JPS5951265B2 - Method for adding sweetness to foods and drinks - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides stevioside, which is a stevia extract, rebaudioside A, α-glucosyl stevioside, and a carbohydrate sweetener, thereby eliminating bitterness and astringency.
The present invention relates to a method for imparting sweetness to foods and drinks, which has a sharp sweetness, no decrease in sweetness multiple, and has succeeded in imparting a richness similar to that of sucrose.

In recent years, various harmful effects caused by excessive intake of sucrose have become a problem, and there is a tendency to move away from sugar.

The safety of synthetic sweeteners, which once attracted attention as an alternative to sugar, has become an issue due to bans on the use of zurtin and chikuguchi, and restrictions on the use of saccharin.

Therefore, consumers and food manufacturers are currently demanding the emergence of safer sweeteners.

Stevia extract was introduced against this historical background.

This is 5te, a perennial plant of the chrysanthemum family native to Paraguay in South America.
It is extracted and purified mainly from the leaves of Via Rebaudiana Bertoni (hereinafter referred to as stevia).

The sweet components contained in the stevia extract include the main components tevioside (hereinafter referred to as ST), R
ebaudioside A, Rebaudiosi
de B, C, D, E (hereinafter referred to as Reb, A, B,
A total of eight substances are known: Dulcoside A, Dulcoside A, and 5teviolbiosidec7).

The ratio of secondary components varies depending on the variety of frozen vegetables and cultivation conditions.

When currently available average Stevia leaves are used, the component ratio in the extract is ST is the highest, and the following are Reb and A.
, Reb, and C, and the others are small in quantity.

The ratio of ST to Reb and A is approximately 7:3.

Comparing the sweetness characteristics of each, first of all, when the corresponding sucrose concentration (hereinafter simply referred to as sweetness level) is 10%, ST is about 90 times as sweet as sucrose, and Reb and A are also about 120 times as sweet.

On the other hand, in terms of taste, ST has a unique bitterness and astringency, while Reb and A have a mild sweetness with little bitterness and astringency.

The sweetness characteristics of stevia extract containing both of these are as follows:
First, it has a high degree of sweetness.

Next, compared to licorice extract and the like, it has a basic characteristic of being quite similar to sucrose in its sharpness of sweetness (the degree of rapid onset and disappearance of sweetness).

In addition, it has excellent properties such as chemical stability, non-browning, non-fermentability, low osmotic pressure, and no calories.

Due to its stable price, it now has economic advantages compared to sugar and is expected to be used in many foods.

There are some problems that must be solved in order to put this Stevia extract into practical use.

The first is the characteristic bitterness and astringency derived from ST, which is the main component of Stevia extract.

Second, although the sharpness of sweetness is very good compared to licorice extract, it is true that it still feels strange compared to sucrose.

Conventionally, various methods have been proposed to improve these drawbacks.

There are two effective methods among them.

One of them is sucrose, glucose, maltose, tsurupit1~
, a method of using a carbohydrate sweetener such as Tulchit in combination with a stevia extract (for example, JP-A-52-145564).

Another method is to add glucose to ST through an α-glucoside bond by enzymatic reaction (Japanese Patent Application Laid-Open No. 54-5070).
There is.

However, none of these methods are yet practically satisfactory.

First, when used in combination with a carbohydrate sweetener, the improvement effect of ST on bitterness and astringency is affected by the sweetness level and sweetness substitution rate at that time.
It is largely influenced by the ratio of the sweetness level (including synergistic effects) of the alternative sweetener to the total sweetness level of the target food or drink.

According to studies, the maximum sweetness substitution rate is 30% for most foods and drinks with a sweetness level of 7 to 8% W/W or higher.

In actual cases where stevia extract is used in coffee drinks or soft drinks, the sweetness substitution rate is often 10 to 20%.

When the sweetness substitution rate is 30% or less, the taste quality becomes more refreshing and firmer than when no stevia extract is used, and in fact becomes more preferable.

Sweetness multiple (hereinafter, sweetness multiple refers to the multiple of sucrose)
The amount increases by more than 300 times due to the synergistic effect with sugar sweeteners.

As a result, the sweetening cost is about 172 times that of sucrose, and sufficient economic benefits can be obtained.

That is, it is possible to enjoy both economic benefits and improved taste.

However, this method does not fully utilize the excellent characteristics of stevia extract, such as being non-caloric, preventing dental caries, non-browning, low osmotic pressure, and inhibiting freezing point drop.

For example, in the case of diet sweeteners, a calorie reduction rate of at least 50% is required.

