TWI886101B - Syneresis-preventing agent and use thereof - Google Patents

Abstract

The subject of the present invention is to provide a dehydration inhibitor and its use which can be used safely and advantageously in the fields of food, cosmetics, quasi-drugs, pharmaceuticals, industrial products, etc. The present invention solves the above-mentioned problem by providing a dehydration inhibitor having a branched α-glucan mixture as an active ingredient and its use, wherein the branched α-glucan mixture has glucose as a constituent sugar, and the non-reducing terminal glucose residue at one end of a linear glucan having a glucose polymerization degree of 3 or more obtained by connecting via an α-1,4 bond has a glucose residue connected via a bond other than an α-1,4 bond. The branched structure of glucose with a degree of polymerization of 1 or more is digested by isomaltoglucanase to produce isomaltose with a solid content of more than 25% by mass and less than 50% by mass per digest, and the ratio of glucose residues obtained by α-1,4 bonds to glucose residues obtained by α-1,6 bonds is in the range of 1:0.6 to 1:4, and the total of the above two types of residues accounts for more than 60% of all glucose residues.

Description

Dehydration inhibitor and its use

The present invention relates to a dehydration inhibitor and various uses thereof, and more particularly to a dehydration inhibitor and uses thereof which can prevent dehydration in the fields of food, cosmetics, pharmaceuticals, etc. without damaging the original quality of the products.

Gel compositions are obtained by mixing a gelling agent such as thickening polysaccharide or gelatin with water. Therefore, compared with general solid compositions, they contain a larger amount of water, and it is important to keep this water in the composition well in order to maintain the function of the composition. For example, it is known that in the case of foods, cosmetics, pharmaceuticals, etc. in the form of gel-like compositions, the behavior of water has a great impact on storage stability. As a function maintained by good moisture retention, if the gel-like composition is a food, the edible feel or flavor and color such as "tongue touch", "melting in the mouth", "throat feeling" can be listed; in the case of cosmetics, the use feel or fragrance and color such as "extensibility", "adhesion", "fusion" can be listed; in the case of pharmaceuticals, the feeling of taking or the stability of the active ingredients can be listed.

For example, most jelly-like processed foods are filled and sealed in containers such as plastic cups, sterilized, and then circulated/supplied to the market. During refrigeration or room temperature storage, water will flow out of the food over time, causing "dehydration". As a result, the original texture, flavor, color, and other appearance of the processed food may be damaged, or when consumers open the container or remove the seal or lid during use, the dehydrated water may scatter, which may lead to a reduction in the value of the product.

Furthermore, in recent years, due to the aging population and the improvement of health aspirations, the market for jelly drinks that are filled in a flexible package with a drinking hole and squeezed out by hand and drunk directly is expanding in the field of nursing food or sports nutrition food. Compared with the conventional jelly food, the gel composition of this kind is softer and more fragile, and generally has a lower concentration of gelling agent, so there is a problem that it is more difficult to inhibit dehydration.

Generally, free water in a gel-like composition is retained in the gaps of a mesh structure made of a substance other than water. On the other hand, it is generally believed that the structure will collapse and become tighter due to stabilization over time, so that the free water physically trapped in the gaps of the structure will change and overflow from the structure, resulting in dehydration. In this way, since the gel-like composition retains a large amount of liquid inside, it will dehydrate over time immediately after production. In order to suppress the quality degradation caused by the dehydration of such a gel-like composition, a gel-like composition characterized by a component useful for dehydration inhibition or a method for producing the same has been reported in the past.

Specifically, there are reports of a gel-like composition that inhibits dehydration by containing natural blue gum (Patent Document 1), a gel-like composition that uses carrageenan as a gelling agent, contains xanthan gum and locust bean gum as gelling aids, and contains a modified polyalkylene oxide as a dehydration inhibitor (Patent Document 2), and a water-based gel-like composition that similarly contains N-vinyl acetamide polymer as a dehydration inhibitor (Patent Document 3). If limited to the food field, it has been reported that A method for improving the physical properties of gel by using a dried konjac product prepared by combining konjac powder, sugar and starch as a physical property improver for gel-like foods is disclosed (Patent Document 4); a method for reducing the water activity and inhibiting dehydration by including trehalose as a moisture regulator in gel-like food components (Patent Document 5); and a method for inhibiting dehydration of gel-like foods by adding starch whose gel-forming ability is enhanced by enzyme treatment (Patent Document 6).

Among all the dehydration inhibition methods of the above-mentioned prior art, it has not yet been achieved to inhibit dehydration for a long time without affecting the texture or flavor. For example, in the techniques disclosed in Patent Documents 1 and 4, the opposite of increasing the structural strength will give a more elastic eating feel, so for a gel-like composition with a high water content, the original eating feel will be greatly changed. In addition, the chemical synthesis products disclosed in Patent Documents 2 and 3 have the disadvantage of being limited in food utilization. On the other hand, although the technology disclosed in Patent Document 5 can be applied to a wide range of fields, including food, and has less impact on the original flavor, color, and eating feel, it will give a slight sweet taste, so the use or dosage is limited. In addition, in the technology disclosed in Patent Document 6, there is a problem that even after enzyme treatment, the peculiar mushy smell of starch may remain. [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 10-150933 [Patent Document 2] Japanese Patent Publication No. 2003-268156 [Patent Document 3] Japanese Patent Publication No. 2003-277253 [Patent Document 4] Japanese Patent Publication No. 2004-166580 [Patent Document 5] Japanese Patent Publication No. 9-56342 [Patent Document 6] Japanese Patent Publication No. 2016-103992

[The problem that the invention wants to solve]

The present invention is completed to solve the above-mentioned problems of the previous dehydration inhibition technology. The subject is to provide a dehydration inhibitor and its use. The dehydration inhibitor is a branched α-glucan mixture prepared from starch. When it is mixed into processed foods, it will exert an excellent dehydration inhibition effect without damaging the original taste, flavor, and color of the food. Therefore, it can be advantageously used for quality improvement purposes, not limited to food, but also in the fields of cosmetics, quasi-drugs, pharmaceuticals, industrial products, etc. It can be safely and advantageously used. [Means for solving the problem]

In the course of conducting research to solve the aforementioned problems, the inventors of the present invention unexpectedly discovered that a branched α-glucan mixture (hereinafter referred to as "the present branched α-glucan mixture") which can be obtained by, for example, the production method disclosed in the pamphlet of International Publication No. WO2008/136331 of the same applicant as in the present case and which is typically characterized by (A) to (E) described below, exhibits an excellent dehydration inhibition effect when blended into a gel-like composition.

It has long been known that high molecular weight polysaccharides such as starch, cellulose, and agar have the property of retaining water in their molecules. This property is due to the mesh structure obtained by the intertwining of the polysaccharide molecular skeleton to retain free water, and the hydroxyl groups of the monosaccharides belonging to the structural unit to retain bound water by forming a hydrogen bond network with the surrounding water molecules. Among them, it is generally believed that the density or strength of the latter hydrogen bond network depends on the stereo coordination of the hydrophilic groups in the constituent monosaccharides or the stereo configuration of the polysaccharide molecular chain, and further, the branching degree and pattern of the molecular chain, etc., but the understanding and prediction of the property of retaining bound water are not yet sufficient. Furthermore, it is extremely difficult to predict/anticipate the performance, physical properties or processing characteristics of such polysaccharides in various compositions formed by blending such polysaccharides with complex compositions and steps.

The strong water-retaining property of the branched α-glucan mixture is as described above. Although the details of its mechanism are unknown, it is generally believed that it is due to the special characteristics of the molecular structure and the coexistence of the function/property as a water-soluble dietary fiber in a good balance. The present invention is based on the characteristics of such compounds and further studies to make progress in this view.

It has been clearly revealed that the dehydration inhibitor characterized by containing the branched α-glucan mixture is not limited to the dehydration inhibition of gel-like compositions. Surprisingly, when mixed into frozen desserts, it exerts a significant quality improvement effect by affecting the growth and stability of ice crystals, thereby imparting a better texture.

That is, the present invention solves the above-mentioned problems by providing a general-purpose and multifunctional dehydration inhibitor having the branched α-glucan mixture as an active ingredient and its use. [Effect of the invention]

According to the dehydration inhibitor of the present invention, the dehydration inhibitor can impart a dehydration inhibitory effect to the gel-like composition that cannot be achieved by conventional gelling aids or admixtures without changing the original taste or eating texture. In particular, the effect is significantly exerted when agar and/or carrageenan are used as the gelling agent.

When the dehydration inhibitor of the present invention is mixed into frozen desserts including frozen desserts, no special equipment, steps or additives are required for adjustment, and the melting property in the mouth or the spoon penetration property of frozen desserts containing milk and dairy products can be improved. In addition, in frozen desserts without milk and dairy products, the looseness in the mouth can also be improved to achieve good spoon penetration property with a crispy touch.

Furthermore, the dehydration inhibitor of the present invention, which uses the branched α-glucan mixture as an active ingredient, has high solubility in water, and the aqueous solution is colorless and transparent. Furthermore, it does not have the sticky smell peculiar to starch, and thus does not have the odor or the loss of flavor and color caused by coloring, which is a problem of the conventional technology using processed starch or roasted dextrin. In addition, it has lower aging properties than general high molecular weight dextrin, and thus can provide a dehydration inhibitor with good storage stability that cannot be achieved by the conventional technology.

