JP3755444B2 - Waste paper recycling additive and recycled paper manufacturing method - Google Patents

Description

【０００８】
（式中、Ｒ¹は炭素数１０〜２４のアルキル基又はアルケニル基、Ｒ²は水素原子、炭素数１０〜２４のアルキル基又はアルケニル基を示す。）
で表されるアミン化合物（ｉ）に対して尿素を０．１〜１．５倍モルの割合で反応させてなる縮合物と、（ｂ）下記（イ）〜（ニ）の中から選ばれる少なくとも一種とを、重量比９９：１ないし６０：４０の割合で含むことを特徴とする古紙再生用添加剤、（イ）炭素数８〜２２の炭化水素基又はアシル基を1個有し、分子量２００〜１，０００のオキシアルキレン鎖を付加させてなるノニオン性界面活性剤、（ロ）分子量１，２００〜１２，０００のオキシエチレンオキシプロピレン共重合体、（ハ）平均重合度３００〜３，０００のポリビニルアルコール、（ニ）ポリジメチルジアリルアンモニウム塩、エピクロルヒドリン−アルキルアミン付加重合物、アリルアミン重合体の酸塩又は四級アンモニウム塩、及びジシアンジアミド−ホルムアルデヒド縮合物の中から選ばれる一種以上のカチオン性ポリマー、及び
（２）上記古紙再生用添加剤を、（ａ）成分と（ｂ）成分との合計量が古紙パルプに対して０．０３〜８重量％になるように添加することを特徴とする再生紙の製造方法、
を提供するものである。
【０００９】
【発明の実施の形態】
本発明の古紙再生用添加剤においては、（ａ）成分として、原料成分のアミン化合物と尿素との縮合物が用いられる。
前記原料成分のアミン化合物（ｉ）は、一般式（Ｉ）
【００１０】
【化３】

