JP4629833B2 - Interlayer adhesive for fiber sheet and paper making method - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、繊維シート状物の澱粉による処理方法に関するものであり、より詳しくは、優れた接着性能を有する層間接着剤及びその層間接着剤を用いた抄紙方法に関する。
【０００２】
【従来の技術】
現在、繊維シート状物の層間接着剤や紙力増強剤として、澱粉が多用されている。澱粉は再生可能な天然物であり、近年、環境問題等の観点からますますその重要性が増している。
一般に、繊維シート状物を層間接着するには、スプレー法と呼ばれる方法が用いられている。そのスプレー法は、抄紙機等を用いて湿潤状態にある繊維シート状物を抄造した後、この繊維シート状物の少なくとも一面に澱粉スラリー又は糊化液をスプレーし、加熱、乾燥するという工程からなっている。
【０００３】
従来、繊維シート状物の層間接着剤として、澱粉スラリーをスプレーして使用する場合、未加工の澱粉が使用されてきた。しかしながら、一般的に未加工澱粉は、糊化開始温度が高く、近年の高速抄紙機では、スプレーされた澱粉が乾燥工程において十分に糊化せず、製品の層間接着強度が所望のレベルに達しない等のトラブルが発生している。この問題を解決するため、澱粉を化学的に変性し、糊化開始温度を低くした化工澱粉が用いられている。その方法も様々で、尿素リン酸エステル澱粉（特開平３−９０６９５号公報）、ジカルボン酸エステル澱粉（特開平５−１０６１９２号公報）、ヒドロキシプロピルエーテル澱粉等を用いる方法が提案されている。
【０００４】
一方、優れた接着性能を有する澱粉を開発するために、多大な努力が払われてきている。前述のような澱粉を化学的に変性する方法も、抄紙機の乾燥工程において澱粉粒が糊化しやすく、安定した接着性能を得やすいという観点からみれば、優れた方法の一つである。一方で、澱粉を加熱膨潤させてスプレーする方法も種々提案されている。加熱糊化した架橋澱粉を用いる方法（特公昭５２−１７１２５号公報）、半糊化したカチオン澱粉を用いる方法（特公昭５３−７５２３号公報）、未加工澱粉を糊化温度以下で加熱しスプレーする方法（特開昭５２−１１１２号公報）等、様々である。一般的に、繊維シート状物の層間接着を最大限に発揮させるには、繊維シート状物の層間にスプレーされた澱粉が膨潤状態にとどまるようにするのがよいとされている。これらの方法も、優れた接着性能を発揮させることに関しては有利な方法であるといえる。
【０００５】
【発明が解決しようとする課題】
しかし、前述したような従来の技術で用いられている澱粉にも様々な欠点がある。一つには、化学的に変性した化工澱粉は、単に糊化開始温度を低めただけであることである。つまり、繊維シート状物の乾燥温度に合わせて、所望の糊化開始温度になるような化工澱粉を選定し、繊維シート状物の層間にスプレーして用いた場合でさえも、澱粉粒が加熱膨潤し膨潤粒が保持された状態にとどまっているものもあれば、膨潤粒が完全に破裂し、いわゆる、完全糊化した状態のものが混在しているというのが現状である。このような状態にある場合、繊維シート状物の層間接着剤として、澱粉を使用した時、澱粉の能力を完全に引き出しているとはいい難い。そのため、製紙会社では、層間接着強度を上げるための方法として、澱粉添加量を上げて対応するのが現状であった。
【０００６】
一方、優れた接着性能を得るために澱粉を膨潤状態に保持しようとする場合、従来の方法においては、予め澱粉粒を加熱膨潤させてスプレーする方法が採られている。しかしながら、加熱しなければならないため、装置的にも大がかりなものとなり、また、作業的にも大きな負担がかかる。また、加熱糊化しすぎた場合には、澱粉の能力を完全に発揮しているとはいい難いし、澱粉の可溶成分の増大から排水中に糊剤が流出し、排水負荷の増大となる等、膨潤状態を一定の水準に制御することは非常に難しい。
本発明は、前記のスプレー用澱粉の欠点を克服し、かつ優れた接着性能を有する層間接着剤及びそれを用いた抄紙方法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
前述した状況を踏まえて、本発明者らは、繊維シート状物に澱粉をスプレー処理するにあたり、澱粉を繊維シート状物にスプレーする以前の工程において、澱粉を加熱する必要がなく、また、澱粉を繊維シート状物に添加後の加熱、乾燥工程において、容易に加熱膨潤し、かつ、一定の膨潤状態を保持できる澱粉を開発すべく、鋭意研究を重ねた結果、本発明を完成するに至った。
【０００８】
即ち、本発明は以下の内容を包含する。
（１）架橋処理及び糊化開始温度を低下させる変性が施されている澱粉誘導体を含む、繊維シート状物の層間接着剤。
（２）澱粉誘導体が、１重量％濃度の澱粉スラリーを９５℃で２０分間加熱し、室温まで冷却した後、その糊化液１００ｍｌをメスシリンダーに投入し、２４時間静置後に測定したときの糊化液の沈降量が５〜９５ｍｌであり、架橋処理及び糊化開始温度を低下させる変性を施す前の澱粉に比し、アミログラフ法による糊化開始温度が２〜４０℃低い澱粉誘導体である前記（１）に記載の層間接着剤。
【０００９】
（３）澱粉誘導体が、１重量％濃度の澱粉スラリーを９５℃で２０分間加熱し、室温まで冷却した後、その糊化液１００ｍｌをメスシリンダーに投入し、２４時間静置後に測定したときの糊化液の沈降量が５〜９５ｍｌであり、アミログラフ法による糊化開始温度が３０〜６８℃である澱粉誘導体である前記（１）に記載の層間接着剤。
（４）前記（１）〜（３）のいずれかに記載の層間接着剤を繊維シート状物の少なくとも一面にスプレーする繊維シート状物の抄紙方法。
【００１０】
【発明の実施の形態】
本発明は、澱粉に、架橋処理とともに、糊化開始温度を低下させる変性を施すことを特徴とする。架橋処理を施すことで、澱粉粒が加熱膨潤した場合、膨潤粒は完全に破裂することはなく、膨潤粒を一定の水準に制御することが可能となる。また、一般に、澱粉に架橋処理を施すと、糊化開始温度を高めることになるが、この点を解消するために、糊化開始温度を低下させる変性を行う。架橋処理と糊化開始温度を低下させる変性を行う順序はどちらでもよく、何ら制限されるものではない。