The reason why the branched α-glucan mixture has the above-mentioned characteristics is not fully understood, but it is presumed that the glucose residues that are bonded to other glucose at the 1-position and 6-position (hereinafter, abbreviated as "α-1,6 bond" and the same notation applies hereinafter) in the α-glucan molecule are contained at a higher composition ratio in the mixture as a whole, or that the ratio of the branched structure of α-1,3,6 bond and α-1,4,6 bond is affected.

The dehydration inhibitor of the present invention is made from starch as a raw material and is substantially colorless, tasteless and odorless. Therefore, the original color, gloss, flavor, edible texture, etc. of the food can be improved by capturing free water and effectively reducing the water activity according to the characteristics of the branched α-glucan mixture. At the same time, in a gel-like composition that retains a large amount of water, surface dehydration can be inhibited and the texture of the edible texture or coating texture can be well maintained without affecting the flavor or color.

1. Definition of terms

In this specification, the following terms have the following meanings.

<Frozen desserts> The term "frozen desserts" in this manual includes ice cream (milk solids 15.0% or more, milk fat 8.0% or more), ice milk (milk solids 10.0% or more, milk fat 3.0% or more), lacto-ice (milk solids 3.0% or more) and other frozen desserts in accordance with the Japanese Ministry of Dairy and Others, which means cold desserts or drinks made by freezing unflavored water or a liquid flavored with milk, dairy products, fruit juice, flavors, and sugars.

<Digestion with isomalto-glucanase> The term "digestion with isomalto-glucanase" used in this manual means that isomalto-glucanase is used to hydrolyze liquefied starch, dextrin, high molecular weight polysaccharides, and other objects. Isomalto-glucanase is an enzyme with the enzyme number (EC) 3.2.1.94, which has the property of hydrolyzing any of the α-1,2, α-1,3, α-1,4, and α-1,6 bonds adjacent to the reducing end of the isomaltose structure in α-glucan. It is more appropriate to use isomalto-glucanase derived from Arthrobacter globiformis.

<Water-soluble food fiber content> The "water-soluble food fiber content" mentioned in this manual is the value obtained by the method "High Performance Liquid Chromatography (Enzyme-HPLC Method)" in the 8th item "Food Fiber" of the Nutrition Labeling Standards "Analysis Methods of Nutritional Components, etc. (Methods disclosed in the 3rd column of the 1st table of the Nutrition Labeling Standards)" of the Ministry of Health, Labor and Welfare Notice No. 146 in May 1998. The outline of this method is as follows. That is, the sample is decomposed by a series of enzyme treatments using heat-stable α-amylase, protease and amyloglucosidase (glucose amylase), and the sample solution for size exclusion analysis is prepared by removing protein, organic acid and inorganic salt from the treated solution by ion exchange resin. Then, the sample solution is subjected to size exclusion analysis, and the peak areas of undigested glucan and glucose in the chromatogram are obtained. The water-soluble dietary fiber content of the sample is calculated using the peak areas and the amount of glucose in the sample solution obtained in advance by the glucose oxidase method according to the conventional method. In addition, the "water-soluble dietary fiber content" referred to throughout this manual, unless otherwise specified, means the water-soluble dietary fiber content obtained by the aforementioned "high performance liquid chromatography (enzyme-HPLC method)".

<Methylation analysis> The term "methylation analysis" in this manual refers to a chemical method for determining the bonding pattern of monosaccharides constituting polysaccharides or oligosaccharides. When "methylation analysis" is applied to the analysis of the bonding pattern of glucose in glucan, first, all free hydroxyl groups in the glucose residues constituting glucan are methylated, and then the completely methylated glucan is hydrolyzed. Next, the methylated glucose obtained by hydrolysis is reduced to produce methylated glucitol in which the mutarotomer is eliminated, and further, the free hydroxyl group in the methylated glucitol is acetylated to obtain partially methylated glucitol acetate (in addition, the acetylated site and the notation of "glucitol acetate" are sometimes omitted and simply referred to as "partial methylation"). By analyzing the obtained partially methylated product by gas chromatography, the percentage (%) of the peak area of each partially methylated product derived from the glucose residue with different bonding patterns in the glucan in the total peak area of all partially methylated products in the gas chromatogram can be shown. Furthermore, the existence ratio of glucose residues with different bonding patterns in the glucan, that is, the existence ratio of each glucoside bonding, can be determined from the peak area %. In addition, the "ratio" for partially methylated products shall mean the "ratio" of the peak area in the gas chromatogram of methylation analysis, and the "%" for partially methylated products shall mean the "area %" in the gas chromatogram of methylation analysis.

<Mw/Mn (mass average molecular weight/number average molecular weight)> The term "Mw/Mn" in this manual means the value obtained by dividing the mass average molecular weight (Mw) by the number average molecular weight (Mn). In addition, Mw/Mn is an index that indicates the spread (dispersion) of the molecular weight distribution. The larger the value, the wider the molecular weight range of the molecular species. The closer the value is to 1, the more uniform the molecular weight of the molecular species. Incidentally, Mw/Mn can be calculated by subjecting the sample to gel filtration high performance liquid chromatography (gel filtration HPLC), analyzing the chromatogram using molecular weight distribution analysis software, and obtaining the mass average molecular weight (Mw) and number average molecular weight (Mn).

<Bonded water, intermediate water and free water> The so-called "bonded water" in this manual refers to water molecules bound to specific molecules through hydrogen bonds. Since it does not freeze even at 0°C, it is also called "non-freezing water". On the other hand, water molecules that can freely change their state depending on environmental conditions such as temperature and humidity and adopt molecular behaviors different from bonded water are called "free water". The so-called "intermediate water" refers to water molecules with properties intermediate between "bonded water" and "free water".

2. Appearance and structural characteristics of the branched α-glucan mixture The branched α-glucan mixture contained as an active ingredient in the dehydration inhibitor of the present invention is a branched α-glucan mixture having the following characteristics (A) to (E); (A) Glucose is used as a constituent sugar. (B) The non-reducing terminal glucose residue at one end of a linear glucan having a glucose polymerization degree of 3 or more obtained by α-1,4 bonding has a branched structure having a glucose polymerization degree of 1 or more obtained by bonding other than α-1,4 bonding. (C) Isomaltose is produced by digestion with isomaltoglucanase. (D) The ratio of glucose residues derived from α-1,4 bonds to glucose residues derived from α-1,6 bonds is in the range of 1:0.6 to 1:4. (E) The total of glucose residues derived from α-1,4 bonds and glucose residues derived from α-1,6 bonds accounts for more than 60% of all glucose residues.

That is, the branched α-glucan mixture is an α-glucan having glucose as the sole constituent sugar (characteristic (A)), and a non-reducing terminal glucose residue at one end of a linear glucan chain having a glucose polymerization degree of 3 or more linked via an α-1,4 bond has a branched structure having a glucose polymerization degree of 1 or more linked via a bond other than an α-1,4 bond (characteristic (B)). In addition, the so-called "non-reducing terminal glucose residue" means a glucose residue at the end of the glucan chain linked via an α-1,4 bond that does not show reducing properties. Furthermore, the branched α-glucan mixture has a characteristic of generating isomaltose by digestion with isomalto-glucanase (characteristic (C)).

The ratio of isomaltose produced by isomalto-glucanase digestion per solid content of the digested product represents the ratio of isomaltose structure obtained by isomalto-glucanase hydrolysis in the structure of branched α-glucan, and can be used as one of the indicators for characterizing the structure of the branched α-glucan mixture as a whole by enzyme means.

Furthermore, the branched α-glucan mixture is characterized in that it can be determined by methylation analysis, and has a ratio of glucose residues obtained by α-1,4 bonds to glucose residues obtained by α-1,6 bonds in the range of 1:0.6 to 1:4 (characteristic D), and the total of glucose residues obtained by α-1,4 bonds and glucose residues obtained by α-1,6 bonds accounts for more than 60% of all glucose residues (characteristic E).

The ratio of α-1,4-bonded glucose residues to α-1,6-bonded glucose residues (Characteristic (D)) and the ratio of α-1,4-bonded glucose residues and α-1,6-bonded glucose residues to all glucose residues (Characteristic (E)) obtained by methylation analysis can be used as one of the indicators for chemically characterizing the structure of the branched α-glucan mixture as a whole.

The so-called "α-1,4-bonded glucose residue" in (D) and (E) above refers to the glucose residue that is bonded to other glucose residues only through the hydroxyl groups bonded to the carbon atoms at the 1- and 4-positions, and is detected as 2,3,6-trimethyl-1,4,5-triacetylglucitol in the methylation analysis. In addition, the so-called "α-1,6-bonded glucose residue" in (1) and (2) above refers to the glucose residue that is bonded to other glucose residues only through the hydroxyl groups bonded to the carbon atoms at the 1- and 6-positions, and is detected as 2,3,4-trimethyl-1,5,6-triacetylglucitol in the methylation analysis.

