JP2001019701A - Amphoteric starch, its production and production of paper or paperboard - Google Patents
Amphoteric starch, its production and production of paper or paperboardInfo
- Publication number
- JP2001019701A JP2001019701A JP11191055A JP19105599A JP2001019701A JP 2001019701 A JP2001019701 A JP 2001019701A JP 11191055 A JP11191055 A JP 11191055A JP 19105599 A JP19105599 A JP 19105599A JP 2001019701 A JP2001019701 A JP 2001019701A
- Authority
- JP
- Japan
- Prior art keywords
- starch
- amphoteric
- paper
- papermaking
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、カチオン澱粉に尿
素と正燐酸を添加して乾式で加熱反応させることによっ
て両性澱粉を製造する方法、該製造方法によって得られ
る両性澱粉、および、該両性澱粉を紙料に添加して抄紙
する方法に関する。本発明の製造方法により得られる両
性澱粉は、抄紙工程において紙料に添加することによ
り、与えられた紙料の濾水性を従来から使用されていた
澱粉に比べ著しく向上させると共に、濾水性の面より従
来制限されていた澱粉の添加量を増大させることによっ
て紙強度を飛躍的に改善することができる。The present invention relates to a method for producing an amphoteric starch by adding urea and orthophosphoric acid to a cationic starch and subjecting it to a dry heating reaction, an amphoteric starch obtained by the production method, and the amphoteric starch. To papermaking by adding to paper stock. The amphoteric starch obtained by the production method of the present invention, when added to the paper stock in the papermaking step, significantly improves the drainage of the given paper stock as compared with the conventionally used starch, and improves the drainage surface. By increasing the amount of starch, which has been conventionally restricted, the paper strength can be dramatically improved.
【０００２】[0002]
【従来の技術】紙または板紙の抄造において、ワイヤー
パートにおける紙料の濾水性を増すこと、ワイヤーパー
トで形成されるシート中の填料や微細繊維のリテンショ
ンを向上させること、または抄造した紙または板紙の強
度を上昇させることなどを目的として、パルプスラリー
には、填料、サイズ剤や硫酸バンドをはじめとする内添
用薬品と共に、カチオン澱粉または両性澱粉の糊液を内
添することは、公知の技術である。2. Description of the Related Art In the papermaking of paper or paperboard, increasing the drainage of stock in the wire part, improving the retention of fillers and fine fibers in the sheet formed by the wire part, or the paper or paperboard made of paper. For the purpose of increasing the strength of the pulp slurry, it is known to add a cationic starch or an amphoteric starch paste solution together with a filler, a sizing agent and internal additives such as a sulfate band to the pulp slurry. Technology.
【０００３】近年の抄紙速度の上昇に伴い、澱粉糊液を
パルプスラリーに内添することによって期待される効果
の中でも、特に、抄紙速度に直接影響を与える紙料の濾
水性に対する効果に関心が注がれている。内添用澱粉の
中でも、特開昭６３−４８３０１号公報に公開されてい
る方法によって製造された両性澱粉、すなわち、原材料
となる澱粉に三級アミンまたは四級アンモニウム塩を導
入した後、引き続きトリポリ燐酸ナトリウムを添加し加
熱反応させて、澱粉分子中に燐酸基を導入した両性澱粉
は、中性抄紙系および酸性抄紙系の双方において内添用
澱粉として優れた濾水性を示すことが知られている。し
かしながら、この両性澱粉においても内添する際の澱粉
糊液の添加率は、対パルプ固形分あたり固形分として
１．０重量%程度までが適量であり、それを超える量の
添加は、ワイヤーパートにおいて形成されるシートの濾
水性の著しい低下をもたらす。[0003] With the recent increase in papermaking speed, among the effects expected by internally adding a starch paste solution to a pulp slurry, there is a particular interest in the effect on the drainage of paper stock, which directly affects the papermaking speed. Has been poured. Among the starches for internal addition, amphoteric starch produced by the method disclosed in JP-A-63-48301, that is, a tertiary amine or quaternary ammonium salt is introduced into a starch as a raw material, and then tripolyamine is added. It is known that amphoteric starch in which a phosphate group is introduced into a starch molecule by adding sodium phosphate and reacting by heating has excellent drainage properties as a starch for internal addition in both a neutral papermaking system and an acidic papermaking system. I have. However, even in this amphoteric starch, the addition rate of the starch paste liquid when internally added is up to about 1.0% by weight as a solid content relative to the pulp solid content, and the addition of an amount exceeding this is not possible with the wire part. Causes a significant reduction in the drainage of the sheet formed in
【０００４】他方、近年では、古紙パルプの配合率の増
加による原料パルプの品質の低下（微細繊維、灰分の増
加）に伴ない紙または板紙の生産性や紙力の低下が余儀
なくされ、これを解決することが課題となっている。従
って、抄造時に、高い濾水性を与えて生産性を上げるこ
とができる、または、ほどほどの濾水性を維持しつつ添
加量を増やして紙力を高めることができる添加物の開発
が強く望まれている。[0004] On the other hand, in recent years, the productivity or paper strength of paper or paperboard has been inevitably reduced due to a decrease in the quality of raw pulp (increase in fine fibers and ash) due to an increase in the mixing ratio of waste paper pulp. The solution is an issue. Therefore, during papermaking, there is a strong demand for the development of an additive that can increase productivity by giving high drainage, or increase paper strength by increasing the amount of addition while maintaining moderate drainage. I have.
