JP4932122B2 - Use of starch compositions containing selected cationic starch materials in papermaking or other than papermaking - Google Patents

Abstract

The invention concerns the use, as paper-making additive other than a standard mass additive or water treatment additive, of a starchy composition containing at least a cationic starch material. The invention is characterised in that said composition has: a fixed nitrogen proportion not more than 2 %, preferably between 0.1 and 1.9 %, said percentages being expressed in dry weight relative to the composition dry weight, and a viscosity, determined in accordance with a test A, of not more than 1600 mPa.s, preferably between 5 and 1500 mPa.s. Some of the starchy compositions, selected on the basis of their fixed nitrogen proportion and their viscosity, are also useful in numerous other fields of application, and in particular as mass additives in paper-making.

Description

【００５９】
電荷密度は、下文の実施例1に記載のように粒子電荷検出器で測定する。
【００６０】
総窒素濃度は、標準ケルダール法に従って測定し、乾燥重量/組成物の乾燥重量で表わす。
【００６１】
上記のCDI値は、カチオン化段階においてもたらされる含窒素基が前記組成物に含まれるデンプン材料に効率よく結合し、それにより、その電荷密度を増加させる効力を反映している。
【００６２】
本出願人の会社は、660〜800のCDI値を有する本発明による組成物は製紙添加剤または工業用水処理添加剤として非常に有利に使用することができることを見出した。
【００６３】
そのようなCDI値は、従来技術による製品において認められる、あるいは推定される値よりも非常に有意に高く、そして、特に、これらの製品における未結合の含窒素種(カチオン試薬およびその加水分解生成物)の大きい存在のため、一般的に600未満、あるいは500未満でさえあり、その結果、飲料水の処理のような特定の適用分野に利用不可能、あるいはほとんど利用できない。
【００６４】
そのことは、上記の「RAIFIX」系列の組成物だけでなく、上記の国際特許公開第97/35068号において例示され、0.48のDSが報告されており、すなわち、1.32meqv/g、すなわち1320μeqv/gの電荷密度に対して理論的固定窒素濃度が約2.7%〜2.8%(乾燥重量/乾燥重量)である高度にカチオン性のデンプンにも当てはまる。したがって、そのような製品は、約1320/4、すなわち約330のCDIを有する。
【００６５】
本発明による組成物のpHは、10までの、またはそれを超えさえする値であってもよいが、他の好ましい変形形態によれば、本発明によるデンプン組成物は9未満、好ましくは4〜8.5のpHを有する。前記pHは標準的方法で測定するが、これは、上記の試験Aによるサンプルの調製について記載したように、そのDMが20%の値に調整された(必要な場合)組成物について測定する。
【００６６】
これらのpH範囲は、かなりより高いアルカリ性で、したがって、ヒトおよび装置にとって潜在的により有害かつ腐食性である「RAIFIX」系列の従来技術による製品の特許請求の範囲に記載された組成物とも絶対的に異なっている。したがって、これらのpH範囲は、前記の従来技術による製品について実際に確保されている以外の適用分野を構想することも可能とするものである。
【００６７】
したがって、標準質量添加剤以外の製紙添加剤として、また工業用水処理添加剤として、特に、製紙用または他の水循環系に含まれ、かつ/またはプロセス装置に貯留されている不都合な物質を低減するための薬剤として、あるいは紙サイズ剤の組成物の調製における添加剤として有効に使用することができる新規の手段が利用可能である。
【００６８】
さらに、出願人が認めたように、この手段は、特に、
紙のしぼ寄せ、表面仕上げまたはコーティング用の組成物の調製における添加剤として、
光学的増白剤、着色剤および/またはポリアクリルアミドまたはポリビニルアミンのような合成ポリマーを含む組成物（当該組成物自体は標準質量添加剤以外の製紙添加剤として使用することができる）の調製における添加剤として、
特に適している。
【００６９】
合成ポリマー/カチオン性デンプン材料の重量比は1/100〜100/1であってよく、前記の比は一方で合成ポリマーの、他方でカチオン性デンプン材料の乾燥重量として表わされる。
【００７０】
有利には、この手段は特に、さらに例示するように、上記のようなデンプン組成物であって、
0.4〜1.5%(乾燥重量/乾燥重量)の固定窒素濃度と、
10〜800mPa.sの前記試験Aに従って測定される粘度
を有することを特徴とするデンプン組成物からなる。
【００７１】
本出願人の会社は特に、一方で、この窒素濃度が有利には、0.5〜1.5%、特に0.6〜1.5%で、他方で、この粘度が有利には、50〜700mPa.sの範囲にあることを発見した。
【００７２】
驚くべきことに、本発明によって使用することができ、流体化され、試験Aに従って、この好ましい範囲の粘度を有する組成物が、同じ固定窒素濃度を有するが、より高い粘度を有する本発明による組成物と比較して、高い電荷密度に達することを可能にしたことが認められた。
【００７３】
特に有利な方法において、本発明によって使用することができる組成物はさらに、15%より大きく、45%より小さく、特に18〜40%の乾燥物質(DM)含量を有する。
【００７４】
本発明の一般的概念はまた、上記の変形形態のいずれかに従うデンプン組成物の調製のための、多くて2%の固定窒素濃度と10⁷ダルトン未満の重量平均分子量を有するカチオン性デンプン材料の使用に基づいている。
【００７５】
有利には、前記カチオン性デンプン材料は、カチオン化処理の前、処理中および/または後に、好ましくはそのカチオン化処理後に、デンプン材料を分枝酵素(EC 2.4.1.18)およびシクロデキストリングリコシルトランスフェラーゼまたは「CGTアーゼ」(EC 2.4.1.19)を含む群から選択した少なくとも1つの、耐熱性またはそうでない、酵素で処理して得られた。
【００７６】
本発明の一般的概念はまた、標準質量添加剤以外の製紙添加剤として、または工業用水処理添加剤として有用なデンプン組成物の調製のための
多くて2%の固定窒素濃度と、
10⁷ダルトン未満の重量平均分子量と、
最大で1600mPa.sの試験Aに従う粘度と、
600より大きいCDI指数
を有するカチオン性デンプン材料の使用に基づいている。
【００７７】
本出願人の会社はさらに、本発明によって使用することができる上記のデンプン組成物のうち、あるものは、他の適用分野において、特に、サイズ剤、合成ポリマー、光学的増白剤および/または着色剤のような、大量製紙に使用することができる活性物質と組み合わせて、有利に使用することもできることを見出した。
【００７８】
そのような組合せは、同じ質量添加剤において、もしくは、そのような組合せの成分を個別に、同時または別の方法で用いて行うことができる。
【００７９】
そのような組合せの時の合成ポリマーとデンプン材料との重量比は、特に、1/100〜100/1(乾燥重量/乾燥重量)であってよい。
【００８０】
他の変形形態によれば、本発明による組成物は、0.5〜1.5%、特に、0.6〜1.5%の選択した固定窒素濃度と、試験Aに従って測定した10〜800mPa.s、特に、50〜700mPa.sの選択した粘度によって特徴付けられる。
【００８１】
本発明による組成物は、10の値までの、またはそれを超えさえするpHを有することができる。しかし、それらは好ましくは、9未満、特に4〜8.5のpHと、600より大きい電荷密度指数CDIを有する。
【００８２】
本出願人の知る限りでは、かくして選択されたかかる組成物は、その産業上の価値が、あらゆるデンプン材料から簡単かつ安価な方法により得られ、一般的にカチオン性デンプン材料を必要とするすべての適用分野、製紙またはその他の分野(大規模製紙および水処理適用分野を含む)において、あるいは、例えば、そのような材料を使用することが知られていない光学的増白剤を含む組成物の調製のような適用分野においてさえも、効果的かつ安全に使用される、特にそれらの能力に起因している新規の製品を構成する。
【００８３】
示したように、前記デンプン組成物は、それらの使用時に、加水分解したカチオン性デンプン材料と1つまたは複数の他の材料との、あらゆる割合での配合物を既に構成しており、前記カチオン性デンプン材料と、サイズ剤、光学的増白剤、着色剤および合成ポリマーを含む群から選択した活性物質とを配合した、特に(質量または非質量)製紙添加剤または水処理添加剤を構成する。
【００８４】
さらに、また、本出願人が認めたように、カチオン性デンプン材料の加水分解は、前記材料が既に、添加剤中で他の活性物質、例えばポリアクリルアミドと接触した状態でありながらも、完全に行うことができる。
【００８５】
他の変形形態によれば、前記デンプン組成物は、加水分解したカチオン性デンプン材料だけを活性物質として含んでいてよく、また、個別、同時または非同時の使用により、上で言及したような他の活性物質を含有した1つまたは複数の他の(質量または非質量)製紙添加剤または水処理添加剤と組み合わせることができる。
【００８６】
例として、本発明によるデンプン組成物は、
製紙法のウエット・エンドで使用される同じ添加剤中で、ポリアクリルアミドのような活性物質と組み合わせて、
大規模製紙において、あるいは、紙表面仕上げまたはコーティング操作中に使用される同じ添加剤中で、光学的増白剤または着色剤のような活性物質と組み合わせて、
ポリアクリルアミドが前記デンプン組成物と個別に、同時に、または別の方法で導入される、工業用水の処理用のポリアクリルアミドと組み合わせて、
材料が循環系の同じ部位(例えば、パルプ製造機の段階)または循環系の異なる部位(例えば、光学的増白剤はパルプ製造機の段階で、デンプン組成物はその下流で)個別に、同時に、または別の方法で導入される、製紙法のウエット・エンドで、光学的増白剤および/または着色剤と組み合わせて、使用することができる。
【００８７】
したがって、本発明の対象はまた、前記のデンプン組成物が、好ましくは、サイズ剤、光学的増白剤、着色剤および合成ポリマー、特に、ポリアクリルアミドまたはポリビニルアミンから選択した、少なくとも1種の他の活性物質と、同時にまたは別の方法で組み合わされることによる、上記のようなデンプン組成物の使用である。
【００８８】
本発明について、以下の全く限定的でない実施例によって、さらに詳細に記載する。
【００８９】
【実施例】
実施例1
1.48%の総窒素濃度(乾燥重量/乾燥重量)を有し、上記の仏国特許第2,434,821号に従って乾燥相中に得たジャガイモ・デンプン粉末を混合し、31%の乾燥物質(「DM」)を含むカチオン性デンプン乳液を得るために冷脱塩水に混合および懸濁する。
【００９０】
前記乳液の各種サンプルを種々の濃度の「FUNGAMYL 800 L」タイプのα-アミラーゼで処理する。この酵素変換処理は、開放タンク中で温度を20分間にわたり20℃から95℃に上昇させ、95℃に5分間保持して行う。その目的は、約300〜3000mPa.sのブルックフィールド粘度(25℃、20回転/分で測定)と約20〜22%のDMを有するカチオン性デンプン組成物を得ることを可能にすることである。
【００９１】
実際に、得られるコロイド溶液は21.5%の最終DMを有する。得られる各溶液について、以下の特性、すなわち、
mPa.s単位で表わされる25℃、20回転/分でのブルックフィールド粘度と、
溶液の乾燥重量1g当たりのマイクロ当量(μeqv/g)の単位で表わされ、「METTLER DL21」型の自動滴定装置と組み合わされた「MUTEK PCD02」型の粒子電荷検出器で測定される電荷密度を、
用いる分解酵素の濃度(最初の乳液の乾燥重量に対する%)の関数として測定する。
【００９２】
得られた結果を以下に示す。
【表１】