【００１１】
で表される化合物である。この一般式（Ｉ）において、Ｒ¹は炭素数１０〜２４のアルキル基又はアルケニル基であり、Ｒ²は水素原子、炭素数１０〜２４のアルキル基又はアルケニル基である。炭素数１０〜２４のアルキル基又はアルケニル基の具体例としては、デシル基、ウンデシル基、ドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、テトラデセニル基、ペンタデシル基、ヘキサデシル基、イソヘキサデシル基、ヘキサデセニル基、ヘプタデシル基、オクタデシル基、オクタデセニル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基、テトラコシル基などの一種又は二種以上の混合物が挙げられる。好ましくは炭素数１２〜２２のアルキル基又はアルケニル基である。炭素数が１０より小さい場合は、嵩高性向上効果及び吸油性向上効果が弱くなり、炭素数が２４より大きい場合、添加剤の取り扱いが困難になる。
【００１２】
本発明の古紙再生用添加剤における（ａ）成分は、前述の原料成分のアミン化合物（ｉ）と尿素との縮合物である。この縮合物は、該アミン化合物に対し、尿素を０．１〜１．５倍モル、好ましくは０．３〜１．０倍モル用い、これらを不活性ガス雰囲気下に加熱し、生成するアンモニアを反応系外に除去しながら反応させることにより、得ることができる。尿素の量が、アミン化合物に対し、０．１倍モル未満であったり、１．５倍モルを超えると充分な嵩高性及び吸油性が得られない。
【００１３】
本発明の古紙再生用添加剤においては、（ｂ）成分として、下記（イ）〜（ニ）成分の中から選ばれる少なくとも一種が用いられる。
（イ）成分は、炭素数８〜２２の炭化水素基又はアシル基を１個有し、分子量２００〜１，０００のオキシアルキレン鎖を付加させてなるノニオン性界面活性剤である。このノニオン性界面活性剤はアルキル基、アルケニル基又はアシル基の炭素数が８〜２２である脂肪族アルコールあるいはアルキルフェノール、脂肪酸、ソルビタンアルキルエステル、アルキルアミン、アルカノールアミドに分子量２００〜１,０００のオキシアルキレン鎖を付加させたものである。ポリオキシアルキレン基としては、オキシエチレン基単独又はオキシエチレン基とオキシプロピレン基とを含むものを挙げることができる。オキシエチレン基とオキシプロピレン基とを含む場合は、ランダム付加、ブロック付加のいずれであってもよい。このノニオン性界面活性剤の中で、炭化水素基又はアシル基の炭素数８〜１８であるポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルアリルエーテル、ポリオキシアルキレンアルキルエステル、ポリオキシアルキレンソルビタンモノアルキルエステル、ポリオキシアルキレンアルキルアミン、ポリオキシアルキレンアルキルアミドなどが好ましい。
【００１４】
（ロ）成分は、分子量１，２００〜１２，０００のオキシエチレンオキシプロピレン共重合体であって、このものはエチレンオキシドとプロピレンオキシドとを共重合させて得られたものであり、オキシエチレン鎖を１０〜８０重量％の範囲で含むブロック又はランダム共重合体が好ましく、特にオキシエチレン鎖を３５〜８０重量％の範囲で含むブロック共重合体が好適である。
（ハ）成分は、平均重合度３００〜３，０００のポリビニルアルコールであって、このポリビニルアルコールはポリ酢酸ビニルのケン化物であり、好ましくは平均重合度が１，５００〜３，０００、ケン化度が７０〜９９モル％のものである。
【００１５】
（ニ）成分は、ポリジメチルジアリルアンモニウム塩、エピクロルヒドリン−アルキルアミン付加重合物、アリルアミン重合体の酸塩又は四級アンモニウム塩及びジシアンジアミド−ホルムアルデヒド縮合物の中から選ばれる一種以上のカチオン性ポリマー、好ましくは重量平均分子量５，０００〜２００，０００のカチオン性ポリマーである。
本発明の古紙再生用添加剤における前記（ａ）成分と（ｂ）成分の含有割合は、重量比で９９：１ないし６０：４０の範囲で選定される。（ｂ）成分の含有割合が上記範囲より少ないと汚れの付着量が多くなり、また上記範囲より多いと充分な嵩高性及び吸油性が得られない。該（ａ）成分と（ｂ）成分の好ましい含有割合は、重量比で９５：５ないし８０：２０の範囲で選定される。
【００１６】
本発明の古紙再生用添加剤は、そのまま古紙再生用添加剤として使用することができるが、水に分散して分散液とすることでパルプへの添加が容易となる。未反応のアミンを無機酸あるいは有機酸と反応させて塩にすることで、水に分散しやすくなる。無機酸としては、塩酸、硫酸、炭酸、硝酸、リン酸等が挙げられる。有機酸としては、蟻酸、酢酸、プロピオン酸、オクチル酸、酪酸、シユウ酸、マロン酸、イタコン酸、アジピン酸、コハク酸、セバシン酸、クエン酸、ヒドロキシ安息香酸、リンゴ酸、ヒドロキシマロン酸、乳酸、サリチル酸、ヒドロキシ吉草酸、アスパラギン酸、グルタミン酸、タウリン、スルファミン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸等が挙げられる。これらの中では、有機酸が好ましく、蟻酸、酢酸、プロピオン酸が特に好ましい。
【００１７】
また、本発明の古紙再生用添加剤はカチオン化デンプン及びカチオン性分散剤、アニオン性分散剤を用いて水に分散させても良い。製紙工業で高頻度に汎用されるカチオン化デンプンで分散させるのが好ましい。
カチオン化デンプンは、タピオカ、馬鈴薯、トウモロコシ等由来のものがあるが、これらのカチオン化デンプンは、使用の際に、過硫酸アンモニウム、次亜塩素酸、過酸化水素等の酸化剤で処理し、分子量を約３万〜５万にして、低粘度として使用する方が好ましい。
分散剤の使用量は、（ａ）成分の縮合物により異なるが、添加剤分散液中の濃度が０．０５〜２０重量％になるような量が好ましく、０．１〜１０重量％になるような量がより好ましい。
【００１８】
本発明の古紙再生用添加剤は、製紙工程において一般的に使用される添加薬剤、例えばポリアクリルアミド、植物グァム等の紙力増強剤、アルキルケテンダイマー、ロジン等のサイズ剤、ポリエチレンイミン等の濾水性・歩留まり向上剤等と併用することも可能である。
また、本発明の再生紙の製造方法によれば、前述の古紙再生用添加剤を、（ａ）成分と（ｂ）成分との合計量が古紙パルプに対して０．０３〜８重量％、好ましくは０．１〜５重量％になるように添加することにより、抄紙工程での装置の汚れを低減し得る上、嵩高性及び吸油性が良好で、かつ汚れの少ない再生紙を容易に製造することができる。添加時期については特に制限はなく、水とパルプが共存するいずれの工程でも添加することができる。特に、抄紙工程中であって、均一にパルプ原料に添加できる時期が望ましい。また、添加量が、０．０３重量％未満では嵩高性向上効果が小さく、８重量％を超えても、使用量に見合った嵩高性及び吸油性の向上は得られず、再生紙のコストアップになり好ましくない。
【００１９】
【実施例】
次に本発明を実施例によりさらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
合成例１
攪拌機、冷却管、温度計及び窒素導入管を備えた１リットル容量の４つ口フラスコに、アミン価２０８、粘度（７０℃）５ｍＰａ・ｓのオクタデセニルアミン５３９ｇ（２．０モル）及び尿素７２ｇ（１．２モル）を仕込み、窒素雰囲気下、１６０〜１７０℃で攪拌した。アンモニアを系外へ除去しながら、２時間反応を行いアミン価２８．１、尿素縮合率８４．７％、粘度（７０℃）５８ｍＰａ・ｓの添加剤ａ−１を得た。尚、尿素縮合率は下記式で定義されるものである。
尿素縮合率（％）＝｛（反応前全アミン価−反応終了後全アミン価）／反応前全アミン価｝×１００
反応前全アミン価：反応前のアミン化合物、尿素混合物の全アミン価
第１表に示す化合物を用いて、合成例１と同様に添加剤ａ−２及びａ−３を合成した。
【００２０】
参考合成例１
攪拌機、冷却管、温度計及び窒素導入管を備えた１リットル容量の４つ口フラスコに、オレイン酸５６９．０ｇ（２モル）及び第１表のａ−４欄に示す一般式（II）
【００２１】
【化４】