【０００５】[0005]
【発明が解決しようとする課題】上記のような従来技術
の現況に鑑み、本発明の目的は、紙料に添加した際に、
優れた濾水性を示すと共に、優れた紙力増強効果が得ら
れる製紙用両性澱粉を提供することにある。本発明の他
の目的は、そのような製紙用両性澱粉を工業的有利に製
造する方法を提供することにある。本発明のさらに他の
目的は、そのような製紙用両性澱粉を用いることによっ
て、良好な濾水性をもって抄紙することができ、かつ紙
力の高い紙または板紙を得ることができる抄紙方法を提
供することにある。In view of the state of the prior art as described above, an object of the present invention is to provide
An object of the present invention is to provide an amphoteric starch for papermaking, which exhibits excellent drainage and an excellent paper strength enhancing effect. Another object of the present invention is to provide a method for industrially advantageously producing such an amphoteric starch for papermaking. Still another object of the present invention is to provide a papermaking method capable of making paper with good drainage and obtaining paper or paperboard having high paper strength by using such amphoteric starch for papermaking. It is in.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、三級アミ
ンまたは四級アンモニウム塩を導入したカチオン性澱粉
に尿素リン酸化反応を施すことにより、高い濾水性の付
与と紙力向上に寄与する両性澱粉を安価に製造し得るこ
とを見出し、本発明の完成に至った。かくして、本発明
によれば、カチオン澱粉に燐酸基を導入して製紙用両性
澱粉を製造するに際し、置換度０．０２〜０．０５の三
級アミンまたは四級アンモニウム塩を有するカチオン澱
粉に、尿素と正燐酸塩を添加し、次いで、乾式で１１０
〜１６０℃において０．２〜数時間加熱反応させて、対
澱粉固形分あたり結合燐として０．１〜０．７重量%の
燐酸基を導入することを特徴とする製紙用両性澱粉の製
造方法が提供される。Means for Solving the Problems The present inventors have contributed to imparting high drainage and improving paper strength by subjecting a cationic starch into which a tertiary amine or quaternary ammonium salt has been introduced to a urea phosphorylation reaction. The present inventors have found that an amphoteric starch can be produced at low cost, and have completed the present invention. Thus, according to the present invention, when a phosphate group is introduced into a cationic starch to produce an amphoteric starch for papermaking, a cationic starch having a tertiary amine or quaternary ammonium salt having a degree of substitution of 0.02 to 0.05, Urea and orthophosphate are added and then dry
A method for producing amphoteric starch for papermaking, characterized by introducing a phosphoric acid group of 0.1 to 0.7% by weight as bound phosphorus per starch solid content by heating and reacting at -160 ° C for 0.2 to several hours. Is provided.
【０００７】さらに、本発明によれば、上記の製造方法
によって得られる製紙用両性澱粉が提供される。さら
に、本発明によれば、上記の製造方法によって得られる
製紙用両性澱粉を添加したパルプスラリーを抄紙するこ
とを特徴とする紙または板紙の製造方法が提供される。Further, according to the present invention, there is provided an amphoteric starch for papermaking obtained by the above-mentioned production method. Further, according to the present invention, there is provided a method for producing paper or paperboard, which comprises making a pulp slurry to which the amphoteric starch for papermaking obtained by the above production method is added.
【０００８】[0008]
【発明の実施の形態】本発明で用いるカチオン性澱粉の
製造に用いる原料澱粉は格別限定されることはなく、タ
ピオカ澱粉、コーン・スターチ、ワキシーコーンスター
チ、ハイアミロースコーンスターチ、馬鈴薯澱粉または
甘藷澱粉などの未加工澱粉、これらの未加工澱粉に公知
の方法によって置換基を導入したアセチル化澱粉、ヒド
ロキシエチル化澱粉、ヒドロキシルプロピル化澱粉など
を用いることができる。これらの原料澱粉は単独でまた
は２種類以上を組み合わせて用いることができる。BEST MODE FOR CARRYING OUT THE INVENTION The raw material starch used in the production of the cationic starch used in the present invention is not particularly limited, and may be tapioca starch, corn starch, waxy corn starch, high amylose corn starch, potato starch or sweet potato starch. Raw starch, acetylated starch, hydroxyethylated starch, hydroxylpropylated starch, etc. obtained by introducing a substituent into these raw starches by a known method can be used. These raw starches can be used alone or in combination of two or more.
【０００９】本発明における原料澱粉のカチオン化は、
三級アミンまたは四級アンモニウム塩が導入される限
り、公知の如何なる技術を用いて行ってもよい。カチオ
ン化剤の具体例としては、ジエチルアミノエチルクロラ
イド塩酸塩などの三級アミン導入剤、および３−クロロ
−２−ヒドロキシプロピルトリメチルアンモニウムクロ
ライド塩酸塩および２，３−エポキシプロピルトリメチ
ルアンモニウムクロライド塩酸塩などの四級アンモニウ
ム塩導入剤が挙げられる。これらのカチオン化剤は単独
でまたは２種類以上を組み合わせて用いることができ
る。In the present invention, the cationization of the raw starch is carried out by
As long as a tertiary amine or quaternary ammonium salt is introduced, the reaction may be performed using any known technique. Specific examples of the cationizing agent include a tertiary amine-introducing agent such as diethylaminoethyl chloride hydrochloride, and 3-chloro-2-hydroxypropyltrimethylammonium chloride hydrochloride and 2,3-epoxypropyltrimethylammonium chloride hydrochloride. A quaternary ammonium salt introducing agent is exemplified. These cationizing agents can be used alone or in combination of two or more.
【００１０】カチオン澱粉の置換度（澱粉を構成する無
水グルコース単位１個あたりの三級アミンおよび／また
は四級アンモニウム塩の個数）は０．０２〜０．０５の
範囲であることが好ましい。置換度が０．０２未満では
本発明の効果を十分に得ることが難しく、逆に、０．０
５を超えると製造コストが増大して実用的ではなくな
る。The degree of substitution of the cationic starch (the number of tertiary amines and / or quaternary ammonium salts per unit of anhydrous glucose constituting the starch) is preferably in the range of 0.02 to 0.05. If the substitution degree is less than 0.02, it is difficult to sufficiently obtain the effects of the present invention.
If it exceeds 5, the production cost increases and it becomes impractical.
