JP3936894B2 - Aggregation treatment agent and method of using the same - Google Patents

Description

一般式（１）
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキルあるいはアルコキシル基、Ｒ４は水素、炭素数１〜３のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い、Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基を表わす、Ｘ１は陰イオンをそれぞれ表わす。
【化２】

一般式（２）
Ｒ５は水素又はメチル基、Ｒ６、Ｒ７は炭素数１〜３のアルキル基、アルコキシ基あるいはベンジル基、Ｘ２は陰イオンをそれぞれ表わす
【化３】

一般式（３）
Ｒ８は水素、メチル基またはカルボキシメチル基、ＱはＳＯ３、Ｃ６Ｈ４ＳＯ３、
ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３、Ｃ６Ｈ４ＣＯＯあるいはＣＯＯ、Ｒ９は水素またはＣＯＯＹ２、Ｙ１あるいはＹ２は水素または陽イオン
【０００７】
請求項２の発明は、前記架橋性イオン性水溶性高分子が噴霧乾燥品であることを特徴とする請求項１に記載の凝集処理薬剤である。
【０００６】
請求項３は、前記架橋性イオン性水溶性高分子が、単量体混合物を塩水溶液中、該塩水溶液に可溶な高分子分散剤共存下、分散重合法により製造された粒径１００μｍ以下の架橋性イオン性水溶性高分子からなる微粒子の分散液であることを特徴とする請求項１に記載の凝集処理薬剤である。
【０００８】
請求項４の発明は、前記複数のビニル基を有する単量体が、下記一般式（５）で表される多官能性水溶性ポリカチオン単量体であることを特徴とする請求項１〜３に記載の凝集処理薬剤である。
【化４】

