JP4532603B1 - Method for producing phosphoric acid crosslinked starch - Google Patents
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Abstract
【課題】トリメタリン酸ナトリウムの使用量を低減でき、比較的低温で効率よく反応させることができ、反応時間を短縮できるようにしたリン酸架橋澱粉の製造方法を提供する。
【解決手段】カルシウム塩類の存在下、ｐＨ８〜１２で、澱粉とトリメタリン酸ナトリウムとを、１０〜４５℃で反応させる。トリメタリン酸ナトリウムの澱粉に対する添加量は０．０１〜１．００％が好ましく、カルシウム塩類が塩化カルシウムであることが好ましい。また、澱粉とトリメタリン酸ナトリウムとの反応時間が、１０分〜１０時間であることが好ましい。
【選択図】なしThe present invention provides a method for producing a phosphoric acid crosslinked starch that can reduce the amount of sodium trimetaphosphate used, can be reacted efficiently at a relatively low temperature, and can shorten the reaction time.
In the presence of calcium salts, starch and sodium trimetaphosphate are reacted at 10 to 45 ° C. at pH 8 to 12. The amount of sodium trimetaphosphate added to the starch is preferably 0.01 to 1.00%, and the calcium salts are preferably calcium chloride. Moreover, it is preferable that reaction time of starch and sodium trimetaphosphate is 10 minutes-10 hours.
[Selection figure] None
Description
本発明は、澱粉にトリメタリン酸ナトリウムを作用させるリン酸架橋澱粉の製造方法に関する。 The present invention relates to a method for producing a phosphate-crosslinked starch in which sodium trimetaphosphate is allowed to act on starch.
リン酸架橋澱粉は、膨潤が抑制される、糊化開始温度が高温側に移行する、ブレークダウンが減少し、ついにはブレークダウンが消失する、などの特徴があり、レトルト食品、ソース、スープ、冷凍食品など過酷な条件で処理される食品に主に使用されている。 Phosphoric acid cross-linked starch has features such that swelling is suppressed, gelatinization start temperature shifts to a high temperature side, breakdown is reduced, and finally breakdown disappears, such as retort food, sauce, soup, It is mainly used for foods processed under harsh conditions such as frozen foods.
澱粉にリン酸架橋を処するためには、下記非特許文献１に示されるように、アルカリ側で澱粉にオキシ塩化リン、無水リン酸、トリメタリン酸塩、ヘキサメタリン酸塩などを反応させる方法が採用されている。 In order to treat phosphate with starch, a method of reacting starch with phosphorus oxychloride, phosphoric anhydride, trimetaphosphate, hexametaphosphate, etc. on the alkali side is adopted as shown in Non-Patent Document 1 below. ing.
澱粉にトリメタリン酸塩を反応させる方法として、下記非特許文献２には、水１８０ｍｌにトリメタリン酸ナトリウム２ｇ、炭酸ナトリウム３ｇを溶解し、トウモロコシ澱粉１００ｇを懸濁させ、ｐＨ１０．２に調整し、５０℃で６時間反応を行ってジ澱粉リン酸エステルを得る方法が記載されている。 As a method of reacting trimetaphosphate with starch, the following Non-Patent Document 2 discloses that 2 g of sodium trimetaphosphate and 3 g of sodium carbonate are dissolved in 180 ml of water, 100 g of corn starch is suspended, adjusted to pH 10.2, 50 A method for obtaining a distarch phosphate by reacting at 6 ° C. for 6 hours is described.
また、下記特許文献１には、澱粉を調製するプロセスであって、トリメタリン酸ナトリウム（ＳＴＭＰ）、又はトリメタリン酸ナトリウムとトリポリリン酸ナトリウム（ＳＴＰＰ）の組み合わせを用いて澱粉を架橋するステップを含み、そこではｐＨが、該架橋反応の前に１１．５と１２．０の間に調整され、該架橋反応の間１１．５〜１２．０に維持される、プロセスが開示されている。また、反応を２５℃から７０℃までの温度で、１０分〜３０時間行うことが記載されている。更に、水酸化ナトリウムを用いてｐＨを調整することが記載されている。 Patent Document 1 below is a process for preparing starch, which includes a step of crosslinking starch using sodium trimetaphosphate (STMP) or a combination of sodium trimetaphosphate and sodium tripolyphosphate (STPP). A process is disclosed wherein the pH is adjusted between 11.5 and 12.0 prior to the crosslinking reaction and maintained between 11.5 and 12.0 during the crosslinking reaction. Further, it is described that the reaction is carried out at a temperature from 25 ° C. to 70 ° C. for 10 minutes to 30 hours. Furthermore, it is described that the pH is adjusted using sodium hydroxide.