【００１１】
本発明において原料として用いる澱粉は、特に制限はなく、一般に使用されている澱粉はいずれも使用でき、例えばコーンスターチ、米澱粉、小麦澱粉、甘藷澱粉、馬鈴薯澱粉、タピオカ澱粉が挙げられ、また、これらの澱粉のうち、２種類以上を組合せて使用してもよいし、本発明の目的を妨げないものであれば、化学的、物理的又は酵素的な化工を軽度に施してもよい。
【００１２】
本発明においては架橋処理による糊化開始温度の上昇を解消するために、糊化開始温度を低下させる変性を行う。本発明における糊化開始温度は、通常用いられているアミログラフ法による粘度図で説明することができる。図１は、澱粉スラリーを２５℃から９５℃まで昇温させ、９５℃で保持したときの澱粉の糊化に伴う粘度変化を示したものである。澱粉スラリーを徐々に加熱していく過程において、澱粉はある温度になると、澱粉が糊化することによる粘度上昇が生じる。本発明における糊化開始温度とは、この粘度上昇が開始した温度と定義することとする。
【００１３】
糊化開始温度を低下させる変性を行う方法としては、特に制限はなく、例えば酸化、酸処理化、尿素リン酸エステル化、リン酸エステル化、アセチル化、ヒドロキシプロピルエーテル化、カルボキシメチルエーテル化等が挙げられる。
【００１４】
これらの変性方法は、公知の方法を用いることができる。例えば、酸化は、澱粉スラリーにアルカリ触媒の存在下、次亜塩素酸ナトリウムを所定の温度にて反応させる方法、酸処理化は、澱粉スラリーに鉱酸等を添加し、所定の温度にて反応させる方法、尿素リン酸エステル化は、澱粉をリン酸又はリン酸塩及び尿素と混合し、加熱焙焼する乾式反応による方法、リン酸エステル化は、澱粉をリン酸塩と混合し、加熱焙焼する乾式反応による方法、アセチル化は、澱粉スラリーにアルカリ触媒の存在下、酢酸ビニルを所定の温度にて反応させる方法、ヒドロキシプロピルエーテル化は、澱粉スラリーにアルカリ触媒の存在下、プロピレンオキシドを所定の温度にて反応させる方法、カルボキシメチルエーテル化は、澱粉スラリーにアルカリ触媒の存在下、モノクロロ酢酸ナトリウムを所定の温度にて反応させる方法（以上、例えば、MODIFIED STARCHES: PROPERTIES and USES, O.B. Wurzburg）により行うことができる。
【００１５】
糊化開始温度低下の程度は、架橋処理及び糊化開始温度を低下させる変性を施した澱粉誘導体のアミログラフ法による糊化開始温度が、架橋処理及び糊化開始温度を低下させる変性を施す前の未化工澱粉のアミログラフ法による糊化開始温度と比較して、通常２〜４０℃、好ましくは５〜３０℃低下するように調整する。例えば、原料澱粉としてコーンスターチを用いた場合、コーンスターチの糊化開始温度は７０℃であるので、前記澱粉誘導体の糊化開始温度が３０〜６８℃、好ましくは４０〜６５℃になるように調整する。また、糊化開始温度を低下させる変性方法を選択する場合にも、糊化開始温度の低下温度が前記範囲内であり、かつ、前記澱粉誘導体が所望の糊化開始温度になるように適宜選択することが好ましい。
【００１６】
架橋処理及び糊化開始温度を低下させる変性を施した澱粉誘導体のアミログラフ法による糊化開始温度は、通常３０〜６８℃、好ましくは４０〜６５℃である。
本発明においては、澱粉粒が加熱膨潤したときに、膨潤粒の破裂を抑制し、膨潤粒を一定の水準に制御するために、架橋処理を施す。
【００１７】
架橋処理に用いられる架橋剤としては、オキシ塩化リン、グリオキサール、エピクロロヒドリン、ホルムアルデヒド、又はトリメタリン酸塩、ヘキサメタリン酸塩等のリン酸塩などの通常使用されているものを用いることができる。前記架橋剤による架橋の程度は、得られた架橋澱粉の糊化液の沈降量によって定義することができる。その測定方法は、１重量％の濃度に調製した架橋澱粉スラリーを９５℃で２０分間加熱し、室温まで冷却した後、その糊化液１００ｍｌを同じ容量のメスシリンダーに投入し、２４時間静置後の糊化液の沈降量をｍｌ単位で測定するものである。一般的に澱粉粒は、加熱すると、水を澱粉粒内に取り込み、膨潤を開始する。更に加熱を続けると膨潤粒は破裂するが、架橋澱粉においてはこの膨潤した澱粉粒の膨潤又は破裂の程度が制御されている。架橋の程度が低い澱粉の場合、澱粉粒は大きく膨潤し、又は、破裂状態に近い粒が多くなる。この場合、糊化液沈降量は多くなる。ただし、沈降量が９５ｍｌを超える場合は、破裂する澱粉粒の割合が多くなり本発明には適さない。一方、架橋の程度が高い澱粉の場合、澱粉粒の膨潤は比較的小さく、糊化液沈降量は少ない。ただし、沈降量が５ｍｌ未満の場合は、膨潤しない粒の割合が多くなり本発明には適さない。従って、本発明で使用する架橋澱粉の架橋の程度は、前記糊化液沈降量が５〜９５ｍｌの範囲内であることが好ましい。
【００１８】
以上のように、澱粉に、架橋処理、及び糊化開始温度を低下させる変性を施すことによって、所望の糊化開始温度を有し、膨潤粒が一定の水準に制御され、優れた接着性能を有する澱粉を得ることができる。
本発明の層間接着剤は、前記澱粉誘導体を含むものであるが、その他に、本発明の目的を妨げないものであれば如何なる添加剤を含んでもよい。
【００１９】
例えば、前記澱粉誘導体以外の澱粉類を適宜混合してもよいし、澱粉以外の高分子化合物として、ポリビニルアルコール（ＰＶＡ）、ポリアクリルアミド、ラテックス、アクリル樹脂、酢酸ビニル樹脂、ウレタン樹脂、ポリアミド樹脂等を適宜混合してもよい。また、硼砂、尿素、苛性ソーダ、炭酸ソーダ、リン酸ソーダ、硫酸アルミニウム等を適宜混合してもよい。
【００２０】
更に、本発明における澱粉スラリーは、サイズ剤、撥水剤、耐水化剤、充填剤等を含んでもよい。例えば、サイズ剤及び撥水剤として、ロジン、石油樹脂を主体とするサイズ剤、脂肪酸誘導体、アルキルケテンダイマー、スチレン−無水マレイン酸共重合体、ワックスエマルジョン、シリコーン樹脂、ポリエチレンワックス、アクリル酸エステル共重合体等がある。耐水化剤として、尿素、メラミン、ケトン、グアナミン又はプロピレン尿素とホルムアルデヒドとの初期反応物又は縮合物、メチロール基を有するポリアミド、アクリル酸アミド等がある。充填剤として、クレー、カオリン、タルク、炭酸カルシウム、水酸化アルミニウム、酸化チタン、サチンホワイト等の白色顔料、着色顔料がある。
