JP2639386B2 - Palatinose condensate, method for producing and using the same - Google Patents

Description

The present invention relates to a palatinose condensate obtained by condensing a disaccharide, paranose, a method for producing the same, and a method for using the same.

[Conventional technology]

Palatinose is also called isomaltulose, a disaccharide in which glucose and fructose are α-1,6 linked,
That is, it is 6-o-α-D-glucopyranosyl-fructofuranose. Palatinose itself has been known for a long time, is a carbohydrate naturally contained in honey, and is industrially obtained by reacting sucrose with glucositransferase. Palatinose has high quality sweetness similar to sucrose and food processing properties, so it can be used in foods in general. In particular, since palatinose is non-cariogenic and anti-cariogenic, it is a natural homogeneous sweet that does not cause dental caries. In recent years, demand for such materials has rapidly increased (Japanese Patent Laid-Open No. 57-71377).

Also, a method is known in which a solution of fructose, which is a monosaccharide, is concentrated and heated at an acidic pH to produce a condensate of fructose (Japanese Patent Application Laid-Open No. H10-163,878).
61-271295). This fructose condensate is a sweetener.
It is also known to utilize a fructose condensate for the growth of bifidobacteria (Japanese Patent Application Laid-Open No. Sho 62-294081).

(Configuration of the present invention)

The present inventor has produced a palatinose condensate formed by condensing a disaccharide, palatinose, and has found that it has extremely useful properties in the food field. First, a method for producing a palatinose condensate and the condensate produced will be described below.

By heating and concentrating an aqueous solution of palatinose having a pH of 3.2 to 5.8, preferably pH 3.5 to 4.4 to a liquid temperature of about 105 to 170 ° C., palatinose is condensed and 2 to 6, mainly 2 to
It has been found that a condensate in which four palatinose units are linked is obtained. For the condensation reaction, aqueous palatinose solution
pH, temperature and concentration have a great influence, and the reaction is promoted at high temperature, low pH and high concentration. However, when these factors are under strong reaction promoting conditions, the production of palatinose condensate increases and the decomposition reaction of palatinose simultaneously occurs, and the decomposition product generated by the decomposition of palatinose,
Monosaccharide and its likely condensate with palatinose 3
Sugar equivalents also increase.

The palatinose condensate is colorless and a substance having a rather weak sweet taste, but the decomposed product resulting from the decomposition of palatinose has a bitter taste. Therefore, when the palatinose condensation reaction product is used as it is (without isolating only the condensate) in a food, the generation of the decomposition product is not more than a certain amount, preferably
It is desirable to set the condensation reaction conditions so as to suppress the concentration to 0.45% by weight or less, or to remove the decomposed product from the condensation reaction product using an exchange resin.

The above-mentioned bitterness can be eliminated by adding an alkaline substance to the product to make it neutral or alkaline. However, coloring becomes remarkable.

In order to suppress the generation of decomposition products, it was found that it is preferable to carry out heat concentration for a relatively short time under reduced pressure conditions, particularly under a pressure of about 110 mmHg (absolute pressure, the same applies hereinafter). The heating time depends on the equipment used, but is generally 1 to 60 minutes. It is preferable to concentrate until the water content becomes 1 to 5% by weight. The liquid temperature at the end of the concentration under reduced pressure is about 105 to 170 ° C, preferably 105 to 160 ° C, particularly 130 to 160 ° C. For vacuum concentration, for example, thin-film spiral-down concentrators or continuous concentrators are suitable, in which the contact time between the charge and the heating surface is short.

It can also be heated and concentrated under normal pressure. Generally, it is necessary to raise the temperature to a high temperature of 140-165 ° C. to make the water suitable for the condensation reaction. The heating time is relatively long.
For this reason, a large amount of palatinose degradation products are produced. The method of raising the temperature using a plate heat exchanger and flashing is preferable because the time for holding at a high temperature is short, but the concentration is insufficient and the amount of water in the solution is relatively large and the condensation reaction tends to be insufficient. .

A method using an extruder is also conceivable as a pressurized melting method, but it is not preferable in terms of generation of decomposition products.
Any of these methods can cause a palatinose condensation reaction.