（式中、Ｒ ³ は炭素数１〜４のアルキレン基、Ｒ ⁴ 及びＲ ⁵ は、それぞれ独立に水素原子、炭素数１〜４のヒドロキシアルキル基又は炭素数１〜３のアルキル基、Ｒ ⁶ は水素原子、炭素数１〜４のヒドロキシアルキル基又は炭素数１〜２４のアルキル基若しくはアルケニル基を示し、ｎは０又は１であり、ｎが０の場合、Ｒ ⁴ は水素原子である。）で表される化合物１０３ｇ（１モル）を仕込み、窒素雰囲気下、１８０〜１９０℃で攪拌した。水を系外へ除去しながら、３時間反応を行い全アミン価９１．３、粘度（７０℃）１２８ｍＰａ・ｓの縮合物を得た。これを１００℃まで放冷した後に尿素３６ｇ（０．６モル）を仕込み、窒素雰囲気下、１６０〜１７０℃で攪拌した。アンモニアを系外へ除去しながら、３時間反応して全アミン価１９．８、尿素縮合率７６．９％、粘度（７０℃）２１２０ｍＰａ・ｓの添加剤ａ−４を得た。
第１表に示す化合物を用いて、参考合成例１と同様に添加剤ａ−５〜ａ−１０を合成した。
【００２２】
【表１】

【００２３】
実施例１
（１）カチオン化デンプン水溶液の調製
高粘度用攪拌機、窒素導入管及び還流冷却管を備えた２リットル容量の４つ口フラスコに、カチオン化デンプン（ＲＯＱＵＥＴＴＥ社製 ＨＩ−ＣＡＴ２６０）１４４ｇ、イオン交換水１３３５ｇ及び過流酸アンモニウム４．８ｇを仕込み、９０℃で２時間攪拌し、カチオン化デンプンの低分子量化を行い、１０重量％濃度のカチオン化デンプン水溶液を調製した。なお、ここで得られたカチオン化デンプンの分子量は、４３，０００であった。なお、分子量は粘度法により求めた。
【００２４】
（２）添加剤分散液の調製
１リットル容量のビーカー中で、縮合物ａ−１：２２．５ｇ、第２表に示す化合物ｂ−１：２．５ｇ、上記（１）で得られたカチオン化デンプン水溶液：５０ｇ、水：４２４．２ｇ及び酢酸：０．７９ｇを７５℃で混合し、ホモミキサー（特殊機化工業（株）製）にて、５０００ｒｐｍで５分間処理した後、加圧乳化機（ＡＰＶ社製マントンゴーリン）により、４０ＭＰａ×２パス処理し、添加剤５重量％、カチオン化デンプン１重量％を含む古紙再生用添加剤分散液Ａを調製した。
【００２５】
（３）抄紙
脱墨古紙パルプを離解機（熊谷理研（株）製）で離解し、硫酸アルミニウムを対パルプ３重量％加えてｐＨ４．５の１重量％パルプスラリーを調製した。このパルプスラリーを２００ミリリットル容量のビーカーに１２０ｇとり、これに上記（２）で得られた古紙再生用添加剤分散液Ａを０．１２ｇ（添加剤対パルプ０．５重量％）添加し、径４．５ｃｍのタービン羽根により、２５０ｒｐｍで２分間攪拌した。その後、ＴＡＰＰＩスタンダードシートマシン（安田精機（株）製）により抄紙し、油圧プレス機（安田精機（株）製）により、０．３５ＭＰａで５分間プレス後、ドラム式ドライヤー（安田精機（株）製）により１０５℃、８０秒の乾燥を行い、再生紙を得た。
【００２６】
（４）再生紙の評価
（４−１）嵩高性
坪量と厚さより求めた密度により行った。坪量はＪＩＳ Ｐ ８１２４に従って求め、厚さは得られた再生紙を４枚重ね合わせ、ＪＩＳ式紙圧測定機（シチズン時計（株）製 ＭＥＩ−１０）により異なる１０箇所の厚さを測定し、その平均値より求めた。
嵩高性の向上は、下記に示すブランク（比較例５）に対する密度の比で評価した。密度は小さくなるほど効果が大きい。
ブランクを１００％とした場合の密度 ９５．０％未満：効果良好〇
９５．０％以上：効果低い×
（４−２）吸油性
再生紙を５．５×１００ｍｍの紙片に加工し、温度２３℃，相対湿度５０％で、混合油（軽油：鉱物油重量比＝８０：２０）３０ミリリットルの入った１００ミリリットル容量ビーカーに下端から５ｍｍ浸漬させ、１分後に紙片が吸い上げた量（液面から、浸透した液の上端までの距離（ｍｍ））を測定し、ブランク（比較例５）に対する吸油量の増加率で評価した。吸油量は大きくなるほど吸油性は良好である。
吸油量増加率（％）＝〔（サンプルの吸油量−ブランク吸油量）／ブランク吸油量〕×１００
吸油量増加率１０％以上 ：○ 効果良好
吸油量増加率１０％未満 ：× 効果低い
これらの結果を第４表に示す。
【００２７】
（５）汚れ付着性の評価
粘着テープからクロロホルムにより粘着成分を抽出し、抽出された粘着成分をクロロホルム＋プロピレングリコール＋水（体積比２：２：１）の混合溶媒にて固形分２重量％に調整し、人工汚れとした。
厚さ１ｍｍのポリエチレンシートを２×２cmに切りとり、１０５℃にて１時間乾燥後、デシケーター中で放冷し、秤量した（重量１）。
５重量％硫酸アルミニウム水溶液でｐＨ４．５に調整した１．０重量％パルプスラリー３００ｇを３００ミリリットル容量のビーカー中に入れ、径４．５ｃｍのタービン羽根により３００ｒｐｍで撹拌しながら６０℃に昇温した。昇温後、古紙再生用添加剤分散液Ａを１．２ｇ（添加剤対パルプ２．０重量％）添加し、さらに３０分間撹拌後、人工汚れを５ミリリットル添加し、あらかじめ秤量したポリエチレンシートをパルプスラリー中に３枚入れ、３時間攪拌した。３時間後、ポリエチレンシートを取出し、水ですすいだ後１０５℃にて1時間乾燥後、デシケーターにて放冷し、ポリエチレンシートの重量を測定（重量２）し、下記の式により汚れ付着量を求めた。
汚れ付着量（ｍｇ）＝重量２−重量１
汚れ付着量（ｍｇ）を求め、その値により下記の基準で評価を行った。
汚れ付着量 ５ｍｇ未満：○ 効果良好
５ｍｇ以上：× 効果低い
この結果を第４表に示す。
【００２８】
実施例２、参考例、比較例および参考比較例
（１）カチオン化デンプン水溶液の調製
実施例１（１）と同様にして、１０重量％濃度のカチオン化デンプン水溶液を調製した。
（２）添加剤分散液の調製
第３表に示す種類の縮合物（ａ）（第１表に記載）と化合物（ｂ）（第２表に記載）とを、第３表に示す割合で用い、かつ第３表に示すカチオン化デンプン濃度になるようにカチオン化デンプン水溶液を用いると共に、第３表に示す種類の酸を用いて、実施例１（２）と同様にして、古紙再生用添加剤分散液Ｂ〜Ｏ（実施例２、各参考例，比較例および参考比較例）を調製した。
なお、比較例４は、ソルビタンモノドコシルエステルのみを用い、実施例１（２）と同様にして、古紙再生用添加剤分散液を調製した。
【００２９】
（３）抄紙
第４表に示す種類の古紙再生用分散液（第３表に記載）を、第４表に示す添加量でパルプスラリーに加えた以外は、実施例１（３）と同様にして抄紙し、再生紙を作製した。
なお、比較例５は、古紙再生用添加剤分散液を使用しなかったこと以外は、実施例１（３）と同様にして抄紙し、再生紙を作製した。
（４）再生紙の評価
実施例１（４）と同様にして、再生紙の嵩高性及び吸油性の評価を行った。結果を第４表に示す。
（５）汚れ付着性の評価
実施例１（５）と同様にして、汚れ付着性の評価を行った。結果を第４表に示す。
【００３０】
【表２】