【００２１】
また、着色剤として、蛍光染料、着色染料を添加することができる。更に必要に応じて、歩留まり向上剤、濾水性向上剤、防滑剤、スリップ防止剤、消泡剤、防腐剤、防カビ剤等を適宜添加することもできる。
前記の添加剤の添加量は、添加剤の種類によって大きく異なるが、原料澱粉に対して３０重量％までとするのが好ましく、より好ましくは、０．０００１〜２０重量％である。
【００２２】
本発明に用いる層間接着剤は、通常当該分野で使用される接着剤と同様に使用される。即ち、例えば接着剤を水中に懸濁させてスラリー化し、スプレーノズル等によりスプレーし、その後、乾燥工程で加熱して接着するなど一般的なスプレー式層間接着に本発明は適用できる。接着剤は繊維シート状物に対し、０．０１〜１０ｇ／ｍ2になるように添加するのが好ましい。また、接着剤スラリーの濃度は０．０１〜５重量％であり、乾燥工程での加熱条件も従来の、乾燥温度５０〜１３０℃などの操業条件が利用できる。
【００２３】
本発明において適用される繊維シート状物は、抄造によって繊維質原料より製造されるシート状物品、即ち、紙、板紙、不織布、インシュレーションボード、ハードボード、パーティクルボード及びロックウールボード類等である。これらの繊維シート状物は、広葉樹パルプ、針葉樹パルプ、その他ケミカルパルプ、破砕木材、綿等のような植物繊維、羊毛その他の動物繊維、ＰＶＡ、ウレタン等の合成繊維、アセテート及びレーヨン等の再生繊維、ガラス繊維、岩綿、石綿等の無機繊維等の１種類又は２種類以上の繊維質原料を水中に懸濁し、この懸濁液から、長網抄紙機、短網抄紙機、円網抄紙機、又はその他の特殊抄紙機を用いてシート状物を抄造し、これを脱水、乾燥することによって得られるものである。
【００２４】
【実施例】
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下において、糊化液の沈降量及び糊化開始温度の測定は次のようにして行った。
（糊化液の沈降量）
１重量％の濃度に調製した層間接着剤スラリーを９５℃で２０分間加熱し、室温まで冷却した後、その糊化液１００ｍｌを同じ容量のメスシリンダーに投入し、２４時間静置後の糊化液の沈降量をｍｌ単位で測定した。
【００２５】
（糊化開始温度）
糊化開始温度はアミログラフ法（澱粉糖関連工業分析法ｐ.４９−５１、澱粉糖技術部会編、（株）食品化学新聞社）にて測定した。測定には、ブラベンダー社の粘度計を用いた。層間接着剤スラリーを１５重量％の濃度に調製し、昇温速度１．５℃／分とし、粘度上昇が開始した温度を糊化開始温度とした。
【００２６】
（実施例１）
濃度３８重量％のコーンスターチのスラリーを、撹拌下、３８℃の温度にし、３％水酸化ナトリウム水溶液でｐＨを１１．２〜１１．５に調整した。このｐＨの範囲を維持しながら、エピクロロヒドリンを対澱粉０．５重量％添加し、１４時間反応した。反応後、塩酸にてｐＨ４．５に調整し、脱水、洗浄後、再び濃度３８重量％のスラリーとした。そのスラリーにリン酸を対澱粉９．０重量％、尿素を対澱粉２５重量％添加し、よく混合した後、脱水した。この脱水ケーキを熱風乾燥機にて水分５％以下まで予備乾燥し、次いで、熱風式加熱機にて１４０℃で１０分間焙焼した。焙焼後、冷却した後、水分９％に調湿し、試作品Ａを得た。試作品Ａについて糊化液の沈降量及び糊化開始温度を測定し、結果を表１に示した。
【００２７】
（実施例２）
濃度３８重量％のコーンスターチのスラリーを、撹拌下、３８℃の温度にし、３％水酸化ナトリウム水溶液でｐＨを１１．２〜１１．５に調整した。このｐＨの範囲を維持しながら、エピクロロヒドリンを対澱粉０．２５重量％添加し、１４時間反応した。反応後、塩酸にてｐＨ４．５に調整し、脱水、洗浄後、再び濃度３８重量％のスラリーとした。そのスラリーにリン酸を対澱粉９．０重量％、尿素を対澱粉２５重量％添加し、よく混合した後、脱水した。この脱水ケーキを熱風乾燥機にて水分５％以下まで予備乾燥し、次いで、熱風式加熱機にて１４０℃で１０分間焙焼した。焙焼後、冷却した後、水分９％に調湿し、試作品Ｂを得た。試作品Ｂについて糊化液の沈降量及び糊化開始温度を測定し、結果を表１に示した。
【００２８】
（実施例３）
濃度３８重量％のコーンスターチのスラリーを、撹拌下、２７℃の温度にし、３％水酸化ナトリウム水溶液でｐＨを１０〜１１に調整した。このｐＨの範囲を維持しながら、オキシ塩化リンを対澱粉０．６重量％添加し、１時間反応した。反応後、塩酸にてｐＨ４．５に調整し、脱水、洗浄後、再び濃度３８重量％のスラリーとした。そのスラリーにリン酸を対澱粉９．０重量％、尿素を対澱粉２５重量％添加し、よく混合した後、脱水した。この脱水ケーキを熱風乾燥機にて水分５％以下まで予備乾燥し、次いで、熱風式加熱機にて１４０℃で１０分間焙焼した。焙焼後、冷却した後、水分９％に調湿し、試作品Ｃを得た。試作品Ｃについて糊化液の沈降量及び糊化開始温度を測定し、結果を表１に示した。
【００２９】
（実施例４）
濃度３８重量％のコーンスターチのスラリーを、撹拌下、３８℃の温度にし、３％水酸化ナトリウム水溶液でｐＨを１０〜１１に調整した。このｐＨの範囲を維持しながら、トリメタリン酸ナトリウムを対澱粉４．５重量％添加し、８時間反応した。反応後、塩酸にてｐＨ４．５に調整し、脱水、洗浄後、再び濃度３８重量％のスラリーとした。そのスラリーにリン酸を対澱粉９．０重量％、尿素を対澱粉２５重量％添加し、よく混合した後、脱水した。この脱水ケーキを熱風乾燥機にて水分５％以下まで予備乾燥し、次いで、熱風式加熱機にて１４０℃で１０分間焙焼した。焙焼後、冷却した後、水分９％に調湿し、試作品Ｄを得た。試作品Ｄについて糊化液の沈降量及び糊化開始温度を測定し、結果を表１に示した。
【００３０】
（実施例５）
実施例１で得た試作品Ａ９重量部と、充填剤としてタルク１重量部とを混合し、試作品Ｅを得た。試作品Ｅについて糊化液の沈降量及び糊化開始温度を測定し、結果を表１に示した。
【００３１】
（比較例１）
本比較例では、市販品の未加工のコーンスターチを使用した。当該品について糊化開始温度を測定し（測定濃度８重量％）、結果を表１に示した。
（比較例２）
