JPH044201A - Etherified starch and production thereof - Google Patents
Etherified starch and production thereofInfo
- Publication number
- JPH044201A JPH044201A JP10673190A JP10673190A JPH044201A JP H044201 A JPH044201 A JP H044201A JP 10673190 A JP10673190 A JP 10673190A JP 10673190 A JP10673190 A JP 10673190A JP H044201 A JPH044201 A JP H044201A
- Authority
- JP
- Japan
- Prior art keywords
- starch
- pts
- weight
- parts
- water
- 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
- 229920002472 Starch Polymers 0.000 title claims abstract description 40
- 235000019698 starch Nutrition 0.000 title claims abstract description 39
- 239000008107 starch Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 240000003183 Manihot esculenta Species 0.000 description 5
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 229920002261 Corn starch Polymers 0.000 description 4
- 239000008120 corn starch Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920006320 anionic starch Polymers 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Abstract
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、保水性か良好なので、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 Field of Application) The etherified starch of the present invention has good viscosity, stability, transparency, and water retention properties of size liquid, so it can be used as a pigment retention agent, coating agent, and surface treatment agent in the paper manufacturing process. It can be used in many fields such as sizing agents, warp yarn sizing agents, textile printing, paint sizing agents, 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（Ｃｌ−ＣＨ
２−ＣＨＯＨ−ＣＨ２Ｓｏ３Ｎａ）を反応させて得られ
るもの、また米国特許３０４６２７２号、同３４４９３
２２号公報にに反応させて得られるもの、さらに特開昭
６１２４３８０２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＝ＣＨＣＯＮＨ
Ｃ（ＣＨ，） ２ＣＨ２ＳＯ３Ｈ）を反応させて得られ
るものが記載されている。(Prior art) As an etherified starch having a sulfonic acid group, sodium chloromethyloisethionate (Cl-CH
2-CHOH-CH2So3Na), and U.S. Pat. Nos. 3,046,272 and 34,493.
No. 22 discloses a product obtained by reacting starch with 2-acrylamide-
2-Methylpropanesulfonic acid (CH2=CHCONH
The product obtained by reacting C(CH,) 2CH2SO3H) is described.
（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、カルホン酸基の
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 starches with phosphoric acid groups or carbonic acid groups have been used, but starches with sulfonic acid groups are desired for various uses. The current situation is that we have not yet obtained enough.
（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、糊剤としての特性か
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 solved the above problems and made extensive studies to obtain even better properties as a sizing agent. The present inventors have discovered that an etherified starch with good viscosity, stability, and transparency of a starch paste can be obtained by reacting in the presence of the starch, and has 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 unprocessed wheat starch, potato starch, corn starch, sweet potato starch, tapioca starch, sago starch, rice starch, waxy corn starch, high amylose corn starch, etc. Starch, or wheat flour, rice flour, corn flour,
Examples include starch-containing materials such as tapioca powder, and various modified starches.
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。In the etherified starch of the present invention, when the amount of butane sultone added increases, the degree of modification increases, and the etherified starch produced cannot be finished in granular form, but becomes pasty. The product that has become a size liquid can be used as it is as a size liquid, or can be dried with a drum dryer or after precipitation with an organic solvent.
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-butanesultone 0.0% per 100 parts by weight of starch.
5 to 10 parts by weight, 120 to 140 parts by weight of water, 30 to 50 parts by weight of sodium sulfate, 0.5 to 4 parts by weight of a known alkali catalyst
By adding .
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 made into a product by neutralizing the pH to 4 to 8, washing with water, dehydrating, 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か、
５ｔ−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、
第三アミン、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, or
5t-O- is a starch molecule, M is hydrogen or its salt (alkali metal, alkaline earth metal, ammonia, primary amine,
tertiary amine, tertiary amine, quaternary ammonium salt).
Ｓ ｔ−０−（ＣＨ２）、−８Ｏ３Ｍ
（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。S t-0-(CH2), -8O3M (Function) Since the etherified starch of the present invention has a novel structure containing a sulfonic acid group, it improves the viscosity, stability, transparency, and
Good water retention.
（実施例） 次に実施例を挙げて、本発明の詳細な説明する。(Example) Next, the present invention will be explained in detail with reference to Examples.
（実施例１）
水６５０ｇに硫酸ナトリウム２５０ ｇ、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) Dissolve 250 g of sodium sulfate and 15 g of sodium hydroxide in 650 g of water, add 500 g of tapioca starch and 25 g of butane sultone (5% to starch), and react at 42° C. for 10 hours. After the reaction was completed, the mixture was neutralized, dehydrated, and dried to obtain 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 in the catalyst was changed to 7 g.
The same procedure as in Example 1 was carried out except that .
（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 same procedure as in Example 1 was conducted except that the starch in Example 1 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 same procedure as in Example 1 was conducted except that the amount of butane sultone was changed to 10 g (2% to starch).
（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−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 2,000 g of water, stirred at 50°C with a kneader to uniformly gelatinize, and then 100g of butane sultone was added and reacted at 50°C for 5 hours. After the reaction, the mixture was neutralized and dried using a drum dryer to obtain etherified starch.
次に実施例１〜５て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 starches 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：
７００ｃｍ−ｇ、回転数。In addition, in Table 1, the gelatinization start temperature is 6
% water suspension was subjected to amyrography (manufactured by Brabender, two-blade paddle type measuring head:
700cm-g, rotation speed.
７５ｒ、ｐ、’ｍ、、温度上昇 １．５°Ｃ／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。75r,p,'m, temperature rise 1.5°C/min) refers to the temperature at which the amylograph rises from the baseline.
置換度は、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。The degree of substitution is determined by converting the sulfonic acid group into acid form with dilute hydrochloric acid, washing the excess hydrochloric acid, gelatinizing, and the number of moles of sodium hydroxide per mole of glucose residue until the pH reaches 8.2. It is calculated in terms of moles of sulfonic acid groups 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 is measured by heating a slurry with a sample concentration of 5% on an anhydrous basis for 10 minutes at 85°C or higher, cooling it, and using a BM type rotational viscometer at 30°C.
（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 gelatinization initiation temperature lower than that of the raw material starch, so it is easy to completely gelatinize, has excellent stability over time, and has a low viscosity. The transparency and viscosity were also good.
Claims (3)
を示す。）(1) Etherified starch represented by the following general formula. St-O-(CH_2)_4-SO_3M (Here, St-O- represents a starch molecule, and M represents hydrogen or its salt.)
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 etherified starch, which comprises reacting starch with 1,4-butanesultone 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３０〜５０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) For 100 parts by weight of starch, 0.5 to 10 parts by weight of 1,4-butanesultone, 120 to 140 parts by weight of water, 30 to 50 parts by weight of sodium sulfate, and 0.5 to 4 parts by weight of alkali catalyst.
．． A method for producing etherified starch, which comprises adding 0 parts by weight 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 true JPH044201A (en) | 1992-01-08 |
| JP2884694B2 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 |
|---|---|---|---|---|
| JPH07223285A (en) * | 1994-02-10 | 1995-08-22 | Ikeda Bussan Co Ltd | Corrugated cardboard and interior material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4564631B2 (en) * | 2000-07-18 | 2010-10-20 | 株式会社サクラクレパス | Aqueous paint composition |
-
1990
- 1990-04-23 JP JP10673190A patent/JP2884694B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07223285A (en) * | 1994-02-10 | 1995-08-22 | Ikeda Bussan Co Ltd | Corrugated cardboard and interior material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2884694B2 (en) | 1999-04-19 |
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