JP3608650B2 - Amphoteric starch, method for producing the same and method for producing paper or paperboard - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、カチオン澱粉に尿素と正燐酸を添加して乾式で加熱反応させることによって両性澱粉を製造する方法、該製造方法によって得られる両性澱粉、および、該両性澱粉を紙料に添加して抄紙する方法に関する。
本発明の製造方法により得られる両性澱粉は、抄紙工程において紙料に添加することにより、与えられた紙料の濾水性を従来から使用されていた澱粉に比べ著しく向上させると共に、濾水性の面より従来制限されていた澱粉の添加量を増大させることによって紙強度を飛躍的に改善することができる。
【０００２】
【従来の技術】
紙または板紙の抄造において、ワイヤーパートにおける紙料の濾水性を増すこと、ワイヤーパートで形成されるシート中の填料や微細繊維のリテンションを向上させること、または抄造した紙または板紙の強度を上昇させることなどを目的として、パルプスラリーには、填料、サイズ剤や硫酸バンドをはじめとする内添用薬品と共に、カチオン澱粉または両性澱粉の糊液を内添することは、公知の技術である。
【０００３】
近年の抄紙速度の上昇に伴い、澱粉糊液をパルプスラリーに内添することによって期待される効果の中でも、特に、抄紙速度に直接影響を与える紙料の濾水性に対する効果に関心が注がれている。内添用澱粉の中でも、特開昭６３−４８３０１号公報に公開されている方法によって製造された両性澱粉、すなわち、原材料となる澱粉に三級アミンまたは四級アンモニウム塩を導入した後、引き続きトリポリ燐酸ナトリウムを添加し加熱反応させて、澱粉分子中に燐酸基を導入した両性澱粉は、中性抄紙系および酸性抄紙系の双方において内添用澱粉として優れた濾水性を示すことが知られている。
しかしながら、この両性澱粉においても内添する際の澱粉糊液の添加率は、対パルプ固形分あたり固形分として１．０重量％程度までが適量であり、それを超える量の添加は、ワイヤーパートにおいて形成されるシートの濾水性の著しい低下をもたらす。
【０００４】
他方、近年では、古紙パルプの配合率の増加による原料パルプの品質の低下（微細繊維、灰分の増加）に伴ない紙または板紙の生産性や紙力の低下が余儀なくされ、これを解決することが課題となっている。
従って、抄造時に、高い濾水性を与えて生産性を上げることができる、または、ほどほどの濾水性を維持しつつ添加量を増やして紙力を高めることができる添加物の開発が強く望まれている。
【０００５】
【発明が解決しようとする課題】
上記のような従来技術の現況に鑑み、本発明の目的は、紙料に添加した際に、優れた濾水性を示すと共に、優れた紙力増強効果が得られる製紙用両性澱粉を提供することにある。
本発明の他の目的は、そのような製紙用両性澱粉を工業的有利に製造する方法を提供することにある。
本発明のさらに他の目的は、そのような製紙用両性澱粉を用いることによって、良好な濾水性をもって抄紙することができ、かつ紙力の高い紙または板紙を得ることができる抄紙方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、三級アミンまたは四級アンモニウム塩を導入したカチオン性澱粉に尿素リン酸化反応を施すことにより、高い濾水性の付与と紙力向上に寄与する両性澱粉を安価に製造し得ることを見出し、本発明の完成に至った。
かくして、本発明によれば、カチオン澱粉に燐酸基を導入して製紙用両性澱粉を製造するに際し、置換度０．０２〜０．０５の三級アミンまたは四級アンモニウム塩を有するカチオン澱粉に、尿素と正燐酸塩を添加し、次いで、乾式で１１０〜１６０℃において０．２〜数時間加熱反応させて、対澱粉固形分あたり結合燐として０．１〜０．７重量％の燐酸基を導入することを特徴とする製紙用両性澱粉の製造方法が提供される。
【０００７】
さらに、本発明によれば、上記の製造方法によって得られる製紙用両性澱粉が提供される。
さらに、本発明によれば、上記の製造方法によって得られる製紙用両性澱粉を添加したパルプスラリーを抄紙することを特徴とする紙または板紙の製造方法が提供される。
【０００８】
【発明の実施の形態】
本発明で用いるカチオン性澱粉の製造に用いる原料澱粉は格別限定されることはなく、タピオカ澱粉、コーン・スターチ、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、馬鈴薯澱粉または甘藷澱粉などの未加工澱粉、これらの未加工澱粉に公知の方法によって置換基を導入したアセチル化澱粉、ヒドロキシエチル化澱粉、ヒドロキシルプロピル化澱粉などを用いることができる。これらの原料澱粉は単独でまたは２種類以上を組み合わせて用いることができる。
【０００９】
本発明における原料澱粉のカチオン化は、三級アミンまたは四級アンモニウム塩が導入される限り、公知の如何なる技術を用いて行ってもよい。