一般式（４）
Ｒ１０〜Ｒ１３は水素又はメチル基、Ｘ３、Ｘ４は陰イオン、ｐは０〜２０の整数をそれぞれ表わす、ただしＰは下記一般式（５）で表わされる。
【化５】

一般式（５）
Ｒ_１４、Ｒ_１５は水素、炭素数１〜３のアルキル基又はベンジル基、炭素数２〜４のアルキレン基あるいはアルコキシレン基、Ｒ_１６は水素又はメチル基、
Ｌは−Ｏ−又は−ＮＨ−、Ｘ５⁻は陰イオン、ただしＲ_１４〜Ｒ_１５が水素である場合は、部分的にＰに置換されても良い
【０００９】
請求項５の発明は、前記多官能性水溶性ポリカチオン単量体がアンモニア、脂肪族第１級アミン、脂肪族第２級アミン、脂肪族第３級アミンから選択された一種以上のアミン類とエピハロヒドリンから生成した重縮合物とジアルキルアミノアルキル（メタ）アクリルアミドとの反応物であることを特徴とする請求項４に記載の凝集処理薬剤である。
【００１０】
請求項６の発明は、請求項１〜５に記載の架橋性イオン性水溶性高分子とアミジン系水溶性高分子からなる凝集処理薬剤を製紙スラッジに添加、凝集させた後、脱水機により脱水することを特徴とする製紙スラッジの脱水方法である。
【００１１】
請求項７の発明は、請求項１〜５に記載の架橋性イオン性水溶性高分子とアミジン系水溶性高分子からなる凝集処理薬剤を有機汚泥に添加、凝集させた後、脱水機により脱水することを特徴とする有機汚泥の脱水方法である。
【００１２】
請求項８の発明は、請求項１〜５に記載の架橋性イオン性水溶性高分子とアミジン系水溶性高分子からなる凝集処理薬剤を抄紙前の製紙原料中に添加、処理することを特徴とする製紙原料の前処理方法である。
【００１３】
【発明の実施の形態】
初めに本発明で使用する複数のビニル基を有する単量体について説明する。このような単量体の例として、メチレンビスアクリルアミドやエチレングルコ−ルジ（メタ）アクリレ−トなどの多官能性単量体、あるいはＮ、Ｎ−ジメチルアクリルアミドのような熱架橋性単量体などがあげられる。また、好ましい複数のビニル基を有する単量体として、前記一般式（４）で表される多官能性水溶性ポリカチオン単量体である。この単量体は、以下のようにして合成することができる。すなわちエピハロヒドリンとアンモニア、第１級アミンまたは第２級アミンのうち、一種以上のアミン類と反応させた生成物を得た後、第３級アミノ基含有アクリルモノマーとを反応させ、その反応物の末端の少なくとも２つがビニル基を有するポリカチオン多官能性単量体である。すなわち、Ｒ１０〜Ｒ１３は水素または炭素数１〜３のアルキル基のなかから選ばれた同種または異種のアルキル基が結合したエピハロヒドリン残基を示す。このエピハロヒドリン残基は、一種類のアミンを使用すれば、同種の繰り返し単位が重合したものとなる。一方、二種以上のアミンを使用すれば異なった繰り返し単位が重合したものとなる。
【００１４】
これらの第１級アミンの中で、好ましくは、メチルアミン及びエチルアミンである。前記第２級アミンは、例えばジメチルアミン、ジエチルアミン、などである。これらの第２級アミンは１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。
【００１５】
前記第３級アミノ基含有アクリルモノマーは、例えばＮ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレートなどを挙げることができる。また最も好ましいものは、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミドである。
【００１６】
複数のビニル基を有する単量体の添加量は以下のようになる。すなわちメチレンビスアクリルアミドやエチレングルコ−ルジ（メタ）アクリレ−トなどの多官能性単量体、あるいはＮ、Ｎ−ジメチルアクリルアミド単量体などの場合は、混合物質量に０．００１〜０．１モル％であり、好ましくは０．００２〜０．０５％であり、更に好ましくは０．００５〜０．０５％である。また多官能性水溶性ポリカチオン単量体の前記単量体混合物に対する添加量は、単量体混合物質量に０．００１〜１モル％であり、好ましくは０．０１〜０．５％であり、更に好ましくは０．０５〜０．５％である。重合温度は前記のような通常の重合条件で行うことができる。また、重合度を調節するためイソプロピルアルコールを対単量体０．１〜５重量％など併用すると効果的である。
【００１７】
前記多官能性水溶性ポリカチオン単量体を前記単量体混合物と共重合することにより製造したイオン性架橋性水溶性高分子は、従来のＮ，Ｎ−メチレンビスアクリルアミドあるいはエチレングリコールジ（メタ）アクリレートなどのような架橋点間の比較的短い架橋剤を使用した場合に較べ、架橋点間が長く、その上カチオン性基が架橋点間に存在する。従って分子が収縮し過ぎず、水中における形態が適度な状態で存在できる。その結果、架橋性高分子の特徴を保持し、懸濁粒子との接触も効率的に行なわれる。
【００１８】
重合法としては、水溶液重合、油中水型エマルジョン重合、油中水型分散重合、塩水中分散重合などによって重合した後、それぞれ水溶液、分散液、エマルジョンあるいは粉末など任意の製品形態にすることができる。好ましい形態としては、濃度を高められ、溶解時間も短い油中水型エマルジョン重合品、あるいは塩水中分散重合品が好ましい。また、油中水型エマルジョン重合品を噴霧乾燥した粉末品も好ましい。
【００１９】
油中水型高分子エマルジョンの製造方法としては、カチオン性単量体、あるいはカチオン性単量体と共重合可能な単量体からなる単量体混合物を水、少なくとも水と非混和性の炭化水素からなる油状物質、油中水型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤を混合し、強攪拌し油中水型エマルジョンを形成させた後、重合することにより合成する。
【００２０】
分散媒として使用する炭化水素からなる油状物質の例としては、パラフィン類あるいは灯油、軽油、中油などの鉱油、あるいはこれらと実質的に同じ範囲の沸点や粘度などの特性を有する炭化水素系合成油、あるいはこれらの混合物があげられる。
【００２１】
油中水型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤の例としては、ＨＬＢ３〜１１のノニオン性界面活性剤であり、その具体例としては、ソルビタンモノオレ−ト、ソルビタンモノステアレ−ト、ソルビタンモノパルミテ−トなどがあげられる。これら界面活性剤の添加量としては、油中水型エマルジョン全量に対して０．５〜１０重量％であり、好ましくは１〜５重量％である。
【００２２】
重合後は、転相剤と呼ばれる親水性界面活性剤を添加して油の膜で被われたエマルジョン粒子が水になじみ易くし、中の水溶性高分子が溶解しやすくする処理を行い、水で希釈しそれぞれの用途に用いる。親水性界面化成剤の例としては、カチオン性界面化成剤やＨＬＢ９〜１５のノニオン性界面化成剤であり、ポリオキシエチレンアルキルエ−テル系、ポリオキシエチレンアルコールエ−テル系などである。
【００１５】
また、油中水型エマルジョン重合した重合物を、そのまま噴霧乾燥することもできる。従来、架橋性の水溶性高分子を粉末化することは、乾燥時、架橋反応が進行する副反応が起き、なかなか実用化が難しかった。しかし、この噴霧乾燥することにより架橋性水溶性高分子の粉末を容易に企業的規模で生産可能となった。噴霧化を用意にするため油中水型エマルジョン重合品の濃度を多少調節後、噴霧乾燥機に送り、７０〜１１０℃程度の温度により、乾燥する。また乾燥時、熱によって架橋反応が進み、その分汚泥脱水剤としての性能が向上することも期待できる。
【００２３】
さらに塩水溶液中に分散した高分子微粒子分散液からなる水溶性重合体に関しては、特開昭６２−１５２５１号公報などによって製造することができる。この方法は、カチオン性単量体あるいはカチオン性単量体と非イオン性単量体を、塩水溶液中で該塩水溶液に可溶な高分子からなる分散剤共存下で、攪拌しながら製造された粒系１００ｍμ以下の高分子微粒子の分散液からなるもである。架橋性イオン性水溶性高分子を製造する場合は、これら単量体に複数のビニル基を有する単量体を重合時共存させる。
【００２４】
高分子からなる分散剤は、カチオン性水溶性高分子としては、ジメチルジアリルアンモニウム塩化物、（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物の単独重合体や非イオン性単量体との共重合体を使用である。また、非イオン性高分子は、ポリビニルピロリドン、アクリルアミド／ポリビニルカプロラクタム共重合体、アクリルアミド／スチレン共重合体、無水マレイン酸／ブテン共重物の完全アミド化物などアミド基と若干の疎水性基を有する水溶性高分子が有効である。
【００２５】
塩水溶液を構成する無機塩類は、多価アニオン塩類が、より好ましく、硫酸塩又は燐酸塩が適当であり、具体的には、硫酸アンモニウム、硫酸ナトリウム、硫酸マグネシウム、硫酸アルミニウム、燐酸水素アンモニウム、燐酸水素ナトリウム、燐酸水素カリウム等を例示することができ、これらの塩を濃度１５％以上の水溶液として用いることが好ましい
【００２６】
油中水型エマルジョン重合の場合は重合濃度として、２０〜５０重量％であり、好ましくは２５〜４０重量％である。また、塩水溶液中分散重合の場合は、１５〜４０重量％であり、好ましくは２０〜３５重量％である。またどちらも重合温度としては、０〜８０℃であり、好ましくは２０〜５０℃、最も好ましくは２０〜４０℃であり、単量体の組成、重合法、開始剤の選択によって適宜重合温度を設定する。
【００２７】
本発明の架橋性水溶性イオン性高分子は、前記一般式（１）及び／又は（２）で表される単量体５〜９９．９９９モル％、下記一般式（３）で表される単量体０〜５０モル％、非イオン性単量体０〜９５モル％及び複数のビニル基を有する単量体０．００１〜１モル％からなる単量体混合物を重合することによって製造することができる。重合はこれら単量体を混合した水溶液を調製した後、既知の重合法によって行うことができる。
【００２８】
前記一般式（１）で表されるカチオン性単量体の例としては、（メタ）アクリル酸ジメチルアミノエチルやジメチルアミノプロピル（メタ）アクリルアミド、メチルジアリルアミンなどの重合体や共重合体が上げられ、四級アンモニウム基含重合体の例は、前記三級アミノ含有単量体の塩化メチルや塩化ベンジルによる四級化物である（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルジメチルベンジルアンモニウム塩化物などである。また前記一般式（２）で表されるカチオン性単量体の例としては、ジメチルジアリルアンモニウム系単量も使用可能であり、その例としてジメチルジアリルアンモニウム塩化物、ジアリルメチルベンジルアンモニウム塩化物などである。
【００２９】