When palatinose is dissolved in water, its pH value will be around 5.8. Since the condensation reaction of palatinose is accelerated by an acidic catalyst, it is preferable to adjust the pH to about 3.2 to 5.8, particularly 3.5 to 4.4 by adding an acid to the starting aqueous solution of palatinose. The acid is not particularly limited, but an acid commonly used in foods, for example, a low-volatile organic acid such as citric acid, malic acid, succinic acid, and tartaric acid is preferably used.
Citric acid is particularly preferred because of its relatively high catalytic activity and low amount of decomposition products. Easily volatile organic acids such as acetic acid evaporate and decrease during concentration and must be replenished, which is not preferable in operation. Also, hydrochloric acid, phosphoric acid,
Inorganic acids such as sulfuric acid are not always preferred because the reproducibility of the reaction is slightly poorer than that of organic acids and the quality of the product becomes unstable. Two or more acids can be used.

The concentration of palatinose in the starting aqueous solution of palatinose is not particularly limited as long as it is in a range that substantially completely dissolves during heating. If the concentration is too low, the concentration time is prolonged, which is not preferable. Generally, a concentration of about 70 to 80% by weight is good.

When the condensation reaction is performed as described above, a product having a solid content of 95 to 99% by weight is obtained. In the product, 2 to 6
4 to 12 saccharides, mainly 4 to 8 saccharides, mainly 10 to 70 saccharides formed by the condensation of individual, mainly 2 to 4 palatinose units.
% By weight. A monosaccharide formed by decomposing palatinose, which is a disaccharide, a trisaccharide equivalent (hereinafter simply referred to as a trisaccharide) which is considered to be produced by condensing pachinose with the monosaccharide or its ring-opened product, and a structure Decomposition products with unknown bitterness generally occur in amounts of up to 20% by weight. Unreacted palatinose also remains.

Hereinafter, the composition analysis of the product thus obtained will be described. As a sample, a heat-concentrated product obtained in Example 1 described later is used. The product was subjected to high performance liquid chromatography under the following conditions.

Column Shodex Ionpak KS-802 Mobile phase Water Mobile phase flow rate 1ml / min Detector Differential refractometer Differential refractometer sensitivity 16 × Chart speed 0.5cm / min Temperature 80 ° C Sample concentration 5w / v% Injection volume 25μ Fig.1 is obtained It is a chromatograph. The substance and amount corresponding to the retention time of each peak are as follows.

In FIG. 1, since the fractionation of the trisaccharide and the tetrasaccharide is insufficient (peak number 3), the same sample was subjected to the following conditions under which the fractionation was good (but the fractionation of the monosaccharide was insufficient). High performance liquid chromatography was applied.

Column ERC-NH-1171 [Elmer Optical Co., Ltd.] Mobile phase acetonitrile / water = 63/37 Mobile phase flow rate 1 ml / min Detector Differential refractometer Differential refractometer sensitivity 16 × chart speed 0.5 cm / min Temperature 25 ° C Sample concentration 5 w / v% Injection amount 25μ The obtained chromatograph is shown in FIG. The substances and amounts corresponding to the retention time of each peak are shown below.

From this, it was found that the ratio of the trisaccharide to the tetrasaccharide was about 1:10. Therefore, when the peak number 3 in Table 1 was proportionally divided, the following composition was obtained.

That is, the sample contains 4 to 8 saccharides according to the present invention.
4.3% was included.

Next, the heat concentrated product was subjected to hydrolysis and analyzed.
That is, an aqueous solution containing 5% of the heat-concentrated product obtained in Example 1 as a solid content was prepared, and 1 ml of 1N hydrochloric acid was added to 10 ml of the solution, followed by heating at 80 ° C. for 15 minutes for neutralization. The product was subjected to high performance liquid chromatography. Conditions are Shod above
It is the same as that of ex Ionpak KS-802.

 The chromatogram as shown in FIG. 3 was obtained.

The substance corresponding to each peak and its amount are as follows.

That is, the palatinose condensate of the present invention becomes almost palatinose by hydrolysis.