本比較例では、市販品の尿素リン酸エステル化コーンスターチを使用した。当該品について糊化開始温度を測定し、結果を表１に示した。
【００３２】
（試作品の評価）
実施例及び比較例で示した試作品について、繊維シート状物の層間接着剤としての評価を以下のようにして行った。
０．５重量％古紙パルプスラリーを撹拌しながら、希硫酸にてｐＨ６．０に調整し、硫酸バンド（硫酸アルミニウム）を対パルプ１．５重量％、次いで、ロジンサイズ剤を対パルプ０．１重量％添加した。水を加え、０．３重量％のパルプスラリーとした後、紙の坪量が５０ｇ／ｍ2になるようにパルプスラリーを採取し、丸形シートマシン（熊谷理機工業（株）製）にて２枚抄紙した。１枚の湿紙に層間接着剤添加量が１．０ｇ／ｍ2になるように、１重量％層間接着剤スラリー２ｍｌをスプレー添加し、もう１枚の湿紙を重ね合わせた。シートマシン用プレス機（熊谷理機工業（株）製）にて、９８ｋＰａ、３０秒間プレスし、直ちに回転式乾燥機（熊谷理機工業（株）製）にて乾燥機表面温度８０℃で３分間乾燥した。乾燥した紙を調湿（温度２３℃、湿度５０％ＲＨ）した後、層間接着強度をインターナルボンドテスター（熊谷理機工業（株）製）で測定し、２層間の層間接着強度とした。
【００３３】
表１に試作品Ａ〜Ｅ及び比較例の層間接着強度を示した。糊化開始温度が４５℃である実施例１〜５の試作品Ａ〜Ｅ及び比較例２の尿素リン酸エステル化コーンスターチは、容易に糊化することができるが、試作品Ａ〜Ｅは、澱粉が膨潤状態を保持しているため、尿素リン酸エステル化コーンスターチよりも優れた層間接着強度を示している。また、比較例１のコーンスターチは糊化開始温度が７０℃であるため、容易に糊化することができず、優れた層間接着強度が得られない。
【００３４】
【表１】
【発明の効果】
本発明によれば、繊維シート状物の層間接着剤として澱粉による処理を行うにあたり、澱粉を繊維シート状物にスプレーする以前の工程において、澱粉を加熱する必要がなく、また、澱粉を繊維シート状物に添加後の加熱、乾燥工程において、該澱粉が容易に加熱膨潤し、かつ、一定の膨潤状態を保持することができる。また、本発明の層間接着剤を繊維シート状物の層間接着剤として使用した時、従来の澱粉を使用した時と比較して、より優れた接着性能を得ることができることにより、使用量が削減できるため、経済的効果の向上が期待できる。
【図面の簡単な説明】
【図１】本発明における糊化開始温度を説明するための図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for treating fiber sheet material with starch, and more particularly to an interlayer adhesive having excellent adhesive performance and a papermaking method using the interlayer adhesive.
[0002]
[Prior art]
At present, starch is frequently used as an interlayer adhesive or a paper strength enhancer for fiber sheets. Starch is a renewable natural product, and its importance has been increasing in recent years from the viewpoint of environmental problems.
In general, a method called a spray method is used for interlaminar bonding of a fiber sheet. The spray method is a process of making a fiber sheet in a wet state using a paper machine and the like, spraying starch slurry or gelatinizing liquid on at least one surface of the fiber sheet, heating and drying. It has become.
[0003]
Conventionally, when starch slurry is sprayed and used as an interlayer adhesive of a fiber sheet material, raw starch has been used. However, in general, raw starch has a high gelatinization start temperature, and in recent high-speed paper machines, the sprayed starch does not sufficiently gelatinize in the drying process, and the interlayer adhesion strength of the product reaches a desired level. Troubles such as not having occurred. In order to solve this problem, modified starch in which starch is chemically modified and gelatinization start temperature is lowered is used. There are various methods, and methods using urea phosphate starch (Japanese Patent Laid-Open No. 3-90695), dicarboxylic acid ester starch (Japanese Patent Laid-Open No. 5-106192), hydroxypropyl ether starch, and the like have been proposed.