The so-called "the ratio of glucose residues derived from α-1,4 bonds to glucose residues derived from α-1,6 bonds is in the range of 1:0.6 to 1:4" specified in (D) above means that in the methylation analysis of the branched α-glucan mixture, the ratio of 2,3,6-trimethyl-1,4,5-triacetylglucitol to 2,3,4-trimethyl-1,5,6-triacetylglucitol is in the range of 1:0.6 to 1:4. In addition, the so-called "the total of glucose residues derived from α-1,4 bonds and glucose residues derived from α-1,6 bonds accounts for more than 60% of all glucose residues" specified in the above (E) means that in the methylation analysis of the branched α-glucan mixture, the total of 2,3,6-trimethyl-1,4,5-triacetylglucitol and 2,3,4-trimethyl-1,5,6-triacetylglucitol accounts for more than 60% of the partially methylated glucitol acetate.

The branched α-glucan mixture may be produced by any method provided that it has the characteristics (A) to (E) above. As an appropriate example, the branched α-glucan mixture obtained by the production method disclosed in the pamphlet of International Publication No. WO2008/136331 can be cited. In addition, the branched α-glucan mixture may also be an enzyme digest obtained by allowing an enzyme such as starch glucosidase (glucoamylase) to act on the aforementioned branched α-glucan mixture, a fraction obtained by fractionating the aforementioned branched α-glucan mixture by size exclusion analysis, or a reduced product obtained by reducing the glucose residue at the reducing end of the aforementioned branched α-glucan mixture by hydrogenation.

In addition, as a more appropriate aspect of the branched α-glucan mixture, a branched α-glucan mixture having a water-soluble dietary fiber content of 40% by mass or more as determined by the high performance liquid chromatography method (enzyme-HPLC method) described herein can be cited. The water-soluble dietary fiber content indicates the content of α-glucan that is not decomposed by α-amylase and amyloglucosidase (glucoamylase), and can be used as one of the indicators for characterizing the structure of the branched α-glucan mixture as a whole by enzyme means.

In addition, the glucose polymerization degree of the branched α-glucan mixture is usually 6 to 430, and the value (Mw/Mn) obtained by dividing the mass average molecular weight (Mw) of the branched α-glucan mixture by the number average molecular weight (Mn) is usually 20 or less. The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained using, for example, size exclusion analysis. In addition, the glucose polymerization degree can be obtained by subtracting 18 from the mass average molecular weight (Mw) and dividing by 162.

The glucose polymerization degree refers to the number of glucose residues constituting the glucan molecule, and can be used as one of the indices for characterizing the structure of the branched α-glucan mixture as a whole by physical means.

Among the branched α-glucan mixtures, the one that can be most suitably used as a dehydration inhibitor is the product name "Fibryxa (registered trademark)" manufactured and sold by Hayashihara Co., Ltd. In the same mixture, the existence ratio of glucose residues with different bonding patterns is, on average, about 50% for α-1,6 bonding, and about 10% for α-1,3,6 bonding and α-1,4,6 bonding combined, which fully satisfies the above-mentioned characteristics (A) to (E).

3. Use and dosage of the dehydration inhibitor of the present invention The dehydration inhibitor of the present invention can be advantageously used in foods, cosmetics, pharmaceuticals, quasi-drugs, industrial products, etc., which are expected to reduce free water while maintaining the moisture content of the composition as a whole. In addition, the amount of the branched α-glucan mixture contained as an active ingredient in the dehydration inhibitor of the present invention is not particularly limited, for example, as long as the branched α-glucan mixture is contained in the range of 1 to 100 mass%. In addition, the lower limit is set to 1 mass% because if the content of the branched α-glucan mixture is lower than that, although it may not be completely ineffective, it becomes difficult to expect the dehydration inhibitory effect.

The blending amount of the dehydration inhibitor of the present invention can be arbitrarily set in foods, cosmetics, pharmaceuticals, quasi-drugs and industrial products without particular limitation according to its use or the intensity of the expected effect. Generally, the branched α-glucan mixture is blended into the target product in an amount within the range of 0.01 to 35% by mass, preferably 0.05 to 25% by mass, and more preferably 0.1 to 10% by mass.

When the dehydration inhibitor of the present invention is blended into a gel-like composition for the purpose of dehydration inhibition, although the appropriate range varies depending on the type or concentration of the gelling agent to be blended, for the present branched α-glucan mixture, it is usually blended into the product in the range of 0.2 to 30 mass %, preferably 0.5 to 20 mass %, and more preferably 1 to 5 mass %.

When the dehydration inhibitor of the present invention is blended into frozen desserts for the purpose of improving spoon penetration or looseness and melting in the mouth, the branched α-glucan mixture is usually blended into the product in an amount of 0.01 to 20% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. In particular, when good spoon penetration is required, the appropriate blending amount for exerting the effect of the dehydration inhibitor of the present invention varies depending on the composition of the frozen dessert. In the case of frozen desserts containing milk and dairy products, a blending amount of 0.2 to 20% by mass, more preferably 0.5 to 10% by mass, is usually selected. On the other hand, for frozen desserts that do not contain milk or dairy products and are mainly ice-based, a concentration range of 0.01 to 0.5 mass %, more preferably 0.05 to 0.25 mass %, is usually selected.

Furthermore, the dehydration inhibitor of the present invention may be a drug consisting only of the branched α-glucan mixture as an effective ingredient, but other materials may also be used in combination, such as water, starch, processed starch, polysaccharides, gelling agents, gelling aids, sweeteners, proteins, enzymes, peptides, amino acids, minerals, pastes, stabilizers, One or more of the following ingredients used in the fields of food, cosmetics, pharmaceuticals and industrial products: extenders, sizing agents, fillers, thickeners, surfactants, foaming agents, defoamers, pH adjusters, stabilizers, flame retardants, release agents, antimicrobial agents, colorants, fragrances, nutrients, flavoring agents, flavoring agents, pharmacological substances and physiologically active substances.

There is no particular limitation on the gelling agent and gelling aid used in combination with the dehydration inhibitor of the present invention, and the gelling agent and gelling aid commonly used in the fields of food, cosmetics, pharmaceuticals and industrial products can be used. Specifically, gelatin, collagen, pectin, agar, carrageenan, xanthan gum, locust bean gum, kelp gum, gum arabic, guar gum, tartrate The gelatin, tamarind seed gelatin, cattleya polysaccharide, psyllium seed gelatin, alginic acid, hyaluronic acid, starch, processed starch, dextrin, dextran, carboxyvinyl polymer, crosslinked polyacrylic acid, hydroxyethyl cellulose, carboxymethyl cellulose, sodium acrylate, etc. are used together to adjust the gel strength or the dehydration rate of the gel composition. Agar, carrageenan, and locust bean gelatin are particularly advantageous. As the carrageenan, any one having gelling ability can be used, and kappa-carrageenan can be preferably used.

In the dehydration inhibitor of the present invention, the branched α-glucan mixture used as an active ingredient has a water-soluble dietary fiber content of 40 mass % or more in a suitable embodiment as described above, and can be particularly suitably used in the case of designing a gel-like food with a high dietary fiber blending amount, etc. However, if the dehydration inhibitor of the present invention is blended into a gel-like composition at a high concentration, the gel surface may become rough and the eating texture (tongue touch) may be reduced. In this case, by using carrageenan and locust bean gum as gelling agents in the dehydration inhibitor of the present invention, dehydration is inhibited and a smooth gel-like food with good taste can be obtained without causing roughness on the gel surface or reducing the eating texture. Furthermore, as a result of examining various gelling agents, when the branched α-glucan mixture of the present invention is blended at a content of more than 15% by weight relative to the weight of the composition, a firm and strong property is exhibited when carrageenan and locust bean gum are used as gelling agents, while a soft and loose gel is completed when carrageenan and agar are used. Therefore, when the branched α-glucan mixture is highly blended, a wide range of gel hardness, touch, or eating feel can be achieved by combining carrageenan and locust bean gum and/or agar as gelling agents and appropriately setting the concentration and blending ratio of each gelling agent.

4. Experimental Examples and Examples of the Present Invention The present invention is described in more detail below based on experiments. In addition, in Experiments 1 to 5, a branched α-glucan mixture prepared by the method described in Example 3 described later (equivalent to the present branched α-glucan mixture) was used.

<Experiment 1: Effect of branched α-glucan mixture on dehydration rate of gel-like composition> It is known that sugars have an inhibitory effect on dehydration when mixed into gel-like composition, so the dehydration inhibitory effect of branched α-glucan mixture mixed into gel-like composition was compared with sucrose.

＜Experiment 1-1＞ As gelling agents, agar and κ-carrageenan, which are generally known to dehydrate more than other gelling agents, were used. The gel-like composition prepared using these gelling agents was mixed with sucrose or a branched α-glucan mixture, and the dehydration rate after 14 days was measured.

Agar (trade name 'ZL', manufactured by Ina Food Industry Co., Ltd.) or κ-carrageenan (trade name 'CSK-1', manufactured by Sanrongyuan FFI Co., Ltd.) was added to water at 2.0 mass % relative to the finished mass, and heated with a heater while stirring to completely dissolve. Then, sucrose or a branched α-glucan mixture was added at 15, 25 and 35 mass % relative to the finished mass, respectively, and dissolved, and then water was added to adjust the total amount. Each gel solution was filled into a conical plastic jelly cup at about 60 g each, and stored at 4°C for 14 days to prepare a test sample. The same procedure was performed to prepare a gel without sugar, except that sugar was not added together with the two gelling agents, agar and κ-carrageenan, to prepare a control sample.

