JP3876522B2 - Papermaking paper strength enhancer and method for producing strong paper - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、酵素変性により低粘度化した酵素変性低粘度化カチオン澱粉水溶液中において（メタ）アクリルアミドを含むビニルモノマー類を重合して得られる水溶性重合体を有効成分とする製紙用紙力増強剤及び該製紙用紙力増強剤を製紙原料に添加して抄造することによって、優れた乾燥時の紙力増強効果が得られると共に地合と離解性に優れた強力紙が製造できる強力紙の製造法に関するものである。
【０００２】
【従来の技術】
従来、製紙工程においては成紙の乾燥時の諸強度を向上させるために、カチオン化澱粉、アクリルアミド系ポリマーなどの水溶性高分子が用いられている。又、一定粘度範囲を持ったカチオン化澱粉水溶液中でアクリルアミドなどのモノマーを重合したグラフトポリマーを製紙用紙力増強剤に用いる提案もある（特開昭６２−２１９６９６号公報、特開昭６３−１７０８３８号公報）。
【０００３】
【発明が解決しようとする課題】
カチオン化澱粉は製紙用紙力増強剤として広く一般に用いられており、特に中性又はアルカリ性の抄造において汎用されている紙力増強剤であるが、紙力増強効果を発揮させるには比較的多量の添加量を必要とし、又、多量に添加しても一定以上の紙力増強効果は得られずに、効果の頭打ち現象を示す欠点がある。さらに、澱粉類の多量使用には製紙マシンの生産性の低下につながるワイヤー上の水切れの悪化を招くだけでなく、製紙工場のＢＯＤ，ＣＯＤの上昇にもつながり、廃水負荷を増やすという欠点もある。
【０００４】
一方、周知の通り、アクリルアミド系ポリマーの内添紙力増強剤が酸性抄紙系を主体として用いられてきたが、近年、カチオン性の製品が中性、アルカリ性抄紙の紙力増強剤として導入され始めており、これら製品は比較的少量の使用で効果を発揮するものではあるが、ポリマーの持つ凝集効果により紙の地合を悪化させる欠点があり、又、使用量が多くなると製紙用具の汚れを誘発する欠点もある。
【０００５】
前記カチオン化澱粉からなる紙力増強剤、アクリルアミド系ポリマーからなる紙力増強剤は、ともに湿潤紙力増強剤ほどではないが、紙の離解性を悪化させるのが通例であり、紙のリサイクル時のエネルギー負荷の増大を招く恐れがある。
【０００６】
前記の各紙力増強剤の諸欠点を改善したものとして、カチオン澱粉グラフト化ポリマーが提案されており、カチオン澱粉グラフト化ポリマーはカチオン化澱粉に比べ少量の添加で紙力増強効果を発揮するが、アクリルアミド系ポリマーからなる紙力増強剤に比べれば同一添加量では紙力増強効果が劣り、又、高価な特殊カチオン化澱粉を原料として使用する必要があり、経済的ではない。
【０００７】
【課題を解決するための手段】
本発明者等は、より優れた製紙用紙力増強剤の開発を目指して、鋭意研究を重ねた結果、カチオン化澱粉を酵素変性により特定の粘度範囲に低粘度化した後、その酵素変性カチオン化澱粉水溶液中において、アクリルアミド及び／又はメタアクリルアミド（以下、「（メタ）アクリルアミド」とする）を必須成分とするビニルモノマー類を重合して得られる水溶性重合体からなる製紙用紙力増強剤を使用する場合には、優れた乾燥時の紙力増強効果が得られると共に地合と離解性に優れた強力紙が得られることを見出し本発明を完成したものである。
【０００８】
即ち、本発明は、カチオン化澱粉を酵素により変性して温度２５℃における固形分１０％水溶液の粘度が１〜５０ｃｐｓ（Ｂ型粘度計、ローター１、回転数６０ｒｐｍ）となるように低粘度化した酵素変性低粘度カチオン化澱粉水溶液中において、（メタ）アクリルアミドを必須成分とするビニルモノマー類を重合して得られる水溶性重合体を有効成分とする製紙用紙力増強剤及び該製紙用増強剤を製紙用原料に添加して抄造する地合と離解性に優れた強力紙の製造法である。
【０００９】
なお、本発明における（メタ）アクリルアミドを必須成分とするビニルモノマー類とは、（メタ）アクリルアミド単独又は（メタ）アクリルアミド及び（メタ）アクリルアミドと共重合可能なビニルモノマーを含有しているビニルモノマー混合物である。
【００１０】