【００９３】
驚くべきことに、最大2%、この例では約1.5%の固定窒素濃度を有し、酵素的経路でバッチ式により液化されたカチオン性デンプンの本実施例において、液化の程度が増加するにつれて、電荷密度が有意に増加する傾向があることが認められる。電荷密度は、DMが21.5%、粘度が試験Aに従ってDMを20%に調整した場合の約700mPa.s未満、特に330Pa.s未満に相当する800mPa.s未満、特に380Pa.s未満の粘度を有するサンプルで最大である。
【００９４】
本出願人の会社はさらに、上記の液化カチオン性デンプンに基づくすべての組成物が貯蔵中に著しい安定性を有し、粘度の増大や老化の現象は25℃での貯蔵の17日または4カ月後に観察されなかったことを認めた。
【００９５】
実施例2
この実施例では、実施例1に記載した1.48%の総窒素を含有するカチオン性ジャガイモ・デンプンの連続酵素変換を行う。そのために、「FUNGAMYL 800 L」酵素と水との混合物を、水100リットル当たり前記酵素6.7ミリリットルの割合で調製した。カチオン性デンプンを以下の条件下で連続的に液化する。
水/酵素混合物の流量：90 l/時、
カチオン性デンプン粉末の流量：60kg/時、よって約40%のDMを含有する乳液の生成、
反応時間：30分、
反応温度：60℃。
【００９６】
酵素活性は、140℃で1分30秒間阻害チューブに通すことによって阻害する。これらの条件下では、26〜30%程度の最終DM含量が得られるが、これは、2000mPa.s未満、特に250〜500mPa.sの粘度を得ることができるため、特に有利である。
【００９７】
さらに、28%の最終DMを有する組成物の特定の例において、サンプルを経時的に回収し、電荷密度を粘度の関数として測定した。
【００９８】
得られた結果を以下に示す。
【表２】

【００９９】
連続的に行い、粘度範囲(DMが28%において250〜500mPa.s)が全体的に平均的液化に対応する酵素液化のこの例では、粘度と電荷密度との間に相関関係はないことが認められる。
【０１００】
いずれにせよ、本実施例の状況において、得られた電荷密度の値と比較して、約300〜400mPa.sの粘度が特に有利であると思われる。
【０１０１】
上記の試験Aに従ってそのDMを20%の値に調整するための、かかる組成物の希釈により、粘度が150mPa.s未満、特に100〜300mPa.s程度になることが好ましい。
【０１０２】
実施例3
この実施例では、ワクシー・トウモロコシ・デンプンから得られ、本出願人によって市販されているマルトデキストリンGLUCIDEX(登録商標)の本例におけるデンプン誘導体のカチオン化を実施する。この誘導体のDMを50%含む水溶液を調製し、この溶液を70〜80℃の温度に加熱する。次いで、上記の仏国特許第2.434,821号に記載されているTMAEPタイプの40%のカチオン試薬と1.5%の水酸化ナトリウムをそれぞれ加える。これらの%は、乾燥重量/マルトデキストリン乾燥重量により表わす。
【０１０３】
反応(50℃で5時間)および6.7のpHでの中和の後に、49%のDMを有し、試験Aに従ってDMを20%に調整した後に測定した粘度が約40mPa.sであるデンプン組成物が得られる。
【０１０４】
前記組成物に含まれているカチオン性デンプン材料は1.8%の固定窒素濃度(乾燥重量/乾燥重量)を有しており、これは、カチオン化試薬によってもたらされる総窒素濃度(2.16%)を考慮に入れて83%程度のカチオン試薬固定収率を示している。
【０１０５】
実施例4
この実施例では、上記のような本発明によるデンプン組成物の特性を、製紙循環系に存在する不都合な物質を低減する薬剤としての用途に「RAIFIX 120」という商品名で市販され、下文で「COMPOSITION T」と称するカチオン性デンプン組成物について測定した特性に関して比較する。本発明による組成物は、先の実施例1、2および3から得られ、それぞれ下文でCOMPOSITION 1、2および3と称するものである。
【０１０６】
測定した特性は、乾燥物質(%単位の「DM」)、pH、総窒素濃度(乾燥重量/乾燥重量に基づく%単位の「TOTAL N」)、固定窒素濃度(乾燥重量/乾燥重量に基づく%単位の「FIXE N」)、試験Aに従って20%DM、25℃および20rpmで測定したブルックフィールド粘度(mPa.s単位の「VISCOSITY」)、組成物に含まれているカチオン性デンプン材料の重量平均分子量(光散乱検出器と組み合わせたサイズ排除クロマトグラフィーにより測定した百万ダルトンすなわち10⁶d単位の「MM」)、電荷密度(μeqv/g単位の「CD」)およびCD/TOTAL N比に相当するCDI指数に関する。
【０１０７】
以下の結果が得られている。
【表３】

【０１０８】
全般的結果は、従来技術によるCOMPOSITION Tに含まれていたデンプン材料よりもカチオン化の程度が有意に低く、かつ液化の程度が高いデンプン材料を含む本発明による組成物は、前記COMPOSITION Tよりもかなり高いCDI値を有している。
【０１０９】
600あるいは、650さえも超えるこれらの高いCDI値は、カチオン化段階によってもたらされる窒素の固定がより良好であり、また、それによって前記COMPOSITION1〜3における含窒素および塩類溶液残留物の存在が減少したことを示している。
【０１１０】
実施例5
COMPOSITION 5(本発明によらない)と上記のCOMPOSITION 2および3(本発明による)を、製紙または別の用途の水循環系に含まれる(および/または装置に貯留する)可能性があるアニオン性または別の不都合な物質(下文で集合的に「ピッチ」と称する)を低減するための薬剤として比較試験した。
【０１１１】
この場合には、適用媒質は、全体として重量で約80%の未使用化学パルプ(広葉質および樹脂質との混合)と20%の製造カセ紙(production casse paper)からなる紙パルプからなっている。これは、約10g/kgの濃度、約1400μS/cmの伝導率、-13.4mVのゼータ電位、7.7のpHおよび140μmのフィルターを通過させた上清について測定した85μeq/lの電荷密度を有する。
【０１１２】
DMが20%に調整されたCOMPOSITION T、2および3を前記パルプに0.3%(乾燥重量/乾燥重量)の割合で導入する。COMPOSITIONのそれぞれとパルプとの接触時間は、1000rpmでかき混ぜながら、5分間である。
【０１１３】
あらゆるデンプン組成物の非存在下で試験を行う。「ピッチ」の計測は、上記の処理後に回収され、30μmのフィルターを通過させた「クロス下方水(water under cloth)」を用いて開始する標準的方法で、ト-マス(THOMAS)セルを用いて行う。
【０１１４】
ゼータ電位(mV単位の「POTENTIAL」)、電荷密度(μeq/l単位の「SCD」)および「ピッチ」の個数(千すなわち10³/mm³クロス下ろ過水の単位の「PITCHS」)の得られた結果を以下に示す。
【表４】

