JP4232189B2 - Paper manufacturing method - Google Patents
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- JP4232189B2 JP4232189B2 JP2002328655A JP2002328655A JP4232189B2 JP 4232189 B2 JP4232189 B2 JP 4232189B2 JP 2002328655 A JP2002328655 A JP 2002328655A JP 2002328655 A JP2002328655 A JP 2002328655A JP 4232189 B2 JP4232189 B2 JP 4232189B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、紙の製造方法に関する。更に詳しくは、ポリアクリルアミド系紙力増強剤を用いた紙の製造方法に関する。
【０００２】
【従来の技術】
従来、紙を製造する際には、紙に強度を付与すべく紙力増強剤が用いられており、性能等の点からポリアクリルアミド系紙力増強剤が広く用いられている。通常、紙力増強剤を用いる場合には、一種の紙力増強剤を一度にまたは分割して紙料に添加される。しかしながら、紙力増強剤を一種類しか用いない場合には、地合いと濾水性のバランスを取ることが困難であり、紙力増強剤を多く使用しなければならなかった。
【０００３】
そのため、このような問題を解決すべく、数種の紙力増強剤を用いる紙の製造方法が提案されている。例えば、両性ポリアクリルアミド系重合体とカチオン性基を有し前記両性ポリアクリルアミド系重合体とは異なるポリマーを含有する添加剤を用いる紙の製造法（特許文献１参照）が提案されており、さらに、両性ポリアクリルアミド系重合体とカチオン性基を有し、前記両性ポリアクリルアミド系重合体とは異なるポリマーとアルミニウム化合物を用いて抄紙する紙の製造法（特許文献２参照）などが提案されている。しかしながら、いずれの方法においても、地合いと濾水性のバランスを取ることが困難であった。
【０００４】
【特許文献１】
特開平５−７８９９７号公報
【特許文献２】
特開平５−９３３９３号公報
【特許文献３】
特開昭６３−１２７９２号公報
【特許文献４】
特開昭５８−６００９４号公報
【０００５】
【発明が解決しようとする課題】
本発明は、地合いと濾水性のバランスを容易にとることができ、このため紙力を向上させ、結果として紙の製造に用いる紙力増強剤の使用量を減少させることができる紙の製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者らは、当該問題を解決すべく、検討を重ねたところ、異種の特定のポリアクリルアミド系紙力増強剤を併用することにより、前記課題を解決し得ることを見出し、さらにはこれら異種のポリアクリルアミド系紙力増強剤をそれぞれ特定の場所で添加することにより、著しい紙力増強効果が得られることを見出した。
【０００７】
すなわち、本発明は、（１）紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差が５０ｍｌ以下となる両性ポリアクリルアミド系紙力増強剤と（２）紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差が５０ｍｌを超えるポリアクリルアミド系紙力増強剤を用い抄紙することを特徴とする紙の製造方法に関する。
【０００８】
【発明の実施の形態】
本発明の紙の製造方法には、（１）紙力増強剤の添加前後におけるＪＩＳ Ｐ８１２１により測定される濾水度の差が５０ｍｌ以下となる両性ポリアクリルアミド系紙力増強剤（以後、（１）成分という）および（２）紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差が５０ｍｌを超えるポリアクリルアミド系紙力増強剤（以後、（２）成分という）を用いる。なお、ここでいう濾水度の差とは、紙料に紙力増強剤を０．５重量％添加したときの、ＪＩＳ Ｐ ８１２１に記載されるカナディアンフリーネステスターを使用した濾水量と、紙力増強剤を添加する前の紙料の、カナディアンフリーネステスターを使用した濾水量の差である。紙力増強剤の添加は、紙料固形分の濃度を１．０％〜３．０％、紙料の温度を２０〜４０℃とし、添加された紙力増強剤が紙料と十分混合させることにより行う。なお、紙力増強剤の他に、硫酸アルミニウムやサイズ剤等を使用する場合には、紙力増強剤を添加する前の濾水度は、紙力増強剤以外の薬品を添加したときの濾水度とする。なお、濾水度の差が５０ｍｌ以下となる両性ポリアクリルアミド系紙力増強剤の代わりに濾水度の差が２０ｍｌ以下となる両性ポリアクリルアミド系紙力増強剤を用いることにより、紙力強度をさらに向上させることができるためより好ましい。
【０００９】
本発明に用いられる（１）成分としては、紙力増強剤の添加前後におけるＪＩＳＰ ８１２１により測定される濾水度の差が５０ｍｌ以下となる両性ポリアクリルアミド系紙力増強剤であれば特に制限されず公知のものを使用することができるが、特に紙力増強効果の点から、分岐構造を有するものが好ましい。（１）成分としては、通常、（ａ）アニオン性ビニルモノマー（以下、（ａ）成分という）、（ｂ）カチオン性ビニルモノマー（以下、（ｂ）成分という）、（ｃ）（メタ）アクリルアミド（以下、（ｃ）成分という）などの共重合体が挙げられる。（ａ）成分としては、例えば、（メタ）アクリル酸、クロトン酸等のモノカルボン酸；マレイン酸、フマル酸、イタコン酸、ムコン酸、シトラコン酸等のジカルボン酸；ビニルスルホン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、などの有機スルホン酸；またはこれら各種有機酸のナトリウム塩、カリウム塩等が挙げられる。（ｂ）成分としては、例えば、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、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）アクリルアミドなどの第三級アミノ基を有するビニルモノマーまたはそれらの塩酸、硫酸、酢酸などの無機酸もしくは有機酸の塩類、または該第三級アミノ基含有ビニルモノマ−とメチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロルヒドリンなどの四級化剤との反応によって得られる第四級アンモニウム塩を含有するビニルモノマ−等が挙げられる。
【００１０】
また、前記（ａ）〜（ｃ）成分と共重合可能なモノマー（ｄ）（以下、（ｄ）成分という）を（ａ）〜（ｃ）成分と共重合させても良い。（ｄ）成分としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル等のアクリル酸アルキルエステル類、アリルアルコール、(メタ)アリルスルホン酸ナトリウム、アリルアミン等のアリル基を含有するアリル系モノマー類、ジメチル（メタ）アクリルアミド、イソプロピルアクリルアミド等のＮ−置換アクリルアミド系モノマー類、（メタ）アクリロニトリルなどの他、２官能ビニルモノマー系としてメチレンビス（メタ）アクリルアミド、エチレンビス（メタ）アクリルアミド等のビスアクリルアミド系モノマー類やエチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート等のジアクリレート系モノマー類、ジビニルベンゼン等であり、３以上のビニル基を有する多官能ビニルモノマー類としては、１、３、５-トリアクロイルヘキサヒドロ−Ｓ−トリアジン、トリアリルイソシアヌレート、トリアリルアミン、テトラメチロールメタンテトラアクリレートなどを単独でまたは複数種を混合して使用することができる。
【００１１】
これら（ｄ）成分の中では、アリル系モノマーを用いることにより、ラジカルの移動（連鎖移動）が生じやすくなり、分子量の調整が容易となるため好ましく、また、Ｎ-置換アクリルアミド系モノマー、ビスアクリルアミド系モノマー、ジアクリレート系モノマー、ジビニルベンゼン、多官能ビニルモノマーを用いることにより得られるポリマーを架橋により高分子量化させることができるため好ましい。
【００１２】