【００１１】本発明においては、三級アミンまたは四級
アンモニウム塩が導入されたカチオン澱粉に、引き続き
尿素燐酸化反応を施し、両性澱粉とする。従来、澱粉に
燐酸基を導入する方法として、主に燐酸化反応と尿素燐
酸化反応の２つがよく知られている。燐酸化反応の代表
的な方法としては、澱粉にトリポリ燐酸ナトリウムなど
をｐＨ４〜８．５の条件下で含浸させ、乾式で１１０〜
１４０℃で加熱する方法が挙げられ、この方法によれ
ば、燐酸基がエステル結合した澱粉を得ることができ
る。一方、尿素燐酸化反応では、原料となる澱粉に尿素
と正燐酸および／またはその塩を添加し、乾式で１１０
〜１６０℃で加熱反応させる方法が一般的である。この
方法では、エステル結合した燐酸基に加えて、カルバミ
ン酸エステル基も導入される。また、正燐酸を中和せず
に用いることは、加熱反応中に澱粉の酸加水分解による
低粘度化を惹起するので、本発明の目的には適さない。In the present invention, the cationic starch into which the tertiary amine or quaternary ammonium salt has been introduced is subjected to a urea phosphorylation reaction to obtain an amphoteric starch. Conventionally, as a method for introducing a phosphate group into starch, mainly two methods, a phosphorylation reaction and a urea phosphorylation reaction, are well known. As a typical method of the phosphorylation reaction, starch is impregnated with sodium tripolyphosphate or the like under the condition of pH 4 to 8.5, and dried by a dry method at 110 to 110.
A method of heating at 140 ° C. is mentioned. According to this method, a starch having a phosphate group ester-bonded can be obtained. On the other hand, in the urea phosphorylation reaction, urea and orthophosphoric acid and / or a salt thereof are added to starch as a raw material, and the starch is dried by a dry method.
A method of performing a heating reaction at -160 ° C is generally used. In this method, a carbamate group is introduced in addition to the ester-bonded phosphate group. In addition, the use of orthophosphoric acid without neutralization is not suitable for the purpose of the present invention because it causes a reduction in viscosity due to acid hydrolysis of starch during the heating reaction.
【００１２】本発明の方法において、カチオン澱粉の尿
素燐酸化反応に際しては、尿素と燐酸第一ナトリウム、
燐酸第二ナトリウムなどの正燐酸塩を組み合わせて用い
てもよいが、溶解作業性の面より次のように行うことが
より好ましい。すなわち、尿素と正燐酸を対澱粉固形分
あたり１５〜３０重量%程度の量の水に溶解し、高濃度
溶液を調製する。この溶液を、水酸化ナトリウムなどの
アルカリを用いてｐＨ６．０〜１０．０に調節（この段
階で正燐酸塩となる）したうえ、カチオン澱粉に均一に
添加する。高濃度溶液のｐＨが６．０未満であると、尿
素燐酸化反応時、澱粉の加水分解が進み低粘度化した両
性澱粉が生成し、本発明の目的には不適なものとなる。
また、ｐＨが１０．０を超えると得られた両性澱粉の着
色が著しくなり、商品価値が失われる。In the method of the present invention, urea and monosodium phosphate,
Although orthophosphates such as disodium phosphate may be used in combination, it is more preferable to carry out as follows from the viewpoint of dissolving workability. That is, urea and orthophosphoric acid are dissolved in water in an amount of about 15 to 30% by weight per starch solid content to prepare a high concentration solution. This solution is adjusted to pH 6.0 to 10.0 using an alkali such as sodium hydroxide (it becomes a normal phosphate at this stage), and then uniformly added to the cationic starch. If the pH of the high-concentration solution is less than 6.0, during the urea phosphorylation reaction, hydrolysis of the starch proceeds to form a low-viscosity amphoteric starch, which is unsuitable for the purpose of the present invention.
On the other hand, if the pH exceeds 10.0, the obtained amphoteric starch becomes remarkably colored and loses commercial value.
【００１３】澱粉への尿素と正燐酸の添加率は、尿素が
対澱粉固形分あたり５．０〜１５．０重量％であるのに
対し、正燐酸塩が対澱粉固形分あたり正燐酸として１．
０〜８．０重量％であることが好ましい。尿素と正燐酸
塩を含浸させたカチオン澱粉は、例えばフラッシュドラ
イヤーを用い、水分が通常１２重量％以下、好ましくは
７重量％以下となるまで乾燥させる。乾燥方法として、
その他のあらゆる公知の方法を用いることができる。尿
素と正燐酸を含浸させたカチオン澱粉を乾燥させた後に
１２重量％を超える水分を含有すると、加熱反応させる
際に、澱粉の部分的糊化の恐れが強くなる。The addition ratio of urea and orthophosphoric acid to starch is 5.0 to 15.0% by weight based on starch solids, while orthophosphate is 1% as orthophosphoric acid per starch solids. .
It is preferably from 0 to 8.0% by weight. The cationic starch impregnated with urea and orthophosphate is dried using, for example, a flash dryer until the water content is usually 12% by weight or less, preferably 7% by weight or less. As a drying method,
Any other known method can be used. If the cationic starch impregnated with urea and orthophosphoric acid is dried and contains more than 12% by weight of water, the possibility of partial gelatinization of the starch is increased during the heating reaction.
【００１４】正燐酸と共に添加する尿素は、加熱反応の
際に、澱粉と燐酸との反応速度を上げる触媒として作用
する。尿素は、高温での加熱によってアンモニアとイソ
シアン酸に分解される。イソシアン酸は澱粉分子中の水
酸基と容易に反応してカルバミン酸エステルを形成し、
また一部は尿素や水と反応して副産物のビウレット、ア
ンモニア、二酸化炭素を生じる。一方、尿素の分解で生
じたアンモニアは、一部が未反応の燐酸塩や澱粉に結合
した燐酸基の水素と置換して、アンモニウムイオンとし
て定着するが、大部分は空気中に飛散する。Urea added together with orthophosphoric acid acts as a catalyst for increasing the reaction rate between starch and phosphoric acid during the heating reaction. Urea is decomposed into ammonia and isocyanic acid by heating at a high temperature. Isocyanic acid readily reacts with hydroxyl groups in starch molecules to form carbamates,
Some also react with urea and water to produce by-products biuret, ammonia and carbon dioxide. On the other hand, ammonia generated by the decomposition of urea partially substitutes unreacted phosphate or hydrogen of a phosphate group bonded to starch and is fixed as ammonium ions, but most of the ammonia is scattered in the air.