【０１１５】
これらの結果は、本発明によるCOMPOSITIONは、比較的低い窒素濃度を有しているが、「ピッチ」を低減させるための薬剤として完全に有効であることを示している。それらは全般的に、それにもかかわらず、調製がより困難で、カチオン化の程度が著しく大きく、したがってより高価で様々な残留物でより多く荷電されているCOMPOSITION Tと同様に有効である。
【０１１６】
特に、COMPOSITION 2はこの適用例に著しく適している。本出願人はさらに、それが、下水汚物浄化プラントから得られる生物学的および/または鉱物スラッジの凝集剤、または製紙機械水の浄化剤としても使用できることを認めた。
【０１１７】
実施例6
この実施例では、27%のDMを含むペーストの形態で提供された、本発明によるCOMPOSITION 2の乳化特性を試験する。コハク酸アルケニル無水物(「ASA」)に基づく、13.5gのサイズ剤“FIBRAN 76”を、100gの前記ペーストに加えた。したがって合計27gのカチオン性デンプン材料を含む。
【０１１８】
次いで、デンプン材料(乾燥重量)/サイズ剤比が2/1である、得られたサイズ組成物を強力なせん断処理、すなわち、20,000回転/分での5分間の均質化に供する。
【０１１９】
かくして得られたエマルションを、1リットルのメスフラスコ中でかき混ぜずにドリリング水で希釈し、1.35%のサイズ剤を含む「FIBRAN 76」のエマルション(「EMULSION 1」)を得て、0.3%のサイズ剤を含むエマルション(「EMULSION 2」)を得るために、EMULSION 1の一部を同じ条件下で再希釈する。
【０１２０】
54時間にわたって定期的に行った観察により、そのようにして得られたEMULSION 1および2は完全に安定かつ均質のままであることがわかった。
【０１２１】
実施例7
本実施例では、上記の国際特許公開第00/66633号の実施例4に記載のように、カチオン性デンプンをグリコーゲン分枝酵素で処理して、本発明による添加剤を調製する。
【０１２２】
この目的のために、150mlの前記酵素をあらかじめ温度を30℃に維持し、pHを7〜8とした2リットルの脱塩水に加えて、希薄な酵素溶液を調製する。
【０１２３】
次いで、前記希釈酵素溶液中に、実施例1で用いたのと同じ、すなわち約1.5%(乾燥重量/乾燥重量)の総窒素濃度および約1.2%(乾燥重量/乾燥重量)の固定窒素濃度を有するジャガイモ・デンプンを緩やかに振りかけて導入した。
【０１２４】
この操作は、できる限り規則的な導入によって、過度の膨潤が起こったり、かき混ぜ時に必要なエネルギー消費が過度になったりせずに、110〜120g/lの濃度を有する前記カチオン性ジャガイモ・デンプンのコロイド溶液が得られるようにするために行った。
【０１２５】
この調製段階中、温度を30℃に、pHを6〜8、好ましくは6.5〜7に注意深く維持する。
【０１２６】
この条件下で、変換を4時間続ける。
【０１２７】
95℃に15分間維持することからなる酵素の不活性化により、変換を中断する。
【０１２８】
実際に、これらのすべての操作の終了時に得られたコロイド溶液は、10%の最終DMと以下の特性を有する。
ブルックフィールド粘度：50mPa.s(25℃、20rpm)、
電荷密度(CD)：922μeqv/g、
CDI：615、
重量平均分子量(MM)：約3.2×10⁶ダルトン。
【０１２９】
分枝酵素による酵素変換のこの例において、試験Aによる300mPa.sより有意に低い値を示すと思われる、得られた比較的低い粘度は、比較的高い重量平均分子量、すなわち2×10⁶ダルトンより高い値を維持することに適合していることが認められる。
【０１３０】
得られたデンプン組成物は、それ自体、あるいは約21.5%のDMまで濃縮した後に、実施例1から得られた組成物で観察された安定性よりもさらに大きい貯蔵中の安定性を有している。
【０１３１】
実施例8
本実施例では、実施例7に記載したのと同じ条件下でデンプン組成物を調製する。但し、
1)ジャガイモ・デンプンは、約1.1%(乾燥重量/乾燥重量)の総窒素濃度と約1.0%(乾燥重量/乾燥重量)の固定窒素濃度を有し、
2)分枝酵素による変換は、45分間(4時間の代わりに)にわたり行い、
3)得られるコロイド溶液の最終DMは16.3%(10%の代わりに)である。
【０１３２】
そのようにして得られたデンプン組成物は、以下の特性を有する。
ブルックフィールド粘度：625mPa.s、
電荷密度(CD)：716μeqv/g、
CDI：650、
重量平均分子量(MM)：約2.5×10⁶ダルトン。
【０１３３】
この組成物は、貯蔵中に著しい安定性を有している。
【０１３４】
さらに、本出願人の会社は、上の実施例5に記載した試験条件下では、前記組成物はCOMPOSITION 2または3で認められたのと同等の効果を得ることができ、この場合は、-6.4mVのゼータ電位、65μeq/lの電荷密度(SCD)および16.4×10³/mm³のクロス下ろ過水の「ピッチ」を有するので、前記組成物は製紙循環系中に存在する不都合な物質を低減するための薬剤として完全に適している可能性があることを立証した。
【０１３５】
実施例9
本実施例では、本発明によるデンプン組成物の価値を、光学的増白剤と、そして、場合によっては、他の着色剤と組み合わせた場合について試験する。
【０１３６】
本発明によるデンプン組成物は、約1.65%の総窒素濃度と約1.5%の固定窒素濃度を有するカチオン性ジャガイモ・デンプンのαアミラーゼによる酵素変換によって得られた。
【０１３７】
そのデンプン組成物は、主な特徴が以下の通りであるペースト形態で提供される。
乾燥物質(DM)：27.9%
ブルックフィールド粘度：450mPa.s(25℃、20rpm)
電荷密度：1056μeqv/g
CDI：約640。
【０１３８】
この場合には、活性物質を、重量でおおよそ以下の通りの紙パルプの塊体に導入する。
20%の樹脂質クラフト・パルプと、
60%の広葉質クラフト・パルプと、
20%のカセ紙(casse paper)。
【０１３９】
前記パルプを分解装置に導入する前に、以下のものを前記装置に満たすための水に逐次的に導入する。
a)上記のカチオン性デンプン組成物またはカチオン性ポリアクリルアミド、これは前記デンプン組成物のDMに相当する量であり、次いで、
b)光学的増白剤、これはa)で使用したカチオン性産物の量の約5倍に相当するものであり、次いで、場合によっては、着色剤の混合物、これはa)で使用したカチオン性産物の量の約2.5倍に相当するものである。
【０１４０】
パルプを導入し、それを30分間分解した後、材料「TECHPAP」を用いて約80g/m²の物質を有するシートを生成させる。
【０１４１】
白さおよび蛍光の測定は、それらにおいて必須に実施される。
【０１４２】
得られた結果から、全般的に、酵素的に変換されたカチオン性デンプン材料を含む本発明によるデンプン組成物は、着色剤の存在する場合と存在しない場合との両方において、合成カチオン高分子を用いて得られるのと少なくとも同様に高い、一般的にそれよりも高い光学的増白剤の効率を有することを可能にすることがわかった。
【０１４３】
実施例10
本実施例では、本発明による、または、本発明によらない、デンプン組成物の水処理の分野における価値を試験する。これは、合成凝析剤、この場合には、HERCULESにより市販されているカチオン性ポリアクリルアミド「PERFORM PA 9430」と組み合わせた状況である。
【０１４４】
TRIAL A、BおよびCにおいて、前記ポリアクリルアミドを、以下に基づくデンプン・ペーストと組み合わせて試験する。すなわち、
TRIAL A：加水分解されておらず、したがって、本発明によらない、約0.64%の固定窒素(乾燥重量/乾燥重量)を含むカチオン性ジャガイモ・デンプン、
TRIAL B：本発明によりα-アミラーゼで加水分解した約1.5%の固定窒素(乾燥重量/乾燥重量)を含むカチオン性ジャガイモ・デンプン、
TRIAL C：本発明により分枝酵素で加水分解したカチオン性ジャガイモ・デンプン(固定窒素:乾燥重量/乾燥重量として約1.5%)。
【０１４５】
さらに、前記ポリアクリルアミドをデンプン組成物と組み合わせない、対照試験(「TRIAL T」)を行う。
【０１４６】
これらのすべての試験において、1.6g/lの程度の懸濁物質濃度を有する製紙廃液を処理する。
【０１４７】
回収した廃液サンプルを直ちに攪拌下におく。以下の一連の操作を行う。
t=1分目:攪拌した廃液へのデンプン組成物の導入を行う(TRIAL A〜C)または行わない(TRIAL T)。これは0.03゜/゜゜(乾燥重量/乾燥重量)の導入率で行う。
t=6分目:合成凝析剤の導入(TRIAL TおよびA〜C)。これは、市販品重量/流出液の乾燥重量として表わした0.001゜/゜゜の割合で行う。
t=7分目:攪拌の終了
t=7分目からt=9分目まで:デカンテーションの観察。
t=12分目:上清の乾燥物質含量(g/l単位の「DMS」)および上清の光学濃度(「OD」)の測定。
【０１４８】
以下の結果は、本発明によらないTRIAL TおよびAならびに本発明によるTRIAL BおよびCで得られている。
【表５】