なお、イソプロピルアルコール、ペンタノール等のアルコール類を連鎖移動剤として用いることにより、得られるアクリルアミド系樹脂の分子量を調整することができる。
【００１３】
前記モノマーを重合させる方法としては特に制限されず、公知の方法を採用することができる。具体的には、前記モノマー類を混合したものに、公知のラジカル重合開始剤を加えることにより行われる。具体的には、例えば、所定の反応容器に溶媒として水を仕込み所定温度まで加温し、上記各種モノマーおよび水を仕込んだ滴下ロートと、重合開始剤と水を仕込んだ滴下ロートから、それぞれの成分を撹拌下に、反応容器中に滴下しながら重合する方法や所定の反応容器に上記各種モノマーを仕込み、所定の温度まで高め、重合開始剤を添加し、重合する方法などが挙げられる。
【００１４】
（１）成分を得るためには、（ａ）成分を０.１〜１５モル％程度、より好ましくは１〜１０モル％、（ｂ）成分を０.１〜１５モル％程度、より好ましくは１〜１０モル％、（ｃ）成分を５８〜９９．８モル％程度、より好ましくは８０〜９８モル％用いる。（ａ）成分、（ｂ）成分とも、０.１モル％未満では定着効果が低く、紙力効果が低くなる傾向があり、１５モル％を越えるとポリマー中のアクリルアミド分が減少することにより紙力効果が低くなる傾向があり、さらには、高価となるため好ましくない。なお、（ｄ）成分として、連鎖移動性モノマーを０．０５〜１０モル％程度、より好ましくは０．１モル％〜５．０モル％を用いることにより、分子量の調整が容易となる。連鎖移動性モノマーの成分が０．０５モル％未満であれば、連鎖移動効果が弱く、また分岐点の生成も少ないために、分岐構造が不十分となる傾向がある。１０モル％を超える場合は、連鎖移動効果が強すぎるため、ポリマー鎖が短くなり、高分子量ポリマーを生成しにくくなる。なお、架橋性モノマーを０．０１〜２．０モル％程度、より好ましくは０．０１〜１．０モル％を用いることにより、重合体の高分子量化ができる。架橋性モノマーを０．０１モル％未満しか用いない場合には高分子量化効果は小さくなり、２．０モル％を超えて用いるとゲル化するおそれがある。
【００１５】
このようにして得られた（１）成分の重量平均分子量は２００万程度以上が好ましい。２００万未満では充分な紙力効果が得られない場合がある。（１）成分は、通常５重量％以上の不揮発物を含有するように調整する。なお、（１）成分の不揮発物を５重量％に調整した場合の粘度は、２００００ｍＰａ・ｓ程度以下とすることが好ましい。粘度が２００００ｍＰａ・ｓを超える場合は地合を乱しやすくなり、紙力向上効果が著しく低下する場合がある。
【００１６】
本発明に用いられる（２）成分としては、紙力増強剤の添加前後におけるＪＩＳ Ｐ ８１２１により測定される濾水度の差が５０ｍｌを超えるポリアクリルアミド系紙力増強剤であれば特に制限されず公知のものを使用することができる。具体的には、前記（１）成分と同種のモノマーを使用することができる。
【００１７】
（２）成分を得るためには、前記（ａ）成分を通常０.１〜２０モル％程度、より好ましくは１〜１５モル％、前記（ｂ）成分を０.１〜２０モル％程度、より好ましくは１〜１５モル％、（ｃ）成分を６０〜９９．８モル％程度、より好ましくは７０〜９８モル％用いる。（ａ）成分、（ｂ）成分とも、０.１モル％未満では定着効果が低く、紙力効果が低くなる傾向があり、２０モル％を越えるとポリマー中のアクリルアミド分が減少することにより紙力効果が低くなる傾向があり、さらには、高価となるため好ましくない。なお、（ｄ）成分として連鎖移動性モノマーを０．０５〜１０モル％程度、より好ましくは０．１モル％〜５．０モル％用いることにより、分子量の調整が容易となり、また、架橋性モノマーを０．０１〜２．０モル％、より好ましくは０．０１〜１．０モル％用いることで重合体の高分子量化ができる。（２）成分は、（１）成分と同様の重合法により重合を行えば良く、通常５重量％以上の不揮発物を含有するように調整する。
【００１８】
なお、（２）成分はアクリルアミド単独重合体あるいはアクリルアミド−アクリル酸共重合体で代表されるアニオン性アクリルアミド共重合体をホルマリンとジメチルアミン等のアルキルアミンを用いてマンニッヒ反応させたものでも良く、ホフマン分解反応させて得られるものでもよい。いずれもカチオン変性率は特に制限はなく、６０モル％程度以下が好ましい。カチオン変性率が６０モル％を超えると、地合が乱れやすくなり、紙力向上効果が著しく低下する。また、（２）成分は濾水度が５０ｍｌを越えれば、２種以上の紙力増強剤を混合して用いてもよい。
【００１９】
これら（２）成分の重量平均分子量は特に制限されないが、不揮発物を５重量％に調整した場合の粘度は、２００００ｍＰａ・ｓ程度以下とすることが好ましい。粘度が２００００ｍＰａ・ｓを超える場合は地合を乱しやすくなり、紙力向上効果が著しく低下する場合がある。
【００２０】
前記（１）成分および（２）成分を添加する際の量は特に制限されないが、通常（１）成分を固形分重量換算で、紙料に対して、０．１〜１．５重量％程度、より好ましくは０．３〜１．０重量％、（２）成分を固形分重量換算で、紙料に対して、０．０５％〜０．７５重量％程度好ましくは０．１％〜０．５重量％とする。（１）の成分の使用量は固形分重量換算で、紙料に対して、０．１重量％未満の場合には紙力効果が十分でない場合があり、１．０重量％を超える場合には定着性が低下し、汚れを誘発しやすくなる。（２）の成分の使用量は固形分重量換算で、紙料に対して、０．０５重量％未満の場合には濾水性が十分でなく、０．７５重量％を超える場合には紙の地合が整いにくくなり、好ましくない。
【００２１】
前記（１）成分と（２）成分の使用量（紙料に対する固形分重量％）にて、比（（１）／（２））を１以上、より好ましくは２以上とすることにより、紙力効果が向上できる。（１）成分と（２）成分の使用固形分重量比が１未満では地合乱れが起こりやすく、紙力効果が向上しにくくなる傾向がある。なお、本発明の効果に影響を与えない範囲で、サイズ剤、ピッチコントロール剤、濾水剤等抄紙に必要な添加剤を添加できる。
【００２２】
（１）成分および（２）成分の添加場所としては特に制限されないが、（１）成分を紙料濃度が１．５重量％以上の場所で、（２）成分を紙料濃度が１．５重量％未満の場所で添加することにより紙力強度の向上が著しくなるため好ましい。なお、紙料濃度が１．５重量％以上の場所としては、例えば、ミキシングチェスト、マシンチェスト、種箱などが挙げられ、紙料濃度が１．５重量％未満の場所としては、例えば、ファンポンプ、白水ピット、スクリーンなどが挙げられる。これらのうち、（１）成分の添加場所をマシンチェストで、（２）成分の添加場所をファンポンプとすることにより、特に著しい紙力効果が得られるため好ましい。
【００２３】
【発明の効果】
本発明によれば、地合いと濾水性のバランスを容易にとることができるため、紙力向上効果を増幅させることができ、その結果、抄紙時の紙力増強剤の使用量を減少させることができる。
【００２４】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。実施例中の部および％はそれぞれ重量部および重量％を示す。また、実施例中の試験法を下記に示す。
【００２５】
（１）濾水度
ＪＩＳ Ｐ ８１２１に準拠して測定した。
【００２６】
（２）破裂強度
ＪＩＳ Ｐ ８１３１に準拠して測定し、比破裂強度（ｋＰａ・ｍ２／ｇ）で示した。
【００２７】
また、実施例中の略語の名称を以下に示す。
（ａ）ＡＡ：アクリル酸 ＳＭＡＳ：メタアリルスルホン酸ナトリウム ＩＡ：イタコン酸
（ｂ）ＤＭ：ジメチルアミノエチルメタクリレート ＤＭＡＥＡ−ＢＱ：ジメチルアミノエチルアクリレートのベンジルクロライド４級化物 ＤＭＬ：ＤＭのベンジルクロライド４級化物 Ｍｎ：マンニッヒ変性物 Ｈｆ：ホフマン変性物
（ｃ）ＡＭ：アクリルアミド
（ｄ）ＤＭＡＡ：ジメチルアクリルアミド ＭＢＡＡ：メチレンビスアクリルアミド ＴＡＩＣ：トリアリルイソシアヌレート ＤＧＡ：ジエチレングリコールジアクリレート ＡＮ：アクリロニトリル
【００２８】
製造例１（ＰＡＭ１の製造法）