カチオン化剤の具体例としては、ジエチルアミノエチルクロライド塩酸塩などの三級アミン導入剤、および３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロライド塩酸塩および２，３−エポキシプロピルトリメチルアンモニウムクロライド塩酸塩などの四級アンモニウム塩導入剤が挙げられる。これらのカチオン化剤は単独でまたは２種類以上を組み合わせて用いることができる。
【００１０】
カチオン澱粉の置換度（澱粉を構成する無水グルコース単位１個あたりの三級アミンおよび／または四級アンモニウム塩の個数）は０．０２〜０．０５の範囲であることが好ましい。置換度が０．０２未満では本発明の効果を十分に得ることが難しく、逆に、０．０５を超えると製造コストが増大して実用的ではなくなる。
【００１１】
本発明においては、三級アミンまたは四級アンモニウム塩が導入されたカチオン澱粉に、引き続き尿素燐酸化反応を施し、両性澱粉とする。
従来、澱粉に燐酸基を導入する方法として、主に燐酸化反応と尿素燐酸化反応の２つがよく知られている。燐酸化反応の代表的な方法としては、澱粉にトリポリ燐酸ナトリウムなどをｐＨ４〜８．５の条件下で含浸させ、乾式で１１０〜１４０℃で加熱する方法が挙げられ、この方法によれば、燐酸基がエステル結合した澱粉を得ることができる。一方、尿素燐酸化反応では、原料となる澱粉に尿素と正燐酸および／またはその塩を添加し、乾式で１１０〜１６０℃で加熱反応させる方法が一般的である。この方法では、エステル結合した燐酸基に加えて、カルバミン酸エステル基も導入される。また、正燐酸を中和せずに用いることは、加熱反応中に澱粉の酸加水分解による低粘度化を惹起するので、本発明の目的には適さない。
【００１２】
本発明の方法において、カチオン澱粉の尿素燐酸化反応に際しては、尿素と燐酸第一ナトリウム、燐酸第二ナトリウムなどの正燐酸塩を組み合わせて用いてもよいが、溶解作業性の面より次のように行うことがより好ましい。すなわち、尿素と正燐酸を対澱粉固形分あたり１５〜３０重量％程度の量の水に溶解し、高濃度溶液を調製する。この溶液を、水酸化ナトリウムなどのアルカリを用いてｐＨ６．０〜１０．０に調節（この段階で正燐酸塩となる）したうえ、カチオン澱粉に均一に添加する。高濃度溶液のｐＨが６．０未満であると、尿素燐酸化反応時、澱粉の加水分解が進み低粘度化した両性澱粉が生成し、本発明の目的には不適なものとなる。また、ｐＨが１０．０を超えると得られた両性澱粉の着色が著しくなり、商品価値が失われる。
【００１３】
澱粉への尿素と正燐酸の添加率は、尿素が対澱粉固形分あたり５．０〜１５．０重量％であるのに対し、正燐酸塩が対澱粉固形分あたり正燐酸として１．０〜８．０重量％であることが好ましい。
尿素と正燐酸塩を含浸させたカチオン澱粉は、例えばフラッシュドライヤーを用い、水分が通常１２重量％以下、好ましくは７重量％以下となるまで乾燥させる。乾燥方法として、その他のあらゆる公知の方法を用いることができる。尿素と正燐酸を含浸させたカチオン澱粉を乾燥させた後に１２重量％を超える水分を含有すると、加熱反応させる際に、澱粉の部分的糊化の恐れが強くなる。
【００１４】
正燐酸と共に添加する尿素は、加熱反応の際に、澱粉と燐酸との反応速度を上げる触媒として作用する。尿素は、高温での加熱によってアンモニアとイソシアン酸に分解される。イソシアン酸は澱粉分子中の水酸基と容易に反応してカルバミン酸エステルを形成し、また一部は尿素や水と反応して副産物のビウレット、アンモニア、二酸化炭素を生じる。一方、尿素の分解で生じたアンモニアは、一部が未反応の燐酸塩や澱粉に結合した燐酸基の水素と置換して、アンモニウムイオンとして定着するが、大部分は空気中に飛散する。
【００１５】
乾燥させて水分を１２重量％以下とした後に、カチオン澱粉を加熱して尿素燐酸化反応を施す。すなわち、正燐酸塩と尿素を含浸させたカチオン澱粉を、１１０〜１６０℃に保持した反応器に入れ、５分間ないし数時間攪拌する。加熱温度が低すぎると十分な量の燐酸基を導入することができず、また、加熱温度が高すぎると澱粉分子の加水分解が進み低粘度化した両性澱粉が生成し、本発明の目的には不適なものとなる。この際、反応時間は反応温度、用いる反応器の種類、薬品添加量および要求する結合燐に依存して適宜調節する。尿素燐酸化反応によって対澱粉固形分当たり結合燐として０．１〜０．７重量％の燐酸基が導入される。燐酸基導入量が少なすぎると、それを内添した紙料の高い濾水性および紙または板紙の高い紙力が得られず、高すぎるとその強い凝集効果のため、地合いの悪い紙または板紙をもたらす。また、燐酸基に基づくアニオンと三級アミンまたは四級アンモニウム塩に基づくカチオンの比は、モル比として０．２５〜０．７５：１であることが望ましい。
【００１６】