【０１４９】
これらの結果から、全般的に、本発明によるデンプン組成物は、特にカチオン性ポリアクリルアミドのような合成ポリマーと組み合わせて、水の処理に有利に用いることができることがわかる(TRIAL BおよびCを参照)。
【０１５０】
これらのデンプン組成物は、上清の乾燥物質含量および光学濃度を減少させることにより、廃液の浄化を非常に有意に改善することを可能にする。これは、本発明によらないデンプン組成物を用いて得ることができる改善よりもはるかに程度が大きい(TRIAL Aを参照)。
【０１５１】
分枝酵素により変換されたカチオン性デンプン材料に基づく、TRIAL Cで試験したデンプン組成物は、カチオン性ポリアクリルアミドと組み合わせた場合に特に効果的であるように思われる。
【０１５２】
実施例11
本実施例では、本発明による加水分解したカチオン性材料と、STOCKHAUSENによって粉末状で市販されている製品「PRAESTOL 853 BC」のようなカチオン性ポリアクリルアミドとを、(大規模または非大規模量の)製紙もしくは水処理に用いることができる同じ添加剤中で組み合わせる。
【０１５３】
かかる組合せは、有利には、この例におけるように、カチオン性デンプン材料を加水分解することを目的とした変換の段階の直前に、デンプン材料と合成材料とを互いに接触させるさせることによって行うことができる。
【０１５４】
30%のDMを含むデンプン乳液を実施例1で用いたのと同じカチオン性ジャガイモ・デンプン粉末から調製する。次いで、5%の前記カチオン性ポリアクリルアミドをこの懸濁液に加える。このパーセントは市販のポリアクリルアミドの重量/乾燥デンプン重量で表わされる。
【０１５５】
次いで、乾燥デンプン重量に対する市販製品の重量で表わして0.15゜/゜゜の「FUNGAMYL 800 L」タイプのα-アミラーゼを加える。
【０１５６】
次いで、開放タンク中で温度を生蒸気で20分間にわたり20℃から95℃に上昇させて酵素変換処理を行い、次に、酵素を阻害するために95℃に5分間保持する。
【０１５７】
次いで、得られる組成物のDMを約22%の値に調整する。
【０１５８】
加水分解されたカチオン性デンプン材料とカチオン性ポリアクリルアミドとを配合して得られるデンプン組成物は、次の主な特性を有する。
DM：22.2%、
ブルックフィールド粘度：1500mPa.s(25℃、20rpm)、
電荷密度：1040μeqv/g。
【０１５９】
この組成物の粘度は、実施例1に従って、0.15゜/゜のα-アミラーゼを用いて、合成ポリマーの不在下で得られた組成物と比較して、増加していることが認められる。
【０１６０】
しかし、この粘度は、目標のセットと一致している。すなわち大きくて1600mPa.sである(試験Aにより)。
【０１６１】
さらに、本出願人によって行われた観察により、この組成物は25℃で25日間の貯蔵後に安定のままであり、それが含有している加水分解されたカチオン性デンプン材料が完全に可溶化されていることがわかっている。[0001]
BACKGROUND OF THE INVENTION
The subject of the present invention is the use of starch compositions containing cationic starch materials with specific properties of fixed nitrogen concentration and viscosity as papermaking additives other than standard mass additives or as industrial water treatment additives It is.
[0002]
The present invention also relates to a method for producing the starch composition.
[0003]
The present invention finally relates to a starch composition of this type as a new industrial product whose cationic starch material is chosen so that it can also be used in particular as a standard mass additive.
[0004]
The expression “standard mass additive” for the purposes of the present invention is in particular:
At the wet end of a paper machine,
Used alone and directly to improve fiber and / or filler retention, paper dehydration and physical properties,
It is understood to mean any composition.
[0005]
[Prior art]
For the standard use of cationic starch as a mass additive, see, for example, Belgian Patent No. 626,712, European Patent No. 139,597, European Patent No. 603,727, International Patent Publication No. 97/46591 and Japanese Patent No. 11- It is described in 12979 (summary).
[0006]
In general, standard mass additives are initially used in containers known to those skilled in the art under the name “machine chest”, and more recently to those skilled in the art under the name “head box” of the papermaking machine itself. It is used at a level just before a known container.
[0007]
In very standard methods, mass additives are used in so-called dilute fibrous pulp compositions with a suspended solids concentration of generally up to 20 g / l.
[0008]
The expression "paper additive other than standard mass additive" can be used in at least one of the papermaking applications other than the specific one standard mass additive application described above and / or the standard mass additive It is understood to mean any composition used in at least one stage other than the above-mentioned stages to be introduced.
[0009]
Especially papermaking additives other than standard mass additives,
Machine chest or upstream stage thereof, for example at any one stage of a container known to the person skilled in the art under the names "pulp making machine", "mixing chest", "broke chest" or in a pulp mill And / or just after leaving
At the very stage of the device that forms the sheet itself and / or
Downstream of these sheet forming equipment, especially at the stage of squeezing, surface finishing or coating equipment, or more generally, spraying or coating on sheets having a moisture content of less than about 60% before processing, eg processing At any equipment stage to do and / or
In the preparation of a composition of paper additive containing non-starch active substance
Can be used.
[0010]
The expression “papermaking additives other than standard mass additives” for the purposes of the present invention is provided in particular in the form of a solid, liquid or paste, for example in the form of a flowable powder, an aqueous dispersion, an emulsion or a colloidal solution, It is understood to mean any composition useful as an agent for the reduction of undesirable anionic substances contained in the water circulation system and / or in the papermaking process equipment.
[0011]
It is also understood to mean in particular a composition useful as an agent for protecting the sizing agent, which is useful for the preparation of a sizing composition used in papermaking.
[0012]
For the purposes of the present invention, the expression “industrial water treatment additive” refers in particular to water obtained from human or industrial activities, or water, textiles and leather for such activities, for example water for human or animal consumption. It is understood to mean any composition that is particularly useful as an agent for the purification and / or purification of waste from the industry, paper and board industry, mineral extraction industry, agriculture / food industry and slaughterhouse.
[0013]
In all the above mentioned fields of application other than the mass additive field, compositions based on cationic natural or synthetic polymers are generally used. They are,
European Patent No. 626,022 and Canadian Patent No. 2,160,103 relating to their use as agents that reduce the anionic substances, which are disadvantageous in the papermaking circulation system,
In WO 97/35068 and WO 99/18288 regarding their use as agents for protecting sizing compositions used in papermaking,
In US Pat. No. 5,543,056 and US Pat. No. 5,236,598 concerning their use as additives for treating industrial water
As recently described, it may consist in particular of a cationic starch material.
[0014]
EP 626,022 is inevitably very high, i.e. reducing undesirable substances in the water cycle of cationic starch with a charge density of 1.5-3.5 meqv / g, preferably 2-3 meqv / g The use as a medicine for doing so is claimed. These charge density ranges correspond to cationic starches having a total nitrogen concentration of about 2.1-4.9%, preferably about 2.8-4.2% (dry weight / dry weight). In the examples of this patent, the method for producing the cationic starch used for this purpose is not described at all, including the plant raw material of starch used for the test.
[0015]
Nevertheless, in view of the level of cationicity required, in the industrial phase, such cationic starches are described, for example, in WO 95/18157 published in the name of the same applicant. As is evident, it seems obvious that it can only be properly prepared in the sticky phase.
[0016]
The examples in this document assume the preparation of a highly cationic potato starch paste characterized by a degree of substitution (“DS”) of 0.72 and 0.75, which represents more than 50% dry matter (“DM”) is from a highly concentrated reaction medium characterized by content, about half of which is occupied by the cationizing agent (“Raisicat 65”).
[0017]
The preparation of such highly cationic and highly concentrated compositions actually requires a preliminary step of the oxidation of potato starch with hydrogen peroxide according to the above examples.
[0018]
However, both in nature and in application, such pastes have many disadvantages.
[0019]
First and then confirmed in the analysis conducted by the applicant on the product marketed under the name "RAIFIX" by the above-mentioned patent holders of European Patent No. 626,022 and International Patent Publication No. 95/18157 As such, these highly cationic pastes have relatively low nitrogen fixation levels, typically less than 65%. As a result, in particular, such a composition itself retains a large amount of a cationic reagent and / or its hydrolysis product, and thus removes inconvenient substances, particularly anionic substances, present in the papermaking circulation system. Inhibits its true efficacy as.
[0020]
Furthermore, such very partial fixation of cationic reagents containing nitrogen envisages the use of these pastes as additives for treating industrial water, especially water for human or animal consumption. Making it difficult.
[0021]
Furthermore, the high pH of these pastes, typically 9 or higher, can create safety and corrosion problems inherent in the preparation, handling and use of alkaline products.
[0022]
Finally, the essential properties of these pastes are
Due to the relatively high viscosity, it is generally not well suited for the operation of dilution and introduction into aqueous media, which is used not only for these pastes, but also for the majority of papermaking fibers as a result (essentially (Cationic) starches can also result in reduced effectiveness and / or variability and / or
Due to their high hydrophilicity, they are generally not well suited for drying or pregelatinization operations to obtain powders or flakes, followed by rehydration of said powders or flakes.
[0023]
These shortcomings are actually amplified for cereal-derived (especially corn, wheat) starch bases, and the preparation and use of such bases in cationic form is described in EP 626,022 and WO 95 / 18157 is not exemplified at all.
[0024]
The same applies to the same applicant claiming the use of starch, which also has a high level of cationicity (DS 0.15-1.30, preferably 0.50-0.80) in the preparation of rosin emulsions for sizing paper The same applies to International Patent Publication No. 99/18288 in the name of In that specification, the total nitrogen concentration of these cationic starches is preferably 3-5%, ideally 3.5%, and such products are described in WO 95/18157 above. It has been shown that it can be advantageously obtained directly according to the method.
[0025]
Only potato starch with a total nitrogen concentration of 3.5% is exemplified in this document.
[0026]
In the same field of application, ie the preparation of sizing compositions, WO 97/35068
A DS greater than 0.1, preferably 0.4 to 1.0;
0.5-3.5 meqv / g, preferably 1.0-2.0 meqv / g charge density
The use of highly cationic starches that simultaneously have
[0027]
Thus, the cationic product used in decomposed or liquid form in the examples of this patent has a DS of 0.48 (i.e., a theoretical fixed nitrogen concentration of about 2.7-2.8%) and a charge density of 1.32 meqv / g. is doing. However, plant properties and preparation conditions, in particular degradation conditions, are not specified.
[0028]
In the field of industrial water treatment, it has recently been proposed in US Pat. No. 5,236,598 to use a cationic starch with a DS preferably between 0.01 and 0.2, i.e. significantly lower than the claims of the above patent. However, such cationic starches must be combined with hydrolyzed polyacrylamide in order to be effective in the intended application (treatment of paint waste). In addition, the inventors
1) Starch bases other than potato starch, especially corn starch are not suitable (see column 4, lines 62-66), and
2) The molecular weight of the cationic starch is not a critical parameter (see column 4, lines 44-45)
Only exemplifies the non-degradable cationic potato starch, in this case the product HI-CAT®, marketed by the applicant, in combination with polyacrylamide.
[0029]
In certain areas of drinking water treatment, it has also recently been recommended to use so-called primary coagulants such as chitosan or cationic starch in combination with clay, in which case the latter is a large proportion in the mixture. Existing.
[0030]
The cationic charge of the primary coagulant subjected to the test, in particular the cationic starch, is not explicitly mentioned. However, it is recalled that chitosan has a high charge density (see column 5, lines 41-45). No further mention is made of the possibility of degradation of the primary coagulant, in particular cationic starch, in terms of its use.
[0031]
On the other hand, the inventors here again prefer to use basic cationic starch, potato starch, the only cationic starch exemplified.
[0032]
The above results in the text show that there is no means to date that has the advantage of being able to: That is,
Addition of papermaking other than standard mass additives, if possible, as agents to reduce inconvenient substances, particularly anionic substances, contained in the papermaking water circulation and / or stored in the papermaking process equipment Being effectively used as an agent,
Being effectively used as an industrial water treatment additive,
Optionally used in other fields, including large-scale papermaking,
Used in the form of a diluted or undiluted paste, an aqueous suspension, or a solid such as powder or flakes;
Obtained from any starch base, including cereals;
It can be obtained simply and inexpensively by standard methods of starch material processing, in particular cationization.
[0033]
Problems to be solved by the invention and means for solving the problems
Applicant's company has the advantage that after many research studies, it has been found that such means are in starch compositions with selected properties in terms of both fixed nitrogen concentration and viscosity.
[0034]
More specifically, the subject of the present invention is the use of a starch composition comprising at least one cationic starch material as a paper additive or water treatment additive other than a standard mass additive,
A fixed nitrogen concentration of at most 2%, preferably 0.1-1.9%, expressed as a percentage of the dry weight to the dry weight of the composition;
Use of a starch composition characterized by having a viscosity of at most 1600 mPa.s, preferably 5 to 1500 mPa.s, measured according to test A.
[0035]
Test A, used to measure the viscosity of the composition, can be applied regardless of its nature, ie, liquid, paste, or solid.
[0036]
It measures the dry matter (DM) content of the composition by standard methods within the abilities of those skilled in the art, and optionally dilutes the composition with distilled water, or It is to concentrate it by any suitable means that cannot significantly change the average molecular weight of the cationic starch material it contains, in order to adjust the DM of the composition to a value of 20%.
[0037]
Thereafter, the Brookfield viscosity of the resulting composition containing 20% DM at 25 ° C. and 20 revolutions / minute is measured in a manner known per se.
[0038]
According to one variant, the starch composition according to the invention is in solid form, e.g. in the form of a free-flowing powder, or in liquid form, e.g. 5-65%, preferably 10-50% DM. Provided in the form of a paste having. This dry matter content is advantageously greater than 15% and less than 45%, in particular 18-40%.
[0039]
The dry matter content of the composition according to the invention may consist exclusively or almost exclusively of at least one cationic starch material, which may or may not contain other chemical species obtained by cationization. Are starches and anionic or nonionic derivatives, optionally cationized hydrogenated starch hydrolysates and hydrogenated sugars such as sorbitol, non-starch derived cationic products, fungicides and other It should be emphasized that it may also contain one or more other ingredients selected from papermaking or non-papermaking actives.
[0040]
According to one preferred variant of the invention, the starch composition has a fixed nitrogen concentration of 0.2-1.5% (dry weight / dry weight). Even more advantageously, this fixed nitrogen concentration is 0.4-1.5% (dry weight / dry weight), in particular 0.5-1.5% (dry weight / dry weight).
[0041]
Surprisingly and unexpectedly, especially considering the teachings of European Patent No. 626,022 above, Applicant's company is actually relatively low, i.e. up to 2%, preferably 0.1 to A starch composition having a fixed nitrogen concentration of a value selected between 1.9%, in particular 0.2-1.5%, likewise in combination with certain viscosity properties, in particular included in the papermaking circulation system and / or It has been found that there is a possibility that it can be a very effective paper additive as a chemical for reducing inconvenient substances stored in the paper manufacturing process equipment.
[0042]
One advantage of such starch compositions having a relatively low fixed nitrogen concentration is that they can be obtained easily and efficiently according to a number of variations. The step of cationization can be carried out either in an aqueous medium as described in the examples of EP 139,597 or in a dry phase or in a solvent phase as described in the examples of French patent 2,434,821. Can be implemented. This is in order to bind one or more electropositive or polyvalent electropositive nitrogen-containing groups to the starch material contained in the composition.
[0043]
It should be emphasized that the cationic starch material that can be used according to the invention may consist of amphoteric products, ie products having both cationic and anionic properties. Anionic substituents can be selected, for example, from the group comprising phosphoric acid, phosphonic acid, sulfuric acid, sulfoalkyl, carboxyl, carboxyalkyl and sulfocarboxyl groups.
[0044]
The expression “starch material” for the purposes of the present invention is understood to mean all starches derived from natural or hybrids, including those obtained by genetic mutation or genetic engineering. The starch is not only from potatoes, but also potatoes with high amylopectin content (waxy potatoes), corn, wheat, wheat with high amylopectin content (waxy wheat), corn with high amylopectin content (waxy corn) Corn, rice, peas, barley or cassava with high amylose content, such as amylose, amylopectin, particle size distribution fraction known to those skilled in the art as wheat starch “A” and wheat starch “B” Cuts or fractions prepared or available, and mixtures of at least any two of the above products, such as at least one tuber starch (especially potato starch) and at least one cereal starch (especially wheat starch `` A ", wheat des Pung "B", can be obtained from corn starch, waxy corn starch) or a mixture of two cereal starches. Starch compounds that can be used according to the present invention may comprise powders or other mixtures, including plant starches and proteins, in which the “starch” composition predominates.
[0045]
This may also include starch derivatives that are subjected to at least one additional modification treatment before, simultaneously with, or after the cationization step, as further described.
[0046]
This is in particular a derivative obtained from the hydrolysis of starch, in particular having a dextrose equivalent (DE) of at most about 5 as marketed by the applicant under the name GLUCIDEX® 2. However, in the present invention, maltodextrin which is cationized after the hydrolysis step may be included.
[0047]
As mentioned above, the starch composition that can be used according to the invention has a viscosity of at most 1600 mPa.s, preferably 5 to 1500 mPa.s, measured according to test A above.
[0048]
Such viscosities are very low and generally require a modification treatment, in particular a degradation treatment, of the starch material contained in the composition. This is either before, simultaneously with, or after the cationization step, as indicated.
[0049]
This treatment is known to those skilled in the art and, as claimed, means that allow for the direct or otherwise production of a starch composition having a viscosity measured by test A, in particular Can be carried out by chemical, enzymatic and / or physical means. It depends on many variations in terms of nature, quantity or form of means of modification, reaction temperature and time, moisture content of the reaction medium, the nature of the substrate (whether the starch material has already been cationized or not), etc. Can be carried out in one or more stages, continuously or batchwise. This may in particular comprise a fluidization treatment by chemical route in an aqueous medium or in the dry phase, as mentioned or described in EP 902,037 in the name of the applicant.
[0050]
This may also advantageously include an enzymatic fluidization treatment (also called enzymatic conversion or liquefaction), the latter being performed, for example, according to the teachings of French Patent 2,149,640 published by the applicant. be able to. These enzymatic means include enzymes of the α-amylase type of bacterial, fungal or other origin, with or without thermostability.
[0051]
This may also be cationized by an enzyme selected from the group comprising branching enzyme (EC 2.4.1.18) and cyclodextrin glycosyltransferase or “CGTase” (EC 2.4.1.19) in an aqueous medium as another advantageous method. It may contain a treatment that makes it possible to convert the natural starch material efficiently. Branching enzymes are in particular starches or glycogens isolated from algae or bacteria whose use is described in the name of the applicant in WO 00/18893 and WO 00/66633 It may consist of a branching enzyme.
[0052]
Applicant's company has found that cationic starch materials treated with branching enzymes before, during or after cationization treatment are generally further improved in storage compared to those treated with α-amylase. It was confirmed that it showed stability. Without wishing to be bound by theory, Applicants have found that this remarkable result can be obtained, at least in part, by hydrolysis with a branching enzyme to obtain a more homogeneous starch material that has been hydrolyzed. The resulting constituent sugars are attributed to having a molecular weight that is generally more regular, symmetrical, and distributed on a narrow Gaussian curve than that obtained with α-amylase. Yes. Preferably, the treatment with the branching enzyme is performed after the cationization step. Indeed, it is noteworthy and surprising that the presence of relatively large cation groups does not interfere with the oligosaccharide or polysaccharide chain transfer action of such enzymes.
[0053]
If desired, enzymatic liquefaction can be achieved by using thermostable enzymes at a temperature of about 90-100 ° C., which is a particularly advantageous condition for obtaining a high quality colloidal solution particularly in terms of solubility and viscosity stability. It becomes possible to do.
[0054]
Modification processes according to non-limiting examples also involve liquefaction combining the acid and enzyme pathways with dextrinization or heat conversion processes.
[0055]
All of the above means generally have a weight average molecular weight of 10 which has already been included in the composition according to the invention or before being included. ⁷ Less than dalton, preferably 5x10 ⁶ Applies to starch materials (already cationized or not) that are less than Dalton.
[0056]
Advantageously, this weight average molecular weight is 10 ^Four ~ 4 × 10 ⁶ Dalton.
[0057]
Applicant's company actually uses a decomposed cationic starch material having a molecular weight in the above range, which makes the composition according to the present invention a papermaking additive or industrial water treatment additive other than a standard mass additive. Handling, storage, transport, pumping and, for example, papermaking circulation systems and equipment, sizing emulsions, squeezing, surface finish or coating compositions, mineral suspensions or consumption, as well as very good effectiveness as It has been found that very good stability is also guaranteed in terms of behavior during operation of introduction into / on application media such as water.
[0058]
According to another variant of the composition that can be used according to the invention, it has a charge density index “CDI” greater than 600, preferably greater than 650. The said value is calculated | required according to the following formula | equation.
[Expression 1]