On the 14th day after the sample preparation, the surface dehydration rate was measured as follows. First, the sample was left at room temperature for 2 hours, and the sample weight (A) including the jelly cup (outer packaging weight: C) was measured. Then, the gel was taken out of the jelly cup, and the water on the surface of the gel was wiped off with a paper towel. The gel weight (B) was measured, and the dehydration amount (A-B-C) was calculated. Divided by the original gel weight (A-C), the dehydrated water amount per gel mass was calculated, that is, the surface dehydration rate. The results of the measurement of three specimens of each sample are shown in Table 1. The surface dehydration rates of the control sample and the sample with added sugar were statistically analyzed by t-test, and the risk ratio p<0.05 was considered to be significantly different, and p<0.05 and p<0.01 are indicated by * and ** in the table, respectively. In addition, the surface dehydration rates of each gel mixed with a mixture of sucrose and branched α-glucan at the same concentration were also statistically analyzed by t-test, and p<0.05 and p<0.01 are indicated by # and ## in the table, respectively.

As shown in Table 1, sucrose, which is known to have a dehydration inhibitory effect, showed a significant dehydration inhibitory effect when blended at 25 and 35 mass % in 2.0 mass % agar gel compared with a control gel containing no sucrose. Similarly, in 2.0 mass % κ-carrageenan gel, by blending sucrose in a range of 15 to 35 mass %, a significant dehydration inhibitory effect was also shown relative to the control gel. In contrast, when a branched α-glucan mixture was added instead of sucrose, the dehydration rate was significantly reduced at 15 and 25 mass % of the blending ratio in the case of agar gel compared to the control without adding the branched α-glucan mixture, and the degree of reduction, that is, the dehydration inhibitory effect of the branched α-glucan mixture was significantly higher than that of sucrose. At 35 mass %, although the effect was slightly weakened, even so, the dehydration inhibitory effect was sufficient when compared to the control. In the case of κ-carrageenan gel, the dehydration inhibitory effect of the branched α-glucan mixture was also significantly higher than that of sucrose, and the dehydration inhibitory effect was shown to be dosage-dependent in the blending range of 15 to 35 mass %.

These results show that the branched α-glucan mixture inhibits the surface dehydration of the gel-like composition more strongly than sucrose in the concentration range of 15 to 35 wt % in agar and κ-carrageenan gels.

<Experiment 1-2> The gel strength and dehydration rate were measured when the blending concentration of the gelling agent and the branched α-glucan mixture was lower than that of the above-mentioned Experiment 1-1.

Agar (trade name 'ZL', manufactured by Ina Food Industry Co., Ltd.) was added to water in an amount of 1.0 mass % relative to the finished mass, and heated with a heater while stirring to completely dissolve it. Next, the branched α-glucan mixture was added in amounts of 5, 10, 15 and 20 mass % relative to the finished mass, and after it was dissolved, water was added to adjust the total amount. Hereinafter, each gel solution was processed in the same manner as Experiment 1-1 to prepare the test sample. In addition, the control sample was prepared in the same manner except that the branched α-glucan mixture was not added. Each gel solution was filled in a conical plastic jelly cup at about 60 g each and stored in a refrigerator at 4°C to prepare the test sample. The gel strength was measured on the next day, and the surface dehydration rate was measured after 14 days.

The surface dehydration rate was measured according to Experiment 1-1. The gel strength was measured using a creep tester (RE2-33005C, manufactured by Yamaden Co., Ltd.). A cylindrical plunger with a diameter of 16 mm was pressed vertically at a speed of 1 mm per second on the gel taken out of the jelly cup. The maximum load at the fracture point at 90% compression was recorded as the fracture load.

The results of measuring the surface dehydration rate for three specimens of each sample and the breaking load for one specimen of each sample are shown in Table 2. The surface dehydration rate was analyzed by t-test for significant differences from the control sample to which the branched α-glucan mixture was not added, and a risk ratio of p<0.05 was considered to be significantly different. p<0.05 and p<0.01 are shown in the table with * and **, respectively.

As shown in Table 2, in the 1.0 mass% agar gel, the gel blended with the branched α-glucan mixture also showed a significant dehydration inhibitory effect, and the dehydration rate decreased in a dosage-dependent manner until 15 mass% was reached. On the other hand, the gel strength increased by blending 5 mass% of the branched α-glucan mixture, but as the concentration became higher, the strength decreased in a dosage-dependent manner. However, this change was small and did not have a significant effect on the actual gel strength.

These results indicate that the branched α-glucan mixture, when used in an amount ranging from 5 to 20% by weight, can exert a dehydration-inhibiting effect without affecting the gel strength even in a soft gel-like composition prepared with a low concentration of a gelling agent.

<Experiment 2: Effect of blending water-soluble polysaccharides on the dehydration rate of gel-like compositions> Secondly, the dehydration inhibitory effect of blending a branched α-glucan mixture or various water-soluble polysaccharides in a low dosage into a gel-like composition was examined. Agar and κ-carrageenan were used as gelling agents as in Experiment 1, and gels were prepared in such a way that the blending concentration of various polysaccharides became 2.5 mass %, and the dehydration rate after 14 days was measured. The branched α-glucan mixture used was the same as that used in Experiment 1.

In the experiment, in addition to the branched α-glucan mixture (mass average molecular weight 4,860), indigestible dextrin (trade name "Fibersol 2", sold by Matsutani Chemical Industry Co., Ltd., mass average molecular weight 2,910), indigestible dextrin (trade name "Nutriose FB06", sold by Roquette Japan Co., Ltd., mass average molecular weight 4,610), inulin (trade name "Orafti GR", sold by DKSH Japan Co., Ltd., mass average molecular weight 2,950) and polydextrose (trade name "Lytess II", manufactured by Danisco Japan Co., Ltd., mass average molecular weight 1,560) were used. In addition, these five polysaccharides are all classified as water-soluble dietary fibers.

Agar gel was prepared by adding agar to the aqueous solution of each polysaccharide so that the amount was 0.5% by mass relative to the final mass, and then heating with a heater while stirring to boil for 15 minutes. Then, water was added to adjust the mass so that the polysaccharide content was 2.5% by mass. In addition, in the case of using a branched α-glucan mixture as the polysaccharide, the same method as above was used, except that the polysaccharide content was 2.5% by mass, and the polysaccharide (branched α-glucan mixture) content was also adjusted to 1.0% by mass. After each gel solution was heated to 50°C, 60 g of each solution was filled in a ziplock bag (Lamizip ZL-9) and stored in a refrigerator for 14 days to prepare a test sample. Instead of agar, κ-carrageenan was used to prepare various gel solutions in the same manner. However, in the case of using κ-carrageenan gel, κ-carrageenan was added to the aqueous solution of each polysaccharide so as to be 0.8 mass % relative to the final mass, stirred in a hot water bath, and heated for 15 minutes from the time when the aqueous solution reached 85°C to dissolve it. Then, water was added to adjust the mass so that the polysaccharide content was 2.5 mass % in the same manner as in the case of agar gel, and 60 g of each was filled in a ziplock bag and stored at 4°C for 14 days to prepare a test sample. A gel without polysaccharide was prepared in the same manner except that the polysaccharide was not added together with the two gelling agents to prepare a control sample.

On the 14th day from the preparation of the sample, the surface dehydration rate was measured as follows. The sample was taken out of the ziplock bag, and the water on the surface of the gel was wiped with a paper towel whose outer packaging mass was measured in advance for 30 seconds. After the water remaining in the bag was absorbed by the paper towel, the increased mass of the paper towel was measured with an electronic balance. This increased mass was regarded as the mass of water obtained from the dehydration of the gel, and the mass % of the dehydrated water mass per gel mass was calculated and regarded as the dehydration rate. The results of measuring 5 samples of each sample for agar gel and 3 samples of each sample for κ-carrageenan gel are shown in Table 3. The results were statistically analyzed using the t-test, and a risk ratio of p<0.05 was considered to be significantly different. p<0.05 and p<0.01 are indicated with * and **, respectively, in the table.

As shown in Table 3, in the 0.5 mass% agar gel, the dehydration rate of the gel blended with the branched α-glucan mixture alone was significantly reduced, and the dehydration was inhibited in a manner dependent on the amount of the branched α-glucan mixture used. On the other hand, in the gel blended with 2.5 mass% inulin, the dehydration rate was significantly increased. In the κ-carrageenan gel, the dehydration rate of the gel blended with 2.5 mass% branched α-glucan mixture and the gel blended with 2.5 mass% indigestible dextrin (Fibersol 2) was significantly reduced, but the dehydration inhibition ability was higher for the branched α-glucan mixture. Nutriose FB06, another indigestible dextrin, also showed a tendency to inhibit dehydration, but the inhibitory effect was not significant.

These results indicate that the branched α-glucan mixture inhibits the dehydration of agar and κ-carrageenan gel compositions more strongly than other water-soluble dietary fibers.

<Experiment 3: Effect of branched α-glucan mixture on dehydration rate of sucrose-added gel> In the case of juice-flavored jelly foods, sucrose, glucose, or high fructose syrup are generally mixed with sweeteners, and their concentrations affect the shape retention or dehydration of the gel composition. Therefore, an experiment was conducted to investigate whether the branched α-glucan mixture has a dehydration inhibitory effect in κ-carrageenan gel with sucrose added. The branched α-glucan mixture used was the same as that used in Experiment 1.

