JPH05103623A - Low-calorific extender - Google Patents

Abstract

PURPOSE:To obtain the subject extender having specific 1 4 glycoside bond content and calorific value by adding hydrochloric acid to potato starch and heating the mixture with a twin-screw extruder. CONSTITUTION:The objective extender having a 1 4 glycoside bond content of <=50% (preferably <=40%), a variation range of Y value defined by formula I and formula II [Y is calorific value (kcal/g); X1 is amount of nonreducing terminal glucose residue (%); X2 is amount of glucose residue having 1 4 glycoside bond (%)] of + or -5% or less and a calorific value of <=2kcal/g (preferably <=1.8kcal/g) is produced by adding hydrochloric acid to porato starch and heating the mixture at 120-200 deg.C (preferably 130-180 deg.C) with a twin-screw extruder.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a low-calorie bulking agent obtained by subjecting potato starch to an acid heat treatment.

[0002]

2. Description of the Related Art Heat-treated starch (roasted dextrin) is a few%
It is obtained by heating the starch containing water of 1. in the presence or absence of an acid. It is known that its structure is mainly composed of glucose, which is a constituent of starch, having 1 → 4, 1 → 6 glycosidic bonds, and also has a slight amount of 1 → 3, 1 → 2 glycosidic bonds. ..

The composition ratio of these glycosidic bonds is JD
Geerdes et al, J. Am. Chem.soc., Vol.79, P.4209 (1957)
And GM Christensen et al, J. Am. Chem. Soc., Vol.79, P.44
92 (1957), which is only described in the following document, in a commercially available cornstarch heat-treated starch with hydrochloric acid addition, a 1 → 4 glycoside bond segment (2,
3,6-Tri-O-Methyl-D-glucose) is 57.3% or more, and the 1 → 6 glycoside bond category (2,3,4-Tri-O-Methyl-D)
-glucose) is 2.6%, the 1 → 3 glycoside bond section (2,4,6-Tri-O-Methyl-D-glucose) is 1.2% or less, 1 → 4 and 1 → 6. The category (2,3-Di-O-Methyl-D-glucose) having both glycoside bonds is 6.3%.

RL Whistler & EF Paschall, Starch
Chemistry & Technology, Vol.1, p430 (1965), amylopectin, which is a constituent of corn starch, and amylose were fractionated and taken out, and then both components were heat-treated with acid to obtain a heat-treated amylopectin and heat-treated amylose. The combined analytical value of the product is described by reference. This value is the value obtained by gelatinizing the starch, then separating the two components and then heat-treating it, and because the morphology of the powder during heat treatment is different from natural starch, it cannot be directly compared, but the value of ordinary cornstarch The composition ratio of both components is about 8: 2
Therefore, when converting this value into cornstarch, 1 → 4 glycoside bond segment (2,3,6-Tri-O-Methl-
D-glucose) is 67%, 1 → 3 glycoside bond segment (2,
4,6-Tri-O-Methyl-D-glucose) is a group (2.7%) having both 1 → 4 and 1 → 6 glycoside bonds (2,3-Di-O-Met).
hyl-D-glucose) corresponds to 7.8%. However, regarding roasted dextrin of potato starch, there is no document that describes glycoside bond. As a conventional method for producing a heat-treated starch and an apparatus for producing the heat-treated starch, U.S. Pat. No. 2,274,789 is continuously treated by adding hydrochloric acid to starch having a water content of about 45%, drying in a fluidized bed, and heating and cooling at 105 to 260 ° C. The law describes how to obtain a product of stable quality without the risk of explosion.

US Pat. No. 2,332,345 to 120-120 with stirring in a cylindrical vessel with a steam jacket.
A method for obtaining a product excellent in tackiness, smoothness of solution, stability and quick drying is described by heating to 176 ° C.

In US Pat. No. 2,565,404, hydrochloric acid was added to starch in a powder or wet state, gas was introduced into an autoclave equipped with a stirrer and heated up to about 100 ° C., steam was introduced up to about 130 ° C. Depending on the heating method,
A method for easily obtaining starch sugar is described.

In US Pat. No. 2,698,818, starch is heated and dried in an autoclave with stirring under vacuum, and is fed with hydrochloric acid gas and further heated to 168 ° C. under vacuum to obtain a wide range of high quality products. The method is described.

Hydrochloric acid was added to starch in US Pat. No. 2,818,357, and the mixture was fed into a heated coil to vibrate the coil to move the starch in the coil while heating it at 115 to 160 ° C. for a short time. According to the method, a method for obtaining a uniform product continuously and efficiently with heat is described.

US Pat. No. 2,845,368 describes a method in which a hydrochloric acid is vaporized and added to a starch in a fluidized state by flowing a gas to the starch in a fluidized state, and the reaction can be carried out under a wide range of conditions by heating for a short time in the fluidized state. ing.