本発明におけるカチオン化澱粉は、例えば、馬鈴薯，さつまいも，タピオカなど各種植物の地下部から得られる澱粉や、小麦，米，とうもろこしなどの各種穀物から得られる澱粉、又は、これら澱粉の誘導体を公知のカチオン化剤、例えば３−クロロ−ヒドロキシプロピルトリメチルアンモニウムクロライドやグリシジルトリメチルアンモニウムクロライド等と触媒の存在下に反応させることによって得られる。中でも、タピオカ原料の澱粉類を上記公知カチオン化剤によってカチオン化したカチオン澱粉が最終製品の安定性、紙力増強効果において最も好ましく、さらに、カチオン化の程度を表すＤＳ（カチオン化置換率）において、０．０３５以上のカチオン化澱粉を使用することが安定性、紙力増強効果の点で特に好ましい。
【００１１】
本発明における酵素変性低粘度カチオン化澱粉を得るために使用する澱粉分解酵素は、各種細菌、動植物の生産するα−アミラーゼが最も好ましく使用される。
【００１２】
なお、未変性澱粉（生澱粉）、又は、アセチル化、エステル化及びエーテル化などの軽度の変性澱粉類に酵素を作用させて低粘度化した後、前記公知カチオン化剤と反応させた低粘度カチオン化澱粉も使用することは可能であるが、残存する副生物がモノマー類の重合反応を阻害するケースがあり、望ましくない。
【００１３】
本発明における酵素変性低粘度カチオン化澱粉は、澱粉分解酵素を用いて調製することが特に重要であり、その他の化学的方法、例えば過硫酸塩、次亜ハロゲン酸塩などの酸化剤を用いて澱粉を低粘度化する方法等により得られた低粘度カチオン化澱粉を使用した場合には大きく紙力増強効果が劣るので、使用に堪えない。
【００１４】
本発明における酵素変性低粘度カチオン化澱粉の粘度範囲は、温度２５℃において固形分１０％水溶液の粘度が１〜５０ｃｐｓ、好ましくは３〜２０ｃｐｓである。粘度が１ｃｐｓ以下の場合には十分な紙力増強効果が得られない。又、粘度が５０ｃｐｓ以上の場合には製品の経時安定性が劣り、紙の再離解性が不十分である。
【００１５】
本発明において使用する（メタ）アクリルアミドと共重合可能なビニルモノマーとしては、アニオン性ビニルモノマーとして、アクリル酸、メタクリル酸、イタコン酸、無水マレイン酸、フマール酸、ビニルスルホン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、メタアリルスルホン酸、又はそれらのナトリウム、カリウム、アンモニウム塩などが挙げられる。又、カチオン性ビニルモノマーとして、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎジメチルアミノプロピル（メタ）アクリルアミド、ビニルピリジン、ビニルイミダゾール、アリルアミン、ジアリルアミン等のアミノ基を有するビニルモノマー、又はそれらの塩類又はそれらの４級化物の塩酸塩、ギ酸塩、酢酸塩、スルファミン酸塩等が挙げられる。又、非イオン性モノマー類として、ジアルキルアクリルアミド、スチレン、アリルアルコール、（メタ）アクリルエステル、アクリロニトリル、酢酸ビニル、ヒドロキシアルキル（メタ）アクリルエステル、ビニルピロリドンなどが挙げられる。
更に、架橋性ビニルモノマーとして、メチロール（メタ）アクリルアミド、ジメチルアクリルアミド、トリアクリルフォルマール、その他２官能性、３官能性、４官能性の各種ビニルモノマーが挙げらる。
【００１６】
本発明における（メタ）アクリルアミドを必須成分とするビニルモノマー類の好ましい使用割合は、（ａ）（メタ）アクリルアミド７０〜９９モル％と（ｂ）アニオン性ビニルモノマー及びカチオン性ビニルモノマーから選ばれるイオン性ビニルモノマーの少なくとも１種１〜３０モル％とである。
【００１７】
本発明に係る製紙用紙力増強剤の製造方法は、周知の重合方法により行なうことができる。例えば、攪拌及び窒素ガス導入管を備えた反応容器に前記酵素変性低粘度化カチオン澱粉の水溶液と（メタ）アクリルアミド又は（メタ）アクリルアミド及び（メタ）アクリルアミドと共重合可能なビニルモノマー類と水とを仕込み、重合開始剤として過酸化水素、過硫酸アンモニウム、過硫酸カリウム、アンモニウムハイドロパーオキサイドなどの過酸化物、又は、これらの過酸化物と重亜硫酸塩などの還元剤とを組み合わせたレドックス開始剤、あるいは、２−２′アゾビス（２−アミノジプロパン）塩酸塩等の水溶性アゾ系重合開始剤などを使用し、重合反応させることにより目的とする重合物を得ることができる。
【００１８】
なお、本発明に係る製紙用紙力増強剤を製造するに際しては、酵素変性低粘度カチオン化澱粉２０〜８０重量部を含有する水溶液中において（メタ）アクリルアミドを必須成分とするビニルモノマー混合物のモノマー分として２０〜８０重量部を重合させることが好ましい。
【００１９】
