said to be a method for compatibilizing the polymer composition or a method for modifying the polymer composition.
[0075]
【The invention's effect】
  Since the compatibilizer composition and the compatibilizer of the present invention are composed of the above-described components, they can be applied to a wide range of polymers with poor compatibility, and the characteristics of a plurality of polymers are effective even when the addition amount is small. In addition to being able to obtain a polymer alloy that is expressed in the above, it is possible to refine the phase separation structure and to impart high reinforcement to the polymer alloy. The compatibilizer composition can be economically advantageously modified by simply adding the compatibilizer composition to the polymer composition without reacting, and a plurality of incompatible polymers can be easily and efficiently compatibilized. The selection range and the degree of freedom of the compatibilizer composition are large.
  In the method of the present invention, the compatibilizer composition and the compatibilizer can be obtained by a simple method such as mixing or reaction of three or four components.
  Furthermore, in the production method of the present invention, the polymer composition can be modified simply by adding a compatibilizer composition or a compatibilizer to a polymer composition containing a plurality of incompatible polymers with each other, and the polymer alloy can be efficiently processed. Can be manufactured.
[0076]
【Example】
  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
  Example 1
  100 g of silicon dioxide powder [manufactured by Nacalai Tesque Co., Ltd., average particle size 5 μm] is stirred and dispersed in 1000 ml of ethyl alcohol [manufactured by Nacalai Tesque Co., Ltd.], and carboxymethyltriethoxysilane [manufactured by Chisso Corporation] is dispersed in the dispersion. , SIC2264.5] 0.255 g was added and reacted under reflux for 8 hours. After cooling the reaction mixture, the powder particles were filtered off, washed thoroughly with tetrahydrofuran, and dried under reduced pressure. To the dried treated powder, 0.131 g of 2,2 ′-(1,3-phenylene) -bis (2-oxazoline) (manufactured by Takeda Pharmaceutical Co., Ltd., 1,3-BPO) was added, and 200 After reacting at 30 ° C. for 30 minutes, 0.06 g of lauric acid (manufactured by NOF Corporation, NAA-122) is added and reacted at 200 ° C. for 30 minutes, so that an oxazoline group and a long-chain alkyl group are formed on the surface. A powdery compatibilizing agent having In addition, when the said reaction with lauric acid was traced by FT-IR (made by JASCO Corporation), 1650 cm of an oxazoline ring.^-1Absorption in the vicinity and 1720cm of carboxylic acid^-1Absorption in the vicinity decreases, and the amide group 1550 cm due to the reaction between the two^-1Nearby absorption increased.
[0077]
  A mixture of 40 parts by weight of polypropylene (manufactured by Tonen Kagaku Co., Ltd., J205), 60 parts by weight of polyamide-6 (manufactured by Toyobo Co., Ltd., T-800), and 10 parts by weight of the above powder compatibilizer is a twin screw. A polymer alloy was obtained by melt-kneading and molding at 200 to 260 ° C. with an extruder. When the cross section of the obtained molded body was observed with an electron microscope, the micro layer was uniformly dispersed in the matrix as shown in FIG. 1, and a highly compatible fine phase was observed. Moreover, the phase separation structure was refined by the dispersion effect of the inorganic powder. Moreover, when it used for the tension test based on JISK-7113, the improvement of the tensile strength and the tensile elasticity modulus of a molded article was recognized, and the reinforcement effect was recognized.
[0078]
  Comparative Example 1
  40 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205), 60 parts by weight of polyamide-6 (manufactured by Toyobo Co., Ltd., T-800), and silicon dioxide powder [manufactured by Nacalai Tesque, Inc., average particle size of 5 μm A polymer alloy was obtained by melting and kneading the mixture with 10 parts by weight at 200 to 260 ° C. with a twin screw extruder and molding. When the cross section of the obtained molded body was observed with an electron microscope, phase separation was observed as shown in FIG.
[0079]
  Example 2
  10 g of silicon dioxide fine particles (manufactured by Nippon Aerosil Co., Ltd., average particle size 12 nm) are stirred and dispersed in 1000 ml of ethyl alcohol [manufactured by Nacalai Tesque Co., Ltd.], and γ-glycidoxypropyltrimethoxysilane [Toray Dow Corning Silicone Co., Ltd., SH6040] 12.1 g was added and reacted under reflux for 8 hours. After cooling the reaction mixture, the particles were centrifuged, washed thoroughly with tetrahydrofuran and dried under reduced pressure. 5.4 g of 1,10-diaminodecane (manufactured by Aldrich Aldrich) was added to the dried treated powder, reacted at 200 ° C. for 30 minutes, and then maleic anhydride-modified polypropylene [manufactured by Sanyo Chemical Co., Ltd., UMEX 1010] 5.4 g was added and reacted at 200 ° C. for 30 minutes to obtain a particulate compatibilizer.
