JP3578932B2 - Self-fixing starch, its production method, its composition and papermaking method - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、紙の抄造時に紙力増強剤として用いられる澱粉に関し、さらに詳しくは、アニオン澱粉の水性スラリーに高分子量カチオンポリマーを添加して、アニオン澱粉の粒子表面に該カチオンポリマーを吸着させて得られる自己定着性澱粉およびその製造方法に関する。
本発明の自己定着性澱粉は、製紙工程において、水性スラリーの状態で紙の抄造時に添加することにより、製紙排水の負荷を上げることなく、澱粉の紙への添加量を増やすことができ、最終的に高い強度の紙を得ることができる。
【０００２】
【従来の技術】
紙力増強剤としての澱粉の使用方法としては、従来三つの方法が知られている。すなわち、
▲１▼ 表面サイズ法
抄造された紙の表面に澱粉糊液を塗布する方法である。この方法では、塗布された澱粉の歩留がほぼ１００％と非常に高い反面、澱粉を糊化する必要があること、塗布量を増やすために澱粉の粘度を低下させると、圧縮強度を除き、紙力が得られ難くなること、サイズプレスなどの塗布装置が必要なことなどの難点を有する。
【０００３】
▲２▼ スプレー法
抄造された湿紙の表面および／または多層抄きにおける抄き合わせ層間に澱粉の水性スラリーをスプレーし、乾燥工程の熱を利用して澱粉を糊化させて紙の強度を高める技術である。この方法では、澱粉を比較的多く紙に付与することができ、結果として高い強度の紙を得ることができるが、スプレーを間断なく行うためにスプレーノズルやスラリーストレーナーの保守管理を厳密に行う必要があること、スプレー装置の設置が必要なこと、スプレーされた澱粉スラリーの霧滴が抄紙機を汚しやすいことなどの問題点がある。
【０００４】
▲３▼ 内添法
紙の抄造時に澱粉を紙料に添加する方法である。塗布装置やスプレー装置が不必要なため、比較的簡便に澱粉を使用できる。しかしながら、パルプを主体とする紙料は通常２重量％以下と低い濃度を有するため、紙料をワイヤーで濾過する際、イオン性のない澱粉やアニオン澱粉ではワイヤーを通過して白水に逃げてしまい、歩留が著しく悪い。そこで、近年パルプの表面（通常、負の荷電をもつ）に定着しやすいカチオン澱粉を糊液の形で添加する方法が普及してきた。この方法は、澱粉添加率が対パルプ１．５重量％以下では高い効果が得られるが、それ以上添加した場合は、カチオン澱粉の歩留が急速に低下するとともに、濾水性が悪化し、抄紙速度の著しい低下を招く。さらに、歩留の低下は、排水処理の負荷を増大させる。結局、カチオン澱粉糊液の内添法では、十分に高い強度の紙を得難いこととなる。
【０００５】
澱粉を高い添加率で紙料に内添する技術として、いくつかの改良方法が考案されている。まず、架橋澱粉の水性スラリーを加熱して澱粉粒子を膨潤状態とした後、紙料に添加する方法がある（特開昭５５−７６２００号）。この方法では、澱粉の歩留が高く、高い強度の紙が得られるが、膨潤状態の澱粉粒子が抄造時に繊維間の間隙を埋めるため、濾水性が著しく悪くなること、澱粉が多量の水を抱き込むため、脱水や乾燥が困難となることなどの不都合が生じ、生産性が要求される一般抄紙機には適さない。
【０００６】
紙の抄造時、微細繊維、填料の歩留向上や濾水性の向上を目的として、いわゆる歩留向上剤が使用されることがある。また、最近では高分子量の歩留向上剤とコロイダルシリカやベントナイトなどのアニオン性無機コロイドを併用する歩留向上システムが開発され、実用化されている。澱粉の水性スラリーをこの歩留向上剤の添加ラインまたはアニオン性無機コロイドの添加ラインに連続的に添加して澱粉の歩留を向上させる技術が開示されている（ＷＯ ９５／３３０９６）。しかしながら、この方法では、単に歩留向上剤の高分子マトリックス中に澱粉の比較的大きな粒子を捕捉する作用が働くだけであり、澱粉の歩留向上に対しては、十分な効果があるとは言い難い。
【０００７】
さらに、澱粉をカチオンポリマーの存在下に、乾式で高温に加熱処理して得たカチオン澱粉をスラリー状態で内添する技術が発表されている（特開平９−２９１１０３号）。しかしながら、この方法も、高価なカチオンポリマーを比較的多量に使用すること、おそらく加熱処理によりカチオンポリマーの一部または全部が熱分解されるため、または高温での加熱処理によりカチオンポリマーが無秩序に配向するために、十分な澱粉歩留効果が得られず、実用性に乏しい。
【０００８】
澱粉を紙力増強剤として用いるうえでの上記の難点を解消するため、特に強度が要求される中芯原紙などの板紙においては、ポリアクリルアミド（ＰＡＭ）系の紙力増強剤が使用されることがある。多量のＰＡＭの内添は、カチオン澱粉糊液のようには濾水性をそれほど悪化させず、紙の強度面でも有効である。しかしながら、その反面、紙の柔軟性が乏しくなるため、例えば中芯原紙では段割れが生じやすくなること、離解性が悪くなるため、紙の損紙回収やリサイクル面において支障が出ること、吸水性が低下するため、段ボール原紙では貼合性が悪くなること、澱粉に比べ製造コストが高いなどの問題がある。
【０００９】
【発明が解決しようとする課題】
上記のような状況に鑑み、本発明の目的は、多量に添加しても歩留が高く、従って十分な紙力増強効果が得られ、かつ操業性に支障を来たさない、安価な紙力増強剤用澱粉を提供するにある。
【００１０】
【課題を解決するための手段】
澱粉を紙力増強剤として用いるうえで上記従来技術の難点を解消すべく、鋭意研究した結果、本発明者らは、アニオン澱粉の水性スラリーに高分子量カチオンポリマーを添加して、アニオン澱粉の粒子表面に該カチオンポリマーを吸着させて得られる自己定着性澱粉を水性スラリーの状態で紙の抄造時に紙料に添加することにより、製紙排水の負荷を上げることなく、澱粉の紙への添加量を増やすことができ、最終的に高い強度の紙を得ることを見出した。
【００１１】
かくして、本発明によれば、アニオン澱粉の粒子の表面に、濃度０．２重量％の水溶液の２０ｏＣ，６０ｒｐｍにおけるＢ型粘度が３０ｍＰａｓ・Ｓ以上である高分子量カチオンポリマーが、澱粉固形分当り固形分で４００〜５，０００ｐｐｍ吸着されてなることを特徴とする自己定着性澱粉が提供される。
