JP3530567B2 - Method for producing resistant starch - Google Patents
Method for producing resistant starchInfo
- Publication number
- JP3530567B2 JP3530567B2 JP04746694A JP4746694A JP3530567B2 JP 3530567 B2 JP3530567 B2 JP 3530567B2 JP 04746694 A JP04746694 A JP 04746694A JP 4746694 A JP4746694 A JP 4746694A JP 3530567 B2 JP3530567 B2 JP 3530567B2
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- Japan
- Prior art keywords
- starch
- acid
- indigestible
- resistant
- treatment
- 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.)
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Description
【0001】[0001]
【産業上の利用分野】本発明は、難消化性澱粉の製造方
法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing resistant starch.
【0002】[0002]
【従来の技術】近年、肥満等の理由でカロリーの過剰摂
取などが問題となっており、多くの低カロリー食品が開
発されている。また、従来、食物に含まれる繊維は消化
管内で消化されないために不要なものとみなされていた
が、最近、健康維持と疾病予防に対して有効であるとい
うことで注目されている。この食物繊維を多く含むもの
としては、穀物の外皮や糠があり、これを加工したもの
もあるが、これらは水に不溶であって食品に利用した場
合にざらつきなどが出て食感を損なったりする。また、
水溶性の食物繊維として天然ガム類などがあるが粘性が
高いので食品に多量に用いることは難しい。2. Description of the Related Art In recent years, excessive intake of calories has become a problem due to obesity, and many low-calorie foods have been developed. Moreover, conventionally, the fiber contained in food has been regarded as unnecessary because it is not digested in the digestive tract, but recently, it has been noted that it is effective for maintaining health and preventing diseases. As the ones that contain a lot of this dietary fiber, there are grain hulls and bran, and there are also processed ones, but these are insoluble in water, and when used in food, they give a rough texture and impair the texture. Or Also,
Although water-soluble dietary fibers include natural gums and the like, their high viscosity makes it difficult to use them in large amounts in foods.
【0003】一方、澱粉を例にとれば、澱粉や澱粉の加
工品であるα−澱粉、焙焼デキストリン、誘導体、ぶど
う糖、粉あめやマルチデキストリンなどが食品素材とし
て各種の加工食品に大量に使用されている。しかし、こ
れら澱粉加工品の大部分は難消化性成分の含量が5%
(w/w)以下である。難消化性澱粉としては、わずか
に焙焼デキストリンが知られているのみであるが、焙焼
デキストリンでも難消化性成分の割合は30%(w/
w)程度にすぎない。近年、この焙焼デキストリンを出
発原料にして、酵素反応により難消化性成分を高め、難
消化性デキストリンを製造する方法が報告されている
(特開平5−148301号公報)。具体的には、原料
澱粉に1%前後の濃度の酸水溶液を数%程度(3〜10
%)添加し、150〜200℃で10〜120分焙焼さ
せて焙焼デキストリンとした後、α−アミラーゼ、グル
コアミラーゼを作用させ、活性炭脱色、イオン交換樹脂
を経て精製するという方法である。しかしながら、本方
法においては、難消化性成分率を向上させるために加熱
時間を長くすることが必要になるが、焙焼が進むに従っ
て着色が進む上、収斂味が増し、独特の加熱臭が付いて
くる。また、高温度による焙焼では脱色等の精製の操作
が必要になるといった問題があるため、焙焼温度は15
0℃〜200℃程度に限られることになり、さらにアミ
ラーゼ処理やα−グルコシダーゼ処理などの酵素処理を
施すことによって難消化性成分の向上が図られている。
そのため、大量の酵素薬品が必要であり、かつ、脱色の
操作も必要といった製造工程上の問題がある。On the other hand, taking starch as an example, starch and processed products of starch such as α-starch, roasted dextrin, derivatives, glucose, starch syrup and multi-dextrin are used as food materials in large amounts in various processed foods. Has been done. However, most of these processed starch products contain 5% of indigestible ingredients.
(W / w) or less. Although only a few roasted dextrins are known as indigestible starches, the proportion of indigestible components in roasted dextrins is 30% (w /
w) No more. Recently, there has been reported a method for producing indigestible dextrin by using this roasted dextrin as a starting material to increase the indigestible component by an enzymatic reaction (Japanese Patent Laid-Open No. 5-148301). Specifically, about a few percent (3 to 10) of an aqueous acid solution having a concentration of about 1% is added to the raw starch.
%) Is added, and the mixture is roasted at 150 to 200 ° C. for 10 to 120 minutes to obtain roasted dextrin, and then α-amylase and glucoamylase are allowed to act on the activated carbon for decolorization and purification through an ion exchange resin. However, in this method, it is necessary to lengthen the heating time in order to improve the indigestible component ratio, but as the roasting progresses, the coloring progresses and the astringent taste increases, giving a unique heating odor. Come on. In addition, roasting at a high temperature requires a refining operation such as decolorization, so the roasting temperature is 15
It will be limited to about 0 ° C. to 200 ° C., and further treatment of enzymes such as amylase treatment and α-glucosidase treatment will improve the indigestible component.
Therefore, there is a problem in the manufacturing process that a large amount of enzyme chemicals are required and a decoloring operation is also required.