[0080]
  A mixture of 40 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205), 60 parts by weight of polybutylene terephthalate (manufactured by GE Plastics, Baroques 310), and 5 parts by weight of the particulate compatibilizer, A polymer alloy was obtained by melt-kneading and molding at 200 to 260 ° C. with a twin screw extruder.
  When the cross section of the obtained molded article was observed with an electron microscope, as shown in FIG. 3, the microphase was uniformly dispersed in the matrix, and a highly compatible fine phase was observed. Moreover, the phase separation structure was refined by the dispersion effect of the inorganic powder.
[0081]
  Example 3
  10 g of carbon black particles (manufactured by Mitsubishi Chemical Corporation, average particle diameter 18 nm) are stirred and dispersed in 1000 ml of ethyl alcohol [manufactured by Nacalai Tesque Co., Ltd.], and 2,2 ′-(1,3-phenylene)-is dispersed in the dispersion. 4.6 g of bis (2-oxazoline) (manufactured by Takeda Pharmaceutical Co., Ltd., 1,3-BPO) was added and reacted for 8 hours under reflux. After cooling the reaction mixture, the particles were centrifuged, washed thoroughly with tetrahydrofuran and dried under reduced pressure. To the dried treated powder, 2.1 g of palmitic acid (manufactured by NOF Corporation, NAA-160) was added and reacted at 200 ° C. for 30 minutes to obtain a particulate compatibilizer.
[0082]
  A mixture of 40 parts by weight of polypropylene (manufactured by Tonen Kagaku Co., Ltd., J205), 60 parts by weight of polyamide-6 (manufactured by Toyobo Co., Ltd., T-800), and 10 parts by weight of the above-mentioned fine particle compatibilizer is a twin screw. A polymer alloy was obtained by melt-kneading and molding at 200 to 260 ° C. with an extruder. When the cross section of the obtained molded body was observed with an electron microscope, the microlayer was uniformly dispersed in the matrix as shown in FIG. 4, and a highly compatible fine phase was observed. Moreover, the phase separation structure was refined by the dispersion effect of the inorganic powder.
[0083]
  Example 4
  100 g of silicon dioxide powder [manufactured by Nacalai Tesque Co., Ltd., average particle size 5 μm] is stirred and dispersed in 1000 ml of ethyl alcohol [manufactured by Nacalai Tesque Co., Ltd.], and carboxymethyltriethoxysilane [manufactured by Chisso Corporation] is dispersed in the dispersion. , SIC2264.5] 0.255 g was added and reacted under reflux for 8 hours. After the reaction mixture was cooled, the powder particles were filtered off, washed thoroughly with tetrahydrofuran, and dried under reduced pressure to obtain powder particles having a carboxyl group on the surface.
  30 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205), 70 parts by weight of polyamide-6 (manufactured by Toyobo Co., Ltd., T-800), 10 parts by weight of dried treated powder, 2,2 ′-(1, 3-Phenylene) -bis (2-oxazoline) (Takeda Pharmaceutical Co., Ltd., 1,3-BPO) 0.131 parts by weight, and lauric acid (Nippon Yushi Co., Ltd., NAA-122) 0.06 A polymer alloy was obtained by melt-kneading the mixture of parts by weight at 200 to 260 ° C. with a twin screw extruder and molding. When the cross section of the obtained molded body was observed with an electron microscope, as shown in FIG. 5, the microlayer was uniformly dispersed in the matrix, and a highly compatible fine phase was observed.
[0084]
  Comparative Example 2
  30 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205), 70 parts by weight of polyamide-6 (manufactured by Toyobo Co., Ltd., T-800), and maleic anhydride-modified polypropylene as a compatibilizing agent (Sanyo Kasei Co., Ltd.) Manufactured, Umex 1010) 10 parts by weight of a mixture was melt-kneaded at 200 to 260 ° C. by a twin screw extruder and molded to obtain a polymer alloy.
  When the cross section of the obtained molded body was observed with an electron microscope, the microlayer was uniformly dispersed in the matrix as shown in FIG. 6, but a large amount of 10 parts by weight was required to obtain high compatibility. A compatibilizer was required.
[0085]
  And about the following molded article, the tensile strength and the tensile elasticity modulus were measured based on JISK-7113. The results are shown in the table.
    ( i )Molded product of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205)
    ( ii )Molded product of polyamide-6 (Toyobo Co., Ltd., T-800)
    ( iii )Molded product of a mixture of 30 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205) and 70 parts by weight of polyamide-6 (manufactured by Toyobo Co., Ltd., T-800)
    ( iv )Molded product of Comparative Example 2
    ( v )Molded product of Example 4
[0086]
[Table 1]