撹拌機、温度計、還流冷却管、窒素ガス導入管および２つの滴下ロートを備えた反応装置に、イオン交換水３５０部を入れ、窒素ガスを通じて反応系内の酸素を除去した後、９０℃まで加熱した。一方の滴下ロートにアクリルアミド１７９部、６２．５％硫酸１１部、８０％アクリル酸水溶液１２．８部、メタアリルスルホン酸ナトリウム２．３部、ジメチルアミノエチルメタクリレ−ト２２．４部、ジメチルアクリルアミド２．８部およびイオン交換水３４０部を仕込み、硫酸によりｐＨを３に調整した。また、他方の滴下ロートに過硫酸アンモニウム０．３部とイオン交換水１００部を入れた。次に、両方の滴下ロートより系内にモノマーおよび触媒を約３時間かけて滴下した。滴下終了後過硫酸アンモニウム０．４５部とイオン交換水１０部を入れ１時間保温し、イオン交換水８０部を投入し、固形分２０．２％、粘度（２５℃）が６０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００２９】
製造例２（ＰＡＭ２製造法）
製造例１と同様の反応装置に、イオン交換水３５０部を入れ、窒素ガスを通じて反応系内の酸素を除去した後、９０℃まで加熱した。一方の滴下ロートにアクリルアミド１８１部、６２．５％硫酸１１部、イタコン酸９．１部、メタアリルスルホン酸ナトリウム２．２部、ジメチルアミノエチルメタクリレ−ト２２部、ジメチルアクリルアミド２．８部およびイオン交換水３４０部を仕込み、硫酸によりｐＨを３に調整した。また、他方の滴下ロートに過硫酸アンモニウム０．３部とイオン交換水１００部を入れた。次に、両方の滴下ロートより系内にモノマーおよび触媒を約３時間かけて滴下した。滴下終了後過硫酸アンモニウム０．４５部とイオン交換水１０部を入れ１時間保温し、イオン交換水８０部を投入し、固形分２０．３％、粘度（２５℃）が３０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３０】
製造例３（ＰＡＭ３製造法）
製造例１と同様の反応装置に、アクリルアミド１８３．１部、７５％ジメチルアミノエチルアクリレートの４級化物水溶液５０．２部、イタコン酸９．１部、メタアリルスルホン酸ナトリウム１．１部、トリアリルイソシアヌレート０．０９部及びイオン交換水８１０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．３部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．４５部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水９０部を投入し、固形分２０．１％、粘度（２５℃）が８，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３１】
製造例４（ＰＡＭ４製造法）
製造例１と同様の反応装置に、アクリルアミド１８３．１部、６２．５％硫酸１１部、ジメチルアミノエチルメタクリレ−ト２２．１部、イタコン酸９．２部、ジメチルアクリルアミド２．８部及びイオン交換水７９０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．３部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．４５部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水８０部を投入し、固形分２０．２％、粘度（２５℃）が８，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３２】
製造例５（ＰＡＭ５の製造法）
製造例１と同様の反応装置に、イオン交換水２６０部を入れ、硫酸によりｐＨを３に調整し、窒素ガスを通じて反応系内の酸素を除去した後、９０℃まで加熱した。一方の滴下ロートにアクリルアミド１３５．２部、６２．５％硫酸８．４部、８０％アクリル酸水溶液９．７部、メタアリルスルホン酸ナトリウム０．９部、ジメチルアミノエチルメタクリレ−ト１６．８部、ジメチルアクリルアミド２．１部およびイオン交換水３１０部を仕込み、硫酸によりｐＨを３に調整した。また、他方の滴下ロートに過硫酸アンモニウム０．２３部とイオン交換水１００部を入れた。次に、両方の滴下ロートより系内にモノマーおよび触媒を約３時間かけて滴下した。滴下終了後過硫酸アンモニウム０．３４部とイオン交換水１０部を入れ１時間保温し、イオン交換水２６０部を投入し、固形分１５．２％、粘度（２５℃）が８０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３３】
製造例６（ＰＡＭ６製造法）
製造例１と同様の反応装置に、アクリルアミド１３５．２部、６２．５％硫酸４．０部、ジメチルアミノエチルメタクリレ−ト８．１部、６０％ジメチルアミノエチルメタクリレ−トの４級化物水溶液２４．４部、イタコン酸６．７部、メタアリルスルホン酸ナトリウム０．８部、メチレンビスアクリルアミド０．０６部及びイオン交換水６６０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．２３部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．３４部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水２６０部を投入し、固形分１５．２％、粘度（２５℃）が８，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３４】
製造例７（ＰＡＭ７製造法）
製造例１と同様の反応装置に、アクリルアミド９５．３部、６２．５％硫酸５．７部、ジメチルアミノエチルメタクリレ−ト１１．４部、イタコン酸４．７部、メチレンビスアクリルアミド０．０４部及びイオン交換水５１０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。過硫酸アンモニウム０．１５部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．２３部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水４９０部を投入し、固形分１０．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３５】
製造例８（ＰＡＭ８製造法）
製造例１と同様の反応装置に、アクリルアミド７５．１部、６２．５％硫酸４．５部、ジメチルアミノエチルメタクリレ−ト９．１部、イタコン酸１．９部、８０％アクリル酸水溶液２．６部、トリアリルイソシアヌレート０．０４部及びイオン交換水４７０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．１２部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．１８部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水５３０部を投入し、固形分８．２％、粘度（２５℃）が８，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３６】
製造例９（ＰＡＭ９製造法）
製造例１と同様の反応装置に、アクリルアミド４７．６部、６２．５％硫酸２．９部、ジメチルアミノエチルメタクリレ−ト５．９部、８０％アクリル酸水溶液３．４部、ジエチレングリコールジアクリレート０．０３部及びイオン交換水３７０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．０８部とイオン交換水１０部および亜硫酸水素ナトリウム０．０３部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．１１部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水６６０部を投入し、固形分５．２％、粘度（２５℃）が１５，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３７】
製造例１０（ＰＡＭ１０製造法）
製造例１と同様の反応装置に、アクリルアミド２９．５部、６２．５％硫酸１．８部、ジメチルアミノエチルメタクリレ−ト３．６部、８０％アクリル酸水溶液２．１部、ジエチレングリコールジアクリレート０．０４部及びイオン交換水３００部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を５５℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．０５部とイオン交換水１０部および亜硫酸水素ナトリウム０．０２部とイオン交換水１０部を投入した。９０℃まで昇温した後３０分保温し、過硫酸アンモニウム０．０７部とイオン交換水１０部を投入して１時間保温した。重合終了後、イオン交換水７６０部を投入し、固形分３．２％、粘度（２５℃）が１５，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３８】