If an attempt is made to achieve a calorie reduction rate of 50% or more by using a combination of stevia extract and carbohydrate sweetener, the current serious drawback is that the taste has to be sacrificed.

On the other hand, in the method of enzymatically adding glucose to ST, ST, which is the root of most of the bitterness and astringency of Stevia extract, is α-glucosylstevioside (hereinafter referred to as α-G).
The sweetness quality is clearly improved compared to the original stevia extract by changing it into a completely different substance called stevia extract.

α-GS is a general term for substances in which D-glucose is α-glycosidic bonded to ST, and consists of different components depending on the bonding position and number of D-glucose bonds, and the taste quality and sweetness multiple of each component also differ.

According to the study results of the present inventors, α-GS has at least 3QW/W% or more of D-glucose bound to ST.
is about 20W/W% of unreacted ST with respect to α-GS.
Even if it contains bitterness and astringency, the sweetness level is LOW/W.
It has been found that it is not impossible to use it alone in the case of food and drinks with a concentration of about 1.5%.

However, this α-glucosylated Stevia extract also has serious drawbacks in practical use.

This is because the sweetness level of this product is considerably lower than that of the produced Stevia extract, and therefore the sweetening cost is much higher than that of sucrose, making it impossible to obtain economic benefits.

Table 1 shows the sweetness characteristics of α-glucosyl stevia extract (same as that used in Example 1) and purified stevia extract (same as that used in Example 1) in terms of sweetness level lQW/W%. The results of a sensory test conducted at 20° C. by 17 panelists regarding the aqueous solution system are shown below.

As is clear from Table 1, compared to Stevia extract, its α
- The bitterness, astringency and sharpness of sweetness of glucoside are considerably improved, and it is possible to use it alone at a sweetness level of 1QW/W%.

There is a marked difference compared to the fact that stevia extract cannot be used alone under the same conditions.

However, when evaluated from a practical standpoint as a sweetener, α-
When glucoside is used alone, bitterness and astringency remain, albeit slightly, and the sweetness remains unsatisfactory.

An even more serious drawback is that, first, the richness is significantly inferior to that of carbohydrate sweeteners.

Therefore, compared to carbohydrate sweeteners, especially sucrose, which is a typical sugar sweetener, it is inferior in taste even though the intensity of sweetness is comparable.

The second is the low sweetness factor.

Considering the current situation where the sweetness factor is 1QW/W%, which is slightly less than 60 times that of sucrose, and the unit price is more than 100 times that of sucrose, it is more than a cost advantage. Although glucosides show significant improvements in bitterness and astringency, as well as considerable improvements in sharpness of sweetness, their serious drawbacks, such as a lower sweetness factor and lack of richness, have hindered their commercialization. The reality is that progress is being hindered.

The purpose of the present invention is to improve the drawbacks of α-GS, such as bitterness and
To provide a natural sweetener that has no astringent taste, has a sharp sweet taste, has a body taste similar to that of sucrose, has a lower sweetening cost than sucrose, and has a calorie reduction of 50% or more.

For this purpose, the present inventors have conducted various studies.

As a result, it was found that combination use with carbohydrate sweeteners was effective in improving the sharpness of sweetness and body taste (Table 1)
).

However, regarding the sweetness factor, as is clear from the results in Table 1, the synergistic sweetness effect obtained by the combination with sucrose is not as great as the synergistic effect obtained by the combination of purified stevia extract and sucrose, so it is not satisfactory.

The same applies when used in combination with carbohydrate sweeteners other than sucrose.

Therefore, as a result of further investigation, we focused on methods to increase the sweetness of the combination system of α-GS-containing substances and carbohydrate sweeteners.
First, the D-glucose addition rate (ratio of added D-glucose to ST in α-GS) is 30 to 120 W/W%.
using α-GS of Reb.
The present invention was completed based on the discovery that when A and ST coexist in an appropriate ratio, a synergistic effect appears on the sweetness of the two.

That is, 31 parts by weight of a-G, and Reb, A or
eb. When a stevia extract containing A to ST ratio of 20 W/W% or more is coexisting at a ratio of 0.4 to 5 parts by weight as total ST content (according to Japan Food Additives Association, Natural Food Additives Voluntary Standards Law) A particularly clear sweet synergistic effect was observed.

An example is shown in Table 2.

However, this compound alone is not satisfactory as a sweetener in terms of bitterness/astringency, sharpness of sweetness, and richness.

It has been found that the object of the present invention can be effectively achieved within the range of sweetness substitution rate of 30 to 80% only by using this in combination with a carbohydrate sweetener.