本発明の両性澱粉は、糊化された形態でパルプスラリーに添加する。使用するパルプの種類は目的とする紙または板紙および抄紙条件に依存して適宜選択することができる。両性澱粉の糊化は、澱粉スラリーに３〜１０ｋｇｆ／ｃｍ２の圧力を保持する蒸気を吹き込み、瞬時に澱粉を糊化させる形式の連続糊化方式によることが好ましいが、バッチ式の糊化方式でもかまわない。糊化された両性澱粉を紙料に内添する位置は、パルプスラリー中に通常の添加剤を添加する場合と同様な位置でよいが、その添加には通常マシンチェストやヘッドボックスなどが使用される。その際、両性澱粉の添加量は、原料パルプ固形分に対して固形分として０．５〜３．０重量％が好ましい。
【００１７】
本発明の両性澱粉を添加したパルプスラリーは、一般的な紙または板紙の製造方法と同様の条件で抄造、脱水、乾燥して紙または板紙を得る。本発明の両性澱粉を内添する抄紙系のｐＨは、酸性からアルカリ性の広範囲にわたり採用することができる。本発明の両性澱粉は、必要に応じて他種澱粉、填料、サイズ剤、硫酸バンド、紙力増強剤などと組み合わせてパルプスラリーに内添することができ、それらの種類は抄紙条件に応じて適宜選択すればよい。
【００１８】
【実施例】
以下に本発明の具体的な実施例を示すが、もちろん、本発明は以下に記載の事項に限定されるものではない。以下の実施例および具体例において、％は重量基準である。
【００１９】
実施例 １（両性澱粉の製造）
タピオカ澱粉１，０００ｇを、１，５００ｍｌの水に溶解し、ＮａＯＨを対澱粉２．８％、Ｎａ２ＳＯ４を対澱粉１０％添加した。４５℃に維持した澱粉スラリー中に、カチオン化剤として四級アンモニウム塩導入剤である３−クロロ−２−ヒドロキシプロピルトリメチルアンモニウムクロライド塩酸塩を対澱粉４．５％添加した後、７時間攪拌下でカチオン化反応を行った。反応は、澱粉スラリーを１０％ＨＣｌでｐＨ７．０に下げることで停止させた。反応停止後のスラリーは、常法により精製、脱水した後、室温で乾燥させた。得られたカチオン澱粉は、湿式分解の後、ケルダール法で窒素量を測定することにより、四級アンモニウム塩の置換度を算出した。
【００２０】
対澱粉９．５％の尿素と、対澱粉２．５％の正燐酸を少量の水に溶解し、１０％ＮａＯＨでｐＨ８．０に調整して得た溶液を上記のカチオン澱粉に攪拌しながら添加して十分に混合した。次いで熱風循環乾燥機中で５０℃で乾燥させ、水分を４．０％に調節した。尿素と正燐酸塩を含浸、乾燥させたカチオン澱粉を固形分重量にして３８０ｇをナス型フラスコに採り、１４０℃に加熱したオイルバス中で５〜９０分間加熱させて尿素燐酸化反応を施し、次いで室温まで冷却させた。得られた両性澱粉の結合燐含量は、メタノールで精製した後、モリブデン比色定量法で定量した。また、澱粉分子に結合したカルバミン酸エステル基は、予め塩酸／メタノール／水混合溶液で遊離のアンモニアを除去した澱粉について、全窒素分をケルダール法で定量した後に、四級アンモニウム塩に由来する窒素分を差し引き、カルバミン酸エステルの重量％で示した。Ｂ型粘度は、蒸留水中に固形分濃度２．０％になるよう両性澱粉を採り、攪拌しながら９５℃で２０分間加熱糊化した後、冷却してブルックフィールド型粘度計で５０℃のときの粘度（Ｂ型粘度）を６０ｒｐｍで測定した。対照として、尿素燐酸化反応の原料として用いたカチオン澱粉について同様の測定を行った。表１に、測定した結合燐、カルバミン酸エステル基、およびＢ型粘度を示す。
【００２１】
【表１】
実施例２
カチオン化反応に際し、カチオン化剤を対澱粉６．５％、ＮａＯＨを対澱粉３．２％とした他は上記実施例１の方法に従って両性澱粉を製造した。得られたカチオン化澱粉と両性澱粉の四級アンモニウム塩の置換度、結合燐、カルバミン酸エステル基、Ｂ型粘度を実施例１と同様の方法に従い測定した。その結果を表２に示す。
【００２３】
【表２】
実施例３
タピオカ澱粉１，０００ｇを、１，５００ｍｌの水に溶解し、ＮａＯＨを対澱粉２．５％、Ｎａ２ＳＯ４を対澱粉９．０％添加した。４５℃に維持した澱粉スラリー中に、カチオン化剤として、三級アミン導入剤のジエチルアミノエチルクロライド塩酸塩を対澱粉４．０％添加した後、４時間攪拌下でカチオン化反応を行った。反応は、澱粉スラリーを１０％ＨＣｌでｐＨ４．０に下げることで停止し、以下は、上記実施例１と同様に両性澱粉の製造を試みた。得られたカチオン澱粉と両性澱粉の結合燐、カルバミン酸エステル基とＢ型粘度は、実施例１と同様の方法で測定した。その結果を表３に示す。
【００２５】
【表３】
比較例１
本項では、実施例１または実施例２で得た両性澱粉との内添用両性澱粉としての性能の比較を行うため、特開昭６３−４８３０１号の方法に従ってトリポリ燐酸塩を用いた燐酸化反応をカチオン澱粉に施して両性澱粉を製造した。
実施例１により得たカチオン澱粉５００ｇを秤量し、３０ｇのトリポリ燐酸ナトリウムを含む８００ｍｌの水に溶解し、１０％ＨＣｌでｐＨ６．５に調節した。このスラリーを２時間攪拌した後、濾過した。濾過ケーキを熱風循環乾燥機中で乾燥させ、水分を４．０％に調節した。得られたトリポリ燐酸ナトリウム含有カチオン澱粉を固形分重量にして３８０ｇをナス型フラスコに採り、１４０℃に加熱されたオイルバス中で２０〜４０分間加熱して燐酸化反応を施した。得られた両性澱粉の結合燐とＢ型粘度を、実施例１と同様の方法で測定した。その結果を表４に示す。当然ながらここで得られた両性澱粉はカルバミン酸エステル基を有しない。