In US Pat. No. 3,200,012, hydrochloric acid was added to fine-grained starch, which was introduced into a rotating cylinder having a heating tube inside and heated to continuously produce a product having less reducing sugar and good solution stability. A method for obtaining the same is described.

Tomasik, P. & Wiejak, S., Advance i
n Carbohydrate Chemistry, Vol.47, 279-343, (1990) provides the latest review of heat-treated starch.

However, the caloric value is 3.1 kcal / g or more when any of the above products is analyzed, and if the heating conditions are changed to obtain more than 2.2 kcal / g, the caloric value is 2.2.
Although it can be reduced to about kilocalories / g, it is not practically applicable because purification is required because the coloring substance increases and irritating odor is generated, and the purification is extremely difficult. Therefore, it is impossible to obtain the low calorie of 2 kcal / g or less which is the object of the present invention.

Regarding decomposition of carbohydrates using an extruder, US Pat. No. 4,316,747 describes a method for producing glucose by heating an acid-added cellulose slurry under pressure in a twin-screw extruder.

[0014]

Recently, in Japan,
The use of processed foods, prepared foods, fast foods, etc. is expanding due to improvements in food processing and distribution technologies as the economic environment matures. Along with this, information on food intake is diversified, and consumer needs are changing from nutrition-satisfied eating habits to health-oriented foods aimed at preventing nutritional disorders and adult diseases caused by eating habits. Among them, the need for low-calorie foods is particularly strong among middle-aged and young women, and bulking agents for low-calorie sweeteners and high-sweeteners have been developed. Among these, various indigestible oligosaccharides and sugar alcohols can be mentioned as low-calorie sweeteners, but they have many problems such as sweetness and sweetness, oligosaccharide content and diarrhea that occur.

Further, polydextrose can only be mentioned as a bulking agent for high-sweeteners such as aspartame, but this polydextrose also has a limited intake, and bitterness and hygroscopicity under acidic conditions. Problems have also been pointed out. Under such circumstances, the advent of a low-calorie bulking agent that satisfies the physical properties of foods and can be used as a safe sweetener is desired.

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 maltodextrin are used as food materials in various processed foods in large amounts. It is used. But,
Most of these processed starch products have a caloric value of 3.9 kcal / g or more, and heat-treated starch (roasted dextrin) is known as a material for low-calorie foods. Only. Hereinafter, in the present invention, the heat-treated starch (roasted dextrin) is simply referred to as dextrin.

The inventors of the present invention have been conducting research on a method for producing dextrin, a hydrolysis method, a method for producing indigestible dextrin using dextrin as a raw material, and the like. Based on the results, we applied for a “method for producing indigestible dextrin”, etc., and then researched the physiological action of this dextrin, intestinal regulation, improvement of hypercholesterolemia, insulin saving, hypertension lowering, low It has been discovered that it has the same effect as dietary fiber such as caloricity, and has applied for it as a food composition.

Furthermore, as a result of the study on the correlation between the structure of dextrin and the caloric value, the caloric value of dextrin was found to be 1 of the glycoside bonds in dextrin.
→ We found that there was an inverse relationship with the amount of 4-glycosidic bonds, and we conducted more detailed research.

As a result of this research, as a result of research on various types of dextrins, the caloric value is closely related to the amount of glycoside bonds such as 1 → 4, 1 → 6, etc., and the degree of correlation is high by statistical numerical analysis. The equation was obtained.

Further, by carrying out the heat treatment under high pressure, in the reaction under normal pressure of the prior art, the progress of the reaction is completely different from that which was a function of time and temperature, that is, the reaction conditions, 1 → 4, We have found a new fact that the correlation between the 1 → 6 bond and the caloric value is expressed by a special function, that is, an equation. However, the dextrin obtained by the conventional technique has a caloric value of 3.3-
It is extremely high at 3 kcal / g, and even if the calorie is reduced by carrying out a reaction at a high temperature for a long time, a coloring substance or an irritating odor is generated and it is impossible to put it into practical use.

Therefore, the problem to be solved by the present invention is
It is to obtain a novel low-calorie bulking agent having a calorie content of 2 kilocalories / g or less, a coloring substance and less irritating odor.

[0022]

This problem is basically solved by reducing the calorie of starch to 2 kcal / g.

[0023]

[Structure and Action of the Invention] The starch used as a raw material of the low-calorie bulking agent of the present invention is potato starch, and it is essential to add an acid as a catalyst. It is particularly preferable to use hydrochloric acid because it is for pharmaceutical use. The dextrin thus obtained has a caloric value of not more than 2 kcal / g because of the necessity as a food and a bulking agent for medicine.
It is preferably limited to 1.8 kcal / g or less.

Among the dextrins, white dextrin, which has been widely used for foods and medicines, has a caloric value of about 3.9 kilocalories / g and therefore should be used as a low-calorie bulking agent. I can't. If the calorie is less than 3 kilocalories / g, it cannot be used because it has a pungent taste.