  Example 5
  0.48 parts by weight of lauric acid (manufactured by NOF Corporation, NAA-122, molecular weight 200.3) and 2,2 '-(1,3-phenylene) -bis (2-oxazoline) (Takeda Pharmaceutical Co., Ltd. ), 1,3-BPO, molecular weight 216.2) and 0.42 parts by weight were reacted with stirring at 150 ° C. in a nitrogen gas atmosphere without using a solvent, and an oxazoline group was introduced at the terminal. A reaction product having an amide bond was obtained.
[0087]
  In the same manner as in Example 2, a mixture of 50 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205) and 50 parts by weight of polybutylene terephthalate (manufactured by GE Plastics, Inc., Baroques 310) was used in the same manner as in Example 2. 5 parts by weight of silicon dioxide fine particles treated with xoxypropyltrimethoxysilane and 0.9 parts by weight of the reaction product were added, and a molded product was obtained in the same manner as in Example 2. And when the cross section of the molded product was observed with an electron microscope, it was recognized that the microphase was made fine and uniform, as in FIG.
[0088]
  Example 6
  In the same manner as in Example 2, a mixture of 50 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205) and 50 parts by weight of polybutylene terephthalate (manufactured by GE Plastics, Inc., Baroques 310) was used in the same manner as in Example 2. 5 parts by weight of silicon dioxide fine particles treated with xylpropyltrimethoxysilane, 0.51 part by weight of myristic acid (NAA-142 manufactured by NOF Corporation), and 2,2 '-(1,3-phenylene) -bis 0.49 parts by weight of (2-oxazoline) (Takeda Pharmaceutical Co., Ltd., 1,3-BPO, molecular weight 216.2) was added and molded in the same manner as in Example 2 to obtain a polymer alloy.
  When the cross section of the obtained molded product was observed with an electron microscope, the microphase was refined and uniform as in FIG. 3, and the polymer component was compatibilized.
[0089]
  Example 7
  In the same manner as in Example 2, a mixture of 50 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205) and 50 parts by weight of polybutylene terephthalate (manufactured by GE Plastics, Inc., Baroques 310) was used in the same manner as in Example 2. 5 parts by weight of silicon dioxide fine particles treated with xylpropyltrimethoxysilane, 0.54 parts by weight of palmitic acid (manufactured by NOF Corporation, NAA-160, molecular weight 256.4), and 2,2 ′-(1,3 -Phenylene) -bis (2-oxazoline) (manufactured by Takeda Pharmaceutical Co., Ltd., 1,3-BPO, molecular weight 216.2) 0.46 part by weight was added and polymerized in the same manner as in Example 2. I got an alloy.
  When the cross section of the obtained molded product was observed with an electron microscope, the microphase was refined and uniform as in FIG. 3, and the polymer component was compatibilized.
[0090]
  Example 8
  In the same manner as in Example 2, a mixture of 50 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205) and 50 parts by weight of polybutylene terephthalate (manufactured by GE Plastics, Inc., Baroques 310) was used in the same manner as in Example 2. 5 parts by weight of silicon dioxide fine particles treated with xylpropyltrimethoxysilane, 0.57 parts by weight of stearic acid (manufactured by NOF Corporation, NAA-180, molecular weight 284.5), and 2,2 ′-(1,3 -Phenylene) -bis (2-oxazoline) (manufactured by Takeda Pharmaceutical Co., Ltd., 1,3-BPO, molecular weight 216.2) was added in an amount of 0.43 parts by weight, and the polymer was molded in the same manner as in Example 2. I got an alloy.
  When the cross section of the obtained molded product was observed with an electron microscope, the microphase was refined and uniform as in FIG. 3, and the polymer component was compatibilized.
[0091]
  Example 9
  In the same manner as in Example 2, a mixture of 50 parts by weight of polypropylene (manufactured by Tonen Chemical Co., Ltd., J205) and 50 parts by weight of polybutylene terephthalate (manufactured by GE Plastics, Inc., Baroques 310) was used in the same manner as in Example 2. 5 parts by weight of silicon dioxide fine particles treated with xylpropyltrimethoxysilane, oxidized low density wax [manufactured by Sanyo Chemical Co., Ltd., Sunwax E-310, average molecular weight 2000, acid value 22 (COOH group concentration: 29 × 10^-FiveMol / g)] 0.94 parts by weight, and 2,2 ′-(1,3-phenylene) -bis (2-oxazoline) (manufactured by Takeda Pharmaceutical Co., Ltd., 1,3-BPO, molecular weight 216.2) ) 0.058 part by weight was added and molded in the same manner as in Example 2 to obtain a polymer alloy.
  When the cross section of the obtained molded product was observed with an electron microscope, the microphase was refined and dispersed uniformly and the polymer component was compatibilized as in FIG.
[0092]
  Example 10
  Oxidized low-density wax [manufactured by Sanyo Chemical Co., Ltd., Sunwax E-310, average molecular weight 2000, acid value 22 (COOH group concentration: 29 × 10^-FiveMol / g)] 0.94 parts by weight, 2,2 ′-(1,3-phenylene) -bis (2-oxazoline) (manufactured by Takeda Pharmaceutical Co., Ltd., 1,3-BPO, molecular weight 216.2) ) 0.058 parts by weight of the compound was reacted with stirring at 150 ° C. in a nitrogen gas atmosphere to obtain a compound having an amide bond in which an oxazoline group remained at the terminal. The formation of such a compound can be attributed to 1650 cm due to the oxazoline ring by FT-IR.^-11720cm due to nearby absorption and carboxylic acid^-11550 cm due to amide group, absorption in the vicinity decreases^-1This was confirmed by the increase in absorption in the vicinity.
[0093]
  Then, in the same manner as in Example 2, γ- 5 parts by weight of silicon dioxide fine particles treated with glycidoxypropyltrimethoxysilane and 1.0 part by weight of the above reaction product were added and molded in the same manner as in Example 2 to obtain a polymer alloy.
  When the cross section of the obtained molded article was observed with an electron microscope, a uniform phase was observed as in FIG. 3, and a polymer alloy having good compatibility in which the microphase was uniformly dispersed in the matrix was obtained.
[Brief description of the drawings]
FIG. 1 is an electron micrograph (drawing substitute photograph) showing a cross section of a molded product obtained in Example 1. FIG.
FIG. 2 is an electron micrograph (drawing substitute photo) showing a cross section of the molded product obtained in Comparative Example 1.
3 is an electron micrograph (drawing substitute photograph) showing a cross section of the molded product obtained in Example 2. FIG.
FIG. 4 is an electron micrograph (drawing substitute photograph) showing a cross section of the molded product obtained in Example 3.
5 is an electron micrograph (drawing substitute photograph) showing a cross section of the molded product obtained in Example 4. FIG.
6 is an electron micrograph (drawing substitute photograph) showing a cross section of the molded product obtained in Comparative Example 2. FIG.