さらに一般式（３）で表されるアニオン性単量体の例としては、スルフォン基でもカルボキシル基でもさしつかいなく、両方を併用しても良い。スルフォン基含有単量体の例は、ビニルスルフォン酸、ビニルベンゼンスルフォン酸あるいは２−アクリルアミド２−メチルプロパンスルフォン酸などである。またカルボキシル基含有単量体の例は、メタクリル酸、アクリル酸、イタコン酸、マレイン酸あるいはｐ−カルボキシスチレンなどである。
【００３０】
水溶性非イオン性単量体の例としては、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、酢酸ビニル、アクリロニトリル、（メタ）アクリル酸２−ヒドロキシエチル、ジアセトンアクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、アクリロイルモルホリン、アクリロイルピペラジンなどがあげられる。
【００３１】
前記単量体あるいは単量体混合物を共重合して得られる架橋性イオン性水溶性高分子の分子量は、５０万〜２，０００万であり、好ましくは５０万〜１５００万、さらに好ましくは５０万〜１０００万である。
【００３２】
次に併用するアミジン系水溶性高分子について説明する。この高分子はＮ−ビニルカルボン酸アミドと（メタ）アクリロニトリルとの共重合物の酸による加水分解反応により合成することができる。単量体であるＮ−ビニルカルボン酸アミドの例としては、Ｎ−ビニルホルムアミドやＮ−ビニルアセトアミドなどをあげることができる。また共重合するビニル系ニトリル類としては、アクリロニトリルが最も一般的である。重合法としては、水溶液重合、油中水型エマルジョン重合、油中水型分散重合、塩水中分散重合などによって重合した後、それぞれ水溶液、分散液、エマルジョンあるいは粉末など任意の製品形態にすることができる。加水分解時使用する酸は、無機の強酸が好ましく、例えば塩酸、硝酸あるいはｐ−トルエンスルフォン酸などである。
【００３３】
加水分解後の分子中アミジン基のモル％は、５〜１００モル％であり、好ましくは１０〜１００モル％、最も好ましくは２０〜８０モル％である。非イオン性構造単位は、未加水分解のカルボン酸アミド基と未反応のニトリル基であり、０〜９５モル％であり、好ましくは０〜９０モル％、最も好ましくは２０〜８０モル％である。最も好ましい形態としては、粉末品である。分子量は、１００万〜１０００万であるが、好ましくは２００万〜５００万である。
【００３４】
これら架橋性イオン性水溶性高分子とアミジン系水溶性高分子の併用比率としては、ニ物質の重量分率として３０〜７０：７０〜３０であり、好ましくは４０〜６０：６０〜４０である。どちらかの物質が３０重量％以下であると、片方の物質の性質しか発現しにくく、同重量に近いほうが好ましい。また併用の仕方としては、混合、順次添加、同時添加など可能であるが、製品あるいは溶解液の混合物を混合して添加するのが最も良く、前記二つの組成の高分子を粉末状で混合した製品形態が最も便利である。また架橋性イオン性水溶性高分子の劣化防止として水溶液混合物または粉末混合物に酸を加えておくと効果がある。特に粉末形態の製品には、スルファミン酸や酒石酸などの粉末酸が便利である。
【００３５】
本発明の架橋性イオン性水溶性高分子とアミジン系水溶性高分子からなる処理剤は、製紙排水、化学工業排水、食品工業排水などの生物処理したときに発生する余剰汚泥、あるいは都市下水の生汚泥、混合生汚泥、余剰汚泥、消化汚泥などの有機汚泥、あるいは製紙スラッジの脱水に使用することができる。さらに、古紙や機械パルプに由来するピッチ類あるいはアニオン性物質の前処理を行うため、抄紙前の製紙原料中に添加して使用することもできる。
【００３６】
更に本発明の架橋性イオン性水溶性高分子とアミジン系水溶性高分子からなる処理剤は、歩留向上及び／又は濾水性向上を目的として抄紙前の製紙原料中に添加し使用することもできる。また、本処理剤と、無機あるいは有機のアニオン性物質と組み合わせて、歩留向上及び／又は濾水性向上を目的として、抄紙前の製紙原料中に添加し使用することもできる。前記アニオン性物質のうち、無機物としては、ベントナイト、カオリン、クレイあるいはタルクなどであり、またコロイダルシリカも使用できる。
【００３７】
前記アニオン性物質が、アニオン性水溶性高分子の場合は、どのようなアニオン性水溶性高分子も使用できるが、前記一般式（３）で表されるアニオン性単量体３〜１００モル％と水溶性非イオン性単量体を０〜９７モル％含有する単量体混合物を塩水溶液中、該塩水溶液に可溶な高分子分散剤共存下、分散重合法により製造された粒径１００μｍ以下のアニオン性水溶性高分子からなる微粒子の分散液を使用することが好ましい。この高分子の製造法は、前記架橋性カチオン性あるいは両性水溶性高分子の場合と同様である。高分子分散剤は、アニオン性高分子を使用することが好ましい。例えば、アクリルアミド２−メチルプロパンスルホン酸（塩）やスチレンスルホン酸（塩）などのアニオン性単量体の（共）重合体である。これらアニオン性単量体とカルボキシル基含有単量体、例えばアクリル酸、メタクリル酸、イタコン酸などとの共重合体も使用可能である。さらに非イオン性の単量体であるアクリルアミドとの共重合体も使用できる。また、場合によっては、無機のアニオン性物質と有機のアニオン性物質とを併用しても良い。
【００３８】
本発明の凝集処理薬剤の添加量は、汚泥固形分に対し重量で０．１〜１．０％であり、好ましくは０．２〜０．５％である。また、前処理として使用するには、製紙原料中乾燥分に対し、５０〜１０，０００ｐｐｍであり、好ましくは１００〜２，０００ｐｐｍである。
【００３９】
【実施例】
以下、実施例および比較例によって本発明をさらに詳しく説明するが、本発明はその要旨を超えない限り、以下の実施例に制約されるものではない。
【００４０】
（合成例１）攪拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２０．０ｇにソルビタンモノオレート６．０ｇ及びポリリシノ−ル酸／ポリオキシエチレンブロック共重合物０．６ｇを仕込み溶解させた。別に脱イオン水３２．０ｇ、アクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＭＱと略記）８０％水溶液１８４．４ｇ、アクリルアミド（ＡＡＭと略記）５０％水溶液２７．０ｇ及び合成例で作成した多官能性水溶性ポリカチオン単量体６０％水溶液１．１ｇ（対単量体０．４重量％）各々採取し前記アクリル酸溶液に添加し、完全に溶解させた。また、ｐＨを４．３５に調節し、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで１５分間攪拌乳化した。この時の単量体組成は、ＤＭＱ／ＡＡＭ＝８０／２０（モル％）である。
【００４１】
得られたエマルジョンにイソプロピルアルコール４０％水溶液２．４ｇ（対単量体０．６重量％）を加え、単量体溶液の温度を３０〜３３℃に保ち、窒素置換を３０分行った後、２、２’−アゾビス〔２−（５−メチル−２−イミダゾリン−２−イル）プロパン〕二塩化水素化物の１０％水溶液０．３５ｇ（対単量体０．０２重量％）を加え、重合反応を開始させた。反応温度を３２±２℃で１２時間重合させ反応を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてポリオキシエチレントリデシルエ−テル１０．０ｇ（対液２．０重量％）を添加混合して試験に供する試料（試料−１）とした。また静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。
組成を表１に、結果を表２に示す。
【００４２】
（合成例２〜４）実施例１と同様な操作により、表１に示す複数のビニル基を有する単量体とその他の単量体組成により、それぞれＤＭＱ／ＡＡＣ／ＡＡＭ＝６０／２０／２０（試料−２）、ＤＭＱ／ＡＡＭ＝８０／２０（試料−３）、ＤＭＱ／ＡＡＣ／ＡＡＭ＝６０／２０／２０（試料−４）（いずれもモル％）からなる組成の油中水型両性高分子エマルジョンを合成した。組成を表１に、結果を表２に示す。
【００４３】
（合成例５）温度計、攪拌機、窒素導入管、ペリスタポンプ（ＳＭＰ−２１型、東京理化器械製）に接続した単量体供給管およびコンデンサ−を備えた５００mＬの４ツ口フラスコ内にメタクロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＭＣと略記）の８０重量水溶液％４６．３ｇ、アクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＭＱと略記）の８０重量％水溶液６０．５ｇ、アクリル酸（以下ＡＡＣと略記）の６０重量％水溶液２０．６ｇ、アクリルアミド（以下ＡＡＭと略記）の５０％水溶液３６．５ｇ、イオン交換水１７３．１ｇ、硫酸アンモニウム１２５．０ｇ、分散剤としてアクリロイルオキシエチルトリメチルアンモニウム塩化物単独重合体３０．０ｇ（２０重量％液、粘度６４５０ｍＰａ・ｓ）をそれぞれしこみｐＨを３．３に調節した。この時各単量体のモル％は、ＤＭＣ／ＤＭＱ／ＡＡＣ／ＡＡＭ＝２５／３５／２０／２０である。次ぎに反応器内の温度を３０±２℃に保ち、３０分間窒素置換をした後、開始剤として２、２’−アゾビス〔２−（５−メチル−２−イミダゾリン−２−イル）プロパン〕ニ塩化水素化物の１％水溶液１．０ｇ（対単量体０．０１％）を添加し重合を開始させた。内部温度を３０±２℃に保ち重合開始から７時間反応させた時点で上記開始剤を対単量体０．０１％追加し、さらに７時間反応させ終了した。得られた分散液のしこみ単量体濃度は２０％であり、ポリマー粒径は１０μｍ以下、分散液の粘度は７５０ｍＰａ・ｓであった。また、静的光散乱法による分子量測定器（大塚電子製ＤＬＳ−７０００）によって重量平均分子量を測定した。この試料を試料−５とする。結果を表１及び表２に示す。
【００４４】
（合成例６）実施例５と同様な操作により、表１に示す複数のビニル基を有する単量体とその他の単量体組成により、ＤＭＱ／ＡＡＭ＝８０／２０（試料−６）からなる組成の塩水溶液中分散重合品を合成した。組成を表１に、結果を表２に示す。
【００４５】
（合成例７〜９）実施例１〜３で製造した油中水型エマルジョン、親水性界面活性剤添加前の試料−１〜試料−３に対応する試料を、スプレードライヤーに噴霧し、粉末品の試料−７〜試料−９を製造した。組成を表１に、結果を表２に示す。
【００４６】
（比較合成例１〜４）実施例１〜４と同様な操作により、複数のビニル基を有する単量体を共存させず表１に示す単量体組成により、比較−１〜比較−２の油中水型エマルジョン重合品を合成した。その後、スプレードライヤーに噴霧し、非架橋性水溶性イオン性高分子である粉末品の試料−３〜試料−４を製造した。組成を表１に、結果を表２に示す。
【００４７】
（架橋性水溶性イオン性高分子とアミジン系水溶性高分子の配合物の調製）
上記架橋性水溶性イオン性高分子（ａ）、試料−1〜９とアミジン系水溶性高分子の塩酸塩（ｂ）（アミジン構造単位６７モル％、ビニルアミン構造単位６モル％、Ｎ−ビニルホルムアミド構造単位７モル％、アクリロニトリル構造単位１６モル％、分子量３００万）とを混合した水溶液と粉末品を調製した。結果を表３に示す。
【００４８】
【表１】

