JP2884694B2 - Etherified starch and method for producing the same - Google Patents
Etherified starch and method for producing the sameInfo
- Publication number
- JP2884694B2 JP2884694B2 JP10673190A JP10673190A JP2884694B2 JP 2884694 B2 JP2884694 B2 JP 2884694B2 JP 10673190 A JP10673190 A JP 10673190A JP 10673190 A JP10673190 A JP 10673190A JP 2884694 B2 JP2884694 B2 JP 2884694B2
- Authority
- JP
- Japan
- Prior art keywords
- starch
- weight
- etherified starch
- parts
- etherified
- 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.)
- Expired - Fee Related
Links
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明のエーテル化澱粉は、糊液の粘性、安定性、透
明性、保水性が良好なので、製紙工程における顔料保持
剤、コーティング剤、表面サイズ剤、たて糸のサイジン
グ剤、捺染、絵具の糊剤、接着剤等多くの分野に利用す
ることができる。DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The etherified starch of the present invention has good viscosity, stability, transparency, and water retention of the size liquid, and therefore, a pigment retainer, a coating agent, and a surface in a papermaking process. It can be used in many fields such as sizing agents, sizing agents for warp yarns, printing, sizing agents for paints, and adhesives.
（従来の技術） スルホン酸基を有するエーテル化澱粉としては、米国
特許第2806857号、同2825727号公報に澱粉にソディウム
クロロメチロイセチオネート（CI−CH2−CHOH−CH2SO3N
a）を反応させて得られるもの、また米国特許3046272
号、同3449322号公報に に反応させて得られるもの、さらに特開昭61−243802号
には、澱粉に２−アクリルアミド−２−メチルプロパン
スルホン酸（CH2＝CHCONHC（CH3）2CH2SO3H）を反応さ
せて得られるものが記載されている。The etherified starch having a (prior art) a sulfonic acid group, U.S. Patent No. 2,806,857, Soddy um chloro methylate Roy cell isethionate starch Publication Nos. 2825727 (CI-CH 2 -CHOH- CH 2 SO 3 N
a) reacting a) and US Pat.
No. 3449322 In addition, JP-A-61-243802 discloses that starch is reacted with 2-acrylamido-2-methylpropanesulfonic acid (CH 2 CHCHCONHC (CH 3 ) 2 CH 2 SO 3 H). Are obtained.
（発明が解決しようとする課題） 従来、アニオン性澱粉としてリン酸基、カルボン酸基
の結合したものが利用されているが、スルホン酸基の結
合したものが種々の用途で要望されているが未だ十分な
ものが得られていないのが現状である。(Problems to be Solved by the Invention) Conventionally, anionic starch having a phosphate group and a carboxylic acid group bonded thereto has been used. However, anionic starch having a sulfonic acid group bonded has been demanded for various uses. At present, not enough has been obtained.
（課題を解決するための手段） 本発明者らは、上記課題を解決し、糊剤としての特性
がさらに良好なものを得るべく鋭意検討した結果、澱粉
に1,4−ブタンサルトン をアルカリ触媒の存在下に反応させることによって、糊
液の粘性、安定性、透明感の良好なエーテル化澱粉が得
られることを見出し本発明を完成するに至った。(Means for Solving the Problems) The present inventors have solved the above problems and have conducted intensive studies in order to obtain a material having even better properties as a sizing agent. As a result, 1,4-butane sultone was added to starch. Was reacted in the presence of an alkali catalyst to obtain an etherified starch having good viscosity, stability, and transparency of the size liquid, and completed the present invention.
本発明のエーテル化澱粉を製造するのに使用できる澱
粉原料としては、小麦澱粉、馬鈴薯澱粉、トウモロコシ
澱粉、甘藷澱粉、タピオカ澱粉、サゴ澱粉、米澱粉、ワ
キシコーンスターチ、ハイアミロースコーンスターチな
どの未処理澱粉、または小麦粉、米粉、コーンフラワ
ー、タピオカ粉末などの澱粉含有物、さらに各種化工澱
粉が挙げられる。Starch raw materials that can be used to produce the etherified starch of the present invention include untreated wheat starch, potato starch, corn starch, sweet potato starch, tapioca starch, sago starch, rice starch, waxy corn starch, high amylose corn starch, and the like. Starch or starch-containing substances such as flour, rice flour, corn flour, tapioca powder, and various modified starches may be mentioned.
本発明のエーテル化澱粉は、ブタンサルトンの添加量
を増すと変性度が上がり、生成されるエーテル化澱粉は
粒状で仕上げることができず、糊状になる。糊液になっ
た生成物は、糊液としてそのまま使用することができ、
またドラムドライヤーによる乾燥、有機溶媒により沈殿
後乾燥させることもできる。The degree of modification of the etherified starch of the present invention increases as the amount of butanesultone added increases, and the resulting etherified starch cannot be finished in a granular form, but becomes a paste. The product that has become a size liquid can be used as a size liquid as it is,
Drying with a drum dryer and drying after precipitation with an organic solvent can also be performed.