製造例１１（ＰＡＭ１１製造法）
製造例１と同様の反応装置に、アクリルアミド１２４部、８０％アクリル酸水溶液２２部、アクリロニトリル２６部及びイオン交換水６５０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を４０℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．２３部とイオン交換水１０部および亜硫酸水素ナトリウム０．０９部とイオン交換水１０部を投入した。９０℃まで昇温した後、２時間保温した。重合終了後、イオン交換水２７０部を投入し、固形分１５．２％、粘度（２５℃）が５，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００３９】
製造例１２（ＰＡＭ１２製造法）
製造例１と同様の反応装置に、アクリルアミド７３部、８０％アクリル酸水溶液１０部及びイオン交換水４４０部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を４０℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．１部とイオン交換水１０部および亜硫酸水素ナトリウム０．１部とイオン交換水１０部を投入した。９０℃まで昇温した後、１時間保温した。イオン交換水３６０部を投入後４０℃まで冷却し、４８％水酸化ナトリウム０．４部、５０％ジメチルアミン４９部、３７％ホルマリン３７部を投入して１時間保温した。重合終了後、イオン交換水１８０部を投入し、固形分１０．２％、粘度（２５℃）が１０，０００ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００４０】
製造例１３（ＰＡＭ１３製造法）
製造例１と同様の反応装置に、アクリルアミド７１．７部及びイオン交換水３９３部を仕込み、窒素ガスを通じて反応系の酸素を除去した。系内を４０℃にし攪拌下に重合開始剤として過硫酸アンモニウム０．１５部とイオン交換水１０部および亜硫酸水素ナトリウム０．１５部とイオン交換水１０部を投入した。９０℃まで昇温した後、１時間保温した。２０℃まで冷却後、１２％次亜塩素酸ナトリウム２５１．７部と４８％水酸化ナトリウム３３．８部を投入し、３０分保温した。重合終了後、イオン交換水３９５部を投入し、ｐＨ４．０、有効成分５．０％、粘度（２５℃）が２０ｍＰａ・ｓの共重合体水溶液を得た。各製造例で用いたモノマー成分と比率を表１に、また得られた共重合体水溶液の性状値を表２に示す。
【００４１】
【表１】
【００４２】
【表２】
ＰＡＭ１３の不揮発物は有効成分を示し、重量平均分子量は変性前のポリマーの測定値。
【００４３】
実施例１
段ボ−ル古紙をナイアガラ式ビーターにて叩解し、カナディアン・スタンダ−ド・フリ−ネス（Ｃ．Ｓ．Ｆ）３５０ｍｌに調整した紙料に硫酸バンドを１．０％添加してｐＨ６．５とした。当該紙料スラリーを抄紙するにおいて、紙料濃度２．０％として製造例１で得られた重合体水溶液を紙力増強剤として対紙料固形量０．４％添加し、その後、紙料濃度１．０％として製造例９で得られた重合体水溶液を紙力増強剤として対紙料０．１％添加し、タッピ・シートマシンにて脱水し、５ｋｇ／ｃｍ２ で２分間プレスして、坪量１５０ｇ／ｍ２ となるよう抄紙した。次いで回転型乾燥機で１０５℃において４分間乾燥し、２３℃、５０％Ｒ．Ｈ．の条件下に２４時間調湿したのち、比破裂強度を測定した。
【００４４】
実施例２〜１１、比較例１〜７
使用紙力増強剤、紙力増強剤添加時の紙料濃度を表３のように変更した他は、実施例１と同様にして比破裂強度を測定した。結果を表３に示す。
【００４５】
【表３】
【００４６】
実施例１２
段ボ−ル古紙をナイアガラ式ビーターにて叩解し、カナディアン・スタンダ−ド・フリ−ネス（Ｃ．Ｓ．Ｆ）３０５ｍｌに調整した紙料に硫酸バンドを１．０％添加してｐＨ６．５とした。当該紙料スラリーを抄紙するにおいて、紙料濃度１．５％として製造例１で得られた重合体水溶液を紙力増強剤として対紙料１．０％添加し、その後、紙料濃度０．８％として製造例３で得られた重合体水溶液を紙力増強剤として対紙料０．２％添加し、タッピ・シートマシンにて脱水し、５ｋｇ／ｃｍ２ で２分間プレスして、坪量１５０ｇ／ｍ２ となるよう抄紙した。次いで回転型乾燥機で１０５℃において４分間乾燥し、２３℃、５０％Ｒ．Ｈ．の条件下に２４時間調湿したのち、比破裂強度を測定した。
【００４７】
実施例１３〜２４、比較例８〜１２
使用紙力増強剤、紙力増強剤添加時の紙料濃度を表４のように変更した他は、実施例１２と同様にして比破裂強度を測定した。結果を表４に示す。
【００４８】
【表４】
【００４９】
表３、４から明らかなように、本発明によれば、紙力剤１液を添加する処方および紙力剤１液を分割添加する処方対比強度が高い板紙を容易に製造することが出来る（実施例１〜２４、比較例１〜４、７、８〜１０）。なお、（１）成分／（２）成分が１未満の場合は、若干紙力効果が低下する傾向にあるため、１以上とすることが好ましい（実施例５と１０、１８と２０）。さらに、（１）成分を紙料濃度１．５％未満として添加し、（２）成分を紙料濃度１．５％以上として添加すると若干紙力効果が低下する傾向にあるため、（１）成分は紙料濃度１．５％以上として、（２）成分は紙料濃度１．５％未満として添加することが好ましい（実施例５と１１、１７と１９）。（１）成分の重量平均分子量が２００万未満の場合、若干紙力効果が低下する傾向にあるため、（１）成分の重量平均分子量は２００万以上とすることが好ましい（実施例４と８、１３と２３）。（２）成分の５重量％水溶液での粘度が２００００ｍＰａ・ｓを越える場合、地合乱れが起こることで若干紙力効果が低下する傾向にあるため、（２）成分の５重量％水溶液での粘度は２００００ｍＰａ・ｓ以下とすることが好ましい（実施例１と９、１２と２４）。異なる（１）成分を紙料濃度１．５％以上として、紙料濃度１．５％未満として添加しても充分な紙力効果が得られない（実施例１〜２４、比較例５、１１）。また、異なる（２）成分を紙料濃度１．５％以上として、紙料濃度１．５％未満として添加しても充分な紙力効果が得られない（実施例１〜２４、比較例６、１２）。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paper manufacturing method. More specifically, the present invention relates to a paper manufacturing method using a polyacrylamide type paper strength enhancer.
[0002]
[Prior art]
Conventionally, when producing paper, a paper strength enhancer is used to impart strength to the paper, and polyacrylamide type paper strength enhancers are widely used from the viewpoint of performance and the like. Usually, when a paper strength enhancer is used, a kind of paper strength enhancer is added to the paper stock at one time or dividedly. However, when only one type of paper strength enhancer is used, it is difficult to balance the texture and drainage, and a large amount of paper strength enhancer must be used.