【００２７】
【表４】
比較例２
実施例３によって得たカチオン澱粉を用い、それ以外は上記比較例１と同様の方法で両性澱粉の製造を試みた。得られた両性澱粉の三級アミン置換度、結合燐とＢ型粘度を実施例１と同様の方法で測定した。その結果を表５に示す。ここで得られた両性澱粉もカルバミン酸エステル基を有しない。
【００２９】
【表５】
抄造例
実施例１〜３、比較例１、２により得られた両性澱粉、これら両性澱粉の原料として使用したカチオン澱粉（内添用カチオン澱粉として代表的なもの）、および市販の両性澱粉を用い、紙の抄造試験を行った。用いた材料、機器および試験内容と試験方法は以下のとおりである。なお、材料に用いた澱粉のアルファベット記号および番号は、表１〜５で示した両性澱粉のアルファベット記号およびカチオン澱粉の番号と一致する。
【００３１】
市販のシート状ＬＢＫＰをナイアガラ式ビーターで叩解し、カナディアン・スタンダード・フリーネス３６０ｍｌに調整した。
使用する澱粉は全て、固形分濃度２．０％のスラリーとし、９５℃で３０分間加熱糊化して、澱粉糊液を調製した。
【００３３】
固形分濃度２．０％に調整したパルプスラリーを攪拌しながら、澱粉糊液を、固形分として対パルプ固形分当たり０．５、１．０または２．０％、サイズ剤を固形分として０．１５％、そして硫酸バンドを有姿として３．０％をそれぞれ順次添加したのち、水を加えて１．０％に希釈した。調製された紙料を角型シートマシンで坪量８０ｇ／ｍ２になるように抄紙した。ブランクとして、澱粉のみを添加しない手抄き紙も抄造した。ウェットシートは、自動シートプレスを用いて３．５ｋｇｆ／ｃｍ２で２分間、濾紙を替えて引き続き３．５ｋｇｆ／ｃｍ２で１分間プレスし、次いで、回転式乾燥機を用い、１０３℃で２分間乾燥した後、２０℃、６５％Ｒ．Ｈ．で一晩調湿した。
【００３４】
調成した紙料の濾水性及び抄造した手抄き紙の物性は、以下の方法で測定した。
濾水度 ＪＩＳ Ｐ ８１２１に準じて測定した。（高いものほど濾水性が優れている。）
坪量 ＪＩＳ Ｐ ８１２４に準じて測定した。
裂断長 ＪＩＳ Ｐ ８１１３に準じて測定した。
比破裂強さ ＪＩＳ Ｐ ８１１２に準じて測定した。
得られた結果を表６および表７に示す。
【００３５】
【表６】
【表７】
本発明による両性澱粉Ｂ〜Ｊは、カチオン澱粉１〜３に比べて著しく、また本発明によらない両性澱粉ａ〜ｄ、市販の両性澱粉「Ｃａｔｏ３２１０」に比べてかなり濾水性が向上した。従って、内添される澱粉の量が同じであれば、本発明による両性澱粉を用いれば、従来のカチオン澱粉や両性澱粉に比べて抄造速度の向上が達成されることは疑いない。
【００３８】
また、濾水性の向上に従って澱粉の添加率を上げることが可能となるので、澱粉の添加率に制限のある従来のカチオン澱粉や両性澱粉に比べて紙力の向上が期待できる。
なお、両性澱粉Ａは、結合燐が本発明の範囲に到達していないため、十分な濾水性向上効果が得られていない。
【００３９】
【発明の効果】
本発明の方法により得られる両性澱粉は、加熱糊化して紙料に内添し、抄造すると、著しく濾水性が向上し、強度が増大した紙または板紙が得られる。澱粉添加率が２．０％に至っても、濾水性の低下は見られず、従って、抄造速度を下げずに、より強度の高い紙又は板紙の抄造が可能である。
【００４０】
このような本発明の効果、すなわち従来の両性澱粉（特開昭６３−４８３０１号に基づくカチオン澱粉をトリポリ燐酸塩により燐酸化したもの）に比べて著しく濾水性が向上する機構は明らかではないが、燐酸基と共に導入されたカルバミン酸エステルとパルプの主成分であるセルロースとの水素結合の形成、トリポリ燐酸塩に比べて正燐酸塩の分子量が低いことによる澱粉粒内への易浸透性（燐酸基のより均一な分布）、トリポリ燐酸塩に比べて正燐酸塩の溶解度が高く、乾燥中、もしくは加熱反応中に析出することがないこと（燐酸基のより均一な分布および高い反応効率）、未反応の塩による悪影響が分子量が小さい分正燐酸塩の方が少ないことなどが考えられる。
【００４１】
本発明の別の効果は、尿素燐酸化に使用する尿素、正燐酸、および水酸化ナトリウムなどのアルカリがトリポリ燐酸に比べて低価格のため、比較的安価に両性澱粉を提供できることにある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing amphoteric starch by adding urea and orthophosphoric acid to cationic starch and subjecting to a dry heating reaction, amphoteric starch obtained by the production method, and adding the amphoteric starch to a paper stock. It relates to a paper making method.