Claims (18)

A carrier (A) having a reactive group, a bifunctional compound (C) having a functional group capable of reacting with the reactive group of the carrier (A), and a functional group of the bifunctional compound (C) Or a compatibilizer composition comprising a compound (D) having a functional group containing an active hydrogen atom that is reactive to the reactive group of the carrier (A) and having a hydrophobic chain. ,
(I) the reactive group is a hydroxyl group, a mercapto group, a carboxyl group, an acid anhydride group, an amino group, or an epoxy group;
(Ii) The carrier constituting the carrier (A) having a reactive group is an inorganic substance,
(Iii) The bifunctional compound (C) is an amino group-containing compound or an oxazoline group-containing compound,
(Iv) The compound (D) is a higher fatty acid having 10 to 26 carbon atoms, or a polyolefin having a carboxyl group or an acid anhydride group introduced by a copolymerization reaction,
(V) The proportion of the bifunctional compound (C) is 0.1 to 150 parts by weight and the proportion of the compound (D) having a hydrophobic main chain is 0.01 to 150 parts per 100 parts by weight of the carrier (A). A compatibilizer composition in parts by weight.   The compatibilizing agent composition according to claim 1, wherein the carrier constituting the carrier (A) having a reactive group is a granular or fibrous inorganic substance.   A carrier (A) in which a carrier (A) is treated with a surface treatment agent (B) having a reactive group for the bifunctional compound (C) and a reactive group is introduced, the surface treatment agent (B) The compatibilizer composition according to claim 1, wherein is a coupling agent.   The compatibilizer composition according to claim 3, wherein the surface treatment agent (B) is a silane coupling agent. The bifunctional compound (C) has the following formula

