WO2014168018A1 - Sweetener composition, method for manufacturing same and use thereof - Google Patents

Abstract

[Problem] To provide a novel sweetener, which is free from a risk of diseases caused by the intake of isomerized sugars and overcomes problems encountered in the course of producing a rare sugar-containing syrup or disadvantages in taste, a method for manufacturing the same, and a use thereof. [Solution] A method for manufacturing a sweetener composition, said method comprising: treating sucrose with an acid and/or an enzyme under specific conditions to thereby efficiently decompose sucrose into glucose and fructose; and then isomerizing the obtained mixture using an alkali and/or an enzyme under specific conditions in such a manner as to allow the resultant isomerized product to contain D-psicose mainly as a rare sugar so that the product comprises, at a specific composition ratio, sucrose, D-glucose, D-fructose and rare sugar(s) at least containing D-psicose, or the product comprises, at a specific composition ratio, D-glucose, D-fructose and rare sugar(s) at least containing D-psicose.

Description

Sweetener composition, method for producing the same, and use thereof

The present invention relates to a method for producing a target sweetener composition using sugar as a raw material, and the produced sweetener composition and use thereof. Specifically, sugar, obtained by hydrolyzing sugar, The present invention relates to a method for producing a sweetener composition containing D-psicose in glucose, and fructose, or a mixed sugar mainly composed of glucose and fructose, and the obtained sweetener composition and use thereof. .

Isomerized sugar produced by saccharifying starch into a saccharified solution and treating it with glucose isomerase is equivalent to the sweetness of sugar and low in production costs. Widely used as a sweetener, the world's total production of isomerized sugar has reached 17.3 million tons (2009 statistics). A typical production method of this isomerized sugar is that starch is hydrolyzed with an enzyme to obtain a hydrolyzed starch (dextrin), then hydrolyzed with another enzyme to obtain a glucose solution (saccharified solution), and then glucose isomerase. This is a method for isomerizing glucose into fructose. Since the isomerization reaction is an equilibrium reaction, the ratio of glucose to fructose in the isomerized sugar obtained by this production method is usually about 58:42. Furthermore, purified fructose may be added in order to eliminate the lack of sweetness. In this case, the ratio of glucose to fructose is generally about 45:55.

On the other hand, in recent years, rare sugars have attracted attention because they have various physiological effects, and research has been actively conducted. However, in order to be widely used industrially, these rare sugars are efficiently produced. It is essential.
Rare sugars are “naturally-occurring monosaccharides” represented by D-glucose (glucose), which are abundant in nature, among the simple sugars that are the basic units of sugar. Monosaccharide "is defined. The abundance of rare sugar is very small, and the abundance is overwhelmingly small compared to D-glucose (glucose).

Among them, the rare sugars that can be mass-produced at present are D-psicose and D-allose. D-psicose is a D-form of psicose classified as ketohexose and is a hexose.
D-allose is a D-form of allose classified as an aldohexose, which is also a hexose. These D-psicose and D-allose are proved to be 0 kcal / g, respectively, in human tests (Non-patent Document 1) and animal tests (Non-patent Document 2).
D-psicose is obtained by allowing a specific enzyme to act on fructose. When D-ketohexose 3-epimerase (Patent Document 1) is allowed to act, it is produced in a yield of 20 to 25%.・ When 3-epimerase (Non-patent Document 3) is allowed to act, it is produced in a yield of about 30%, and when boric acid is used in combination, it is reported that it is produced in a yield of about 60% ( Non-patent document 4). When attempting industrial mass production of rare sugars using this enzyme, it is necessary to check the safety of the enzyme, cultivate bacterial cells that are the source of the enzyme, purify the enzyme, immobilize the enzyme, etc. These problems must be overcome sequentially.
As for D-allose, it is known that L-arabinose isomerase is allowed to act on a solution containing D-psicose to produce D-allose from D-psicose (Patent Document 2).

As described above, rare sugars are obtained by allowing specific enzymes to act on specific raw sugars, but some other acquisition methods are also disclosed. For example, since the 1800s, isomerization reactions of aldoses and ketoses via enediol have been known, which is called Robry de Bruin-fan Eckenstein (Lobry de Bruyn and Alberda van Ekenstein) rearrangement reaction. This isomerization reaction is a reaction that can be isomerized to another sugar by placing a certain sugar under alkaline conditions. By utilizing this reaction, it is possible to isomerize the sugar, so that a slight amount of rare sugar can be obtained (Non-Patent Document 5), but an isomerized product containing a rare sugar at a concentration exhibiting the above physiological activity. In order to obtain the product, there are problems such as requiring reaction time that does not match the actual industrial production efficiency, coloring of products due to side reactions such as caramelization, and subsequent purification being difficult. It is considered difficult to use.

Japanese Patent Laid-Open No. 6-125776 JP 2002-17392 A International Publication No. 2010/113785 JP 2009-515091 A PCT / JP2012 / 67209

[0003] Carbohydrates represented by isomerized sugars and sugars (assimilable sugars) have recently been regarded as a problem with diabetes and obesity. On the other hand, the above-mentioned rare sugar has various useful physiological effects, and in particular, it has been clarified that when it is used as a mixed sweetener composition with glucose and fructose, it exhibits an excellent anti-obesity effect. A method for producing a syrup containing a rare sugar by alkaline isomerization of sugar (Patent Document 3) and a method for producing a syrup containing a rare sugar using an enzyme have also been reported (Patent Document 4). . However, these syrups are composed only of monosaccharides, so that the sweetness is slightly light, and in order to be familiar to consumers for a long time, there remains room for improvement in terms of sweetness balance.

There are no sweeteners and production methods that have overcome the above-mentioned drawbacks related to sweetness, and there is no industrially practical production method that takes production efficiency and safety into consideration. . The disadvantage of sweetness is that isomerized sugar (the composition consisting mainly of glucose and fructose obtained by the decomposition of starch, etc.) is used as a raw material, and the isomerized sugar contains oligosaccharide and has a different composition. Since it is considered that the sweetness and sweetness are different from sugar, it was decided to try to produce a sweetener containing rare sugar from sugar. Since sugar was expensive before the spread of isomerized sugar, it has continued to be replaced by isomerized sugar, but now it is produced around 180 million tons worldwide. Has also become relatively stable. By using sugar as a raw material, the high-quality sweetness of sugar can be used, and since sugar is a disaccharide in which glucose and fructose are combined, it can also be used as a feedstock for glucose and fructose. It is thought that it will become cheaper in cost. Furthermore, as described above, sweeteners containing rare sugars using sugar as a raw material also have an advantage that they have less miscellaneous taste than sweeteners using isomerized sugar as a raw material. Based on these assimilating sugars, it is desired to market sweeteners that are superior in sweetness and physical properties and do not cause these diseases.

Therefore, the present invention provides a novel sweetener, a method for producing the same, and a use thereof, which overcome the above-mentioned disease risk by ingesting isomerized sugar, and defects in the production process or taste quality of rare sugar-containing syrup. It is something to be offered.

The inventors of the present invention have made extensive studies to solve the above-mentioned problems. As a result, an acid and / or enzyme is allowed to act on sugar under specific conditions to produce glucose (D-glucose) and fructose (D-fructose). After efficiently decomposing, it is isomerized with alkali and / or enzyme under specific conditions, and D-psicose is mainly contained as a rare sugar in the isomerized product, thereby The present inventors have found that a sweetener composition having a composition can be obtained, and have completed the present invention.