An extruder used for the production of snack foods and the like can be exemplified as a preferable apparatus for carrying out the heat treatment in a highly pressurized state used in the method of the present invention.

The most preferred apparatus is a twin-screw extruder.

The extruder is one of pressure extruders.
It is a kind of uniaxial type in which one screw that rotates in a cylinder is inserted, and a two-axis type in which two screws that rotate in the same direction or different directions are inserted in a cylinder with a cross section of 8 It is roughly divided into the types. The screw is generally removable, and the type of the screw itself can be appropriately combined and used with various pitches including reverse pitch, and can be selected according to the properties of the raw material to be treated. Usually, this is an apparatus used for heating a cylinder, supplying the raw material from one end of a rotating screw, and utilizing the frictional heat between the screw and the raw material while treating the raw material in a pressurized / heated state.

The normal size of this extruder is
The screw diameter is 30 to 340 mm, the screw length to diameter ratio is about 10: 1 to 45: 1, and there are methods such as steam electric heating and induction heating. Further, in actual operation, a raw material container, a raw material supply device, a product cooling device, a product transportation device, a product container, etc. are required.

As operating conditions, the heating temperature is 120
~ 200 ° C. Furthermore, in order to use this equipment as a reactor, it is essential that the raw materials and products move smoothly in the extruder.Therefore, the number of revolutions depends on the nature of the raw materials, heating temperature, reaction time and addition of acid. It is closely related to the amount, and it is necessary to measure the caloric value of the product and select the optimum condition, but it is usually 120 to 400 revolutions.

The amount of hydrochloric acid added is about several percent (3 to 10%) of starch in an aqueous solution having a concentration of about 1%. Since the aqueous acid solution is added before the heat treatment, in order to uniformly mix the starch and the acid, after stirring and aging in a mixer, 100
After pre-drying at about 120 ° C and moisture to about 8%, which is higher than that in the conventional atmospheric pressure heating method,
The heat treatment is carried out by continuously feeding into the heated extruder, and the product discharged from the outlet of the extruder is rapidly cooled to terminate the heat treatment.

The greatest feature of the heat treatment method using the extruder is that the starch is reacted in a molten state. Therefore, in the conventional heating method, even after the heat treatment, the starch is in the powder state as it is when it is untreated, and the heat-treated product is in an amorphous state because it is melted.

A higher temperature during the reaction lowers the caloric value in the target product, but it is not preferable because the coloring substance increases from around 170 ° C. Specific reaction temperature is 1
20 to 200 ° C, preferably 130 to 180 ° C, more preferably 140 to 180 ° C.

Next, the experimental data will be described in detail in order to clarify the characteristics of the present invention.

[0033]

[Experimental example]

I. Method of measuring caloric value The effective caloric value of the dextrin sample was determined by the sum of the caloric value generated by digestive absorption up to the upper digestive tract and the caloric value generated by intestinal fermentation after reaching the large intestine.

Test 1. Method for measuring caloric value generated by digestive absorption in the upper digestive tract up to the small intestine Samples containing 0.9 mM calcium chloride, 45 mM
4.5 after dissolving in (bis) Tris buffer (pH 6.0)
A 5% solution was added to which human saliva α-amylase (SIGMA
Type IX-A) is added at 160 U / g and reacted at 37 ° C. for 30 minutes. After deactivating the enzyme, it is desalted with an ion exchange resin to adjust the concentration to 1.1%. Then 2 ml of 50 m
4 ml of this aqueous solution is added to M-hydrochloric acid-potassium chloride buffer (pH 2.0), and the mixture is kept at 37 ° C for 100 minutes. This is desalted with an ion exchange resin. Next, 45 mM of (bis) Tris buffer (pH 6.0) containing 0.9 mM of calcium chloride was added to this desalted solution to give a concentration of 0.4.
It was adjusted to 5%, and porcine pancreatic amylase (Boehringer Mannheim Yamanouchi Co., Ltd.) was added to this.
U / g is allowed to act and the reaction is carried out at 37 ° C. for 6 hours. After deactivating the enzyme, it is desalted with an ion exchange resin, concentrated and freeze-dried.

The powder sample thus obtained was treated with 45 mM.
It was dissolved in a sodium maleate buffer solution (pH 6.6) to give a 0.45% solution, and a rat small intestinal mucosal enzyme (manufactured by SIGMA) was allowed to act at 86 U / g, and after reacting at 37 ° C. for 3 hours,
The amount of glucose produced was measured by the pyranose oxidase method. Next, the caloric value generated by digestion and absorption is calculated by the following formula.

[0036]

Test 2. Method for determining caloric value produced by intestinal fermentation

The caloric value of the fraction reaching the large intestine was determined by the growth curve method using the rat shown below.