(In the formula, E represents an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, or an arylene group which may have a substituent, and R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
The compatibilizer composition according to claim 1, which is a bisoxazoline compound represented by the formula: Relative to 100 parts by weight of the carrier (A) having a reactivity group, compatibilizer composition ratio according to claim 3, wherein a 0.1 to 250 parts by weight of the surface treatment agent (B). The following formula (I) or (II)
A-[(B1) _m -CD] _n (I)
[D- (B2) _r ] _s- A-[(B1) _p- C] _q (II)
Units (in the formula, A carrier having a reactivity group (A), C is bifunctional compound having a functional group reactive with respect to the reactive group before Ki担 body (A) (C), D Is a unit of a compound (D) having a hydrophobic chain, B1 and B2 are organic groups linking A and C or D, m, p and r are 0 or 1, n, q and s are 1 or more Represents an integer, m, p and r may be different depending on n, q and s, respectively)
A compatibilizing agent represented by:
(I) The carrier (A) is composed of an inorganic substance,
(Iii) The bifunctional compound (C) is an amino group-containing compound or an oxazoline group-containing compound,
(Iv) A compatibilizing agent in which the compound (D) is a higher fatty acid having 10 to 26 carbon atoms, or a polyolefin having a carboxyl group or an acid anhydride group introduced by a copolymerization reaction. Formula (i) below

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group. E represents an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, or an arylene group which may have a substituent, and A, B1, D, m , N are the same as above.)
The compatibilizer of Claim 7 represented by these. The following formula (ii)

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group. E represents an alkylene group which may have a substituent, an cycloalkylene group which may have a substituent, or an arylene group which may have a substituent, and A, B1, B2, D , P, q, r, and s are the same as above.)
The compatibilizer of Claim 7 represented by these. The following formula (ia)

(Wherein D1 represents a unit of a higher fatty acid (D1) having 10 to 26 carbon atoms, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a C _1-4 alkyl group, and R ¹ and At least one of R ² is a hydrogen atom, and at least one of R ³ and R ⁴ is a hydrogen atom (A, B1, m, and n are the same as above)
The compatibilizer of Claim 7 represented by these. The following formula (ia)

(Wherein D1 represents a unit of a higher fatty acid (D1) having 10 to 26 carbon atoms, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a C _1-4 alkyl group, and R ¹ and At least one of R ² is a hydrogen atom, and at least one of R ³ and R ⁴ is a hydrogen atom (A, B1, B2, p, q, r, s are the same as above)
The compatibilizer of Claim 7 represented by these. The following formula (ib)