In the case of a neutral aqueous solution as well, the effects of the present invention were confirmed as shown in Table 2.

Preparation of aqueous solution: 10WOW% orange juice 1') p
Add sweetener to H3,0 citric acid aqueous solution with sweetness level Low/W%
(Added as shown.

Contents of various sweeteners: A...Reb, A
(HPLC method thread thickness 97%) B・・・・・・・・・A and ST (HPLC method purity 98%)
%) 1:2 mixture C......α-GS (same sample as Example 1)
Mixture of and A (2: 1) D・・・・・・・・・Mixture of α-GS and B (2: 1
)E・・・・・・・・・Mixture of C and sucrose (sweetness substitution rate 50%) F・・・・・・・・・Mixture of D and sucrose (sweetness substitution rate 50%) Bitterness/astringency, The evaluation criteria for sharpness of sweetness and richness are the same as in Table 1.

When using stevia extract and carbohydrate sweetener, Table 1
It is known that a sweet synergistic effect as shown in
It was unexpected that a significant sweet synergistic effect as shown in Table 2 would occur when α-GS, Reb, A or Stevia extracts and carbohydrate sweeteners were co-present.

The mechanism by which such a synergistic effect occurs is completely unknown.

To put it simply, the sweetness synergistic effects of α-GS, ST, Reb, and A and sucrose are in the order ST > Reb, A > a-GS ■, and the sweetness persistence of each is ST > Reb, From the fact that A > a - GS, it is thought that the difference in sweetness behavior over time is somehow involved.

In any case, by utilizing this sweetness synergistic effect, both the sweetness multiple and the taste characteristics (bitterness/astringency, sharpness of sweetness, and richness) were improved, and the object of the present invention could be achieved.

The present invention will be explained in more detail below.

α-GS used in the present invention is obtained by reacting ST or Stevia extract and saccharides such as sucrose starch partial hydrolyzate with enzymes such as α-glucosidase, dextran sucrase, cyclodextrin, and glucosyltransferase in an aqueous solution. Contained in reaction products.

In the case of ST generation, a small amount of unreacted ST is included and a mixture of one or more glucoses added to glucose residues in the ST molecule through α-glucosidic bonds.

In the case of stevia extract, some of the stevia sweet ingredients other than ST, such as Reb and A, are also α-glucosylated.

They are recognized to have taste improvement effects equal to or greater than those produced by ST.

The taste improving effect of α-GS differs depending on the ratio of added sugar.

As a tendency, a higher D-glucose addition rate contributes to the improvement of the taste of the present invention.
The one to which glucose is added is used.

α-GS with a D-glucose addition rate of 30 W/W% or less is inferior in taste quality improvement effects such as bitterness and astringency, and therefore cannot achieve the object of the present invention.

On the other hand, if the D-glucose addition rate is 120 W/W% or more, it is difficult to obtain the synergistic sweetness effect of the present invention.

ST, Reb, and A used in the present invention may be used as a stevia extract, or may be used as low to high purity products of ST, Reb, and A separated from the stevia extract by a known fractionation method such as a crystallization method or a column chromatography method, or their respective low to high purity products. A mixture of the following can be used.

In the method of the present invention, the ratio of ST, Reb, and A is important, and if Reb and A are less than 20W/W% of ST, S
The bitterness and astringency become strong due to the influence of T, and even if the ratio of α-GS is increased to the limit where sweetness synergistic effect can no longer be expected, it cannot be compensated for.

In addition, when the ratio of ST, Reb, and A is the same, Stevia extract or its crystallized mother liquor is superior to the pure products of each in terms of synergistic sweetness effect and taste quality. Most preferred is the crystallization mother liquor.

Sono The carbohydrate sweeteners referred to in the present invention include fructose, glucose,
Monosaccharides such as xylose; disaccharides such as sucrose, maltose, and lactose; sugar alcohols such as sorbitol, xylitol, and maltitol; each can be used alone or as a mixture of two or more 1. ) can be done.

When the mixed sweetener consisting of α-GS, ST, Reb, and A used in the present invention is used in combination with a carbohydrate sweetener having a total sweetness of 20 W/W% or more, the sweetness multiple is lower than that of relatively low sweetness foods such as coffee drinks. In some cases, the amount is more than 100 times higher, and even in the case of relatively highly sweetened foods such as jam, it reaches several tens of times, so the amount added for the necessary sweetness is significantly lower than that of carbohydrate sweeteners.