<Experiment 3-1> The sample was prepared as follows. 8 parts by mass of κ-carrageenan and 25 parts by mass of a branched α-glucan mixture were mixed in advance, and 967 parts by mass of water was added and heated to 85°C while stirring to dissolve for 15 minutes. After the residual heat was removed to 60°C, 50 ml of the mixture was filled into a plastic cup, solidified at room temperature, and stored at 4°C for 14 days to prepare a sample. The surface dehydration rate was measured. This sample was used as a control (sucrose concentration 0% by mass). Three samples with different sucrose concentrations (sucrose concentrations of 2.5%, 10%, and 40% by mass) were prepared in the same manner except that 25, 100, and 400 parts by mass of the 967 parts by mass of water were replaced with sucrose, and the surface dehydration rate was measured. The surface dehydration rate was measured in the same manner as in Experiment 1. The results of the measurement of 5 specimens of each sample are shown in Table 4. The results were statistically analyzed using the t-test, and a risk ratio of p < 0.05 was considered to be significantly different. In the gel composition of the same sucrose concentration, the significant difference caused by the presence or absence of the branched α-glucan mixture was indicated by ** and **, p < 0.01 and p < 0.001, respectively, and the significant difference caused by the presence or absence of sucrose addition in the gel composition without branched α-glucan was indicated by #, p < 0.001.

As shown in Table 4, the dehydration of the κ-carrageenan gel mixed with sucrose was inhibited compared with the κ-carrageenan gel without sucrose, but the dehydration rate was significantly reduced by containing 2.5 mass% of the branched α-glucan mixture.

<Experiment 3-2> In the above Experiment 3-1, in the κ-carrageenan gel containing sucrose, a significant dehydration inhibitory effect was observed in the present branched α-glucan mixture. On the other hand, in the above Experiment 2, in the κ-carrageenan gel, a dehydration inhibitory effect was confirmed for both the branched α-glucan mixture and the indigestible dextrin (Fibersol 2). Therefore, in order to compare the effects of the two, the dehydration inhibitory effect in the gel-like composition containing orange juice to which sucrose was added was measured next.

That is, 25 parts by mass of sucrose, 25 parts by mass of the same branched α-glucan mixture as used in Experiment 1, and 8 parts by mass of κ-carrageenan were mixed into powders in advance, and 942 parts by mass of orange juice (trade name "Pom Juice", sold by Ehime Beverage Co., Ltd.) was added to prepare a gel sample in the same manner as in Experiment 3-1. In addition, the gel sample was prepared in the same manner except that the branched α-glucan mixture was replaced with indigestible dextrin (Fibersol 2). As a control, orange jelly was prepared without these two polysaccharides and the blending amount of sucrose was increased to 50 parts by mass as a substitute. These samples were stored at 4°C for 5 days, and the surface dehydration rate was measured in the same manner as in Experiment 1. Similarly, the samples stored at 4°C for 14 days were also tested. The results are shown in Table 5. The results were statistically analyzed using the t-test, and a risk ratio of p < 0.05 was considered to be significantly different. The significant difference between the polysaccharide-blended orange jelly and the control orange jelly blended with 5 mass% sucrose is indicated by * in the table when p < 0.05.

As shown in Table 5, the κ-carrageenan gel prepared with orange juice with the addition of 5 mass% sucrose tended to decrease the dehydration rate during 5 days of storage at 4°C by replacing half of the sucrose with a branched α-glucan mixture, and significantly decreased during 14 days of storage. Meanwhile, in the orange gel jelly obtained by replacing half of the sucrose with indigestible dextrin (Fibersol 2), no inhibition of dehydration was observed on either the 5th or 14th day.

It is known that indigestible dextrin (Fibersol 2) and branched α-glucan have common properties in their structures, physical properties, and part of their physiological functions. On the other hand, according to methylation analysis, differences can be seen in the pattern or amount ratio of multi-branched bonds, so it can be inferred that the difference in the dehydration inhibitory effect is related to the difference in these structures. In this way, even if it is a similar water-soluble dietary fiber material, compared with other water-soluble dietary fibers, the present branched α-glucan mixture shows that it functions advantageously as a dehydration inhibitor, and even in a gel-like composition mixed with a large amount of carbohydrates, or a gel-like composition using pure fruit juice rich in vitamins, minerals, etc., it also has a significant dehydration inhibitory performance.

<Experiment 4: Improved eating texture of gel with highly blended branched α-glucan mixture> In the above-mentioned Experiment 1, it was clearly known that the branched α-glucan mixture can be blended into a gel-like composition at a high concentration of 35% by mass while maintaining the dehydration inhibition effect. On the other hand, since the branched α-glucan mixture has the property of being a water-soluble food fiber, it can be fully assumed that it can be blended into a gel-like food at a high concentration for the purpose of nutritional enhancement. Therefore, carrageenan jelly obtained by blending the branched α-glucan mixture at a high concentration (30% by mass) was prepared, and the gel strength, surface smoothness and eating texture when agar or locust bean gel was added were evaluated.

<Experiment 4-1: Comparison of the strength of gels with highly mixed branched α-glucan mixtures> The κ-carrageenan gel mixed with 30% by mass of the present branched α-glucan mixture was prepared according to Experiment 1. That is, κ-carrageenan (trade name "CSK-1", manufactured by Sanrongyuan FFI Co., Ltd.) was added to water in an amount of 2.0% by mass relative to the finished mass, and the mixture was heated with a heater while being stirred to completely dissolve. Then, the same branched α-glucan mixture as used in Experiment 1 was added in an amount of 30% by mass relative to the finished mass, and after dissolving, water was added to adjust the total amount. When κ-carrageenan was used in combination with other gelling agents as gelling agents, the gelling agent was dissolved in a solution of 1.0 mass% κ-carrageenan and 1.0 mass% agar, or in a solution of 1.0 mass% κ-carrageenan and 1.0 mass% locust bean gum (trade name "GENU (registered trademark) GUM type RL-200-J", manufactured by San Jing Co., Ltd.) instead of the above 2.0 mass% κ-carrageenan. Each gelling solution was filled in a conical plastic freezer cup in an amount of about 60 g, and stored at 4°C overnight to prepare a sample. The gel strength of each sample was measured three times using a creep meter according to the method of Experiment 1-2. The breaking load of the gel was used as an index of gel strength and is shown in Table 6. At the same time, a small number of sensory taste assessors evaluated the texture of each sample, such as the feel, chewiness, and tongue feel, and recorded the characteristics in the table.

As shown in Table 6, in the gel-like composition obtained by blending the branched α-glucan mixture at 30 mass%, the combination of gelling agents can achieve the contrasting textures of a firm and strong gel and a soft gel. Therefore, it is considered that the hardness or strength of the gel, and further, the elasticity and other textures can be changed in a wide range by the combination and blending of gelling agents. On the other hand, when the branched α-glucan mixture was blended into carrageenan gel at a high concentration, it was confirmed that the gel surface became rough and the smoothness of the gel was lost. However, this problem was solved by using locust bean gum as a gelling agent.

<Experiment 4-2: Sensory test> The improvement in the texture of the gel of the highly mixed branched α-glucan mixture caused by the combined use of κ-carrageenan and locust bean gum, which was clearly known in Experiment 4-1, was confirmed by a sensory test. The sensory test was conducted by 10 trained male and female tasters (7 females and 3 males) on the appearance (smoothness) and eating feel (tongue touch) of the jelly containing orange juice and the highly mixed branched α-glucan mixture containing 0.5 mass% of κ-carrageenan and locust bean gum as gelling agents, and the same jelly obtained by gelling with only 1.0 mass% of κ-carrageenan.

The jelly was prepared in the following order. 150 parts by mass of the branched α-glucan mixture obtained by the method of Example 1, 0.25 parts by mass of sucralose, and 5.0 parts by mass of κ-carrageenin (trade name "Carrageenin CSK-1", sold by Sanrongyuan FFI Co., Ltd.) as a gelling agent were added to 250 parts by mass of water and heated while mixing to bring to a boil, and the boiling state was maintained for more than 5 minutes. The liquid was cooled to about 70°C, 5 parts by mass of a 50% by mass citric acid aqueous solution, 100 parts by mass of orange juice, and 1 part by mass of orange flavor were added, and the final weight was adjusted to 500 parts by mass with water, filled in a jelly cup container, and sterilized at 80°C for 30 minutes. Then, a jelly with orange flavor was obtained by refrigerating and storing at 4°C to prepare a control sample. Next, a sample was prepared by the same operation except that half the amount (2.5 parts by mass) of κ-carrageenan as a gelling agent was replaced with locust bean gum to prepare a test sample.

