JPH0358702B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, palatinose converting enzyme is applied to a sucrose solution to convert more than 70% of sucrose into palatinose, and after crystallizing palatinose, 1-
The present invention relates to a method for separating honey containing 30 to 70% O-α-D-glucopyranosyl-D-fructofuranose and 10 to 30% palatinose and utilizing it as a low-cariogenic and hardly crystallized syrup. The present inventors have been conducting research on palatinose for some time, and have published Japanese Patent Application No. 55-113982.
58-36959) revealed a method for producing palatinose using an immobilized enzyme. He also discovered that palatinose has low cariogenicity and filed a patent application as a low cariogenic sweetener (patent application filed in 1983-
No. 147553 (Japanese Unexamined Patent Publication No. 57-71377)). Palatinose is a saccharide that crystallizes relatively easily and can be used as a solid (crystalline) sweetener with low cariogenicity and good taste. On the other hand, there is a strong demand for a syrup that has low cariogenicity, good taste, and is difficult to crystallize, so the present inventors conducted intensive research on this subject and completed the present invention. The enzymes used to produce the syrup of the present invention can be used in the production of certain types of bacteria, such as Protaminobacter rubrum.
CBS57477) and Serratia plymuthica (NCIB No.8285) are cultivated in the presence of sucrose. Since this enzyme is present within the bacterial cells, the bacterial cells themselves or those immobilized with a fixative can be used as enzyme preparations. Usually, a sucrose aqueous solution with a concentration of 20 to 50% is used as the raw material sucrose solution, and this and the above enzyme agent are mixed at a temperature of 5 to 30°C.
React under conditions of pH 5 to 7. The reaction solution in which 70% or more of the sucrose has been converted to palatinose is usually desalted and purified using an ion exchange resin, concentrated under reduced pressure, and then palatinose crystal seeds are added to generate palatinose crystals. Centrifuge to separate Palatinose crystals and honey.
The shimitsu is further concentrated and the operation for obtaining crystals is repeated to separate it into crystals and shimitsu. In this way, the palatinose in the reaction solution is separated as crystals, and the solid content concentration is usually 60-80%, the sugar content is 30-70% 1-O-α-D glucopyranosyl-D-fructofuranose, and the palatinose is 10-30%. %
A low-cariogenic and non-crystallizable syrup containing . Its sugar composition is as follows. Sugar composition of the syrup of the present invention 1-O-α-D-glucopyranosyl-D-fructofuranose 30-70% Palatinose (monohydrate) 10-30% Fructose 0-25% Glucose 0-20% Isomaltose 0- 10% Sucrose 0-20% Isomeretitose 0-5% Others 0-5% The present inventors tested the syrup obtained in this manner using the glass rod method to test for caries-inducing bacteria S.
We conducted plaque formation experiments using mutans and caries induction experiments using rats, and found that the syrup of the present invention inhibits plaque formation from sucrose in the same way as palatinose, and has low cariogenicity. The saccharide composition of the syrup of the present invention used in the experiments and the Examples and Comparative Examples described below is as follows. 1-O-α-D-glucopyranosyl-D-fructofuranose 41% Palatinose (monohydrate) 24% Fructose 14% Glucose 11% Sucrose 5% Isofumaltose 3% Isomeretitose, others 2% First, the present inventors The following is an explanation of the dental plaque production experiment conducted. [Experimental method] A medium prepared by adding a prescribed concentration of sugar (described later) to brain heart infusion broth (BHI broth, containing 0.2% glucose) was placed in a test tube (φ18 mm
18 cm) and prepared 10 ml each. At this time, the basal medium and sugar at twice the concentration were separately autoclaved (120°C, 15 minutes), and after cooling, they were mixed at a ratio of 1:1.