(In the formula, Y and Z each represent a hydrocarbon group constituting the main chain of a polyolefin into which a carboxyl group or an acid anhydride group has been introduced by a copolymerization reaction, Z may have an unsaturated bond, a / (a + b) = 0.1-20 mol% R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a C _1-4 alkyl group, and at least ^one of R ¹ and R ² is The compatibilizer according to claim 7, wherein at least one of a hydrogen atom, R ³ and R ⁴ is a hydrogen atom, and A, B1, m, and n are the same as above. The following formula (iib)

(In the formula, Y ¹ and Z each represent a hydrocarbon group constituting a polyolefin main chain into which a carboxyl group or an acid anhydride group has been introduced by a copolymerization reaction, and Z may have an unsaturated bond) A / (a + b) = 0.1-20 mol% R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a C _1-4 alkyl group, and at least ^one of R ¹ and R ² 8 is a hydrogen atom, and at least one of R ³ and R ⁴ is a hydrogen atom, A, B1, B2, p, q, r, and s are the same as above. A carrier (A) having a reactive group, a bifunctional compound (C) having a functional group capable of reacting with the reactive group of the carrier, and a functional group of the bifunctional compound or the reactivity of the carrier A method for producing a compatibilizer composition comprising mixing a compound (D) having a functional group containing an active hydrogen atom having reactivity with a group and having a hydrophobic main chain,
(I) the reactive group is a hydroxyl group, a mercapto group, a carboxyl group, an acid anhydride group, an amino group, or an epoxy group;
(Ii) The carrier constituting the carrier (A) having a reactive group is an inorganic substance,
(Iii) The bifunctional compound (C) is an amino group-containing compound or an oxazoline group-containing compound,
(Iv) The compound (D) is a higher fatty acid having 10 to 26 carbon atoms, or a polyolefin having a carboxyl group or an acid anhydride group introduced by a copolymerization reaction,
(V) The proportion of the bifunctional compound (C) is 0.1 to 150 parts by weight and the proportion of the compound (D) having a hydrophobic main chain is 0.01 to 150 parts per 100 parts by weight of the carrier (A). The manufacturing method which is a weight part. A carrier (A) having a reactive group, a bifunctional compound (C) having a functional group capable of reacting with the reactive group of the carrier, and a functional group of the bifunctional compound (C) or the carrier The method for producing a compatibilizer according to (1) or (2) below, wherein the compound (D) having a reactive group with respect to the reactive group of (A) and having a hydrophobic chain is reacted,
(I) the reactive group is a hydroxyl group, a mercapto group, a carboxyl group, an acid anhydride group, an amino group, or an epoxy group;
(Ii) The carrier constituting the carrier (A) having a reactive group is an inorganic substance,
(Iii) The bifunctional compound (C) is an amino group-containing compound or an oxazoline group-containing compound,
(Iv) A production method in which the compound (D) is a higher fatty acid having 10 to 26 carbon atoms, or a polyolefin into which a carboxyl group or an acid anhydride group has been introduced by a copolymerization reaction.
(1) Compatibilizer in which the residue of the compound (D) having a hydrophobic chain is bonded to the carrier (A) via the residue of the bifunctional compound (C). (2) To the carrier (A) Compatibilizer in which the residue of the bifunctional compound (C) and the residue of the compound (D) having a hydrophobic chain are bound   A method for producing a polymer alloy, wherein the compatibilizer composition or the compatibilizer according to any one of claims 1 to 13 is added to mutually incompatible polymer compositions.   The polymer which adds the compatibilizer composition or the compatibilizer according to any one of claims 1 to 13 to a polymer composition comprising a nonpolar polymer and a polar polymer incompatible with the polymer. Alloy manufacturing method.   The method for producing a polymer alloy according to claim 16 or 17, wherein the amount of the compatibilizer composition or the compatibilizer added is 0.01 to 100 parts by weight with respect to 100 parts by weight of the polymer composition.

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