By adding the amphoteric starch obtained by the production method of the present invention to the stock in the papermaking process, the drainage of the given stock is remarkably improved as compared to the starch used conventionally, and the drainage surface is also improved. The paper strength can be drastically improved by increasing the amount of starch that has been conventionally limited.
[0002]
[Prior art]
In paper or board making, increase the drainage of the stock in the wire part, improve the retention of fillers and fine fibers in the sheet formed by the wire part, or increase the strength of the paper or board made For this purpose, it is a well-known technique to internally add a paste solution of cationic starch or amphoteric starch to the pulp slurry together with chemicals for internal addition such as filler, sizing agent and sulfuric acid band.
[0003]
Along with the recent increase in papermaking speed, attention has been focused on the effect on the freeness of the stock that directly affects the papermaking speed, among the effects expected by adding starch paste to the pulp slurry. ing. Among the starches for internal addition, amphoteric starch produced by the method disclosed in JP-A-63-48301, that is, after introducing a tertiary amine or quaternary ammonium salt into the raw material starch, It is known that amphoteric starch in which phosphoric acid groups are introduced into starch molecules by adding sodium phosphate and reacting with heat exhibits excellent drainage as starch for internal use in both neutral papermaking systems and acidic papermaking systems. Yes.
However, in this amphoteric starch, the addition rate of the starch paste liquid when added internally is an appropriate amount up to about 1.0% by weight as the solid content with respect to the solid content of the pulp. Result in a significant decrease in the freeness of the sheet formed in
[0004]
On the other hand, in recent years, paper or paperboard productivity and paper strength have been inevitably reduced due to a decrease in raw pulp quality (increase in fine fibers and ash content) due to an increase in the ratio of wastepaper pulp. Has become an issue.
Therefore, it is strongly desired to develop an additive that can increase productivity by giving high drainage at the time of papermaking, or can increase paper strength by increasing the amount of addition while maintaining moderate drainage. Yes.
[0005]
[Problems to be solved by the invention]
In view of the current state of the prior art as described above, an object of the present invention is to provide an amphoteric starch for papermaking that exhibits excellent drainage and an excellent paper strength enhancing effect when added to a stock. It is in.
Another object of the present invention is to provide a method for industrially producing such amphoteric starch for papermaking.
Still another object of the present invention is to provide a papermaking method capable of producing paper or paperboard having high paper strength and capable of producing paper with good drainage by using such amphoteric starch for papermaking. There is.
[0006]
[Means for Solving the Problems]
The present inventors can inexpensively produce amphoteric starch that contributes to imparting high drainage and improving paper strength by subjecting cationic starch introduced with tertiary amine or quaternary ammonium salt to urea phosphorylation. As a result, the present invention has been completed.
Thus, according to the present invention, when producing an amphoteric starch for papermaking by introducing a phosphate group into the cationic starch, the cationic starch having a tertiary amine or quaternary ammonium salt with a substitution degree of 0.02 to 0.05 is obtained. Urea and orthophosphate are added, followed by a dry reaction at 110 to 160 ° C. for 0.2 to several hours to give 0.1 to 0.7 wt% of phosphate groups as bound phosphorus per starch solids. A method for producing amphoteric starch for papermaking, which is characterized by being introduced.
[0007]
Furthermore, according to this invention, the amphoteric starch for paper manufacture obtained by said manufacturing method is provided.
Furthermore, according to the present invention, there is provided a method for producing paper or paperboard, which comprises making a pulp slurry to which an amphoteric starch for papermaking obtained by the above production method is added.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The raw material starch used for the production of the cationic starch used in the present invention is not particularly limited. It is possible to use acetylated starch, hydroxyethylated starch, hydroxylpropylated starch or the like in which a substituent is introduced into the processed starch by a known method. These raw material starches can be used alone or in combination of two or more.
[0009]
The cationization of the raw material starch in the present invention may be performed using any known technique as long as a tertiary amine or a quaternary ammonium salt is introduced.
Specific examples of the cationizing agent include tertiary amine introducing agents such as diethylaminoethyl chloride hydrochloride, and 3-chloro-2-hydroxypropyltrimethylammonium chloride hydrochloride and 2,3-epoxypropyltrimethylammonium chloride hydrochloride. A quaternary ammonium salt introduction agent can be mentioned. These cationizing agents can be used alone or in combination of two or more.
[0010]
The degree of substitution of the cationic starch (the number of tertiary amines and / or quaternary ammonium salts per anhydroglucose unit constituting the starch) is preferably in the range of 0.02 to 0.05. If the degree of substitution is less than 0.02, it is difficult to sufficiently obtain the effects of the present invention. Conversely, if the degree of substitution exceeds 0.05, the production cost increases, making it impractical.
[0011]
In the present invention, the urea starch is subsequently subjected to a urea phosphorylation reaction to the cationic starch into which a tertiary amine or quaternary ammonium salt has been introduced to obtain an amphoteric starch.
Conventionally, two main methods for introducing a phosphate group into starch are well-known: phosphorylation and urea phosphorylation. As a typical method of the phosphorylation reaction, a method in which starch is impregnated with sodium tripolyphosphate or the like under a condition of pH 4 to 8.5 and heated at 110 to 140 ° C. in a dry manner, according to this method, A starch having an ester bond with a phosphate group can be obtained. On the other hand, in the urea phosphorylation reaction, a method is generally employed in which urea and orthophosphoric acid and / or a salt thereof are added to starch as a raw material and heated at 110 to 160 ° C. in a dry manner. In this method, in addition to the ester-linked phosphate group, a carbamic acid ester group is also introduced. In addition, use of orthophosphoric acid without neutralization is not suitable for the purpose of the present invention because it causes a decrease in viscosity due to acid hydrolysis of starch during the heating reaction.