[0003]
Therefore, in order to solve such a problem, a paper manufacturing method using several kinds of paper strength enhancers has been proposed. For example, a paper manufacturing method using an additive containing an amphoteric polyacrylamide polymer and a cationic group and a polymer different from the amphoteric polyacrylamide polymer has been proposed (see Patent Document 1). In addition, there has been proposed a method for producing paper (see Patent Document 2) having an amphoteric polyacrylamide polymer and a cationic group and using a polymer and an aluminum compound different from the amphoteric polyacrylamide polymer. . However, in any method, it is difficult to balance the texture and the drainage.
[0004]
[Patent Document 1]
JP-A-5-78997
[Patent Document 2]
Japanese Patent Laid-Open No. 5-93393
[Patent Document 3]
JP-A-63-12792
[Patent Document 4]
Japanese Patent Laid-Open No. 58-60094
[0005]
[Problems to be solved by the invention]
The present invention makes it possible to easily balance the texture and drainage, thereby improving the paper strength and consequently reducing the amount of paper strength enhancer used for paper production. The purpose is to provide.
[0006]
[Means for Solving the Problems]
As a result of repeated studies to solve the problem, the present inventors have found that the above-mentioned problems can be solved by using a different specific polyacrylamide-based paper strength enhancer in combination. It was found that a remarkable paper strength enhancing effect can be obtained by adding each of the polyacrylamide type paper strength enhancing agents at specific locations.
[0007]
That is, the present invention relates to (1) an amphoteric polyacrylamide type paper strength enhancer in which the difference in freeness measured by JIS P 8121 before and after the addition of the paper strength enhancer is 50 ml or less, and (2) a paper strength enhancer. The present invention relates to a paper manufacturing method characterized in that paper making is carried out using a polyacrylamide paper strength enhancer having a difference in freeness measured by JIS P 8121 before and after the addition of styrene exceeding 50 ml.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The paper production method of the present invention includes (1) an amphoteric polyacrylamide type paper strength enhancer (hereinafter referred to as (1) where the difference in freeness measured by JIS P8121 before and after the addition of the paper strength enhancer is 50 ml or less. ) Component) and (2) a polyacrylamide paper strength enhancer (hereinafter referred to as component (2)) having a freeness difference measured by JIS P 8121 before and after the addition of the paper strength enhancer exceeds 50 ml. . The difference in the freeness here refers to the amount of drainage using the Canadian Freeness Tester described in JIS P 8121 and the paper strength when 0.5% by weight of a paper strength enhancer is added to the stock. It is the difference in the amount of drainage using a Canadian freeness tester of the stock before adding the enhancer. The addition of the paper strength enhancer is such that the solid content of the paper stock is 1.0% to 3.0%, the temperature of the paper stock is 20 to 40 ° C., and the added paper strength enhancer is sufficiently mixed with the paper stock. By doing. When aluminum sulfate or sizing agent is used in addition to the paper strength enhancer, the freeness before adding the paper strength enhancer is the same as that when chemicals other than the paper strength enhancer are added. Set the water level. In addition, instead of the amphoteric polyacrylamide paper strength enhancer having a freeness difference of 50 ml or less, the amphoteric polyacrylamide paper strength enhancer having a freeness difference of 20 ml or less is used, thereby reducing the paper strength. Since it can improve further, it is more preferable.
[0009]
The component (1) used in the present invention is not particularly limited as long as it is an amphoteric polyacrylamide type paper strength enhancer in which the difference in freeness measured by JISP 8121 before and after the addition of the paper strength enhancer is 50 ml or less. Although a well-known thing can be used, what has a branched structure is especially preferable from the point of the paper strength enhancement effect. The component (1) is usually (a) an anionic vinyl monomer (hereinafter referred to as component (a)), (b) a cationic vinyl monomer (hereinafter referred to as component (b)), (c) (meth) acrylamide. And the like (hereinafter referred to as component (c)). Examples of the component (a) include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, muconic acid and citraconic acid; vinyl sulfonic acid, styrene sulfonic acid, Examples thereof include organic sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid; and sodium salts and potassium salts of these various organic acids. Examples of the component (b) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl. Vinyl monomers having a tertiary amino group such as (meth) acrylamide or salts of inorganic or organic acids such as hydrochloric acid, sulfuric acid and acetic acid, or the tertiary amino group-containing vinyl monomer and methyl chloride, benzyl chloride, Examples thereof include vinyl monomers containing a quaternary ammonium salt obtained by a reaction with a quaternizing agent such as dimethyl sulfate or epichlorohydrin.
[0010]
Further, the monomer (d) copolymerizable with the components (a) to (c) (hereinafter referred to as the component (d)) may be copolymerized with the components (a) to (c). Examples of the component (d) include alkyl acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, allyl alcohol, sodium (meth) allylsulfonate, allylamine, and the like. Allyl monomers containing allyl groups, N-substituted acrylamide monomers such as dimethyl (meth) acrylamide, isopropylacrylamide, (meth) acrylonitrile, etc., as well as bifunctional vinyl monomer systems such as methylenebis (meth) acrylamide, ethylene Bisacrylamide monomers such as bis (meth) acrylamide, diacrylate monomers such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, divinylbenzene, etc. As polyfunctional vinyl monomers having 1,3,5-triacroylhexahydro-S-triazine, triallyl isocyanurate, triallylamine, tetramethylolmethanetetraacrylate, etc. alone or in combination Can be used.
[0011]
Among these components (d), use of an allyl monomer is preferable because radical transfer (chain transfer) is likely to occur and molecular weight can be easily adjusted. N-substituted acrylamide monomers and bisacrylamide are also preferable. It is preferable because a polymer obtained by using a monomer, a diacrylate monomer, divinylbenzene, or a polyfunctional vinyl monomer can be polymerized by crosslinking.
[0012]
In addition, the molecular weight of the acrylamide-type resin obtained can be adjusted by using alcohols, such as isopropyl alcohol and pentanol, as a chain transfer agent.
[0013]
The method for polymerizing the monomer is not particularly limited, and a known method can be adopted. Specifically, it is carried out by adding a known radical polymerization initiator to a mixture of the monomers. Specifically, for example, water is charged in a predetermined reaction vessel as a solvent and heated to a predetermined temperature, and a dropping funnel charged with the above various monomers and water, and a dropping funnel charged with a polymerization initiator and water, Examples of the polymerization method include dropping the components into the reaction vessel under stirring, and charging the above-mentioned various monomers into a predetermined reaction vessel, raising the temperature to a predetermined temperature, adding a polymerization initiator, and performing polymerization.
[0014]
In order to obtain the component (1), the component (a) is about 0.1 to 15 mol%, more preferably 1 to 10 mol%, and the component (b) is about 0.1 to 15 mol%, more preferably 1 to 10 mol%, and component (c) is used in an amount of about 58 to 99.8 mol%, more preferably 80 to 98 mol%. When both component (a) and component (b) are less than 0.1 mol%, the fixing effect tends to be low and the paper strength effect tends to be low, and when it exceeds 15 mol%, the acrylamide content in the polymer decreases, thereby reducing the paper content. The force effect tends to be low, and further, it is not preferable because it becomes expensive. In addition, adjustment of molecular weight becomes easy by using about 0.05-10 mol%, more preferably 0.1 mol%-5.0 mol% of a chain transfer monomer as (d) component. If the component of the chain transfer monomer is less than 0.05 mol%, the chain transfer effect is weak and the generation of branch points is small, so that the branch structure tends to be insufficient. When it exceeds 10 mol%, the chain transfer effect is too strong, so that the polymer chain becomes short and it becomes difficult to produce a high molecular weight polymer. The polymer can have a high molecular weight by using about 0.01 to 2.0 mol%, more preferably 0.01 to 1.0 mol% of the crosslinkable monomer. When the crosslinkable monomer is used in an amount of less than 0.01 mol%, the effect of increasing the molecular weight is reduced.