Specifically, the present invention comprises the following methods (1) to (9) for producing a sweetener composition.
(1) Using sugar as a raw material to obtain a mixture of sugar, D-glucose and D-fructose, or a mixture of D-glucose and D-fructose by hydrolysis of the raw sugar, and the sugar A mixture of rare sugars including sugar, D-glucose, D-fructose and at least D-psicose, or D-glucose, D-fructose and at least D-psicose, which are end products by isomerizing the hydrolyzate A step of obtaining a mixture of rare sugars containing, adjusting the content of sugar in the final product according to the degree of hydrolysis reaction of the raw sugar, and the final product is sugar, D-glucose, D-fructose And a rare sugar containing at least D-psicose in a specific composition ratio, or D- Glucose, D- fructose, and a method for making a sweetener composition, characterized in that the rare saccharide to be included in a particular composition ratio comprising at least D- psicose.
(2) The raw material sugar hydrolysis step is a step of isomerizing a sugar hydrolyzate by decomposition using an acid and / or an enzyme, and an alkali isomerization, an isomerization using calcium ion catalysis and / or The manufacturing method of the sweetener composition of the said (1) description performed by enzyme isomerization.
(3) Alkaline isomerization produces rare sugars including D-psicose, D-allose, D, L-sorbose, D-tagatose, and D-mannose. The final product consists of these monosaccharides, sugar, The method for producing a sweetener composition according to the above (2), which is a mixture of D-glucose and D-fructose or a mixture of D-glucose and D-fructose.
(4) Enzymatic isomerization produces only D-psicose from fructose, and the final product is a mixture of D-psicose and sugar, D-glucose and D-fructose, or D-glucose and D- The manufacturing method of the sweetener composition of said (2) description used as a mixture with fructose.
(5) The method for producing a sweetener composition according to (2) or (4) above, wherein the enzyme isomerization is performed using an isomerase derived from Arthrobacter globiformis M30 (deposit number NITE BP-1111). .
(6) Enzymatic isomerization is performed using an immobilized enzyme having an activity of 1000 U / wet weight resin (g), and the production of the sweetener composition according to (2), (4) or (5) above Method.
(7) The method for producing a sweetener composition according to any one of the above (1) to (6), wherein the final product is a sweetness composition having a low sweetness intensity and an unpleasant taste.
(8) The method for producing a sweetener composition according to any one of (1) to (6), wherein the final product is a sweetening composition that enhances flavor release.
(9) The sweetener composition according to any one of the above (1) to (6), wherein the final product is a sweet composition having a good richness and sweetness balance in which the ratio of sugar is 10 to 75 parts. Manufacturing method.
(10) Any of the above (1) to (6), wherein the final product is a sweetening composition having a function of significantly reducing the amount of insulin secretion when the sugar ratio is 10 to 80 parts. A method for producing the sweetener composition described in 1.

Further, the present invention comprises the following sweetener composition (11), foods and drinks (12) and (13), pharmaceuticals (14) and (15), quasi drugs and cosmetics.
(11) A sweetener composition obtained by the production method according to any one of (1) to (10) above.
(12) A food or drink comprising the sweetener composition according to (11) above.
(13) The food or drink according to (12) above, which is labeled to suppress an increase in body weight and an increase in body fat accumulation.
(14) A pharmaceutical, quasi-drug, or cosmetic comprising the sweetener composition as described in (11) above.
(15) The pharmaceutical, quasi-drug, or cosmetic according to (14) above for suppressing an increase in body weight and an increase in body fat accumulation.

According to the present invention, since sugar is used as a raw material, the high-quality sweetness of sugar can be used, and since sugar is a disaccharide in which glucose and fructose are combined, it can also be used as a feedstock for glucose and fructose. Thus, it is possible to provide a sweetener that is cheaper than isomerized sugar as a raw material, is excellent in sweetness and physical properties, and does not cause these diseases, based on these assimilating sugars. Provided a new sweetener, a method for producing the same, and a use thereof, which overcomes the risk of morbidity associated with diabetes and obesity caused by ingestion of isomerized sugar, and defects in the production process or taste quality of rare sugar-containing syrup can do. That is, according to the present invention, it is possible to provide a sweetener composition close to the taste of sugar containing rare sugars such as sugar, D-glucose, D-fructose, and D-psicose in a well-balanced manner. . In addition, since the present invention is a production method that is excellent not only in physical properties but also in cost performance, it can be used inexpensively and safely for pharmaceuticals or quasi drugs, oral compositions, cosmetics and foods, and food additives. An agent can be provided. Furthermore, since the product of the present invention is a sweetener with better taste and functionality than isomerized sugar or sugar itself, it has anti-obesity agents, antifeedants, insulin resistance improvers, Or it becomes possible to give the quality as a low-calorie sweetener.

The manufacturing flow of the sweetener containing rare sugar which uses sugar as a raw material is shown. The area under a blood glucose level curve when each sweetener composition of the present invention is ingested by a human is shown. The area under the insulin concentration curve when a human being ingested each sweetener composition of the present invention is shown.

The present invention relates to a sweetener composition using sugar as a raw material and containing sugar, D-glucose, D-fructose, rare sugar (D-psicose, etc.), etc. in a specific composition ratio, a method for producing the same, and use thereof Consists of.
It is possible to adjust the sugar content in the finally obtained sweetener composition by the degree of hydrolysis reaction of the raw sugar, and finally, depending on the degree of isomerization reaction in the next step. Although the content of rare sugar in the resulting sweetener composition can be adjusted, in order to obtain the taste-quality effect of the present invention, the sugar in the final sweetener composition should be 3 to 80%. Desirably, it is desirable that D-psicose is contained in an amount of 3% or more (hereinafter, unless otherwise specified,% indicates mass% in the sugar composition (solid)), but the sweetness prepared so as not to contain sugar. Even when the compositions are compared, a sweetener composition with less miscellaneous taste is obtained by using sugar as a raw material than when isomerized sugar is used as a raw material.

A taste effect is obtained when the D-psicose content in the sweetener composition of the present invention is 3% or more, but the alkali isomerization described later was selected as the isomerization method performed after the decomposition of sugar. In some cases, D-mannose, D-sorbose, L-sorbose and the like are produced in addition to rare sugars such as D-allose, D-tagatose, and D-altrose other than D-psicose. When the alkali isomerization reaction proceeds excessively, the coloration proceeds remarkably and subsequent purification is difficult. Therefore, the composition of D-psicose and D-allose is determined as the degree of isomerization reaction that does not cost this purification step. 0.5 to 17.0% (preferably 1 to 15%) and 0.2 to 10.0% (preferably 0.1 to 0.1%) of the sugar mass when the sugar in the final sweetener composition is removed. 4-8%) is desirable, and by setting this composition, it is possible to obtain a sweetener composition in which both the effect on taste of the present invention and the cost reduction of the purification process are compatible. In addition, when D-psicose and D-allose contained in the final sweetener composition together with other produced rare sugars except for sugar are 2.3% or more and 1.3% or more, respectively, The sweetener composition of the present invention exhibits characteristics that can be used as an anti-obesity agent, an antifeedant, and an insulin resistance improving agent. It can also be used.

[Raw sugar]
The sugar used as a raw material in the present invention may be any sugar containing D-glucose (glucose) and D-fructose (fructose) combined. Different manufacturing methods such as sugar and dense sugar, and product categories such as white disaccharide, medium disaccharide, granulated sugar, super white sugar, tri-warm sugar, invert sugar, sugar cube, rock sugar, brown sugar, red sugar, and Wasanbon There is no limitation, and any sugar solution in the sugar refining process may be used. Furthermore, in the present invention, oligosaccharides containing three or more sugars including sugar (fructo-oligosaccharide, coupling sugar, lactosucrose, theandelose, etc.) can be used as the raw material sugar.