澱粉100重量部に対し、1,4−ブタンサルトン0.5〜10
重量部、水120〜140重量部、硫酸ナトリウム30〜50重量
部、公知のアルカリ触媒0.5〜4.0重量％添加し、反応温
度25〜45℃で反応させることにより、本発明のエーテル
化澱粉は粒状で得ることができ、十分な水洗も可能とな
る。1,4-butane sultone 0.5 to 10 per 100 parts by weight of starch
Parts by weight, 120 to 140 parts by weight of water, 30 to 50 parts by weight of sodium sulfate, and 0.5 to 4.0% by weight of a known alkali catalyst are added, and the reaction is carried out at a reaction temperature of 25 to 45 ° C. And sufficient washing with water is also possible.
反応生成物は、pHを４〜８に中和後、可能であれば水
洗、脱水、乾燥することにより製品化される。The reaction product is commercialized by neutralizing the pH to 4 to 8, followed by washing with water, dehydration and drying if possible.
本発明のエーテル化澱粉は、下記一般式で示される
が、St−Ｏ−は澱粉分子、Ｍは水素またはその塩（アル
カリ金属、アルカリ土類金属、アンモニア、第一アミ
ン、第二アミン、第三アミン、第四アンモニウム塩）を
示す。The etherified starch of the present invention is represented by the following general formula, wherein St-O- is a starch molecule, M is hydrogen or a salt thereof (alkali metal, alkaline earth metal, ammonia, primary amine, secondary amine, secondary amine, Triamine, quaternary ammonium salts).
St−Ｏ−（CH2）４−SO3M （作用） 本発明のエーテル化澱粉は、スルホン酸基を含有する
新規な構造を有するので、糊液の粘性、安定性、透明
性、保水性が良好である。St-O- (CH 2 ) 4 —SO 3 M (Action) The etherified starch of the present invention has a novel structure containing a sulfonic acid group, so that the viscosity, stability, transparency and water retention of the size liquid are obtained. Is good.
（実施例） 次に実施例を挙げて、本発明を詳細に説明する。(Examples) Next, the present invention will be described in detail with reference to examples.
（実施例１） 水650gに硫酸ナトリウム250g、水酸化ナトリウム15g
を溶かし、タピオカ澱粉500gとブタンサルトン25g（対
澱粉５％）を入れ、42℃で10時間反応する。反応終了
後、中和、脱水、乾燥してエーテル化澱粉を得た。(Example 1) 250 g of sodium sulfate and 15 g of sodium hydroxide in 650 g of water
Are dissolved, 500 g of tapioca starch and 25 g of butane sultone (5% of starch) are added, and reacted at 42 ° C. for 10 hours. After completion of the reaction, neutralization, dehydration and drying were performed to obtain an etherified starch.
（実施例２） 実施例１において、触媒の水酸化ナトリウムの量を7g
に変える以外は、実施例１と同様に行なった。(Example 2) In Example 1, the amount of sodium hydroxide as a catalyst was 7 g.
The procedure was performed in the same manner as in Example 1 except for changing to.
（実施例３） 実施例１において、澱粉をタピオカ澱粉から、トウモ
ロコシ澱粉に変える以外は、実施例１と同様に行なっ
た。(Example 3) The procedure of Example 1 was repeated, except that the starch was changed from tapioca starch to corn starch.
（実施例４） 実施例１において、ブタンサルトンの量を10g（対澱
粉２％）に変える以外は、実施例１と同様に行なった。(Example 4) The procedure of Example 1 was repeated, except that the amount of butane sultone was changed to 10 g (based on starch 2%).
（実施例５） 水2000gにタピオカ澱粉500gと水酸化ナトリウム60g加
えニーダーで50℃にて撹拌し、均一に糊化した後、ブタ
ンサルトン100g添加し、50℃で５時間反応させる。反応
後、中和しドラムドライヤーにて乾燥しエーテル化澱粉
を得た。(Example 5) 500 g of tapioca starch and 60 g of sodium hydroxide were added to 2000 g of water, and the mixture was stirred at 50 ° C with a kneader and uniformly gelatinized. Then, 100 g of butanesultone was added, and the mixture was reacted at 50 ° C for 5 hours. After the reaction, the mixture was neutralized and dried with a drum dryer to obtain an etherified starch.
次に実施例１〜５で得られたエーテル化澱粉の諸物性
を測定し、その結果を第１表に示す。Next, various physical properties of the etherified starch obtained in Examples 1 to 5 were measured, and the results are shown in Table 1.