【００３１】
【表３】

【００３２】
【表４】

（注）
１）ブランク（比較例５）を１００％とした場合の％を示す。
【００３３】
参考比較例１は化合物（ｂ）が含まれていないので、汚れの付着量が多い。比較例１は縮合物（ａ）が含まれていないので、嵩高性および吸油性が十分ではない。比較例２は縮合物（ａ）が本発明の範囲外であるので、嵩高性および吸油性が十分ではない。比較例３は化合物（ｂ）が本発明の範囲外であるので、汚れの付着量が多い。比較例４は公知の嵩高性を向上させる添加剤であるが、十分な嵩高性と吸油性が得られず、汚れ付着量も多い。第４表に示したように、本発明の添加剤を用いることで、古紙を原料とする再生紙の嵩高性と吸油性を向上できると同時に汚れ付着量を低減することができる。
【００３４】
【発明の効果】
本発明の古紙再生用添加剤は、古紙を原料とする再生紙の嵩高性と吸油性を向上させることができ、かつ抄紙の際の抄紙装置および紙製品への汚れの付着を低減できる。また、本発明の再生紙の製造方法により、簡便に嵩高く吸油性に優れる再生紙を製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an additive for recycling used paper and a method for producing recycled paper. More specifically, the present invention can improve the bulkiness and oil absorption of recycled paper made from used paper as a raw material, and can reduce waste of equipment and recycled paper in the papermaking process, The present invention relates to a method for producing recycled paper using an additive for recycling used paper.
[0002]
[Prior art]
In recent years, the importance of recycling recycled paper has increased from the viewpoint of effective use of resources and environmental protection. Recycled waste paper is usually recovered and then disaggregated into waste paper pulp slurry. Alkaline agents such as sodium hydroxide, sodium carbonate, sodium silicate, deinking agents, hydrogen peroxide, hypochlorite, etc. A method is employed in which a bleaching agent is added, the ink is desorbed from the used paper pulp, and then the detached ink is separated from the used paper pulp slurry by flotation.
In the recycled paper obtained in this way, the waste paper pulp fiber is shorter than the virgin pulp fiber, so the recycled paper made from waste paper has a problem that the bulkiness is lowered. It was.
As a method for improving the bulkiness of recycled paper, a method of reacting a pulp with a crosslinking agent (Japanese Patent Laid-Open Nos. 4-1859571 and 4-185957) is disclosed. However, these methods have a problem in further reuse because the fibers are shortened during defibration after crosslinking.
[0003]
A method for improving bulkiness without using a crosslinking agent has also been proposed. For example, a method using an additive using an oil or fat or a sugar alcohol-based nonionic surfactant (Japanese Patent Laid-Open No. 11-200283), a method using an additive comprising a polyoxyalkylene adduct of a fatty acid and a fatty acid ester (JP-A-11-200284), quaternary ammonium salt, alkylamine, a method using an additive in which a betaine amphoteric surfactant and a nonionic surfactant are used in combination (JP-A-11-269799) A method of using an additive which is an ester of a polyhydric alcohol and a fatty acid (Japanese Patent Application Laid-Open No. 11-35080) is disclosed. However, the method using these additives cannot provide sufficient bulkiness.
[0004]
Further, as a method that does not use a crosslinking agent or an additive, there is a method of physically fluffing fibers to improve the bulkiness of the pulp. However, this method is also insufficient in bulkiness and requires complicated operations to be repeated.
Further, the waste paper contains more stain-causing substances such as residual ink, adhesive, and resin than virgin pulp. These stain-causing substances agglomerate in the paper making process and adhere to the paper making apparatus and the paper product, thereby causing problems such as deterioration in quality such as dirt on the paper product and operational troubles.
In addition, as an effective method of using recycled paper made from waste paper, oil removal from crepe paper, tissue paper, human body or machine, etc. that is bulky and requires oil absorption from human body, machine oil, light oil, etc. There is paper. As a method of improving the oil absorbency of paper, there is a method (Japanese Patent Laid-Open No. 8-13381) in which a pulp raw material is defibrated by a disaggregator, fibers are twisted, and a water-soluble polymer film is laminated thereon. It is disclosed. However, this method has the disadvantages that the work is complicated and that a large amount of high-molecular-weight chemical is used, and that recycled paper cannot be avoided. Further, as a method for producing a wiping cloth, a method of mechanically laminating long fibers of pulp (Japanese Patent Laid-Open No. 5-214654), and as a method for producing an oil-repellent paper, unevenness is formed by embossing on a flat portion of the paper to absorb oil. Although a method for improving the properties (Japanese Patent Application Laid-Open No. 11-322536) is disclosed, none of these methods has a sufficient liquid absorbency.
[0005]
[Problems to be solved by the invention]
Under such circumstances, the present invention can improve the bulkiness and oil absorption of recycled paper made from used paper as a raw material, and can reduce the contamination of equipment and recycled paper in the papermaking process. It is another object of the present invention to provide a method for producing recycled paper using the additive for recycling recycled paper.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that a condensate of a specific amine compound and urea, and a specific substance containing a specific ratio in a predetermined ratio The waste paper recycling additive can be added to the waste paper pulp at a predetermined ratio to reduce the contamination of the equipment in the paper making process, and the bulkiness and oil absorption can be reduced. The present inventors have found that recycled paper having good properties and little dirt can be obtained. The present invention has been completed based on such findings.
That is, the present invention
(1) (a) General formula (I)
[0007]
[Chemical 2 ]