Regarding the concentration when using the raw material sugars listed above for production, considering the simplification of the subsequent concentration process, the higher the concentration of the raw sugar solution, the better. However, the lower the concentration of the raw material sugar solution, the lower the concentration of the rare sugar. Since the yield can be increased, considering the production efficiency at the same time, the concentration of the raw sugar solution is 3 to 80%, preferably 10 to 60%, and more preferably 20 to 40%.
On the other hand, from the viewpoint of preventing floating of the immobilized enzyme carrier resin and the resin used for purification, about 3 to 40% is more preferable.
It is also possible to obtain mixed sugars with different product composition ratios by adjusting the sugar concentration. For example, the raw material having a sugar concentration of 100%, that is, the powder or the powder is produced by spraying acid or alkali. Is also possible.

[Hydrolysis of raw sugar]
The raw sugar hydrolysis step is performed by decomposition using an acid and / or an enzyme. An acid (acidic solution) can be used to hydrolyze the raw sugar. Decomposition with an acid is carried out using an inorganic acid, sulfonic acid or carboxylic acid as the acidic solution. More specifically, in the present invention, the acidic solution includes inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hypochlorous acid, perchloric acid, phosphoric acid, boric acid, fluorosulfonic acid, etc.), sulfone Acids, carboxylic acids (acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, tartaric acid, etc.) can be used as appropriate, but hydrochloric acid is preferred from the viewpoint of safety and cost. The optimum acid concentration depends on the reaction time and temperature, but it is usually preferable to contain about 0.01 to 5 mol / l in the raw sugar solution. The acid decomposition reaction temperature is preferably 20 ° C. or higher, more preferably 30 ° C. to 100 ° C.

As a method for hydrolyzing sugar, an enzyme can be used instead of the above acid decomposition. Degradation using an enzyme is performed using invertase. More specifically, examples of the enzyme include saccharase; invertase (IUPAC-IUB strain name is β-D-fructofuranosidase (EC 3.2.1.26)), and the strain origin is particularly limited. Not.
Although the enzyme concentration varies depending on the substrate concentration and reaction time, it is usually preferable to use 100 unit / mg enzyme at 0.00075-0.003% (w / w) relative to the substrate. Depending on the immobilization conditions of the enzyme and the enzyme, it can be appropriately changed. In addition, the reaction temperature of the enzyme is preferably 20 ° C. or higher, more preferably 30 ° C. to 100 ° C. The optimum temperature is around 60 ° C.
For immobilization of invertase enzyme, commercially available invertase is dissolved in a buffer solution (pH 7) and allowed to pass through the column-filled resin at 4 ° C., so that the invertase enzyme protein is bound to the ion exchange resin. Get the enzyme.

As described above, hydrolysis of raw sugar can be performed by either acid or decomposition using invertase, but in general, it can be used properly depending on the composition of the product to be obtained. Only one of them can be used, or they can be used together.

[Isomerization of sugar hydrolyzate]
The step of isomerizing the sugar hydrolyzate is performed by alkali isomerization, isomerization using calcium ion catalysis and / or enzymatic isomerization.
First, enzyme isomerization will be described.
In order to generate D-psicose from fructose after hydrolysis of the raw sugar, a method using an isomerization (epimerization) enzyme such as tagatose-3 epimerase or psicose-3 epimerase can be selected. The origin of the microorganism strain from which the isomerase, tagatose-3-epimerase or psicose-3 epimerase, is obtained is not particularly limited, but is a safe species that can also be used for food.
From high-yield D-fructose to D-psicose from bacterial species that are listed on the existing additive list that is approved for use in food production It is desirable to be a bacterium belonging to the genus Arthrobacter (Patent Document 5) that produces a novel ketose 3-epimerase that catalyzes isomerization, more preferably an genus Arthrobacter globiformis, and Arthrobacter globiformis M30 (Deposit number NITE BP-1111) is more preferable. Regarding the enzyme concentration, an appropriate range varies depending on the substrate concentration and the reaction time, but when the enzyme is immobilized, one having an activity of about 1000 U / wet weight resin (g) is preferable.
The reaction temperature for carrying out the enzyme isomerization is preferably 20 ° C. or higher, more preferably 30 ° C. to 80 ° C. Practically, around 45 ° C. is preferable.

The above Arthrobacter globiformis will be described. The ketose 3-epimerase that can be used in the present invention belongs to the genus Arthrobacter , cultivates a microorganism having the ability to produce ketose 3-epimerase, and ketose 3-epimerase from the cells grown in the culture solution. It can be prepared by collecting epimerase. As microorganisms belonging to the genus Arthrobacter , for example, the Arthrobacter globiformis M30 (deposition number NITE BP-1111) strain and mutants thereof can be advantageously used. The M30 strain has a relatively high ability to produce ketose 3-epimerase and is suitable for obtaining the enzyme of the present invention. The M30 strain is based on NITE P-1111 deposited on June 22, 2011 at the Japan Patent Evaluation Depositary Center for Product Evaluation Technology (2-5-8 Higashi Kazusa Kamashika, Kisarazu City, Chiba, Japan). A transfer to the deposit under the Budapest Treaty was requested on May 2, 2012, and the deposit was made internationally under the deposit number NITE BP-1111.

That is, a preferred ketose 3-epimerase that can be used in the present invention is a ketose 3-epimerase that can be obtained from a microorganism belonging to the genus Arthrobacter and has the following substrate specificities (A) and (B). .
(A) Epimerize position 3 of D- or L-ketose to produce the corresponding D- or L-ketose.
(B) Among D- or L-ketoses, the substrate specificity for D-fructose and D-psicose is the highest.
The ketose 3-epimerase derived from Arthrobacter globiformis M30 (deposit number NITE BP-1111) has a subunit molecular weight of about 32 kDa by SDS-PAGE, a molecular weight of 120 kDa by gel filtration, and a subunit molecular weight of 120 kDa. It has a 32 kDa homotetramer structure, has the following physicochemical properties (a) to (e), and has the following substrate specificity: ~ 8. (See Patent Document 5).
(A) Optimum pH
Reaction at 30 ° C. for 30 minutes, 6 to 11 in the presence of 20 mM magnesium (Mg ²⁺ ).
(B) Optimal temperature
pH 7.5, reaction for 30 minutes, 60 to 80 ° C. in the presence of 20 mM magnesium (Mg ²⁺ ).
(C) pH stability
Stable at least in the range of pH 5 to 11 under the condition of holding at 4 ° C. for 24 hours.
(D) Thermal stability
Stable at about 50 ° C. or lower under conditions of pH 7.5, 1 hour hold, 4 mM magnesium ion (Mg ²⁺ ). Stable at about 40 ° C. or lower in the absence of magnesium ions (Mg ²⁺ ).
(E) Activation by metal ions It is activated by divalent manganese ions (Mn ²⁺⁾ , divalent cobalt ions (Co ²⁺ ), calcium (Ca ²⁺ ) and magnesium ions (Mg ²⁺ ).
1. The relative activity when D-fructose is used as a substrate is 43.8%,
2. 100% activity when D-psicose is used as a substrate,
3. The relative activity when using D-sorbose as a substrate is 1.13%,
4). The relative activity when D-tagatose is used as a substrate is 18.3%,
5. The relative activity when using L-fructose as a substrate is 0.97%,
6). The relative activity when L-psicose is used as a substrate is 21.2%,
7). The relative activity when using L-sorbose as a substrate is 16.6%,
8. The relative activity is 44.0% when L-tagatose is used as a substrate.
However, the activity for each ketose is shown as a relative activity, where the epimerization activity of D-psicose is 100.