本発明に係る製紙用紙力増強剤は、通常、固形分１０〜４０重量％程度の水性分散液の形で得られる。
【００２０】
本発明に係る製紙用紙力増強剤は、通常、製紙工程のウエットエンドと称される位置において水中に分散された製紙原料のスラリー中に添加されて効率よく繊維原料に定着し、抄き上がった紙に優れた乾燥時の紙力効果をもたらすと共に地合と離解性に優れた性質を付与するものである。
【００２１】
本発明に係る製紙用紙力増強剤を使用するに当っては、既知の製紙用内添薬品、例えば硫酸バンド、内添サイズ剤、他の紙力増強剤、填料等を併用することは何ら差し支えなく、又、本発明に係る製紙用紙力増強剤がカチオン性を示す時にはアニオン性の添加剤が併用効果を示す場合が多く、本発明に係る製紙用紙力増強剤がアニオン性を示す時にはカチオン性の添加剤が併用効果を示す場合が多い。
【００２２】
本発明に係る製紙用紙力増強剤を使用する紙は特に限定されず、例えば、上質紙、中質紙、コート原紙、新聞用紙、加工原紙、ライナー段ボール原紙、白板紙、ＰＰＣ用紙、インクジェット用紙、感熱紙、特殊紙、プリンター用紙、石膏ボード原紙、トイレットペーパー、ティッシュペーパー、その他衛生紙、建材用紙等に使用することができる。
【００２３】
【発明の実施の形態】
本発明の実施の形態は次の通りである。
【００２４】
［製紙用紙力増強剤の調製］
カチオン化澱粉１部に水３部を添加してスラリーとした後、ｐＨを６に調整、酵素の所定量を添加混合して徐々に加温して酵素変性を行い、４０分後に９０℃に昇温せしめ、硫酸を用いてｐＨを４として酵素反応を終結、水を加えて、酵素変性低粘度カチオン化澱粉水溶液を得た。
【００２５】
ここに得た酵素変性カチオン化澱粉水溶液、（メタ）アクリルアミド、アクリル酸、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、水の所定量を混合し、希硫酸を用いてｐＨを５に調整した。全量を攪拌機を付したフラスコ中に入れ、湯浴中で加温、内温５５℃で過硫酸アンモニウム及び重亜硫酸ソーダを所定量添加、４０〜８０℃で１〜５時間重合反応を行なった後冷却、所定量の水を加えて、製紙用紙力増強剤を得た。
【００２６】
［強力紙の製造］
１％パルプスラリーに、調製した前記製紙用紙力増強剤を所定量添加し、ＴＡＰＰＩスタンダードシートマシンにより常法通り手抄シートを調製した。得られたシートは１１０℃のプレートドライヤーにより２分間乾燥し、米坪６０ｇ／ｍ２に相当する手抄紙を得た。
【００２７】
［強力紙の評価方法］
手抄紙は２０℃、相対湿度６５％の室内に一昼夜調湿後、乾燥時の紙力、地合及び離解性を試験した。なお紙力は、ＪＩＳ Ｐ８１１３に準じて裂断長、及びＪＩＳ Ｐ８１１２に準じ比破裂度を測定した。地合は肉眼判定、離解性テストは下記によった。
【００２８】
［離解性テスト法］
１ｃｍ２に裂いたテスト紙片１ｇを２００ｃｃの２０℃のイオン交換水中に投入し、試験用ブレンダー中で６０Ｖの電圧で１分間離解した後、ＴＡＰＰＩスタンダードシートマシンにより手抄シートを調製し、１１０℃のプレートドライヤーにより２分間乾燥して、５０ｇ／ｍ２に相当する再生紙を調製、成紙の均一性を比較して離解性の目安とした。
【００２９】
［製紙用紙力増強剤の安定性試験方法］
製品を２℃の冷蔵庫中に３０日間冷蔵した後、外観の変化及び２５℃におけるＢ型粘度計による粘度を測定して冷蔵前の粘度からの変化を調べ、安定性の目安とした。
【００３０】
【実施例】
以下、実施例、比較例を挙げて、本発明をより詳しく説明するが、本発明はこれら各例に限定されるものではない。尚、各例中、部及び％は、特記しない限り全て重量基準である。
【００３１】
実施例１：
［製紙用紙力増強剤の調製］
置換度（ＤＳ）０．０４のカチオン化タピオカ澱粉１部に水３部を添加してスラリーとした後、ｐＨを６に調整、αアミラーゼ（スピターゼＰＧ−２：ナガセ生化学工業（株）製）０．０００５部を添加混合して徐々に加温して酵素変性を行い、４０分後に９０℃に昇温せしめ、硫酸を用いてｐＨを４として酵素反応を終結、水を加えて、固形分１５％に調整し、２５℃１０％液の粘度８ｃｐｓを有する酵素変性低粘度カチオン化澱粉水溶液を得た。
【００３２】
ここに得た酵素変性低粘度カチオン化澱粉水溶液１３３部、アクリルアミド１７．１部、アクリル酸０．５８部、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド２．４６部を混合し、水を加えて、全量を１８０部とし、希硫酸を用いてｐＨを５に調製した。全量を攪拌機を付したフラスコ中に入れ、湯浴中で加温、内温５５℃で過硫酸アンモニウム及び重亜硫酸ソーダの各０．０２部を添加、６５〜７０℃で３時間重合反応を行った後冷却、水を加え全量を２０５部として、２５℃の粘度５０００ｃｐｓを有する製紙用紙力増強剤を得た。その製品性状を表１に示す。