[0012]
In the method of the present invention, urea and phosphorylation reaction of cationic starch may be used in combination with urea and orthophosphate such as monosodium phosphate and dibasic sodium phosphate. It is more preferable to carry out. That is, urea and orthophosphoric acid are dissolved in water in an amount of about 15 to 30% by weight per starch solid to prepare a high concentration solution. This solution is adjusted to pH 6.0 to 10.0 using an alkali such as sodium hydroxide (becomes a normal phosphate at this stage) and then uniformly added to the cationic starch. When the pH of the high-concentration solution is less than 6.0, during the phosphorylation of urea, hydrolysis of starch proceeds and amphoteric starch with reduced viscosity is produced, which is unsuitable for the purpose of the present invention. On the other hand, when the pH exceeds 10.0, the amphoteric starch obtained is remarkably colored and the commercial value is lost.
[0013]
The addition ratio of urea and orthophosphoric acid to starch is from 5.0 to 15.0% by weight of urea per starch solid content, whereas 1.0 to 1.0% of normal phosphate as regular phosphoric acid per starch solid content. It is preferably 8.0% by weight.
The cationic starch impregnated with urea and orthophosphate is dried using, for example, a flash dryer until the water content is usually 12% by weight or less, preferably 7% by weight or less. Any other known method can be used as the drying method. If the cationic starch impregnated with urea and orthophosphoric acid contains more than 12% by weight of water after drying, there is a strong risk of partial gelatinization of the starch during the heating reaction.
[0014]
Urea added with normal phosphoric acid acts as a catalyst for increasing the reaction rate between starch and phosphoric acid during the heating reaction. Urea is decomposed into ammonia and isocyanic acid by heating at high temperature. Isocyanic acid easily reacts with hydroxyl groups in starch molecules to form carbamates, and some reacts with urea and water to produce by-products biuret, ammonia, and carbon dioxide. On the other hand, ammonia generated by the decomposition of urea partially substitutes for hydrogen of a phosphate group bonded to unreacted phosphate or starch, and is fixed as ammonium ions, but most of it is scattered in the air.
[0015]
After drying to make the water content 12% by weight or less, the cationic starch is heated to perform a urea phosphorylation reaction. That is, cationic starch impregnated with orthophosphate and urea is placed in a reactor maintained at 110 to 160 ° C. and stirred for 5 minutes to several hours. If the heating temperature is too low, a sufficient amount of phosphoric acid groups cannot be introduced, and if the heating temperature is too high, hydrolysis of starch molecules proceeds and a reduced viscosity amphoteric starch is produced, which is the object of the present invention. Is inappropriate. At this time, the reaction time is appropriately adjusted depending on the reaction temperature, the type of reactor used, the amount of chemical added, and the required bound phosphorus. The urea phosphorylation reaction introduces 0.1-0.7% by weight of phosphate groups as bound phosphorus per starch solids. If the amount of phosphate groups introduced is too small, high drainage of the paper material containing the phosphate group and high paper strength of the paper or paperboard cannot be obtained. Bring. The ratio of the anion based on the phosphate group and the cation based on the tertiary amine or quaternary ammonium salt is preferably 0.25 to 0.75: 1 as a molar ratio.
[0016]
The amphoteric starch of the present invention is added to the pulp slurry in a gelatinized form. The kind of pulp to be used can be appropriately selected depending on the target paper or paperboard and papermaking conditions. Gelatinization of amphoteric starch is preferably performed by a continuous gelatinization method in which the starch slurry is blown with steam that maintains a pressure of 3 to 10 kgf / cm 2 to instantly gelatinize the starch. But it doesn't matter. The position where gelatinized amphoteric starch is internally added to the paper stock may be the same position as when adding a normal additive to the pulp slurry, but a machine chest or head box is usually used for the addition. The At that time, the amount of amphoteric starch added is preferably 0.5 to 3.0% by weight as the solid content with respect to the solid content of the raw material pulp.
[0017]
The pulp slurry to which the amphoteric starch of the present invention is added is subjected to papermaking, dehydration and drying under the same conditions as in general paper or paperboard production methods to obtain paper or paperboard. The pH of the papermaking system in which the amphoteric starch of the present invention is internally added can be employed over a wide range from acidic to alkaline. The amphoteric starch of the present invention can be internally added to the pulp slurry in combination with other types of starch, fillers, sizing agents, sulfuric acid bands, paper strength enhancers, etc., if necessary, and the types thereof depend on the papermaking conditions. What is necessary is just to select suitably.
[0018]
【Example】
Although the specific Example of this invention is shown below, of course, this invention is not limited to the matter as described below. In the following examples and specific examples,% is based on weight.