[Immobilization of isomerase]
It is most practical to use the isomerase immobilized on an appropriate base material such as an ion exchange resin. The entire manufacturing process is a simple process consisting of mixing and heat treatment, and can be applied in either a batch type or a continuous type. In the case of a continuous type, the process of hydrolyzing the raw sugar and the process of isomerizing the sugar hydrolyzate are performed in a series of steps, and the enzyme obtained from Arthrobacter globiformis M30 (Deposit number NITE BP-1111) is immobilized Done. In this way, hydrolysis and isomerization processes using sugar as a raw material are carried out in a series of steps, and furthermore, there is no production method that has been used for production by immobilizing an enzyme obtained from this bacterial species. It's a law. Enzymatic isomerization is performed using an immobilized enzyme having an activity of 1000 U / wet weight resin (g). The isomerase produced by Arthrobacter is prepared by suspending cells obtained by culturing in a buffer solution (pH 7.0), disrupting the cells by sonication while cooling, or treating the cells with lysozyme. It can be collected as a crude enzyme solution from a solution of disrupted cells obtained by digesting the polysaccharide components present on the cell walls of the body to destroy the cells. The crude enzyme solution is passed through the ion-exchange resin packed in the column at a low temperature (4 ° C), the crude enzyme protein is bound to the ion-exchange resin, purified water is passed through and washed, and the immobilized enzyme is washed. Obtainable. An immobilization system that can withstand continuous production in terms of stability (maintenance of activity) completely satisfactory for commercial production was obtained. A large amount of epimerization reaction can be continuously performed using the obtained immobilized enzyme.
For immobilization of M30 cells, active ketose 3-epimerase is added to the supernatant obtained after heat treatment at 40 to 70 ° C. for 5 to 60 minutes after crushing treatment with 0.1 to 2% sodium chloride and lysozyme. Since it was found that many can be obtained, a separate patent application is planned.

The means for isomerization after decomposing the raw material sugar is not limited to the isomerization (epimerization) by the above enzyme, and a method utilizing alkali isomerization can also be selected. Examples of the alkaline solution used for the alkali isomerization reaction include sodium hydroxide, potassium hydroxide, ammonia, calcium hydroxide, calcium oxide, barium hydroxide, lead hydroxide, strontium hydroxide, magnesium hydroxide, hydroxide Although tin and aluminum hydroxide are mentioned, sodium hydroxide and calcium hydroxide are preferable in terms of safety and cost.
The optimum alkali concentration depends on whether or not an ion exchange resin is used in combination, but usually it is preferably contained in a hexose (hexasaccharide) solution in an amount of 0.005 mol / l or more.
The reaction temperature for the alkali isomerization is preferably 20 ° C. or higher, more preferably 30 ° C. to 100 ° C.

Furthermore, isomerization using the catalytic action of calcium ions is carried out by advancing the isomerization reaction of hexose in the presence of a calcium salt that generates calcium ions.
Patent Document 3 describes a method for isomerizing glucose using calcium chloride. In the present invention, an isomerization reaction using a catalytic action of calcium ions can also be performed. In the present invention, the isomerization reaction of hexose proceeds in the presence of a calcium salt that generates calcium ions, for example, calcium chloride, that is, for example, a sugar composition containing D-psicose and D-allose from fructose. Can be manufactured. The calcium salt is desirably in the presence of an alkali, and is preferably contained in the sugar solution by 0.005 mol / l or more. In a system in which a calcium salt is present, the coexistence of a basic ion exchange resin is not always necessary.

[Final product]
The sugar content in the final product is adjusted according to the degree of hydrolysis of the raw sugar. The final product includes sugar, D-glucose, D-fructose, and a rare sugar containing at least D-psicose in a specific proportion, or includes D-glucose, D-fructose, and at least D-psicose. Rare sugar was included at a specific composition ratio. Alkaline isomerization produces rare sugars including D-psicose, D-allose, D, L-sorbose, D-tagatose, and D-mannose, and the final products are these simple sugars, sugars, glucose, And a mixture of fructose. Isomerization using calcium ion catalysis produces rare sugars including D-psicose and D-allose from fructose, and the final product is a mixture of these monosaccharides, sugar, glucose and fructose. Enzymatic isomerization produces only D-psicose from fructose and the final product is a mixture of D-psicose, sugar, glucose and fructose, or a mixture of D-psicose, glucose and fructose . Whether to use alkaline isomerization or enzymatic isomerization can be selected depending on the amount of hydrolysis and the composition of the product to be obtained. Either one can be used or both can be used. Can do.

In addition, it is possible to adjust the sugar composition of the composition to be produced by appropriately changing the raw sugar concentration, acid concentration, alkali concentration, enzyme concentration, reaction temperature, etc. A composition adjusted to have physical properties can be obtained. In addition, when particularly strict composition ratio adjustment is required, sugar, glucose, fructose, rare sugar and the like can be appropriately added and adjusted. If it is desired to increase the reaction time, productivity can be improved by applying pressure.

In addition, for purification of the obtained reaction solution, ion exchange resin, activated carbon, and purification by filtration usually used in the sugar industry can be appropriately used. Separation can be removed by column chromatography, or precipitation separation can be performed using an agent chelating with sugar. According to the method of the present invention, significant browning does not occur before separation by column chromatography, but generally known purification steps such as deodorization and decolorization processes using activated carbon are added to the previous stage in consideration of the lifetime of the column. You can also. As for the chromatographic separation mode, pseudo mobile phase chromatography is optimal for this purpose, but is not particularly limited.

Furthermore, in view of the advantages of the separation step, it is possible to separate only rare sugars from the resulting reaction solution and appropriately add to the mixed sugars to obtain the target composition. The remaining sugar solution can be reused. That is, a continuous plant can be constructed by recombining the residual sugar solution with the raw material sugar and guiding it again to the hydrolysis reaction step, so that the manufacturing process can be simplified.
A preferred embodiment of the present invention is shown schematically in FIG.

According to the production method of the present invention, the production flow (apparatus) shown in FIG. 1 can be assembled, and the sweetener composition of the present invention can be easily obtained through this series of steps.
In FIG. 1, Step 1 is a tank for dissolving raw material sugar, Step 2 is a tank for acid hydrolysis of raw material sugar, and 3 is an invertase-immobilized column for hydrolyzing raw material sugar. For hydrolysis of sugar, Step 2 or 3 can be used in consideration of hydrolysis time and reaction efficiency. Next, steps 4 and 5 are an isomerization step with an alkali or an isomerization step with an enzyme, and any of them may be used. However, isomerization with an alkali also produces rare sugars other than D-psicose, whereas Since isomerization produces only D-psicose as a rare sugar, the process can be selected according to the purpose. Step 6 is a general purification step used for sugar purification of ion exchange resins, activated carbon, filters, and the like. Further, the process can proceed to step 7 to separate and acquire a rare sugar single product. When the rare sugar is separated and acquired in step 7, the remaining sugar, glucose, and fructose mixed sugar solution can be returned to step 1 and reused as the raw sugar.