In the sensory evaluation, each panelist evaluated the smoothness of the cross-section of the jelly exposed by scooping up a piece of jelly with a metal spoon, and evaluated the feeling of eating (tongue touch) by crushing the jelly with the tongue in the mouth. For both items, the evaluation of the control sample was set to 3 points (median value), and the evaluation of the test sample was set to 5 stages. The average scores of the 10 panelists (rounded to the first decimal place) were summed up according to the following criteria, and the results are shown in Table 7. For the control and the test samples, statistical analysis was performed using the t-test, and the risk rate p < 0.05 was considered to be significantly different, and p < 0.01 was indicated by ** in the table. In addition, photographs of representative gel cross-sections of the control and test samples are shown in Figure 1. ＜Grading Criteria＞ 5 points: Considerably superior to the control 4 points: Relatively superior to the control 3 points: Equal to the control 2 points: Relatively inferior to the control 1 point: Considerably inferior to the control

As shown in Table 7, the test sample containing 30 mass% of the branched α-glucan mixture and replacing half of the κ-carrageenan as a gelling agent with locust bean gum has a smoother appearance of the gel cross section than the control jelly gelled with κ-carrageenan alone, and has a good eating feel when crushed with the tongue. FIG1 shows cross-sectional photographs of the control and test jelly. In the control jelly, the roughness of the gel is manifested as a wavy cross section, while the test sample presents a very smooth gel cross section, and a clear difference can be seen visually. From these results, it is clearly known that when a branched α-glucan mixture is blended into a gel-like composition at a high concentration, by combining locust bean gum with κ-carrageenan used as a gelling agent, the roughness of the gel surface is suppressed, and the smoothness, appearance, and eating feel are improved, thereby providing a better texture for jelly foods.

<Experiment 5: Improvement of the eating texture of lactic acid ice> In the above-mentioned experiments 1 to 3, it was found that the branched α-glucan mixture has a dehydration inhibitory effect on the gel-like composition. In order to investigate whether this property can be applied to other compositions with higher water content, it was mixed into lactic acid ice and the properties of the composition were evaluated.

The sample was prepared as follows. 1.0 or 2.5 parts by weight of the same branched α-glucan mixture as used in Experiment 1 was added to 14 parts by weight of sugar, and then 0.2 parts by weight of an emulsifier (trade name 'Homogen', sold by San-Ei-Yuan FFI Co., Ltd.) and 0.3 parts by weight of a stabilizer (trade name 'San Best NN-305', sold by San-Ei-Yuan FFI Co., Ltd.) were added and mixed. Next, 58 parts by weight of milk, 15 parts by weight of fresh cream, and 10 parts by weight of egg yolk were added, and after heating to 85°C and sterilizing, the mixture was mixed for 10 minutes with a mixer to perform pre-emulsification. Then, a high-pressure homogenizer was used to emulsify the mixture at 150 kg/ ^cm2 , and the mixture was cooled and frozen at -20°C while being stirred in an ice cream freezer to produce lactic acid ice. In addition, lactic acid ice obtained by the same method as above except that no branched α-glucan was blended was used as a control.

The sensory test was conducted by 6 trained tasters (3 males and 3 females) and the results are shown in Table 8. The spoon penetration, melting feeling in the mouth and flavor were evaluated in the form of relative evaluation when compared with the control according to the following criteria. ◎ was regarded as 3 points, ○ was regarded as 2 points, △ was regarded as 1 point, and × was regarded as 0 points. The average score of the 6 tasters (rounded off to the first decimal place) was recorded in Table 8 as the evaluation of the sample. In addition, the overrun was calculated by the following formula. Expansion rate (%) = [(Wm-Wp)/Wp] × 100 Wm: Weight of the mixture before freezing (g) Wp: Weight of the product (ice milk) of the same volume (g) ＜Spoon penetration＞ ◎: Good spoon penetration ○: Slightly better spoon penetration △: Spoon penetration equal to the control ×: Poorer spoon penetration compared to the control ＜Melting in the mouth＞ ◎: Smooth melting in the mouth ○: Slightly smooth melting in the mouth △: Same melting in the mouth as the control ×: Poorer melting in the mouth than the control ＜Flavor＞ ○: Enhanced flavor △: Same flavor as the control ×: Poorer flavor than the control

As shown in Table 8, the lactic acid ice blended with the branched α-glucan mixture has better spoon penetration and melting feeling in the mouth than the control. In the present branched α-glucan, the property of partially generating uneven ice crystal packing morphology can be confirmed together with the stabilization of ice crystals by microscopic observation, and it is presumed that these characteristics improve the spoon penetration or melting feeling in the mouth of frozen desserts such as ice cream.

<Experiment 6: Evaluation of the hydration capacity of water-soluble polysaccharides by pulse NMR> From the above-mentioned experiments 1 to 3, it is clear that the branched α-glucan mixture has a dehydration inhibition effect and a food texture improvement effect. The components used in these experiments all have a high water content. The interaction between the branched α-glucan mixture and water is considered to be an important factor in the performance. Therefore, pulse NMR is used to examine the interaction between water-soluble polysaccharides and water molecules in the aqueous solution state.

In the determination, in addition to the branched α-glucan mixture and indigestible dextrin (Fibersol 2) used in Experiment 1, dextran (trade name "Dextran T3.5", sold by Pharmacosmos, average mass molecular weight 3,500) was also used. Indigestible dextrin (Fibersol 2) is used as a model of a multi-branched polysaccharide with α-1,4 bonds as the main component and α-1,2 and α-1,3 bonds in addition to α-1,6 bonds. Indigestible dextrin is a water-soluble dietary fiber prepared by enzymatic hydrolysis of roasted dextrin obtained by treating starch with hydrochloric acid using α-amylase and glucoamylase. In addition, dextran was used as a model for polysaccharides containing essentially only α-1,6 bonds.

JMM-MU25 manufactured by JEOL Ltd. was used as a pulse NMR analyzer. Each polysaccharide was dissolved in ultrapure water at 5, 10, 15, 20 and 25 mass to volume %, and 1 ml was transferred to a dedicated measuring glass tube for measurement. Ultrapure water was used for control. The measurement parameters for the spin-spin relaxation time (T2 relaxation time) measurement are RF pulse interval (Pi1) set to 1.0 milliseconds, signal integration times (SCAN) set to 8 times, pulse train repetition time (REP) set to 5.0 seconds, the number of times the RF pulse is continuously generated (LOOP) set to 1,000 times, and the pulse width (PW1) set to 2.0 microseconds. The measurement is carried out at room temperature. In the fitting of the T2 relaxation time to the complex components, the analysis software attached to JNM-MU25 is used to calculate the T2 relaxation time of each component and its component ratio (percentage) using the calculation formula through the Lorentz function.

In this measurement, for example, as shown in the Journal of the Japanese Society of Crop Science, Vol. 77, No. 4, pp. 527-532, "Monitoring the Temperature Response of Crops by ¹ H-NMR" (Mari Inoue, 2008), the free induced decay signal can be separated into three components with different T2 relaxation times, namely, a short component, an intermediate component, and a long component, and each component is interpreted as representing bound water, intermediate water, and free water in order from the one with the shorter T2 relaxation time. A graph comparing the ratio of the short component representing the amount of bound water in the polysaccharide aqueous solution is shown in FIG2.

As shown in FIG2 , in the aqueous solution of the branched α-glucan mixture, the ratio of the short component considered to represent the amount of bonded water is significantly larger than that of other polysaccharides in the range of 5 to 25 mass to volume %, and the value is higher than that of dextran composed only of α-1,6 bonds which are generally considered to easily form hydrogen bonds with water molecules.

If the estimated bound water amount of each polysaccharide in a 15 mass to volume % aqueous solution is calculated based on the short component ratio of T2 relaxation time shown in Figure 2, ignoring the presence of protons derived from polysaccharides, the bound water amount per mass of each polysaccharide is 0.302 g/g for the branched α-glucan mixture, 0.256 g/g for the indigestible dextrin (Fibersol 2), and 0.266 g/g for dextran, indicating that the branched α-glucan mixture retains more bound water than dextran by more than 10%. Although the detailed molecular behavior of this phenomenon is unknown, it is speculated that the complex multi-branched structure unique to the branched α-glucan mixture helps to replenish bound water, which is the main reason for the higher dehydration inhibition effect when mixed into gel-like compositions, etc. In addition, the factors that show characteristic texture changes in other uses are also considered to be related to the hydration of this structure as an important factor.

The following examples will be used to describe in detail the dehydration inhibitor of the present invention using the branched α-glucan mixture as an active ingredient and its use, but the present invention is not limited to these examples. [Example 1] ＜Dehydration inhibitor＞

According to the method described in Example 5 of International Publication No. WO2008/136331, sodium bisulfite was added to a 27 mass % corn starch liquefaction liquid (hydrolysis rate 3.6%) in a manner to make the final concentration 0.3 mass %, and calcium chloride was added in a manner to make the final concentration 1 mM, and then cooled to 50°C. Per 1 gram of solids, 11.1 units of Bacillus circulans PP710 (FERM The concentrated crude enzyme solution of α-glucosidase of BP-10771) was further reacted at 50°C and pH 6.0 for 48 hours. The reaction solution was kept at 80°C for 60 minutes, cooled, filtered and the obtained filtrate was decolorized with activated carbon according to the usual method, desalted and purified by H-type and OH-type ionic resins, concentrated and spray dried to produce a branched α-glucan mixture. In addition, the obtained branched α-glucan mixture was analyzed by the α-glucosidase and glucoamylase digestion test method described in paragraph 0080 of the International Publication No. WO2008/136331, the methylation analysis method described in paragraphs 0076 to 0078, the isomalto-glucanase digestion test method described in paragraph 0079, and the high performance liquid chromatography method (enzyme-HPLC method) for determining the water-soluble dietary fiber content described in paragraphs 0069 to 0075, and the results showed the following characteristics (A) to (D). (A) Glucose is used as the constituent sugar. (B) The non-reducing terminal glucose residue at one end of a linear glucan having a glucose polymerization degree of 3 or more linked by an α-1,4 bond has a branched structure having a glucose polymerization degree of 1 or more linked by a bond other than an α-1,4 bond. (C) Digestion with isomalto-glucanase produces 37% isomaltose in solids per digest. (D) The water-soluble dietary fiber content is 80.2% by mass.