[0008]
(In the formula, R ¹ represents an alkyl group or alkenyl group having 10 to 24 carbon atoms, and R ² represents a hydrogen atom, an alkyl group or alkenyl group having 10 to 24 carbon atoms.)
A condensate obtained by reacting urea at a ratio of 0.1 to 1.5 moles with respect to the amine compound (i) represented by formula (b), and (b) selected from the following (a) to (d) Containing at least one kind in a ratio of 99: 1 to 60:40 by weight ratio, (i) having one hydrocarbon group or acyl group having 8 to 22 carbon atoms, A nonionic surfactant obtained by adding an oxyalkylene chain having a molecular weight of 200 to 1,000, (b) an oxyethyleneoxypropylene copolymer having a molecular weight of 1,200 to 12,000, and (c) an average degree of polymerization of 300 to 3. , 000 polyvinyl alcohol, (d) polydimethyldiallylammonium salt, epichlorohydrin-alkylamine addition polymer, allylamine polymer acid salt or quaternary ammonium salt, and dicyandiamide-form One or more cationic polymers selected from aldehyde condensates, and (2) the above-mentioned additive for recycling recycled paper, the total amount of component (a) and component (b) is 0.03 to the recycled paper pulp. A method for producing recycled paper, characterized by being added so as to be 8% by weight,
Is to provide.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the additive for recycling used paper of the present invention, a condensate of an amine compound as a raw material component and urea is used as the component (a).
The amine compound (i) as the raw material component has the general formula (I)
[0010]
[Chemical 3 ]