2 shows two embodiments of the method for producing a palatinose condensate according to the present invention. First, as a batch method, a stainless steel kettle concentrator with a stirrer for manufacturing 20 volumes of hard candy was used, and 15 kg of an aqueous solution of palatinose (75% by weight) was charged. The final heating temperature is set at 10 ° C intervals from 100 ° C to 170 ° C, and the citric acid amount is 0%, 0.001%, 0.01%, 0.1%, respectively.
And 1.0% (both by weight). In all cases, the pressure was 50 mmHg and the heating time was about 25-30 minutes. The results are shown in FIGS. 4 and 5. In FIG. 4, the vertical axis indicates the percentage of palatinose decreased (reaction rate), and the horizontal axis indicates the amount of citric acid added (% based on the solid content). In FIG. 5, the vertical axis indicates the amount (yield) of the generated palatinose condensate, and the horizontal axis indicates the amount of citric acid added.
In each bar graph group, the case where the final heating temperature is 170, 160, 150, 140, 130, 120, 110 and 100 ° C. is shown from right to left from each bar. The case where the bar graph is not visible on the low temperature side in the figure indicates that the result was almost zero. The palatinose reaction rate increases as the amount of citric acid added increases and as the reaction temperature increases, but the yield of the condensate is 0.01% when the amount of citric acid added is 0.01%.
%, Maximum when the temperature is 150 to 160 ° C. However, under these conditions, it is difficult to suppress the generation of coloring components and bitter components. Therefore, the final heating temperature is preferably 140 ° C. under the above reaction conditions.

In another embodiment, a continuous pressure evaporator was used. The aqueous solution of palatinose is sent from the storage tank by a metering pump to a tubular vacuum heating can and stays there for about 1 minute, and then sent to a vacuum evaporator and stays there for about 3 minutes. In the tube-type reduced pressure heating tube, an aqueous solution of palatinose is transported through the tube, and the outer wall of the tube is heated to a predetermined temperature between 125 ° C and 150 ° C by high-pressure steam. When the temperature of the tube-type vacuum heating tube exceeds 130 ° C, the concentration temperature in the vacuum evaporator is about 10 ° C lower than that temperature.
Lower, about 6 ° C below 130 ° C. In all cases, the amount of citric acid was 0.01% by weight and the pressure was 50 mmHg. The results are shown in FIG. The vertical axis indicates the content (% by weight), and the horizontal axis indicates the heating temperature of the tubular vacuum heating can. The three curves in the figure respectively correspond to palatinose, palatinose condensate, and the sum of the decomposition products, monosaccharides, and trisaccharide equivalents in the heat concentrated product from the top.

Although the amount of the condensate produced in the continuous vacuum concentration evaporator is lower than that in the case of heating for 25 to 30 minutes by the above-mentioned batch method, the production of decomposition products, monosaccharides and trisaccharide equivalents is 4 times smaller than that of the batch method.
% Or less. Therefore, there is room for raising the reaction temperature but increasing the amount of condensate by increasing the amount of the organic acid added.

Hereinafter, the properties and utilization of the palatinose condensate of the present invention will be described.

The palatinose condensate of the present invention has an extremely low sweetness as compared to palatinose as well as sucrose. Since the condensate returns to palatinose when hydrolyzed, the condensate is also non-cariogenic and anti-cariogenic like palatinose. Therefore, the palatinose condensate can be used to change the texture and the like without changing the sweetness of the food, and is particularly suitable for use in foods characterized by non-cariogenic or anti-cariogenic properties. Above all, it has a special effect when used in foods that use palatinose as a sweetener. That is, since palatinose has a lower solubility than sucrose, its use is limited. For example, jam, sheep can, hard jelly, caramel and the like cannot be produced due to precipitation of palatinose crystals, that is, "return" and "shari". In order to prevent "return" and "shari", it is conceivable to add sorbitol, starch hydrolyzate, reduced malt starch syrup, sucrose, coupling sugar, etc., but in this method, it is inevitably contained in confectionery. As a result, the content of palatinose is reduced, and it cannot be said that the confectionery does not become caries or is hardly caries. It has been found that when the palatinose condensate of the present invention is used in foods together with palatinose, the precipitation of palatinose crystals can be prevented, and such foods have low caries.