Furthermore, the analysis results of the above-mentioned methylation analysis method show that the branched α-glucan mixture has the following characteristics (E) to (O) in addition to the above-mentioned characteristics. (E) The ratio of glucose residues obtained by α-1,4 bond to glucose residues obtained by α-1,6 bond is 1:2.5. (Hex) The total of glucose residues obtained by α-1,4 bond and glucose residues obtained by α-1,6 bond is 69.3% of all glucose residues. (Hept) Glucose residues obtained by α-1,3 bond are 2.3% of all glucose residues. (Oct) Glucose residues obtained by α-1,3,6 bond are 6.0% of all glucose residues.

Furthermore, the molecular weight distribution of the obtained branched α-glucan mixture was analyzed by the conventional gel filtration HPLC method described in paragraph 0081 of the international publication No. WO2008/136331. The results showed that the branched α-glucan mixture had the following characteristics of (nonane) and (decane) in addition to the above characteristics. The mass average molecular weight of (nonane) was 4,430. The Mw/Mn of (decane) was 2.0.

As described above, the branched α-glucan mixture obtained in this example satisfies the characteristics (A) to (E) described above for characterizing the branched α-glucan mixture.

In addition, the branched α-glucan mixture obtained in this example also satisfies the characteristics (F) and (G) mentioned above for characterizing the branched α-glucan mixture.

Furthermore, the branched α-glucan mixture satisfies the characteristic that Mw/Mn is less than 20.

This product can be blended into food, cosmetics, pharmaceuticals, etc., so it can be used alone or mixed with other suitable ingredients and widely used as a dehydration inhibitor. In addition, it is highly water-soluble and its aqueous solution is colorless and transparent. Since food fiber content is high, it can also be blended into food for the purpose of nutritional enhancement. This product is a white powder, which is tasteless/odorless in itself, does not absorb moisture or change color even at room temperature, and is stable for more than 1 year. [Example 2] ＜Dehydration inhibitor＞

According to the method described in Example 3 of International Publication No. WO2008/136331, a branched α-glucan mixture powder was prepared. In addition, the obtained branched α-glucan mixture powder has the following characteristics (A) to (D). (A) Glucose is used as a constituent sugar. (B) The non-reducing terminal glucose residue at one end of a linear glucan with a glucose polymerization degree of 3 or more obtained by α-1,4 bonding has a branched structure with a glucose polymerization degree of 1 or more obtained by bonding other than α-1,4 bonding. (C) Isomaltose is produced by digestion with isomaltoglucanase at a solid content of 36.5% by mass per digest. (D) The water-soluble dietary fiber content determined by high performance liquid chromatography (enzyme-HPLC) is 79.4% by mass. (E) The ratio of glucose residues obtained by α-1,4 bond to glucose residues obtained by α-1,6 bond is 1:2.5. (F) The total of glucose residues obtained by α-1,4 bond and glucose residues obtained by α-1,6 bond accounts for 68.4% of all glucose residues. (G) Glucose residues obtained by α-1,3 bond account for 2.6% of all glucose residues. (H) Glucose residues obtained by α-1,3,6 bond account for 6.8% of all glucose residues. (N) The mass average molecular weight is 4,097. (癸)Mw/Mn is 2.1.

As described above, the branched α-glucan mixture obtained in this embodiment satisfies the characteristics (A) to (E) described above for characterizing the branched α-glucan mixture. In addition, it also satisfies the characteristics (F) and (G) described above.

This product is similar to the branched α-glucan mixture prepared in Example 1, and can be mixed into food, cosmetics, pharmaceuticals, etc., so it can be widely used as a dehydration inhibitor. This product itself is tasteless and has no odor. It will not absorb moisture or change color even at room temperature and is stable for more than 1 year. [Example 3] ＜Dehydration inhibitor＞

According to the method described in Example 6 of International Publication No. WO2008/136331, a branched α-glucan mixture powder was prepared. In addition, the obtained branched α-glucan mixture powder has the following characteristics (A) to (D). (A) Glucose is used as a constituent sugar. (B) The non-reducing terminal glucose residue at one end of a linear glucan with a glucose polymerization degree of 3 or more obtained by α-1,4 bonding has a branched structure with a glucose polymerization degree of 1 or more obtained by bonding other than α-1,4 bonding. (C) Isomaltose is produced by digestion with isomaltoglucanase at a solid content of 32.7% by mass per digest. (D) The water-soluble dietary fiber content determined by high performance liquid chromatography (enzyme-HPLC method) is 80.7% by mass. (E) The ratio of glucose residues obtained by α-1,4 bond to glucose residues obtained by α-1,6 bond is 1:3.4. (F) The total of glucose residues obtained by α-1,4 bond and glucose residues obtained by α-1,6 bond accounts for 66.7% of all glucose residues. (G) Glucose residues obtained by α-1,3 bond account for 2.8% of all glucose residues. (H) Glucose residues obtained by α-1,3,6 bond account for 7.6% of all glucose residues. (N) The mass average molecular weight is 4,860. (癸)Mw/Mn is 2.1.

As described above, the branched α-glucan mixture obtained in this embodiment satisfies the characteristics (A) to (E) described above for characterizing the branched α-glucan mixture. In addition, it also satisfies the characteristics (F) and (G) described above.

This product is the same as the branched α-glucan mixture prepared in Example 1 or 2, and is a white powder with excellent fluidity. It is tasteless and odorless. In addition, it has low hygroscopicity, thermal stability, and good cold water solubility, so it can be mixed into food, cosmetics, pharmaceuticals, etc., and can be widely used as a dehydration inhibitor. [Example 4] ＜Dehydration inhibition of orange jelly＞

930 parts by mass of orange juice was heated to 85°C, 8 parts by mass of κ-carrageenin (trade name "Carrageenin CSK-1", sold by Sanrongyuan FFI Co., Ltd.), 20 parts by mass of sugar, and 50 parts by mass of the branched α-glucan mixture obtained by the method of Example 1 as a dehydration inhibitor were added thereto, and the mixture was dissolved while stirring for 15 minutes. After cooling to 60°C, 1 part by mass of 2-O-α-D-glucoside-L-ascorbic acid (trade name "Ascofresh", manufactured by Hayashibara Co., Ltd.) was added and dissolved while stirring. The mixture was filled into a container and stored in a refrigerator to obtain orange jelly. This product has a good taste and flavor. The branched α-glucan mixture has a water-retaining function. Even if it is stored at 4°C for 14 days, dehydration is inhibited, and it is a stable and high-quality orange jelly. [Example 5] ＜Dehydration inhibition of drinking jelly＞

842 parts by mass of water, 55 parts by mass of sugar, 15 parts by mass of trehalose (trade name "TREHA", manufactured by Hayashibara Co., Ltd.), 6 parts by mass of a gelling agent (trade name "Inagel DJ-88K", manufactured by Ina Food Industry Co., Ltd.), and 0.6 parts by mass of calcium lactate as a gelling aid were heated and dissolved at 85°C for 5 minutes, and 60 parts by mass of 5-fold concentrated orange juice, 15 parts by mass of a 15 mass-to-volume % citric acid aqueous solution, 1 part by mass of a flavor, and 5 parts by mass of the branched α-glucan mixture obtained by the method of Example 2 as a dehydration inhibitor were added thereto and mixed. The mixture is filled into a plastic container with a drinking mouth, sterilized at 80°C for 20 minutes, and then cooled to obtain an orange-flavored drinking jelly. This product has a good throat feel or eating texture, and also has a good flavor. The branched α-glucan mixture has a water-retaining effect, and is a high-quality drinking jelly with long-term dehydration suppressed. [Example 6] <Frozen cosmetic>

0.8 parts by mass of acrylate/alkyl acrylate (C10-30) crosslinked polymer (sold by Sumitomo Seika Co., Ltd., trade name "AQUPEC HV501"), which is a synthetic water-soluble thickener, was dissolved in 40 parts by mass of purified water, and an appropriate amount of sodium hydroxide aqueous solution was added to neutralize it and gelled. 6.0 parts by mass of concentrated glycerin, 3.0 parts by mass of pentanediol, 2.0 parts by mass of 1,3-butylene glycol, 3.0 parts by mass of dipropylene glycol, 1.5 parts by mass of polyethylene glycol-8, and 4.0 parts by mass of the branched α-glucan mixture of Example 1, which were pre-dissolved in 20 parts by mass of purified water, were added thereto and mixed thoroughly. Furthermore, an aqueous solution prepared by dissolving 2 parts by mass of ascorbic acid 2-glucoside (sold by Hayashibara Co., Ltd., trade name "AA2G (registered trademark)") in 10 parts by mass of purified water and adjusting the pH with an appropriate amount of sodium citrate aqueous solution is added thereto, and the mixture is thoroughly mixed. Finally, the pH is adjusted to 6.5 to 6.8 with sodium hydroxide aqueous solution, and the total mass is combined to 100 with purified water to prepare a weakly acidic whitening gel-like cosmetic. Due to the properties of the branched α-glucan mixture, dehydration is suppressed for a long time without affecting the color or fragrance of the gel, so it is a gel-like cosmetic with excellent feel and appearance. [Example 7] ＜Improvement of edible texture of slush＞