[0011]
It is a compound represented by these. In this general formula (I), R ¹ is an alkyl group or alkenyl group having 10 to 24 carbon atoms, and R ² is a hydrogen atom, an alkyl group or alkenyl group having 10 to 24 carbon atoms. Specific examples of the alkyl group or alkenyl group having 10 to 24 carbon atoms include decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, tetradecenyl group, pentadecyl group, hexadecyl group, isohexadecyl group, hexadecenyl group. 1 type, or 2 or more types of mixtures, such as a group, a heptadecyl group, an octadecyl group, an octadecenyl group, a nonadecyl group, an icosyl group, a heneicosyl group, a docosyl group, a tricosyl group, a tetracosyl group. Preferably, it is a C12-22 alkyl group or alkenyl group. When the carbon number is smaller than 10, the bulkiness improving effect and the oil absorption improving effect are weakened. When the carbon number is larger than 24, handling of the additive becomes difficult.
[0012]
The component (a) in the waste paper recycling additive of the present invention is a condensate of the amine compound (i) as a raw material component and urea. This condensate uses 0.1 to 1.5 moles, preferably 0.3 to 1.0 moles, of urea with respect to the amine compound, and heats them in an inert gas atmosphere to produce ammonia. Can be obtained by reacting while removing from the reaction system. When the amount of urea is less than 0.1 times mol or more than 1.5 times mol with respect to the amine compound, sufficient bulkiness and oil absorption cannot be obtained.
[0013]
In the additive for recycling used paper of the present invention, as the component (b), at least one selected from the following components (a) to (d) is used.
Component (a) is a nonionic surfactant having one hydrocarbon group or acyl group having 8 to 22 carbon atoms and having an oxyalkylene chain having a molecular weight of 200 to 1,000 added thereto. This nonionic surfactant is an aliphatic alcohol or alkylphenol having 8 to 22 carbon atoms in an alkyl group, alkenyl group or acyl group, an alkylphenol, a fatty acid, a sorbitan alkyl ester, an alkylamine or an alkanolamide and having a molecular weight of 200 to 1,000. An alkylene chain is added. Examples of the polyoxyalkylene group include those containing an oxyethylene group alone or an oxyethylene group and an oxypropylene group. When an oxyethylene group and an oxypropylene group are included, either random addition or block addition may be used. Among these nonionic surfactants, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan monoalkyl ester having 8 to 18 carbon atoms of hydrocarbon group or acyl group , Polyoxyalkylene alkylamine, polyoxyalkylene alkylamide and the like are preferable.
[0014]
The component (b) is an oxyethylene oxypropylene copolymer having a molecular weight of 1,200 to 12,000, which is obtained by copolymerizing ethylene oxide and propylene oxide. A block or random copolymer containing in the range of 10 to 80% by weight is preferred, and a block copolymer containing oxyethylene chains in the range of 35 to 80% by weight is particularly preferred.
The component (c) is polyvinyl alcohol having an average degree of polymerization of 300 to 3,000, and this polyvinyl alcohol is a saponified product of polyvinyl acetate, preferably having an average degree of polymerization of 1,500 to 3,000. The degree is 70 to 99 mol%.
[0015]
The component (d) is at least one cationic polymer selected from polydimethyldiallylammonium salt, epichlorohydrin-alkylamine addition polymer, allylamine polymer acid salt or quaternary ammonium salt, and dicyandiamide-formaldehyde condensate, Is a cationic polymer having a weight average molecular weight of 5,000 to 200,000.
The content ratio of the component (a) and the component (b) in the used paper recycling additive of the present invention is selected in a range of 99: 1 to 60:40 by weight. When the content ratio of the component (b) is less than the above range, the amount of dirt attached increases, and when it exceeds the above range, sufficient bulkiness and oil absorption cannot be obtained. A preferred content ratio of the component (a) and the component (b) is selected in the range of 95: 5 to 80:20 by weight.
[0016]
The additive for recycling used paper of the present invention can be used as it is as an additive for recycling used paper, but it can be easily added to pulp by dispersing in water to obtain a dispersion. By reacting an unreacted amine with an inorganic acid or an organic acid to form a salt, it becomes easy to disperse in water. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, phosphoric acid and the like. Organic acids include formic acid, acetic acid, propionic acid, octylic acid, butyric acid, oxalic acid, malonic acid, itaconic acid, adipic acid, succinic acid, sebacic acid, citric acid, hydroxybenzoic acid, malic acid, hydroxymalonic acid, lactic acid , Salicylic acid, hydroxyvaleric acid, aspartic acid, glutamic acid, taurine, sulfamic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like. Among these, organic acids are preferable, and formic acid, acetic acid, and propionic acid are particularly preferable.
[0017]
The additive for recycling used paper of the present invention may be dispersed in water using a cationized starch, a cationic dispersant, or an anionic dispersant. It is preferable to disperse with a cationized starch that is frequently used in the paper industry.
Although cationized starch is derived from tapioca, potato, corn, etc., these cationized starches are treated with an oxidizing agent such as ammonium persulfate, hypochlorous acid, hydrogen peroxide, etc. when used. Is preferably about 30,000 to 50,000 and used as a low viscosity.
The amount of the dispersant used varies depending on the condensate of component (a), but is preferably such that the concentration in the additive dispersion is 0.05 to 20% by weight, and 0.1 to 10% by weight. Such an amount is more preferred.
[0018]
The additive for recycling used paper of the present invention is an additive generally used in the papermaking process, for example, a paper strength enhancer such as polyacrylamide and plant guam, a sizing agent such as alkyl ketene dimer and rosin, and a filter such as polyethyleneimine. It can also be used in combination with an aqueous / yield improving agent or the like.
Moreover, according to the method for producing recycled paper of the present invention, the above-mentioned additive for recycling recycled paper has a total amount of the component (a) and the component (b) of 0.03 to 8% by weight based on the recycled paper pulp, By adding preferably 0.1 to 5% by weight, it is possible to reduce the contamination of the apparatus in the paper making process, and easily produce recycled paper with good bulkiness and oil absorption and less contamination. can do. There is no restriction | limiting in particular about an addition time, It can add in any process in which water and a pulp coexist. In particular, it is desirable that it is during the paper making process and can be uniformly added to the pulp raw material. Also, if the addition amount is less than 0.03% by weight, the effect of improving the bulkiness is small, and if it exceeds 8% by weight, the improvement in bulkiness and oil absorption corresponding to the amount used cannot be obtained, and the cost of recycled paper is increased. It is not preferable.
[0019]
【Example】
EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.
Synthesis example 1
In a 1-liter four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, 539 g (2.0 mol) of octadecenylamine having an amine number of 208, a viscosity (70 ° C.) of 5 mPa · s, and urea 72 g (1.2 mol) was charged and stirred at 160 to 170 ° C. in a nitrogen atmosphere. While removing ammonia out of the system, the reaction was carried out for 2 hours to obtain an additive a-1 having an amine value of 28.1, a urea condensation rate of 84.7%, and a viscosity (70 ° C.) of 58 mPa · s. The urea condensation rate is defined by the following formula.
Urea condensation rate (%) = {(total amine value before reaction−total amine value after reaction) / total amine value before reaction} × 100
Total amine value before reaction: Total amine value of amine compound before reaction and urea mixture Additives a-2 and a-3 were synthesized in the same manner as in Synthesis Example 1 using the compounds shown in Table 1.
[0020]
Reference synthesis example 1
In a 4-liter flask having a capacity of 1 liter equipped with a stirrer, a condenser tube, a thermometer and a nitrogen inlet tube, 569.0 g (2 moles) of oleic acid and the general formula (II) shown in column a-4 of Table 1
[0021]
[Formula 4]