When a palatinose condensate is used with palatinose according to the present invention, it is not necessary to separate the palatinose condensate from the palatinose condensation reaction product. In addition to the palatinose condensate, the entire reaction product mixture containing unreacted palatinose and the third class (hereinafter referred to as the product mixture) can be used, and the residual palatinose contained therein may be included in the calculation of the food formulation. . At this time, it is usually preferable to use a product mixture in which the amount of the above-mentioned bitter decomposition product is small, for example, 0.45% by weight or less. However,
Since the presence or absence of bitterness also depends on the amount of the product mixture added to the food, the value of 0.45% by weight is merely an example.

Further, the palatinose condensate or product mixture of the present invention includes:
Can be used as a substitute for conventional syrup. That is, they have the same viscosity increase, freeze prevention, food moisturizing effect, body effect, and growth inhibitory effect of putrefactive bacteria as in the case of conventional starch syrup.

Furthermore, the palatinose condensate of the present invention is extremely useful as an intestinal bifidobacterium growth promoting substance. When humans take palatinose, it is known that palatinose is hydrolyzed and digested and absorbed by the disaccharide hydrolase isomaltase present in the small intestinal mucosa, and therefore the rate of utilization by bifidobacteria is considered to be low. However, it was found that the palatinose condensate reached the large intestine and was used by bifidobacteria. For this reason, the palatinose condensate is preferably contained in the composition (food) for growing Bifidobacterium in an amount of about 0.5 to 80% by weight, particularly about 1 to 70% by weight (Japanese Patent Application No. 63-97870).

Hereinafter, the present invention will be described with reference to examples. In the examples, parts and% are parts by weight and% by weight unless otherwise specified.

Example 1 Production of Palatinose Condensate 100 parts of palatinose crystals and 0.01 part of citric anhydride were added to 33 parts.
The mixture was heated to 105 ° C. with stirring to dissolve, heated to 150 ° C. within 1 minute in a heating can under the pressure of 60 mmHg using the continuous vacuum evaporator described above, and then heated. 3
The mixture was concentrated in an evaporator for minutes. Next, it was solidified to a size of 6 g / piece by a stamping machine and pulverized by a pulverizer. A product containing a palatinose condensate having the following composition was obtained.

The product has a solids content of 99.0%, pH 4.2, color value (ICUMSA
(Unit: 31) No bitterness, a little sweetness. The product was subjected to high performance liquid chromatography as described above and was found to contain 44.3% (composition excluding water) of the palatinose condensate.

Example 2 Production of Palatinose Condensate 100 parts of palatinose crystals and 0.02 part of citric anhydride were added to 33 parts.
Of boiling water, dissolve by heating to 105 ° C with stirring, and raise the temperature of the concentrate under a pressure of 30 mmHg in a vacuum concentrator.
It was boiled down for 35 minutes until it reached 150 ° C. Thereafter, the heating was stopped, and the size was reduced to 6 g / piece by a stamping machine, solidified, and pulverized by a pulverizer.

The product had a solids content of 99.0%, a pH of 4.0, and a color value of 88 (ICUMSA units).

According to the high performance liquid chromatography, the composition was as follows. The percentage is a composition excluding water in the concentrated product.

Palatinose condensate 70.8% Palatinose 22.1% Trisaccharide 6.0% Monosaccharide 0.6% Decomposition 0.5% This product has a slightly bitter, pale yellow color and can be used in all foods.

Example 3 Production of Palatinose Condensate 100 parts of palatinose crystals and 0.05 part of anhydrous citric acid were added to 33 parts.
The mixture was heated to 105 ° C. with stirring to dissolve, and the reaction was carried out in the same manner as in Example 1 at a pressure of 60 mmHg using the above-mentioned continuous vacuum evaporator. This was made into a size of 6 g / piece by a stamping machine, solidified, and pulverized by a pulverizer.

The product has a solid content of 99.1%, pH 3.8, color value (ICUMSA
(Unit: 30), almost no bitterness. The composition (excluding water) was as follows.