【0004】また、澱粉の湿熱処理により、澱粉の物理
的な特性が変化することが知られている。湿熱処理によ
る澱粉の物理的特性の変化としては、平衡水分の変化、
X線回析図の変化、澱粉粒の膨潤性の変化、糊化開始温
度の上昇などが知られている。さらに、ハイアミロース
コーンスターチに、3.5倍の水を添加し、134℃7
0分の湿熱処理を2回行うとα−アミラーゼで分解され
ない抵抗性澱粉が生成することが知られている(澱粉科
学 40巻 第3号 p.285 〜290, 1993 )。しかし、本
方法においては酸処理を行っていないため、澱粉の分解
が起こりにくく、またオートクレーブ中の相対湿度10
0%条件下で134℃70分の湿熱処理が2回も必要と
すると上、含有率が28%(w/w)程度で低いという
問題点がある。It is also known that the physical properties of starch are changed by wet heat treatment of starch. Changes in the physical properties of starch due to heat-moisture treatment include changes in equilibrium water content,
Changes in X-ray diffraction pattern, changes in swelling property of starch granules, increase in gelatinization start temperature, etc. are known. Furthermore, 3.5 times water was added to high amylose corn starch, and the temperature was kept at 134 ° C for 7 hours.
It is known that a resistant starch that is not decomposed by α-amylase is produced by performing heat treatment for 0 minutes twice (starch science 40, No. 3, p. 285-290, 1993). However, in this method, no acid treatment is performed, so that the starch is less likely to be decomposed and the relative humidity in the autoclave is 10
There is a problem that the wet heat treatment at 134 ° C. for 70 minutes under the condition of 0% is required twice, and the content rate is low at about 28% (w / w).
【0005】[0005]
【発明が解決しようとする課題】本発明の課題は、従来
より低温度でかつ短時間の湿熱処理により、着色・加熱
臭の少なく、単糖およびオリゴ糖含量の少ない難消化性
澱粉を簡便かつ高収率で得られる方法を提供することに
ある。SUMMARY OF THE INVENTION An object of the present invention is to easily and easily produce an indigestible starch having less coloring and heating odor and less monosaccharide and oligosaccharide contents by heat-moisture treatment at a lower temperature and a shorter time than before. It is to provide a method which can be obtained in high yield.
【0006】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意研究を重ねた結果、酸触媒による澱粉
加水分解工程に、低水分含有率下での湿熱処理を導入す
ることにより、難消化性澱粉を効率的に製造できること
を見いだし、本発明を完成した。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have introduced a moist heat treatment with a low water content in a starch hydrolysis process using an acid catalyst. As a result, they have found that resistant starch can be efficiently produced, and completed the present invention.
【0007】すなわち、本発明は、酸処理した澱粉を原
料にし、その水分含有率を3〜7%(w/w)に維持し
ながら、130℃〜140℃で湿熱処理を行うことを特
徴とする難消化性澱粉の製造方法である。That is, the present invention is characterized in that the acid-treated starch is used as a raw material, and the wet heat treatment is carried out at 130 ° C. to 140 ° C. while maintaining the moisture content thereof at 3 to 7% (w / w). It is a method for producing resistant starch.
【0008】本発明において、難消化性澱粉とは、難消
化性でかつ難吸収性の食品成分である食物繊維のうち、
澱粉を原料にして生成される難消化成分をいう。In the present invention, the resistant starch is defined as a dietary fiber which is a food component which is resistant to and digestible.
It means an indigestible component produced from starch as a raw material.
【0009】本発明に使用できる澱粉は、コーンスター
チ、馬鈴薯澱粉、米澱粉、小麦澱粉等の穀物澱粉が挙げ
られる。価格が低い点や、反応のしやすさ等によりコー
ンスターチが好ましい。また、本発明で使用する澱粉
は、水分含有率が約10%(w/w)のものである。The starch which can be used in the present invention includes grain starch such as corn starch, potato starch, rice starch and wheat starch. Corn starch is preferable because of its low price and easiness of reaction. The starch used in the present invention has a water content of about 10% (w / w).
【0010】本発明における酸処理は、上記澱粉に対し
て、0.03〜0.1%(w/w)、好ましくは0.0
5〜0.07%(w/w)の塩酸、硫酸、硝酸などの無
機酸、好ましくは塩酸を、10〜30分間、室温にて澱
粉に平衡吸着させることにより行う。0.1%(w/
w)以上の添加では、副反応(メイラード反応)が生
じ、カラメル化して着色が激しくなり、また0.03%
(w/w)以下の低濃度では難消化性澱粉の収率が悪く
なる。酸処理を行わない場合、湿熱処理後の澱粉の結合
様式は消化性のα−1→4結合がほとんどであるため、
難消化性澱粉の製造には当該酸処理が必須である。The acid treatment in the present invention is 0.03 to 0.1% (w / w), preferably 0.0 to the above starch.
It is carried out by equilibrium adsorption of 5 to 0.07% (w / w) of an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, preferably hydrochloric acid, on starch for 10 to 30 minutes at room temperature. 0.1% (w /
w) Addition of more than this causes side reaction (Maillard reaction), caramelization and intense coloring, and 0.03%
When the concentration is lower than (w / w), the yield of resistant starch becomes poor. When acid treatment is not carried out, most of the starch binding patterns after heat-moisture treatment are digestive α-1 → 4 bonds.