The sugar composition of the medium was as follows. The symbol of the medium is shown in parentheses. 1 Glucose 0.2% only (Control) 2 Sucrose 1% (Suc1%) 3 Sucrose 2% (Suc2%) 4 Sucrose 4% (Suc4%) 5 Sucrose 4% + Palatinose 1% (S4 + P1%) 6 Sucrose 4% + Palatinose 2% (S4 + P2%) 7 Sucrose 4% + Palatinose 4% (S4 + P4%) 8 Palatinose 4% (Pal4%) 9 Sucrose 4% + Sirap of the present invention 2% (S4 +
PM2%) 10 Sucrose 4% + syrup 4% of the present invention (S4+
PM4%) 11 The syrup of the present invention 4% (HPM4%) obtained by hydrolyzing the sucrose it contains 12 The syrup of the present invention 4% (PM4%) The syrup of the present invention used here has a content of about 5% based on the solid content. Since it contained sucrose, we also tested a product obtained by hydrolyzing the sucrose with hydrochloric acid (PH2.0, 70°C, 60mm). When sucrose remains in the syrup of the present invention as described above, only sucrose can be selectively hydrolyzed with acid. Sucrose can be hydrolyzed using invertase, and sucrose, glucose, and fructose can also be removed by fermentation using yeast of the genus Satucharomyces. The strain used was S. mutans MT8148 (serotype: C). This strain was cultured in BHI broth,
Planted in a test tube with a φ3mm glass rod inserted at 37℃.
The cells were cultured anaerobically for 4 days while renewing the medium every day. At the start of the culture on the 4th day (immediately after the medium has been updated, the liquid will be clear), the glass rod should be kept in the test tube, and at the end of the culture on the 4th day, it should be removed from the test tube. Examined. The state of the glass rod at the end of the culture on the 4th day is shown in the drawing, and the state of the glass rod at the start of the culture on the 4th day was almost the same. In addition, in the drawing, the number of the glass rod is the number of the sugar composition of the medium described above. [Experimental Results] As is clear from the drawings, palatinose and the syrup of the present invention were shown to suppress the formation of dental plaque from sucrose. Next, a caries induction experiment in rats using the syrup of the present invention will be explained. [Experimental method] After administering antibiotics to 15-day-old SD male rats to suppress rat-specific oral bacteria, they were infected with S. mutans strain 6715 by oral inoculation with a pipette for 5 days starting on the 18th day after birth. Ta. At the same time, sucrose (Suc), which contains 56% of sucrose in cariogenic feed, is shown in the table.
The animals were fed with feed in which predetermined amounts of the syrup (PM) and wheat flour (W) of the present invention were substituted. After bacterial inoculation
Rats were sacrificed on day 55, and caries scores and plaque index were calculated. Result

[Table] Groups B and E, which were given diets containing 40% and 20% palatinose nectar, had significantly higher levels of palatinose than groups A and D, which were given diets containing 40% and 20% sucrose as positive controls. had lower plaque index and caries score. Group F, which contained 20% each of sucrose and the syrup of the present invention, had a significantly lower plaque index and caries score than Group A, and also had a significantly lower plaque index than Group D. Since the syrup of the present invention has a slightly higher solubility than sucrose, it can be used in areas where crystalline palatinose is difficult to use due to solubility. Due to its composition, it has difficulty crystallizing, and also has moisture absorption and moisturizing properties almost similar to invert sugar. Therefore, it can be preferably used as a substitute for Visco used in refined white sugar. Normally, Visco is produced and used by hydrolyzing sucrose with hydrochloric acid and then neutralizing it, but this syrup can be used directly without such treatment. 1-O-α- which is the main component of the syrup of the present invention