Palatinose condensate 66.6% Palatinose 28.9% Trisaccharide 3.6% Monosaccharide 0.5% Decomposition 0.4% Example 4 Production of palatinose condensate 100 parts of palatinose crystals are placed in 33 parts of boiling water until the temperature of the contents reaches 160 ° C. The mixture was concentrated in a copper pot with stirring for about 10 minutes under normal pressure. This was solidified to a size of 3 g / piece by a stamping machine.

The product has a solid content of 97.0%, pH 4.3, color value (ICUMSA
(Unit: 287), was fairly colored, had little bitterness, and had a tortoise-like flavor. The composition was as follows. In the present example, heat concentration was carried out at normal pressure, but the concentration time was relatively short to reduce the amount of thermal decomposition products.

Palatinose condensate 18.1% Palatinose 77.7% Trisaccharide 2.9% Monosaccharide 1.0% Decomposed product 0.3% (Note: The composition does not include water in the product.) Example 5 Production of Palatinose condensate 50 liter stainless steel Palatinose crystal 30 in container
Kg and 9 kg of water were added, and the mixture was heated and dissolved to 105 ° C. with stirring. The whole amount of this palatinose aqueous solution was transferred to a vacuum cooker equipped with a stirrer, and 3.0 g of anhydrous citric acid was added and stirred. At this time, the pH of the aqueous palatinose solution was 4.1.
Subsequently, the pressure was reduced to 60 mmHg, and the mixture was concentrated while heating. The time required for the temperature of the concentrate to reach 135 ° C. was 30 minutes. 135
Heating was stopped when the temperature reached ° C. It had a solids concentration of 98% and the composition was as follows:

Palatinose condensate 53.4% Palatinose 42.0% Trisaccharide 3.6% Monosaccharide 0.6% Decomposed product 0.4% (Note: The composition does not include the moisture in the product) Example 6 Production of Palatinose Hard Jelly In the usual hard jelly formulation The sugar concentration is as high as around 80%. However, since palatinose tends to crystallize, hard jelly containing palatinose cannot be produced. Therefore, an attempt was made to produce palatinose hard jelly using a palatinose condensate.

The product mixture containing the palatinose condensate used in this example was the product prepared in Example 3 (99.1% solids)
It is. The following palatinose syrup is a syrup remaining after crystallizing palatinose from a crude product obtained by enzymatic conversion of sucrose into palatinose, and has the following composition.

Composition of Palatinose Syrup Solids 71.1% Glucose 10.5% Fructose 9.2% Sucrose 2.5% Palatinose 13.8% Trehalulose 28.0% Isomaltose 3.7% Other Sugars 3.4% The ingredients of Palatinose Hard Jelly are as follows.

Ingredients Ingredients (parts) Citric anhydride 14 Pectin (polar slow set Sag 150) 22 Palatinose powdered sugar 50 Product mixture 834 Palatinose syrup 616 Fragrance a little Coloring a little Water 322 Production method Mix pectin and palatinose powdered sugar and vacuum cooker And dissolved in water. This was boiled over a fire, and the pressure was sufficiently reduced. Palatinose syrup and the resulting mixture were drawn in through a suction nozzle and boiled down to a solids concentration of 80%. After releasing the vacuum and stopping the heating, the 50% aqueous citric acid solution was converted with vigorous stirring, and then the flavor and color were added, mixed and allowed to flow. After cooling, the jelly removed from the shape was dusted with palatinose crystals to obtain a product.

The jelly did not crystallize in a one-month room temperature storage test. Further, the taste was also preferable with reduced sweetness, and had good texture and body. Thus, a good hard jelly can be made by using the palatinose condensate of the present invention instead of the conventional starch syrup, and such hard jelly has low cariogenic and anti-cariogenic properties.

Example 7 Production of Palatinose Ice Cream In general, in ice cream, sugar is crystallized in the course of distribution and may exhibit an undesirable texture. When palatinose is used, it is very difficult to prevent crystallization because of its low solubility. Palatinose ice cream was made using palatinose condensate to overcome this problem. The product mixture and palatinose syrup used were the same as in Example 6. The composition is as follows.