ＤＭＣ：メタクロイルオキシエチルトリメチルアンモニウムクロリド
ＤＭＱ：アクリロイルオキシエチルトリメチルアンモニウムクロリド、ＡＡＣ：アクリル酸、ＡＡＭ：アクリルアミド、架橋剤：対単量体モル％、ＰＣＭ：多官能性水溶性ポリカチオン単量体、ＭＢＡ；メチレンビスアクリルアミド、
製品形態：Ｅ；油中水型エマルジョン、Ｄ；塩水溶液中分散重合品、
Ｐ；噴霧乾燥品
【００４９】
【表２】

エマルジョン粘度：ｍＰａ・ｓ、分子量：万
【００５０】
【表３】

配合比(重量比)；架橋性水溶性イオン性高分子(a)：アミジン系水溶性高分子（ｂ）
配合物形態；Ａｑ：水溶液（重量％濃度）、Ｐ：粉末
【００５１】
【実施例１〜９】
表３の架橋性水溶性イオン性高分子とアミジン系水溶性高分子からなる混合物、Ｍ−１〜Ｍ−９のうち、水溶液については０．３％に希釈し、また粉末品については０．３％水溶液に各々溶解した。化学品製造排水余剰汚泥（ｐＨ６．１５、全ｓｓ分２１，４００ｍｇ／Ｌ）２００ｍＬをポリビ−カ−に採取し、Ｍ−１〜Ｍ−９を対汚泥固形分０．６％添加し、ビ−カ−移し変え攪拌１０回行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、３０秒後の濾液量を測定した。また濾過した汚泥をプレス圧２Ｋｇ／ｍ2で１分間脱水する。その後、濾布剥離性を目視によりチェックし、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）を測定した。結果を表４に示す。
【００５２】
【比較例１〜６】
表３の比較試料、ＣＭ−１〜ＣＭ−４の試料及び架橋性水溶性イオン性高分子単独試料ＣＭ−５〜ＣＭ−６を用い、実施例１〜９と同様な操作によって試験した。結果を表４に示す。
【００５３】
【実施例１０〜１８】
表３の架橋性水溶性イオン性高分子とアミジン系水溶性高分子からなる混合物、Ｍ−１〜Ｍ−９のうち、水溶液については０．３％に希釈し、また粉末品については０．３％水溶液に各々溶解した。都市下水混合生汚泥（ｐＨ６．８９、全ｓｓ分４０、３００ｍｇ／Ｌ）２００ｍＬをポリビ−カ−に採取し、ポリ塩化第二鉄を対汚泥固形分０．１％添加しビ−カ−移し変え攪拌５回行った。この時の汚泥ｐＨは、４．９０であった。次ぎに表３のＭ−１〜Ｍ−９を対汚泥固形分０．５％添加し、ビ−カ−移し変え攪拌１０回行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、３０秒後の濾液量を測定した。また濾過した汚泥をプレス圧２Ｋｇ／ｍ2で１分間脱水する。その後、濾布剥離性を目視によりチェックし、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）を測定した。結果を表５に示す。
【００５４】
【比較例７〜１２】
表３の比較試料、ＣＭ−１〜ＣＭ−４の試料及び架橋性水溶性イオン性高分子単独試料ＣＭ−５〜ＣＭ−６を用い、実施例１０〜１８と同様な操作によって試験した。結果を表５に示す。
【００５５】
【実施例１９〜２７】
表３の架橋性水溶性イオン性高分子とアミジン系水溶性高分子からなる混合物、Ｍ−１〜Ｍ−９の０．３％水溶液を用い試験をおこなった。 製紙会社抄紙現場の製紙スラッジ（ｐＨ６．３５、全ｓｓ分２５，０００ｍｇ／Ｌ）２００ｍｌをポリビ−カ−に採取し、Ｍ−１〜Ｍ−９を対乾燥固形分液０．２添加し、ビ−カ−移し変え攪拌１０回行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、３０秒後の濾液量を測定した。また濾過した汚泥をプレス圧４Ｋｇ／ｍ2で１分間脱水する。その後ケ−キの濾布剥離性及びケ−キ含水率（１０５℃で２０ｈｒ乾燥）を測定した。結果を表６に示す。
【００５６】
【比較例１３〜１８】
表３の比較試料、ＣＭ−１〜ＣＭ−４の試料及び架橋性水溶性イオン性高分子のみの試料ＣＭ−５〜ＣＭ−６を用い、実施例１９〜２７と同様な操作によって試験した。結果を表６に示す。
【００５７】
【実施例２８〜３６】
製紙原料の前処理試験を行なった。機械パルプ、ＬＢＫＰ及びチラシ古紙からなる中質紙製紙原料（ｐＨ５．８２、濁度１２５０ＦＡＵ、全ｓｓ３．０５％、灰分０．２５％、カチオン要求量０．０５５ｍｅｑ／Ｌ、ゼ−タポテンシャル−９ｍＶ）１００ｍＬ採取し、攪拌機にセットした。また合成例１〜９と同様な操作により表７の試料−１０〜試料−１１及び比較−５の油中水型エマルジョン重合品あるいは試料−１２〜試料−１３及び試料−６の噴霧乾燥品をそれぞれ製造した。これら試料をアミジン系水溶性高分子と混合した試料、表８のＭ−１０〜Ｍ−１３をそれぞれ対ｓｓ分３００ｐｐｍ添加し、５００回転／分で６０秒間攪拌する。その後、ワットマン製ＮＯ．４１（９０ｍｍ）の濾紙にて全量濾過し、濾液のカチオン要求量をミュ−テック社製、ＰＣＤ−０３型により、また濁度をＨＡＣＨ、ＤＲ２０００Ｐ型濁度計にて測定した。結果を表９に示す。
【００５８】
【比較例１３〜１７】
比較として重縮合系カチオン性ポリマー、ジメチルアミン／エピクロロヒドリン／ポリアミン反応物（分子量：１５，０００、カチオン当量値：７．５１ｍｅｑ／ｇ）（ＣＭ−１１）、及び表７の比較試料、ＣＭ−７〜ＣＭ−８の試料及び架橋性水溶性イオン性高分子のみの試料ＣＭ−９〜ＣＭ−１０を用い、実施例２８〜３６と同様な操作によって試験した。結果を表９に示す。
【００５９】
【表４】

３０秒後濾液量：ｍｌ、ケーキ含水率：質量％
濾布剥離性：○＞△＞×の順に良いことを示す。
【００６０】
【表５】

３０秒後濾液量：ｍｌ、ケーキ含水率：質量％
濾布剥離性１４：○＞△＞×の順に良いことを示す。
【００６１】
【表６】

３０秒後濾液量：ｍｌ、ケーキ含水率：質量％
濾布剥離性１４：○＞△＞×の順に良いことを示す。
【００６２】
【表７】

（ａ及び（ｂは多官能性水溶性ポリカチオン単量体、（ｃ及び（ｄはＭＢＡ；メチレンビスアクリルアミド、添加量は対単量体モル％、製品形態：Ｅ；油中水型エマルジョン、Ｄ；塩水溶液中分散重合品、Ｐ；噴霧乾燥品
【００６３】
【表８】

配合比(重量比)；架橋性水溶性イオン性高分子(a)：アミジン系水溶性高分子（ｂ）
配合物形態；Ａｑ：水溶液（重量％濃度）、Ｐ：粉末
【００６４】
【表９】

濾液カチオン要求量：ｍｅｑ／Ｌ
濾液濁度：ＦＡＵ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aggregating agent and a method for using the same, and more specifically, a crosslinkable ion obtained by polymerizing a monomer mixture containing a specific ionic monomer and a monomer having a plurality of vinyl groups as essential components. The present invention relates to an aggregating treatment agent comprising a water-soluble polymer and an amidine-based water-soluble polymer, and a method for using the same.
[0002]
[Prior art]
Conventionally, cationic polymer flocculants have been used for sludge dewatering such as yield improvers and sewage in papermaking. In particular, sludge dewatering agents have increased sludge generation and sludge properties in recent years, so conventional cationic polymer flocculants have limited sludge throughput, dewatered cake moisture content, SS recovery rate, The treatment state is not always satisfactory in terms of the peelability of the cake from the filter cloth, and improvements are required. In order to improve the drawbacks of these conventional cationic polymer flocculants, various amphoteric polymer flocculants have been proposed, but these amphoteric polymer dehydrating agents are not always satisfactory. Further, for the purpose of reducing the moisture content of the dehydrated cake and improving the peelability from the filter cloth, for example, Japanese Patent Application Laid-Open No. 2-219887 and Japanese Patent Publication No. 8-164 disclose crosslinkable ionic polymer flocculants. ing.
[0003]
With regard to the yield improver in papermaking, the application of crosslinkable polymers has not been considered because the cohesive strength has been pursued in order to cope with the increase in papermaking speed and the increase in impurities in papermaking raw materials. It was. The polymer flocculant has been pursued to increase the molecular weight in one direction to improve the performance, so the cohesive force has certainly improved, but especially when used as a yield improver in the paper industry, disorder of formation etc. There have been frequent cases of side effects. On the other hand, the crosslinkable polymer has a relatively small molecular spread in water as compared with the linear polymer, and therefore, the cohesive force is suppressed and is suitable as a process chemical in the paper industry.
[0004]
As described above, the crosslinkable water-soluble polymer has various features and functions, but may be used as a sludge dehydrating agent or a yield improving agent in papermaking because of its relatively small molecular spread in an aqueous solution. When applied, there is a problem that the amount of addition increases compared to a linear polymer. In order to improve such disadvantages of the crosslinkable water-soluble polymer, Japanese Patent Application Laid-Open No. 7-256299 or Japanese Patent Application Laid-Open No. 7-256300 includes a quaternary ammonium base, a methacrylate monomer, an acrylate. An amphoteric polymer dehydrating agent in which a monomer and an anionic monomer are copolymerized at a certain ratio is disclosed. However, these also do not fully satisfy the purpose.
[0005]
[Problems to be solved by the invention]
When a crosslinkable water-soluble polymer is used as a sludge dewatering agent or a yield improver, it exhibits excellent points such as a reduction in the moisture content of the dewatered cake or the maintenance of the formation, but on the other hand, However, the amount of addition is inevitably increased until the effect is manifested, resulting in a problem of increased cost. The object of the present invention is to develop a treatment agent that retains the advantages of a crosslinkable water-soluble polymer and solves the problem of reducing the amount of addition.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor has reached the following invention. That is, the invention of claim 1 of the present invention is a monomer represented by the following general formula (1) and / or (2) 5 to 99.999 mol%, a single amount represented by the following general formula (3) Crosslinkable ionicity obtained by polymerizing a monomer mixture consisting of 0 to 50 mol% of a body, 0 to 95 mol% of a water-soluble nonionic monomer and 0.001 to 1 mol% of a monomer having a plurality of vinyl groups The present invention relates to an aggregating treatment agent comprising a water-soluble polymer and an amidine-based water-soluble polymer.
[Chemical 1]