【００１５】乾燥させて水分を１２重量％以下とした後
に、カチオン澱粉を加熱して尿素燐酸化反応を施す。す
なわち、正燐酸塩と尿素を含浸させたカチオン澱粉を、
１１０〜１６０℃に保持した反応器に入れ、５分間ない
し数時間攪拌する。加熱温度が低すぎると十分な量の燐
酸基を導入することができず、また、加熱温度が高すぎ
ると澱粉分子の加水分解が進み低粘度化した両性澱粉が
生成し、本発明の目的には不適なものとなる。この際、
反応時間は反応温度、用いる反応器の種類、薬品添加量
および要求する結合燐に依存して適宜調節する。尿素燐
酸化反応によって対澱粉固形分当たり結合燐として０．
１〜０．７重量％の燐酸基が導入される。燐酸基導入量
が少なすぎると、それを内添した紙料の高い濾水性およ
び紙または板紙の高い紙力が得られず、高すぎるとその
強い凝集効果のため、地合いの悪い紙または板紙をもた
らす。また、燐酸基に基づくアニオンと三級アミンまた
は四級アンモニウム塩に基づくカチオンの比は、モル比
として０．２５〜０．７５：１であることが望ましい。After drying to reduce the water content to 12% by weight or less, the cationic starch is heated to perform a urea phosphorylation reaction. That is, the cationic starch impregnated with orthophosphate and urea,
Put into a reactor maintained at 110 to 160 ° C. and stir for 5 minutes to several hours. If the heating temperature is too low, a sufficient amount of phosphoric acid groups cannot be introduced, and if the heating temperature is too high, hydrolysis of the starch molecules proceeds to form a low-viscosity amphoteric starch, which is an object of the present invention. Is unsuitable. On this occasion,
The reaction time is appropriately adjusted depending on the reaction temperature, the type of reactor used, the amount of chemicals added, and the required bound phosphorus. The urea phosphorylation reaction results in 0.1 as bound phosphorus per starch solids.
1 to 0.7% by weight of phosphoric acid groups are introduced. If the amount of the introduced phosphate group is too small, high drainage of the paper stock containing it and high paper strength of the paper or paperboard cannot be obtained, and if it is too high, paper or paperboard with poor formation may be produced due to its strong coagulation effect. Bring. The ratio of the anion based on the phosphate group to the cation based on the tertiary amine or the quaternary ammonium salt is desirably 0.25 to 0.75: 1 as a molar ratio.
【００１６】本発明の両性澱粉は、糊化された形態でパ
ルプスラリーに添加する。使用するパルプの種類は目的
とする紙または板紙および抄紙条件に依存して適宜選択
することができる。両性澱粉の糊化は、澱粉スラリーに
３〜１０ｋｇｆ／ｃｍ2の圧力を保持する蒸気を吹き込
み、瞬時に澱粉を糊化させる形式の連続糊化方式による
ことが好ましいが、バッチ式の糊化方式でもかまわな
い。糊化された両性澱粉を紙料に内添する位置は、パル
プスラリー中に通常の添加剤を添加する場合と同様な位
置でよいが、その添加には通常マシンチェストやヘッド
ボックスなどが使用される。その際、両性澱粉の添加量
は、原料パルプ固形分に対して固形分として０．５〜
３．０重量％が好ましい。The amphoteric starch of the present invention is added to the pulp slurry in a gelatinized form. The type of pulp to be used can be appropriately selected depending on the target paper or paperboard and papermaking conditions. The gelatinization of the amphoteric starch is preferably performed by a continuous gelatinization method of instantaneously gelatinizing the starch by blowing steam maintaining a pressure of 3 to 10 kgf / cm 2 into the starch slurry. But it doesn't matter. The location where the gelatinized amphoteric starch is internally added to the paper stock may be the same location as when a normal additive is added to the pulp slurry, but a machine chest or a head box is usually used for the addition. You. At this time, the added amount of the amphoteric starch is 0.5 to
3.0% by weight is preferred.
【００１７】本発明の両性澱粉を添加したパルプスラリ
ーは、一般的な紙または板紙の製造方法と同様の条件で
抄造、脱水、乾燥して紙または板紙を得る。本発明の両
性澱粉を内添する抄紙系のｐＨは、酸性からアルカリ性
の広範囲にわたり採用することができる。本発明の両性
澱粉は、必要に応じて他種澱粉、填料、サイズ剤、硫酸
バンド、紙力増強剤などと組み合わせてパルプスラリー
に内添することができ、それらの種類は抄紙条件に応じ
て適宜選択すればよい。The pulp slurry to which the amphoteric starch of the present invention is added is paper-formed, dewatered, and dried under the same conditions as those of a general method for producing paper or paperboard to obtain paper or paperboard. The pH of the papermaking system to which the amphoteric starch of the present invention is internally added can be adopted in a wide range from acidic to alkaline. The amphoteric starch of the present invention can be internally added to the pulp slurry in combination with other types of starch, fillers, sizing agents, sulfate bands, paper strength enhancers, and the like, if necessary, depending on the papermaking conditions. What is necessary is just to select suitably.
【００１８】[0018]
【実施例】以下に本発明の具体的な実施例を示すが、も
ちろん、本発明は以下に記載の事項に限定されるもので
はない。以下の実施例および具体例において、％は重量
基準である。EXAMPLES Specific examples of the present invention will be shown below, but of course the present invention is not limited to the matters described below. In the following examples and specific examples,% is based on weight.
【００１９】実施例1(両性澱粉の製造) タピオカ澱粉１，０００ｇを、１，５００ｍｌの水に溶
解し、ＮａＯＨを対澱粉２．８％、Ｎａ2ＳＯ4を対澱粉
１０％添加した。４５℃に維持した澱粉スラリー中に、
カチオン化剤として四級アンモニウム塩導入剤である３
−クロロ−２−ヒドロキシプロピルトリメチルアンモニ
ウムクロライド塩酸塩を対澱粉４．５％添加した後、７
時間攪拌下でカチオン化反応を行った。反応は、澱粉ス
ラリーを１０％ＨＣｌでｐＨ７．０に下げることで停止
させた。反応停止後のスラリーは、常法により精製、脱
水した後、室温で乾燥させた。得られたカチオン澱粉
は、湿式分解の後、ケルダール法で窒素量を測定するこ
とにより、四級アンモニウム塩の置換度を算出した。 Example 1 ( Preparation of amphoteric starch) 1,000 g of tapioca starch was dissolved in 1,500 ml of water, and 2.8% of NaOH was added to starch and 10% of Na 2 SO 4 was added to starch. In a starch slurry maintained at 45 ° C,
3 is a quaternary ammonium salt introducing agent as a cationizing agent;
-Chloro-2-hydroxypropyltrimethylammonium chloride hydrochloride was added after 4.5% of starch,
The cationization reaction was performed under stirring for hours. The reaction was stopped by lowering the starch slurry to pH 7.0 with 10% HCl. After the reaction was stopped, the slurry was purified and dehydrated by a conventional method, and then dried at room temperature. After the obtained cationic starch was subjected to wet decomposition, the degree of substitution of the quaternary ammonium salt was calculated by measuring the amount of nitrogen by the Kjeldahl method.