The acid treatment is essential for the production of resistant starch.
【0011】次に、酸吸着澱粉を濾別後、風乾、減圧乾
燥により乾燥させて、その水分含有率を3〜7%(w/
w)とする。上記のような低水分含有率とするのは、原
料に用いられる澱粉に含有する水分の存在が、湿熱処理
による澱粉分解に伴うグルコースあるいは還元糖の生成
を促進すると同時に難消化性澱粉の生成反応量を阻害す
る方向及び高分子化に導くため、水分含有率を低めるこ
とによって単糖およびオリゴ糖の生成量が少なく、かつ
難消化性澱粉含量を多くするためである。Next, the acid-adsorbed starch is separated by filtration, dried by air drying and vacuum drying, and the water content thereof is 3 to 7% (w / w).
w). The low water content as described above means that the presence of water contained in the starch used as a raw material promotes the production of glucose or reducing sugars associated with the decomposition of starch by the heat-moisture treatment, and at the same time, the reaction of producing indigestible starch. This is because the amount of monosaccharides and oligosaccharides is reduced and the content of resistant starch is increased by lowering the water content in order to inhibit the amount and lead to higher molecular weight.
【0012】この後、乾燥した酸吸着澱粉を耐熱性のテ
フロン製テトラパックに詰めた後、テトラパックの爆発
を防ぐために脱気を行い、密封する。この場合、容器に
ついては、耐熱耐圧で、かつ密封が行えるものであれば
この限りではなく、耐熱耐圧容器を使用する時は脱気の
必要がない。密封後、定温恒温器中で、130℃〜14
0℃、30分から60分、好ましくは約135℃で30
分の湿熱処理を行う。After that, the dried acid-adsorbed starch is packed in a heat-resistant Teflon tetra-pack, and then deaerated to prevent the tetra-pack from exploding and sealed. In this case, the container is not limited to this as long as it is heat resistant and pressure resistant and can be hermetically sealed, and degassing is not necessary when using the heat resistant pressure resistant container. After sealing, in a constant temperature incubator, 130 ℃ ~ 14
30 minutes at 0 ° C, 30 to 60 minutes, preferably about 135 ° C
Wet heat treatment for a minute.
【0013】湿熱処理を終えた澱粉は水に溶解し、pH
を調整する。pHの調整には一般のアルカリがいずれも
使用可能であるが、好ましくは炭酸ナトリウムを用い
る。炭酸ナトリウム水溶液でpHを5〜5.5、好まし
くはpH5.2に調整したのち、遠心により水不溶性画
分を除去する。水不溶性画分に対し、この操作を2〜3
回繰り返し行い、上澄液を集め、減圧濃縮を行う。濃縮
した上澄液をアルコール中に攪拌しながら注入し、アル
コール不溶画分を遠心により分離、上澄液を除去する。
アルコールはエタノール、メタノールなどいずれのアル
コールも使用可能であり、またアセトンでもよい。分別
した沈殿物は数回アルコールで洗浄、脱水を繰り返した
後、アルコールを除去し風乾する。以上の操作で得た粉
末を難消化性澱粉含有デキストリンと定義する。このア
ルコール処理により、着色性物質及び低分子糖の一部が
除去される。また、低分子糖の除去には、パン酵母に低
分子糖を資化させる方法も用いることができる。かくし
て平均分子量がゲル濾過分析により約2000、難消化
性澱粉含量約60%(w/w)の難消化性澱粉含有デキ
ストリンが高効率で得られる。Starch that has been subjected to the moist heat treatment dissolves in water,
Adjust. Any ordinary alkali can be used to adjust the pH, but sodium carbonate is preferably used. After adjusting the pH to 5-5.5, preferably pH 5.2 with an aqueous sodium carbonate solution, the water-insoluble fraction is removed by centrifugation. Repeat this procedure for water-insoluble fraction 2-3
Repeat repeatedly to collect the supernatant and concentrate under reduced pressure. The concentrated supernatant is poured into alcohol with stirring, the alcohol-insoluble fraction is separated by centrifugation, and the supernatant is removed.
As the alcohol, any alcohol such as ethanol and methanol can be used, and acetone may be used. The separated precipitate is washed several times with alcohol and dehydrated repeatedly, then the alcohol is removed and air-dried. The powder obtained by the above operation is defined as indigestible starch-containing dextrin. By this alcohol treatment, a part of the coloring substance and the low molecular weight sugar is removed. In addition, a method of assimilating the low-molecular-weight sugar into baker's yeast can also be used for removing the low-molecular-weight sugar. Thus, a dextrin containing an indigestible starch having an average molecular weight of about 2000 and an indigestible starch content of about 60% (w / w) can be obtained with high efficiency.
【0014】[0014]
【実施例】以下、本発明を実施例、実験例により具体的
に説明するが、これらにより本発明の範囲が限定される
ものではない。尚、実施例、ならびに実験例において用
いた各測定方法を以下に参考例として説明する。EXAMPLES The present invention will be specifically described below with reference to Examples and Experimental Examples, but the scope of the present invention is not limited by these. The measuring methods used in the examples and the experimental examples will be described below as reference examples.
【0015】〔参考例〕
(1) 難消化性澱粉含有量の測定
難消化性澱粉含有量の測定は、食物繊維定量法として採
用されている、Prosky-AOAC 法(J. Assoc. off. Anal.
Chem., 71, 1017-1023, 1988)により行う。試料1gを
正確に秤り、0.06Mリン酸緩衝液(pH6.0)5
0mlを加え、1N−NaOHにてpH6.0とし、タ
ーマミル(ノボ社製のα−アミラーゼ)0.1mlを添
加し、90℃で60分間反応させる。冷却後、1N−N
aOHにてpH7.5とし、プロテアーゼ(Sigma 社
製)5.0mgを添加し、90℃で60分間反応させ
る。続いて1M酢酸緩衝液(pH4.5)5.0mlを
加え、冷却し、0.5Mリン酸緩衝液にてpH4.5と
し、アミログルコシダーゼ(Sigma 社製)0.1mlを
添加し、60℃で60分間反応させる。この後、60℃
エタノール(99.5%(v/v))を添加し、1時間
以上放置後、30mlエタノールにて2回脱水処理を行
い、10mlアセトンにて2回洗浄し、減圧乾燥後秤量
し、難消化性澱粉量とした。Reference Example (1) Measurement of Indigestible Starch Content Measurement of the indigestible starch content was carried out by the Prosky-AOAC method (J. Assoc. Off. Anal. .
Chem., 71, 1017-1023, 1988). Accurately weigh 1 g of sample, and add 0.06 M phosphate buffer (pH 6.0) 5
0 ml was added, the pH was adjusted to 6.0 with 1N-NaOH, 0.1 ml of Termamyl (α-amylase manufactured by Novo Co.) was added, and the mixture was reacted at 90 ° C. for 60 minutes. After cooling, 1N-N
The pH is adjusted to 7.5 with aOH, 5.0 mg of protease (Sigma) is added, and the mixture is reacted at 90 ° C. for 60 minutes. Then, 5.0 ml of 1 M acetate buffer (pH 4.5) was added, cooled, adjusted to pH 4.5 with 0.5 M phosphate buffer, 0.1 ml of amyloglucosidase (Sigma) was added, and the temperature was 60 ° C. React for 60 minutes. After this, 60 ℃
Ethanol (99.5% (v / v)) was added, left for 1 hour or more, dehydrated twice with 30 ml ethanol, washed twice with 10 ml acetone, dried under reduced pressure, weighed, and indigestible The amount of natural starch.
【0016】(2) 平均分子量の測定
試料を水に溶解し、1000ppm(W/W)濃度に調製した試料液
を用い、下記の条件下で高速液体クロマトグラフィーを
行い測定する。
カラム :東ソーG3000PWXL 30cm
温度 :40℃
溶出液 :水
流速 :1ml/min.
検出器 :RI
標準試料:オリゴ糖α−1,4mix〔(株)中埜酢店
製(M.W.2000)〕
マルトペンタオース
マルトトリオース(2) Measurement of average molecular weight Dissolve a sample in water and use a sample solution prepared to a concentration of 1000 ppm (W / W), and perform measurement by high performance liquid chromatography under the following conditions. Column: Tosoh G3000PWXL 30 cm Temperature: 40 ° C. Eluent: Water flow rate: 1 ml / min. Detector: RI Standard sample: oligosaccharide α-1,4mix [M. P. vinegar shop (MW 2000)] Maltopentaose Maltotriose
【0017】(3) グリコシド結合様式の検討方法
グリコシド結合様式は、下記のメチル化法[R. Gonda e
t al., Chem. Pham. Bull., 38(10), 2771-2774 (199
0)]でメチル化し、加水分解後にガスクロマトグラフィ
ーにより各グリコシド結合の定量を行うことにより調べ
る。(3) Method for examining glycoside bond mode The glycoside bond mode is determined by the following methylation method [R. Gonda e
t al., Chem. Pham. Bull., 38 (10), 2771-2774 (199
[0)], and after hydrolysis, each glycosidic bond is quantified by gas chromatography to investigate.
【0018】 メチル化
脱水した試料(10mg)をネジ付試験管に入れ、1m
lの脱水DMSOを加えて溶解する。これにNaOHを
100mg加え、直ちに0.5mlのヨウ化メチルを加
える。窒素ガスによる置換を行った後、スターラーで攪
拌しながら1〜2時間反応させ、水5mlを加える。こ
れに5mlのクロロホルムを加えて十分に振とうし、ク
ロロホルム層を三角フラスコにとる。同様の操作を5回
繰り返し、三角フラスコにとったクロロホルム層に蒸留
水25mlを加え、振とう後、クロロホルム層を回収す
る操作を3回繰り返す。次にエバポレーターで減圧乾燥
する。A methylated and dehydrated sample (10 mg) was placed in a test tube with a screw for 1 m.
Add 1 liter of dehydrated DMSO and dissolve. To this is added 100 mg of NaOH and immediately 0.5 ml of methyl iodide. After replacement with nitrogen gas, the mixture was reacted with stirring with a stirrer for 1 to 2 hours, and 5 ml of water was added. To this, 5 ml of chloroform was added and shaken well, and the chloroform layer was transferred to an Erlenmeyer flask. The same operation is repeated 5 times, 25 ml of distilled water is added to the chloroform layer taken in the Erlenmeyer flask, and after shaking, the operation of collecting the chloroform layer is repeated 3 times. Next, it is dried under reduced pressure by an evaporator.
【0019】 完全メチル化の確認
クロロホルム1〜2mlで試料を溶解した後、クロロホ
ルムを対照としてIRを測定し、水酸基がないことを確
認する。Confirmation of Complete Methylation After dissolving the sample with 1 to 2 ml of chloroform, IR is measured with chloroform as a control to confirm that there is no hydroxyl group.
【0020】 分離
セファデックスLH−20(ファルマシア社製)で糖画
分を分離する。溶媒は、クロロホルム:メタノール=
2:1を用い、試料を溶媒1mlに溶かして分離する。
糖画分をフェノール硫酸法で確認後、回収し、減圧乾燥
する。Separation Sephadex LH-20 (Pharmacia) is used to separate the sugar fraction. Solvent is chloroform: methanol =
The sample is dissolved in 1 ml of solvent using 2: 1 and separated.
After confirming the sugar fraction by the phenol-sulfuric acid method, it is collected and dried under reduced pressure.
【0021】 加水分解
メチル化物に1〜2mlの90%(w/v)ギ酸を加え
て窒素ガス置換を行い、100℃で3〜8時間反応さ
せ、減圧乾燥する。1〜2Mのトルフルオロ酢酸1〜2
mlを添加し、窒素ガス置換して密封する。100℃で
3〜10時間反応させ、トリフルオロ酢酸が完全に除去
されるまで乾燥する。To the hydrolyzed methylated product, 1 to 2 ml of 90% (w / v) formic acid is added to perform nitrogen gas replacement, and the mixture is reacted at 100 ° C. for 3 to 8 hours and dried under reduced pressure. 1-2M trifluoroacetic acid 1-2
Add ml, replace with nitrogen gas and seal. The mixture is reacted at 100 ° C. for 3 to 10 hours and dried until trifluoroacetic acid is completely removed.
【0022】 還元
加水分解物を1〜2mlの50%(v/v)以下のエタ
ノールで溶解し、試料の5〜10倍量のホウ水素化ナト
リウムを加えて室温で2〜4時間放置する。アンバーラ
イトCG−120〔H+ 〕(オルガノ社製)を蒸留水に
懸濁させて、試料に少量ずつ滴下する。十分量を添加
し、10分以上静置する。濾過後、残渣を50%エタノ
ールで洗浄し、さらに99.5%(v/v)エタノール
で洗浄した後、減圧乾燥する。減圧乾燥後、析出したホ
ウ酸結晶を5〜10mlのメタノールに溶解し、減圧乾
燥する。この操作を2回繰り返す。The reduced hydrolyzate is dissolved in 1 to 2 ml of 50% (v / v) or less of ethanol, 5 to 10 times the amount of sodium borohydride of the sample is added, and the mixture is left at room temperature for 2 to 4 hours. Amberlite CG-120 [H + ] (manufactured by Organo Corporation) is suspended in distilled water and added little by little to a sample. Add a sufficient amount and let stand for 10 minutes or more. After filtration, the residue is washed with 50% ethanol, further 99.5% (v / v) ethanol, and then dried under reduced pressure. After drying under reduced pressure, the precipitated boric acid crystals are dissolved in 5 to 10 ml of methanol and dried under reduced pressure. This operation is repeated twice.
【0023】 アセチル化
試料にピリジン0.3mlを加え、溶解させた後、無水
酢酸0.3mlを加える。オイルバス上、95〜100
℃で90〜120分反応させ、反応後冷却する。トルエ
ン1ml添加し、40℃以下で減圧濃縮し、乾固する。To the acetylated sample, 0.3 ml of pyridine is added and dissolved, and then 0.3 ml of acetic anhydride is added. 95-100 on oil bath
The mixture is reacted at 90 ° C. for 90 to 120 minutes, and cooled after the reaction. Add 1 ml of toluene, concentrate under reduced pressure at 40 ° C. or lower, and dry to dryness.
【0024】 溶解
試料を0.5mlのクロロホルムに溶解してガスクロマ
トグラフで分析する。The dissolved sample is dissolved in 0.5 ml of chloroform and analyzed by gas chromatography.
【0025】 ガスクロマトグラフィーの条件
[TIC]
Mode : MF-EI[Pos.]
Carrier gas : He 1.14 cm3/min
Capillary column : 0.25 mm, 3m, HiCap-CBP10 (GLサ
イエンス)120 scan/minConditions for gas chromatography [TIC] Mode: MF-EI [Pos.] Carrier gas: He 1.14 cm 3 / min Capillary column: 0.25 mm, 3m, HiCap-CBP10 (GL Science) 120 scan / min
【0026】〔実施例1〕市販のコーンスターチ500
gを1Lの0.05%(w/w)希塩酸水溶液に10分
間処理し、濾紙で濾過後、風乾した。室温で水分含有率
5%(w/w)まで減圧乾燥した。この酸吸着澱粉を耐
熱性のテフロン製テトラパックにつめ、脱気し、135
℃30分間、定温恒温器中で湿熱処理した。湿熱処理
後、35%(w/w)水溶液にし、pH5.2に調整し
た後、遠心により、水不溶性画分を除去した。水不溶性
画分に対し、この操作を2回繰り返し行い、上澄液を集
め、減圧濃縮を行った。濃縮した上澄液をエタノール中
に攪拌しながら注入し、エタノール不溶画分を遠心分離
により分離して上澄液を除去した。分別した沈殿物は、
数回エタノール洗浄、及び脱水を繰り返した後、エタノ
ールを除去し風乾し、難消化性澱粉含有デキストリンを
得た。食物繊維定量法(Prosky-AOAC 法)にしたがって
難消化性澱粉を定量した結果、含量は64%(w/w)
であり、202gの難消化性澱粉を得た。この結果より
明らかなように、本発明により製造した難消化性澱粉含
有デキストリンの難消化性成分含量は高く、このため非
常に難消化性になっているといえる。また、その平均分
子量は2000で、単糖および重合度2〜9のオリゴ糖
含量は、6.9%であった。Example 1 Commercially available corn starch 500
g was treated with 1 L of 0.05% (w / w) dilute hydrochloric acid aqueous solution for 10 minutes, filtered through filter paper, and air dried. It was dried under reduced pressure at room temperature to a water content of 5% (w / w). This acid-adsorbed starch was packed in a heat-resistant Teflon tetra pack and degassed.
The wet heat treatment was carried out at a temperature of 30 minutes in a constant temperature incubator. After the moist heat treatment, a 35% (w / w) aqueous solution was prepared to adjust the pH to 5.2, and then the water-insoluble fraction was removed by centrifugation. This operation was repeated twice for the water-insoluble fraction, and the supernatant was collected and concentrated under reduced pressure. The concentrated supernatant was poured into ethanol while stirring, and the ethanol-insoluble fraction was separated by centrifugation to remove the supernatant. The separated precipitate is
After repeating washing with ethanol several times and dehydration, ethanol was removed and air-dried to obtain dextrin containing indigestible starch. Indigestible starch was quantified according to the dietary fiber quantification method (Prosky-AOAC method), and the content was 64% (w / w)
And 202 g of resistant starch was obtained. As is clear from this result, the content of the indigestible component in the dextrin containing the indigestible starch produced by the present invention is high, and therefore it can be said that it is extremely indigestible. The average molecular weight was 2000, and the content of monosaccharides and oligosaccharides having a polymerization degree of 2 to 9 was 6.9%.
【0027】〔実施例2〕米澱粉100gを200ml
の0.05%(w/w)希塩酸水溶液に10分間処理
し、濾紙で濾過後、風乾した。室温で水分含有率5%
(w/w)まで減圧乾燥した。この酸吸着澱粉を耐圧ガ
ラス製容器につめ、140℃30分間、定温恒温器中で
湿熱処理した。湿熱処理後、35%(w/w)水溶液に
し、pH5.2に調整した後、遠心により、水不溶性画
分を除去した。水不溶性画分に対し、この操作を2回繰
り返し行い、上澄液を集め、減圧濃縮を行った。濃縮し
た上澄液をエタノール中に攪拌しながら注入し、エタノ
ール不溶画分を遠心分離により、分離して上澄液を除去
した。分別した沈殿物は、数回エタノール洗浄、及び脱
水を繰り返した後、エタノールを除去し風乾し、難消化
性澱粉含有デキストリンを得た。食物繊維定量法(Pros
ky-AOAC 法)にしたがって難消化性澱粉を定量した結
果、含量は60%(w/w)であり、48gの難消化性
澱粉を得た。Example 2 200 ml of 100 g of rice starch
Was treated with a 0.05% (w / w) dilute hydrochloric acid aqueous solution for 10 minutes, filtered through filter paper, and air dried. Water content of 5% at room temperature
It was dried under reduced pressure to (w / w). The acid-adsorbed starch was packed in a pressure-resistant glass container and subjected to wet heat treatment at 140 ° C. for 30 minutes in a constant-temperature incubator. After the moist heat treatment, a 35% (w / w) aqueous solution was prepared to adjust the pH to 5.2, and then the water-insoluble fraction was removed by centrifugation. This operation was repeated twice for the water-insoluble fraction, and the supernatant was collected and concentrated under reduced pressure. The concentrated supernatant was poured into ethanol while stirring, and the ethanol-insoluble fraction was separated by centrifugation to remove the supernatant. The separated precipitate was repeatedly washed with ethanol and dehydrated several times, then ethanol was removed and air-dried to obtain dextrin containing indigestible starch. Dietary Fiber Assay (Pros
As a result of quantifying the resistant starch according to the ky-AOAC method), the content was 60% (w / w), and 48 g of resistant starch was obtained.
【0028】〔実験例1〕 湿熱温度と難消化性澱粉生
成率の関係
(方法)コーンスターチを原料として実施例1と同様に
して酸処理を行った酸吸着澱粉について、水分含有率を
7%(w/w)に維持しながら、125、130、13
5、140、145℃の各温度で30分間湿熱処理を行
った。その後、エタノール処理により回収し、難消化性
澱粉の含量をProsky-AOAC 法により測定した。
(結果)図1に示すように、130〜140℃の範囲で
は、難消化性成分の生成率は30%以上だが、145
℃、125℃ではその生成率は著しく減少した。[Experimental Example 1] Relationship between moist heat temperature and indigestible starch production rate (method) The acid content of the acid-adsorbed starch treated with corn starch as the raw material in the same manner as in Example 1 was 7% ( w / w), 125, 130, 13
Wet heat treatment was performed at temperatures of 5, 140, and 145 ° C. for 30 minutes. Then, it was recovered by ethanol treatment and the content of resistant starch was measured by the Prosky-AOAC method. (Results) As shown in FIG. 1, in the range of 130 to 140 ° C., the production rate of the indigestible component was 30% or more, but 145
The production rate remarkably decreased at ℃ and 125 ℃.
【0029】〔実験例2〕 水分含有率と難消化性澱粉
生成率の関係
(方法)コーンスターチを原料として実施例1と同様に
して酸処理を行った酸吸着澱粉ついて、水分含有率を
3、5、7、10、15%(w/w)に維持しながら、
135℃で30分間湿熱処理を行った。その後、エタノ
ール処理により回収し、難消化性澱粉の含量をProsky-A
OAC 法により測定した。
(結果)図2に示すように、水分含有率7%(w/w)
以下の範囲では、難消化性澱粉の生成率30%以上であ
るが、水分含有率の上昇とともに生成率が下がる傾向が
認められた。[Experimental Example 2] Relationship between water content and indigestible starch production rate (method) Regarding acid-adsorbed starch treated with acid from corn starch in the same manner as in Example 1, the water content was 3, While maintaining at 5, 7, 10, 15% (w / w),
The wet heat treatment was performed at 135 ° C. for 30 minutes. Then, it was recovered by ethanol treatment and the content of resistant starch was adjusted to Prosky-A.
It was measured by the OAC method. (Result) As shown in FIG. 2, the water content is 7% (w / w)
In the range below, the production rate of resistant starch was 30% or more, but it was observed that the production rate tended to decrease as the water content rate increased.
【0030】〔実験例3〕 生成した難消化性澱粉のグ
リコシド結合様式の検討
(方法)実施例1と同様にして酸処理を行った酸吸着澱
粉、ならびに比較として酸処理を行わない酸未吸着澱粉
を試料とし、それぞれ水分含有率を5%(w/w)に維
持しながら、酸吸着澱粉は135℃30分間、酸未吸着
澱粉は135℃3時間湿熱処理した。湿熱処理後、エタ
ノール処理により回収し、難消化性澱粉を得た。それぞ
れの難消化性澱粉の結合様式を、試料をメチル化し、加
水分解および還元、アセチル化を行った後、GLS−M
S法により調べた。
(結果)酸吸着澱粉は、α−1→6結合、及びわずかだ
が、α−1→2結合の生成が認められた。一方、酸未吸
着澱粉は、α−1→4結合が大部分であり、他の結合は
ほとんど認められなかった(図3)。また、Prosky-AOA
C 法により測定した難消化性澱粉の含量は4%(w/
w)であった。[Experimental Example 3] Examination of glycoside binding mode of produced indigestible starch (method) Acid-adsorbed starch treated with acid in the same manner as in Example 1 and non-adsorbed acid not treated with acid for comparison Using starch as a sample, the acid-adsorbed starch was subjected to wet heat treatment at 135 ° C. for 30 minutes, and the acid-unadsorbed starch was subjected to wet heat treatment at 135 ° C. for 3 hours while maintaining the water content at 5% (w / w). After wet heat treatment, it was recovered by ethanol treatment to obtain indigestible starch. The binding mode of each indigestible starch was measured by subjecting the sample to methylation, hydrolysis and reduction, and acetylation, followed by GLS-M.
It investigated by the S method. (Results) In the acid-adsorbed starch, the formation of α-1 → 6 bond and a slight amount of α-1 → 2 bond was observed. On the other hand, in the acid-unadsorbed starch, most of the α-1 → 4 bonds were observed, and other bonds were hardly observed (Fig. 3). Also, Prosky-AOA
The indigestible starch content measured by the C method was 4% (w /
w).
【0031】[0031]
【発明の効果】本発明の難消化性澱粉の製造方法によれ
ば、従来より低温度でかつ短時間の湿熱処理により、着
色・加熱臭の少なく、単糖およびオリゴ糖の含量の少な
い難消化性澱粉を簡便かつ高収率で得られる。また本発
明の方法により製造される難消化性澱粉は非常に難消化
性で低カロリーであるため、カロリーや炭水化物の摂取
を制限する必要のある人のための低カロリー食品素材と
して、また、各種食品、例えば、清涼飲料水、アイスク
リーム、食パン、ドレッシング、キャンディー、水産練
り製品など多くの食品に添加混合して利用できる。EFFECTS OF THE INVENTION According to the method for producing indigestible starch of the present invention, the indigestion with less coloring and heating odor and less content of monosaccharides and oligosaccharides can be achieved by wet heat treatment at a lower temperature and a shorter time than before. Starch can be easily obtained in high yield. Moreover, since the resistant starch produced by the method of the present invention is extremely resistant to digestion and has low calories, it is used as a low-calorie food material for people who need to restrict intake of calories and carbohydrates, and It can be used by being added to and mixed with many foods such as soft drinks, ice creams, breads, dressings, candies and fish paste products.
【図1】 湿熱温度と難消化性澱粉生成率の関係を示
す。FIG. 1 shows the relationship between moist heat temperature and production rate of resistant starch.
【図2】 水分含有率と難消化性澱粉生成率の関係を示
す。FIG. 2 shows the relationship between the water content rate and the indigestible starch production rate.
【図3】 酸吸着澱粉、ならびに酸未吸着澱粉のグリコ
シド結合様式の変化を示す。[Fig. 3] Fig. 3 shows changes in the glycoside binding mode of acid-adsorbed starch and acid-unadsorbed starch.
フロントページの続き (56)参考文献 特開 平5−148301(JP,A) 特開 平3−84001(JP,A) 特開 平4−130102(JP,A) 小林恒夫,湿熱処理澱粉の膵臓α−ア ミラーゼによる分解性と湿熱処理による 抵抗性澱粉の生成,澱粉科学,1993年, 第40巻第3号,285−290 (58)調査した分野(Int.Cl.7,DB名) C08B 30/00 - 30/20 JICSTファイル(JOIS)Continuation of front page (56) References JP-A-5-148301 (JP, A) JP-A-3-84001 (JP, A) JP-A-4-130102 (JP, A) Tsuneo Kobayashi, pancreas of heat-treated starch Degradability by α-amylase and formation of resistant starch by heat-moisture treatment, Starch Science, 1993, Vol. 40, No. 3, 285-290 (58) Fields investigated (Int. Cl. 7 , DB name) C08B 30/00-30/20 JISST file (JOIS)
Claims (2)
有率を3〜7%(w/w)に維持しながら、130℃〜
140℃で湿熱処理を行うことを特徴とする難消化性澱
粉の製造方法。1. A starch obtained by acid treatment is used as a raw material, and the moisture content thereof is maintained at 3 to 7% (w / w) while maintaining the temperature at 130.degree.
A method for producing indigestible starch, which comprises performing a heat-moisture treatment at 140 ° C.
1%(w/w)の無機酸を澱粉に平衡吸着させて行うも
のであることを特徴とする請求項1記載の難消化性澱粉
の製造方法。2. The acid treatment is performed in the range of 0.03 to 0.
The method for producing indigestible starch according to claim 1, wherein 1% (w / w) of an inorganic acid is equilibrated and adsorbed on the starch.
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JP04746694A JP3530567B2 (en) | 1994-03-17 | 1994-03-17 | Method for producing resistant starch |
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JP04746694A JP3530567B2 (en) | 1994-03-17 | 1994-03-17 | Method for producing resistant starch |
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JPH07252301A JPH07252301A (en) | 1995-10-03 |
JP3530567B2 true JP3530567B2 (en) | 2004-05-24 |
Family
ID=12775934
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JP04746694A Expired - Lifetime JP3530567B2 (en) | 1994-03-17 | 1994-03-17 | Method for producing resistant starch |
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Cited By (1)
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US8377492B2 (en) | 2007-10-19 | 2013-02-19 | Matsutani Chemical Industries Co., Ltd. | Dietary fiber-enriching agent and dietary fiber-enriched food |
Families Citing this family (10)
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---|---|---|---|---|
AUPN881396A0 (en) * | 1996-03-20 | 1996-04-18 | Arnott's Biscuits Limited | Enhancement of microbial colonization of the gastrointestinal tract |
FR2786775B1 (en) * | 1998-12-04 | 2001-02-16 | Roquette Freres | BRANCHED MALTODEXTRINS AND THEIR PREPARATION PROCESS |
DE19959863A1 (en) * | 1999-12-10 | 2001-06-13 | Axiva Gmbh | Process for increasing the content of a-amylase-resistant starch (RS content) of a polysaccharide, polysaccharides, their use and foods with these polysaccharides |
DE10007061A1 (en) * | 2000-02-16 | 2001-09-06 | Aventis Cropscience Gmbh | Process for the production of acid-modified starch |
EP1716768B1 (en) * | 2005-04-25 | 2009-07-08 | Nestec S.A. | Extended energy beverages |
JP5410004B2 (en) * | 2007-03-30 | 2014-02-05 | フタムラ化学株式会社 | Ultrasonic irradiation resistant starch |
EP2138514A4 (en) | 2007-06-21 | 2010-04-21 | J Oil Mills Inc | Method of producing starch having high less digestible starch content |
JP2009254265A (en) * | 2008-04-15 | 2009-11-05 | Osaka Prefecture Univ | Hardly-digestible rice, and hardly-digestible starch |
JP4482611B1 (en) * | 2009-10-16 | 2010-06-16 | 株式会社J−オイルミルズ | Resistant starch-rich starch and food and drink using the same |
KR101400966B1 (en) * | 2011-12-05 | 2014-05-29 | 서울대학교산학협력단 | Method for production of slowly digestible starch from Water Yam starch with hydrothermal treatment |
-
1994
- 1994-03-17 JP JP04746694A patent/JP3530567B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
小林恒夫,湿熱処理澱粉の膵臓α−アミラーゼによる分解性と湿熱処理による抵抗性澱粉の生成,澱粉科学,1993年,第40巻第3号,285−290 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8377492B2 (en) | 2007-10-19 | 2013-02-19 | Matsutani Chemical Industries Co., Ltd. | Dietary fiber-enriching agent and dietary fiber-enriched food |
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