[0059]
The charge density is measured with a particle charge detector as described in Example 1 below.
[0060]
The total nitrogen concentration is measured according to the standard Kjeldahl method and is expressed as dry weight / dry weight of the composition.
[0061]
The above CDI values reflect the efficacy of the nitrogen-containing groups provided in the cationization step to efficiently bind to the starch material contained in the composition, thereby increasing its charge density.
[0062]
Applicant's company has found that compositions according to the invention having CDI values of 660 to 800 can be used very advantageously as papermaking additives or industrial water treatment additives.
[0063]
Such CDI values are significantly significantly higher than those found or estimated in prior art products, and in particular, unbound nitrogenous species (cationic reagents and their hydrolysis products) in these products. Is generally less than 600, or even less than 500, so that it is not available or rarely available for specific applications such as drinking water treatment.
[0064]
This is illustrated not only in the composition of the “RAIFIX” series mentioned above, but also in the above-mentioned International Patent Publication No. 97/35068, and a DS of 0.48 is reported, ie 1.32 meqv / g, ie 1320 μeqv / This also applies to highly cationic starches with a theoretical fixed nitrogen concentration of about 2.7% to 2.8% (dry weight / dry weight) for g charge density. Thus, such a product has a CDI of about 1320/4, or about 330.
[0065]
The pH of the composition according to the invention may be values up to 10 or even above, but according to other preferred variants, the starch composition according to the invention is less than 9, preferably 4 to Has a pH of 8.5. The pH is measured by a standard method, which is measured for a composition whose DM is adjusted to a value of 20% (if necessary), as described for sample preparation according to Test A above.
[0066]
These pH ranges are also significantly higher than alkaline, and therefore absolute with the compositions described in the RAIFIX series of prior art products that are potentially more harmful and corrosive to humans and devices Is different. Therefore, these pH ranges also make it possible to envisage application fields other than those actually reserved for the products according to the prior art.
[0067]
Therefore, as a papermaking additive other than standard mass additives, and as an industrial water treatment additive, especially to reduce inconvenient substances contained in papermaking or other water circulation systems and / or stored in process equipment New means are available which can be used effectively as agents for the preparation or as additives in the preparation of paper sizing compositions.
[0068]
In addition, as the Applicant has acknowledged, this means, in particular,
As an additive in the preparation of compositions for paper squeezing, surface finishing or coating,
In the preparation of a composition comprising an optical brightener, a colorant and / or a synthetic polymer such as polyacrylamide or polyvinylamine (the composition itself can be used as a papermaking additive other than standard mass additives) As an additive,
Especially suitable.
[0069]
The weight ratio of the synthetic polymer / cationic starch material may be 1 / 100-100 / 1, said ratio expressed as the dry weight of the synthetic polymer on the one hand and the cationic starch material on the other hand.
[0070]
Advantageously, this means is a starch composition as described above, in particular, as further illustrated:
A fixed nitrogen concentration of 0.4-1.5% (dry weight / dry weight);
Viscosity measured according to test A above from 10 to 800 mPa.s
It consists of a starch composition characterized by having.
[0071]
The applicant's company in particular is on the one hand that this nitrogen concentration is advantageously between 0.5 and 1.5%, in particular between 0.6 and 1.5%, on the other hand, this viscosity is advantageously in the range from 50 to 700 mPa.s. I discovered that.
[0072]
Surprisingly, a composition according to the invention that can be used according to the invention and is fluidized and according to test A has a viscosity in this preferred range, has the same fixed nitrogen concentration, but has a higher viscosity. It was observed that it was possible to reach a high charge density compared to the object.
[0073]
In a particularly advantageous manner, the composition that can be used according to the invention further has a dry matter (DM) content of greater than 15%, less than 45%, in particular 18-40%.
[0074]
The general concept of the present invention is also a fixed nitrogen concentration of at most 2% and 10% for the preparation of starch compositions according to any of the above variants. ⁷ Based on the use of cationic starch materials having a weight average molecular weight of less than Dalton.
[0075]
Advantageously, said cationic starch material is obtained by separating the starch material from branching enzyme (EC 2.4.1.18) and cyclodextrin glycosyltransferase before, during and / or after cationization treatment, preferably after its cationization treatment. Obtained by treatment with at least one thermostable or not enzyme selected from the group comprising “CGTase” (EC 2.4.1.19).
[0076]
The general concept of the present invention is also for the preparation of starch compositions useful as papermaking additives other than standard mass additives or as industrial water treatment additives.
With a fixed nitrogen concentration of at most 2%,
Ten ⁷ A weight average molecular weight less than Dalton,
Viscosity according to test A of up to 1600 mPa.s,
CDI index greater than 600
Based on the use of a cationic starch material having
[0077]
Applicant's company further provides that among the above-mentioned starch compositions that can be used according to the present invention, some are in other applications, in particular sizing agents, synthetic polymers, optical brighteners and / or It has been found that it can also be used advantageously in combination with active substances that can be used in large amounts of papermaking, such as colorants.
[0078]
Such combinations can be made in the same mass additive or using the components of such a combination individually, simultaneously or otherwise.
[0079]
The weight ratio of synthetic polymer to starch material in such a combination may in particular be 1/100 to 100/1 (dry weight / dry weight).
[0080]
According to another variant, the composition according to the invention has a fixed nitrogen concentration of 0.5 to 1.5%, in particular 0.6 to 1.5%, and 10 to 800 mPa.s, in particular 50 to 700 mPa, measured according to test A. Characterized by a selected viscosity of .s.
[0081]
The composition according to the invention can have a pH of up to a value of 10 or even above. However, they preferably have a pH of less than 9, in particular 4 to 8.5, and a charge density index CDI of more than 600.
[0082]
To the best of Applicant's knowledge, such compositions thus selected have all their industrial value obtained from any starch material in a simple and inexpensive manner and generally require any cationic starch material. Preparation of compositions containing optical brighteners in areas of application, papermaking or other areas (including large-scale papermaking and water treatment applications) or, for example, where it is not known to use such materials Constitute new products that are used effectively and safely, especially due to their capabilities.
[0083]
As indicated, the starch compositions already constituted a blend of hydrolyzed cationic starch material and one or more other materials in any proportion at the time of their use. Composed of a reactive starch material and an active substance selected from the group comprising sizing agents, optical brighteners, colorants and synthetic polymers, in particular constituting (mass or non-mass) papermaking or water treatment additives .
[0084]
Furthermore, as Applicants have observed, the hydrolysis of the cationic starch material is completely complete even though the material is already in contact with other active substances such as polyacrylamide in the additive. It can be carried out.
[0085]
According to another variant, said starch composition may contain only hydrolyzed cationic starch material as active substance, and other, as mentioned above, by separate, simultaneous or non-simultaneous use. Can be combined with one or more other (mass or non-mass) papermaking or water treatment additives containing
[0086]
By way of example, the starch composition according to the invention is
In the same additive used in the wet end of the papermaking process, in combination with an active substance such as polyacrylamide,
In combination with active substances such as optical brighteners or colorants in large scale papermaking or in the same additives used during paper surface finishing or coating operations,
In combination with polyacrylamide for the treatment of industrial water, wherein polyacrylamide is introduced separately from the starch composition, simultaneously or otherwise;
The material is the same part of the circulatory system (e.g. at the pulp machine stage) or a different part of the circulatory system (e.g. the optical brightener is at the pulp machine stage and the starch composition is downstream) individually and simultaneously Or can be used in combination with optical brighteners and / or colorants at the wet end of the papermaking process, or otherwise introduced.
[0087]
The subject of the present invention is therefore also that the starch composition is preferably at least one other selected from sizing agents, optical brighteners, colorants and synthetic polymers, in particular polyacrylamide or polyvinylamine. Use of a starch composition as described above, either simultaneously or in combination with other active substances.
[0088]
The invention is described in more detail by the following non-limiting examples.
[0089]
【Example】
Example 1
Potato starch powder having a total nitrogen concentration of 1.48% (dry weight / dry weight) and obtained in the dry phase according to the above-mentioned French Patent No. 2,434,821, mixed with 31% dry substance (`` DM '') Mix and suspend in cold demineralized water to obtain a cationic starch emulsion containing
[0090]
Various samples of the emulsion are treated with various concentrations of “FUNGAMYL 800 L” type α-amylase. This enzyme conversion treatment is carried out by raising the temperature from 20 ° C. to 95 ° C. over 20 minutes in an open tank and holding at 95 ° C. for 5 minutes. Its purpose is to make it possible to obtain a cationic starch composition having a Brookfield viscosity (measured at 25 ° C., 20 rev / min) of about 300-3000 mPa.s and a DM of about 20-22%. .
[0091]
Indeed, the resulting colloidal solution has a final DM of 21.5%. For each resulting solution, the following characteristics:
Brookfield viscosity at 25 ° C. and 20 revolutions / minute expressed in mPa.s,
Charge density expressed in microequivalents (μeqv / g) per gram dry weight of the solution and measured with a particle charge detector of the “MUTEK PCD02” type combined with an automatic titrator of the “METTLER DL21” type The
It is measured as a function of the concentration of degrading enzyme used (% with respect to the dry weight of the initial emulsion).
[0092]
The obtained results are shown below.
[Table 1]