非特許文献２及び特許文献１に示されるように、澱粉にトリメタリン酸ナトリウムを反応させる方法としては、炭酸ナトリウムや、水酸化ナトリウムなどを用いてｐＨ１０以上に調整し、５０℃前後の温度で反応させる方法が一般的に採用されている。このように、従来は、ナトリウム塩を触媒として、高アルカリで、澱粉が糊化しない範囲で、できるだけ高温で処理するほど、反応速度が増加し、架橋度の高いリン酸架橋澱粉が得られると考えられていた。 As shown in Non-Patent Document 2 and Patent Document 1, as a method of reacting sodium trimetaphosphate with starch, the pH is adjusted to 10 or more using sodium carbonate or sodium hydroxide, and the reaction is performed at a temperature around 50 ° C. This method is generally adopted. As described above, conventionally, when the sodium salt is used as a catalyst and the alkali is high and the starch is not gelatinized, the higher the temperature, the higher the reaction rate and the higher the degree of cross-linking phosphate-crosslinked starch. It was thought.
しかしながら、上記従来の方法では、トリメタリン酸ナトリウムの使用量が多く、高温に維持するためのエネルギーコストがかかり、反応時間が長いので生産効率が悪いという問題があった。 However, the above-described conventional methods have a problem that the amount of sodium trimetaphosphate used is large, energy costs for maintaining it at a high temperature are required, and the reaction time is long, resulting in poor production efficiency.
したがって、本発明の目的は、トリメタリン酸ナトリウムの使用量を低減でき、比較的低温で効率よく反応させることができ、反応時間を短縮できるようにしたリン酸架橋澱粉の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing a phosphate-crosslinked starch capable of reducing the amount of sodium trimetaphosphate used, allowing efficient reaction at a relatively low temperature, and shortening the reaction time. is there.
上記目的を達成するため、本発明のリン酸架橋澱粉の製造方法は、カルシウム塩類の存在下、ｐＨ８〜１２で、澱粉とトリメタリン酸ナトリウム（以下「ＳＴＭＰ」と略称する場合もある）とを、１０〜４５℃で反応させることを特徴とする。 In order to achieve the above object, the method for producing a phosphate-crosslinked starch of the present invention comprises a starch and sodium trimetaphosphate (hereinafter sometimes abbreviated as “STMP”) at pH 8-12 in the presence of calcium salts. The reaction is performed at 10 to 45 ° C.
本発明のリン酸架橋澱粉の製造方法によれば、カルシウム塩類を触媒として、ｐＨ８〜１２のアルカリ条件下で、澱粉とトリメタリン酸ナトリウムとを反応させることにより、１０〜４５℃という比較的低い反応温度で効率よく反応させることが可能となる。カルシウム塩類を触媒とした場合、意外にも、反応温度は３３℃前後が最も反応効率が向上し、架橋度が高い製品が得られることがわかった。その結果、反応温度を下げると共に、反応時間を短縮することができ、更にはトリメタリン酸ナトリウムの使用量を低減できる。また、反応温度の低下に伴ってｐＨ調整に必要なアルカリ剤の使用量も低減でき、中和時の酸の使用量も低減できる。また、大規模な製造においても反応温度を一定に保ち易いため、製品の架橋度のばらつきも少なくなり、製品品質をより安定化することができる。 According to the method for producing phosphate-crosslinked starch of the present invention, a relatively low reaction of 10 to 45 ° C. is obtained by reacting starch with sodium trimetaphosphate under alkaline conditions of pH 8 to 12 using calcium salts as a catalyst. It becomes possible to make it react efficiently at temperature. Surprisingly, it has been found that when calcium salts are used as a catalyst, a reaction temperature of around 33 ° C. has the highest reaction efficiency and a product with a high degree of crosslinking. As a result, the reaction temperature can be lowered, the reaction time can be shortened, and the amount of sodium trimetaphosphate used can be reduced. Moreover, the usage-amount of the alkaline agent required for pH adjustment can also be reduced with the fall of reaction temperature, and the usage-amount of the acid at the time of neutralization can also be reduced. Moreover, since it is easy to keep reaction temperature constant also in large-scale manufacture, the dispersion | variation in the crosslinking degree of a product decreases, and product quality can be stabilized more.