[Use of final product]
According to the present invention, it is possible to obtain a sweetening composition having a low sweetness intensity and a little miscellaneous taste using sugar as a raw material. A sweetening composition that enhances flavor release using sugar as a raw material can be obtained. From the viewpoint of the advantage that sweeteners containing rare sugars using sugar as a raw material have less miscellaneous taste than sweeteners using isomerized sugar as a raw material, the ratio of sugar is 10 to 75 parts. A sweetening composition having a feeling and a sweetness balance can be obtained. Furthermore, from the viewpoint of a sweetener that is superior in sweetness and physical properties as described above and does not cause diseases such as diabetes and obesity, insulin secretion is significantly increased even if the proportion of sugar is increased to about 80 parts. This proved to be a sweetening composition with reduced function. Therefore, this invention relates to the food / beverage products which used the said sweetener composition, the food / beverage products which attached | subjected the display which suppresses the raise of a body weight, and a body fat accumulation. In addition, the present invention relates to a pharmaceutical comprising a sweetener composition, a quasi-drug, a cosmetic, a pharmaceutical for suppressing an increase in body weight and an increase in body fat accumulation, a quasi-drug, and a cosmetic.
When the sweetener composition of the present invention is used in foods and drinks, the form is not particularly limited, and the form as it is, the form diluted with a solvent such as oil, the emulsion form, or common in the food industry Any form such as a form to which a carrier used in the preparation is added may be used.

Specific examples of target foods and drinks using the sweetener composition of the present invention include the following. That is, confectionery (pudding, jelly, gummy candy, candy, drop, caramel, chewing gum, chocolate, pastry, butter cream, custard cream, cream puff, hot cake, bread, potato chips, french fries, popcorn, biscuits, crackers, pie , Sponge cakes, castella, waffles, cakes, donuts, biscuits, cookies, rice crackers, rice crackers, rice cakes, manju, candy, etc., dry noodle products (macaroni, pasta), egg products (mayonnaise, fresh cream), beverages (functionality) Beverages, lactic acid beverages, lactic acid bacteria beverages, concentrated milk beverages, fruit juice beverages, fruitless beverages, fruit beverages, transparent carbonated beverages, carbonated beverages with fruit juice, fruit colored carbonated beverages, alcoholic beverages, beer-like beverages), luxury products (green tea, Tea, inn Tanto coffee, cocoa, canned coffee drinks), dairy products (ice cream, yogurt, coffee milk, butter, butter sauce, cheese, fermented milk, processed milk), pastes (marmalade, jam, flower paste, peanut paste, Fruit paste, pickled fruit syrup), livestock products (ham, sausage, bacon, dry sausage, beef jerky, lard), seafood products (fish meat ham, fish sausage, salmon, chikuwa, hampen, dried fish, bonito, bonito , Boiled and dried, sea urchin, squid salted fish, squid, dried fish, shellfish, dried fish such as salmon), boiled fish (small fish, shellfish, wild vegetables, salmon, kelp), curry (instant curry, retort curry) , Canned curry), seasoning (Miso, powdered miso, soy sauce, powdered soy sauce, moromi, fish sauce, sauce, ke Cap, oyster sauce, solid bouillon, grilled meat sauce, curry roux, stew element, soup element, dashi element, paste, instant soup, sprinkle, dressing, salad oil), fried products (fried food, fried confectionery, instant ramen), Examples include soy milk, margarine, and shortening.

The food and drink can also be used as functional foods, nutritional supplements, or health foods. The form is not particularly limited. For example, proteins such as milk proteins with high amino acid balance, soy protein, egg albumin, etc., their degradation products, egg white oligopeptides, soybean hydrolysates, It can be used according to a conventional method together with a mixture of amino acids alone. Moreover, it can also utilize with forms, such as a soft capsule, a tablet, and a film.

Examples of the above dietary supplements or functional foods include liquid foods, semi-digested nutritional foods, ingredient nutritional foods, drinks, capsules, sugars, fats, trace elements, vitamins, emulsifiers, fragrances, etc. Examples of processing forms such as enteral nutrients. Among these various foods and drinks, for example, foods and drinks such as sports drinks and nutritional drinks, for the purpose of improving nutritional balance and flavor, further nutritional additives such as amino acids, vitamins, minerals, sweeteners, spices, A fragrance | flavor, a pigment | dye, etc. can also be mix | blended.

In addition to the above, the sweetener composition of the present invention can be used as a food material or food additive for the purpose of improving abnormal carbohydrate metabolism and / or abnormal lipid metabolism, and when used as a drug, It can be used in the form of capsules, solid agents such as powders and granules for use in beverages, semi-solid bodies such as jelly, liquids such as drinking water, and high-concentration solutions used after dilution.
Furthermore, the sweetener composition of the present invention can be appropriately added to foods and drinks to provide health foods or sick foods for the purpose of improving abnormal sugar metabolism and / or abnormal lipid metabolism. Vitamins, carbohydrates, pigments, fragrances and the like to be added can be appropriately blended. The form of the capsule may be liquid, solid, or a soft capsule encapsulated by gelatin or the like. For example, the capsule is dissolved by adding water to raw material gelatin, and a plasticizer ( A gelatin film prepared by adding glycerin, D-sorbitol, etc.).

In addition, the sweetener composition of the present invention can be applied to feed for livestock, poultry and pets. For example, it can mix | blend with livestock feeds, such as dry dog food, dry cat food, wet dog food, wet cat food, semi-moist dock food, poultry feed, cattle, and pigs. The feed itself can be prepared according to a conventional method.
These therapeutic agents and prophylactic agents include non-human animals, for example, domestic mammals such as cattle, horses, pigs and sheep, poultry such as chickens, quails and ostriches, pets such as reptiles, birds and small mammals, It can also be used for farmed fish.

Further, the sweetener composition according to the present invention is a high-intensity sweetener such as aspartame, sucralose, acesulfame K, stevia, monatin, monelin, miraculin, sugar alcohols such as sorbitol, xylitol, erythritol, lactitol, maltitol, ketose, Sweeteners can be prepared by adjusting the sweetness by further mixing with a sweetener such as aldose.

The sweetener composition of the present invention is a food, health food, patient food, food material, health food material, patient food material, food additive, health food additive, patient food additive, beverage, Health drinks, patient drinks, drinking water, health drinks, patient drinks, medicines, pharmaceutical ingredients, feeds, livestock and / or feeds for patients, pharmaceuticals or quasi drugs, oral compositions, cosmetics It is possible to provide a sweetener composition that can be used for all foods that require sweetness or functionality, such as food additives, and can be used safely and conveniently.
In addition, according to the present invention, a sugar composition containing a specific hexose, focusing on the physiological action of the specific hexose, and a specific health food, pharmaceutical or quasi-drug using the same, and oral use A composition, cosmetics, etc. can be provided. Specifically, it contains sugar, glucose, fructose, and D-psicose, and when an alkali isomerization reaction is selected as a means for isomerization, D-allose Can be obtained, which is superior in taste, physical properties, and physiologically, and is therefore superior in taste to assimilable sugars such as isomerized sugar and sugar. It is possible to have the characteristics as a sweetener, anti-obesity agent, antifeedant, insulin resistance improver, low calorie sweetener, blood pressure suppressor.
It should be noted that the obtained sweetener composition of the present invention is different from the monosaccharides known so far in that it has a low calorie and has an appetite suppressing effect, and therefore has a new anti-obesity effect and the like. It has the characteristics. The sweetener composition of the present invention can be widely used as a low calorie sweetener because the sweetness is close to sugar and the calories are low.

The said food / beverage products can be processed and manufactured by mix | blending the sweetener composition of this invention as the raw material, and the compounding quantity of the sweetener composition of this invention with respect to the said food / beverage products is the food / drink of object. Since it varies depending on the form, it is not particularly limited, but it is usually preferably 0.1 to 50% by mass in food and drink.
The novel sugar composition of the present invention can be expected to be widely used as a sweetener for soft drinks and other beverages, and can be used in foods, pharmaceuticals or quasi drugs, oral compositions, and cosmetics. There is expected.

The present invention will be described in more detail with reference to experimental examples and examples, but the present invention is not limited to the examples.