(Wherein R ³ is an alkylene group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are each independently a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 3 carbon atoms, R ⁶ Represents a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms, or an alkyl group or alkenyl group having 1 to 24 carbon atoms, n is 0 or 1, and when n is 0, R ⁴ is a hydrogen atom. The compound 103g (1 mol) represented by this was prepared, and it stirred at 180-190 degreeC under nitrogen atmosphere. While removing water out of the system, the reaction was performed for 3 hours to obtain a condensate having a total amine number of 91.3 and a viscosity (70 ° C.) of 128 mPa · s. After cooling this to 100 ° C., 36 g (0.6 mol) of urea was charged and stirred at 160 to 170 ° C. in a nitrogen atmosphere. While removing ammonia out of the system, the reaction was performed for 3 hours to obtain an additive a-4 having a total amine number of 19.8, a urea condensation rate of 76.9%, and a viscosity (70 ° C.) of 2120 mPa · s.
Additives a-5 to a-10 were synthesized in the same manner as in Reference Synthesis Example 1 using the compounds shown in Table 1.
[0022]
[Table 1]

[0023]
Example 1
(1) Preparation of cationized starch aqueous solution In a 2-liter four-necked flask equipped with a stirrer for high viscosity, a nitrogen inlet tube and a reflux condenser, 144 g of cationized starch (HI-CAT260 manufactured by ROQUETETE), ion-exchanged water 1335 g and 4.8 g of ammonium persulfate were charged and stirred at 90 ° C. for 2 hours to lower the molecular weight of the cationized starch to prepare a 10% by weight aqueous cationized starch solution. The molecular weight of the cationized starch obtained here was 43,000. The molecular weight was determined by the viscosity method.
[0024]
(2) Preparation of additive dispersion In a 1-liter beaker, condensate a-1: 22.5 g, compound b-1 shown in Table 2: 2.5 g, cation obtained in (1) above Aqueous starch solution: 50 g, water: 424.2 g, and acetic acid: 0.79 g were mixed at 75 ° C., treated with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 5000 rpm for 5 minutes, and then pressure emulsified A waste paper recycling additive dispersion A containing 5% by weight of additive and 1% by weight of cationized starch was prepared using a machine (Manton Gorin manufactured by APV).
[0025]
(3) Papermaking The deinked waste paper pulp was disaggregated with a disaggregator (manufactured by Kumagai Riken Co., Ltd.), and 3 wt% of aluminum sulfate was added to the pulp to prepare a 1 wt% pulp slurry having a pH of 4.5. 120 g of this pulp slurry is taken in a 200 ml capacity beaker, and 0.12 g (additive to 0.5% by weight of pulp) of the used paper recycling additive dispersion A obtained in (2) above is added to the pulp slurry. The mixture was stirred for 2 minutes at 250 rpm with a 4.5 cm turbine blade. After that, paper is made with a TAPPI standard sheet machine (manufactured by Yasuda Seiki Co., Ltd.), pressed by a hydraulic press machine (manufactured by Yasuda Seiki Co., Ltd.) at 0.35 MPa for 5 minutes, and then a drum dryer (manufactured by Yasuda Seiki Co., Ltd.). ) And dried at 105 ° C. for 80 seconds to obtain recycled paper.
[0026]
(4) Evaluation of recycled paper (4-1) Bulkiness It was carried out according to the density determined from the basis weight and thickness. The basis weight is determined according to JIS P 8124, and the thickness is measured by stacking four sheets of recycled paper, and measuring the thickness of 10 different locations with a JIS paper pressure measuring machine (MEI-10 manufactured by Citizen Watch Co., Ltd.). The average value was obtained.
The improvement in bulkiness was evaluated by the ratio of density to the blank (Comparative Example 5 ) shown below. The smaller the density, the greater the effect.
Density when blank is 100% Less than 95.0%: Good effect
95.0% or more: low effect ×
(4-2) Oil absorbency Recycled paper was processed into a 5.5 × 100 mm piece of paper and contained 30 ml of mixed oil (light oil: mineral oil weight ratio = 80: 20) at a temperature of 23 ° C. and a relative humidity of 50%. Immerse 5mm from the lower end in a 100ml capacity beaker, measure the amount of paper sucked up after 1 minute (distance from the liquid surface to the upper end of the infiltrated liquid (mm)), and the oil absorption amount for the blank (Comparative Example 5 ) The rate of increase was evaluated. The greater the oil absorption, the better the oil absorption.
Oil absorption increase rate (%) = [(sample oil absorption−blank oil absorption) / blank oil absorption] × 100
Oil absorption increase rate of 10% or more: Good effect Oil absorption increase rate of less than 10%: × Low effect These results are shown in Table 4.
[0027]
(5) Evaluation of dirt adhesion The adhesive component is extracted from the adhesive tape with chloroform, and the extracted adhesive component is 2% by weight in a mixed solvent of chloroform + propylene glycol + water (volume ratio 2: 2: 1). Adjusted to artificial dirt.
A 1 mm thick polyethylene sheet was cut into 2 × 2 cm, dried at 105 ° C. for 1 hour, allowed to cool in a desiccator, and weighed (weight 1).
300 g of a 1.0 wt% pulp slurry adjusted to pH 4.5 with a 5 wt% aqueous aluminum sulfate solution was placed in a 300 ml beaker and heated to 60 ° C. while stirring at 300 rpm with a turbine blade having a diameter of 4.5 cm. . After raising the temperature, 1.2 g of additive dispersion A for recycling used paper (2.0% by weight of additive to pulp) was added, and after stirring for another 30 minutes, 5 ml of artificial soil was added, and a polyethylene sheet weighed in advance was added. Three pieces were put into the pulp slurry and stirred for 3 hours. After 3 hours, take out the polyethylene sheet, rinse with water, dry at 105 ° C for 1 hour, allow to cool in a desiccator, measure the weight of the polyethylene sheet (weight 2), Asked.
Dirt adhesion amount (mg) = weight 2−weight 1
The amount of dirt adhered (mg) was determined, and the evaluation was performed based on the value according to the following criteria.
Dirt adhesion less than 5 mg: ○ Good effect
Table 5 shows the results.
[0028]
Example 2 , Reference Example , Comparative Example and Reference Comparative Example (1) Preparation of Cationized Starch Aqueous Solution A 10% by weight cationized starch aqueous solution was prepared in the same manner as in Example 1 (1).
(2) Preparation of additive dispersions Condensates of the type shown in Table 3 (a) (described in Table 1) and compound (b) (described in Table 2) at the ratios shown in Table 3. In addition to using the cationized starch aqueous solution so as to have the cationized starch concentration shown in Table 3, and using the kind of acid shown in Table 3, in the same manner as in Example 1 (2), for recycling used paper Additive dispersions B to O (Example 2 , reference examples , comparative examples, and reference comparative examples ) were prepared.
In Comparative Example 4 , an additive dispersion for recycling used paper was prepared in the same manner as in Example 1 (2) using only sorbitan monodocosyl ester.
[0029]
(3) Papermaking The same procedure as in Example 1 (3) except that the waste paper recycling dispersion of the type shown in Table 4 (described in Table 3) was added to the pulp slurry in the addition amount shown in Table 4. Paper was made to make recycled paper.
In Comparative Example 5 , paper was made in the same manner as in Example 1 (3) except that the used paper recycling additive dispersion was not used to produce recycled paper.
(4) Evaluation of recycled paper The bulkiness and oil absorption of the recycled paper were evaluated in the same manner as in Example 1 (4). The results are shown in Table 4.
(5) Evaluation of dirt adhesion The dirt adhesion was evaluated in the same manner as in Example 1 (5). The results are shown in Table 4.
[0030]
[Table 2]