なお、第１表中、糊化開始温度とはエーテル化澱粉の
６％水懸濁液450gをアミログラフィー（ブラベンダー社
製、二枚翼パドル式ヘッド・メジャーリングヘッド:700
cm・ｇ、回転数:75r.p.m、温度上昇:1.5℃／分）に付し
た際のアミログラフが基線から立ち上がる点の温度をい
う。In Table 1, the gelatinization start temperature refers to amylography (Brabender, two-bladed paddle-type measuring head: 700 g) of 450 g of a 6% aqueous suspension of etherified starch.
cm.g, rotation speed: 75 rpm, temperature rise: 1.5 ° C./min) means the temperature at which the amyograph rises from the baseline.
置換後は、スルホン酸基を希塩酸で酸型にし、余分な
塩酸を洗浄後、糊化させ、pHが8.2になるまでの水酸化
ナトリウムの、グルコース残基１モルに対するモル数よ
り、何モルのスルホン酸基が結合しているかに換算した
ものである。After the substitution, the sulfonic acid group is converted to the acid form with dilute hydrochloric acid, excess hydrochloric acid is washed, gelatinized, and a number of moles of sodium hydroxide until the pH becomes 8.2, based on the number of moles per mole of glucose residue. It is converted to whether a sulfonic acid group is bonded.
粘度は、無水換算試料濃度５％のスラリーを85℃以上
で10分間加熱後、冷却し30℃においてBM型回転粘度計で
測定したものである。The viscosity was measured by heating a slurry having a sample concentration of 5% in terms of anhydrous content at 85 ° C. or higher for 10 minutes, cooling, and then measuring the temperature at 30 ° C. using a BM-type rotational viscometer.
（発明の効果） 第１表より明らかなように、本発明のエーテル化澱粉
は、糊化開始温度が原料澱粉より低いため完全糊化させ
るのが容易であり、経日安定性に優れ、粘度の透明性、
粘性も良好であった。(Effects of the Invention) As is clear from Table 1, the etherified starch of the present invention has a lower gelatinization start temperature than the raw starch, so that it can be easily completely gelatinized, has excellent stability over time, and has excellent viscosity. Transparency,
The viscosity was also good.
フロントページの続き 審査官 弘實 謙二 (58)調査した分野(Int.Cl.6，ＤＢ名) C08B 31/12 Continuing from the front page Examiner Kenji Hiromi (58) Field surveyed (Int. Cl. 6 , DB name) C08B 31/12
Claims (3)
示す。）An etherified starch represented by the following general formula: St-O- (CH 2) 4 -SO 3 M ( wherein St-O-starch molecule, M is hydrogen or a salt thereof.)
媒の存在下に反応させることを特徴とするエーテル化澱
粉の製造方法。2. A method for producing an etherified starch, comprising reacting 1,4-butanesultone with starch in the presence of an alkali catalyst.
ン0.5〜10重量部、水120〜140重量部、硫酸ナトリウム3
0〜50重量部、アルカリ触媒0.5〜4.0重量部添加し、反
応温度25〜45℃で反応させることを特徴とするエーテル
化澱粉の製造方法。3. 100 parts by weight of starch, 0.5 to 10 parts by weight of 1,4-butane sultone, 120 to 140 parts by weight of water, sodium sulfate 3
A method for producing etherified starch, comprising adding 0 to 50 parts by weight of an alkali catalyst and 0.5 to 4.0 parts by weight of an alkali catalyst and reacting at a reaction temperature of 25 to 45 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10673190A JP2884694B2 (en) | 1990-04-23 | 1990-04-23 | Etherified starch and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10673190A JP2884694B2 (en) | 1990-04-23 | 1990-04-23 | Etherified starch and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH044201A JPH044201A (en) | 1992-01-08 |
| JP2884694B2 true JP2884694B2 (en) | 1999-04-19 |
Family
ID=14441082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10673190A Expired - Fee Related JP2884694B2 (en) | 1990-04-23 | 1990-04-23 | Etherified starch and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2884694B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002030244A (en) * | 2000-07-18 | 2002-01-31 | Sakura Color Prod Corp | Aqueous color composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2743328B2 (en) * | 1994-02-10 | 1998-04-22 | 池田物産株式会社 | Interior materials |
-
1990
- 1990-04-23 JP JP10673190A patent/JP2884694B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002030244A (en) * | 2000-07-18 | 2002-01-31 | Sakura Color Prod Corp | Aqueous color composition |
| JP4564631B2 (en) * | 2000-07-18 | 2010-10-20 | 株式会社サクラクレパス | Aqueous paint composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH044201A (en) | 1992-01-08 |
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