D-glucopyranosyl-D-fructofuranose and palatinose, which is the second most common, are difficult to hydrolyze with acids, so they also have the advantage of being less likely to undergo deterioration even when used in acidic foods such as soft drinks. The syrup of the present invention becomes slightly colored when heated at a temperature of 100°C for 1 hour, but there is no change in flavor. A desirable flavor is added at a boiling temperature of 120-140°C. During fruit processing, products that take advantage of the aroma of the raw fruit can be created. When the syrup of the present invention is added to high-fructose sugar solution, sorbitol solution, glucose solution, and other sugar solutions whose taste quality is inferior to that of sucrose solution, the taste quality, especially the rich taste and the persistence of sweetness, etc. are improved. A syrup with low cariogenicity and difficult to crystallize is obtained. Furthermore, when mixed with high-intensity sweeteners such as aspartame, saccharin, and stevia, the unpleasant aftertaste characteristic of these sweeteners is eliminated, resulting in a preferable low-cariogenic syrup. The syrup according to the invention or mixed with other sweeteners as described above is suitable as a material for producing jams, marmalades, fruit sauces, ice creams, yokans, etc. with low cariogenicity. For example, a jam made by a conventional method using the syrup of the present invention, fresh strawberries, citric acid, and pectin has a higher functional value when compared with a jam made by replacing the solid content of the syrup of the present invention with granulated sugar in the same amount. Tests have shown that the sweetness is refreshing and suitable. In addition, in a sensory test comparison between a low-cariogenic ice cream using the syrup of the present invention and an ice cream made from refined sugar with the same sweetness and the same ingredients, it was found that the ice cream using the syrup of the present invention Cream has a “crispy sweetness”
Results include ``smoothness'' and ``good milk flavor''. In this case, in order to achieve the same sweetness, the solid content of the syrup of the present invention was used to be approximately 1.4 times that of caster sugar, but this reduced the amount of ice cream ingredients that were more expensive than the sweetener.
Moreover, since the taste quality is improved, it is also economically advantageous. Next, examples of the present invention will be described. An enzyme that converts sucrose to palatinose acts on the sucrose solution, converting more than 70% of the sucrose into palatinose. After desalting and purifying the reaction solution and concentrating under reduced pressure, palatinose crystal seeds are added to generate palatinose crystals, and the resulting white mixture is centrifuged to separate palatinose crystals and honey. The shimitsu is further concentrated and the operation for obtaining crystals is repeated to separate it into crystals and shimitsu. Examples and comparative examples of the use of the low-cariogenic and non-crystalline syrup thus obtained are shown below. (1) Solid content concentration 10% for 1 part by weight of isomerized sugar solution with solid content concentration 10% (fructose content in solid content 42%)
A mixture was prepared by adding 1 part by weight of the syrup of the present invention. As a control, an isomerized sugar solution with a solid content concentration of 9% (fructose content in solid content of 42%) was used as a control.
%), and a sensory test was conducted using 12 experienced panelists to determine which is preferable. The results obtained were as follows. 9 people who prefer the mixed solution 2 people who say there is little or no difference 1 person who prefers the isomerized sugar solution Most of the people who prefer the mixed solution Most people cite the rich flavor similar to sucrose and the long-lasting pleasant sweetness as reasons for this. (2) A mixed solution was prepared by adding 3 parts by weight of the syrup of the present invention having a solid content concentration of 10% to 7 parts by weight of a sorbitol solution for food additives having a solid content concentration of 10%. As a control, a sorbitol solution with the same degree of sweetness and a solid content concentration of 10% was used, and 11 experienced panelists conducted a sensory test to determine which was preferable. The results obtained were as follows. 10 people who prefer the mixed solution 1 person who says there is little or no difference 0 people who prefer the sorbit solution Most of the people who prefer the mixed solution The reasons for this are that the watery feeling is gone and the sweetness lasts longer. (3) Strawberry jam Ingredients:

[Table] How to make: 1. Mix and stir 10 times the amount of sugar or syrup of the present invention than pectin. 2 Place the pulp in a separate pot and heat. 3 Sprinkle 1 over the pulp while stirring vigorously and bring to a complete boil. 4. Next, add the remaining sugar or the syrup of the present invention gradually to the extent that it does not impair boiling. 5 The concentration of the liquid part of jam is the solid content concentration 64-65
Heat and concentrate until %. 6 Add citric acid dissolved in a small amount of water while stirring vigorously. 7 Pour into a designated container and cool with water. The results of the sensory test were as follows. 7 people preferred the prototype 1 person preferred the standard product Those who preferred the prototype cited the crispness of the sweetness and the sharpness of the sweetness as reasons. . (4) Ice cream ingredients:

[Table] Directions: 1. Place sugar or syrup of the present invention and egg yolk in a bowl and mix well with a whisk. 2. After heating the milk to 60-70℃, add it to 1 and mix well over low heat. 3 In a separate container, make 6 portions of fresh cream 2
Add vanilla essence and mix well. 4 Stir in an Ooster ice creamer for 20 minutes, then cool in a freezer at -25 to -30°C for 24 hours. The results of the sensory test were as follows. 9 people preferred the prototype 2 people preferred the standard product Those who preferred the prototype said that the sweetness was refreshing and smooth, and the milk flavor was good. are listed. (5) Mizu Yokan Materials:

[Table] How to make: 1 Soak 1 part of powdered Sarashian in 1.5 parts of water. 2. Add agar to water in a separate container from step 1 and heat it. Once it has melted, add the syrup or sugar of the invention and dissolve it. Once it has completely melted, pass it through four pieces of gauze. 3 Mix 1 and 2 and heat again. Once it comes to a boil, stop heating and let it cool off. 4 Pour into a mold and place in the refrigerator at 5℃ to cool. The results of the sensory test were as follows. 5 people preferred the prototype 1 person preferred the standard product Those who preferred the prototype cited the crispness of the sweetness and the sharpness of the sweetness as reasons. . (6) Milk caramel After boiling down 5 kg of the raw materials from recipe 1 in the atmosphere to 118°C in a 10-volume tanker, cool it to 75°C with stirring, then add recipe 2, Stirred for an additional 30 minutes. This was made into a cooling plate, rolled out to a thickness of 1 cm using a roller, and cut into 2 cm square dice to produce the product. Fondant in Formulation Table 2 is obtained by boiling down 50 parts of Palatinol and 70 parts of the syrup of the present invention to a moisture content of 16% to crystallize fine crystals. Formulation table 1 Palatinose 170g Inventive syrup (Bx.71) 1000g Evaporated milk (concentration 28.1) 1040g Hardened oil 188g Emulsifier 1.5g Formulation table 2 Fondane 233g Flavoring 1g This product has a moderately elegant sweetness, and has a milky flavor that melts in the mouth. It is a good milk caramel, exhibiting viscoelasticity, crisp texture and excellent gloss. The shape retention was good even under the storage temperature condition of 40°C, and the condition was good after 6 months of storage, with no difference observed from the time of manufacture. (7) Montelimar Nougat The syrup of the present invention shown in Formulation Table 1 and starch syrup were added to sufficiently whipped egg whites to prepare a basic frappée. Boil down the ingredients in recipe 2 to a moisture content of 16%.
After cooling, cool at 50℃ and add 55% of Palatinose powdered sugar.