【００２０】対澱粉９．５％の尿素と、対澱粉２．５％
の正燐酸を少量の水に溶解し、１０％ＮａＯＨでｐＨ
８．０に調整して得た溶液を上記のカチオン澱粉に攪拌
しながら添加して十分に混合した。次いで熱風循環乾燥
機中で５０℃で乾燥させ、水分を４．０％に調節した。
尿素と正燐酸塩を含浸、乾燥させたカチオン澱粉を固形
分重量にして３８０ｇをナス型フラスコに採り、１４０
℃に加熱したオイルバス中で５〜９０分間加熱させて尿
素燐酸化反応を施し、次いで室温まで冷却させた。得ら
れた両性澱粉の結合燐含量は、メタノールで精製した
後、モリブデン比色定量法で定量した。また、澱粉分子
に結合したカルバミン酸エステル基は、予め塩酸／メタ
ノール／水混合溶液で遊離のアンモニアを除去した澱粉
について、全窒素分をケルダール法で定量した後に、四
級アンモニウム塩に由来する窒素分を差し引き、カルバ
ミン酸エステルの重量％で示した。Ｂ型粘度は、蒸留水
中に固形分濃度２．０％になるよう両性澱粉を採り、攪
拌しながら９５℃で２０分間加熱糊化した後、冷却して
ブルックフィールド型粘度計で５０℃のときの粘度（Ｂ
型粘度）を６０ｒｐｍで測定した。対照として、尿素燐
酸化反応の原料として用いたカチオン澱粉について同様
の測定を行った。表１に、測定した結合燐、カルバミン
酸エステル基、およびＢ型粘度を示す。9.5% urea based on starch and 2.5% based on starch
Is dissolved in a small amount of water and the pH is adjusted with 10% NaOH.
The solution obtained by adjusting to 8.0 was added to the above-mentioned cationic starch while stirring, and mixed well. Subsequently, it was dried at 50 ° C. in a hot air circulating drier to adjust the water content to 4.0%.
380 g of the cationic starch impregnated with urea and orthophosphate and dried was placed in a eggplant-shaped flask in terms of solid weight, and
The urea phosphorylation reaction was performed by heating in an oil bath heated to 5 ° C. for 5 to 90 minutes, and then cooled to room temperature. The bound phosphorus content of the obtained amphoteric starch was determined by molybdenum colorimetry after purification with methanol. The carbamate group bonded to the starch molecule is determined by determining the total nitrogen content of starch from which free ammonia has been removed with a mixed solution of hydrochloric acid / methanol / water by the Kjeldahl method, and then determining the nitrogen content derived from the quaternary ammonium salt. Minutes were subtracted, and the results were shown in terms of% by weight of the carbamate. B-type viscosity is obtained by taking an amphoteric starch in distilled water so as to have a solid concentration of 2.0%, heating and gelatinizing at 95 ° C for 20 minutes with stirring, and then cooling it to 50 ° C with a Brookfield viscometer. Viscosity (B
Mold viscosity) was measured at 60 rpm. As a control, the same measurement was performed on the cationic starch used as a raw material for the urea phosphorylation reaction. Table 1 shows the measured bound phosphorus, carbamate groups, and B-type viscosities.
【００２１】[0021]
【表１】 [Table 1]
【００２２】実施例２ カチオン化反応に際し、カチオン化剤を対澱粉６．５
％、ＮａＯＨを対澱粉３．２％とした他は上記実施例１
の方法に従って両性澱粉を製造した。得られたカチオン
化澱粉と両性澱粉の四級アンモニウム塩の置換度、結合
燐、カルバミン酸エステル基、Ｂ型粘度を実施例1と同
様の方法に従い測定した。その結果を表２に示す。 Example 2 In the cationization reaction, a cationizing agent was added to starch 6.5.
%, And NaOH was changed to 3.2% with respect to starch.
An amphoteric starch was produced according to the method described above. The degree of substitution of the quaternary ammonium salt of the obtained cationized starch and amphoteric starch, bound phosphorus, carbamate group, and B-type viscosity were measured in the same manner as in Example 1. Table 2 shows the results.
【００２３】[0023]
【表２】 [Table 2]
【００２４】実施例３ タピオカ澱粉１，０００ｇを、１，５００ｍｌの水に溶
解し、ＮａＯＨを対澱粉２．５％、Ｎａ2ＳＯ4を対澱粉
９．０％添加した。４５℃に維持した澱粉スラリー中
に、カチオン化剤として、三級アミン導入剤のジエチル
アミノエチルクロライド塩酸塩を対澱粉４．０％添加し
た後、４時間攪拌下でカチオン化反応を行った。反応
は、澱粉スラリーを１０％ＨＣｌでｐＨ４．０に下げる
ことで停止し、以下は、上記実施例１と同様に両性澱粉
の製造を試みた。得られたカチオン澱粉と両性澱粉の結
合燐、カルバミン酸エステル基とＢ型粘度は、実施例１
と同様の方法で測定した。その結果を表３に示す。 Example 3 1,000 g of tapioca starch was dissolved in 1,500 ml of water, and NaOH was added to 2.5% of starch and Na 2 SO 4 was added to 9.0% of starch. A tertiary amine-introducing agent, diethylaminoethyl chloride hydrochloride (4.0% relative to starch) was added as a cationizing agent to the starch slurry maintained at 45 ° C., and then a cationization reaction was performed with stirring for 4 hours. The reaction was stopped by lowering the pH of the starch slurry to pH 4.0 with 10% HCl, and the production of amphoteric starch was attempted in the same manner as in Example 1 above. The bound phosphorus, carbamate group and B-type viscosity of the obtained cationic starch and amphoteric starch were determined in Example 1.