[0039]

[Table 1]

For the purpose of acclimatizing to the laboratory environment and the basic diet shown in Table 1, the rats preliminarily cultivated for 5 days were divided into groups (10 / group) after confirming their weight and health condition. The average initial weight of all experimental groups was 79.6-80.8 g, and the weight range of each group was 9-16 g. The calorie content of all test ingredients and basic feed was measured by a bomb calorimeter.

[0041]

[Table 2]

After grouping, each rat was individually housed in a steel cage and fed according to the experimental plan shown in Table 2. All rats ingest the basic diet 5.4g / rat / kg
(22.7 kcal / rat / day) was fed. In the test group, 0.5, 1.0, 2.0 and 4.0 g of glucose or the above sample was further added to the basic feed. That is, the added feed was fed at calories of about 2, 4, 8 and 16 kcal / rat / day. Food consumption was measured daily and weight gain was measured on days 0, 5, 10 and 15. The general condition was observed every day. The results are shown in Table 3.

[0043]

[Table 3]

From the results of Table 3, the calorie value in the animal test is (0.013 ÷ 0.023 × 3.8 + 0.009 ÷
0.051 × 3.8) /2=1.41 kcal / g
Becomes In addition, the caloric value generated by digestion and absorption in the upper digestive tract of the sample

[0045]

Therefore, the caloric value generated by intestinal fermentation is 1.41-0.39 = 1.02 kcal / g.

From this data, the caloric value produced by the intestinal fermentation of dextrin was set to 1.02 ÷ 0.912 (ratio reaching the large intestine) = 1.1 kcal / g = about 1 kcal / g.

Therefore, the calorie value was calculated by the method of Test 1 and Test 2 using the following formula.

[0049]

II. Quantitative method of glycoside bond format The measuring method is described below in "Hakomori's methylation method" (S. Hakomori,
J. Biochem., 55, 205 (1964)), and after hydrolysis, the composition of each glycoside bond type was quantified by gas chromatography.

1) Methylation A dehydrated sample (100 to 200 μg) was placed in a test tube with a screw (15φ × 100 mm), and 0.3 ml of DMSO was added.
Add and dissolve. To this is added 20 mg of NaH, and immediately 0.1 ml of methyl iodide is added. After stirring for 6 minutes with a touch mixer, cooling in ice water and adding 2 ml of water. Two
Add ml of chloroform and shake well. Pipette the upper layer (water layer) and discard. Add 2 ml of water and wash similarly. This operation is repeated 6 times. Spread cotton on the bottom of a Pasteur pipette and add 4 ~ of anhydrous sodium sulfate.
The solution is packed into a 5 cm layer, passed through the solution to dehydrate, and then washed with chloroform. Next, concentrate and dry to dryness using a rotary evaporator.

2) Hydrolysis 0.5 ml of trifluoroacetic acid was added to the methylated product to give 1
It is hydrolyzed at 00 ° C. for 4 hours, concentrated to dryness at 60 ° C. on a rotary evaporator.

3) Reduction The hydrolyzate was dissolved in 0.5 ml of water, 10 mg of sodium borohydride was added, and the mixture was allowed to stand at room temperature for 2 hours. The reaction is stopped by adding a few drops of acetic acid until bubbling stops. Next, after drying at room temperature, 1 ml of methanol is added in order to remove the generated boric acid, and the mixture is dried at room temperature. This operation is repeated 6 times.

4) Acetylation 0.5 ml of acetic anhydride was added to the reduced product, and the mixture was stirred at 100 ° C. for 4 hours.
The mixture is heated for acetylation for 1 hour, 1 ml of toluene is added, and the mixture is concentrated and dried on a rotary evaporator.

5) Desalination The acetylated product was dissolved in 1 ml of chloroform and 1 ml was added.
After adding water and shaking, discard the aqueous layer. This operation is repeated 5 times, and finally chloroform is evaporated by a rotary evaporator.

6) Dissolution The desalted product is dissolved in 0.5 ml of chloroform and analyzed by gas chromatography.

7) Conditions for gas chromatography Column DB-1 fused silica capillary column 60mX0.255mm ID, 1.0μm film Column temperature 50 ° C for 1 minute, temperature up to 280 ° C at 10 ° C / min, holding sample vaporization Room temperature 300 ° C Detection temperature 300 ° C Flow rate 2.5 ml / min, Helium detector unit Hydrogen flame ionization detector

[0058]

[Experimental Example 1] (Preparation and structure of dextrin by extruder and analysis of calorie value)

300 kg of potato starch on the market was put in a ribbon type mixer, and a 1% hydrochloric acid solution 2 was added while rotating the mixer.
2.5 L was sprayed with pressurized air, then homogenized through a crusher and then 1 more in a ribbon mixer
Mixed for hours. This mixture was pre-dried with a flash dryer to a water content of about 8%, and 270 kg of this mixture was loaded into a twin-screw extruder (manufactured by Japan Steel Works, model TEX-32F).
SS-20AW-V, screw diameter 32mm, for food,
Same direction / different direction rotation switching type, motor output 7.5KW,
400 rotations maximum, screw length / diameter = 20, aluminum casting heater, water cooling type, with vent) and heat treated under the following conditions, heating temperature 130 ° C, 1
A total of about 220 kg of 5 kinds of dextrin was obtained at 40 ° C, 150 ° C, 160 ° C and 170 ° C.