[0019]
Example 1 (Production of amphoteric starch)
1,000 g of tapioca starch was dissolved in 1,500 ml of water, and 2.8% NaOH to starch and 10% Na 2 SO 4 to starch were added. After adding 4.5% starch to 3-chloro-2-hydroxypropyltrimethylammonium chloride hydrochloride, which is a quaternary ammonium salt introducing agent, as a cationizing agent in the starch slurry maintained at 45 ° C., the mixture was stirred for 7 hours. The cationization reaction was carried out. The reaction was stopped by lowering the starch slurry to pH 7.0 with 10% HCl. The slurry after the termination of the reaction was purified and dehydrated by a conventional method and then dried at room temperature. The degree of substitution of the quaternary ammonium salt of the obtained cationic starch was calculated by measuring the amount of nitrogen by the Kjeldahl method after wet decomposition.
[0020]
While stirring 9.5% urea for starch and 2.5% orthophosphoric acid for starch in a small amount of water and adjusting the pH to 8.0 with 10% NaOH, the above cationic starch was stirred. Added and mixed well. Subsequently, it dried at 50 degreeC in the hot air circulation dryer, and adjusted the water | moisture content to 4.0%. 380 g of cation starch impregnated and dried with urea and orthophosphate in a solid weight is taken in an eggplant-shaped flask and heated in an oil bath heated to 140 ° C. for 5 to 90 minutes to give a phosphorylation reaction of urea. It was then allowed to cool to room temperature. The bound phosphorus content of the amphoteric starch obtained was purified by methanol and then quantified by a molybdenum colorimetric method. In addition, the carbamic acid ester group bonded to the starch molecule is the nitrogen derived from the quaternary ammonium salt after quantifying the total nitrogen content by the Kjeldahl method for starch from which free ammonia has been removed with a hydrochloric acid / methanol / water mixed solution. Minutes were subtracted and expressed as weight percent of the carbamate. B-type viscosity is obtained by taking amphoteric starch in distilled water to a solid content concentration of 2.0%, heating and gelatinizing at 95 ° C. for 20 minutes with stirring, then cooling and using a Brookfield viscometer at 50 ° C. The viscosity (B-type viscosity) was measured at 60 rpm. As a control, the same measurement was performed on the cationic starch used as a raw material for the urea phosphorylation reaction. Table 1 shows the measured bound phosphorus, carbamate group, and B-type viscosity.
[0021]
[Table 1]
Example 2
In the cationization reaction, amphoteric starch was produced according to the method of Example 1 except that the cationizing agent was 6.5% starch and NaOH was 3.2% starch. The degree of substitution of quaternary ammonium salts of the obtained cationized starch and amphoteric starch, bound phosphorus, carbamate group, and B-type viscosity were measured in the same manner as in Example 1. The results are shown in Table 2.
[0023]
[Table 2]
Example 3
1,000 g of tapioca starch was dissolved in 1,500 ml of water, and NaOH was added to starch 2.5% and Na 2 SO 4 to 9.0% starch. To the starch slurry maintained at 45 ° C., 4.0% of a tertiary amine-introducing agent diethylaminoethyl chloride hydrochloride as a cationizing agent was added to starch, and then the cationization reaction was performed with stirring for 4 hours. The reaction was stopped by lowering the starch slurry to pH 4.0 with 10% HCl, and the following attempted to produce amphoteric starch as in Example 1 above. The combined phosphorus, carbamic acid ester group and B-type viscosity of the obtained cationic starch and amphoteric starch were measured in the same manner as in Example 1. The results are shown in Table 3.
[0025]
[Table 3]
Comparative Example 1
In this section, in order to compare the performance as amphoteric starch for internal addition with the amphoteric starch obtained in Example 1 or Example 2, phosphorylation using tripolyphosphate in accordance with the method of JP-A-63-48301 The reaction was applied to cationic starch to produce amphoteric starch.
500 g of the cationic starch obtained in Example 1 was weighed, dissolved in 800 ml of water containing 30 g of sodium tripolyphosphate, and adjusted to pH 6.5 with 10% HCl. The slurry was stirred for 2 hours and then filtered. The filter cake was dried in a hot air circulating dryer, and the water content was adjusted to 4.0%. The obtained sodium tripolyphosphate-containing cationic starch was taken as a solid weight and 380 g was taken in an eggplant-shaped flask and subjected to phosphorylation by heating in an oil bath heated to 140 ° C. for 20 to 40 minutes. The bound phosphorus and B type viscosity of the amphoteric starch obtained were measured in the same manner as in Example 1. The results are shown in Table 4. Of course, the amphoteric starch obtained here has no carbamate groups.
[0027]
[Table 4]
Comparative Example 2
Using the cationic starch obtained in Example 3, an attempt was made to produce amphoteric starch in the same manner as in Comparative Example 1 above. The degree of tertiary amine substitution, bound phosphorus and B type viscosity of the obtained amphoteric starch were measured in the same manner as in Example 1. The results are shown in Table 5. The amphoteric starch obtained here also has no carbamate group.
[0029]
[Table 5]
Papermaking Examples Amphoteric starches obtained in Examples 1 to 3 and Comparative Examples 1 and 2, cationic starches used as raw materials for these amphoteric starches (representative examples of cationic starches for internal addition), and commercially available products Paper making tests were conducted using amphoteric starch. The materials, equipment, test contents and test methods used are as follows. In addition, the alphabetical symbol and number of the starch used for material correspond with the alphabetic symbol and the number of cationic starch of the amphoteric starch shown in Tables 1-5.
[0031]
A commercially available sheet-like LBKP was beaten with a Niagara beater and adjusted to 360 ml Canadian Standard Freeness.
All starches used were slurries with a solid content concentration of 2.0%, and gelatinized by heating at 95 ° C. for 30 minutes to prepare starch paste liquid.