【００３３】
【表１】
実施例２〜７：
実施例１において、カチオン化澱粉の種類、ビニルモノマーの重量割合、ビニルモノマー成分の種類、その配合組成（モル％）を表１に示す通りに変え、過硫酸アンモニウム、重亜硫酸ソーダの使用量を変更した以外は、実施例１と同様の方法で反応を行い、それぞれ紙力増強剤を得た。その製品性状と安定性を表１に併記する。
【００３５】
比較例１〜３：
実施例２〜７と同様に、カチオン化澱粉の種類とビニルモノマーの重量割合、ビニルモノマー成分の種類、その配合組成（モル％）を表１に示す通りに変え、過硫酸アンモニウム、重亜硫酸ソーダの使用量を適宜変更した以外は、実施例１と同様の方法で反応を行い、それぞれ比較の為の紙力増強剤１〜３を得た。
その製品性状と安定性を表１に併記する。
【００３６】
［強力紙の製造］
カナディアンフリーネス４００ｃｃに叩解した晒しクラフトパルプ（Ｌ−ＢＫＰ）の１％パルプスラリーに実施例及び比較例で調製した各製紙用紙力増強剤を対気乾パルプ重量固形分０．５％添加し、ＴＡＰＰＩスタンダードシートマシンにより常法に従って手抄シートとし、得られたシートを１１０℃のプレートドライヤーにより２分間乾燥し、米坪６０ｇ／ｍ２に相当する手抄紙を得た。
【００３７】
実施例及び比較例の各紙力増強剤を使用して得た各手抄紙の評価試験結果を表２に示す。
【００３８】
【表２】
【発明の効果】
本発明によれば、実施例にも示した通り、優れた乾燥時の紙力増強効果が得られると共に、地合と離解性に優れた強力紙を製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paper-making paper strength enhancer comprising, as an active ingredient, a water-soluble polymer obtained by polymerizing a vinyl monomer containing (meth) acrylamide in an enzyme-modified low-viscosity cationic starch aqueous solution whose viscosity has been reduced by enzyme modification. And a method for producing strong paper capable of producing a strong paper excellent in formation and disintegration as well as an excellent paper strength enhancing effect during drying by adding the paper-making paper strength-enhancing agent to the papermaking raw material and making paper It is about.
[0002]
[Prior art]
Conventionally, water-soluble polymers such as cationized starch and acrylamide-based polymers have been used in the papermaking process in order to improve various strengths during drying of the resultant paper. There is also a proposal to use a graft polymer obtained by polymerizing a monomer such as acrylamide in an aqueous cationized starch solution having a certain viscosity range as a paper-making paper strength enhancer (Japanese Patent Laid-Open Nos. 62-219696 and 63-170838). Issue gazette).