本発明においては、トリメタリン酸ナトリウムの澱粉に対する添加量が、０．０１〜１．００％であることが好ましい。本発明では、トリメタリン酸ナトリウムの添加量が上記のように少なくても、架橋度の高い製品が得られる。 In this invention, it is preferable that the addition amount with respect to starch of sodium trimetaphosphate is 0.01 to 1.00%. In the present invention, a product having a high degree of crosslinking can be obtained even if the amount of sodium trimetaphosphate added is small as described above.
また、本発明においては、カルシウム塩類が塩化カルシウムであることが好ましい。触媒として塩化カルシウムを用いることにより、反応時間を短縮し、架橋度を上昇できるという利点が得られる。 In the present invention, the calcium salt is preferably calcium chloride. By using calcium chloride as a catalyst, there are obtained advantages that the reaction time can be shortened and the degree of crosslinking can be increased.
更に、本発明においては、澱粉とトリメタリン酸ナトリウムとの反応時間が、１０分〜１０時間であることが好ましい。本発明では、上記のように比較的短い反応時間でも架橋度の高い製品を得ることができ、生産効率を高めることができる。 Furthermore, in this invention, it is preferable that reaction time of starch and sodium trimetaphosphate is 10 minutes-10 hours. In the present invention, a product having a high degree of crosslinking can be obtained even in a relatively short reaction time as described above, and the production efficiency can be increased.
本発明においては、上記リン酸架橋の他、必要に応じてアセチル化、ヒドロキシプロピル化、リン酸化、オクテニルコハク酸化などの化学加工や湿熱処理、油脂加工、微粉砕処理などの物理加工を組み合わせることができるが、これらは特に限定されるものではない。 In the present invention, in addition to the above-mentioned phosphoric acid cross-linking, chemical processing such as acetylation, hydroxypropylation, phosphorylation, octenyl succination, and other physical processing such as wet heat treatment, oil processing, fine grinding processing may be combined as necessary. However, these are not particularly limited.
本発明によれば、カルシウム塩類を触媒として、アルカリ条件下で澱粉とトリメタリン酸ナトリウムとを反応させることにより、比較的低い反応温度で、しかも比較的短い反応時間で、架橋度が高いリン酸架橋澱粉を効率よく製造することができ、加熱エネルギーコストを低減できると共に、生産効率を高めることができる。また、従来製品と同等な架橋度にするのに必要なトリメタリン酸ナトリウムの添加量も低減でき、原料コストも低減できる。 According to the present invention, phosphoric acid crosslinking having a high degree of crosslinking at a relatively low reaction temperature and in a relatively short reaction time by reacting starch with sodium trimetaphosphate under alkaline conditions using calcium salts as a catalyst. Starch can be produced efficiently, heating energy costs can be reduced, and production efficiency can be increased. In addition, the amount of sodium trimetaphosphate added to achieve the same degree of crosslinking as that of conventional products can be reduced, and the raw material cost can be reduced.
本発明において、澱粉としては、特に限定されないが、例えばトウモロコシ澱粉、タピオカ澱粉、サゴ澱粉、米澱粉、馬鈴薯澱粉などを用いることができる。 In the present invention, the starch is not particularly limited, and for example, corn starch, tapioca starch, sago starch, rice starch, potato starch and the like can be used.
カルシウム塩類としては、例えば塩化カルシウム、乳酸カルシウム、酢酸カルシウム、水酸化カルシウムなどを用いることができるが、中でも、溶解性が高いという理由から、塩化カルシウム、乳酸カルシウムが特に好ましい。 As calcium salts, for example, calcium chloride, calcium lactate, calcium acetate, calcium hydroxide and the like can be used. Among them, calcium chloride and calcium lactate are particularly preferable because of their high solubility.