[0033]
While stirring the pulp slurry adjusted to a solid content concentration of 2.0%, the starch paste is 0.5, 1.0, or 2.0% per pulp solid content as a solid content, and the sizing agent is 0 as a solid content. .15%, and 3.0% with a sulfate band as a solid, were sequentially added, and then diluted with water to 1.0%. The prepared stock was made with a square sheet machine so that the basis weight was 80 g / m 2 . As a blank, hand-made paper without adding only starch was also made. The wet sheet was pressed with an automatic sheet press at 3.5 kgf / cm 2 for 2 minutes, the filter paper was changed and subsequently pressed with 3.5 kgf / cm 2 for 1 minute, and then at 103 ° C. for 2 minutes using a rotary dryer. After drying for minutes, 20 ° C., 65% R.D. H. Conditioned overnight.
[0034]
The drainage of the prepared stock and the physical properties of the handmade paper were measured by the following methods.
Freeness was measured according to JIS P 8121. (The higher the value, the better the drainage.)
Basis weight Measured according to JIS P 8124.
Breaking length Measured according to JIS P8113.
Specific burst strength Measured according to JIS P8112.
The obtained results are shown in Tables 6 and 7.
[0035]
[Table 6]
[Table 7]
The amphoteric starches B to J according to the present invention were remarkably higher than the cationic starches 1 to 3, and the drainage was considerably improved as compared with the amphoteric starch ad not based on the present invention and the commercially available amphoteric starch “Cato3210”. Therefore, if the amount of starch to be internally added is the same, there is no doubt that if the amphoteric starch according to the present invention is used, an improvement in the paper making speed can be achieved as compared with conventional cationic starch or amphoteric starch.
[0038]
Moreover, since it becomes possible to raise the addition rate of starch according to the improvement of drainage, improvement in paper strength can be expected as compared with conventional cationic starches and amphoteric starches, which have limitations on the addition rate of starch.
In addition, since amphoteric starch A does not reach the scope of the present invention with bound phosphorus, a sufficient drainage improvement effect is not obtained.
[0039]
【The invention's effect】
When the amphoteric starch obtained by the method of the present invention is heat-gelatinized and internally added to a paper stock and made into paper, paper or paperboard with significantly improved drainage and increased strength can be obtained. Even when the starch addition rate reaches 2.0%, no decrease in drainage is observed, and therefore paper or paperboard with higher strength can be produced without lowering the papermaking speed.
[0040]
The effect of the present invention, that is, the mechanism for significantly improving the drainage compared with the conventional amphoteric starch (the one obtained by phosphorylating cationic starch based on JP-A-63-48301 with tripolyphosphate) is not clear. , Formation of hydrogen bonds between the carbamate ester introduced together with the phosphate group and cellulose, which is the main component of the pulp, easy penetration into starch granules due to the lower molecular weight of orthophosphate compared to tripolyphosphate (phosphoric acid) More uniform distribution of groups), higher solubility of orthophosphate than tripolyphosphate, and no precipitation during drying or heating reaction (more uniform distribution of phosphate groups and higher reaction efficiency), The adverse effect of unreacted salt may be due to the smaller amount of orthophosphoric acid having a lower molecular weight.
[0041]
Another effect of the present invention is that amphoteric starch can be provided at a relatively low cost because alkalis such as urea, orthophosphoric acid, and sodium hydroxide used for urea phosphorylation are less expensive than tripolyphosphoric acid.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19105599A JP3608650B2 (en) | 1999-07-05 | 1999-07-05 | Amphoteric starch, method for producing the same and method for producing paper or paperboard |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19105599A JP3608650B2 (en) | 1999-07-05 | 1999-07-05 | Amphoteric starch, method for producing the same and method for producing paper or paperboard |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001019701A JP2001019701A (en) | 2001-01-23 |
| JP3608650B2 true JP3608650B2 (en) | 2005-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP19105599A Expired - Lifetime JP3608650B2 (en) | 1999-07-05 | 1999-07-05 | Amphoteric starch, method for producing the same and method for producing paper or paperboard |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2833599B1 (en) * | 2001-12-18 | 2004-01-30 | Oreal | AMPHOTERIC POLYSACCHARIDE, COMPOSITION AND USE |
| JP3921096B2 (en) * | 2002-02-13 | 2007-05-30 | 王子コーンスターチ株式会社 | Surface-sized press paper using low-viscosity amphoteric starch |
| JP4794224B2 (en) * | 2005-06-27 | 2011-10-19 | 日本エヌエスシー株式会社 | Formulation for gelatinized paper strength enhancer, gelatinized paper strength enhancer, and papermaking method |
| JP7378198B2 (en) * | 2017-05-15 | 2023-11-13 | 大王製紙株式会社 | Cellulose fine fiber and its manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62116602A (en) * | 1985-11-18 | 1987-05-28 | Sanwa Denpun Kogyo Kk | Production of urea-phosphate starch |
| JPS6348301A (en) * | 1986-08-13 | 1988-03-01 | ナシヨナル・スターチ・アンド・ケミカル・インベストメント・ホルデイング・コーポレイシヨン | Improved amphoteric starches and manufacture |
| JPH08296193A (en) * | 1995-04-25 | 1996-11-12 | Nippon Shokuhin Kako Co Ltd | Production of paper board |
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1999
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| JP2001019701A (en) | 2001-01-23 |
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