General formula (1)
R1 is hydrogen or a methyl group, R2 and R3 are alkyl or alkoxyl groups having 1 to 3 carbon atoms, R4 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group, which may be the same or different. Represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X1 represents an anion.
[Chemical 2]

General formula (2)
R5 represents hydrogen or a methyl group, R6 and R7 each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X2 represents an anion.
[Chemical 3]

General formula (3)
R8 is hydrogen, methyl group or carboxymethyl group, Q is SO3, C6H4SO3,
CONHC (CH3) 2CH2SO3, C6H4COO or COO, R9 is hydrogen or COOY2, Y1 or Y2 is hydrogen or cation
[0007]
The invention according to claim 2 is the aggregating agent according to claim 1, wherein the crosslinkable ionic water-soluble polymer is a spray-dried product.
[0006]
The cross-linkable ionic water-soluble polymer may have a particle size of 100 μm or less produced by a dispersion polymerization method in the presence of a monomer mixture in a salt solution in the presence of a polymer dispersant soluble in the salt solution. The aggregating agent according to claim 1, which is a dispersion of fine particles comprising a crosslinkable ionic water-soluble polymer.
[0008]
The invention according to claim 4 is characterized in that the monomer having a plurality of vinyl groups is a polyfunctional water-soluble polycation monomer represented by the following general formula (5). 3. The aggregating treatment agent according to 3.
[Formula 4]

General formula (4)
R10 to R13 are hydrogen or a methyl group, X3 and X4 are anions, p is an integer of 0 to 20, respectively, where P is represented by the following general formula (5).
[Chemical formula 5]