[0031]
[Table 3]

[0032]
[Table 4]

(note)
1) Shows% when blank (Comparative Example 5 ) is taken as 100%.
[0033]
Since Reference Comparative Example 1 does not contain the compound (b), the amount of dirt attached is large. Since Comparative Example 1 does not contain the condensate (a), the bulkiness and oil absorption are not sufficient. In Comparative Example 2, the condensate (a) is outside the scope of the present invention, so that the bulkiness and oil absorption are not sufficient. In Comparative Example 3, since the compound (b) is outside the scope of the present invention, the amount of dirt attached is large. Comparative Example 4 is a known additive for improving bulkiness, but sufficient bulkiness and oil absorption cannot be obtained, and the amount of dirt adhered is large. As shown in Table 4, by using the additive of the present invention, it is possible to improve the bulkiness and oil absorption of recycled paper made from used paper, and to reduce the amount of dirt attached.
[0034]
【The invention's effect】
The additive for recycling used paper of the present invention can improve the bulkiness and oil absorption of recycled paper made from used paper, and can reduce the adhesion of dirt to the papermaking apparatus and paper products during papermaking. Further, the recycled paper manufacturing method of the present invention makes it possible to easily manufacture recycled paper that is bulky and excellent in oil absorption.

Claims (2)

(A) General formula (I)

(In the formula, R ¹ represents an alkyl group or alkenyl group having 10 to 24 carbon atoms, and R ² represents a hydrogen atom, an alkyl group or alkenyl group having 10 to 24 carbon atoms.)
A condensate obtained by reacting urea at a ratio of 0.1 to 1.5 moles with respect to the amine compound (i) represented by the formula (b): An additive for recycling used paper, comprising at least one kind in a weight ratio of 99: 1 to 60:40.
(A) Nonionic surfactant having one hydrocarbon group or acyl group having 8 to 22 carbon atoms and having an oxyalkylene chain having a molecular weight of 200 to 1,000 added (b) Molecular weight 1,200 to 12 1,000 oxyethyleneoxypropylene copolymer (c) Polyvinyl alcohol (d) polydimethyldiallylammonium salt having an average degree of polymerization of 300 to 3,000, epichlorohydrin-alkylamine addition polymer, acid salt or quaternary of allylamine polymer One or more cationic polymers selected from ammonium salts and dicyandiamide-formaldehyde condensates   The recycled paper additive according to claim 1 is added so that the total amount of the component (a) and the component (b) is 0.03 to 8% by weight based on the waste paper pulp. Paper manufacturing method.