g was added to form a fondant. Fondant was added and mixed to the basic fratsupe, then finely crushed almonds were added, and the product was cut into 2 cm squares and cooled. Composition table 1 Egg white 300g Invention syrup (Bx87.5) 1000g Starch syrup (Bx87) 160g Composition table 2 Palatinose 1600g Invention syrup (Bx71) 680g Starch syrup (Bx87) 400g Palatinose powdered sugar 5g Almonds 1250g This product has an elegant sweet taste. It is a nougat that brings out its flavor, and the taste and texture did not change even after being stored for 6 months. (8) Cream Fondant Boil the ingredients listed in Formulation Table 1 to a temperature of 125℃ in a jar, add pre-warmed orange juice, cool to 40℃, and add a small amount of palatinose powdered sugar. Butter was added, stirred for 30 minutes, and then stored to prepare a product. Formulation table 1 Palatinose 420g Starch syrup (Bx87) 130g Inventive syrup (Bx71) 290g Evermilk 140g Water 60g Formulation table 2 Concentrated orange juice (1/5 concentration) 34g Butter 75g This product has a fine-textured, smooth and elegant sweetness. It is a cream foundation, and when molded in morsed starch, it retains its shape and is easy to handle. Fondant is used in various hardnesses depending on the purpose, but basic fondant has a palatinose content of 40 to 70 W/w%,
In addition, the boiling temperature can be adjusted freely by changing it from 108 to 115°C. (9) Hard jelly Put the ingredients in recipe 1 into a jacket-type heating concentration pot, heat to a temperature of 90℃, melt, then add the ingredients in recipe 2, boil down to a temperature of 110℃, and add fruit juice and flavor just before stopping heating. was added, poured into a mold, cooled and cut, dried in a ventilation dryer at 60°C for 18 hours, and then packaged. Formulation table 1 Agar 1g Water 29g Formulation table 2 Palatinose 100g Inventive syrup (Bx71) 420g Concentrated orange juice (1/5 concentration) 10g Orange flavor 0.1g This product is slightly soft and has a good texture that brings out the taste of fruit juice. It became a hard jelly. There was no change in quality even after storage for 6 months. (10) Strawberry yam Put coarsely crushed strawberries into a jacket-type concentrator, dissolve the palatinose while heating and stirring,
After the solid content concentration was set to about 60, the syrup of the present invention was added and brought to a boil, the pectin solution was added thereto, heating was stopped, citric acid was added with vigorous stirring, and the mixture was dispensed into 100 ml glass containers. Allowed to cool naturally. Composition list Strawberry fruit 3500g Palatinose 530g Inventive syrup (Bx71) 2200g Pectin (Rapid Set 150Sag) 3g Citric acid 15g This product is a high-quality jam with a refreshing sweetness and a good strawberry flavor. Even after storage for 6 months, there was no precipitation of crystals, the texture was good, and no mold was observed. (11) Soft drink with fruit juice Formulation list Concentrated apple juice (1/5 concentration) 400g Palatinose 400g Inventive syrup (Bx71) 1600g Malic acid 25g Citric acid 5g Apple flavor 16g Water 2454g This product has a sharp sweetness and an apple flavor. It is a soft drink that leaves your mouth feeling refreshed after drinking it. (12) Kneading the bean paste Mix the specified amount of sweetener and 60 parts of the raw bean paste in a bean paste kneading pot, add water and bring to a boil. Pass through a hair sieve to remove impurities, then add the remaining 240 parts of the raw bean paste. , While kneading thoroughly, the water content in the bean paste is about 35%.
It was boiled down to %. Composition table Palatinose 78g Inventive syrup (Bx71) 326g Fresh bean paste 300g Water 141g This product has a smooth texture with less sweetness and no starch graininess than products using sucrose, and has a well-balanced color. It's the taste. In a storage test that was kept in a constant temperature and humidity chamber set at 20℃ and 55% relative humidity for 5 days, there was almost no difference in water evaporation and crystal precipitation compared to products using sucrose, and the gloss was almost the same as when manufactured. It showed the condition of. (13) Ice cream: Mix the ingredients in the recipe list with a pastelizer at a temperature of 80℃.
Mix and dissolve for 10 minutes, then 100 in a pressure homogenizer.
After passing under the conditions of Kg/cm ² and 60°C, it was aged in a refrigerator at 4°C. Cream this in a 5-volume freezer, put it in a 100ml container, and store it at -3℃.
stored in the refrigerator. Composition list Palatinose 720g Inventive syrup (Bx71) 1680g Milk 4000g Fresh cream 1650g Skim milk powder 600g Stabilizer 2.5g Water 1342g Vanilla flavor 1.5g This product contains milk solids 8.0%, non-fat milk solids 10.8%,
The total solid content is 38.7%. The ice cream has a temperature of -3.3℃ and is smooth with small crystals and has a refreshing milky taste. (14) Fruit jelly Dissolve the gelling agent in the specified amount of water by heating at approximately 60℃, then add the other ingredients listed in the recipe list, dissolve, and mix.