[0004]
On the other hand, great efforts have been made to develop starch having excellent adhesion performance. The method of chemically modifying starch as described above is one of excellent methods from the viewpoint that starch granules are easily gelatinized in the drying process of the paper machine and that stable adhesive performance is easily obtained. On the other hand, various methods for spraying starch by heating and swelling have been proposed. A method using a heat-gelatinized cross-linked starch (Japanese Patent Publication No. 52-17125), a method using a semi-gelatinized cationic starch (Japanese Patent Publication No. 53-7523), and heating and spraying raw starch below the gelatinization temperature. There are various methods such as Japanese Patent Application Laid-Open No. 52-1112. In general, in order to maximize the interlayer adhesion of the fiber sheet material, it is preferable that the starch sprayed between the layers of the fiber sheet material stays in a swollen state. These methods can also be said to be advantageous methods for exhibiting excellent adhesion performance.
[0005]
[Problems to be solved by the invention]
However, the starch used in the prior art as described above has various drawbacks. For one thing, chemically modified modified starch simply lowers the gelatinization start temperature. In other words, the starch starch is heated even when it is used by spraying between the layers of the fiber sheet material by selecting the modified starch so that the desired gelatinization start temperature is reached according to the drying temperature of the fiber sheet material. In the present situation, some swell and remain in a state where the swelled particles are retained, while other swelled particles are completely ruptured and so-called completely gelatinized materials are mixed. In such a state, when starch is used as an interlayer adhesive of the fiber sheet material, it is difficult to say that the ability of starch is completely drawn. For this reason, in the paper manufacturing companies, the current situation is to increase the amount of starch added as a method for increasing the interlayer adhesive strength.
[0006]
On the other hand, in order to maintain starch in a swollen state in order to obtain excellent adhesive performance, a conventional method employs a method in which starch granules are heated and swollen in advance and sprayed. However, since it has to be heated, it becomes a large scale in terms of apparatus, and a large burden is imposed on work. In addition, when it is heated and gelatinized too much, it is difficult to say that the ability of starch is fully exhibited, and the amount of starch soluble component increases, so that the glue flows out into the waste water, increasing the drainage load. It is very difficult to control the swelling state to a certain level.
An object of the present invention is to provide an interlayer adhesive that overcomes the disadvantages of the starch for spraying described above and has excellent adhesive performance, and a papermaking method using the same.
[0007]
[Means for Solving the Problems]
In light of the above-described situation, the present inventors do not need to heat starch in the step before spraying starch onto the fiber sheet when spraying starch onto the fiber sheet, As a result of intensive research to develop starch that can be easily heated and swelled in a heating and drying process after the addition of fiber sheet to maintain a certain swelling state, the present invention has been completed. It was.
[0008]
That is, the present invention includes the following contents.
(1) A fiber sheet-like interlayer adhesive comprising a starch derivative that has been subjected to a crosslinking treatment and a modification that lowers the gelatinization start temperature.
(2) The starch derivative is a starch slurry having a concentration of 1% by weight heated at 95 ° C. for 20 minutes and cooled to room temperature. Then, 100 ml of the gelatinized solution is put into a measuring cylinder and measured after standing for 24 hours. It is a starch derivative with a precipitating amount of the gelatinization liquid of 5 to 95 ml and a gelatinization start temperature by the amylograph method of 2 to 40 ° C. lower than the starch before the crosslinking treatment and the modification before reducing the gelatinization start temperature. The interlayer adhesive according to (1) above.
[0009]
(3) After starch starch having a starch derivative concentration of 1% by weight was heated at 95 ° C. for 20 minutes and cooled to room temperature, 100 ml of the gelatinized solution was put into a graduated cylinder and measured after standing for 24 hours. The interlayer adhesive according to the above (1), which is a starch derivative having a gelatinization liquid sedimentation amount of 5 to 95 ml and a gelatinization start temperature by amylograph method of 30 to 68 ° C.
(4) A method for making a fiber sheet, wherein the interlayer adhesive according to any one of (1) to (3) is sprayed on at least one surface of the fiber sheet.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is characterized in that the starch is modified with a crosslinking treatment to lower the gelatinization start temperature. By performing the crosslinking treatment, when the starch particles are heated and swollen, the swollen particles are not completely ruptured, and the swollen particles can be controlled to a certain level. In general, when starch is subjected to a crosslinking treatment, the gelatinization start temperature is increased. In order to eliminate this point, modification is performed to lower the gelatinization start temperature. The order of performing the crosslinking treatment and the modification for lowering the gelatinization start temperature may be either, and is not limited at all.
[0011]
The starch used as a raw material in the present invention is not particularly limited, and any commonly used starch can be used, and examples thereof include corn starch, rice starch, wheat starch, sweet potato starch, potato starch, and tapioca starch. Among these starches, two or more types may be used in combination, and chemical, physical or enzymatic modification may be mildly applied as long as the object of the present invention is not impaired.
[0012]
In the present invention, in order to eliminate the increase in the gelatinization start temperature due to the cross-linking treatment, a modification that lowers the gelatinization start temperature is performed. The gelatinization start temperature in the present invention can be explained by a viscosity diagram obtained by a commonly used amylograph method. FIG. 1 shows the change in viscosity associated with gelatinization of starch when the starch slurry is heated from 25 ° C. to 95 ° C. and held at 95 ° C. In the process of gradually heating the starch slurry, when the starch reaches a certain temperature, the viscosity increases due to the gelatinization of the starch. The gelatinization start temperature in the present invention is defined as the temperature at which this viscosity increase has started.
[0013]
There are no particular limitations on the method of modifying the gelatinization start temperature to be lowered. For example, oxidation, acid treatment, urea phosphate esterification, phosphate esterification, acetylation, hydroxypropyl etherification, carboxymethyl etherification, etc. Is mentioned.