General formula (5)
R _14, R ₁₅ Is hydrogen, an alkyl or benzyl group having 1 to 3 carbon atoms, an alkylene or alkoxylene group having 2 to 4 carbon atoms, R ₁₆ Is hydrogen or a methyl group,
L is -O- or -NH-, X5 ⁻ Is an anion, but R ₁₄ ~ R ₁₅ May be partially substituted with P when is hydrogen
[0009]
The invention according to claim 5 is characterized in that the polyfunctional water-soluble polycation monomer is one or more amines selected from ammonia, aliphatic primary amines, aliphatic secondary amines and aliphatic tertiary amines. 5. The aggregating agent according to claim 4, which is a reaction product of a polycondensate generated from bismuth and epihalohydrin and a dialkylaminoalkyl (meth) acrylamide.
[0010]
The invention of claim 6 is to add a coagulation treatment agent comprising the crosslinkable ionic water-soluble polymer and amidine-based water-soluble polymer according to claims 1 to 5 to the paper sludge and coagulate it, followed by dehydration by a dehydrator. A dewatering method for papermaking sludge.
[0011]
The invention of claim 7 is to add the aggregation treatment agent comprising the crosslinkable ionic water-soluble polymer and amidine-based water-soluble polymer according to claims 1 to 5 to the organic sludge, and then dehydrate it with a dehydrator. An organic sludge dehydration method characterized by:
[0012]
The invention according to claim 8 is characterized in that the aggregating treatment agent comprising the crosslinkable ionic water-soluble polymer according to claims 1 to 5 and the amidine-based water-soluble polymer is added to and processed in a papermaking raw material before paper making. This is a pretreatment method for the papermaking raw material.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
First, the monomer having a plurality of vinyl groups used in the present invention will be described. Examples of such monomers include polyfunctional monomers such as methylenebisacrylamide and ethylene glycol di (meth) acrylate, or thermally crosslinkable monomers such as N, N-dimethylacrylamide. Can be given. Moreover, it is a polyfunctional water-soluble polycation monomer represented by the general formula (4) as a preferable monomer having a plurality of vinyl groups. This monomer can be synthesized as follows. That is, after obtaining a product obtained by reacting epihalohydrin with one or more amines among ammonia, primary amine or secondary amine, reacting with a tertiary amino group-containing acrylic monomer, It is a polycation polyfunctional monomer having at least two terminals having a vinyl group. That is, R10 to R13 represent an epihalohydrin residue to which the same or different alkyl group selected from hydrogen or an alkyl group having 1 to 3 carbon atoms is bonded. This epihalohydrin residue is obtained by polymerizing the same type of repeating units when one kind of amine is used. On the other hand, when two or more kinds of amines are used, different repeating units are polymerized.
[0014]
Of these primary amines, methylamine and ethylamine are preferred. Examples of the secondary amine include dimethylamine and diethylamine. These secondary amines can be used alone or in combination of two or more.
[0015]
Examples of the tertiary amino group-containing acrylic monomer include N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and N, N. -Diethylaminoethyl (meth) acrylate etc. can be mentioned. Most preferred is N, N-dimethylaminopropyl (meth) acrylamide.
[0016]
The addition amount of the monomer having a plurality of vinyl groups is as follows. That is, in the case of polyfunctional monomers such as methylene bisacrylamide and ethylene glycol di (meth) acrylate, or N, N-dimethylacrylamide monomer, the amount of the mixed material is 0.001 to 0.1 mol. %, Preferably 0.002 to 0.05%, more preferably 0.005 to 0.05%. The addition amount of the polyfunctional water-soluble polycation monomer to the monomer mixture is 0.001 to 1 mol%, preferably 0.01 to 0.5%, based on the amount of the monomer mixture. More preferably, it is 0.05 to 0.5%. The polymerization temperature can be carried out under the usual polymerization conditions as described above. In order to adjust the degree of polymerization, it is effective to use isopropyl alcohol in combination with 0.1 to 5% by weight of the monomer.
[0017]
The ionic crosslinkable water-soluble polymer prepared by copolymerizing the polyfunctional water-soluble polycation monomer with the monomer mixture may be conventional N, N-methylenebisacrylamide or ethylene glycol di (meta). ) Compared with the case of using a relatively short cross-linking agent between cross-linking points such as acrylate, the cross-linking point is longer, and a cationic group exists between the cross-linking points. Therefore, the molecules do not shrink too much and can exist in an appropriate state in water. As a result, the characteristics of the crosslinkable polymer are retained, and contact with the suspended particles is also efficiently performed.
[0018]
As the polymerization method, after polymerization by aqueous solution polymerization, water-in-oil emulsion polymerization, water-in-oil dispersion polymerization, salt water dispersion polymerization, etc., each product form such as aqueous solution, dispersion, emulsion or powder can be obtained. it can. A preferred form is a water-in-oil emulsion polymer or a salt-in-water dispersion polymer that has a high concentration and a short dissolution time. A powder product obtained by spray-drying a water-in-oil emulsion polymerization product is also preferable.
[0019]
As a method for producing a water-in-oil polymer emulsion, a monomer mixture composed of a cationic monomer or a monomer copolymerizable with a cationic monomer is mixed with water, at least water-immiscible carbonization. An oily substance composed of hydrogen, an amount effective to form a water-in-oil emulsion, and at least one surfactant having HLB are mixed and stirred vigorously to form a water-in-oil emulsion, followed by polymerization. To synthesize.
[0020]
Examples of oily substances composed of hydrocarbons used as a dispersion medium include paraffins, mineral oils such as kerosene, light oil, and middle oil, or hydrocarbon-based synthetic oils having characteristics such as boiling point and viscosity substantially in the same range as these. Or a mixture thereof.
[0021]
Examples of at least one surfactant having an amount effective to form a water-in-oil emulsion and HLB are HLB 3-11 nonionic surfactants, specific examples of which include sorbitan monooleate Sorbitan monostearate, sorbitan monopalmitate and the like. The amount of these surfactants to be added is 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the water-in-oil emulsion.
[0022]
After the polymerization, a hydrophilic surfactant called a phase inversion agent is added to make the emulsion particles covered with the oil film easy to adjust to water, and the water-soluble polymer therein is easily dissolved. Dilute with and use for each application. Examples of hydrophilic interfacial chemicals are cationic interfacial chemicals and HLB 9-15 nonionic interfacial chemicals, such as polyoxyethylene alkyl ether systems and polyoxyethylene alcohol ether systems.
[0015]
The polymer obtained by water-in-oil emulsion polymerization can be spray-dried as it is. Conventionally, powdering a crosslinkable water-soluble polymer has caused a side reaction in which a crosslinking reaction proceeds during drying, and it has been difficult to put it into practical use. However, this spray-drying made it possible to easily produce a cross-linkable water-soluble polymer powder on a corporate scale. In order to prepare for atomization, the concentration of the water-in-oil emulsion polymer is slightly adjusted, and then sent to a spray dryer and dried at a temperature of about 70 to 110 ° C. Moreover, at the time of drying, the crosslinking reaction proceeds by heat, and it can be expected that the performance as a sludge dewatering agent is improved accordingly.
[0023]
Furthermore, a water-soluble polymer comprising a polymer fine particle dispersion dispersed in an aqueous salt solution can be produced according to JP-A-62-1251. This method is produced by stirring a cationic monomer or a cationic monomer and a nonionic monomer in a salt aqueous solution in the presence of a dispersant composed of a polymer soluble in the salt aqueous solution. It consists of a dispersion of fine polymer particles having a particle size of 100 mμ or less. When producing a crosslinkable ionic water-soluble polymer, these monomers are allowed to coexist with a monomer having a plurality of vinyl groups during polymerization.
[0024]
Polymeric dispersing agents include cationic water-soluble polymers such as dimethyldiallylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride homopolymers and copolymers with nonionic monomers. Is use. Nonionic polymers have amide groups and some hydrophobic groups such as polyvinylpyrrolidone, acrylamide / polyvinylcaprolactam copolymers, acrylamide / styrene copolymers, and fully amidated products of maleic anhydride / butene copolymer. Water-soluble polymers are effective.
[0025]
The inorganic salts constituting the aqueous salt solution are more preferably polyvalent anion salts, and sulfates or phosphates are suitable. Specifically, ammonium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, ammonium hydrogen phosphate, hydrogen phosphate Examples thereof include sodium and potassium hydrogen phosphate, and these salts are preferably used as an aqueous solution having a concentration of 15% or more.
[0026]
In the case of water-in-oil emulsion polymerization, the polymerization concentration is 20 to 50% by weight, preferably 25 to 40% by weight. In the case of dispersion polymerization in an aqueous salt solution, it is 15 to 40% by weight, preferably 20 to 35% by weight. In both cases, the polymerization temperature is from 0 to 80 ° C., preferably from 20 to 50 ° C., and most preferably from 20 to 40 ° C. The polymerization temperature is appropriately determined depending on the monomer composition, the polymerization method, and the selection of the initiator. Set.
[0027]
The crosslinkable water-soluble ionic polymer of the present invention is represented by 5 to 99.999 mol% of the monomer represented by the general formula (1) and / or (2), and the following general formula (3). Produced by polymerizing a monomer mixture consisting of 0 to 50 mol% monomer, 0 to 95 mol% nonionic monomer and 0.001 to 1 mol% monomer having a plurality of vinyl groups. be able to. The polymerization can be performed by a known polymerization method after preparing an aqueous solution in which these monomers are mixed.
[0028]
Examples of the cationic monomer represented by the general formula (1) include polymers and copolymers such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and methyldiallylamine. Examples of the quaternary ammonium group-containing polymer include (meth) acryloyloxyethyltrimethylammonium chloride and (meth) acryloyloxy 2-methylated quaternization product of the above-mentioned tertiary amino-containing monomer with methyl chloride or benzyl chloride. Hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxy 2-hydroxypropyldimethylbenzylammonium chloride, (meth) a Leroy Le aminopropyl dimethyl benzyl ammonium chloride, and the like. Moreover, as an example of the cationic monomer represented by the general formula (2), a dimethyldiallylammonium monomer can be used, and examples thereof include dimethyldiallylammonium chloride and diallylmethylbenzylammonium chloride. is there.
[0029]
Furthermore, examples of the anionic monomer represented by the general formula (3) may be either a sulfone group or a carboxyl group, and both may be used in combination. Examples of the sulfone group-containing monomer are vinyl sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido 2-methylpropane sulfonic acid, and the like. Examples of the carboxyl group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, maleic acid, and p-carboxystyrene.