Therefore, by controlling the amount and type of carbohydrate sweetener used in conjunction with the method of the present invention, it is possible to easily cut calories and/or control blood sugar levels.
Suitable for sweetening beauty foods, health foods, and diet foods.

Furthermore, in order to prevent dental caries, which has recently become a problem, the carbohydrate sweetener used in the present invention may be selected from other than sucrose, such as glucose, maltose, sorbitol, maltitol, etc.

Examples of such foods include confectionery such as chewing gum, chocolate, caramel, candy, and biscuits; drinking water such as carbonated drinks, fruit juice drinks, and lactic acid bacteria drinks; particularly suitable for the purpose of preventing dental caries.

It is also suitable for sweetening cosmetics and medicines that require a cavity prevention function, such as gargling water and line brushes.

The method of the present invention is not limited to applications related to the maintenance and promotion of second-class health, but can be used to sweeten various general foods and drinks.

Beverages such as soft drinks and milk drinks; ice cream,
Frozen desserts such as ice candy; Confectionery such as Japanese sweets and Western sweets; Side dishes such as vinegared dishes and boiled dishes; Seasonings such as seasoned vinegar, mayonnaise, dressing, and dashi stock; Pickles such as Bettaramasu and Rakkyozuke ;Other linear tooth brushing,
It can be used to sweeten various cosmetics and medicines such as lip balms, oral solutions, troches, and gargles.

In order to sweeten the above-mentioned foods, beverages, luxury foods, cosmetics, pharmaceuticals, etc. by the method of the present invention, the steps required to prepare each product include, for example, mixing, kneading, dissolving, permeating, dipping, spraying, etc.
Known methods such as coating, spraying, and injection may be selected as appropriate.

Finally, the effects of the method of the present invention are summarized as follows.

First of all, the method of the present invention improves the serious drawback of α-GS, which is that it has a low sweetness level and does not offer any cost benefits, by reducing bitterness and astringency, improving the sharpness of sweetness, and dramatically increasing body taste. As a result, we were able to achieve sweetness with a sweetness substitution rate of 30% or more, which was not possible with conventional stevia extracts, by combining it with carbohydrate sweeteners. This has become possible while satisfying economic efficiency.

The second point, although not noteworthy, is that the stability of the solution form of α-GS is improved by the method of the present invention.

When α-GS is stored in food in the form of an aqueous solution, it may become somewhat unstable depending on the conditions.

That is, in the study conducted by the present inventors, when the sterilization conditions were insufficient, a slight decrease in clarity was observed in the α-GS alone system or the combination system of α-GS and a carbohydrate sweetener.

However, such a phenomenon was not observed in the method of the present invention.

Although the detailed mechanism of this phenomenon is unknown, it is possible that the presence of ST, Reb, and A had some influence on the presence of microorganisms.

Example 1 (1) Preparation of α-GS Total stevioside content was 85.2 W/W%, high performance liquid chromatography (abbreviated as HPLC method).

The following HPLC measurements of α-GS and Stevia extracts were performed using a column: Shimadzu PNH2-10/52504, carrier;
CH3CN/H20 (78/22) 0.9ml/rr
nn, detector: Purified stevia extract with ST content of 49.2 W/W%, Reb, A content of 18.4 W/W%, Reb, C6.8 W/W%, all conducted under UV 200 nm conditions. Steviafin (trade name: Steviafin H1 manufactured by Sanyo Kokusaku Pulp Co., Ltd.) is taken, and maltodex 1-phosphorus of E, 28 is mixed with cyclodextrin glucano-1 helansferase (E, C02,4,1,19) in a known method. The reaction was carried out according to (Japanese Unexamined Patent Publication No. 54-5070, Experiment 1-2).

The reaction solution inactivated by heating is mixed with a porous synthetic adsorption resin (trade name H).
P-20, manufactured by Mitsubishi Chemical Industries, Ltd.), cation exchange resin ■R-120 (H type), anion exchange resin IRA-9
3 (CH type) and a known method (Japanese Patent Publication No. 55-47871) using powdered activated carbon to obtain a purified α-glucosylated stevia extract (sample A).

Sample Acr) GC method Total ST content 54.2%, HPLC
Unreacted sT, Reb, A and Reb, determined by the method
C is 5.8W/W%, 1.3W/W% and 0.4W, respectively.
/'W%.

For HPLC Char 1, ST and Reb, A
There were many peaks due to various α-glucosylated products.

As a result of investigation using the method of Experiment 4 in JP-A No. 54-5070, these peak components were α-monoglucosyl ST, α-
Diglucosyl ST, α-triglucosyl ST, α-monoglucosyl Reb, A and α-diglucosyl Reb,
It was confirmed that each of B and other stevia sweet ingredients contained a small amount of α-glucoside.