[0003]
[Problems to be solved by the invention]
Cationized starch is widely used as a paper-making paper strength enhancer, and is a paper strength enhancer that is widely used especially in neutral or alkaline papermaking. The addition amount is required, and even if it is added in a large amount, the paper strength enhancing effect of a certain level or more cannot be obtained, and there is a drawback that the effect reaches its peak. Furthermore, the use of large amounts of starch not only leads to worsening of the water drainage on the wire, which leads to a decrease in the productivity of the papermaking machine, but also increases the BOD and COD of the paper mill and has the disadvantage of increasing the wastewater load. .
[0004]
On the other hand, as is well known, acrylamide polymer internal paper strength enhancers have been used mainly for acidic papermaking, but in recent years, cationic products have begun to be introduced as paper strength enhancers for neutral and alkaline papermaking. Although these products are effective when used in relatively small amounts, they have the disadvantage of deteriorating the texture of the paper due to the cohesive effect of the polymer. There are also disadvantages.
[0005]
Both the paper strength enhancer made of the cationized starch and the paper strength enhancer made of the acrylamide polymer are not as good as the wet paper strength enhancer, but usually deteriorate the disintegration property of the paper. There is a risk of increasing the energy load.
[0006]
A cationic starch grafted polymer has been proposed as an improvement of the various disadvantages of each paper strength enhancer, and the cationic starch grafted polymer exhibits a paper strength enhancing effect with a small amount of addition compared to cationized starch. Compared with a paper strength enhancer comprising an acrylamide polymer, the same amount of addition is inferior in paper strength enhancement effect, and it is necessary to use expensive special cationized starch as a raw material, which is not economical.
[0007]
[Means for Solving the Problems]
As a result of intensive research aimed at developing a better paper-making paper strength enhancer, the present inventors have reduced the viscosity of cationized starch to a specific viscosity range by enzyme modification, and then performed enzyme-modified cationization. Uses a paper-making paper strength enhancer made of a water-soluble polymer obtained by polymerizing vinyl monomers containing acrylamide and / or methacrylamide (hereinafter referred to as “(meth) acrylamide”) as essential components in an aqueous starch solution. In this case, the present invention has been completed by finding that it is possible to obtain an excellent paper strength enhancing effect during drying and to obtain a strong paper excellent in formation and disaggregation.
[0008]
That is, the present invention reduces the viscosity so that the viscosity of a 10% solid content aqueous solution at 25 ° C. is 1 to 50 cps (B-type viscometer, rotor 1, rotation speed 60 rpm) by modifying the cationized starch with an enzyme. Paper-making paper strength enhancer comprising water-soluble polymer obtained by polymerizing vinyl monomer having (meth) acrylamide as an essential component in the enzyme-modified low-viscosity cationized starch aqueous solution and the paper-making enhancer Is a method for producing strong paper with excellent formation and disaggregation.
[0009]
The vinyl monomers having (meth) acrylamide as an essential component in the present invention are (meth) acrylamide alone or a vinyl monomer mixture containing (meth) acrylamide and a vinyl monomer copolymerizable with (meth) acrylamide. It is.
[0010]
As the cationized starch in the present invention, for example, starch obtained from the underground part of various plants such as potato, sweet potato, tapioca, starch obtained from various grains such as wheat, rice, corn, or derivatives of these starches are known. It can be obtained by reacting with a cationizing agent such as 3-chloro-hydroxypropyltrimethylammonium chloride or glycidyltrimethylammonium chloride in the presence of a catalyst. Among them, a cation starch obtained by cationizing a tapioca raw material starch with the above-mentioned known cationizing agent is most preferable in terms of the stability and paper strength enhancing effect of the final product, and further, in DS (cationization substitution rate) representing the degree of cationization. It is particularly preferable to use a cationized starch of 0.035 or more in terms of stability and paper strength enhancing effect.
[0011]
As the amylolytic enzyme used for obtaining the enzyme-modified low-viscosity cationized starch in the present invention, α-amylase produced by various bacteria and animals and plants is most preferably used.
[0012]
In addition, the low viscosity which made it react with the said well-known cationizing agent after making an enzyme act on unmodified starch (raw starch) or mild modified starches, such as acetylation, esterification, and etherification. Although cationized starch can also be used, it is not desirable because the remaining by-products may inhibit the polymerization reaction of the monomers.
[0013]
It is particularly important that the enzyme-modified low-viscosity cationized starch in the present invention is prepared using an amylolytic enzyme, and other chemical methods, for example, using an oxidizing agent such as persulfate or hypohalite. When low viscosity cationized starch obtained by a method for reducing the viscosity of starch is used, the effect of enhancing paper strength is greatly inferior, so it cannot be used.
