JPS6291501A - Production of nondigestible polysaccharide from reduced starch hydrolyzate - Google Patents

Abstract

PURPOSE:To produce a nondigestible polysaccharide being free from bitter and coloration and having excellent heat stability within a short time, by heating a reduced starch hydrolyzate in the presence of an acid catalyst in an anhydrous condition. CONSTITUTION:To a reduce starch hydrolyzate obtained by hydrogenating a starch hydrolyzate obtained by acid or enzymatic saccharification of starch (e.g., reduced branched dextrin), 0.3-0.5wt% inorganic acid (e.g., phosphoric acid) or 5-20wt% organic acid (e.g., citric acid) as a catalyst is added, and the obtained mixture is dewatered and dried by slowly heating to about 130 deg.C in a vacuum. The dried product is heated at 150-250 deg.C for 1-3hr to obtain a powdered nondigestible polysaccharide comprising an aggregate of a nonreducing polymer of various degrees of polymerization, formed by rearrangement of the glucose residues of the nonreducing sugar mainly at 1 6 linkage.

Description

[Detailed Description of the Invention] The present invention relates to a method for producing so-called low-calorie polysaccharides that are easily digested in the human body. It is used as a food material for dietary therapy of people who need to limit their intake of carbohydrates and carbohydrates.

2. Prior Art Conventionally, as a method for producing the above-mentioned low-calorie polysaccharides, glucose, maltose or a mixture thereof is added in the presence of a polycarboxylic acid catalyst and, if desired, in the coexistence of a sugar alcohol. In addition, a method of heating and polymerizing under reduced pressure (Japanese Patent Publication No. 53-47280) and a method of heating starch or starch melted product with polycarboxylic acid and its anhydride under reduced pressure (Japanese Patent Publication No. 56-29512) were proposed. ing.

However, among these methods, the
In the method of No. 280, glucose, maltose, or a mixture thereof as a starting material is polymerized by heating with a sugar alcohol in the presence of a polycarboxylic acid at a temperature below the decomposition point of these sugars. Among various possible bonding methods for maltose, a polymer is formed mainly by a dehydration condensation reaction in which 1-6 bonds are predominant, and the polycarboxylic acid used as a catalyst is ester bonded to the glucose polymer. Further, the polymers are crosslinked by ester bonds to form a large-molecular polymer. In the above polymerization reaction, the sugar alcohol is incorporated into the polymer through dehydration condensation with the reducing end group of the glucose polymer, and has the effect of suppressing coloration during the reaction.

However, according to this method, as mentioned above, since the dehydration condensation reaction mainly occurs, the production of so-called gentiobiose, which is composed of β1-6 bonds of glucose, is unavoidable.
The disadvantage is that the polysaccharide tastes bitter due to this.

Furthermore, since this method uses sugar alcohol in an amount ranging from about 5 to 20%, the physical properties of the polysaccharide obtained by polycondensation are also limited to a narrow range.

Furthermore, the method disclosed in Japanese Patent Publication No. 56-29512 involves polymerization by heating starch or starch partial hydrolyzate as a starting material under reduced pressure in the presence of polycarboxylic acid and less than 5% by weight of water. However, during this polymerization reaction, the sugar components that make up starch and starch partial hydrolyzate all have reducing end groups, so these participate in the reaction and aggregate to form resin-like giants. It forms molecules.

Furthermore, since this phenomenon in the polymerization reaction occurs regardless of the degree of starch decomposition, the resulting polymers are almost the same, and the physical properties are therefore limited to a narrow range. .

In addition, in the above method, the reaction is carried out in the presence of free reducing groups, so there is a problem that coloration during the reaction is significant.

The present invention was made in view of the problems in the production of polysaccharides by the conventional method as described above, and by using a reduced starch hydrolyzate as a starting material, To provide a method for advantageously producing a non-digestible polysaccharide having a sugar composition corresponding to the sugar composition of the starting material and having a wide range of physical properties in a short time and without substantially causing bitterness or coloring. The purpose is to

The present invention will be explained in detail below.