【００１２】
さらに、本発明によれば、アニオン澱粉の水性スラリーに、濃度０．２重量％の水溶液の２０ｏＣ，６０ｒｐｍにおけるＢ型粘度が３０ｍＰａｓ・Ｓ以上である高分子量カチオンポリマーを澱粉固形分当り固形分で５００〜５，０００ｐｐｍ添加して、アニオン澱粉の粒子の表面に該カチオンポリマーを吸着させることを特徴とする上記の自己定着性澱粉の製造方法が提供される。
【００１３】
さらに、本発明によれば、紙の抄造時に、上記の自己定着性澱粉を水性スラリーの状態で紙料中に添加することを特徴とする製紙方法が提供される。
さらに、本発明によれば、アニオン澱粉の粉体に、濃度０．２重量％の水溶液の２０ｏＣ，６０ｒｐｍにおけるＢ型粘度が３０ｍＰａｓ・Ｓ以上である固形状高分子量カチオンポリマーをアニオン澱粉粉体当り固形分で５００〜５，０００ｐｐｍ配合してなることを特徴とする自己定着性澱粉組成物が提供される。
【００１４】
【作用】
本発明による自己定着性澱粉が、歩留向上剤や凝集剤などの助けを必要とせず、「自己定着性」を示す機構は、以下のとおりと考えられる。
パルプ繊維の表面は通常マイナスに帯電しており、イオン性のない澱粉やアニオン澱粉では、非常に歩留が悪い。そこで、カチオン澱粉を糊液の状態で添加し、パルプ繊維上のアニオンとカチオン澱粉のカチオンとのイオン結合により澱粉の歩留を高める方法が採用されている。しかしながら、この方法が有効なのは、澱粉添加率が低く、せいぜい１．５重量％までであり、それ以上添加した場合は、カチオンが過剰となり、もはやイオン結合による定着が期待できなくなる。一方、カチオン澱粉を未糊化の水性スラリーとして添加した場合は、澱粉粒子の表面に存在するカチオン（全体のカチオンの一部でしかない）のみがパルプ繊維上のアニオンと点接着的にイオン結合することとなるため、抄造時の水の流れに伴う水力学的作用を受けて、カチオン澱粉粒子は脱落して水と一緒にワイヤーを容易に通過してしまう。従って、この場合も、澱粉の歩留は、イオン性のない澱粉よりは多少よいものの依然低いレベルにある。
【００１５】
上記とは対照的に、本発明による自己定着性澱粉では、アニオン澱粉の粒子表面に吸着されたカチオンポリマーが、カチオン相互の反撥作用により澱粉粒子の表面から放射状に分布し、より多くのパルプ繊維上のアニオンと結合することとなる。すなわち、全体として面接着的に強固な結合を形成し、パルプ繊維から澱粉粒子を引き離そうとする水力学的作用に対抗し得ることとなり、結果的に高い澱粉歩留が得られる。このように、本発明の自己定着性澱粉では、アニオン澱粉の粒子表面に存在するアニオンにカチオンポリマー上のカチオンの一部が結合し、残余の大半のカチオンがパルプ繊維上のアニオンとの結合に関与することによって高い澱粉歩留が得られる。
【００１６】
【発明の実施の形態】
本発明に使用されるアニオン澱粉は、その粒子表面にアニオンを有する澱粉であって、アニオン化度は０．０１ｍｅｑ／ｇ以上であることが好ましい。アニオン化度が低すぎるとカチオンポリマーの吸着が不十分となり、本発明の効果が満足には得られない。
【００１７】
本発明に使用されるアニオン澱粉の具体例としては、従来より知られている次亜塩素酸ナトリウムなどの次亜塩素酸塩で処理された酸化澱粉、無水こはく酸や無水マレイン酸などの二塩基酸無水物を反応させた澱粉二塩基酸ハーフエステル、および燐酸／尿素（併用）、燐酸ナトリウム、トリポリ燐酸ナトリウムなどの燐酸および／または燐酸塩で処理した澱粉燐酸エステルが挙げられる。 これらは、経済性よりみて好適に使用できるが、無論これらに限定されるものではない。
【００１８】
本発明で使用されるアニオン澱粉の調製に用いられる原料澱粉の具体例としては、コーンスターチ、タピオカ澱粉、馬鈴薯澱粉、甘藷澱粉、小麦澱粉、ワキシーコーンスターチ、ハイアミロースコーンスターチなどが挙げられ、市販のいずれの澱粉も使用できる。
【００１９】
本発明に使用されるカチオンポリマーの具体例としては、カチオン変性ポリアクリルアミド（ＰＡＭ）、ポリエチレンイミン、カチオン変性ポリ（メタ）アクリレート、ポリジアリルジメチルアンモニウムクロライド、キトサンなどが挙げられる。これらの中でも、経済性と紙力向上効果からみて、カチオン変性ポリアクリルアミド（ＰＡＭ）系のもの、例えば、ジエチルアミノエチルメタクリレート、ジアリルジメチルアンモニウムクロライド、ジアリルジエチルアンモニウムクロライド、メタクリロイルオキシエチルトリメチルアンモニウムメチルサルフェート、メタクリロイルオキシエチルトリメチルアンモニウムクロライド、メタクリルアミドプロピルトリメチルアンモニウムクロライドなどのカチオン性モノマーを共重合体せしめた共重合ＰＡＭ、マンニッヒ変性ＰＡＭ、ホフマン分解ＰＡＭなどが好適である。また、カチオンのほか、ノニオン、アニオン（ネットカチオン量が０．２ｍｅｑ／ｇを下回らない範囲で）の置換基を有していてもよい。
【００２０】
カチオンポリマーの分子量は、高いほどよい。しかしながら、非常に高い分子量をもつポリマーの分子量を正確に測ることは困難であり、また、測定方法による誤差も大きいため、本特許では、水溶液粘度を指標として規定した。すなわち、本特許では、カチオンポリマーを蒸留水で希釈または溶解して０．２％濃度の水溶液としたものの２０℃、６０ｒｐｍにおけるＢ型粘度が３０ｍＰａｓ・Ｓ以上であることが必要である。粘度がこれ未満では、澱粉の歩留向上、ひいては紙力増強効果が満足には得られない。
【００２１】
本発明の自己定着性澱粉において、アニオン澱粉への高分子量カチオンポリマーの吸着量は、アニオン澱粉固形分当り固形分で４００〜５，０００ｐｐｍの範囲が好ましい。吸着量が４００ｐｐｍ未満では、澱粉の歩留向上、すなわち紙力増強が十分でなく、逆に５，０００ｐｐｍを超えると、アニオン澱粉の凝集が強すぎて、紙層内での定着が不均一となる、紙の地合いが悪くなる、経済性に見合った効果が得られないなどの不都合が生ずる。上記吸着量を得るには、高分子量カチオンポリマーの添加量が、アニオン澱粉固形分当り固形分で５００〜５，０００ｐｐｍの範囲であることが好ましい。アニオン澱粉とカチオンポリマーの組合せ次第で、５，０００ｐｐｍを超える添加量でも良好な結果が得られることがあるが、経済的には好ましくない。