[0014]
The viscosity range of the enzyme-modified low-viscosity cationized starch in the present invention is such that the viscosity of a 10% solid content aqueous solution is 1 to 50 cps, preferably 3 to 20 cps at a temperature of 25 ° C. When the viscosity is 1 cps or less, a sufficient paper strength enhancing effect cannot be obtained. On the other hand, when the viscosity is 50 cps or more, the stability with time of the product is inferior, and the re-disintegration property of paper is insufficient.
[0015]
As a vinyl monomer copolymerizable with (meth) acrylamide used in the present invention, anionic vinyl monomers include acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, fumaric acid, vinyl sulfonic acid, styrene sulfonic acid, 2 -Acrylamide-2-methylpropane sulfonic acid, methallyl sulfonic acid, or sodium, potassium, ammonium salt thereof, etc. are mentioned. As cationic vinyl monomers, N, N-dimethylaminoethyl (meth) acrylate, N, N diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl ( (Meth) acrylamide, N, N dimethylaminopropyl (meth) acrylamide, vinyl monomers having an amino group such as vinyl pyridine, vinyl imidazole, allylamine, diallylamine, or salts or quaternized hydrochlorides, formates thereof, Examples include acetate and sulfamate. Nonionic monomers include dialkyl acrylamide, styrene, allyl alcohol, (meth) acrylic ester, acrylonitrile, vinyl acetate, hydroxyalkyl (meth) acrylic ester, vinyl pyrrolidone and the like.
Furthermore, examples of the crosslinkable vinyl monomer include methylol (meth) acrylamide, dimethylacrylamide, triacryl formal, and various other bifunctional, trifunctional, and tetrafunctional vinyl monomers.
[0016]
In the present invention, the preferred use ratio of vinyl monomers containing (meth) acrylamide as an essential component is (a) 70 to 99 mol% of (meth) acrylamide and (b) ions selected from anionic vinyl monomers and cationic vinyl monomers. 1 to 30 mol% of at least one kind of vinyl monomer.
[0017]
The method for producing a paper-making paper strength enhancer according to the present invention can be performed by a known polymerization method. For example, in a reaction vessel equipped with a stirring and nitrogen gas introduction tube, an aqueous solution of the enzyme-modified low-viscosity cationic starch, (meth) acrylamide or (meth) acrylamide and vinyl monomers copolymerizable with (meth) acrylamide and water As a polymerization initiator, peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate and ammonium hydroperoxide, or a redox initiator combining these peroxides with a reducing agent such as bisulfite. Alternatively, a desired polymer can be obtained by carrying out a polymerization reaction using a water-soluble azo polymerization initiator such as 2-2′azobis (2-aminodipropane) hydrochloride.
[0018]
In producing the paper-making paper strength enhancer according to the present invention, the monomer content of the vinyl monomer mixture containing (meth) acrylamide as an essential component in an aqueous solution containing 20 to 80 parts by weight of enzyme-modified low-viscosity cationized starch. It is preferable to polymerize 20 to 80 parts by weight.
[0019]
The papermaking paper strength enhancer according to the present invention is usually obtained in the form of an aqueous dispersion having a solid content of about 10 to 40% by weight.
[0020]
The paper-making paper strength enhancer according to the present invention is usually added to the paper-making raw material slurry dispersed in water at a position called the wet end of the paper-making process, and efficiently fixed to the fiber raw material. It provides paper with excellent paper strength effects during drying and imparts properties excellent in formation and disaggregation.
[0021]
When using the papermaking paper strength enhancer according to the present invention, it is possible to use a known internal additive for papermaking, such as sulfuric acid band, internal sizing agent, other paper strength enhancing agent, filler, etc. in combination. In addition, when the paper-making paper strength enhancer according to the present invention is cationic, anionic additives often show a combined effect, and when the paper-making paper strength enhancer according to the present invention is anionic, it is cationic. In many cases, these additives exhibit a combined effect.
[0022]
The paper using the paper-making paper strength enhancer according to the present invention is not particularly limited. For example, high-quality paper, medium-quality paper, coated base paper, newsprint paper, processed base paper, liner corrugated base paper, white paperboard, PPC paper, inkjet paper, It can be used for thermal paper, special paper, printer paper, gypsum board base paper, toilet paper, tissue paper, other sanitary paper, and building paper.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
The embodiment of the present invention is as follows.
[0024]
[Preparation of paper-making paper strength enhancer]
Add 3 parts of water to 1 part of cationized starch to make a slurry, adjust the pH to 6, add and mix a predetermined amount of enzyme, warm gradually and perform enzyme denaturation. The temperature was raised, the pH was adjusted to 4 with sulfuric acid, the enzyme reaction was terminated, and water was added to obtain an enzyme-modified low-viscosity cationized starch aqueous solution.