A feature of the present invention is that a non-digestible polysaccharide is obtained by heating a reduced starch hydrolyzate under anhydrous conditions in the presence of a catalyst consisting of an inorganic acid or an organic acid.

The term "reduced starch hydrolyzate" as used herein refers to a mixture of non-reducing saccharides obtained by hydrogenating starch hydrolyzate having various DE and sugar compositions obtained by acid saccharification or enzymatic saccharification of starch. It means something. Therefore, the reduced starch hydrolyzate includes a wide range of decomposition products.

As mentioned above, the reduced starch hydrolyzate used as a starting material in the present invention for determining starch content has a wide range of saccharification, including those with E and sugar compositions, but when selecting its use, The polysaccharide is selected based on the physical properties required of the target polysaccharide, that is, the physical properties required as a dietary food material.

Examples of the reduced starch hydrolyzate used in the present invention include reduced branched dextrin and hydrogenated starch obtained by saccharifying starch with an acid or an enzyme, commonly called reduced starch syrup.

In addition, the inorganic acid and organic acid used as a catalyst in the present invention may be any non-volatile acid, and phosphoric acid is suitable as the inorganic acid, and the amount used is 0% based on the solid content of the reduced starch hydrolyzate. The amount is preferably about .3 to 0.5% by weight. In addition, as the organic acid, when ester crosslinking with carboxylic acid is required for the reaction for producing multiple m, polycarboxylic acids such as citric acid, fumaric acid, tartaric acid, and malic acid are preferable, and the amount used is is suitably 5 to 20% by weight based on the above solid content.

In carrying out the present invention, first, the target multi-tJ
Select a reduced starch hydrolyzate as a starting material according to category i, add an acid catalyst to it as a powder or make it a liquid, and if it is in a liquid form, concentrate it under reduced pressure to make a powder. Then, the powdered material or powdered material was collected on a tray or rotary evaporator and heated at 130°C.
After confirming that it is still in a powder state, the temperature is further raised to 160° C. to 180° C. and held for about 1 to 3 hours. Since the reactant thus obtained is in powder form, it can be easily taken out from the reaction container.

Note that when a reduced starch hydrolyzate obtained by hydrogenating a starch hydrolyzate with a high DE is used as a starting material, the reaction will be carried out in a molten state, and in this case, the same operation as above can be performed.

The reactant has almost no color, so it can be used as a product as it is, but if deacidification is necessary, it can be redissolved in water, deoxidized using an ion exchange resin, etc., and then concentrated to form a silub, or dried. It is best to powder it into a product.

The polysaccharide obtained by the present invention is obtained by heating reduced starch hydrolyzate under anhydrous conditions, and the glucose residues of the non-reducing sugars constituting the polysaccharide are mainly transferred through 1-6 bonds. It consists of a collection of non-reduced polymers with various degrees of polymerization. In addition, in the polysaccharide obtained by the present invention, since no condensation reaction occurs between non-reduced polymers,
This results in a non-digestible polysaccharide corresponding to the sugar composition of the reduced starch hydrolyzate used as the starting material.

Therefore, according to the present invention, as described above, by selecting the above-mentioned reduced starch hydrolyzate, it is possible to obtain a product having a corresponding sugar composition and various physical properties.

Furthermore, the reduced starch hydrolyzate used in the present invention is
Non-refundable! Since it is composed of M class, it has much better thermal stability than starch sugar made of reducing sugars, and therefore, in the present invention, even under anhydrous conditions,
It has the advantage of being able to produce the target polysaccharide in a short time because it can be heated at a low temperature.

The present invention will be described in more detail with reference to Examples. Example I 5 g of citric acid is added to 145 g of reduced starch hydrolyzate (30% moisture) obtained by hydrogenating the starch hydrolyzate using α-amylase of DE22. Dissolve and heat in a vacuum oven for 10 minutes.
It was dehydrated and dried at 0° C. under reduced pressure of 760 mm and 11 g.