[0030]
Examples of water-soluble nonionic monomers include (meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N -Vinylformamide, N-vinylacetamide, acryloylmorpholine, acryloylpiperazine and the like.
[0031]
The molecular weight of the crosslinkable ionic water-soluble polymer obtained by copolymerizing the monomer or monomer mixture is 500,000 to 20 million, preferably 500,000 to 15 million, more preferably 50. 10 to 10 million.
[0032]
Next, the amidine-based water-soluble polymer used in combination will be described. This polymer can be synthesized by an acid hydrolysis reaction of a copolymer of N-vinylcarboxylic amide and (meth) acrylonitrile. Examples of the monomer N-vinylcarboxylic acid amide include N-vinylformamide and N-vinylacetamide. The most common vinyl nitriles to be copolymerized are acrylonitrile. As the polymerization method, after polymerization by aqueous solution polymerization, water-in-oil emulsion polymerization, water-in-oil dispersion polymerization, salt water dispersion polymerization, etc., each product form such as aqueous solution, dispersion, emulsion or powder can be obtained. it can. The acid used at the time of hydrolysis is preferably an inorganic strong acid, such as hydrochloric acid, nitric acid or p-toluenesulfonic acid.
[0033]
The mol% of the amidine group in the molecule after hydrolysis is 5 to 100 mol%, preferably 10 to 100 mol%, and most preferably 20 to 80 mol%. The nonionic structural unit is an unhydrolyzed carboxylic acid amide group and an unreacted nitrile group, and is 0 to 95 mol%, preferably 0 to 90 mol%, most preferably 20 to 80 mol%. . The most preferred form is a powder product. The molecular weight is 1 million to 10 million, but preferably 2 million to 5 million.
[0034]
The combined ratio of these crosslinkable ionic water-soluble polymer and amidine-based water-soluble polymer is 30 to 70:70 to 30 and preferably 40 to 60:60 to 40 as the weight fraction of the two substances. . If one of the substances is 30% by weight or less, only the property of one of the substances is hardly expressed, and it is preferable that the substance is close to the same weight. As a method of combination, mixing, sequential addition, simultaneous addition, etc. are possible, but it is best to mix and add a mixture of products or solution, and the two polymers of the above composition were mixed in powder form The product form is the most convenient. In addition, it is effective to add an acid to the aqueous solution mixture or the powder mixture in order to prevent deterioration of the crosslinkable ionic water-soluble polymer. In particular, powdered products such as sulfamic acid and tartaric acid are convenient for products in powder form.
[0035]
The treatment agent comprising the crosslinkable ionic water-soluble polymer and amidine-based water-soluble polymer of the present invention is surplus sludge generated during biological treatment such as papermaking wastewater, chemical industry wastewater, food industry wastewater, or municipal sewage. Organic sludge such as raw sludge, mixed raw sludge, surplus sludge, digested sludge, or paper sludge can be used for dewatering. Furthermore, since pretreatment of pitches or anionic substances derived from waste paper or mechanical pulp is performed, it can be used by adding to the papermaking raw material before papermaking.
[0036]
Furthermore, the treatment agent comprising the crosslinkable ionic water-soluble polymer and amidine-based water-soluble polymer of the present invention may be added to the papermaking raw material before papermaking for the purpose of improving yield and / or drainage. it can. Further, in combination with the present treatment agent and an inorganic or organic anionic substance, it can be added to the papermaking raw material before papermaking for the purpose of improving yield and / or drainage. Among the anionic substances, the inorganic substance is bentonite, kaolin, clay, talc, or the like, and colloidal silica can also be used.
[0037]
When the anionic substance is an anionic water-soluble polymer, any anionic water-soluble polymer can be used, but the anionic monomer represented by the general formula (3) is 3 to 100 mol%. And a monomer mixture containing 0 to 97 mol% of a water-soluble nonionic monomer in a salt aqueous solution, and a particle size of 100 μm produced by a dispersion polymerization method in the presence of a polymer dispersant soluble in the salt aqueous solution. It is preferable to use a dispersion of fine particles comprising the following anionic water-soluble polymer. The production method of this polymer is the same as that of the crosslinkable cationic or amphoteric water-soluble polymer. As the polymer dispersant, an anionic polymer is preferably used. For example, it is a (co) polymer of anionic monomers such as acrylamide 2-methylpropanesulfonic acid (salt) and styrenesulfonic acid (salt). Copolymers of these anionic monomers and carboxyl group-containing monomers such as acrylic acid, methacrylic acid and itaconic acid can also be used. Furthermore, a copolymer with acrylamide which is a nonionic monomer can also be used. In some cases, an inorganic anionic substance and an organic anionic substance may be used in combination.
[0038]
The addition amount of the aggregating treatment agent of the present invention is 0.1 to 1.0% by weight with respect to the sludge solid content, and preferably 0.2 to 0.5%. Moreover, when using as a pre-processing, it is 50-10,000 ppm with respect to the dry part in a papermaking raw material, Preferably it is 100-2,000 ppm.
[0039]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in more detail with an Example and a comparative example, this invention is not restrict | limited to a following example, unless the summary is exceeded.
[0040]
(Synthesis Example 1) In a reaction vessel equipped with a stirrer and a temperature control device, 120.0 g of isoparaffin having a boiling point of 190 ° C to 230 ° C, 6.0 g of sorbitan monooleate and a polyricinoleic acid / polyoxyethylene block copolymer 0 .6 g was charged and dissolved. Separately, 32.0 g of deionized water, 184.4 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride (hereinafter abbreviated as DMQ), 27.0 g of 50% aqueous solution of acrylamide (abbreviated as AAM), and the polyfunctional water solution prepared in the synthesis example Each 1.1 g of a 60% aqueous polycation monomer solution (0.4 wt% monomer) was collected and added to the acrylic acid solution to completely dissolve it. Moreover, pH was adjusted to 4.35, oil and aqueous solution were mixed, and it stirred and emulsified for 15 minutes at 1000 rpm with the homogenizer. The monomer composition at this time is DMQ / AAM = 80/20 (mol%).
[0041]
After adding 2.4 g of isopropyl alcohol 40% aqueous solution (0.6% by weight of monomer) to the obtained emulsion, keeping the temperature of the monomer solution at 30 to 33 ° C. and performing nitrogen substitution for 30 minutes, 2,5′-Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride 10% aqueous solution 0.35 g (0.02% by weight of monomer) was added and polymerized. The reaction was started. The reaction was completed at a reaction temperature of 32 ± 2 ° C. for 12 hours to complete the reaction. After the polymerization, 10.0 g of polyoxyethylene tridecyl ether (2.0% by weight with respect to the liquid) was added to and mixed with the resulting water-in-oil emulsion as a phase inversion agent to prepare a sample for use in the test (Sample-1). . Moreover, the weight average molecular weight was measured with the molecular weight measuring device (DLS-7000 by Otsuka Electronics) by a static light scattering method.
The composition is shown in Table 1, and the results are shown in Table 2.
[0042]
(Synthesis Examples 2 to 4) By the same operation as in Example 1, DMQ / AAC / AAM = 60/20/20 respectively according to the monomer having a plurality of vinyl groups and other monomer compositions shown in Table 1. (Sample-2), DMQ / AAM = 80/20 (Sample-3), DMQ / AAC / AAM = 60/20/20 (Sample-4) (all in mol%) A polymer emulsion was synthesized. The composition is shown in Table 1, and the results are shown in Table 2.
[0043]
(Synthesis Example 5) Metacloyl in a 500 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a monomer supply tube connected to a peristaltic pump (SMP-21 type, manufactured by Tokyo Rika Kikai Co., Ltd.) and a condenser 46.3 g of 80 wt% aqueous solution of oxyethyltrimethylammonium chloride (hereinafter abbreviated as DMC), 60.5 g of 80 wt% aqueous solution of acryloyloxyethyltrimethylammonium chloride (hereinafter abbreviated as DMQ), acrylic acid (hereinafter abbreviated as AAC) ) (20.6 g), 50% aqueous solution of acrylamide (hereinafter abbreviated as AAM) 36.5 g, 173.1 g of ion-exchanged water, 125.0 g of ammonium sulfate, acryloyloxyethyltrimethylammonium chloride homopolymer as a dispersant 30.0 g (20 wt% liquid, viscosity 6450 mPa · s ) And the pH was adjusted to 3.3. At this time, the mol% of each monomer is DMC / DMQ / AAC / AAM = 25/35/20/20. Next, the temperature in the reactor was kept at 30 ± 2 ° C., and after replacing with nitrogen for 30 minutes, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] as an initiator was used. Polymerization was initiated by adding 1.0 g of a 1% aqueous solution of dihydrochloride (0.01% monomer). When the internal temperature was kept at 30 ± 2 ° C. and the reaction was carried out for 7 hours from the start of polymerization, 0.01% of the initiator was added to the above monomer, and the reaction was further completed for 7 hours. The resulting dispersion had a squeeze monomer concentration of 20%, a polymer particle size of 10 μm or less, and a viscosity of the dispersion of 750 mPa · s. Moreover, the weight average molecular weight was measured with the molecular weight measuring device (DLS-7000 by Otsuka Electronics) by a static light scattering method. This sample is designated as Sample-5. The results are shown in Tables 1 and 2.
[0044]
(Synthesis Example 6) By the same operation as that of Example 5, DMQ / AAM = 80/20 (Sample-6) was formed by the monomer having a plurality of vinyl groups shown in Table 1 and other monomer compositions. A dispersion polymerized product in a salt solution having the composition was synthesized. The composition is shown in Table 1, and the results are shown in Table 2.
[0045]
(Synthesis Examples 7 to 9) Water-in-oil emulsions produced in Examples 1 to 3 and samples corresponding to Samples 1 to 3 before addition of the hydrophilic surfactant were sprayed on a spray dryer to obtain powder products Sample-7 to Sample-9 were prepared. The composition is shown in Table 1, and the results are shown in Table 2.
[0046]
(Comparative Synthesis Examples 1 to 4) By the same operation as in Examples 1 to 4, the monomers having a plurality of vinyl groups were not allowed to coexist, and the monomer compositions shown in Table 1 were used. A water-in-oil emulsion polymer was synthesized. Then, it sprayed on the spray dryer and the sample-3-sample-4 of the powder goods which are non-crosslinkable water-soluble ionic polymers were manufactured. The composition is shown in Table 1, and the results are shown in Table 2.
[0047]
(Preparation of crosslinkable water-soluble ionic polymer and amidine-based water-soluble polymer)
Crosslinkable water-soluble ionic polymer (a), Samples 1 to 9 and hydrochloride of amidine-based water-soluble polymer (b) (amidine structural unit 67 mol%, vinylamine structural unit 6 mol%, N-vinylformamide An aqueous solution and a powder product in which 7 mol% of structural units, 16 mol% of acrylonitrile structural units, and a molecular weight of 3 million) were mixed were prepared. The results are shown in Table 3.
[0048]
[Table 1]