The measurement was performed in the same manner as described above. Table 3 shows the results.
【００２５】[0025]
【表３】 [Table 3]
【００２６】比較例１ 本項では、実施例1または実施例２で得た両性澱粉との
内添用両性澱粉としての性能の比較を行うため、特開昭
６３−４８３０１号の方法に従ってトリポリ燐酸塩を用
いた燐酸化反応をカチオン澱粉に施して両性澱粉を製造
した。実施例１により得たカチオン澱粉５００ｇを秤量
し、３０ｇのトリポリ燐酸ナトリウムを含む８００ｍｌ
の水に溶解し、１０％ＨＣｌでｐＨ６．５に調節した。
このスラリーを２時間攪拌した後、濾過した。濾過ケー
キを熱風循環乾燥機中で乾燥させ、水分を４．０％に調
節した。得られたトリポリ燐酸ナトリウム含有カチオン
澱粉を固形分重量にして３８０ｇをナス型フラスコに採
り、１４０℃に加熱されたオイルバス中で２０〜４０分
間加熱して燐酸化反応を施した。得られた両性澱粉の結
合燐とＢ型粘度を、実施例１と同様の方法で測定した。
その結果を表４に示す。当然ながらここで得られた両性
澱粉はカルバミン酸エステル基を有しない。 Comparative Example 1 In this section, in order to compare the performance as an amphoteric starch for internal addition with the amphoteric starch obtained in Example 1 or Example 2, tripolyphosphate was prepared according to the method of JP-A-63-48301. Phosphorylation using a salt was applied to the cationic starch to produce an amphoteric starch. 500 g of the cationic starch obtained according to Example 1 is weighed, and 800 ml containing 30 g of sodium tripolyphosphate is weighed.
And adjusted to pH 6.5 with 10% HCl.
The slurry was stirred for 2 hours and then filtered. The filter cake was dried in a hot air circulating drier to adjust the water content to 4.0%. 380 g of the obtained sodium starch containing sodium tripolyphosphate in terms of solid content was placed in an eggplant-shaped flask and heated in an oil bath heated to 140 ° C. for 20 to 40 minutes to perform a phosphorylation reaction. The bound phosphorus and B-type viscosity of the resulting amphoteric starch were measured in the same manner as in Example 1.
Table 4 shows the results. Naturally, the amphoteric starch obtained here has no carbamate group.
【００２７】[0027]
【表４】 [Table 4]
【００２８】比較例２ 実施例３によって得たカチオン澱粉を用い、それ以外は
上記比較例１と同様の方法で両性澱粉の製造を試みた。
得られた両性澱粉の三級アミン置換度、結合燐とＢ型粘
度を実施例１と同様の方法で測定した。その結果を表５
に示す。ここで得られた両性澱粉もカルバミン酸エステ
ル基を有しない。 Comparative Example 2 An amphoteric starch was produced in the same manner as in Comparative Example 1 except that the cationic starch obtained in Example 3 was used.
The degree of tertiary amine substitution, bound phosphorus and B-type viscosity of the obtained amphoteric starch were measured in the same manner as in Example 1. Table 5 shows the results.
Shown in The amphoteric starch obtained here also has no carbamate group.
【００２９】[0029]
【表５】 [Table 5]
【００３０】抄造例 実施例１〜３、比較例１、２により得られた両性澱粉、
これら両性澱粉の原料として使用したカチオン澱粉（内
添用カチオン澱粉として代表的なもの）、および市販の
両性澱粉を用い、紙の抄造試験を行った。用いた材料、
機器および試験内容と試験方法は以下のとおりである。
なお、材料に用いた澱粉のアルファベット記号および番
号は、表１〜５で示した両性澱粉のアルファベット記号
およびカチオン澱粉の番号と一致する。 Papermaking Examples Amphoteric starches obtained in Examples 1 to 3 and Comparative Examples 1 and 2,
Paper making tests were carried out using the cationic starch used as a raw material of these amphoteric starches (representative as a cationic starch for internal addition) and a commercially available amphoteric starch. Materials used,
The equipment, test contents and test method are as follows.
The alphabetic symbols and numbers of the starch used for the materials correspond to the alphabetic symbols of the amphoteric starch and the numbers of the cationic starches shown in Tables 1 to 5.
【００３１】 材料 パルプ ＬＢＫＰ 硫酸バンド 酸化アルミニウムとして８．０％の液状品 サイズ剤 ハーサイズNES 405(ハリマ化成（株）製) 澱粉 カチオン澱粉１〜３ 両性澱粉Ａ〜Ｊ 両性澱粉ａ〜ｄ Cato3210(日本NSC（株）製両性澱粉 ※四級アンモニウム塩 置換度０．０３０結合燐０．２９％、Ｂ型粘度１１０cP、 カルバミン酸エステル基無し) 抄造 角型シートマシン（熊谷理機工業（株）製） 脱水 自動シートプレス（熊谷理機工業（株）製） 乾燥 回転式乾燥機（熊谷理機工業（株）製）Material Pulp LBKP Sulfate band 8.0% liquid product as aluminum oxide Sizing agent Hersize NES 405 (manufactured by Harima Chemicals, Inc.) Starch Cationic starch 1-3 Amphoteric starch A-J Amphoteric starch a-d Cato3210 ( Amphoteric starch manufactured by NSC Japan * Quaternary ammonium salt Substitution degree 0.030 bound phosphorus 0.29%, B-type viscosity 110 cP, no carbamic acid ester group) Papermaking Square sheet machine (manufactured by Kumagaya Riki Kogyo Co., Ltd.) ) Dehydration Automatic sheet press (manufactured by Kumagai Riki Kogyo Co., Ltd.)