[0014]
As these denaturing methods, known methods can be used. For example, oxidation is a method in which starch hypochlorite is reacted with sodium hypochlorite at a predetermined temperature in the presence of an alkali catalyst, and acid treatment is performed at a predetermined temperature by adding mineral acid or the like to the starch slurry. The method of making the urea phosphate esterification is a method by a dry reaction in which starch is mixed with phosphoric acid or phosphate and urea, followed by heating and baking. The phosphate esterification is a method in which starch is mixed with phosphate and heating and roasting. A method using a dry-type baking method, acetylation is a method in which vinyl acetate is reacted at a predetermined temperature in the presence of an alkali catalyst in the starch slurry, and hydroxypropyl etheration is a method in which propylene oxide is added to the starch slurry in the presence of an alkali catalyst. Carboxymethyl etherification is a method of reacting at a predetermined temperature. Sodium monochloroacetate is added to a starch slurry in the presence of an alkali catalyst at a predetermined temperature. How to respond (or, for example, MODIFIED STARCHES: PROPERTIES and USES, OB Wurzburg) can be carried out by.
[0015]
The degree of the gelatinization start temperature decrease is the degree before the gelatinization start temperature by the amylograph method of the starch derivative subjected to the modification that reduces the crosslinking treatment and the gelatinization start temperature is before the modification that reduces the crosslinking treatment and the gelatinization start temperature. Compared with the gelatinization start temperature of the unmodified starch by the amylograph method, the temperature is usually adjusted to 2 to 40 ° C., preferably 5 to 30 ° C. For example, when corn starch is used as the raw material starch, the gelatinization start temperature of corn starch is 70 ° C., and thus the gelatinization start temperature of the starch derivative is adjusted to 30 to 68 ° C., preferably 40 to 65 ° C. . In addition, when selecting a modification method that lowers the gelatinization start temperature, an appropriate selection is made so that the temperature at which the gelatinization start temperature falls is within the above range and the starch derivative has the desired gelatinization start temperature. It is preferable to do.
[0016]
The gelatinization start temperature by the amylograph method of the starch derivative which modified | denatured which reduces a crosslinking process and gelatinization start temperature is 30-68 degreeC normally, Preferably it is 40-65 degreeC.
In the present invention, when the starch granules are heated and swollen, a crosslinking treatment is applied in order to suppress the burst of the swollen grains and to control the swollen grains to a certain level.
[0017]
As the crosslinking agent used for the crosslinking treatment, those commonly used such as phosphorus oxychloride, glyoxal, epichlorohydrin, formaldehyde, or phosphates such as trimetaphosphate and hexametaphosphate can be used. The degree of crosslinking by the crosslinking agent can be defined by the amount of sedimentation of the gelatinized solution of the obtained crosslinked starch. The measurement method was as follows: a crosslinked starch slurry prepared to a concentration of 1% by weight was heated at 95 ° C. for 20 minutes and cooled to room temperature, and then 100 ml of the gelatinized solution was put into a graduated cylinder of the same volume and left for 24 hours. The amount of sedimentation of the subsequent gelatinization solution is measured in ml. In general, when starch granules are heated, they take water into the starch granules and start to swell. When the heating is further continued, the swollen grains are ruptured. In the crosslinked starch, the degree of swelling or rupture of the swollen starch grains is controlled. In the case of starch having a low degree of cross-linking, the starch granules swell greatly, or the grains close to the rupture state increase. In this case, the amount of gelatinized liquid settling increases. However, if the sedimentation amount exceeds 95 ml, the proportion of starch granules that burst is increased, which is not suitable for the present invention. On the other hand, in the case of starch having a high degree of cross-linking, the swelling of starch granules is relatively small and the amount of gelatinized solution settled is small. However, when the sedimentation amount is less than 5 ml, the ratio of the particles that do not swell is increased, which is not suitable for the present invention. Therefore, it is preferable that the degree of cross-linking of the cross-linked starch used in the present invention is such that the gelatinized liquid sedimentation amount is within a range of 5 to 95 ml.
[0018]
As described above, the starch is subjected to crosslinking treatment and modification to lower the gelatinization start temperature, thereby having a desired gelatinization start temperature, the swollen grains are controlled to a certain level, and excellent adhesion performance. The starch which has can be obtained.
The interlayer adhesive of the present invention contains the starch derivative, but may contain any other additive as long as it does not interfere with the object of the present invention.
[0019]
For example, starches other than the starch derivative may be mixed as appropriate, and as a polymer compound other than starch, polyvinyl alcohol (PVA), polyacrylamide, latex, acrylic resin, vinyl acetate resin, urethane resin, polyamide resin, etc. May be mixed as appropriate. Further, borax, urea, caustic soda, sodium carbonate, sodium phosphate, aluminum sulfate and the like may be mixed as appropriate.
[0020]
Furthermore, the starch slurry in the present invention may contain a sizing agent, a water repellent, a water resistant agent, a filler and the like. For example, as sizing agent and water repellent agent, sizing agent mainly composed of rosin, petroleum resin, fatty acid derivative, alkyl ketene dimer, styrene-maleic anhydride copolymer, wax emulsion, silicone resin, polyethylene wax, acrylic acid ester copolymer There are polymers and the like. Examples of water-proofing agents include urea, melamine, ketone, guanamine, or an initial reaction product or condensate of propylene urea and formaldehyde, polyamide having a methylol group, acrylic acid amide, and the like. Examples of the filler include white pigments and colored pigments such as clay, kaolin, talc, calcium carbonate, aluminum hydroxide, titanium oxide, and satin white.
[0021]
Moreover, fluorescent dyes and colored dyes can be added as colorants. Furthermore, a yield improver, a drainage improver, an anti-slip agent, an anti-slip agent, an antifoaming agent, an antiseptic, an antifungal agent and the like can be added as necessary.
The amount of the additive added varies greatly depending on the type of additive, but is preferably up to 30% by weight, more preferably 0.0001 to 20% by weight, based on the raw material starch.
[0022]
The interlayer adhesive used in the present invention is usually used in the same manner as the adhesive used in this field. That is, for example, the present invention can be applied to general spray-type interlayer adhesion in which an adhesive is suspended in water to form a slurry, sprayed by a spray nozzle or the like, and then heated and bonded in a drying process. The adhesive is preferably added so as to be 0.01 to 10 g / m 2 with respect to the fiber sheet. Moreover, the density | concentration of an adhesive slurry is 0.01 to 5 weight%, Operation conditions, such as the conventional drying temperature 50-130 degreeC, can be utilized also for the heating conditions in a drying process.