The pH of a 10% solution of this dried product is 2.6, and the sugar composition by weight is Gl: 3.0%, G2 = 7.1%, G3:
9.0%, G4: 6.7%, G5: 7.2%, G
6:23.1%, Gn >6:43.9% (Gn indicates the degree of polymerization of non-reducing saccharides).Then, the dehydrated and dried product was collected in a rotary evaporator, and 750 +++ m
The polymerization reaction was carried out in a silicone oil bath under a reduced pressure of 11 g, and the zero rotation speed was 80 r, p, a+.

Initially, the temperature was gradually raised to 130°C, and a molten state was obtained. Subsequently, the temperature was raised to 170°C and held at that state for 1 hour. The sugar composition of the obtained reaction product was Gl: 3 by weight.
．． 0%, G2: 6.2%, G3 knee 5.5%, G4
: 5.8%, G5: 4.4%, Gn>5 near 5.
1% (Gn indicates the degree of polymerization of non-reducing sugars). .

The degree of coloration of a 10% solution of this reactant is 430 mμ, 10I
The result measured with IIIll cell was 0.02. Also, for the same wave (pif 5.0), Amylo (1', 4)
An enzyme consisting of a mixed system of glucosidase, amylo(1,4,1,6) glucosidase, and amylo(1,4) dextrinase was added in excess and saccharified at 55°C for 2 hours. The resulting sugar composition was glucose 710 by weight. .8%, GI: 3.
8%, G2: 7.8%, G3: 6.9%, G4: 4
．． 9%, G5: 3.9%, On>5: 61.9%.

The reaction product was ground to obtain a white powder with no bitter taste.

Example 2 0.3 g of phosphoric acid was added to 145 g of reduced starch hydrolyzate (moisture 30%) obtained by hydrogenating starch hydrolyzate using DE35 α-amylase, and the mixture was heated at 100°C in a vacuum oven.
, 760+nn+I1gk under reduced pressure. The pi of a 10% solution of this product is 2.6, and the sugar composition by weight is Gl: 9.9%, G2: 9.8%, G3: 11
．． 4%, G4: 6.7%, G5: 7.6%, G6: 1
7.3%, Gn>6:37.3%.

Next, the dehydrated and dried product was collected in a rotary evaporator, and a polymerization reaction was carried out at 170° C. in a silicone oil bath under reduced pressure of 750 mm and 1 g. The sugar composition of the reaction product after 1 hour was as follows: G1: 5%, G2: 9.5%, G
3: 10.6%, G4: 7.6%, 05: 6.9%
, Gn>5:57.9% (Gn indicates the degree of polymerization of non-reducing sugars). Further, the degree of coloring of a 10% solution of this reactant was 430111μ and 0.04 as measured in a 10m111 cell.

The same wave (pi 15.0) was saccharified using the same enzyme system as in Example 1 at 55°C for 12 hours, and the sugar composition was as follows.

Glucose: 11.7%, Gl: 7.2%, G2:
9.2%, G3: 9.5%, G4: 6.3%, G
5:5.5%, Gn>5:50.6%. The reaction product was ground to obtain a white powder with no bitter taste.

Example 3 A reduced branched dextrin obtained by hydrogenating a DE8 branched dextrin was used as a starting material. 100g of this starting material
Add water to 20g of citric acid and dissolve completely, and make 100g of citric acid.
It was dried in brine under reduced pressure at 76011 mHg. Next, this dehydrated dry product is collected in a rotary evaporator,
The reaction was carried out at 170° C. for 2 hours in a silicone oil bath. The reaction intermediate was in the form of a powder. The reactant only swelled slightly in water and was insoluble, and did not undergo any enzymatic reaction. After grinding, a slightly yellow powder was obtained.

Claims (2)

[Claims] (1) A method for producing a non-digestible polysaccharide, which comprises heating a reduced starch hydrolyzate under anhydrous conditions in the presence of a catalyst consisting of an inorganic or organic acid. (2) The manufacturing method according to claim (1), wherein heating is performed at a temperature of 150°C to 250°C for about 1 to 3 hours.