[0015]
The weight average molecular weight of the component (1) thus obtained is preferably about 2 million or more. If it is less than 2 million, sufficient paper strength effect may not be obtained. The component (1) is usually adjusted to contain 5% by weight or more of non-volatile materials. In addition, it is preferable that the viscosity at the time of adjusting the non-volatile substance of (1) component to 5 weight% shall be about 20000 mPa * s or less. When the viscosity exceeds 20000 mPa · s, the formation tends to be disturbed, and the paper strength improvement effect may be significantly reduced.
[0016]
The component (2) used in the present invention is not particularly limited as long as it is a polyacrylamide type paper strength enhancer in which the difference in freeness measured by JIS P 8121 before and after the addition of the paper strength enhancer exceeds 50 ml. A well-known thing can be used. Specifically, the same type of monomer as the component (1) can be used.
[0017]
In order to obtain the component (2), the component (a) is usually about 0.1 to 20 mol%, more preferably 1 to 15 mol%, and the component (b) is about 0.1 to 20 mol%. More preferably, 1 to 15 mol%, and component (c) is used in an amount of about 60 to 99.8 mol%, more preferably 70 to 98 mol%. When both component (a) and component (b) are less than 0.1 mol%, the fixing effect tends to be low and the paper strength effect tends to be low, and when it exceeds 20 mol%, the acrylamide content in the polymer decreases, thereby reducing the paper content. The force effect tends to be low, and further, it is not preferable because it becomes expensive. In addition, by using about 0.05 to 10 mol%, more preferably 0.1 to 5.0 mol% of the chain transfer monomer as the component (d), the molecular weight can be easily adjusted, and the crosslinkability is improved. By using the monomer in an amount of 0.01 to 2.0 mol%, more preferably 0.01 to 1.0 mol%, the polymer can have a high molecular weight. The component (2) may be polymerized by the same polymerization method as the component (1), and is usually adjusted to contain 5% by weight or more of non-volatiles.
[0018]
The component (2) may be one obtained by subjecting an anionic acrylamide copolymer typified by an acrylamide homopolymer or an acrylamide-acrylic acid copolymer to a Mannich reaction using formalin and an alkylamine such as dimethylamine. It may be obtained by a decomposition reaction. In any case, the cation modification rate is not particularly limited, and is preferably about 60 mol% or less. When the cation modification rate exceeds 60 mol%, the formation is likely to be disturbed, and the paper strength improvement effect is significantly reduced. The component (2) may be used by mixing two or more kinds of paper strength enhancers as long as the freeness exceeds 50 ml.
[0019]
The weight average molecular weight of these components (2) is not particularly limited, but the viscosity when the nonvolatiles are adjusted to 5% by weight is preferably about 20000 mPa · s or less. When the viscosity exceeds 20000 mPa · s, the formation tends to be disturbed, and the paper strength improvement effect may be significantly reduced.
[0020]
The amount when the component (1) and the component (2) are added is not particularly limited, but the component (1) is usually about 0.1 to 1.5% by weight in terms of solid content, based on the paper stock. More preferably, it is 0.3 to 1.0% by weight, and the component (2) is about 0.05% to 0.75% by weight, preferably 0.1% to 0% with respect to the paper, in terms of solid content. .5% by weight. The amount of the component (1) used in terms of solid content is less than 0.1% by weight based on the weight of paper, and the paper strength effect may not be sufficient. Is less fixable and more easily induces stains. The amount of the component (2) used in terms of solid content is less than 0.05% by weight based on the weight of the paper, and the drainage is insufficient when it exceeds 0.75% by weight. It is difficult to form the formation, which is not preferable.
[0021]
By setting the ratio ((1) / (2)) to 1 or more, more preferably 2 or more, based on the amount used of the component (1) and the component (2) (solid content% by weight with respect to the stock) Power effect can be improved. If the weight ratio of the used solid content of the component (1) and the component (2) is less than 1, formation disturbance tends to occur and the paper strength effect tends to be difficult to improve. In addition, additives necessary for papermaking, such as a sizing agent, a pitch control agent, and a filtering agent, can be added within a range that does not affect the effects of the present invention.
[0022]
There are no particular restrictions on the location of addition of component (1) and component (2), but component (1) is at a location where the stock concentration is 1.5 wt% or more, and component (2) is at a stock concentration of 1.5%. It is preferable to add it at a location of less than% by weight because the strength of paper strength is remarkably improved. Examples of the place where the stock concentration is 1.5% by weight or more include a mixing chest, a machine chest, and a seed box. Examples of the place where the stock concentration is less than 1.5% by weight include, for example, a fan. Examples include pumps, white water pits, and screens. Of these, it is preferable to use a machine chest for the component (1) addition and a fan pump for the component (2) because a particularly remarkable paper strength effect can be obtained.
[0023]
【The invention's effect】
According to the present invention, the balance between the texture and the drainage can be easily taken, so that the paper strength improvement effect can be amplified, and as a result, the amount of the paper strength enhancer used during papermaking can be reduced. it can.
[0024]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the examples, parts and% represent parts by weight and% by weight, respectively. The test methods in the examples are shown below.
[0025]
(1) Freeness
The measurement was performed according to JIS P 8121.
[0026]
(2) Burst strength
Measured according to JIS P 8131, specific burst strength (kPa · m 2 / G).
[0027]
Moreover, the name of the abbreviation in an Example is shown below.