[0025]
A predetermined amount of the enzyme-modified cationized starch aqueous solution, (meth) acrylamide, acrylic acid, N, N-dimethylaminopropylacrylamide and water obtained here were mixed, and the pH was adjusted to 5 using dilute sulfuric acid. The whole amount is put in a flask equipped with a stirrer, heated in a hot water bath, ammonium persulfate and sodium bisulfite are added in predetermined amounts at an internal temperature of 55 ° C., and a polymerization reaction is carried out at 40 to 80 ° C. for 1 to 5 hours, followed by cooling. Then, a predetermined amount of water was added to obtain a papermaking paper strength enhancer.
[0026]
[Manufacture of strong paper]
A predetermined amount of the prepared paper-making paper strength enhancer was added to 1% pulp slurry, and a handsheet was prepared as usual using a TAPPI standard sheet machine. The obtained sheet was dried by a plate dryer at 110 ° C. for 2 minutes to obtain a handmade paper corresponding to 60 g / m 2 of rice basis weight.
[0027]
[Evaluation method of strong paper]
The paper was hand-conditioned in a room at 20 ° C. and a relative humidity of 65% overnight, and then tested for paper strength, texture and disaggregation during drying. In addition, the paper strength measured the tear length according to JISP8113, and the specific burst degree according to JISP8112. The formation was determined by the naked eye, and the disaggregation test was as follows.
[0028]
[Disintegration test method]
1 g of a test paper piece split into 1 cm 2 is put into 200 cc of ion exchange water at 20 ° C. and separated in a test blender at a voltage of 60 V for 1 minute, and then a handsheet is prepared by a TAPPI standard sheet machine. The recycled paper corresponding to 50 g / m 2 was prepared by drying with a plate dryer for 2 minutes, and the uniformity of the formed paper was compared and used as a measure of disaggregation.
[0029]
[Stability test method for paper-making paper strength enhancer]
After the product was refrigerated for 30 days in a refrigerator at 2 ° C., the change in appearance and the viscosity with a B-type viscometer at 25 ° C. were measured to examine the change from the viscosity before refrigeration, and used as a measure of stability.
[0030]
【Example】
Hereinafter, although an example and a comparative example are given and the present invention is explained in detail, the present invention is not limited to these examples. In each example, all parts and% are based on weight unless otherwise specified.
[0031]
Example 1:
[Preparation of paper-making paper strength enhancer]
After adding 3 parts of water to 1 part of cationized tapioca starch having a substitution degree (DS) of 0.04 to make a slurry, the pH was adjusted to 6, α-amylase (Spitase PG-2: manufactured by Nagase Seikagaku Corporation) ) Add 0.0005 part, mix and gradually heat to perform enzyme denaturation. After 40 minutes, raise the temperature to 90 ° C., terminate the enzyme reaction with sulfuric acid at pH 4 and add water to solid. The content was adjusted to 15% and an enzyme-modified low-viscosity cationized starch aqueous solution having a viscosity of 10 cps at 25 ° C. and a viscosity of 8 cps was obtained.
[0032]
133 parts of the enzyme-modified low-viscosity cationized starch aqueous solution obtained here, 17.1 parts of acrylamide, 0.58 parts of acrylic acid, 2.46 parts of N, N-dimethylaminopropylacrylamide were mixed, water was added, and the total amount Was 180 parts, and the pH was adjusted to 5 using dilute sulfuric acid. The whole amount was placed in a flask equipped with a stirrer, heated in a hot water bath, 0.02 parts of ammonium persulfate and sodium bisulfite were added at an internal temperature of 55 ° C., and a polymerization reaction was carried out at 65 to 70 ° C. for 3 hours. After cooling and adding water to make a total amount of 205 parts, a papermaking paper strength enhancer having a viscosity of 5000 cps at 25 ° C. was obtained. The product properties are shown in Table 1.
[0033]
[Table 1]
Examples 2-7:
In Example 1, the type of cationized starch, the weight ratio of vinyl monomer, the type of vinyl monomer component, and the blending composition (mol%) were changed as shown in Table 1, and the amounts of ammonium persulfate and sodium bisulfite were changed. Except that, the reaction was carried out in the same manner as in Example 1 to obtain paper strength enhancers. The product properties and stability are shown in Table 1.
[0035]
Comparative Examples 1-3:
In the same manner as in Examples 2 to 7, the type of cationized starch and the weight ratio of vinyl monomer, the type of vinyl monomer component, and the composition (mol%) thereof were changed as shown in Table 1, and ammonium persulfate and sodium bisulfite were used. Except having changed the usage-amount suitably, it reacted by the method similar to Example 1, and obtained the paper strength enhancers 1-3 for a comparison, respectively.