Rotation speed 150 rotations / minute, rotation in the same direction Inlet temperature Room temperature (about 20 ° C.) Maximum temperature (product outlet product temperature) 170 ° C. Reaction time 9 seconds

Quantification of caloric value for this sample,
As a result of analyzing the content of various glycosidic bonds by the “box protection methylation method”, glucose residues at non-reducing terminals were
Glucose residue having → 4 bond, glucose residue having 1 → 6 bond, glucose residue having 1 → 3 bond, and glucose having both 1 → 4 and 1 → 6 glycoside bonds in the same glucose residue A glucose residue having both 1-> 3 and 1-> 4 glycosidic bonds and 1->
A glucose residue having both 2 and 1 → 4 glycosidic bonds and a glucose residue having another bond were detected. Table 4 shows this numerical value and calorie value.

This quantification method is a complicated method, and the usual error is about ± 5%, and at least ± 2% is considered unavoidable.

[0063]

[Table 4]

In Table 4, the caloric value decreases in inverse proportion to the increase in temperature, and the amounts of glucose residues having various glycosidic bonds are non-reducing end, 1 → 6 glycosidic bond, 1 → 3 glycosidic bond. In addition to the above and 1 →
4 and 1 → 6 both glycoside bonds, 1 → 3 and 1 → 4 both glycoside bonds, and bonds other than both 1 → 2 and 1 → 4 both glycoside bonds (described as other bonds in Table 4) It is increasing in proportion to the rise. Also, only the 1 → 4 bond decreases in inverse proportion to the increase in temperature,
It was first revealed by this experiment.

Next, the relationship between the caloric value and each binding form in Table 4 was analyzed by multiple regression analysis capable of obtaining the correlation of multiple variables, and the relational expression and the correlation coefficient were obtained. In the multiple regression analysis, the amount of glucose residues in each glycoside bond was used as an explanatory variable, and the caloric value was used as an objective variable.

First, the correlation between the amount of glucose residue in each glucoside bond and the caloric value was analyzed, and the respective coefficients A0, A1, A2, A3, A4, A5, A6, A7, A8 of the obtained relational expressions were analyzed. And the correlation coefficient are shown in Table 5.

Y = A0 + An.Xn where Y ... Caloric value (kcal / g) X1 ... Amount of glucose residue at non-reducing end (%) X2 ... 1 → 4 having glycoside bond Amount of glucose residue (%) X3 ・ ・ ・ Amount of glucose residue having 1 → 6 glycoside bond (%) X4 ・ ・ ・ Amount of glucose residue having 1 → 3 glycoside bond (%) X5 ・ ・ ・Amount of glucose residue having both 1 → 4 and 1 → 6 glycosidic bonds (%)

X6 ... Amount of glucose residue having both glycoside bonds of 1 → 3 and 1 → 4 (%) X7 ... Amount of glucose residue having both glycoside bonds of 1 → 2 and 1 → 4 (%) X8: Amount of glucose residue having a glycoside bond other than the above (%)

[0069]

[Table 5]

As a result, among the eight types of glycoside bonds,
X5 (amount of glucose residues having both 1 → 4 and 1 → 6 glycosidic bonds), X6 (amount of glucose residues having both 1 → 3 and 1 → 4 glycosidic bonds) and X7 (1 → 2 and 1
→ 4 has a very low correlation coefficient for glucose residues having both glycosidic bonds (No. 5, N in Table 5)
o. 6 and No. 6 0.519, 0.6 in 7 respectively
54 and 0.837), which revealed no correlation with the caloric value. Therefore, next 3
The multiple regression analysis of the amount of each glucose residue having the following 5 types of glycoside bonds excluding the types of glycoside bonds and the calorie value was performed, and the multiple correlation coefficient was 0.9 in the obtained relational expression. Table 6 shows the coefficients A0, A1, A2, A3, A4, and A5 and the multiple correlation coefficients of the above-mentioned total 31 relational expressions.

Y = A0 + A1 * X1 + A2 * X2 + A3 * X3 + A4 * X4 + A5 * X5 However, Y ... Caloric value (kcal / g) X1 ... Non-reducing terminal glucose residue Amount (%) X2 ・ ・ ・ 1 → 4 amount of glucose residue having glycoside bond (%) X3 ・ ・ ・ 1 → 6 amount of glucose residue having glycoside bond (%) X4 ・ ・ ・ 1 → 3 Amount of glucose residue having glycoside bond (%)

X5 ... Glucose residue having both glycoside bonds 1 → 4 and 1 → 6 mentioned above and glucose residue having both glycoside bonds 1 → 3 and 1 → 4 and 1 → 2
And the amount of glucose residues having a glycosidic bond other than the glucose residue having both 1 → 4 glycosidic bonds (%)

[0073]

[Table 6]

In the multiple regression analysis, among the five explanatory variables,
There are 31 kinds of combinations of variables having 1 to 5 explanatory variables in all, and in all the 31 kinds of combinations, the multiple correlation coefficient is 0.924 or more. It shows that there is a very close correlation between the amount of glucose residues having each glycosidic bond and the caloric value.