【００３２】市販のシート状ＬＢＫＰをナイアガラ式ビ
ーターで叩解し、カナディアン・スタンダード・フリーネ
ス３６０ｍｌに調整した。使用する澱粉は全て、固形分
濃度２．０％のスラリーとし、９５℃で３０分間加熱糊
化して、澱粉糊液を調製した。A commercially available sheet-like LBKP was beaten with a Niagara beater to adjust the Canadian Standard Freeness to 360 ml. All the starches used were made into a slurry having a solid content of 2.0%, and gelatinized by heating at 95 ° C. for 30 minutes to prepare a starch paste liquid.
【００３３】固形分濃度２．０％に調整したパルプスラ
リーを攪拌しながら、澱粉糊液を、固形分として対パル
プ固形分当たり０．５、１．０または２．０％、サイズ
剤を固形分として０．１５％、そして硫酸バンドを有姿
として３．０％をそれぞれ順次添加したのち、水を加え
て１．０％に希釈した。調製された紙料を角型シートマ
シンで坪量８０ｇ／ｍ2になるように抄紙した。ブラン
クとして、澱粉のみを添加しない手抄き紙も抄造した。
ウェットシートは、自動シートプレスを用いて３．５ｋ
ｇｆ／ｃｍ2で２分間、濾紙を替えて引き続き３．５ｋ
ｇｆ／ｃｍ2で１分間プレスし、次いで、回転式乾燥機
を用い、１０３℃で２分間乾燥した後、２０℃、６５％
Ｒ．Ｈ．で一晩調湿した。While stirring the pulp slurry adjusted to a solid content concentration of 2.0%, the starch paste solution was converted to a solid content of 0.5, 1.0 or 2.0% per pulp solid content, and the sizing agent was solidified. Then, 0.15% as a fraction and 3.0% in the form of a sulfate band were sequentially added, and then diluted with water to 1.0%. The prepared stock was made with a square sheet machine so that the basis weight was 80 g / m 2 . As a blank, a handmade paper to which only starch was not added was also prepared.
Wet sheet is 3.5k using automatic sheet press
gf / cm 2 for 2 minutes, change the filter paper and continue to 3.5k
gf / cm 2 for 1 minute, and then dried at 103 ° C. for 2 minutes using a rotary drier.
R. H. For overnight.
【００３４】調成した紙料の濾水性及び抄造した手抄き
紙の物性は、以下の方法で測定した。 濾水度 ＪＩＳ Ｐ ８１２１に準じて測定した。
(高いものほど濾水性が優れている。) 坪量 ＪＩＳ Ｐ ８１２４に準じて測定した。 裂断長 ＪＩＳ Ｐ ８１１３に準じて測定した。 比破裂強さ ＪＩＳ Ｐ ８１１２に準じて測定した。 得られた結果を表６および表７に示す。The drainage of the prepared stock and the physical properties of the handmade paper were measured by the following methods. Freeness Measured according to JIS P8121.
(The higher the value, the better the drainage.) Basis Weight Measured according to JIS P8124. Break length Measured according to JIS P 8113. Specific burst strength Measured according to JIS P8112. Tables 6 and 7 show the obtained results.
【００３５】[0035]
【表６】 [Table 6]
【００３６】[0036]
【表７】 [Table 7]
【００３７】本発明による両性澱粉Ｂ〜Ｊは、カチオン
澱粉１〜３に比べて著しく、また本発明によらない両性
澱粉ａ〜ｄ、市販の両性澱粉「Cato3210」に比べてかな
り濾水性が向上した。従って、内添される澱粉の量が同
じであれば、本発明による両性澱粉を用いれば、従来の
カチオン澱粉や両性澱粉に比べて抄造速度の向上が達成
されることは疑いない。The amphoteric starches B to J according to the present invention have markedly improved drainage as compared with the cationic starches 1 to 3, and also have significantly improved drainage as compared with the amphoteric starches a to d not according to the present invention and the commercially available amphoteric starch “Cato3210”. did. Therefore, if the amount of starch to be internally added is the same, there is no doubt that the use of the amphoteric starch according to the present invention will achieve an improvement in the papermaking speed as compared with conventional cationic starch and amphoteric starch.
【００３８】また、濾水性の向上に従って澱粉の添加率
を上げることが可能となるので、澱粉の添加率に制限の
ある従来のカチオン澱粉や両性澱粉に比べて紙力の向上
が期待できる。なお、両性澱粉Ａは、結合燐が本発明の
範囲に到達していないため、十分な濾水性向上効果が得
られていない。Further, since the starch addition rate can be increased with the improvement of drainage, paper strength can be expected to be improved as compared with conventional cationic starch and amphoteric starch having a limited starch addition rate. In addition, in the amphoteric starch A, since the bound phosphorus has not reached the range of the present invention, a sufficient drainage improvement effect has not been obtained.
【００３９】[0039]
【発明の効果】本発明の方法により得られる両性澱粉
は、加熱糊化して紙料に内添し、抄造すると、著しく濾
水性が向上し、強度が増大した紙または板紙が得られ
る。澱粉添加率が２．０％に至っても、濾水性の低下は
見られず、従って、抄造速度を下げずに、より強度の高
い紙又は板紙の抄造が可能である。The amphoteric starch obtained by the method of the present invention is gelatinized by heating, internally added to the paper stock, and paper-made to obtain paper or paperboard with remarkably improved drainage and increased strength. Even when the starch addition rate reaches 2.0%, no decrease in drainage is observed, and therefore, paper or paperboard with higher strength can be produced without lowering the papermaking speed.
【００４０】このような本発明の効果、すなわち従来の
両性澱粉（特開昭６３−４８３０１号に基づくカチオン
澱粉をトリポリ燐酸塩により燐酸化したもの）に比べて
著しく濾水性が向上する機構は明らかではないが、燐酸
基と共に導入されたカルバミン酸エステルとパルプの主
成分であるセルロースとの水素結合の形成、トリポリ燐
酸塩に比べて正燐酸塩の分子量が低いことによる澱粉粒
内への易浸透性(燐酸基のより均一な分布)、トリポリ燐
酸塩に比べて正燐酸塩の溶解度が高く、乾燥中、もしく
は加熱反応中に析出することがないこと（燐酸基のより
均一な分布および高い反応効率）、未反応の塩による悪
影響が分子量が小さい分正燐酸塩の方が少ないことなど
が考えられる。The effect of the present invention, that is, the mechanism by which drainage is remarkably improved as compared with the conventional amphoteric starch (cationic starch based on JP-A-63-48301 which is phosphorylated with tripolyphosphate) is apparent. However, the formation of hydrogen bonds between the carbamate introduced together with the phosphate group and cellulose, which is the main component of the pulp, facilitates penetration into the starch granules due to the lower molecular weight of orthophosphate compared to tripolyphosphate. Properties (more uniform distribution of phosphate groups), higher solubility of orthophosphate than tripolyphosphate, and no precipitation during drying or heating reaction (more uniform distribution of phosphate groups and higher reaction It is conceivable that the adverse effects of unreacted salts are less in the case of orthophosphate because of the lower molecular weight.