The product properties and stability are shown in Table 1.
[0036]
[Manufacture of strong paper]
Each paper-making paper strength enhancer prepared in Examples and Comparative Examples was added to 1% pulp slurry of bleached kraft pulp (L-BKP) beaten to 400 cc Canadian freeness, and 0.5% air dry pulp weight solids content was added. Using a standard sheet machine, a hand-made sheet was obtained according to a conventional method, and the obtained sheet was dried for 2 minutes with a plate dryer at 110 ° C. to obtain a hand-made paper corresponding to 60 g / m 2 .
[0037]
Table 2 shows the evaluation test results of the respective hand-made papers obtained using the paper strength enhancers of the examples and comparative examples.
[0038]
[Table 2]
【The invention's effect】
According to the present invention, as shown in the examples, it is possible to produce a strong paper excellent in formation and disaggregation as well as having an excellent paper strength enhancing effect during drying.
Claims (4)
（ａ）（メタ）アクリルアミド ７０〜９９モル％と、
（ｂ）アニオン性ビニルモノマー及びカチオン性ビニルモノマーから選ばれるイオン性ビニルモノマーの少なくとも一種 １〜３０モル％とを含有してなるビニルモノマー混合物である請求項１又は２記載の製紙用紙力増強剤。Vinyl monomers containing (meth) acrylamide as an essential component
(A) (meth) acrylamide 70-99 mol%,
(B) A paper-making paper strength enhancer according to claim 1 or 2, which is a vinyl monomer mixture containing 1 to 30 mol% of an ionic vinyl monomer selected from anionic vinyl monomers and cationic vinyl monomers. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08015298A JP3876522B2 (en) | 1998-02-20 | 1998-02-20 | Papermaking paper strength enhancer and method for producing strong paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08015298A JP3876522B2 (en) | 1998-02-20 | 1998-02-20 | Papermaking paper strength enhancer and method for producing strong paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11241294A JPH11241294A (en) | 1999-09-07 |
| JP3876522B2 true JP3876522B2 (en) | 2007-01-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP08015298A Expired - Lifetime JP3876522B2 (en) | 1998-02-20 | 1998-02-20 | Papermaking paper strength enhancer and method for producing strong paper |
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| RU2733729C2 (en) * | 2016-03-01 | 2020-10-06 | Кемира Ойй | Polymer composition, use thereof and surface sizing |
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| FI113968B (en) * | 2001-05-23 | 2004-07-15 | Raisio Chem Oy | Solution polymer stabilized with a cationic polysaccharide |
| JP2004100135A (en) * | 2003-07-22 | 2004-04-02 | Daiki:Kk | Sanitary paper and absorber using the same |
| JP2004137660A (en) * | 2003-09-30 | 2004-05-13 | Daiki:Kk | Method for producing absorbent material |
| JP2004137661A (en) * | 2003-09-30 | 2004-05-13 | Daiki:Kk | Method for producing sanitary paper and absorbent material |
| EP1819788B1 (en) * | 2004-12-03 | 2019-07-24 | Sun Chemical Corporation | Printing ink and coating compositions containing starch |
| JP4948796B2 (en) * | 2005-07-15 | 2012-06-06 | 日本製紙株式会社 | Coated paper for printing |
| JP5471034B2 (en) * | 2009-05-25 | 2014-04-16 | 王子ホールディングス株式会社 | Method for producing starch paste liquid, starch paste liquid and coated paper coated or impregnated with the starch paste liquid |
| JP2011195809A (en) * | 2010-02-26 | 2011-10-06 | Saiden Chemical Industry Co Ltd | Method for producing polymer composition |
| JP2012214943A (en) * | 2011-03-28 | 2012-11-08 | Harima Chemicals Inc | Papermaking method of paper or cardboard, and paper or cardboard made by the papermaking method |
| JP7047310B2 (en) * | 2017-09-28 | 2022-04-05 | 荒川化学工業株式会社 | Paper strength enhancer and paper |
| CN115260397B (en) * | 2022-08-17 | 2023-11-21 | 深圳百市达生物技术有限公司 | Hydrogen peroxide bleaching silicon-free stabilizer |
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1998
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2733729C2 (en) * | 2016-03-01 | 2020-10-06 | Кемира Ойй | Polymer composition, use thereof and surface sizing |
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| JPH11241294A (en) | 1999-09-07 |
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