After heating and sterilizing this through a heat exchanger at 100℃,
The product was filled into ml cups. Formulation list Palatinose 800g Inventive syrup (Bx71) 2100g Concentrated cloudy apple juice (1/4 concentration) 875g Gelling agent (carrageenan preparation) 40g Citric acid 40g Malic acid 1g Sodium citrate 29g Apple flavor 10g Water 5725g This product has a solid content It is a chilled jelly with a relatively low hydrophilicity of 30% and pH 3.3, and its mild and sharp sweetness brings out the fresh taste of fruit, and the gel melts smoothly on the tongue, giving it a luxurious feel. (15) Gummy jelly Melt Palatinose and the syrup of the present invention by heating at 100°C using a vacuum cleaner, and further,
Maltopentaose was dissolved and concentrated under reduced pressure using Bx88. A gelatin solution was mixed therein, a 50% citric acid solution, flavor and colorant were added and mixed, and the mixture was poured into a starch box at 75°C. 35℃
The product was dried for 24 hours in a ventilation dryer. Composition table Palatinose 450g Inventive syrup (Bx71) 1000g Maltopentaose 80g Gelatin (acid treated) 120g Citric acid 5g Orange flavor 5g Carotene 1g Water 200g This product has viscoelasticity, relatively firm chewing properties, and a pleasant taste. It's gummy jelly. (16) Sponge cake A sponge cake was produced using the raw materials shown in the recipe below according to a standard method. Mixed table Raw egg 200g Wheat flour (soft flour) 120g Inventive syrup (Bx71) 106g Palatinose powdered sugar 25g Xanthan gum 0.6g Emulsifier (lyotoester SP) 9.2g Baking powder 2.4g A little flavoring This product has a firm texture and melts in the mouth. The sponge cake had moderate sweetness and flavor, and no crystals were deposited even after long-term storage, and no change in quality was observed. (17) Yogurt After dissolving skim milk powder and sugar in the specified water,
Sterilize separately for 15 minutes at a temperature of 90°C. Mix this and bring it to 42℃, add the starter and mix.
Ferment it in a constant temperature bath at 42℃ until the acidity reaches 0.75%, then store it at a temperature of 0 to 5℃. Composition List Skimmed milk powder 210g Inventive syrup (Bx71) 150g Palatinose 90g Granulated sugar 20g Starter (plain yogurt) 60g Water 1500g This product is a yogurt with a harmonious sourness and sweetness, with an enhanced flavor unique to lactic acid bacteria-fermented foods.

[Brief explanation of drawings]

Figure 1 is an explanatory diagram of the state of glass rods in plaque production experiments from various sugar composition media. %, Figure 1 4 is sucrose 4%, Figure 1 5
is 4% sucrose + 2% palatinose, Figure 1 6 is 4% sucrose + 2% palatinose, and Figure 1 7 is 4% sucrose +
Palatinose 4%, Figure 1 8 is Palatinose 4
%, Figure 1 9 shows 4% sucrose + syrup 2 of the present invention.
%, Figure 1 10 is 4% sucrose + syrup 4 of the present invention.
11 shows the syrup of the present invention containing 4% of the sucrose hydrolyzed, and FIG. 12 shows the case of the syrup of the present invention of 4%.

Claims (1)

[Claims] 1 An enzyme that converts sucrose to palatinose is applied to the sucrose solution to convert more than 70% of the sucrose into palatinose, and after crystallizing palatinose, 1 in the sugar content is
-O-α-D-Glucopyranosyl-D-Fructofuranose 30-70% and palatinose 10-30% honey is separated and used as a low cariogenic and hardly crystallized syrup. How to use molasses whose main component is oligosaccharide.