DMC: methacryloyloxyethyltrimethylammonium chloride
DMQ: acryloyloxyethyltrimethylammonium chloride, AAC: acrylic acid, AAM: acrylamide, crosslinker: mol% to monomer, PCM: polyfunctional water-soluble polycation monomer, MBA; methylenebisacrylamide,
Product form: E: Water-in-oil emulsion, D: Polymer dispersion in salt solution,
P: Spray-dried product
[0049]
[Table 2]

Emulsion viscosity: mPa · s, molecular weight: 10,000
[0050]
[Table 3]

Compounding ratio (weight ratio): Crosslinkable water-soluble ionic polymer (a): Amidine-based water-soluble polymer (b)
Formulation form; Aq: aqueous solution (weight% concentration), P: powder
[0051]
Examples 1-9
Of the mixture of the cross-linkable water-soluble ionic polymer and amidine-based water-soluble polymer in Table 3, M-1 to M-9, the aqueous solution was diluted to 0.3%, and the powdered product was reduced to 0.3%. Each was dissolved in a 3% aqueous solution. Collect 200 mL of excess sludge (pH 6.15, total ss content 21,400 mg / L) from a chemical manufacturing wastewater and add M-1 to M-9 to the sludge solid content 0.6%. -After transferring and stirring 10 times, the mixture was filtered through a T-1179L filter cloth (made of nylon), and the amount of filtrate after 30 seconds was measured. The filtered sludge is dehydrated at a press pressure of 2 kg / m @ 2 for 1 minute. Thereafter, the filter cloth peelability was visually checked, and the cake water content (dried at 105 ° C. for 20 hours) was measured. The results are shown in Table 4.
[0052]
[Comparative Examples 1-6]
Using the comparative samples in Table 3, the samples CM-1 to CM-4, and the crosslinkable water-soluble ionic polymer single samples CM-5 to CM-6, they were tested in the same manner as in Examples 1-9. The results are shown in Table 4.
[0053]
Examples 10 to 18
Of the mixture of the cross-linkable water-soluble ionic polymer and amidine-based water-soluble polymer in Table 3, M-1 to M-9, the aqueous solution was diluted to 0.3%, and the powdered product was reduced to 0.3%. Each was dissolved in a 3% aqueous solution. 200 mL of municipal sewage mixed raw sludge (pH 6.89, total ss 40, 300 mg / L) was collected in a poly beaker, poly ferric chloride was added to the sludge solid content 0.1%, and the beaker was transferred. Change and stir 5 times. The sludge pH at this time was 4.90. Next, M-1 to M-9 shown in Table 3 were added to the sludge solid content of 0.5%, and the beaker was transferred and stirred 10 times, and then filtered through a T-1179L filter cloth (made of nylon). The amount of filtrate after 30 seconds was measured. The filtered sludge is dehydrated at a press pressure of 2 kg / m @ 2 for 1 minute. Thereafter, the filter cloth peelability was visually checked, and the cake water content (dried at 105 ° C. for 20 hours) was measured. The results are shown in Table 5.
[0054]
[Comparative Examples 7-12]
Using the comparative samples in Table 3, samples of CM-1 to CM-4, and crosslinkable water-soluble ionic polymer single samples CM-5 to CM-6, they were tested in the same manner as in Examples 10-18. The results are shown in Table 5.
[0055]
Examples 19-27
The test was performed using a mixture of the crosslinkable water-soluble ionic polymer and the amidine-based water-soluble polymer in Table 3 and a 0.3% aqueous solution of M-1 to M-9. 200 ml of papermaking sludge (pH 6.35, total ss content 25,000 mg / L) at a papermaking company papermaking site was collected in a poly-bicker, and M-1 to M-9 was added to dry solids liquid 0.2. The beaker was transferred and stirred 10 times, then filtered through a T-1179L filter cloth (made of nylon), and the amount of filtrate after 30 seconds was measured. The filtered sludge is dehydrated at a press pressure of 4 kg / m 2 for 1 minute. Thereafter, the filter cloth peelability of the cake and the moisture content of the cake (dried at 105 ° C. for 20 hours) were measured. The results are shown in Table 6.
[0056]
[Comparative Examples 13-18]
Tests were carried out in the same manner as in Examples 19 to 27 using the comparative samples in Table 3, samples CM-1 to CM-4, and samples CM-5 to CM-6 containing only the crosslinkable water-soluble ionic polymer. The results are shown in Table 6.
[0057]
Examples 28 to 36
A pretreatment test for papermaking raw materials was conducted. Medium-sized papermaking raw material consisting of mechanical pulp, LBKP and leaflet waste paper (pH 5.82, turbidity 1250 FAU, total ss 3.05%, ash content 0.25%, cation requirement 0.055 meq / L, zeta potential -9 mV ) 100 mL was collected and set in a stirrer. In addition, by performing the same operations as in Synthesis Examples 1 to 9, the water-in-oil emulsion polymerization products of Sample-10 to Sample-11 and Comparative-5 in Table 7 or the spray-dried products of Sample-12 to Sample-13 and Sample-6 were prepared. Each was manufactured. A sample obtained by mixing these samples with an amidine-based water-soluble polymer and M-10 to M-13 shown in Table 8 are each added at 300 ppm to the ss, and stirred at 500 rpm for 60 seconds. After that, NO. The total amount was filtered with a 41 (90 mm) filter paper, and the cation required amount of the filtrate was measured with a PCD-03 type manufactured by Mutech, and the turbidity was measured with a HACH, DR2000P type turbidimeter. The results are shown in Table 9.
[0058]
[Comparative Examples 13-17]
For comparison, a polycondensation cationic polymer, a dimethylamine / epichlorohydrin / polyamine reactant (molecular weight: 15,000, cation equivalent value: 7.51 meq / g) (CM-11), and a comparative sample in Table 7, Using samples CM-7 to CM-8 and samples CM-9 to CM-10 containing only a crosslinkable water-soluble ionic polymer, the test was conducted in the same manner as in Examples 28 to 36. The results are shown in Table 9.
[0059]
[Table 4]

After 30 seconds, filtrate amount: ml, cake moisture content: mass%
Filter cloth peelability: Good in the order of ◯>Δ> ×.
[0060]
[Table 5]

After 30 seconds, filtrate amount: ml, cake moisture content: mass%
Filter cloth peelability 14: It shows that it is good in order of (circle)>(DELTA)> *.
[0061]
[Table 6]

After 30 seconds, filtrate amount: ml, cake moisture content: mass%
Filter cloth peelability 14: It shows that it is good in order of (circle)>(DELTA)> *.
[0062]
[Table 7]

(A and (b are polyfunctional water-soluble polycation monomers, (c and (d are MBA; methylenebisacrylamide, added amount is monomer mol%, product form: E; water-in-oil emulsion, D: Polymer dispersion in salt solution, P: Spray-dried product
[0063]
[Table 8]

Compounding ratio (weight ratio): Crosslinkable water-soluble ionic polymer (a): Amidine-based water-soluble polymer (b)
Formulation form; Aq: aqueous solution (weight% concentration), P: powder
[0064]
[Table 9]

Filtrate cation requirement: meq / L
Filtrate turbidity: FAU

Claims (8)

5 to 99.999 mol% of a monomer represented by the following general formula (1) and / or (2), 0 to 50 mol% of a monomer represented by the following general formula (3), water-soluble nonionic Crosslinkable ionic water-soluble polymer and amidine-based water-soluble polymer obtained by polymerizing a monomer mixture composed of 0 to 95 mol% of a polymerizable monomer and 0.001 to 1 mol% of a monomer having a plurality of vinyl groups An aggregating agent comprising:

General formula (1)
R1 is hydrogen or a methyl group, R2 and R3 are alkyl or alkoxyl groups having 1 to 3 carbon atoms, R4 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group, which may be the same or different. Represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X1 represents an anion.

General formula (2)
R5 represents hydrogen or a methyl group, R6 and R7 each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X2 represents an anion.

General formula (3)
R8 is hydrogen, methyl group or carboxymethyl group, Q is SO3, C6H4SO3,
CONHC (CH3) 2CH2SO3, C6H4COO or COO, R9 is hydrogen or COOY2, Y1 or Y2 is hydrogen or cation The aggregating agent according to claim 1, wherein the crosslinkable ionic water-soluble polymer is a spray-dried product. The crosslinkable ionic water-soluble polymer is a crosslinkable ion having a particle size of 100 μm or less produced by a dispersion polymerization method in the presence of the monomer mixture in a salt aqueous solution and in the presence of a polymer dispersant soluble in the salt aqueous solution. The aggregating agent according to claim 1, which is a dispersion of fine particles comprising a water-soluble polymer. The crosslinkable ion according to claim 1, wherein the monomer having a plurality of vinyl groups is a polyfunctional water-soluble polycation monomer represented by the following general formula (4): A coagulation treatment drug consisting of water-soluble polymer.

General formula (4)
R10 to R13 are hydrogen or a methyl group, X3 and X4 are anions, p is an integer of 0 to 20, respectively, where P is represented by the following general formula (5).

General formula (5)
R _{14 and} R ₁₅ are hydrogen, an alkyl group having 1 to 3 carbon atoms or a benzyl group, an alkylene group having 2 to 4 carbon atoms or an alkoxylene group, R ₁₆ is hydrogen or a methyl group,
L is —O— or —NH—, X 5 ^— is an anion, and when R _{14 to} R ₁₅ are hydrogen, they may be partially substituted with P. The polyfunctional water-soluble polycation monomer is a polycondensation formed from one or more amines selected from ammonia, aliphatic primary amines, aliphatic secondary amines and aliphatic tertiary amines and epihalohydrins. The aggregating agent according to claim 4, which is a reaction product of a product and a dialkylaminoalkyl (meth) acrylamide. A papermaking process comprising adding a coagulation treatment agent comprising the crosslinkable ionic water-soluble polymer and the amidine-based water-soluble polymer according to claim 1 to papermaking sludge, and then dehydrating the papermaking sludge. Sludge dewatering method. An organic substance characterized in that the coagulation treatment agent comprising the crosslinkable ionic water-soluble polymer and the amidine-based water-soluble polymer according to claim 1 is added to and coagulated with organic sludge, and then dehydrated by a dehydrator. Sludge dewatering method. A pretreatment of a papermaking raw material, characterized in that the aggregating treatment agent comprising the crosslinkable ionic water-soluble polymer and amidine water-soluble polymer according to claim 1 is added to and processed in the papermaking raw material before papermaking. Method.