[0023]
The fiber sheet material applied in the present invention is a sheet-like article manufactured from a fiber raw material by papermaking, that is, paper, paperboard, nonwoven fabric, insulation board, hard board, particle board, rock wool board, and the like. . These fiber sheets are made of hardwood pulp, softwood pulp, other chemical pulp, crushed wood, cotton and other plant fibers, wool and other animal fibers, PVA, urethane and other synthetic fibers, acetate and rayon and other regenerated fibers. , One or more fiber raw materials such as glass fiber, rock wool, asbestos, etc. are suspended in water, and from this suspension, long paper machine, short paper machine, circular paper machine Or, it is obtained by making a sheet using a special paper machine, and dehydrating and drying the sheet.
[0024]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples. In the following description, the amount of gelatinization liquid and the gelatinization start temperature were measured as follows.
(Settling amount of gelatinized solution)
The interlayer adhesive slurry prepared to a concentration of 1% by weight is heated at 95 ° C. for 20 minutes and cooled to room temperature, and then 100 ml of the gelatinized solution is put into a graduated cylinder of the same volume and gelatinized after standing for 24 hours. The amount of sedimentation of the liquid was measured in ml.
[0025]
(Beginning temperature)
The gelatinization start temperature was measured by an amylograph method (starch sugar related industrial analysis method p.49-51, edited by Starch Sugar Technical Committee, Food Chemical Newspaper Co., Ltd.). A Brabender viscometer was used for the measurement. The interlayer adhesive slurry was prepared to a concentration of 15% by weight, the temperature increase rate was 1.5 ° C./min, and the temperature at which the viscosity increase started was defined as the gelatinization start temperature.
[0026]
Example 1
The slurry of corn starch having a concentration of 38% by weight was brought to a temperature of 38 ° C. with stirring, and the pH was adjusted to 11.2 to 11.5 with a 3% aqueous sodium hydroxide solution. While maintaining this pH range, epichlorohydrin was added at 0.5% by weight to starch and reacted for 14 hours. After the reaction, the pH was adjusted to 4.5 with hydrochloric acid, and after dehydration and washing, a slurry with a concentration of 38% by weight was obtained again. To the slurry, 9.0% by weight of phosphoric acid with respect to starch and 25% by weight of urea with respect to starch were added, mixed well, and dehydrated. This dehydrated cake was pre-dried to a moisture content of 5% or less with a hot air dryer, and then roasted at 140 ° C. for 10 minutes with a hot air heater. After roasting and cooling, the moisture was adjusted to 9% to obtain prototype A. For Prototype A, the amount of gelatinization and the gelatinization start temperature were measured, and the results are shown in Table 1.
[0027]
(Example 2)
The slurry of corn starch having a concentration of 38% by weight was brought to a temperature of 38 ° C. with stirring, and the pH was adjusted to 11.2 to 11.5 with a 3% aqueous sodium hydroxide solution. While maintaining this pH range, 0.25% by weight of epichlorohydrin was added to the starch and reacted for 14 hours. After the reaction, the pH was adjusted to 4.5 with hydrochloric acid, and after dehydration and washing, a slurry with a concentration of 38% by weight was obtained again. To the slurry, 9.0% by weight of phosphoric acid with respect to starch and 25% by weight of urea with respect to starch were added, mixed well, and dehydrated. This dehydrated cake was pre-dried to a moisture content of 5% or less with a hot air dryer, and then roasted at 140 ° C. for 10 minutes with a hot air heater. After roasting and cooling, the humidity was adjusted to 9% to obtain prototype B. For prototype B, the sedimentation amount of the gelatinization solution and the gelatinization start temperature were measured, and the results are shown in Table 1.
[0028]
(Example 3)
The corn starch slurry having a concentration of 38% by weight was brought to a temperature of 27 ° C. with stirring, and the pH was adjusted to 10 to 11 with a 3% aqueous sodium hydroxide solution. While maintaining this pH range, 0.6% by weight of phosphorus oxychloride was added to the starch and reacted for 1 hour. After the reaction, the pH was adjusted to 4.5 with hydrochloric acid, and after dehydration and washing, a slurry with a concentration of 38% by weight was obtained again. To the slurry, 9.0% by weight of phosphoric acid with respect to starch and 25% by weight of urea with respect to starch were added, mixed well, and dehydrated. This dehydrated cake was pre-dried to a moisture content of 5% or less with a hot air dryer, and then roasted at 140 ° C. for 10 minutes with a hot air heater. After roasting and cooling, the moisture was adjusted to 9% to obtain prototype C. For prototype C, the sedimentation amount of the gelatinization solution and the gelatinization start temperature were measured, and the results are shown in Table 1.
[0029]
Example 4
The slurry of corn starch having a concentration of 38% by weight was brought to a temperature of 38 ° C. with stirring, and the pH was adjusted to 10 to 11 with a 3% aqueous sodium hydroxide solution. While maintaining this pH range, sodium trimetaphosphate was added at 4.5% by weight of starch and reacted for 8 hours. After the reaction, the pH was adjusted to 4.5 with hydrochloric acid, and after dehydration and washing, a slurry with a concentration of 38% by weight was obtained again. To the slurry, 9.0% by weight of phosphoric acid with respect to starch and 25% by weight of urea with respect to starch were added, mixed well, and dehydrated. This dehydrated cake was pre-dried to a moisture content of 5% or less with a hot air dryer, and then roasted at 140 ° C. for 10 minutes with a hot air heater. After roasting and cooling, the humidity was adjusted to 9% to obtain prototype D. For Prototype D, the amount of gelatinization settled and the gelatinization start temperature were measured, and the results are shown in Table 1.
[0030]
(Example 5)
A prototype E was obtained by mixing 9 parts by weight of the prototype A obtained in Example 1 and 1 part by weight of talc as a filler. For Prototype E, the amount of gelatinization and the gelatinization start temperature were measured, and the results are shown in Table 1.