300 parts by mass of mango puree, 185 parts by mass of water, 35 parts by mass of trehalose, 70 parts by mass of granulated sugar and 1.5 parts by mass of the branched α-glucan mixture of Example 2 as a dehydration inhibitor were added, and the mixture was heated to completely dissolve the sugars. After the mixture was cooled, it was stirred while being frozen by a Sorbeture (slush maker) to make mango slush. In addition, a slush obtained by the same method as above except that the branched α-glucan mixture was not mixed was used as a control. Compared with the control, the slush of the present invention has less sandy feeling of ice crystals and is smoother, and the looseness in the mouth is also good. The branched α-glucan mixture can improve the eating feel of frozen desserts by changing the filling shape of ice crystals. [Example 8] ＜Improvement of ice cream quality＞

8 parts by mass of the branched α-glucan mixture of Example 1 was added to 3 parts by mass of skimmed milk powder, 10 parts by mass of sugar, and 4 parts by mass of trehalose and mixed thoroughly. Then, 55 parts by mass of milk, 18 parts by mass of fresh cream, 2 parts by mass of egg yolk, and 0.2 parts by mass of emulsifier were added and stirred with a mixer while heating until the solid content was completely dissolved. 0.1 parts by mass of vanilla essence was added as a flavoring. After heating and sterilizing at 90°C, the mixture was cooled again and ripened, and then frozen with an ice cream freezer while stirring to produce ice cream. In addition, slush obtained by the same method as above except that the branched α-glucan mixture was not mixed was used as a control, and both were stored in a freezer at -20°C. Compared with the control, the ice cream using the dehydration inhibitor of the present invention is uniform when spooned in, melts smoothly in the mouth, and has less frost on the surface during storage, showing high quality. [Example 9] ＜Improvement of the eating texture of frozen desserts containing fruit juice＞

30 parts by mass of sugar, 20 parts by mass of trehalose, 0.1 parts by mass of flavoring, and 0.5 parts by mass of the branched α-glucan mixture of Example 2 were completely dissolved in 600 parts by mass of grapefruit juice and 350 parts by mass of water. The mixture was stirred while being frozen by a Sorbeture (slush maker) to make grapefruit-flavored slush, which was then filled into a plastic cup and stored in a -20°C freezer. In addition, a frozen dessert obtained by the same method as above except that the branched α-glucan mixture was not mixed was used as a control. The frozen dessert of the present invention has a low solid content and sugar content, so it has a refreshing low sweetness and the eating feel of the ice itself is characteristic. Compared with the control, the ice cubes are smaller and the particles are consistent, and the looseness in the mouth is also good. [Example 10] ＜Improvement of the quality of Italian ice cream＞

22 parts by mass of sugar, 12 parts by mass of trehalose, 0.8 parts by mass of pectin, and 1 part by mass of the branched α-glucan mixture of Example 1 were added to 100 parts by mass of peach juice, 30 parts by mass of milk, and 35 parts by mass of water, and the mixture was stirred and mixed with a mixer while heating until the solid content was completely dissolved. After heat sterilization at 90°C, the mixture was cooled again and ripened, and then frozen with an ice cream freezer while stirring to produce Italian ice cream. In addition, Italian ice cream obtained by the same method as above except that the branched α-glucan mixture was not mixed was used as a control, and both were stored in a -20°C freezer. Compared with the control, the Italian ice cream using the dehydration inhibitor of the present invention is easier to pour with a spoon and melts smoothly in the mouth, showing high quality. [Example 11] <Gel base for external use on skin>

Blending ingredients (parts by weight) (1) Trioctanoin                          50.0 (2) Branched α-glucan mixture prepared in Example 1       8.0 (3) Polyglyceryl monomyristate-10                       5.2 (4) Polyglyceryl monostearate-10                                1.75 (5) Ascorbic acid 2-glucoside                           1.0 (6) Licorice extract                                           0.1 (7) Hyaluronic acid                                             0.25 (8) 1,2-Pentanediol                                       0.1 (9) Flavor Add appropriate amount of purified water to make the total amount 100 parts by mass.

The skin external refrigerant of the aforementioned blending example can continuously exert the desired effect by appropriately blending the pharmaceutical active ingredient. Due to the dehydration inhibitory effect of the branched α-glucan, dehydration is suppressed for a long time, so it is a high-quality pharmaceutical refrigerant with excellent stability. [Example 12] ＜Refrigeration agent＞

20 parts by weight of the branched α-glucan mixture prepared in Example 2 was added to 0.8 parts by weight of agar and 2.0 parts by weight of sodium chloride as a dehydration inhibitor, and after heating and dissolving with an appropriate amount of water, additional water was added to adjust the total amount to 100 parts by weight. The mixture was filled into a plastic flexible package and cooled to make a refrigerant by gelling it. It was frozen in a -20℃ freezer for 1 week, then repeatedly frozen and thawed at room temperature and evaluated for appearance and performance. The results showed that the refrigerant mixed with the dehydration inhibitor of the present invention maintained the shape and transparency of gel even after repeated freezing and thawing, and no dehydration was observed, and no change was seen in the refrigerant performance. This refrigerant is not limited to food, cosmetics, medicine, industry, etc. Since it is made from food raw materials, it is a refrigerant with high durability suitable for repeated use and can be safely used even for beverages. [Industrial Applicability]

As described above, according to the present invention, a dehydration inhibitor can be provided that can be widely used in a variety of applications without damaging the original color, flavor, and eating texture of food. Furthermore, the present invention can provide a dehydration inhibitor that can be safely and advantageously used in the fields of cosmetics, quasi-drugs, pharmaceuticals, industrial products, etc., not limited to food, and its use. Products using the dehydration inhibitor of the present invention are of very high value as commodities, and are a very meaningful invention that has made a huge contribution to this field.

In Figure 1 A: Control gel (containing 30% by mass of a branched α-glucan mixture and 1.0% by mass of κ-carrageenan as a gelling agent) B: Test gel (containing 30% by mass of a branched α-glucan mixture and 0.5% by mass of κ-carrageenan and 0.5% by mass of locust bean gum as gelling agents) In Figure 2 a: Branched α-glucan mixture b: Indigestible dextrin c: Dextran

[Figure 1] A diagram comparing the cross-sectional appearances caused by differences in gelling agents in a gel-like composition containing a high concentration of the present branched α-glucan mixture. [Figure 2] A diagram showing the concentration of an aqueous solution of a water-soluble polysaccharide and the ratio of the short component of the T2 relaxation time in pulse NMR measurement.

Claims (8)

A gel composition comprising carrageenan and/or agar as a gelling agent, and comprising a branched α-glucan mixture having the following characteristics (A) to (E): (A) glucose is used as a constituent sugar; (B) a branched α-glucan mixture having a glucose polymerization degree of 1 or more linked via a bond other than an α-1,4 bond is present at a non-reducing terminal glucose residue at one end of a linear glucan having a glucose polymerization degree of 3 or more linked via an α-1,4 bond; structure; (C) the solid content of each digestate produced by isomalto-glucanase digestion is 25% or more and 50% or less of isomaltose; (D) the ratio of glucose residues derived from α-1,4 bonds to glucose residues derived from α-1,6 bonds is in the range of 1:0.6 to 1:4; and (E) the total of glucose residues derived from α-1,4 bonds and glucose residues derived from α-1,6 bonds accounts for more than 60% of all glucose residues. The gel-like composition of claim 1, wherein the branched α-glucan mixture further has the following characteristics (F) and (G): (F) the glucose residues obtained by α-1,3 linkages account for more than 0.5% and less than 10% of all glucose residues; and (G) the glucose residues obtained by α-1,3,6 linkages account for more than 0.5% of all glucose residues. A gel-like composition as claimed in claim 1 or 2, wherein the water-soluble dietary fiber content of the branched α-glucan mixture determined by high performance liquid chromatography (enzyme-HPLC method) is 40% by mass or more. The gel-like composition of claim 1 or 2, wherein the value (Mw/Mn) obtained by dividing the mass average molecular weight (Mw) of the branched α-glucan mixture by the number average molecular weight (Mn) is less than 20. A food in the form of a gel composition as claimed in claim 1 or 2. For example, the food in claim 5 contains 0.2 to 30% by weight of a branched α-glucan mixture in the product. For food in claim 5 or 6, the water content is 60% by mass or more. A frozen dessert comprising milk and dairy products, and containing 0.5 to 10% by weight of a branched α-glucan mixture having the following characteristics (A) to (E) as an effective ingredient of a dehydration inhibitor, and having good spoonability and good melting in the mouth: (A) glucose is used as a constituent sugar; (B) the non-reducing terminal glucose residue at one end of a linear glucan having a glucose polymerization degree of 3 or more obtained by connecting glucose via α-1,4 bonds has a bond other than the α-1,4 bond. (C) the solid content of each digestate is 25% to 50% isomaltose by isomaltoglucanase digestion; (D) the ratio of glucose residues obtained by α-1,4 bonds to glucose residues obtained by α-1,6 bonds is in the range of 1:0.6 to 1:4; and (E) the total of glucose residues obtained by α-1,4 bonds and glucose residues obtained by α-1,6 bonds accounts for more than 60% of all glucose residues.