[0093]
Surprisingly, in this example of cationic starch having a fixed nitrogen concentration of up to 2%, in this example about 1.5%, and liquefied batchwise in an enzymatic route, as the degree of liquefaction increases, It can be seen that the charge density tends to increase significantly. The charge density is less than about 800 mPa.s, especially less than 380 Pa.s, corresponding to less than about 700 mPa.s, especially less than 330 Pa.s when DM is adjusted to 21.5% and DM is adjusted to 20% according to test A. It is the largest with samples.
[0094]
Applicant's company further states that all compositions based on the above liquefied cationic starch have significant stability during storage, and the phenomenon of viscosity increase and aging is 17 days or 4 months of storage at 25 ° C. It was admitted that it was not observed later.
[0095]
Example 2
In this example, continuous enzymatic conversion of cationic potato starch containing 1.48% total nitrogen as described in Example 1 is performed. To that end, a mixture of “FUNGAMYL 800 L” enzyme and water was prepared at a rate of 6.7 milliliters of the enzyme per 100 liters of water. Cationic starch is liquefied continuously under the following conditions.
Water / enzyme mixture flow rate: 90 l / h,
Cationic starch powder flow rate: 60 kg / hr, thus producing an emulsion containing about 40% DM,
Reaction time: 30 minutes,
Reaction temperature: 60 ° C.
[0096]
Enzyme activity is inhibited by passing through an inhibition tube at 140 ° C. for 1 minute 30 seconds. Under these conditions, a final DM content of around 26-30% is obtained, which is particularly advantageous since a viscosity of less than 2000 mPa.s, in particular 250-500 mPa.s, can be obtained.
[0097]
In addition, in a specific example of a composition having 28% final DM, a sample was collected over time and the charge density was measured as a function of viscosity.
[0098]
The obtained results are shown below.
[Table 2]