【００２２】
本発明により、アニオン澱粉に高分子量カチオンポリマーを吸着させて自己定着性澱粉を得る方法としては、アニオン澱粉を水に懸濁した水性スラリーと高分子量カチオンポリマーの水溶液を接触させ、その際所望量の高分子量カチオンポリマーをアニオン澱粉に吸着させるに足る十分な時間が取れさえすれば、どのような方法でもよい。最も簡便な方法は、アニオン澱粉の水性スラリーに高分子量カチオンポリマーの水溶液または粉末状高分子量カチオンポリマーを添加し、暫く攪拌を続ける方法である。また、アニオン澱粉の水性スラリーを連続的に紙料に添加し、この添加ラインに連続的に高分子量カチオンポリマーの水溶液を添加する方法も採用することができるが、この場合高分子量カチオンポリマーの均一な吸着を促進するため、スタティックミキサーなどのインラインミキサーを設けることが好ましい。
【００２３】
さらに、利便性を高めることを目的として、アニオン澱粉の粉体に、アニオン澱粉粉体当り固形分で５００〜５，０００ｐｐｍの固形状高分子量カチオンポリマーを予め配合し、オンサイトで自己定着性澱粉が得られるように設計した自己定着性澱粉組成物とすることもできる。この自己定着性澱粉組成物は、抄紙工程において、水に懸濁し、水性スラリーの状態として紙料に添加することができる。
【００２４】
自己定着性澱粉は水性スラリーの状態で紙料に添加される。添加場所は、特に限定しないが、ミキシングチェストからファンポンプの手前までの紙料との攪拌が十分に期待される場所が適している。
自己定着性澱粉の紙料への添加量は、紙の種類、原料パルプの種類や配合割合、目標とする紙の強度などにより決定される。対パルプ固形分あたり１重量％以下の低い添加量でも効果が得られるが、本発明の効果を顕著に発揮せしめるには２重量％以上が好ましく、３重量％以上がより好ましい。
【００２５】
抄紙工程において、本発明の自己定着性澱粉を紙料に添加する手法などは、従来のカチオン澱粉やＰＡＭなどの他の紙力増強剤と同様でよい。本発明の自己定着性澱粉を使用するに当たり、必要に応じてカチオン澱粉やＰＡＭなどの他の紙力増強剤、填料、サイズ剤、歩留向上剤、アニオン性無機コロイドなどを併用することは何ら差し支えないが、本発明の自己定着性澱粉との相容性を考慮して添加場所などを選定する必要が生じることがある。
本発明による自己定着性澱粉は、特に紙力や剛度が要求される段ボール原紙（ライナー、中芯原紙）や紙管原紙の製造に好適であるが、白板紙などのその他の板紙や洋紙に使用することもできる。
【００２６】
【実施例】
本発明の態様を実施例をもって説明する。無論、本発明はこれら実施例にのみ限定されるものではない。実施例および比較例において、％は重量基準である。なお、アニオン澱粉粒子への高分子量カチオンポリマーの吸着量は次の方法で測定した。
【００２７】
自己定着性澱粉を含む水性スラリーを採取し、希釈し、卓上型遠心分離機により３，０００ｒｐｍで５分間遠心分離する。上澄み液の一部を採取し、トルイジンブルーを指示薬として０．００２５規定のポリビニル硫酸カリウム標準液でコロイド滴定する。澱粉を用いないで同様の操作を行い（遠心分離をする際のポリマー濃度および被適定液の量を同じにする。）、ブランク試験とする。
高分子量カチオンポリマーの吸着量Ａは下記式により算出する。
Ａ ＝ Ｂ ×（Ｙ − Ｘ）／Ｙ
Ａ： ポリマー吸着量（重量ｐｐｍ対澱粉固形分）
Ｂ： ポリマー添加率（重量ｐｐｍ対澱粉固形分）
Ｘ： 滴定値（ｍｌ）
Ｙ： ブランク滴定値（ｍｌ）
【００２８】
《自己定着性澱粉の調製》
実施例１
コーンスターチに次亜塩素酸ナトリウムを反応させて得た市販酸化澱粉（商品名：ＭＳ＃３８００／日本食品化工、澱粉粒子表面のアニオン化度０．０１７ｍｅｑ／ｇ）、コーンスターチに燐酸ナトリウムと尿素を反応させて得た市販燐酸エステル化澱粉（商品名：スプレット＃２００／日本食品化工、澱粉粒子表面のアニオン化度０．０８９ｍｅｑ／ｇ）および既知の方法によりコーンスターチに対澱粉固形分当たり１％の無水こはく酸を反応させて得た澱粉こはく酸ハーフエステル（澱粉粒子表面のアニオン化度０．０１８ｍｅｑ／ｇ）を各々水に懸濁してアニオン澱粉の水性スラリーとした。
【００２９】
次いで、高分子量カチオンポリマーとして、予め希薄水溶液にした共重合型カチオン変性ポリアクリルアミド（ＰＡＭ）−Ａ（濃度０．２％の水溶液の２０℃，６０ｒｐｍにおけるＢ型粘度〔以下、単に「水溶液粘度」と略称する〕９０ｍＰａｓ・Ｓ、カチオン化度０．９ｍｅｑ／ｇ）、共重合型カチオン変性ＰＡＭ−Ｂ（水溶液粘度５０ｍＰａｓ・Ｓ、カチオン化度０．３ｍｅｑ／ｇ）、共重合型カチオン変性ＰＡＭ−Ｃ（水溶液粘度８０ｍＰａｓ・Ｓ、カチオン化度２．６ｍｅｑ／ｇ）または両性ＰＡＭ−Ａ（水溶液粘度３０ｍＰａｓ・Ｓ、カチオン化度０．２ｍｅｑ／ｇ）を各々のアニオン澱粉に対し、対澱粉固形分当たり固形分で１，０００ｐｐｍ添加し、３分間攪拌して表１記載の自己定着性澱粉１〜１２を得た。カチオンポリマーの吸着量を表１に示す。
【００３０】
実施例２
実施例１記載の燐酸エステル化澱粉を水に懸濁してアニオン澱粉の水性スラリーとした。次いで、高分子量カチオンポリマーとして、予め希薄水溶液にした実施例１記載の共重合型カチオン変性ＰＡＭ−Ａまたは両性ＰＡＭ−Ａを対澱粉固形分当たり固形分で５００、２，０００または５，０００ｐｐｍ添加し、３分間攪拌して表１記載の自己定着性澱粉１３〜１８を得た。カチオンポリマーの吸着量を表１に示す。
【００３１】
比較例１
コーンスターチ（粒子表面のアニオン化度ゼロ）の水性スラリーに、予め希薄水溶液にした実施例１記載の高分子量カチオンポリマー（共重合型カチオンＰＡＭ−Ａ、共重合型カチオンＰＡＭ−Ｂ、共重合型カチオンＰＡＭ−Ｃまたは両性ＰＡＭ−Ａ）を対澱粉固形分当たり固形分で１，０００ｐｐｍ添加し、３分間攪拌して表１記載の対照澱粉１〜４を得た。 カチオンポリマーの吸着量を表１に示す。
【００３２】
比較例２
実施例１記載の酸化澱粉、燐酸エステル化澱粉または澱粉こはく酸ハーフエステルの水性スラリーに、予め水で希釈した両性ＰＡＭ−Ｂ（水溶液粘度１５ｍＰａｓ・Ｓ、カチオン化度０．４ｍｅｑ／ｇ）またはポリジアリルジメチルアンモニウムクロライド（ｐ−ＤＡＤＭＡＣ）（水溶液粘度５ｍＰａｓ・Ｓ、カチオン化度６．５ｍｅｑ／ｇ）を対澱粉固形分当たり、固形分で１，０００ｐｐｍ添加し、３分間攪拌して、表１記載の対照澱粉５〜１０を得た。カチオンポリマーの吸着量を表１に示す。
【００３３】
比較例３
実施例１記載の燐酸エステル化澱粉を水に懸濁してアニオン澱粉の水性スラリーとした。次いで、高分子量カチオンポリマーとして、予め希薄水溶液にした実施例１記載の共重合型カチオン変性ＰＡＭ−Ａまたは両性ＰＡＭ−Ａを対澱粉固形分当たり固形分で１００または１０，０００ｐｐｍ添加し、３分間攪拌して表１記載の対照澱粉１１〜１４を得た。カチオンポリマーの吸着量を表１に示す。
【００３４】
【表１】
【００３５】
応用試験例１
離解、洗浄されたパルプ（段ボール古紙）を１．５％濃度に調整し、攪拌しながら硫酸バンドを対パルプ固形分当たり１％添加した。次いで、１分後に表１記載の自己定着性澱粉または対照澱粉を３％濃度の水性スラリーとして対パルプ固形分当たり固形分で５％添加した。１分間攪拌した後、希釈水を加えてパルプ濃度０．６％の紙料を調製した（ｐＨ約６．８）。さらに３０秒攪拌を続け、以下の動的濾水歩留試験に供した。
【００３６】
《動的濾水歩留試験》
製紙業界にて汎用的に使用される動的濾水歩留試験機（ブリットジャー）に６０メッシュのワイヤーを取り付け、上記で得られた紙料を５００ｇ入れた。直ちに攪拌速度１，２５０ｒｐｍにて３０秒間攪拌した。次いで、攪拌速度を８００ｒｐｍに落し、１０秒後濾過を開始してその５秒後より３０秒間濾液を採取した。採取した濾液の重量とその濾液中の澱粉量より、澱粉の歩留を算出した。結果を表２に示す。
【００３７】
【表２】
※対照澱粉のＮｏ１２及び１４は、カチオンポリマー添加後、澱粉スラリーが強い凝集 状態となり、実用性に乏しいと思われた。
本試験は、パルプ繊維が絡み合ったマットが形成される初期段階での澱粉の歩留を求めたものである。一般に、この試験では、微細繊維や添加薬品の歩留が低くなるが、実機との高い相関が得られることが知られている。
【００３９】
表２によると、本発明によらない対照澱粉がいずれも低い歩留であったのに対し（Ｎｏ１２および１４は歩留は高いが、澱粉スラリーが強い凝集状態となり、実用化に際して、沈澱の生成など種々トラブルが予想される）、本発明による自己定着性澱粉は、対パルプ５％の高い添加率ながら、いずれも高い歩留を示した。従って、本発明の自己定着性澱粉を使用した場合には、排水負荷が低減され、澱粉をより多く添加することが可能であり、これに応じて紙の強度の上昇が期待される。
【００４０】
応用試験例２
離解、洗浄されたパルプ（段ボール古紙）を２％濃度に調整し、攪拌しながら硫酸バンドを対パルプ固形分当たり１％添加した。次いで、１分後に表１記載の自己定着性澱粉または対照澱粉を５％濃度の水性スラリーとして対パルプ固形分当たり固形分で５％添加した。１分間攪拌した後、希釈水を加えてパルプ濃度１％の紙料を調製した（ｐＨ約６．５）。さらに３０秒間攪拌を続けた後、実験用角型シートマシン（２５０ｍｍ×２５０ｍｍ）を用い、紙料濃度０．１％にて坪量１２０ｇ／ｍ２を目標として手抄きシートを作製した。次いでろ紙で脱水した後、表面温度１３０℃の回転乾燥機で２分間乾燥し、中芯原紙を得た。
これを、２０℃、関係湿度６５％の恒温恒湿室にて調湿した後、ＪＩＳ Ｐ８１２６に準じて比圧縮強度、ＪＩＳ Ｐ８１１３に準じて引張強度（裂断長）およびαアミラーゼ分解・抽出法により澱粉量（澱粉歩留を算出）の測定を行った。また、紙の地合いを指触および目視で評価し、２等級試験により評価した
（〇：地合いが良好、×：地合いが不良）。結果を表３に示す。
【００４１】
【表３】
※澱粉の紙中での定着状態を顕微鏡にて観察したところ、対照澱粉のＮｏ１２および１４ を用いた紙は、地合いが悪く、凝集状態で添加された澱粉が紙の中で固まって存在していた。なお、紙中での澱粉の糊化状態は、自己定着性澱粉、対照澱粉の全てにおいて良好であった。
【００４３】
本試験は、静的な状態での抄紙であり、さらに澱粉粒が形成されたマットに物理的にトラップされる作用が働くこともあり、一般に比較的高い歩留が得られることが知られている。しかしながら、対照澱粉に比べ、本発明による自己定着性澱粉を用いたものは、いずれも高い澱粉歩留を示しており、これに対応して比圧縮強度や裂断長などの紙力が高くなった。また、カチオンポリマーを過剰に添加した場合（対照澱粉Ｎｏ１２および１４）は、凝集状態のまま添加された澱粉が、紙の中で不均一に定着し、紙の地合いも目視で判別できるほど劣ったものとなり、実用性に乏しいものと判断された。
【００４４】
【発明の効果】
本発明による自己定着性澱粉を水性スラリーの状態で紙の抄造時に添加することにより、澱粉の紙への歩留を飛躍的に向上させることができる。従って、製紙排水の負荷を上げることなく、澱粉の紙への添加量を増やすことができ、最終的に高い強度の紙が得られる。
本発明の自己定着性澱粉を用いると、操業性を損なわずにより高い強度の紙（またはより低い強度の原料パルプより同じ強度の紙）を、より安価に製造することが可能となる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to starch used as a paper strength agent during papermaking, and more particularly, by adding a high molecular weight cationic polymer to an aqueous slurry of anionic starch and adsorbing the cationic polymer on the particle surface of the anionic starch. The present invention relates to a self-fixing starch obtained and a method for producing the same.
By adding the self-fixing starch of the present invention in the papermaking process during papermaking in the form of an aqueous slurry, the amount of starch added to the paper can be increased without increasing the load on papermaking wastewater, High strength paper can be obtained.
[0002]
[Prior art]
Conventionally, three methods have been known for using starch as a paper strength agent. That is,
{Circle around (1)} Surface size method This is a method in which a starch paste solution is applied to the surface of the paper produced. In this method, the yield of the applied starch is very high at almost 100%, but it is necessary to gelatinize the starch. If the viscosity of the starch is decreased to increase the amount of application, the compressive strength is reduced. It has disadvantages such as difficulty in obtaining paper strength and necessity of a coating device such as a size press.
[0003]
(2) Spraying method An aqueous slurry of starch is sprayed between the surface of the wet paper made by papermaking and / or between the laminating layers in the multi-layer papermaking, and the starch is gelatinized using the heat of the drying process to reduce the strength of the paper. It is a technology to enhance. With this method, a relatively large amount of starch can be applied to the paper, and as a result a high-strength paper can be obtained, but strict maintenance of the spray nozzle and the slurry strainer is necessary for continuous spraying. However, there are problems such as the necessity of installing a spraying device, and the fact that the sprayed starch slurry easily fouls the paper machine.
[0004]
{Circle around (3)} This is a method in which starch is added to paper stock during papermaking of internally added paper. Since an application device and a spray device are unnecessary, starch can be used relatively easily. However, since the pulp-based stock has a low concentration of usually 2% by weight or less, when the stock is filtered through a wire, non-ionic starch or anionic starch passes through the wire and escapes into white water. , The yield is remarkably bad. Therefore, in recent years, a method of adding a cationic starch which is easily fixed on the surface of pulp (usually having a negative charge) in the form of a paste liquid has become widespread. In this method, a high effect is obtained when the starch addition ratio is 1.5% by weight or less with respect to pulp. However, when the starch addition ratio is higher than that, the yield of the cationic starch is rapidly reduced, and the drainage is deteriorated. This results in a significant decrease in speed. Further, a decrease in yield increases the load of wastewater treatment. As a result, it is difficult to obtain a paper having a sufficiently high strength by the internal addition method of the cationic starch paste liquid.
[0005]
Several improved methods have been devised as a technique for internally adding starch to a stock at a high addition rate. First, there is a method in which an aqueous slurry of cross-linked starch is heated to make the starch particles in a swollen state, and then added to a stock (Japanese Patent Application Laid-Open No. 55-76200). According to this method, the starch yield is high and high strength paper is obtained.However, since the starch particles in the swollen state fill the gaps between fibers during papermaking, the drainage becomes extremely poor, and the starch has a large amount of water. Because of the embrace, inconveniences such as difficulty in dehydration and drying occur, and it is not suitable for general paper machines that require productivity.
[0006]
During papermaking, so-called retention aids are sometimes used for the purpose of improving the retention of fine fibers and fillers and improving drainage. Recently, a yield improving system using a high molecular weight retention improver and an anionic inorganic colloid such as colloidal silica or bentonite has been developed and put into practical use. There is disclosed a technology for continuously adding an aqueous slurry of starch to a line for adding a retention aid or an anionic inorganic colloid to improve the retention of starch (WO 95/33096). However, in this method, the action of simply trapping relatively large particles of starch in the polymer matrix of the retention aid only works, and it is not considered that the method has a sufficient effect on the improvement of the retention of starch. Hard to say.
[0007]
Furthermore, a technique has been disclosed in which cationic starch obtained by heat-treating starch in the presence of a cationic polymer at a high temperature in a dry manner is internally added in a slurry state (JP-A-9-291103). However, this method also involves the use of relatively large amounts of expensive cationic polymers, possibly due to the thermal decomposition of some or all of the cationic polymers, or the heat treatment at high temperatures, which results in random orientation of the cationic polymers. Therefore, a sufficient starch retention effect cannot be obtained, and the utility is poor.
[0008]
In order to solve the above-mentioned difficulties in using starch as a paper strength enhancer, a polyacrylamide (PAM) -based paper strength enhancer is used especially for paperboard such as core base paper which requires strength. There is. Internal addition of a large amount of PAM does not deteriorate drainage so much like a cationic starch paste solution, and is effective also in terms of paper strength. However, on the other hand, the flexibility of the paper is poor, so that, for example, the core base paper is liable to break, and the disintegration is poor, so that there is a problem in the recovery and recycling of the waste paper, and the water absorption. Therefore, there are problems such as poor bonding property of cardboard base paper and higher production cost than starch.
[0009]
[Problems to be solved by the invention]
In view of the above situation, an object of the present invention is to provide an inexpensive paper that has a high yield even when added in a large amount, and thus can obtain a sufficient paper strength enhancing effect and does not impair operability. To provide a starch for a force enhancer.
[0010]
[Means for Solving the Problems]
In order to solve the above-mentioned disadvantages of the prior art in using starch as a paper strength agent, as a result of intensive studies, the present inventors have added a high molecular weight cationic polymer to an aqueous slurry of anionic starch to obtain particles of anionic starch. By adding a self-fixing starch obtained by adsorbing the cationic polymer to the surface of the paper in the form of an aqueous slurry during papermaking, the amount of starch added to the paper can be reduced without increasing the load of papermaking wastewater. It has been found that it can be increased and finally obtains a high strength paper.
[0011]
Thus, according to the present invention, a high-molecular-weight cationic polymer having a B-type viscosity of not less than 30 mPas · S at 20 ° C. and 60 rpm of an aqueous solution having a concentration of 0.2% by weight is provided on the surface of the particles of anionic starch. The present invention provides a self-fixing starch characterized by being adsorbed at a solid content of 400 to 5,000 ppm.
[0012]
Further, according to the present invention, a high-molecular-weight cationic polymer having a B-type viscosity of not less than 30 mPas · S at 20 ° C. and 60 rpm of an aqueous solution having a concentration of 0.2% by weight is added to an aqueous slurry of anionic starch at a solid content per starch solid content. The method of producing a self-fixing starch as described above, wherein the cationic polymer is adsorbed on the surface of the anionic starch particles by adding 500 to 5,000 ppm per minute.
[0013]
Further, according to the present invention, there is provided a papermaking method characterized by adding the above-mentioned self-fixing starch to a stock in the form of an aqueous slurry during papermaking.
Furthermore, according to the present invention, a solid high molecular weight cationic polymer having a B-type viscosity of not less than 30 mPas · S at 20 ° C. and 60 rpm of an aqueous solution having a concentration of 0.2% by weight is added to the anionic starch powder. The present invention provides a self-fixing starch composition characterized by being blended at a solid content of 500 to 5,000 ppm per body.
[0014]
[Action]
The mechanism by which the self-fixing starch according to the present invention exhibits "self-fixing property" without the need for the aid of a retention aid or a flocculant is considered as follows.
The surface of pulp fibers is usually negatively charged, and non-ionic or anionic starches have very poor yields. Therefore, a method has been adopted in which cationic starch is added in the form of a size liquid to increase the starch yield by ionic bonding between the anion on the pulp fiber and the cation of the cationic starch. However, this method is effective when the starch addition ratio is low and is at most 1.5% by weight, and when it is added more than that, the cation becomes excessive and fixing by ionic bonding can no longer be expected. On the other hand, when cationic starch is added as an ungelatinized aqueous slurry, only cations (only a part of the total cations) present on the surface of the starch particles are ionically bonded to the anions on the pulp fiber in a point-adhesive manner. Therefore, the cationic starch particles fall off due to the hydrodynamic action accompanying the flow of water during papermaking, and easily pass through the wire together with the water. Thus, in this case also, the starch yield is still at a lower level, albeit somewhat better than non-ionic starch.
[0015]
In contrast to the above, in the self-fixing starch according to the present invention, the cationic polymer adsorbed on the particle surface of the anionic starch is distributed radially from the surface of the starch particles due to repulsion of cations, and more pulp fibers It will bind to the above anion. In other words, a strong bond is formed as a whole in terms of surface adhesion, and it is possible to counteract the hydrodynamic action of separating the starch particles from the pulp fiber, and as a result, a high starch yield is obtained. As described above, in the self-fixing starch of the present invention, some of the cations on the cationic polymer are bonded to the anions present on the particle surface of the anionic starch, and most of the remaining cations are bonded to the anions on the pulp fiber. A high starch yield is obtained by participating.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
The anionic starch used in the present invention is a starch having anions on its particle surface, and preferably has an anionization degree of 0.01 meq / g or more. If the anionization degree is too low, the adsorption of the cationic polymer becomes insufficient, and the effect of the present invention cannot be obtained satisfactorily.
[0017]
Specific examples of the anionic starch used in the present invention include conventionally known oxidized starch treated with hypochlorite such as sodium hypochlorite, dibasic acid such as succinic anhydride and maleic anhydride. Starch dibasic acid half-esters reacted with acid anhydrides and starch phosphates treated with phosphoric acid and / or phosphates such as phosphoric acid / urea (in combination), sodium phosphate, sodium tripolyphosphate and the like. These can be suitably used from the viewpoint of economy, but are not limited to them.
[0018]
Specific examples of the raw starch used in the preparation of the anionic starch used in the present invention include corn starch, tapioca starch, potato starch, sweet potato starch, wheat starch, waxy corn starch, high amylose corn starch, and any commercially available starch. Starch can also be used.
[0019]
Specific examples of the cationic polymer used in the present invention include cation-modified polyacrylamide (PAM), polyethyleneimine, cation-modified poly (meth) acrylate, polydiallyldimethylammonium chloride, chitosan, and the like. Among them, cation-modified polyacrylamide (PAM) -based ones, for example, diethylaminoethyl methacrylate, diallyldimethylammonium chloride, diallyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium methylsulfate, methacryloyl, from the viewpoint of economic efficiency and paper strength improving effect. Copolymerized PAM obtained by copolymerizing a cationic monomer such as oxyethyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride, Mannich-modified PAM, and Hoffman-decomposed PAM are preferable. Further, in addition to the cation, it may have a substituent of a nonion or an anion (as long as the amount of the net cation does not fall below 0.2 meq / g).
[0020]
The higher the molecular weight of the cationic polymer, the better. However, it is difficult to accurately measure the molecular weight of a polymer having a very high molecular weight, and the error due to the measuring method is large. Therefore, in this patent, the viscosity of the aqueous solution is specified as an index. That is, in this patent, the cationic polymer is diluted or dissolved in distilled water to obtain a 0.2% concentration aqueous solution, but the B-type viscosity at 20 ° C. and 60 rpm must be 30 mPas · S or more. If the viscosity is less than this, the starch yield cannot be improved and the paper strength enhancing effect cannot be obtained satisfactorily.
[0021]
In the self-fixing starch of the present invention, the amount of the high molecular weight cationic polymer adsorbed on the anionic starch is preferably in the range of 400 to 5,000 ppm in terms of solids per anionic starch solids. If the amount of adsorption is less than 400 ppm, the starch yield improvement, that is, the paper strength enhancement is not sufficient, and if it exceeds 5,000 ppm, the aggregation of the anionic starch is too strong and the fixation in the paper layer is not uniform. Inconveniences such as poor paper texture, inability to obtain an effect commensurate with economic efficiency, and the like occur. In order to obtain the above adsorption amount, the amount of the high molecular weight cationic polymer to be added is preferably in the range of 500 to 5,000 ppm in terms of solids per anionic starch solids. Depending on the combination of the anionic starch and the cationic polymer, good results may be obtained with an addition amount of more than 5,000 ppm, but this is economically undesirable.
[0022]
According to the present invention, as a method for obtaining a self-fixing starch by adsorbing a high molecular weight cationic polymer on an anionic starch, an aqueous slurry of anionic starch suspended in water is brought into contact with an aqueous solution of a high molecular weight cationic polymer. Any method may be used as long as it has sufficient time to adsorb the high molecular weight cationic polymer to the anionic starch. The simplest method is a method in which an aqueous solution of a high molecular weight cationic polymer or a powdery high molecular weight cationic polymer is added to an aqueous slurry of anionic starch and stirring is continued for a while. Further, a method of continuously adding an aqueous slurry of anionic starch to the stock and continuously adding an aqueous solution of a high molecular weight cationic polymer to this addition line can be adopted. In order to promote efficient adsorption, it is preferable to provide an in-line mixer such as a static mixer.
[0023]
Furthermore, for the purpose of enhancing convenience, anionic starch powder is preliminarily blended with a solid high molecular weight cationic polymer having a solid content of 500 to 5,000 ppm based on anionic starch powder, and an on-site self-fixing starch is prepared. And a self-fixing starch composition designed to obtain This self-fixing starch composition can be suspended in water in the papermaking step and added to the stock as an aqueous slurry.
[0024]
The self-fixing starch is added to the stock in the form of an aqueous slurry. The place of addition is not particularly limited, but a place where mixing with the stock from the mixing chest to just before the fan pump is sufficiently expected is suitable.
The amount of the self-fixing starch added to the paper stock is determined by the type of paper, the type and blending ratio of the raw pulp, the target paper strength, and the like. The effect can be obtained even with a low addition amount of 1% by weight or less based on the pulp solid content. However, in order to remarkably exert the effect of the present invention, it is preferably 2% by weight or more, more preferably 3% by weight or more.
[0025]
In the papermaking process, the method of adding the self-fixing starch of the present invention to the stock may be the same as other paper strength agents such as conventional cationic starch and PAM. In using the self-fixing starch of the present invention, if necessary, other paper strength enhancers such as cationic starch and PAM, fillers, sizing agents, retention enhancers, anionic inorganic colloids and the like are not used at all. Although there is no problem, it may be necessary to select an addition place in consideration of compatibility with the self-fixing starch of the present invention.
The self-fixing starch according to the present invention is suitable for the production of cardboard base paper (liner, core base paper) and paper tube base paper which require paper strength and stiffness, but is used for other paperboards such as white paperboard and Western paper. You can also.
[0026]
【Example】
The embodiments of the present invention will be described with reference to examples. Of course, the invention is not limited to only these examples. In Examples and Comparative Examples,% is based on weight. The amount of the high molecular weight cationic polymer adsorbed on the anionic starch particles was measured by the following method.
[0027]
The aqueous slurry containing the self-fixing starch is collected, diluted and centrifuged at 3,000 rpm for 5 minutes in a tabletop centrifuge. A part of the supernatant is collected and subjected to colloid titration with a 0.0025 N polyvinyl potassium sulfate standard solution using toluidine blue as an indicator. The same operation is performed without using starch (the polymer concentration and the amount of the solution to be subjected to centrifugation are made the same), and a blank test is performed.
The adsorption amount A of the high molecular weight cationic polymer is calculated by the following equation.
A = B × (Y−X) / Y
A: Polymer adsorption amount (weight ppm vs. starch solids)
B: Polymer addition rate (wt ppm vs. starch solids)
X: Titration value (ml)
Y: Blank titration value (ml)
[0028]
<< Preparation of self-fixing starch >>
Example 1
Commercially available oxidized starch obtained by reacting corn starch with sodium hypochlorite (trade name: MS # 3800 / Nippon Shokuhin Kako, degree of anionization of starch particles on the surface of 0.017 meq / g), and sodium phosphate and urea reacting with corn starch A commercially available phosphorylated starch (trade name: SPRET # 200 / Nippon Shokuhin Kako Co., Ltd., degree of anionization of starch particles at 0.089 meq / g) and corn starch were added to corn starch by a known method in an amount of 1% anhydrous based on starch solids. Starch succinic acid half ester obtained by reacting succinic acid (degree of anionization on the surface of starch particles: 0.018 meq / g) was suspended in water to form an aqueous slurry of anionic starch.
[0029]
Next, as a high molecular weight cationic polymer, a copolymer-type cation-modified polyacrylamide (PAM) -A prepared in a dilute aqueous solution (B-type viscosity of a 0.2% aqueous solution at 20 ° C. and 60 rpm [hereinafter simply referred to as “aqueous solution viscosity”) 90 mPas · S, cationization degree 0.9 meq / g), copolymerized cation-modified PAM-B (aqueous solution viscosity 50 mPas · S, cationization degree 0.3 meq / g), copolymerized cation-modified PAM- C (aqueous solution viscosity: 80 mPas · S, degree of cationization: 2.6 meq / g) or amphoteric PAM-A (aqueous solution viscosity: 30 mPas · S, degree of cationization: 0.2 meq / g) The solid content per solid was 1,000 ppm, and the mixture was stirred for 3 minutes to obtain self-fixing starches 1 to 12 shown in Table 1. Table 1 shows the adsorption amount of the cationic polymer.
[0030]
Example 2
The phosphorylated starch described in Example 1 was suspended in water to form an aqueous slurry of anionic starch. Then, as a high molecular weight cationic polymer, 500, 2,000 or 5,000 ppm of a copolymer-type cation-modified PAM-A or amphoteric PAM-A described in Example 1, which was previously made into a dilute aqueous solution, was added at a solid content per starch solid content. The mixture was stirred for 3 minutes to obtain self-fixing starches 13 to 18 shown in Table 1. Table 1 shows the adsorption amount of the cationic polymer.
[0031]
Comparative Example 1
A high-molecular-weight cationic polymer (copolymerized cation PAM-A, copolymerized cation PAM-B, copolymerized cation) described in Example 1 previously prepared as a dilute aqueous solution was added to an aqueous slurry of corn starch (zero degree of anionization of the particle surface). PAM-C or amphoteric PAM-A) was added at a solid content of 1,000 ppm based on the starch solid content, and the mixture was stirred for 3 minutes to obtain control starches 1 to 4 shown in Table 1. Table 1 shows the adsorption amount of the cationic polymer.
[0032]
Comparative Example 2
Amphoteric PAM-B (aqueous solution viscosity: 15 mPas.S, degree of cationization: 0.4 meq / g) or poly (polymethacrylate) previously diluted with water was added to the aqueous slurry of oxidized starch, phosphorylated ester or starch succinic acid half ester described in Example 1. Diallyldimethylammonium chloride (p-DADMAC) (aqueous solution viscosity: 5 mPas · S, degree of cationization: 6.5 meq / g) was added in an amount of 1,000 ppm based on the solid content of the starch and stirred for 3 minutes. Of control starches 5 to 10 were obtained. Table 1 shows the adsorption amount of the cationic polymer.
[0033]
Comparative Example 3
The phosphorylated starch described in Example 1 was suspended in water to form an aqueous slurry of anionic starch. Then, as a high molecular weight cationic polymer, 100 or 10,000 ppm of a copolymer-type cation-modified PAM-A or amphoteric PAM-A described in Example 1, which was previously made into a dilute aqueous solution, was added at a solid content per starch solid content of 3 minutes. After stirring, control starches 11 to 14 shown in Table 1 were obtained. Table 1 shows the adsorption amount of the cationic polymer.
[0034]
[Table 1]
Application test example 1
The disintegrated and washed pulp (recycled corrugated paper) was adjusted to a concentration of 1.5%, and a sulfuric acid band was added thereto with stirring at a concentration of 1% per pulp solid content. Then, one minute later, the self-fixing starch or the control starch shown in Table 1 was added as a 3% aqueous slurry at 5% solids per pulp solids. After stirring for 1 minute, diluting water was added to prepare a stock having a pulp concentration of 0.6% (pH about 6.8). Stirring was further continued for 30 seconds and subjected to the following dynamic drainage retention test.
[0036]
《Dynamic drainage yield test》
A 60-mesh wire was attached to a dynamic drainage tester (brit jar) generally used in the papermaking industry, and 500 g of the stock obtained above was charged. The mixture was immediately stirred at a stirring speed of 1,250 rpm for 30 seconds. Next, the stirring speed was reduced to 800 rpm, filtration was started 10 seconds later, and the filtrate was collected 30 seconds after 5 seconds. The starch yield was calculated from the weight of the collected filtrate and the amount of starch in the filtrate. Table 2 shows the results.
[0037]
[Table 2]
* Control starches Nos. 12 and 14 seemed to be poor in practicality because the starch slurry was in a strongly agglomerated state after the addition of the cationic polymer.
This test determined the starch retention at an early stage when a mat in which pulp fibers were entangled was formed. Generally, in this test, it is known that the yield of fine fibers and additive chemicals is low, but a high correlation with the actual machine is obtained.
[0039]
According to Table 2, the control starches not according to the present invention both had low yields (Nos. 12 and 14 had high yields, but the starch slurry was in a strong agglomerated state. Various troubles are expected), and the self-fixing starch according to the present invention exhibited a high yield in spite of a high addition ratio of 5% to pulp. Therefore, when the self-fixing starch of the present invention is used, the drainage load is reduced, and it is possible to add more starch, and accordingly, the strength of the paper is expected to increase.
[0040]
Application test example 2
The disintegrated and washed pulp (recycled corrugated paper) was adjusted to a concentration of 2%, and a sulfuric acid band was added at 1% per pulp solid content with stirring. One minute later, the self-fixing starch or the control starch shown in Table 1 was added as a 5% aqueous slurry at 5% solids per pulp solids. After stirring for 1 minute, dilution water was added to prepare a stock having a pulp concentration of 1% (pH about 6.5). After stirring was further continued for 30 seconds, a hand-made sheet was produced using a square sheet machine for experiment (250 mm × 250 mm) with a target of 120 g / m 2 at a stock density of 0.1%. Next, after dehydration with filter paper, the resultant was dried with a rotary dryer having a surface temperature of 130 ° C. for 2 minutes to obtain a core base paper.
This was conditioned in a constant temperature and humidity chamber at 20 ° C. and a relative humidity of 65%, and then subjected to a specific compression strength according to JIS P8126, a tensile strength (break length) according to JIS P8113, and α-amylase decomposition / extraction method. Was used to measure the amount of starch (calculated starch yield). The formation of the paper was evaluated by finger touch and visual observation, and evaluated by a 2 grade test (〇: good formation, ×: poor formation). Table 3 shows the results.
[0041]
[Table 3]
* When the fixing state of the starch in the paper was observed with a microscope, the paper using the control starch Nos. 12 and 14 had poor formation, and the starch added in a coagulated state was solidified in the paper. Was. The gelatinization state of the starch in the paper was good for both the self-fixing starch and the control starch.
[0043]
In this test, papermaking was performed in a static state, and it was also known that a relatively high yield could be obtained in general because the effect of being physically trapped on the mat on which the starch granules were formed might work. I have. However, those using the self-fixing starch according to the present invention showed a higher starch yield than the control starch, and the paper strength such as specific compressive strength and breaking length was correspondingly increased. Was. When the cationic polymer was excessively added (control starches Nos. 12 and 14), the starch added in an agglomerated state was fixed unevenly in the paper, and the texture of the paper was inferior enough to be visually identified. It was judged to be impractical.
[0044]
【The invention's effect】
By adding the self-fixing starch according to the present invention in the form of an aqueous slurry during papermaking, the yield of starch on paper can be dramatically improved. Therefore, the amount of starch to be added to paper can be increased without increasing the load of papermaking wastewater, and high strength paper is finally obtained.
The use of the self-fixing starch of the present invention makes it possible to produce higher-strength paper (or paper having the same strength as lower-strength raw pulp) at a lower cost without impairing operability.
Claims (4)
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| JP2009249785A (en) * | 2008-04-09 | 2009-10-29 | Sansho Kk | Starch-based interlayer adhesive, and method for papermaking using the same |
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| JP2005232604A (en) * | 2004-02-18 | 2005-09-02 | Nippon Shokuhin Kako Co Ltd | Bulkiness reduction inhibitor, paper making method, and paper |
| JP2007169821A (en) * | 2005-12-21 | 2007-07-05 | Nippon Shokuhin Kako Co Ltd | Method for producing combination board |
| JP5217240B2 (en) * | 2007-05-21 | 2013-06-19 | 星光Ｐｍｃ株式会社 | Paper additive and paper making method using the same |
| EP3019547B1 (en) | 2013-03-05 | 2020-07-22 | The Penn State Research Foundation | Composite materials |
| JP6525896B2 (en) * | 2016-01-20 | 2019-06-05 | 三晶株式会社 | Paper strength agent and method of producing paper |
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| JP2009249785A (en) * | 2008-04-09 | 2009-10-29 | Sansho Kk | Starch-based interlayer adhesive, and method for papermaking using the same |
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