Next, the α-GS content determined by column chromatography treatment of sample A was 48.6 W/W of sample A as a solid content.
%Met.

Further, this α-GS was treated with α-darcosidase by a known method, and then D-glucose in the effluent and washing liquid obtained by column treatment using HP-20 in a conventional manner was analyzed by HPLC method (column: Shimadzu PNH2- 10/S-2504, carrier: CH3CN/H20 (78 ml/22 ml), detector: differential refractometer).

As a result, the glycosylation rate of α-GS was 66.9 W/W%.

On the other hand, 90V/■% methanol was passed through the HP-20 column after washing with water, and the stevia sweet component in the eluate was removed by H
Analyzed by PLC method.

The multiple peaks of α-glucoside that were observed before α-glucosidase treatment disappeared.

(2) Preparation of coffee beverage and sensory test Sample A Stevia extract crystallization mother liquor [see Japanese Patent Publication No. 55-26819, main sweet component content (HPLC method, solid content W/'W
%) 5T22,01Reb, A39,3,Reb,
C12, O) and sugar mixed glucose fructose corn syrup (trade name:
Sunfract S30” [Sanmatsu Kogyo Co., Ltd.% formula% M%); fructose 22.4, glucose 25.9, sucrose 22.
'5) to obtain a coffee beverage according to the formulation shown in Table 3.

The table shows the sensory test results conducted by a panel of 17 people at a liquid temperature of 20°C. The coffee beverage preparation conditions are shown in the same table: 5g of instant coffee is added as a sweetener and milk diluted 1:1 to make a total volume of 1kg, and heated at 120°C. It was sterilized by heating in an autoclave for 30 minutes.

Criteria for evaluating richness and aftertaste of sweetness; Same as Table-1.

Example 2 (1) Preparation of α-GS ST and sucrose with a total ST content of 100 W/W% (based on solid content) and HPLC method purity of 99.8 W/W% were prepared using a known method (Japanese Patent Laid-Open No. 54-5070). The reaction solution obtained by the reaction in accordance with Example 3) was treated in the same manner as in Example 1 to obtain a purified reaction product (Sample B).

As a result of analyzing sample B in the same manner as in Example 1, the GC method total ST
The content was 58.3 W/'w%, unreacted S by HPLC method.
T was 7.8 W/'w%.

Other α-monoglucosyl ST, α-diglucosyl ST
, the presence of α-triglucosyl ST was confirmed.

Also, 69.4W/W for the total ST content of the generated ST raw material
% of D-glucose was added through α-glucosidic bonds, and it was found that D-glucose was added to 86.6 W/W % of ST in the starting material.

Sample B Stevia extract eJ (same as that used in Example 1) and high fructose glucose liquid sugar (trade name: Sunfruct 550J [
A carbonated drink was prepared under the conditions shown in Table 4 using Sanmatsu Kogyo Co., Ltd., solid content 75 W/W%, ingredients (based on solid content): fructose 55, glucose 40] as a sweetener.

The results of the sensory test conducted by a panel of 17 people at a room temperature of 30°C and a liquid temperature of 10°C are shown in the same table along with comparative examples.

Preparation conditions for carbonated beverage: Add drinking water to sweetener, 0.7 g of citric acid, 0.3 g of malic acid, and 1 g of lemon essence to make a total amount of 1 kg.
After filtering with a membrane filter with a pore size of 0.1 μm,
While cooling, carbon dioxide gas was injected under pressure at 4.5 kg/cm2, and a transparent glass bottle was filled and capped.

Some of the heat sterilized at 65℃ for 15 minutes were subjected to sensory test I.
Some of the solutions were allowed to stand at room temperature for 2 months, and then the transparency of the solutions was visually observed.

Claims (1)

[Scope of Claims] 1 Stevia extract which is rebaudioside A alone or a mixture of stevioside and rebaudioside A of 20W/W% or more of stevioside, and a D-glucose addition rate of 3QW/W% or more A method for imparting sweetness to foods and drinks, which comprises using α-glucosyl stevioside and a carbohydrate sweetener in combination. 2. The method for imparting sweetness to foods and drinks according to claim 1, wherein the weight ratio of stevia extract to α-glucosyl stevioside is 1:0.4 to 5. 3. The sweetening agent according to claim 1 or 2, wherein the sweetness substitution rate of α-glucosyl stevioside and stevia extract for the carbohydrate sweetener is 30 to 80%. A method for adding sweetness to foods and drinks.