<Experimental example A: Acid hydrolysis of sugar>
A 0.7 mol / l hydrochloric acid solution containing 3% (w / v) sugar was prepared using sugar and hydrochloric acid. This was hydrolyzed at a temperature of 40 ° C. for 20 minutes, 30 minutes, 50 minutes and 80 minutes, respectively. The decomposition solution was neutralized with sodium hydroxide, and then analyzed by HPLC (detector; RI, column; Mitsubishi Kasei MCI GEL CK 08EC, mobile phase; water, flow rate; 0.4 ml / min). The same applies to the following experimental examples).
The sugar composition (%) of the obtained hydrolyzate is shown in Table 1 below.

Next, in order to confirm whether the sugar composition obtained by acid hydrolysis is similarly decomposed even at different concentrations, the sugar composition was confirmed at 90 ° C. under the acid hydrolysis conditions for a sugar 80% (w / w) solution. As a result, decomposition was confirmed.
In addition, in order to confirm whether the sugar composition obtained by acid hydrolysis is decomposed by different acid concentrations, the sugar composition obtained by hydrolysis with hydrochloric acid having a hydrochloric acid concentration of 0.01 to 5 mol / l is used. When confirmed, decomposition was confirmed.

<Experimental Examples B to D: Enzymatic hydrolysis of sugar>
Using sugar and invertase (MP Biomeicals, Inc., 100 unit / mg), a 3% (w / v) sugar solution containing invertase (0.003% w / w; sugar g) was prepared. This was hydrolyzed at a temperature of 40 ° C. for 20 minutes, 30 minutes, and 40 minutes, and HPLC analysis was performed in the same manner as in Example 1.
The sugar composition (%) of the obtained hydrolyzate is shown in Table 2 below.

Next, a 25% (w / v) sugar solution containing invertase (0.00075% w / w; sugar g) was prepared, and this was made at a temperature of 40 ° C. for 10 minutes, 20 minutes, 30 minutes, 40 minutes. , 50 minutes, 60 minutes, 70 minutes and 80 minutes of hydrolysis, respectively, and HPLC analysis was performed in the same manner.
The sugar composition (%) of the obtained hydrolyzate is shown in Table 3 below.

Further, commercially available invertase (manufactured by DSM; 200 U / mg) was immobilized on an ion exchange resin (resin: IRA904, column inner diameter 1.5 cm, immobilized enzyme 1500 U / wet weight (g)). Using 30 ml of this resin, a 30% sugar solution was fed and reacted at a temperature of 45 ° C., a feeding speed of 3 ml / min, a speed of 2 ml / min, and a speed of 1 ml / min. At this time, the reaction solution eluted from the column was sampled and subjected to HPLC analysis.
Table 4 shows the sugar composition (%) of the obtained hydrolyzate.

Immobilization of invertase enzyme:
0.2 g of commercially available invertase (manufactured by DSM, 200000 U / g) was dissolved in a phosphate buffer (pH 7), and 200 ml of the solution was passed through a 20 ml column packed resin at 4 ° C. (SV = 1). The invertase enzyme protein was bound to the ion exchange resin. The immobilization efficiency was 75%. Subsequently, 1 L of purified water was passed through and washed to finally obtain an immobilized enzyme (1500 U / wet weight (g)).

<Experimental example E: Isomerization reaction of enzyme hydrolyzate of sugar with alkali>
Each solution of the enzyme hydrolyzate obtained in the experimental sections C3, C4, and C5 in Experimental Example 2 was prepared to be 0.1 M NaOH, and an isomerization reaction was performed at a temperature of 60 ° C. for 2 hours. A part of the reaction solution after the isomerization reaction was sampled, and the sugar composition was analyzed by HPLC.
The sugar composition of the resulting alkali isomerization reaction product is shown in Table 5 below.

<Experimental Example F: Enzymatic Isomerization of Sugar Enzyme Hydrolyzate>
The hydrolyzate obtained in the experimental sections C1, C3, C4, and C8 in Experimental Example 2 was extracted from Arthrobacter globiformis M30 (deposit number NITE BP-1111) and used for the enzyme immobilized on the ion exchange resin. An isomerization reaction was performed (the immobilization technique is shown below). Isomerization is performed by feeding the solution to a 50 ml ion exchange resin (resin: Amberlite IRA900J, column inner diameter 1.5 cm) at a temperature of 45 ° C. and a feed rate of 0.5 ml / min, and sampling the column eluate. The sugar composition was analyzed.
The sugar composition (%) of the obtained enzyme isomerization reaction product is shown in Table 6 below.

* Immobilization of isomerase produced by Arthrobacter:
<Extraction of intracellular enzymes by ultrasound>
60 g of the cells obtained by culturing were suspended in 600 ml of 10 mM phosphate buffer (pH 7.0), disrupted with an ultrasonic homogenizer (SONICS & MATERIALS) while cooling in ice water, and heat shock at 50 ° C. for 15 minutes. Gave. About 500 ml of the supernatant obtained by centrifuging this crushed material at 12,000 rpm for 20 minutes was used as a crude enzyme solution.
<Immobilization of crude enzyme>
The crude enzyme solution was passed through the ion-exchange resin (Amberlite IRW904J, column inner diameter 1.5 cm) packed in the column (4 ° C., SV = 1) to bind the crude enzyme protein to the ion-exchange resin. Subsequently, 1 L of purified water was passed through and washed to obtain an immobilized enzyme (immobilized enzyme 1000 U / wet weight (g)). <Liquid reaction>
As the raw sugar, high fructose liquid sugar was prepared using 10 mM phosphate buffer (pH 7.5) so as to be Bx30, and was fed to 50 ml of the above immobilized enzyme resin at a liquid feed rate of 0.5 ml / min. (40 ° C). The half-life is 51 days, and it can be said that this immobilization method is very excellent in industry.

[Example 1]
<Sensory evaluation 1 of sugar composition>
Using 5 panelists familiar with the tastes of the 20s to 40s, the composition of the sugar solution obtained in Experimental Examples E and F (E1, E3, F1, F3) and each sugar were appropriately mixed. G1 (glucose 49: fructose 42: D-psicose 7), G2 (glucose 51: fructose 36: D-psicose 10), G3 (sugar 10: glucose 48: fructose 38) and G4 (sugar 40: glucose 25: fructose 25) Sensory evaluation was performed about the taste quality of each saccharide | sugar composition. All sugar compositions were adjusted to a solid content of 10%, and the evaluation was based on a 5-point scale (1 point: bad to 5 points: very good) for the “richness” and “balance” of sweetness. Table 7 shows the results (total score of five panelists).

Compared to G1, G2, G3, and G4, E1, E3, F1, and F3 had a good balance between richness and sweetness.
That is, the sugar is not completely hydrolyzed to the end, and the presence of D-psicose in this composition makes it more sweet compared to the sugar composition obtained by isomerization after complete hydrolysis of the sugar. It became clear that richness and balance improved.
Moreover, when the ratio of the sugar in a sweetener is 10 parts or less, or when it exceeds 75 parts, a thick feeling and the tendency to lose | balance are recognized, and it manufactures so that it may set to the sugar ratio in this range. Is good.

<Sensory evaluation 2 of sugar composition>
Next, H1 (D-psicose 10: erythritol 30: sucralose 0.1) and H2 (D-psicose 60: erythritol 20: sucralose) prepared by appropriately mixing E1, E3, F1, F3 and each sweetener. The taste of each saccharide composition of 0.055) was subjected to sensory evaluation in the same procedure as above. The results (total score of 5 panelists) are shown in Table 8.
However, since a high-intensity sweetener is included, it is difficult to compare with a solid content in the sweetener composition constant, and the sweetness of the sweetener composition is fixed to compare the sweetness.

It is generally known that high-intensity sweeteners have a bad aftertaste (there is an odd taste) compared to low-intensity sweeteners. In fact, when using sucralose, which is a high-intensity sweetener, It was an evaluation result that the aftertaste was bad (Table 7). High-intensity sweeteners have a long-lasting sweetness and off-flavor, and are often used in combination with sugar alcohols that have a refreshing sweet taste. It is very difficult to give the sweetness a unity (a sense of unity), and there is a problem that the sweetness of each sweetener is felt separately. E1, E3, F1, which are the sweetening compositions of the present invention, Compared with H1 and H2 containing high-intensity sweeteners, F3 and F3 had a coherent and highly desirable sweetness without any drawbacks such as off-taste.
That is, a sweetener containing a rare sugar containing at least D-psicose in a sweet composition comprising sugar, glucose, and fructose is obtained by adding D-psicose to a sweet composition comprising a sugar alcohol and a high-intensity sweetener. When compared with sweeteners, it can be said that it is a sweetener with more sweet quality.

A composition obtained by completely enzymatically hydrolyzing sugar according to the procedure of Experimental Example C was further isomerized with an isomerizing enzyme according to Experimental Example F to obtain Composition I1 (glucose 50: fructose 38: D-psicose 12). It was. In addition, a commercially available general isomerized sugar (glucose 50: fructose 45: oligosaccharide 5) is isomerized with an isomerase according to Experimental Example F, and composition I2 (glucose 50: fructose 34: D-psicose 11: Oligosaccharide 5) was obtained. The taste of each sugar composition was subjected to sensory evaluation by the same evaluation method as described above (<Sensory evaluation 1 of sugar composition>). However, the evaluation items were “strength of the start of sweet taste” and “miscellaneous taste”.

As a result, I1 was superior as a sweetener in terms of not only having a strong start of sweetness compared to I2, but also having less miscellaneous taste. From this, it can be said that the isomerized sweet composition obtained by the above method using sugar as a raw material is superior to the isomerized sweet composition obtained by the above method using isomerized sugar as a raw material as a sweetener. This is probably because contaminants such as oligosaccharides contained in commercially available general isomerized sugars slightly suppress the onset of the sweet taste and make it feel miserable.
From this result, it can be said that the sweet taste composition obtained using sugar as a raw material is more preferable as a sweetener than using a commercially available general isomerized sugar as a raw material.

[Example 2]
<Preparation of acidic beverage and sensory evaluation 1>
The sugar compositions (E1, E3, F1, F3) obtained in the above Experimental Examples E and F, G1 (glucose 45: fructose 42: D-psicose 7) and G2 (glucose) prepared by appropriately mixing each sugar 51: Fructose 36: D-psicose 10) Using each saccharide composition, an acidic beverage was prepared according to the formulation shown in Table 9. About this acidic drink, the sensory evaluation by five panelists was performed similarly to Example 1. The results are shown in Table 10.

Similar to the sensory evaluation results of the sugar composition itself, compared to G1 and G2, the acidic beverages using the sugar compositions of E1, E3, F1, and F3 each had good richness and sweetness balance.

<Preparation of acidic beverage and sensory evaluation 2>
G5 (glucose 60: fructose 38: D-psicose 10), G6 (dextrose 55: fructose 30: prepared by appropriately mixing the sugar compositions (E2, F4) obtained in the above experimental examples E and F. Using each sugar composition of D-psicose 20), G7 (sugar 36: glucose 45: fructose 22), and G8 (sugar 12: glucose 50: fructose 33), an acidic beverage was prepared according to the composition shown in Table 11. About this acidic drink, the sensory evaluation by five panelists was performed similarly to Example 1. The results are shown in Table 12.

Acidic beverages using E2 and F4 sugar compositions had better richness and sweetness balance than acidic beverages using sugar compositions lacking either sugar or D-psicose.

<Preparation of acidic beverage and sensory evaluation 3>
Sugar composition F3 (sugar 35: glucose 33: fructose 22: D-psicose 8) obtained in Experimental Example F or G1 (glucose 45: fructose 42: D-psicose 7) prepared by appropriately mixing each sugar The composition obtained by adding 0.002 part of stevia to 1 part by weight of each of F3-1, G1-1, and the composition obtained by adding 0.003 part of acesulfame K3 respectively. , G1-2, and 0.003 part of aspartame were designated as F3-3 and G1-3, respectively. Using each of these sugar compositions, an acidic beverage was prepared according to the formulation shown in Table 13. About this acidic drink, the sensory evaluation by five panelists was performed similarly to Example 1. The results are shown in Table 14.

As a result, the acidic beverage using the sweet composition containing sugar was better in both aftertaste and sweetness as compared with the acidic beverage using the sweet composition containing no sugar.
In the recent food and beverage market, there is a tendency to improve the taste quality while reducing calories by using a saccharide sweetener and a high-intensity sweetener together. In a sweetening composition in which stevia, acesulfame K, or aspartame, which are high-intensity sweeteners, are used in combination with sugar-based sweeteners, a good richness and sweetness balance are obtained by including sugar. be able to.

<Preparation of acidic beverage and sensory evaluation 4>
Sugar composition F3 obtained in Experimental Example F (sugar 35: glucose 33: fructose 22: D-psicose 10) and G1 (glucose 45: fructose 42: D-psicose 7) prepared by appropriately mixing each sugar ) Was used to prepare acidic beverages having the composition shown in Table 15, and the flavors of the flavors were compared by the same sensory evaluation method as in Example 1.

As a result, it was recognized that the acidic beverage using F3 has a more balanced sweetness than the acidic beverage using G1, and the flavor is enhanced. From this, it was found that the sweetening composition containing D-psicose and sugar has not only a good sweetness balance but also good flavor standing.

[Example 3]
Crystallization at a low temperature of the sugar solution is a major obstacle during storage and transportation. Therefore, the number of days for crystallization of the composition containing the present sugar was compared with the composition containing no sugar. Specifically, a 70% (w / w) solution was stored at 4 ° C., and the number of days required for crystallization during refrigeration storage of compositions E3, F1, and G2 was measured.
As a result, E3, F1, and the number of days required for crystallization were larger than G2, and improvement was recognized. From this, the tendency for the composition containing sugar to be harder to crystallize than the composition containing no sugar was recognized, and it became clear that it was effective during storage and transportation.

[Example 4]
<Effects of the sweetener composition of the present invention on blood glucose level and insulin secretion in humans>
The sweetener composition obtained by the production method of the present invention, that is, the blood sugar level and insulin secretion when each human sweetener composition obtained by allowing alkali to act on the enzyme hydrolyzate of sugar is ingested by humans. The effect was examined. Table 16 shows the sugar composition of each sweetener composition (J1 to J4) used. J1 is a raw material for obtaining each sweetener composition (manufactured by Mitsui Sugar Co., Ltd., trade name “Kami Shirasu”), and this was used as a comparative control group.
Each of the sweet tastes shown in Table 16 is given to 6 healthy persons who have no smoking habits (average age 34.7 years old, 4 men, 2 women, average BMI 22.1 kg / m2, average fasting blood glucose 92.4 mg / dL) After ingesting a 38.5% aqueous solution of the food composition, changes in blood glucose level and insulin concentration were measured. The test was conducted by a single blind crossover method in which an aqueous sugar composition solution described in Table 16 was ingested. Each test was conducted at an interval of about one week.
First, the subjects were fasted from 12 hours before the test day, and then blood was collected on an empty stomach. Next, 200 mL of any one of the 38.5% aqueous solution of the sweetener composition shown in Table 16 was ingested, and blood was collected at 30, 60, and 90 minutes after ingestion. In order to adjust the water content of the blood, 50 mL of water was ingested for each blood collection during the test, and the rest were fasted. The blood glucose level and insulin concentration of the collected blood were measured, and changes in blood glucose level and insulin concentration over time were recorded. The results obtained were expressed as mean values and standard deviations, and statistical tests were performed using Student's t test. The significance level of the test was less than 5% on both sides.
The blood glucose level was measured using Glucose CII-Test Wako (Wako Pure Chemical Industries, Ltd.), and the insulin concentration was measured using an ultrasensitive human insulin ELISA kit (Mercodia).

FIG. 2 shows the numerical results of the area under the blood glucose level curve obtained by plotting the elapsed time (minutes) from the intake of the aqueous solution of each sweetener composition on the horizontal axis and plotting the blood glucose level for each elapsed time on the vertical axis. . As a result, J3 was reduced to about 81.0% of J1, and J4 was reduced to 70.0% of J1, and it was found that the sweetener of the present invention significantly suppressed an increase in blood sugar level as compared with sugar. On the other hand, J2 was reduced to about 93.1% of J1, but no significant difference was observed.
In addition, the numerical value of the area under the blood glucose level curve is 50.4 mg · h / dL for J1, 46.9 mg · h / dL for J2, 40.8 mg · h / dL for J3, and 35.3 mg · h / dL for J4. Met.

The results of the area under the insulin concentration curve are shown in FIG. J2 was reduced to about 70.2% of J1, and J4 was reduced to 61.7% of J1, indicating that insulin secretion was significantly suppressed. On the other hand, J3 was reduced to about 80.9% of J1, but no significant difference was observed.
The area under the insulin curve was 28.2 mU · h / L for J1, 19.8 mU · h / L for J2, 22.8 mU · h / L for J3, and 17.4 mU · h / L for J4. .

When sugar is ingested, sugar is broken down into glucose and fructose by internal enzymes, and a portion corresponding to glucose is involved in an increase in blood glucose level and an increase in insulin secretion. Therefore, in the control group J1 (sugar), a part (50%) corresponding to 1/2 of sugar is involved in the increase in blood glucose level and the increase in insulin secretion, and the sweetener composition J2 of the present invention, As for J3 and J4, glucose is involved in addition to the portion corresponding to 1/2 of sugar, so that 48.7%, 49.0%, and 46.8% increase blood glucose level and It will be involved in an increase in insulin secretion.
Therefore, when the sweetener compositions J2, J3 and J4 of the present invention were ingested, it was estimated that the same increase in blood glucose level and increase in insulin secretion amount as in J1 were observed. Was particularly significantly reduced, and in J3, the increase in blood glucose level was particularly significantly suppressed. In J4, both the blood glucose level and the amount of insulin secretion were significantly reduced.
That is, the sweetener composition of the present invention can be used as a sweetener that is imparted with an effect of suppressing an increase in blood glucose level and / or insulin secretion amount when ingested, although it has a sweetness almost equivalent to that of sugar. .

It is more desirable that the sweetener of the present invention has a composition in which sugar is used as a raw material and the sugar is left in the finally obtained sweetener composition. Even when sugar is added as appropriate after obtaining a sweetener composition that does not remain, a sweetener composition having the same composition can be obtained.
Therefore, for reference, the sugar composition produced by the method described in Table 2010/113785 (as the composition is equivalent to the one obtained by removing the sugar portion of the sweetener composition of the present invention) When a sugar composition corresponding to the above-mentioned J2 to J4 obtained by adding A was prepared and a human test similar to that of Example 4 was performed, almost the same results were obtained.

From the above, the sweetener composition of the present invention is a sweetener composition having an effect of suppressing blood sugar level and / or insulin secretion, and can be said to be a sweetener composition that can be expected to reduce the risk of developing diabetes. In addition, continuous intake of the sweetener may ultimately reduce body fat accumulation.

The novel sugar composition of the present invention can be expected to be widely used as a sweetener for soft drinks and other beverages, and can be used in foods, pharmaceuticals or quasi drugs, oral compositions, and cosmetics. There is expected. Moreover, since the novel sugar composition of the present invention can be mass-produced and provided at a low production cost, it is expected that the application range will be further expanded.

1 Sugar dissolution tank 2 Hydrolysis tank and neutralization tank 3 Invertase immobilization column 4 Isomerization tank 5 Epimerase immobilization tank 6 Purification apparatus 7 Separation apparatus

Claims (15)

1. A step of obtaining sugar, a mixture of D-glucose and D-fructose, or a mixture of D-glucose and D-fructose by hydrolysis of the raw material sugar, and the sugar hydrolyzate Is a mixture of rare sugars containing sugar, D-glucose, D-fructose, and at least D-psicose, or a rare product containing D-glucose, D-fructose, and at least D-psicose. Through a step of obtaining a mixture of sugars, adjusting the sugar content in the final product according to the degree of hydrolysis reaction of the raw sugar, the final product comprising sugar, D-glucose, D-fructose, and at least D-psicose-containing rare sugar was included at a specific composition ratio, or D-glucose Over scan, D- fructose, and a method for making a sweetener composition, characterized in that the rare saccharide to be included in a particular composition ratio comprising at least D- psicose.
2. The process of hydrolyzing the raw material sugar is a process of isomerizing the sugar hydrolyzate by acid and / or enzyme decomposition, alkali isomerization, isomerization using calcium ion catalysis and / or enzyme isomerization. The method for producing a sweetener composition according to claim 1, wherein
3. Alkaline isomerization produces rare sugars including D-psicose, D-allose, D, L-sorbose, D-tagatose, and D-mannose, and the final product consists of these monosaccharides, sugar, D-glucose The method for producing a sweetener composition according to claim 2, wherein the mixture is a mixture with D-fructose or a mixture with D-glucose and D-fructose.
4. Enzymatic isomerization only produces D-psicose from fructose, and the final product is a mixture of D-psicose and sugar, D-glucose and D-fructose, or D-glucose and D-fructose. The manufacturing method of the sweetener composition of Claim 2 used as a mixture.
5. The method for producing a sweetener composition according to claim 2 or 4, wherein the enzyme isomerization is performed using an isomerase derived from Arthrobacter Globiformis M30 (deposit number NITE BP-1111).
6. The method for producing a sweetener composition according to claim 2, 4 or 5, wherein the enzyme isomerization is performed using an immobilized enzyme having an activity of 1000 U / wet weight resin (g).
7. The method for producing a sweetener composition according to any one of claims 1 to 6, wherein the final product is a sweetness composition having a low sweetness intensity and a little miscellaneous taste. .
8. The method for producing a sweetener composition according to any one of claims 1 to 6, wherein the final product is a sweetening composition that enhances flavor release.
9. The method for producing a sweetener composition according to any one of claims 1 to 6, wherein the final product is a sweetening composition having a good richness and a sweetness balance with a sugar ratio of 10 to 75 parts.
10. The method for producing a sweetener composition according to any one of claims 1 to 6, wherein the final product is a sweetening composition having a function of significantly reducing the amount of insulin secretion with a sugar ratio of 10 to 80 parts. .
11. A sweetener composition obtained by the production method according to any one of claims 1 to 10.
12. Food and drink comprising the sweetener composition according to claim 11.
13. The food and drink according to claim 12, which is labeled to suppress an increase in body weight and an increase in body fat accumulation.
14. Pharmaceuticals, quasi-drugs and cosmetics comprising the sweetener composition according to claim 11.
15. The pharmaceutical product, quasi-drug, and cosmetic product according to claim 14 for suppressing an increase in body weight and an increase in body fat accumulation.
    

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