Ingredients Ingredients (parts) Milk (fat 3.5%) 40.0 Cream (fat 40%) 18.0 Skim milk powder 6.0 Product mixture 15.0 Palatinose syrup 7.0 Emulsifier 0.3 Stabilizer 0.3 Fragrance a little water 15.4 Production method Stabilizer and emulsifier in pasteurizer And heated to a temperature of 70 ° C., and after adding other raw materials as appropriate, passing through a pressure homogenizer and storing in a refrigerator. Put this in a freezer at -7 ° C, fill it into a cup,
It was cured in a 25 ° C. curing bath. About the obtained product, 5
An abuse test in which the temperature was raised and lowered five times between −25 ° C. and −3 ° C. per day was performed, but no palatinose crystals were precipitated. The taste was a refreshing sweet good quality ice cream.

Example 8 Production of Palatinose Chewing Gum In general, the amount of sugar used in chewing gum is preferably 0.1 to 3.3 times by weight based on the gum base and 10 to 100 times by weight based on the flavor, for connection and enhancement of flavor. However, when palatinose is used alone in chewing gum, the viscoelasticity of the gum is insufficient and the texture is impaired.
Therefore, in this example, a part of palatinose was replaced with the product mixture powder obtained in Example 1, and palatinose chewing gum was produced as a trial. The composition is as follows.

Ingredients (parts) Sugar ester 20 Ingredients (parts) Ester gum resin 100 Vinyl acetate 120 Wax 80 Peppermint flavor 10 Palatinose powdered sugar (200 mesh) 450 Product mixture powder 150 Glycerin fatty acid ester 30 Talc 40 Manufacturing method Was mixed at 90 ° C., cooled, and then rolled and rolled to give 3 g of palatinose chewing gum.
A favorable chewing gum with a texture with sustained flavor was obtained.

When only palatinose was used as the sugar, twice the amount of the gum base was the upper limit for good viscoelasticity.
However, by using a palatinose condensate as in this example, it became possible to use a larger amount of palatinose.

〔The invention's effect〕

According to the present invention, a palatinose condensate which is a useful substance is provided. The present invention also provides a method for producing a palatinose condensate. The palatinose condensate of the present invention is a substance having very little sweetness, and can improve the texture without changing the sweetness of the food. Especially,
Since palatinose condensate can prevent crystallization of palatinose in the presence of palatinose, it increases the likelihood of using palatinose in foods, and such foods are low cariogenic and anti-cariogenic . In addition, the palatinose condensate of the present invention is not only completely decomposed and absorbed in the small intestine, but reaches the large intestine and is used by bifidobacteria. The palatinose condensate-containing starch syrup obtained by the method for producing a palatinose condensate of the present invention has the same viscosity increase as conventional syrups, the prevention of freezing, the improvement of the moisturizing property of food, the body effect, the growth inhibitory effect of putrefactive bacteria and the like. It can be used as a substitute for syrup.

[Brief description of the drawings]

1 to 3 show high performance liquid chromatography of the substance obtained according to the present invention. 4 and 5 show the reaction rate of palatinose and the yield of palatinose condensate under various conditions in the batch method, respectively. FIG. 6 shows the heating temperature and the product composition in the continuous method.

Claims (5)

(57) [Claims] 1. A palatinose condensate comprising 2 to 6 palatinose units. 2. A method for producing a palatinose condensate, comprising heating and concentrating an aqueous solution of palatinose having a pH of about 3.2 to 5.8 to a liquid temperature of about 105 to 170 ° C. 3. A pressure of about 110 mmHg up to a liquid temperature of about 105 to 160 ° C.
3. The method according to claim 2, wherein the heat concentration is performed under an environment of (absolute pressure) or less. 4. The process according to claim 2, wherein the solution is concentrated by heating under a normal pressure environment to a liquid temperature of about 140 to 165 ° C. 5. A method for producing a food, comprising adding a palatinose condensate-containing product mixture produced by the heat concentration according to claim 2 or a palatinose condensate separated therefrom to a food.