[0075]

Comparative Example 1 (Preparation of dextrin by conventional method and analysis of structure and caloric value) The remaining 5 kg of Experimental Example 1 was placed in a dryer and heated to 150 ° C., and 15 minutes after starting heating, 30 minutes
After the lapse of minutes, 60 minutes, 120 minutes, and 180 minutes, 800 g of each sample was collected to obtain a total of 5 types of samples.

As a result of analyzing the contents of various glycosidic bonds in this sample by the “Hakomori's methylation method” as well, glucose residues at the non-reducing end, glucose residues having 1 → 4 bonds, 1 → 6 bonds A glucose residue having
A glucose residue having a 1 → 3 bond, a glucose residue having both a 1 → 4 bond and a 1 → 6 bond in the same glucose residue, a glucose residue having a 1 → 3 bond and a 1 → 4 bond, and Glucose residues having both 1 → 2 and 1 → 4 bonds and glucose residues having other bonds were detected. Table 7 shows these numerical values and calorie values.

[0077]

[Table 7]

In Table 7, the caloric value decreases in inverse proportion to the increase in heating time, which is similar to the result in Table 1, but the amount of glucose residues having various glycosidic bonds. Regarding 1), the fact that the 1 → 4 glycoside bond decreased almost inversely with the increase of the heating time and that the 1 → 6 glycoside bond increased almost proportionally showed the same tendency as the result of Table 1. is there. However, it was clarified for the first time by the present experiment that the correlation between the non-reducing end and other bonds was not observed in the heating conditions, which is significantly different from the results in Table 4.

[0079]

[Experimental Example 2] 1% of 300 kg of potato starch on the market
Hydrochloric acid was added in an amount of 17.5 L, the same treatment as in Experimental Example 1 was performed, and then the heat treatment was performed at 180 ° C., and the same treatment as in Experimental Example 1 was performed to obtain about 220 Kg of dextrin. This was analyzed in the same manner as in Experimental Example 1.

[0080]

[Experimental Example 3] 1% of 300 kg of potato starch on the market
Hydrochloric acid was added in an amount of 17.5 L, the same treatment as in Experimental Example 1 was carried out, and then the treatment was carried out in the same manner as in Experimental Example 1 except that heat treatment was carried out at 160 ° C. to obtain about 220 Kg of dextrin. This was analyzed in the same manner as in Experimental Example 1. Experimental Example 2 and Experimental Example 3
Table 8 shows the results of the analysis.

[0081]

[Table 8]

Next, the caloric value Y is calculated by substituting the respective numerical values of Table 8 into the relational expressions 1 to 30 of Table 6, and the numerical values obtained by converting the results into% are summarized in Table 9.

[0083]

[Table 9]

In Table 2, in the experimental example 2 of the dextrin by the extruder, the fluctuation range from the measured value of the calculated value Y is within ± 15% for all 30 cases, and within ± 10% of the fluctuation. Only one was done. Also ±
29 cases within 5%, 2 cases within ± 2%
There were 5 cases.

Similarly, in Experimental Example 3, the fluctuation range of the calculated value Y from the measured value is within ± 10% for all 30 cases, and ±
None of them fluctuated more than 10%. ± 5
There are 29 cases within%, 22 cases within ± 2%
It was a matter. From these results, it is shown that each relational expression in Table 6 has a very high correlation with each glycoside bond of dextrin and the caloric value.

Similarly, the caloric value Y is calculated by substituting each numerical value of Table 7 into the relational expressions 1 to 31 of Table 6 and calculating the result by%.
Table 10 summarizes the converted values.

[0087]

[Table 10]

In Table 10, it is clear that the conventional heat treatment dextrin has an extremely large fluctuation range in any of the samples, and almost no correlation with the relational expression in Table 6 is recognized. It is shown that the structure of the product also greatly differs depending on the heating method even for the starch.

[0089]

[Comparative Example 2] 2300 L of 1% hydrochloric acid was added to 300 kg of commercially available cornstarch, the same treatment as in Experimental Example 1 was performed, and then the heat treatment was carried out at 140 ° C. Then, about 240 Kg of dextrin was obtained.
This was analyzed in the same manner as in Experimental Example 1.

[0090]

[Comparative Example 3] Similar to Experimental Example 1 except that 22.5 L of 1% hydrochloric acid was added to 300 kg of commercially available sweet potato starch, the same treatment as in Experimental Example 1 was performed, and then heat treatment was performed at 140 ° C. It was processed to give about 230 Kg of dextrin. This was analyzed in the same manner as in Experimental Example 1. Table 11 shows the analysis results of Comparative Example 2 and Comparative Example 3.