(A) AA: Acrylic acid SMAS: Sodium methallyl sulfonate IA: Itaconic acid
(B) DM: dimethylaminoethyl methacrylate DMAEA-BQ: benzyl chloride quaternized product of dimethylaminoethyl acrylate DML: benzyl chloride quaternized product of DM Mn: Mannich modified product Hf: Hoffman modified product
(C) AM: acrylamide
(D) DMAA: Dimethylacrylamide MBAA: Methylenebisacrylamide TAIC: Triallyl isocyanurate DGA: Diethylene glycol diacrylate AN: Acrylonitrile
[0028]
Production Example 1 (PAM1 production method)
In a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and two dropping funnels, 350 parts of ion-exchanged water was added, oxygen in the reaction system was removed through nitrogen gas, and then up to 90 ° C. Heated. In one dropping funnel, 179 parts of acrylamide, 11 parts of 62.5% sulfuric acid, 12.8 parts of 80% aqueous acrylic acid solution, 2.3 parts of sodium methallylsulfonate, 22.4 parts of dimethylaminoethyl methacrylate, dimethyl 2.8 parts of acrylamide and 340 parts of ion-exchanged water were charged, and the pH was adjusted to 3 with sulfuric acid. Moreover, 0.3 part of ammonium persulfate and 100 parts of ion-exchange water were put into the other dropping funnel. Next, a monomer and a catalyst were dropped into the system from both dropping funnels over about 3 hours. After completion of the dropping, 0.45 part of ammonium persulfate and 10 parts of ion exchange water are added and kept warm for 1 hour, 80 parts of ion exchange water are added, and the solid content is 20.2% and the viscosity (25 ° C.) is 6000 mPa · s. A combined aqueous solution was obtained. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0029]
Production Example 2 (PAM2 production method)
In a reactor similar to Production Example 1, 350 parts of ion-exchanged water was added, oxygen in the reaction system was removed through nitrogen gas, and then heated to 90 ° C. In one dropping funnel, 181 parts of acrylamide, 11 parts of 62.5% sulfuric acid, 9.1 parts of itaconic acid, 2.2 parts of sodium methallylsulfonate, 22 parts of dimethylaminoethyl methacrylate, 2.8 parts of dimethylacrylamide And 340 parts of ion-exchanged water was charged, and the pH was adjusted to 3 with sulfuric acid. Moreover, 0.3 part of ammonium persulfate and 100 parts of ion-exchange water were put into the other dropping funnel. Next, a monomer and a catalyst were dropped into the system from both dropping funnels over about 3 hours. After completion of the dropping, 0.45 part of ammonium persulfate and 10 parts of ion exchange water are added and kept warm for 1 hour, 80 parts of ion exchange water are added, and the solid content is 20.3% and the viscosity (25 ° C.) is 3000 mPa · s. A combined aqueous solution was obtained. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0030]
Production Example 3 (PAM3 production method)
In the same reactor as in Production Example 1, 183.1 parts of acrylamide, 50.2 parts of a quaternized 75% dimethylaminoethyl acrylate solution, 9.1 parts of itaconic acid, 1.1 parts of sodium methallylsulfonate, 0.09 part of allyl isocyanurate and 810 parts of ion exchange water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.3 parts of ammonium persulfate and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.45 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 90 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 20.1% and a viscosity (25 ° C.) of 8,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0031]
Production Example 4 (PAM4 production method)
In the same reaction apparatus as in Production Example 1, 183.1 parts of acrylamide, 11 parts of 62.5% sulfuric acid, 22.1 parts of dimethylaminoethyl methacrylate, 9.2 parts of itaconic acid, 2.8 parts of dimethylacrylamide, and 790 parts of ion-exchanged water was charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.3 parts of ammonium persulfate and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.45 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 80 parts of ion-exchanged water was added to obtain a copolymer aqueous solution having a solid content of 20.2% and a viscosity (25 ° C.) of 8,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0032]
Production Example 5 (PAM5 production method)
In a reactor similar to Production Example 1, 260 parts of ion-exchanged water was added, the pH was adjusted to 3 with sulfuric acid, oxygen in the reaction system was removed through nitrogen gas, and then heated to 90 ° C. In one dropping funnel, 135.2 parts of acrylamide, 8.4 parts of 62.5% sulfuric acid, 9.7 parts of 80% aqueous acrylic acid solution, 0.9 parts of sodium methallylsulfonate, dimethylaminoethyl methacrylate, 16. 8 parts, 2.1 parts of dimethylacrylamide and 310 parts of ion-exchanged water were charged, and the pH was adjusted to 3 with sulfuric acid. Moreover, 0.23 part of ammonium persulfate and 100 parts of ion-exchange water were put into the other dropping funnel. Next, a monomer and a catalyst were dropped into the system from both dropping funnels over about 3 hours. After completion of dropping, 0.34 part of ammonium persulfate and 10 parts of ion-exchanged water are added, and the temperature is kept for 1 hour, 260 parts of ion-exchanged water is added, and the solid content is 15.2% and the viscosity (25 ° C.) is 8000 mPa · s. A combined aqueous solution was obtained. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0033]
Production Example 6 (PAM6 production method)
In the same reactor as in Production Example 1, quaternary acrylamide 135.2 parts, 62.5% sulfuric acid 4.0 parts, dimethylaminoethyl methacrylate 8.1 parts, 60% dimethylaminoethyl methacrylate quaternary. 24.4 parts of an aqueous solution of chemicals, 6.7 parts of itaconic acid, 0.8 part of sodium methallylsulfonate, 0.06 part of methylenebisacrylamide and 660 parts of ion-exchanged water were added, and oxygen in the reaction system was removed through nitrogen gas. . The system was brought to 55 ° C., and 0.23 parts of ammonium persulfate and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, 0.34 parts of ammonium persulfate and 10 parts of ion-exchanged water were added, and the temperature was kept for 1 hour. After completion of the polymerization, 260 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 15.2% and a viscosity (25 ° C.) of 8,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0034]
Production Example 7 (PAM7 production method)
In the same reactor as in Production Example 1, 95.3 parts of acrylamide, 5.7 parts of 62.5% sulfuric acid, 11.4 parts of dimethylaminoethyl methacrylate, 4.7 parts of itaconic acid, 0.7% of methylenebisacrylamide. 04 parts and 510 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. 0.15 part of ammonium persulfate and 10 parts of ion exchange water were added. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.23 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 490 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 10.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0035]
Production Example 8 (PAM8 production method)
In the same reactor as in Production Example 1, 75.1 parts of acrylamide, 4.5 parts of 62.5% sulfuric acid, 9.1 parts of dimethylaminoethyl methacrylate, 1.9 parts of itaconic acid, 80% aqueous acrylic acid solution 2.6 parts, 0.04 part of triallyl isocyanurate and 470 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.12 part of ammonium persulfate and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.18 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 530 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 8.2% and a viscosity (25 ° C.) of 8,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0036]
Production Example 9 (PAM9 production method)
In the same reactor as in Production Example 1, acrylamide 47.6 parts, 62.5% sulfuric acid 2.9 parts, dimethylaminoethyl methacrylate 5.9 parts, 80% aqueous acrylic acid solution 3.4 parts, diethylene glycol diethylene glycol 0.03 part of acrylate and 370 parts of ion exchange water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.08 part of ammonium persulfate, 10 parts of ion-exchanged water, 0.03 part of sodium hydrogen sulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.11 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 660 parts of ion exchange water was added to obtain a copolymer aqueous solution having a solid content of 5.2% and a viscosity (25 ° C.) of 15,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0037]
Production Example 10 (PAM10 production method)
In the same reactor as in Production Example 1, acrylamide 29.5 parts, 62.5% sulfuric acid 1.8 parts, dimethylaminoethyl methacrylate 3.6 parts, 80% aqueous acrylic acid solution 2.1 parts, diethylene glycol diethylene glycol 0.04 part of acrylate and 300 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.05 parts of ammonium persulfate, 10 parts of ion-exchanged water, 0.02 part of sodium hydrogen sulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.07 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 760 parts of ion-exchanged water was added to obtain a copolymer aqueous solution having a solid content of 3.2% and a viscosity (25 ° C.) of 15,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0038]
Production Example 11 (PAM11 production method)
In a reactor similar to Production Example 1, 124 parts of acrylamide, 22 parts of 80% aqueous acrylic acid solution, 26 parts of acrylonitrile and 650 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was heated to 40 ° C., and 0.23 parts of ammonium persulfate, 10 parts of ion-exchanged water, 0.09 part of sodium hydrogensulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 2 hours. After completion of the polymerization, 270 parts of ion-exchanged water was added to obtain a copolymer aqueous solution having a solid content of 15.2% and a viscosity (25 ° C.) of 5,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0039]
Production Example 12 (PAM12 production method)
A reaction apparatus similar to Production Example 1 was charged with 73 parts of acrylamide, 10 parts of an 80% aqueous acrylic acid solution, and 440 parts of ion-exchanged water, and oxygen in the reaction system was removed through nitrogen gas. The system was heated to 40 ° C., and 0.1 parts of ammonium persulfate, 10 parts of ion-exchanged water, 0.1 part of sodium bisulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 1 hour. After adding 360 parts of ion exchange water, it was cooled to 40 ° C., 0.4 parts of 48% sodium hydroxide, 49 parts of 50% dimethylamine and 37 parts of 37% formalin were added and kept warm for 1 hour. After completion of the polymerization, 180 parts of ion-exchanged water was added to obtain a copolymer aqueous solution having a solid content of 10.2% and a viscosity (25 ° C.) of 10,000 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0040]
Production Example 13 (PAM13 production method)
In a reactor similar to Production Example 1, 71.7 parts of acrylamide and 393 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 40 ° C., and 0.15 parts of ammonium persulfate, 10 parts of ion-exchanged water, 0.15 part of sodium hydrogensulfite and 10 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 1 hour. After cooling to 20 ° C., 251.7 parts of 12% sodium hypochlorite and 33.8 parts of 48% sodium hydroxide were added and kept warm for 30 minutes. After completion of the polymerization, 395 parts of ion exchange water was added to obtain a copolymer aqueous solution having a pH of 4.0, an active ingredient of 5.0%, and a viscosity (25 ° C.) of 20 mPa · s. Table 1 shows the monomer components and ratios used in each production example, and Table 2 shows the property values of the aqueous copolymer solution obtained.