[0031]
(Comparative Example 1)
In this comparative example, a commercially available raw corn starch was used. The gelatinization start temperature of the product was measured (measured concentration: 8% by weight), and the results are shown in Table 1.
(Comparative Example 2)
In this comparative example, a commercially available urea phosphated corn starch was used. The gelatinization start temperature of the product was measured, and the results are shown in Table 1.
[0032]
(Evaluation of prototype)
About the prototype shown by the Example and the comparative example, evaluation as an interlayer adhesive of a fiber sheet-like thing was performed as follows.
While stirring the 0.5% by weight waste paper pulp slurry, the pH is adjusted to 6.0 with dilute sulfuric acid, the sulfuric acid band (aluminum sulfate) is 1.5% by weight with respect to the pulp, and then the rosin sizing agent is 0.1% with respect to the pulp. Weight percent was added. After adding water to make a pulp slurry of 0.3% by weight, the pulp slurry is collected so that the basis weight of the paper is 50 g / m 2 , and the round sheet machine (manufactured by Kumagai Riki Kogyo Co., Ltd.) is used. Two sheets were made. 2 ml of 1% by weight interlayer adhesive slurry was sprayed onto one wet paper so that the amount of interlayer adhesive added was 1.0 g / m 2 , and another wet paper was overlaid. Press at 98 kPa for 30 seconds with a sheet machine press (Kumagaya Riki Kogyo Co., Ltd.) and immediately use a rotary dryer (Kumagaya Riki Kogyo Co., Ltd.) with a dryer surface temperature of 80 ° C. 3 Dried for minutes. After the dried paper was conditioned (temperature 23 ° C., humidity 50% RH), the interlayer adhesion strength was measured with an internal bond tester (manufactured by Kumagaya Riki Kogyo Co., Ltd.) to obtain the interlayer adhesion strength between the two layers.
[0033]
Table 1 shows the interlayer adhesion strength of the prototypes A to E and the comparative example. The prototypes A to E of Examples 1 to 5 having a gelatinization start temperature of 45 ° C. and the urea phosphate esterified corn starch of Comparative Example 2 can be easily gelatinized, but the prototypes A to E are Since starch maintains a swollen state, it exhibits better interlayer adhesion strength than urea phosphated corn starch. In addition, since the corn starch of Comparative Example 1 has a gelatinization start temperature of 70 ° C., it cannot be easily gelatinized, and an excellent interlayer adhesion strength cannot be obtained.
[0034]
[Table 1]
【The invention's effect】
According to the present invention, it is not necessary to heat starch in the step before spraying starch onto the fiber sheet in order to perform the treatment with starch as an interlayer adhesive of the fiber sheet, and the starch is used in the fiber sheet. In the heating and drying steps after addition to the product, the starch can be easily heated and swollen and can maintain a certain swelling state. In addition, when the interlayer adhesive of the present invention is used as an interlayer adhesive for fiber sheet-like materials, the amount used can be reduced by being able to obtain better adhesive performance than when using conventional starch. Therefore, the economic effect can be expected to improve.
[Brief description of the drawings]
FIG. 1 is a diagram for explaining a gelatinization start temperature in the present invention.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2000157185A JP4629833B2 (en) | 2000-05-26 | 2000-05-26 | Interlayer adhesive for fiber sheet and paper making method |
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| JP2000157185A JP4629833B2 (en) | 2000-05-26 | 2000-05-26 | Interlayer adhesive for fiber sheet and paper making method |
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| JP2001336090A JP2001336090A (en) | 2001-12-07 |
| JP4629833B2 true JP4629833B2 (en) | 2011-02-09 |
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| JP2000157185A Expired - Fee Related JP4629833B2 (en) | 2000-05-26 | 2000-05-26 | Interlayer adhesive for fiber sheet and paper making method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014930A1 (en) * | 2003-08-11 | 2005-02-17 | Tokushu Paper Mfg. Co., Ltd. | Oil-resistant sheet material |
| JP4527972B2 (en) * | 2003-12-22 | 2010-08-18 | 王子コーンスターチ株式会社 | Heat-saving adhesive for bonding |
| WO2007004980A2 (en) * | 2005-07-01 | 2007-01-11 | Akzo Nobel Coatings International B.V. | Adhesive system and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0241384A (en) * | 1988-08-01 | 1990-02-09 | Matsutani Kagaku Kogyo Kk | Adhesive composition for corrugated board |
| JPH0390695A (en) * | 1989-08-30 | 1991-04-16 | Sanwa Denpun Kogyo Kk | Method for forming paper |
| JP2001115121A (en) * | 1999-10-18 | 2001-04-24 | Shikishima Starch Kk | Interlaminar adhesive and paper-manufacturing process using the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5217125B2 (en) * | 1972-05-12 | 1977-05-13 | ||
| JPS521112A (en) * | 1975-06-24 | 1977-01-06 | Honshu Paper Co Ltd | Adding method of starch for paper |
| JPH05106192A (en) * | 1991-06-29 | 1993-04-27 | Honen Corp | Interlaminar adhesive for paperboard and the like and papermaking process |
| JPH08120251A (en) * | 1994-10-20 | 1996-05-14 | Sekisui Chem Co Ltd | Water-soluble pressure-sensitive adhesive composition and pressure-sensitive adhesive tape for masking |
| JP4173213B2 (en) * | 1997-10-15 | 2008-10-29 | 王子コーンスターチ株式会社 | Interlayer adhesive for fiber sheet and paper making method |
| JP4585650B2 (en) * | 2000-05-26 | 2010-11-24 | 王子コーンスターチ株式会社 | Papermaking method using interlayer adhesive for fiber sheet |
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2000
- 2000-05-26 JP JP2000157185A patent/JP4629833B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0241384A (en) * | 1988-08-01 | 1990-02-09 | Matsutani Kagaku Kogyo Kk | Adhesive composition for corrugated board |
| JPH0390695A (en) * | 1989-08-30 | 1991-04-16 | Sanwa Denpun Kogyo Kk | Method for forming paper |
| JP2001115121A (en) * | 1999-10-18 | 2001-04-24 | Shikishima Starch Kk | Interlaminar adhesive and paper-manufacturing process using the same |
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| JP2001336090A (en) | 2001-12-07 |
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