[0091]

[Table 11]

Table 12 shows the results of calculating the calorie values by substituting the analysis results of the above two comparative examples into the equation 31 using all the five explanatory variables, in comparison with the actually measured values.

[0093]

[Table 12]

Table 12 shows that, even if the heat treatment method is the same, the structure of the product is significantly different when the type of the starting starch is different.

[0095]

[Experimental Example 4] With respect to a total of 11 dextrin samples obtained in Experimental Examples 1, 2, and 3 and Comparative Example 1, the degree of coloring was measured by using a blue filter with a Kett photoelectric whiteness meter to determine the whiteness of magnesium oxide. The whiteness of the sample was measured as 100%. The results are shown in Table 13.

[0096]

[Table 13]

It was shown that the whiteness decreases inversely with heating temperature and inversely with heating time.

[0098]

[Summary of Analytical Results of Experimental Data] To summarize the analytical results of the above experimental data, the dextrin obtained by heat treatment with the extruder according to the present invention is significantly different from the conventionally known dextrin in the following points. There is. That is, if the calorie value is less than 2 kcal / g

1) The minimum calorie value is 1.44 kcal / g,

2) The content of glucose residues having a 1 → 4 glycosidic bond is about 29 to about 60% of the conventional content.
49%,

3) The content of glucose residues having 1 → 6 glycosidic bond is about 7% to 13% compared to the conventional 4% or less.
%,

4) The content of glucose residues having a 1 → 3 glycoside bond is about 5%, compared with the conventional content of about 1.5%.
~ 9%,

5) The content of glucose residues having other glycosidic bonds is about 3 to about 20% of the conventional content.
8%,

6) Further, other than those having the above-mentioned bond and both glycoside bonds of 1 → 4 and 1 → 6, both glycoside bonds of 1 → 3 and 1 → 4 and both glycoside bonds of 1 → 2 and 1 → 4. There is a close correlation between the content of glucose residues having each glycoside bond and the caloric value.

7) Among 31 kinds of relational expressions, the expression 31 using all 5 explanatory variables is the whole glycoside bond and calorie of each starch in the starch which is obtained by adding acid to potato starch and heat-treating with an extruder. It shows the closest relationship with the value. Therefore, as starch other than potato starch, cornstarch and sweet potato starch were similarly heat-treated with acid in an extruder, and the analytical value of the glycoside bond of the obtained dextrin was substituted into Equation 31 to obtain the caloric value. Is
It is very different from the measured value, and it is clear that this relational expression is a relational expression applied only to potato starch.

8) When the heating temperature is increased, the coloring substances of the product are increased, and the whiteness is lowered to around 20% which is considered to be the lower limit as a food material, which is a practical limit.

From the above experimental results, it was revealed that the dextrin of the present invention is a novel substance having a low caloric value and a large difference in structure as compared with those obtained by the conventional heat treatment method. ..

Next, as the heating conditions of the extruder, it is preferable to carry out a high temperature treatment in order to reduce the caloric value, as shown in Table 4, and the caloric value is 2
About 130 to get less than kcal / g
A product having a caloric value of 1.8 kcal / g or less can be obtained by a treatment at a temperature of not less than 0 ° C, more preferably at not less than 140 ° C. However, in the case of a large-sized extruder, the reaction time becomes long due to the structure of the equipment, so that the treatment may be performed at a relatively low temperature. However, when the temperature is higher than 180 ° C., for example, the amount of coloring substances produced increases and the quality deteriorates, which is not preferable. However, the products are dissolved in water to perform decolorization treatment with activated carbon, or desalting and decolorization treatment with ion exchange resins. It is also possible to improve the quality of the product by

Further, the progress of the reaction can be adjusted by increasing the amount of the acid to be added. However, if the amount of the acid is extremely increased, it causes corrosion and wear of the extruder. The optimum condition is 3000 ppm or less, more preferably about 1000 ppm, relative to starch.

It is also possible to further reduce calories by separating and removing the high-calorie portion by continuous chromatography using an alkali metal type or alkaline earth metal type ion exchange resin after purification.

[0111]

EXAMPLES Next, examples of the present invention will be described.

[0112]

[Example 1] 500 kg of commercially available potato starch was placed in a ribbon mixer, and a 1% hydrochloric acid solution 5 was added while rotating the mixer.
0 L was sprayed with pressurized air, then homogenized through a grinder and then further mixed for 1 hour in a ribbon mixer. After pre-drying this mixture with a flash dryer to a water content of about 6%, a twin-screw extruder (manufactured by Japan Steel Works, model TEX-52FSS-20AW-V, screw diameter 52 mm, for food, same-direction / different-direction rotation switching) Type, motor output 22 kW, maximum 400 rotations, screw length: diameter = 20: 1, aluminum casting heater, water cooling type, with vent) and heat treated under the following conditions, total dextrin approx. 360 kg was obtained.