[0041]
[Table 1]
[0042]
[Table 2]
The non-volatile substance of PAM13 represents an active ingredient, and the weight average molecular weight is a measured value of the polymer before modification.
[0043]
Example 1
Corrugated cardboard paper is beaten with a Niagara beater and adjusted to 350 ml of Canadian Standard Freeness (C.S.F.) 1.0% sulfuric acid band is added to the stock to a pH of 6.5. It was. In making the paper slurry, the aqueous polymer solution obtained in Production Example 1 with a paper concentration of 2.0% was added as a paper strength enhancer to 0.4% of the solid amount of the paper, and then the paper concentration 1.0% of the aqueous polymer solution obtained in Production Example 9 as a paper strength enhancer was added as 1.0%, dehydrated with a tapi sheet machine, and 5 kg / cm. 2 Press for 2 minutes, basis weight 150g / m 2 Paper was made so that Subsequently, it dried for 4 minutes at 105 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. After conditioned for 24 hours under the above conditions, the specific burst strength was measured.
[0044]
Examples 2-11, Comparative Examples 1-7
The specific burst strength was measured in the same manner as in Example 1 except that the paper strength at the time of adding the paper strength enhancer and the strength enhancer was changed as shown in Table 3. The results are shown in Table 3.
[0045]
[Table 3]
[0046]
Example 12
Corrugated cardboard paper is beaten with a Niagara beater and adjusted to 305 ml of Canadian Standard Freeness (C.S.F.) 1.0% of sulfuric acid band is added to the stock to pH 6.5. It was. In making the paper slurry, the aqueous polymer solution obtained in Production Example 1 with a paper stock concentration of 1.5% was added as a paper strength enhancer to 1.0% of the paper stock. 8% of the aqueous polymer solution obtained in Production Example 3 was added as a paper strength enhancer to 0.2% of the paper stock, dehydrated with a tapi sheet machine, and 5 kg / cm. 2 Press for 2 minutes, basis weight 150g / m 2 Paper was made so that Subsequently, it dried for 4 minutes at 105 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. After conditioned for 24 hours under the above conditions, the specific burst strength was measured.
[0047]
Examples 13-24, Comparative Examples 8-12
The specific burst strength was measured in the same manner as in Example 12 except that the paper strength at the time of adding the paper strength enhancer and the strength enhancer was changed as shown in Table 4. The results are shown in Table 4.
[0048]
[Table 4]
[0049]
As is apparent from Tables 3 and 4, according to the present invention, it is possible to easily produce a paperboard having a high prescription strength to which a prescription for adding a paper strength agent 1 solution and a prescription for adding a paper strength agent 1 solution are divided ( Examples 1 to 24, Comparative Examples 1 to 4, 7, 8 to 10). In addition, when the component (1) / (2) is less than 1, the paper strength effect tends to be slightly reduced, so that it is preferably 1 or more (Examples 5 and 10, 18 and 20). Further, when the component (1) is added with a paper stock concentration of less than 1.5% and the component (2) is added with a paper stock concentration of 1.5% or more, the paper strength effect tends to slightly decrease. The component is preferably added at a paper stock concentration of 1.5% or more, and the component (2) is preferably added at a paper stock concentration of less than 1.5% (Examples 5 and 11, 17 and 19). When the weight average molecular weight of the component (1) is less than 2 million, the paper strength effect tends to be slightly reduced. Therefore, the weight average molecular weight of the component (1) is preferably 2 million or more (Examples 4 and 8). 13 and 23). When the viscosity of the (2) component in a 5% by weight aqueous solution exceeds 20000 mPa · s, the paper strength effect tends to be slightly reduced due to formation disturbance, so the component (2) in the 5% by weight aqueous solution The viscosity is preferably 20000 mPa · s or less (Examples 1 and 9, 12 and 24). Even if the different component (1) is added at a stock concentration of 1.5% or more and less than a stock concentration of less than 1.5%, sufficient paper strength effect cannot be obtained (Examples 1 to 24, Comparative Examples 5 and 11) ). Further, even when different component (2) is added at a paper stock concentration of 1.5% or more and less than a paper stock concentration of 1.5%, sufficient paper strength effect cannot be obtained (Examples 1 to 24, Comparative Example 6). 12).
Claims (5)
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| JP4817109B2 (en) * | 2005-11-02 | 2011-11-16 | 荒川化学工業株式会社 | Paper manufacturing method |
| JP2007126770A (en) * | 2005-11-02 | 2007-05-24 | Arakawa Chem Ind Co Ltd | Method for making paper |
| JP4784857B2 (en) * | 2005-11-02 | 2011-10-05 | 荒川化学工業株式会社 | Paper manufacturing method |
| JP5240500B2 (en) * | 2007-03-12 | 2013-07-17 | 荒川化学工業株式会社 | Bulky paper manufacturing method and bulky paper |
| JP5273352B2 (en) * | 2008-05-12 | 2013-08-28 | 荒川化学工業株式会社 | Bulky paper manufacturing method and bulky paper |
| JP5618213B2 (en) * | 2011-05-31 | 2014-11-05 | 星光Pmc株式会社 | Polyacrylamide internal paper strength agent and paper manufacturing method |
| JP6779163B2 (en) * | 2017-03-28 | 2020-11-04 | 大王製紙株式会社 | How to make paper towels |
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| JPS5747998A (en) * | 1980-08-29 | 1982-03-19 | Sumitomo Chemical Co | Dry paper strength increasing method of paper or cardboard |
| JPS5854097A (en) * | 1981-09-22 | 1983-03-30 | 荒川化学工業株式会社 | Making of peper |
| JPH0657685A (en) * | 1991-08-28 | 1994-03-01 | Arakawa Chem Ind Co Ltd | Paper-making process |
| JP3189330B2 (en) * | 1991-09-11 | 2001-07-16 | 日本ピー・エム・シー株式会社 | Paper manufacturing method |
| JP3494414B2 (en) * | 1993-02-12 | 2004-02-09 | 富士写真フイルム株式会社 | Photographic paper support |
| JP3549330B2 (en) * | 1996-05-07 | 2004-08-04 | 三井化学株式会社 | Papermaking additives |
| JP3648735B2 (en) * | 1996-10-18 | 2005-05-18 | 荒川化学工業株式会社 | Paper additive and paper manufacturing method |
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