【００４１】本発明の別の効果は、尿素燐酸化に使用す
る尿素、正燐酸、および水酸化ナトリウムなどのアルカ
リがトリポリ燐酸に比べて低価格のため、比較的安価に
両性澱粉を提供できることにある。Another effect of the present invention is that alkalis such as urea, orthophosphoric acid, and sodium hydroxide used for urea phosphorylation are lower in price than tripolyphosphoric acid, so that an amphoteric starch can be provided relatively inexpensively. is there.
Claims (3)
両性澱粉を製造するに際し、置換度０．０２〜０．０５
の三級アミンまたは四級アンモニウム塩を有するカチオ
ン澱粉に、尿素と正燐酸塩を添加し、次いで、乾式で１
１０〜１６０℃において加熱反応させ、対澱粉固形分あ
たり結合燐として０．１〜０．７重量%の燐酸基を導入
することを特徴とする製紙用両性澱粉の製造方法。1. When a phosphate group is introduced into a cationic starch to produce an amphoteric starch for papermaking, the degree of substitution is from 0.02 to 0.05.
Urea and orthophosphate are added to a cationic starch having a tertiary amine or quaternary ammonium salt of
A process for producing amphoteric starch for papermaking, which comprises heating and reacting at 10 to 160 ° C. to introduce 0.1 to 0.7% by weight of a phosphoric acid group as bound phosphorus per starch solid content.
れる製紙用両性澱粉。2. An amphoteric starch for papermaking obtained by the production method according to claim 1.
したパルプスラリーを抄紙することを特徴とする紙また
は板紙の製造方法。3. A method for producing paper or paperboard, comprising making a pulp slurry to which the amphoteric starch for papermaking according to claim 2 is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19105599A JP3608650B2 (en) | 1999-07-05 | 1999-07-05 | Amphoteric starch, method for producing the same and method for producing paper or paperboard |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19105599A JP3608650B2 (en) | 1999-07-05 | 1999-07-05 | Amphoteric starch, method for producing the same and method for producing paper or paperboard |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001019701A true JP2001019701A (en) | 2001-01-23 |
| JP3608650B2 JP3608650B2 (en) | 2005-01-12 |
Family
ID=16268147
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19105599A Expired - Lifetime JP3608650B2 (en) | 1999-07-05 | 1999-07-05 | Amphoteric starch, method for producing the same and method for producing paper or paperboard |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3608650B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2833599A1 (en) * | 2001-12-18 | 2003-06-20 | Oreal | Amphoteric polysaccharide used in cosmetic products comprises an anionic group(s) and a cationic group(s) directly attached to the polysaccharide |
| JP2003239196A (en) * | 2002-02-13 | 2003-08-27 | Oji Cornstarch Co Ltd | Surface-sized pressed paper using amphoteric starch with low viscosity |
| JP2007002375A (en) * | 2005-06-27 | 2007-01-11 | Nippon Nsc Ltd | Mixture for gelatinized paper-strengthening agent, gelatinized paper-strengthening agent and papermaking method |
| WO2018212012A1 (en) * | 2017-05-15 | 2018-11-22 | 大王製紙株式会社 | Cellulose microfibers and method for producing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62116602A (en) * | 1985-11-18 | 1987-05-28 | Sanwa Denpun Kogyo Kk | Production of urea-phosphate starch |
| JPS6348301A (en) * | 1986-08-13 | 1988-03-01 | ナシヨナル・スターチ・アンド・ケミカル・インベストメント・ホルデイング・コーポレイシヨン | Improved amphoteric starches and manufacture |
| JPH08296193A (en) * | 1995-04-25 | 1996-11-12 | Nippon Shokuhin Kako Co Ltd | Production of paper board |
-
1999
- 1999-07-05 JP JP19105599A patent/JP3608650B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62116602A (en) * | 1985-11-18 | 1987-05-28 | Sanwa Denpun Kogyo Kk | Production of urea-phosphate starch |
| JPS6348301A (en) * | 1986-08-13 | 1988-03-01 | ナシヨナル・スターチ・アンド・ケミカル・インベストメント・ホルデイング・コーポレイシヨン | Improved amphoteric starches and manufacture |
| JPH08296193A (en) * | 1995-04-25 | 1996-11-12 | Nippon Shokuhin Kako Co Ltd | Production of paper board |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2833599A1 (en) * | 2001-12-18 | 2003-06-20 | Oreal | Amphoteric polysaccharide used in cosmetic products comprises an anionic group(s) and a cationic group(s) directly attached to the polysaccharide |
| WO2003054025A3 (en) * | 2001-12-18 | 2003-12-18 | Oreal | Amphoteric polysaccharide, composition and use |
| JP2003239196A (en) * | 2002-02-13 | 2003-08-27 | Oji Cornstarch Co Ltd | Surface-sized pressed paper using amphoteric starch with low viscosity |
| JP2007002375A (en) * | 2005-06-27 | 2007-01-11 | Nippon Nsc Ltd | Mixture for gelatinized paper-strengthening agent, gelatinized paper-strengthening agent and papermaking method |
| WO2018212012A1 (en) * | 2017-05-15 | 2018-11-22 | 大王製紙株式会社 | Cellulose microfibers and method for producing same |
| US11441243B2 (en) | 2017-05-15 | 2022-09-13 | Daio Paper Corporation | Fine cellulose fiber and method for producing same |
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| Publication number | Publication date |
|---|---|
| JP3608650B2 (en) | 2005-01-12 |
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