Rotation speed 150 rotations / minute, rotation in the same direction Inlet temperature Room temperature (about 20 ° C) Heating temperature (product outlet product temperature) 150 ° C Reaction time 9 seconds

[0114]

[Example 2] 500 kg of commercially available potato starch was placed in a ribbon mixer, and a 1% hydrochloric acid solution 3 was added while rotating the mixer.
5 L was sprayed with pressurized air, then homogenized through a crusher and then further mixed for 1 hour in a ribbon mixer. This mixture was pre-dried with a flash dryer to a water content of about 6%, then continuously fed to the same twin-screw extruder as in Example 1 and heat-treated under the following conditions to obtain a total of about 360 kg of dextrin.

Rotation speed 200 rotations / minute, rotation in the same direction Entrance temperature Room temperature (about 20 ° C) Heating temperature (product outlet product temperature) 200 ° C Reaction time 7 seconds

[0116]

[Example 3] Commercially available potato starch (500 kg) was placed in a ribbon mixer, and a 1% hydrochloric acid solution 7 was added while rotating the mixer.
5 L was sprayed with pressurized air, then homogenized through a crusher and then further mixed for 1 hour in a ribbon mixer. This mixture was pre-dried with a flash dryer to a water content of about 6%, then continuously fed to the same twin-screw extruder as in Example 1 and heat-treated under the following conditions to obtain a total of about 360 kg of dextrin.

Rotation speed 135 rotations / minute, rotation in the same direction Inlet temperature Room temperature (about 20 ° C.) Heating temperature (product temperature at product outlet) 140 ° C. Reaction time 10 seconds The potato starch obtained in Examples 1 to 3 Similarly, for dextrin, the analysis values of the content of various glycoside bonds and the analysis value of the calorie value by the “Hakomori's methylation method” are collectively shown in Table 14.

[0118]

[Table 14]

The results of caloric value calculation by substituting the analysis results of the examples of Table 14 into the equation 31 using all five explanatory variables are shown in Table 15 in comparison with the actually measured values.

[0120]

[Table 15]

The fluctuation range of the calculated value from the measured value is +11.7.
% To -4.1%.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuo Katsuta 4-3-7 Kushiro, Kawanishi-shi, Hyogo Matsutani Chemical Single dormitory

Claims (6)

[Claims] 1. The amount of (A) 1 → 4 glycoside bond is 50%.
And (B) the caloric value is 2 kilocalories / g or less, and (C) this caloric value is a change from the numerical value Y calculated by the relational expression of any one or more of the following 1 to 30: The range is within ± 5%, and (D) a low-calorie weight increase characterized by being obtained by adding hydrochloric acid to potato starch and heating it to 120 to 200 ° C. using a twin-screw extruder. Agent. However, Y: Caloric value (kcal / g) X1: Amount of non-reducing terminal glucose residue (%) X2: Amount of glucose residue having 1 → 4 glycosidic bond (%) X3 ...・ Amount of glucose residue having 1 → 6 glycoside bond (%) X4 ... Amount of glucose residue having 1 → 3 glycoside bond (%) X5 ... Both of the above and 1 → 4 and 1 → 6 Glucose residue having glycoside bond, glucose residue having both 1 → 3 and 1 → 4 glycoside bond and glucose residue having glycoside bond other than glucose residue having both 1 → 2 and 1 → 4 glycoside bond Amount (%) (However, X1, X2, X3, X4, and X5 are numerical values quantified by the “box protection methylation method.”) [Equation 1] [Equation 2] [Equation 3] [Equation 4] [Equation 5] [Equation 6] [Equation 7] [Equation 8] [Equation 9] [Equation 10] [Equation 11] [Equation 12] [Equation 13] [Equation 14] [Equation 15] [Equation 16] [Equation 17] [Equation 18] [Formula 19] [Equation 20] [Equation 21] [Equation 22] [Equation 23] [Equation 24] [Equation 25] [Equation 26] [Equation 27] [Equation 28] [Equation 29] [Equation 30] 2. The low-calorie bulking agent according to claim 1, wherein the variation range from the numerical value Y is within ± 2%. 3. The low-calorie bulking agent according to claim 1, wherein the range of fluctuation of the caloric value from the numerical value Y calculated by the following relational expression is within ± 15%. [Equation 31] 4. The low-calorie bulking agent according to claim 3, wherein the variation range from the numerical value Y is within ± 10%. 5. The amount of (A) 1 → 4 glycosidic bond is 40%.
The low-calorie bulking agent according to any one of claims 1 to 4, characterized in that (B) the caloric value is 1.8 kilocalories / g or less. 6. The low calorie bulking agent according to any one of claims 1 to 5, wherein the heating temperature is 130 to 180 ° C.