トリメタリン酸ナトリウムの澱粉１００質量部に対する添加量は、０．０１〜１．００質量部であることが好ましく、０．０１〜０．７０質量部であることが更に好ましい。トリメタリン酸ナトリウムの澱粉に対する添加量が０．０１質量部未満では、試薬量が少ないため架橋澱粉の特性が得られないという問題があり、１．００質量部を超えると、反応効率が低下して試薬量に見合った架橋度が得られないという問題がある。 The amount of sodium trimetaphosphate added to 100 parts by mass of starch is preferably 0.01 to 1.00 parts by mass, and more preferably 0.01 to 0.70 parts by mass. If the amount of sodium trimetaphosphate added to the starch is less than 0.01 parts by mass, there is a problem that the characteristics of the crosslinked starch cannot be obtained because the amount of the reagent is small, and if it exceeds 1.00 parts by mass, the reaction efficiency decreases. There is a problem that the degree of crosslinking corresponding to the amount of reagent cannot be obtained.
本発明のリン酸架橋澱粉の製造方法について、その好ましい態様を工程順に説明すると次の通りである。 About the manufacturing method of the phosphoric acid crosslinked starch of this invention, it is as follows when the preferable aspect is demonstrated in order of a process.
（１）澱粉スラリー調製工程
澱粉に予め水を添加してスラリー状にする。スラリー中の澱粉の濃度は、３０〜４５質量％とすることが好ましく、３８〜４２質量％とすることが更に好ましい。
(1) Starch slurry preparation step Water is added to starch in advance to form a slurry. The starch concentration in the slurry is preferably 30 to 45 mass%, more preferably 38 to 42 mass%.
（２）触媒添加工程
塩化カルシウム等のカルシウム塩類からなる触媒を添加する。スラリー中のカルシウム塩類の添加量は、カルシウム量として０．０１〜１．００質量％が好ましく、０．０５〜０．５０質量％がより好ましい。
(2) Catalyst addition step A catalyst comprising calcium salts such as calcium chloride is added. The addition amount of calcium salts in the slurry is preferably 0.01 to 1.00% by mass, and more preferably 0.05 to 0.50% by mass as the amount of calcium.
（３）ｐＨ調整工程
例えば水酸化ナトリウム、水酸化カルシウム、炭酸ナトリウムなどのアルカリ剤を添加して、ｐＨ８〜１２、好ましくは９〜１１．５に調整する。ｐＨ８未満では、リン酸架橋反応が起こり難いという問題があり、ｐＨ１２を超えると、澱粉がアルカリ糊化するという問題がある。
(3) pH adjustment step For example, an alkali agent such as sodium hydroxide, calcium hydroxide or sodium carbonate is added to adjust the pH to 8 to 12, preferably 9 to 11.5. If the pH is less than 8, there is a problem that the phosphoric acid crosslinking reaction hardly occurs, and if the pH is more than 12, there is a problem that starch is gelatinized.
（４）リン酸架橋反応工程
スラリーの温度を１０〜４５℃、好ましくは２０〜４０℃、より好ましくは２５〜３５℃に調整し、トリメタリン酸ナトリウムを、澱粉に対して、好ましくは０．０１〜１．００％、より好ましくは０．０５〜０．７０％添加して、好ましくは１０分〜１０時間、より好ましくは１５分〜５時間反応させる。
(4) Phosphoric acid crosslinking reaction step The temperature of the slurry is adjusted to 10 to 45 ° C, preferably 20 to 40 ° C, more preferably 25 to 35 ° C, and sodium trimetaphosphate is preferably 0.01 with respect to starch. ˜1.00%, more preferably 0.05 to 0.70%, and preferably 10 minutes to 10 hours, more preferably 15 minutes to 5 hours.
スラリーの温度が１０℃未満では、リン酸架橋の反応効率が低下すると共に、冷却に関わるコストが高くなるという問題があり、４５℃を超えると、リン酸架橋の反応効率が低下するという問題がある。 When the temperature of the slurry is less than 10 ° C., there is a problem that the reaction efficiency of phosphoric acid crosslinking is lowered and the cost related to cooling is increased, and when it exceeds 45 ° C., the reaction efficiency of phosphoric acid crosslinking is lowered. is there.
また、トリメタリン酸ナトリウムの添加量が、澱粉に対して０．０１％未満では、試薬量が少ないため架橋澱粉の特性が得られないという問題があり、１．００％を超えると、反応効率が低下して試薬量に見合った架橋度が得られないという問題がある。 Further, when the amount of sodium trimetaphosphate added is less than 0.01% with respect to the starch, there is a problem that the characteristics of the crosslinked starch cannot be obtained because the amount of the reagent is small, and when it exceeds 1.00%, the reaction efficiency is increased. There is a problem that the degree of crosslinking cannot be obtained in accordance with the amount of the reagent.
更に、反応時間が、１０分未満では、反応時間が短すぎて架橋澱粉の特性が得られないという問題があり、１０時間を超えると、ランニングコストが高いという問題がある。 Furthermore, if the reaction time is less than 10 minutes, there is a problem that the reaction time is too short to obtain the characteristics of the crosslinked starch, and if it exceeds 10 hours, the running cost is high.
（５）中和工程
例えば塩酸などの酸を添加して、スラリーを中和する。
(5) Neutralization step For example, an acid such as hydrochloric acid is added to neutralize the slurry.
（６）水洗・脱水・乾燥工程
以上の処理を行ったスラリーに、水を添加し、水洗・脱水した後、乾燥させる。
(6) Washing / Dehydration / Drying Step Water is added to the slurry subjected to the above treatment, followed by washing / dehydration and drying.
こうして本発明のリン酸架橋澱粉を得ることができるが、本発明では、こうして得られた澱粉に、必要に応じてアセチル化、ヒドロキシプロピル化、リン酸化、オクテニルコハク酸化などの化学加工や湿熱処理、油脂加工、微粉砕処理などの物理加工を更に施すことができる。 Thus, the phosphoric acid cross-linked starch of the present invention can be obtained. In the present invention, the starch thus obtained can be subjected to chemical processing such as acetylation, hydroxypropylation, phosphorylation, octenyl succination and wet heat treatment, if necessary. Physical processing such as oil processing and fine grinding processing can be further performed.
以下に実施例を挙げて本発明の詳細を説明するが、本発明は以下の実施例に限定されるものではない。なお、以下の実施例において、各測定数値は下記のような条件で測定した値である。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples. In the following examples, each measured numerical value is a value measured under the following conditions.
（Ａ）アミログラム測定：無水物換算で６％に調製した澱粉スラリーの糊化特性を、アミログラフを用いて測定した（測定条件：３０℃で測定を開始した後、１．５℃／分で９５℃まで昇温させ、その後９５℃を３０分間維持した）。 (A) Amyogram measurement: The gelatinization property of starch slurry prepared to 6% in terms of anhydride was measured using an amylograph (measurement condition: 95% at 1.5 ° C./min after starting measurement at 30 ° C. The temperature was raised to 0 ° C., and then maintained at 95 ° C. for 30 minutes).
（Ｂ）アミロ粘度：アミログラム測定結果から、９５℃・０分時の粘度を読み取り、これをアミロ粘度とした。アミロ粘度が低いほど架橋度が高い傾向があるため、架橋度の指標となる。 (B) Amylo viscosity: From the amylogram measurement results, the viscosity at 95 ° C. for 0 minute was read and used as the amylo viscosity. The lower the amylo viscosity is, the higher the degree of cross-linking tends to be, and thus an index of the degree of cross-linking.
（Ｃ）ブレークダウン：アミログラム測定結果から、一度上昇した粘度が低下した場合、粘度低下前の最大値（ピーク粘度）と９５℃・３０分時の粘度の差をブレークダウンとした。ブレークダウンが高いほど架橋度が低くなり、架橋度が高い場合にはブレークダウンは認められないことから、架橋度の指標となる。 (C) Breakdown: From the results of amylogram measurement, when the viscosity once increased, the difference between the maximum value before the viscosity decrease (peak viscosity) and the viscosity at 95 ° C. for 30 minutes was taken as breakdown. The higher the breakdown, the lower the cross-linking degree. When the cross-linking degree is high, the breakdown is not recognized, and this is an index of the cross-linking degree.
（Ｄ）架橋度：前述したアミロ粘度とブレークダウンを合わせて評価することで、各澱粉の架橋度の高さを順位法で評価した。 (D) Crosslinking degree: By evaluating together the above-mentioned amylo viscosity and breakdown, the high degree of crosslinking degree of each starch was evaluated by the ranking method.
実施例１
未加工のタピオカ澱粉３００ｇ（乾物重量）に、水を加えて４０％濃度の澱粉スラリーを調整した。このスラリーに塩化カルシウム（ＣａＣｌ２）を澱粉に対して０．５質量％となるように添加し、４５℃となるように温度調整した。更に、上記スラリーに、３％水酸化ナトリウムを添加してｐＨ１１．０となるようにｐＨ調整した。次いで、澱粉に対して０．１７％のトリメタリン酸ナトリウム（ＳＴＭＰ）を添加し、４５℃に保って９０分間反応させた。更に、９％塩酸を添加してｐＨ５．０となるようにｐＨ調整し、水道水３Ｌを加えて希釈し、２５０メッシュの篩にかけて脱水し、更に２Ｌの水を加えて同様に脱水した。この脱水物を棚式乾燥機によって乾燥し、リン酸架橋澱粉を得た。
Example 1
Water was added to 300 g (dry matter weight) of raw tapioca starch to prepare a 40% starch slurry. Calcium chloride (CaCl 2 ) was added to this slurry so as to be 0.5% by mass with respect to starch, and the temperature was adjusted to 45 ° C. Furthermore, 3% sodium hydroxide was added to the slurry to adjust the pH to 11.0. Next, 0.17% sodium trimetaphosphate (STMP) was added to the starch, and the mixture was reacted at 90 ° C. for 90 minutes. Further, the pH was adjusted to 9 by adding 9% hydrochloric acid, diluted by adding 3 L of tap water, dehydrated through a 250 mesh sieve, and further dehydrated by adding 2 L of water. The dehydrated product was dried by a shelf dryer to obtain phosphoric acid crosslinked starch.
実施例２
実施例１において、スラリー温度を３３℃に調整し、反応時の温度を３３℃に保った他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Example 2
In Example 1, phosphoric acid cross-linked starch was obtained in the same manner as in Example 1 except that the slurry temperature was adjusted to 33 ° C and the temperature during the reaction was maintained at 33 ° C.
比較例１
実施例１において、スラリー温度を５℃に調整し、反応時の温度を５℃に保った他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Comparative Example 1
In Example 1, phosphoric acid cross-linked starch was obtained in the same manner as in Example 1 except that the slurry temperature was adjusted to 5 ° C and the temperature during the reaction was maintained at 5 ° C.
比較例２
実施例１において、スラリー温度を５０℃に調整し、反応時の温度を５０℃に保った他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Comparative Example 2
In Example 1, phosphoric acid cross-linked starch was obtained in the same manner as in Example 1 except that the slurry temperature was adjusted to 50 ° C. and the temperature during the reaction was maintained at 50 ° C.
比較例３
実施例１において、塩化カルシウム（ＣａＣｌ２）を添加しなかった（触媒無添加）他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Comparative Example 3
A phosphoric acid crosslinked starch was obtained in the same manner as in Example 1 except that calcium chloride (CaCl 2 ) was not added (no catalyst was added).
比較例４
実施例１において、塩化カルシウム（ＣａＣｌ２）を澱粉に対して０．５質量％となるように添加する代わりに、硫酸ナトリウム（Ｎａ２ＳＯ４）を澱粉に対して２．０質量％となるように添加した他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Comparative Example 4
In Example 1, instead of adding calcium chloride (CaCl 2 ) to 0.5% by mass with respect to starch, sodium sulfate (Na 2 SO 4 ) becomes 2.0% by mass with respect to starch. A phosphoric acid crosslinked starch was obtained in the same manner as in Example 1 except that it was added as described above.
比較例５
実施例１において、塩化カルシウム（ＣａＣｌ２）を澱粉に対して０．５質量％となるように添加する代わりに、硫酸ナトリウム（Ｎａ２ＳＯ４）を澱粉に対して２．０質量％となるように添加し、スラリー温度を３３℃に調整し、反応時の温度を３３℃に保った他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Comparative Example 5
In Example 1, instead of adding calcium chloride (CaCl 2 ) to 0.5% by mass with respect to starch, sodium sulfate (Na 2 SO 4 ) becomes 2.0% by mass with respect to starch. Thus, phosphoric acid crosslinked starch was obtained in the same manner as in Example 1 except that the slurry temperature was adjusted to 33 ° C. and the temperature during the reaction was maintained at 33 ° C.
比較例６
実施例１において、塩化カルシウム（ＣａＣｌ２）を澱粉に対して０．５質量％となるように添加する代わりに、塩化ナトリウム（ＮａＣｌ）を澱粉に対して１．１５質量％となるように添加し、スラリー温度を４５℃に調整し、反応時の温度を４５℃に保った他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Comparative Example 6
In Example 1, the addition of calcium chloride (CaCl 2), instead of added in an amount of 0.5 mass% with respect to starch, sodium chloride so that 1.15 mass% (NaCl) against starch Then, a phosphoric acid crosslinked starch was obtained in the same manner as in Example 1 except that the slurry temperature was adjusted to 45 ° C and the temperature during the reaction was maintained at 45 ° C.
比較例７
実施例１において、塩化カルシウム（ＣａＣｌ２）を澱粉に対して０．５質量％となるように添加する代わりに、塩化ナトリウム（ＮａＣｌ）を澱粉に対して１．１５質量％となるように添加し、スラリー温度を３８℃に調整し、反応時の温度を３８℃に保った他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Comparative Example 7
In Example 1, instead of adding calcium chloride (CaCl 2 ) to 0.5 mass% with respect to starch, sodium chloride (NaCl) was added to 1.15 mass% with respect to starch. Then, a phosphoric acid crosslinked starch was obtained in the same manner as in Example 1 except that the slurry temperature was adjusted to 38 ° C and the temperature during the reaction was maintained at 38 ° C.
比較例８
実施例１において、塩化カルシウム（ＣａＣｌ２）を澱粉に対して０．５質量％となるように添加する代わりに、塩化ナトリウム（ＮａＣｌ）を澱粉に対して１．１５質量％となるように添加し、スラリー温度を３３℃に調整し、反応時の温度を３３℃に保った他は、実施例１と同様にして、リン酸架橋澱粉を得た。
Comparative Example 8
In Example 1, the addition of calcium chloride (CaCl 2), instead of added in an amount of 0.5 mass% with respect to starch, sodium chloride so that 1.15 mass% (NaCl) against starch Then, a phosphoric acid crosslinked starch was obtained in the same manner as in Example 1 except that the slurry temperature was adjusted to 33 ° C. and the temperature during the reaction was maintained at 33 ° C.
試験例１
実施例１、２及び比較例１〜８で得られた各リン酸架橋澱粉について、アミロ粘度及びブレークダウンを測定し、その結果に基づいて架橋度を評価した。その結果を下記表１に示す。表中の「ＳＴＭＰ」は、トリメタリン酸ナトリウムを表す。
Test example 1
About each phosphoric acid bridge | crosslinking starch obtained in Example 1, 2 and Comparative Examples 1-8, amylo viscosity and breakdown were measured and the crosslinking degree was evaluated based on the result. The results are shown in Table 1 below. “STMP” in the table represents sodium trimetaphosphate.
表１の結果から、トリメタリン酸ナトリウム（ＳＴＭＰ）の添加量が澱粉に対して０．１７％という条件下では、触媒として塩化カルシウム（ＣａＣｌ２）を用いた実施例１及び２は、いずれも架橋度が十分に高く、また、反応温度を３３℃にした実施例２の方が、反応温度を４５℃にした実施例１よりも架橋度が高くなっていることがわかる。また、触媒として塩化カルシウム（ＣａＣｌ２）を用い、反応温度を５℃とした比較例１、及び反応温度を５０℃とした比較例２では、いずれも架橋度が低下することがわかる。
これに対して、触媒を添加しない比較例３、触媒として硫酸ナトリウム（Ｎａ２ＳＯ４）を用いて反応温度を４５℃、３３℃とした比較例４及び５、触媒として塩化ナトリウム（ＮａＣｌ）を用いて反応温度を４５℃、３８℃、３３℃とした比較例６〜８では、架橋度を十分に高めることができなかった。
From the results of Table 1, under the condition that the amount of sodium trimetaphosphate (STMP) added is 0.17% with respect to starch, both Examples 1 and 2 using calcium chloride (CaCl 2 ) as a catalyst are crosslinked. It can be seen that the degree of crosslinking was higher in Example 2 in which the degree of reaction was sufficiently high and the reaction temperature was 33 ° C. than in Example 1 in which the reaction temperature was 45 ° C. It can also be seen that the degree of cross-linking decreases in both Comparative Example 1 in which calcium chloride (CaCl 2 ) is used as the catalyst and the reaction temperature is 5 ° C., and in Comparative Example 2 in which the reaction temperature is 50 ° C.
On the other hand, Comparative Example 3 in which no catalyst was added, Comparative Examples 4 and 5 in which the reaction temperature was 45 ° C. and 33 ° C. using sodium sulfate (Na 2 SO 4 ) as the catalyst, and Sodium chloride (NaCl) as the catalyst In Comparative Examples 6 to 8 in which the reaction temperatures were set to 45 ° C, 38 ° C, and 33 ° C, the degree of crosslinking could not be sufficiently increased.
更に、触媒として硫酸ナトリウム（Ｎａ２ＳＯ４）を用いて反応温度を４５℃、３３℃とした比較例４及び５を比較すると、高温の方で反応効率が高いことがわかる。同様に、触媒として塩化ナトリウム（ＮａＣｌ）を用いて反応温度を４５℃、３８℃、３３℃とした比較例６〜８を比較すると、高温の方で反応効率が高いことがわかる。 Further, when Comparative Examples 4 and 5 in which the reaction temperature is 45 ° C. and 33 ° C. using sodium sulfate (Na 2 SO 4 ) as a catalyst are compared, it is understood that the reaction efficiency is higher at higher temperatures. Similarly, when Comparative Examples 6 to 8 in which the reaction temperature is 45 ° C., 38 ° C., and 33 ° C. using sodium chloride (NaCl) as a catalyst are compared, it can be seen that the reaction efficiency is higher at higher temperatures.
実施例３
実施例２において、トリメタリン酸ナトリウムの添加量を澱粉に対して０．０９％とした他は、実施例２と同様にして、リン酸架橋澱粉を得た。
Example 3
In Example 2, phosphoric acid crosslinked starch was obtained in the same manner as in Example 2 except that the amount of sodium trimetaphosphate added was 0.09% with respect to the starch.
実施例４
実施例２において、トリメタリン酸ナトリウムの添加量を澱粉に対して０．１２％とした他は、実施例２と同様にして、リン酸架橋澱粉を得た。
Example 4
In Example 2, phosphoric acid crosslinked starch was obtained in the same manner as in Example 2 except that the amount of sodium trimetaphosphate added was 0.12% with respect to the starch.
実施例５
実施例２において、トリメタリン酸ナトリウムの添加量を澱粉に対して０．１５％とした他は、実施例２と同様にして、リン酸架橋澱粉を得た。
Example 5
In Example 2, phosphoric acid cross-linked starch was obtained in the same manner as in Example 2, except that the amount of sodium trimetaphosphate added was 0.15% with respect to the starch.
実施例６
実施例２において、トリメタリン酸ナトリウムの添加量を澱粉に対して０．５０％とした他は、実施例２と同様にして、リン酸架橋澱粉を得た。
Example 6
In Example 2, phosphoric acid crosslinked starch was obtained in the same manner as in Example 2 except that the amount of sodium trimetaphosphate added was 0.50% with respect to the starch.
試験例２
実施例３〜６で得られた各リン酸架橋澱粉について、アミロ粘度及びブレークダウンを測定し、その結果に基づいて架橋度を評価した。その結果を、前記実施例２の結果と併せて、下記表２に示す。表中の「ＳＴＭＰ」は、トリメタリン酸ナトリウムを表す。
Test example 2
About each phosphoric acid bridge | crosslinking starch obtained in Examples 3-6, amylo viscosity and breakdown were measured and the crosslinking degree was evaluated based on the result. The results are shown in Table 2 below together with the results of Example 2. “STMP” in the table represents sodium trimetaphosphate.
表２に示されるように、触媒として塩化カルシウム（ＣａＣｌ２）を用いた本願発明では、トリメタリン酸ナトリウム（ＳＴＭＰ）の添加量の増加に伴って架橋度が増大することがわかる。 As shown in Table 2, as in the present invention using calcium chloride (CaCl 2) catalyst, it can be seen that the degree of crosslinking increases with increasing amount of sodium trimetaphosphate (STMP).
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| JP6393455B2 (en) * | 2013-04-16 | 2018-09-19 | 松谷化学工業株式会社 | A clouding agent for food and drink and a method for imparting a cloudiness to food and drink |
| JP6783016B2 (en) * | 2016-03-31 | 2020-11-11 | 日清食品ホールディングス株式会社 | Phosphate cross-linked psyllium seed coat |
| WO2019163965A1 (en) * | 2018-02-22 | 2019-08-29 | 三和澱粉工業株式会社 | Starch with high dietary fiber content suitably usable in foods and beverages |
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