[0099]
In this example of enzyme liquefaction, where the viscosity range (250-500 mPa.s at DM 28%) generally corresponds to an average liquefaction, there is no correlation between viscosity and charge density. Is recognized.
[0100]
In any case, in the context of this example, a viscosity of about 300-400 mPa.s appears to be particularly advantageous compared to the value of charge density obtained.
[0101]
It is preferred that the viscosity be less than 150 mPa.s, especially about 100 to 300 mPa.s, by dilution of such a composition to adjust its DM to a value of 20% according to test A above.
[0102]
Example 3
In this example, cationization of the starch derivative in this example of maltodextrin GLUCIDEX® obtained from waxy corn starch and marketed by the applicant is performed. An aqueous solution containing 50% DM of this derivative is prepared and the solution is heated to a temperature of 70-80 ° C. Then, 40% cationic reagent of TMAEP type and 1.5% sodium hydroxide described in French Patent 2.434,821 above are added respectively. These percentages are expressed as dry weight / maltodextrin dry weight.
[0103]
After reaction (5 hours at 50 ° C.) and neutralization at pH 6.7, starch composition with 49% DM and viscosity measured after adjusting DM to 20% according to test A is about 40 mPa.s A thing is obtained.
[0104]
The cationic starch material contained in the composition has a fixed nitrogen concentration (dry weight / dry weight) of 1.8%, which takes into account the total nitrogen concentration (2.16%) provided by the cationizing reagent. The cationic reagent immobilization yield is about 83%.
[0105]
Example 4
In this example, the properties of the starch composition according to the present invention as described above are marketed under the trade name `` RAIFIX 120 '' for use as an agent to reduce inconvenient substances present in the papermaking circulation system, and A comparison is made with respect to the properties measured for the cationic starch composition designated "COMPOSITION T". The compositions according to the invention are obtained from the previous Examples 1, 2 and 3 and are respectively referred to below as COMPOSITION 1, 2 and 3.
[0106]
Measured properties include dry matter (% DM), pH, total nitrogen concentration (% dry weight /% dry weight TOTAL N), fixed nitrogen concentration (% dry weight /% dry weight%) `` FIXE N ''), Brookfield viscosity (`` VISCOSITY '' in mPa.s units) measured at 20% DM, 25 ° C. and 20 rpm according to test A, weight average of the cationic starch material contained in the composition Molecular weight (million Dalton or 10 measured by size exclusion chromatography in combination with light scattering detector ⁶ dMM “MM”), charge density (“eq” in μeqv / g “CD”) and CDI index corresponding to the CD / TOTAL N ratio.
[0107]
The following results are obtained.
[Table 3]

[0108]
The overall result is that the composition according to the present invention comprising a starch material with a significantly lower degree of cationization and a higher degree of liquefaction than the starch material contained in COMPOSITION T according to the prior art It has a fairly high CDI value.
[0109]
These high CDI values above 600, or even 650, have better nitrogen fixation provided by the cationization step and thereby reduced the presence of nitrogen-containing and saline residues in the COMPOSITION 1-3 It is shown that.
[0110]
Example 5
COMPOSITION 5 (not according to the present invention) and COMPOSITION 2 and 3 (according to the present invention) as described above may be included in (and / or stored in the equipment) water circulation system for papermaking or other uses or A comparative test was conducted as an agent to reduce another inconvenient substance (collectively referred to below as “pitch”).
[0111]
In this case, the application medium consists of paper pulp consisting of about 80% of unused chemical pulp (mixed with broad leaf and resinous materials) and 20% production casse paper as a whole. Yes. It has a concentration of about 10 g / kg, a conductivity of about 1400 μS / cm, a zeta potential of −13.4 mV, a pH of 7.7 and a charge density of 85 μeq / l measured for the supernatant passed through a 140 μm filter.
[0112]
COMPOSITION T, 2 and 3 with DM adjusted to 20% are introduced into the pulp at a rate of 0.3% (dry weight / dry weight). The contact time between each COMPOSITION and the pulp is 5 minutes while stirring at 1000 rpm.
[0113]
The test is performed in the absence of any starch composition. The “pitch” measurement is a standard method starting with a “water under cloth” collected after the above treatment and passed through a 30 μm filter, using a THOMAS cell. Do it.
[0114]
Zeta potential (`` POTENTIAL '' in mV), charge density (`` SCD '' in μeq / l) and number of `` pitch '' (thousands or 10 ^Three / mm ^Three The obtained results of “PITCHS” in the unit of filtered water under cloth are shown below.
[Table 4]

[0115]
These results show that COMPOSITION according to the present invention has a relatively low nitrogen concentration, but is completely effective as an agent for reducing “pitch”. They are generally as effective as COMPOSITION T, which is nevertheless more difficult to prepare, has a significantly higher degree of cationization, and is therefore more expensive and more charged with various residues.
[0116]
In particular, COMPOSITION 2 is particularly well suited for this application. The Applicant has further recognized that it can also be used as a flocculant for biological and / or mineral sludge obtained from sewage sewage purification plants, or as a cleaner for papermaking machine water.
[0117]
Example 6
This example tests the emulsifying properties of COMPOSITION 2 according to the present invention, provided in the form of a paste containing 27% DM. 13.5 g of sizing agent “FIBRAN 76” based on alkenyl succinic anhydride (“ASA”) was added to 100 g of the paste. Therefore, a total of 27 g of cationic starch material is included.
[0118]
The resulting size composition with a starch material (dry weight) / sizing ratio of 2/1 is then subjected to a strong shearing treatment, ie 5 minutes homogenization at 20,000 revolutions / minute.
[0119]
The emulsion thus obtained is diluted with drilling water without stirring in a 1 liter volumetric flask to obtain an emulsion of `` FIBRAN 76 '' (`` EMULSION 1 '') containing 1.35% sizing agent, with a size of 0.3% To obtain an emulsion containing the agent (“EMULSION 2”), a portion of EMULSION 1 is re-diluted under the same conditions.
[0120]
Observations made periodically over 54 hours showed that the EMULSION 1 and 2 so obtained remained completely stable and homogeneous.
[0121]
Example 7
In this example, the cationic starch is treated with glycogen branching enzyme to prepare the additive according to the present invention as described in Example 4 of the above-mentioned International Patent Publication No. 00/66633.
[0122]
For this purpose, a dilute enzyme solution is prepared by adding 150 ml of the enzyme in advance to 2 liters of demineralized water, previously maintained at a temperature of 30 ° C. and having a pH of 7-8.
[0123]
The diluted enzyme solution is then subjected to the same as used in Example 1, ie about 1.5% (dry weight / dry weight) total nitrogen concentration and about 1.2% (dry weight / dry weight) fixed nitrogen concentration. The potato starch which has is gently sprinkled and introduced.
[0124]
This operation is achieved by introducing the cationic potato starch having a concentration of 110 to 120 g / l without excessive swelling or excessive energy consumption required for stirring by introducing as regularly as possible. This was done in order to obtain a colloidal solution.
[0125]
During this preparation phase, the temperature is carefully maintained at 30 ° C. and the pH at 6-8, preferably 6.5-7.
[0126]
Under this condition, the conversion is continued for 4 hours.
[0127]
The conversion is interrupted by inactivation of the enzyme consisting of maintaining at 95 ° C for 15 minutes.
[0128]
In fact, the colloidal solution obtained at the end of all these operations has 10% final DM and the following properties:
Brookfield viscosity: 50 mPa.s (25 ° C, 20 rpm),
Charge density (CD): 922μeqv / g,
CDI: 615,
Weight average molecular weight (MM): Approximately 3.2 × 10 ⁶ Dalton.
[0129]
In this example of enzyme conversion by a branching enzyme, the relatively low viscosity obtained, which appears to be significantly lower than 300 mPa.s according to test A, is a relatively high weight average molecular weight, i.e. 2 x 10 ⁶ It is observed that it is compatible with maintaining values higher than Dalton.
[0130]
The resulting starch composition has a stability during storage that is greater than that observed with the composition obtained from Example 1 by itself or after concentration to about 21.5% DM. Yes.
[0131]
Example 8
In this example, a starch composition is prepared under the same conditions as described in Example 7. However,
1) Potato starch has a total nitrogen concentration of about 1.1% (dry weight / dry weight) and a fixed nitrogen concentration of about 1.0% (dry weight / dry weight),
2) Conversion by branching enzyme is performed over 45 minutes (instead of 4 hours)
3) The final DM of the resulting colloidal solution is 16.3% (instead of 10%).
[0132]
The starch composition thus obtained has the following properties:
Brookfield viscosity: 625 mPa.s,
Charge density (CD): 716μeqv / g,
CDI: 650,
Weight average molecular weight (MM): Approximately 2.5 × 10 ⁶ Dalton.
[0133]
This composition has significant stability during storage.
[0134]
Further, Applicant's company, under the test conditions described in Example 5 above, can achieve an effect equivalent to that observed in COMPOSITION 2 or 3, in which case- 6.4 mV zeta potential, 65 μeq / l charge density (SCD) and 16.4 × 10 ^Three / mm ^Three Having a "pitch" of filtered water below the cloth, it proved that the composition may be perfectly suitable as an agent for reducing undesirable substances present in the papermaking circulation.
[0135]
Example 9
In this example, the value of the starch composition according to the present invention is tested in combination with an optical brightener and, optionally, other colorants.
[0136]
The starch composition according to the present invention was obtained by enzymatic conversion of cationic potato starch with α-amylase having a total nitrogen concentration of about 1.65% and a fixed nitrogen concentration of about 1.5%.
[0137]
The starch composition is provided in paste form with the main features as follows.
Dry matter (DM): 27.9%
Brookfield viscosity: 450 mPa.s (25 ° C, 20 rpm)
Charge density: 1056μeqv / g
CDI: about 640.
[0138]
In this case, the active substance is introduced into a mass of paper pulp as follows by weight.
20% resinous kraft pulp,
60% broad leaf kraft pulp,
20% casse paper.
[0139]
Before introducing the pulp into the cracker, the following are introduced sequentially into the water to fill the apparatus.
a) the above cationic starch composition or cationic polyacrylamide, which is an amount corresponding to DM of said starch composition;
b) Optical brightener, which corresponds to about 5 times the amount of cationic product used in a), and then optionally a mixture of colorants, which is the cation used in a) This is equivalent to about 2.5 times the amount of sex products.
[0140]
After introducing the pulp and decomposing it for 30 minutes, using the material "TECHPAP" about 80g / m ² A sheet having the following materials is generated.
[0141]
Measurements of whiteness and fluorescence are carried out essential in them.
[0142]
From the results obtained, in general, the starch composition according to the present invention comprising the enzymatically converted cationic starch material has a synthetic cationic polymer in both the presence and absence of the colorant. It has been found that it is possible to have an optical brightener efficiency that is at least as high as that obtained using, generally higher.
[0143]
Example 10
This example tests the value of starch compositions in the field of water treatment according to or not according to the present invention. This is the situation in combination with a synthetic coagulant, in this case the cationic polyacrylamide “PERFORM PA 9430” marketed by HERCULES.
[0144]
In TRIAL A, B and C, the polyacrylamide is tested in combination with a starch paste based on: That is,
TRIAL A: Cationic potato starch with about 0.64% fixed nitrogen (dry weight / dry weight), not hydrolyzed and therefore not according to the invention,
TRIAL B: Cationic potato starch containing about 1.5% fixed nitrogen (dry weight / dry weight) hydrolyzed with α-amylase according to the present invention,
TRIAL C: Cationic potato starch hydrolyzed with a branching enzyme according to the present invention (fixed nitrogen: about 1.5% as dry weight / dry weight).
[0145]
In addition, a control test (“TRIAL T”) is performed in which the polyacrylamide is not combined with the starch composition.
[0146]
In all these tests, papermaking effluents with a suspended solids concentration on the order of 1.6 g / l are treated.
[0147]
Immediately stir the collected waste liquid sample. Perform the following series of operations.
t = 1 minute: The starch composition is introduced into the stirred waste liquid (TRIAL A to C) or not (TRIAL T). This is done at an introduction rate of 0.03 ° / °° (dry weight / dry weight).
t = 6 min: introduction of synthetic coagulant (TRIAL T and AC). This is done at a rate of 0.001 ° / ° expressed as the weight of commercial product / dry weight of the effluent.
t = 7 min: End of stirring
From t = 7 min to t = 9 min: Observation of decantation.
t = 12 min: determination of the dry matter content of the supernatant (“DMS” in g / l) and the optical density (“OD”) of the supernatant.
[0148]
The following results have been obtained with TRIAL T and A not according to the invention and TRIAL B and C according to the invention.
[Table 5]

[0149]
These results generally indicate that the starch composition according to the present invention can be advantageously used for water treatment, especially in combination with synthetic polymers such as cationic polyacrylamides (see TRIAL B and C). ).
[0150]
These starch compositions make it possible to improve the effluent purification very significantly by reducing the dry matter content and optical density of the supernatant. This is far greater than the improvement that can be obtained with starch compositions not according to the invention (see TRIAL A).
[0151]
Starch compositions tested with TRIAL C, based on cationic starch materials converted by branching enzymes, appear to be particularly effective when combined with cationic polyacrylamide.
[0152]
Example 11
In this example, a hydrolyzed cationic material according to the invention and a cationic polyacrylamide such as the product `` PRAESTOL 853 BC '' marketed in powder form by STOCKHAUSEN (large or non-large scale quantities) ) Combine in the same additive that can be used for papermaking or water treatment.
[0153]
Such a combination is advantageously carried out by bringing the starch material and the synthetic material into contact with each other just prior to the stage of conversion aimed at hydrolyzing the cationic starch material, as in this example. it can.
[0154]
A starch emulsion containing 30% DM is prepared from the same cationic potato starch powder used in Example 1. 5% of the cationic polyacrylamide is then added to this suspension. This percentage is expressed as the weight of commercially available polyacrylamide / weight of dry starch.
[0155]
Next, 0.15 ° / °° of “FUNGAMYL 800 L” type α-amylase, expressed as the weight of the commercial product relative to the dry starch weight, is added.
[0156]
The enzyme conversion treatment is then carried out by raising the temperature from live steam to 20 ° C. to 95 ° C. over 20 minutes in an open tank, and then held at 95 ° C. for 5 minutes to inhibit the enzyme.
[0157]
The DM of the resulting composition is then adjusted to a value of about 22%.
[0158]
The starch composition obtained by blending the hydrolyzed cationic starch material and the cationic polyacrylamide has the following main characteristics.
DM: 22.2%
Brookfield viscosity: 1500 mPa.s (25 ° C, 20 rpm),
Charge density: 1040 μeqv / g.
[0159]
It can be seen that the viscosity of this composition is increased according to Example 1 using 0.15 ° / ° α-amylase compared to the composition obtained in the absence of synthetic polymer.
[0160]
However, this viscosity is consistent with the target set. That is, it is 1600 mPa.s at most (according to test A).
[0161]
Moreover, according to observations made by the applicant, the composition remains stable after storage for 25 days at 25 ° C., and the hydrolyzed cationic starch material it contains is completely solubilized. I know that

Claims (9)

As an agent for reducing inconvenient substances contained in a water circulation system and / or stored in a paper processing apparatus, as an additive in the preparation of a sizing composition used in papermaking, paper squeezing, Additives for papermaking selected from additives used as additives in the preparation of compositions containing optical brighteners, colorants and / or synthetic polymers as additives in the preparation of compositions for surface finishing or coatings as or as industrial water treatment additive, agent, a use of a starch composition comprising at least one cationic starch material, wherein the starch composition,
- expressed in percentage against the dry weight of the set Narubutsu, a fixed concentration of nitrogen 0.4 to 1.5%,
-Measured according to Test A , corresponding to measuring the viscosity of a composition having a dry matter content of 20% on a Brookfield viscometer at 25 ° C and 20 revolutions per minute , 10-800 mPa.s characterized in that it has a s viscosity <br/> of use. Use according to claim 1, cationic starch material and having a weight average molecular weight of less than 10 ⁷ daltons. Use according to claim 2 , characterized in that the cationic starch material has a weight average molecular weight of 10 ⁴ to 4 x 10 ⁶ daltons. The starch composition has a charge density index ( CDI ) defined by a ratio of charge density expressed in μeqv / g to the total nitrogen concentration of the composition greater than 600. Use as described in any one of thru | or 3 . Use according to claim 4 , characterized in that the starch composition has a CDI value of 660-800. Use according to any one of claims 1 to 5 , characterized in that the starch composition has a pH of 4 to 8.5. The starch composition
- and 0.5% to 1.5% of fixed nitrogen concentration,
-Measured according to test A, 50-700 mPa.s 7. Use according to any one of claims 1 to 6, characterized in that it has a viscosity of s. Use of the starch composition according to any one of claims 1 to 7, characterized in that it has a dry matter content of 1 8% to 40%. The starch material, prior to cationization treatment, during and / or after, or without having heat resistance, branching enzymes (EC 2.4.1.18) and cyclodextrin glycosyltransferase (EC 2.4.1 Use according to any one of claims 1 to 8, characterized in that the cationic starch material is obtained by treatment with at least one enzyme selected from the group comprising: