JP6187892B2 - Moisturizer and method for producing the same - Google Patents

Description

  The present invention relates to a sugar composition containing D-dihydroxypropylglucopyranoside as a main component and a method for producing the same.

It is known that α-D-dihydroxypropyl glucopyranoside (hereinafter abbreviated as α-D-DHPG) is contained in about 0.5% by mass in sake and gives a refreshing sweetness. . In recent years, it has been reported that α-D-DHPG has functions such as non-cariogenicity, indigestibility, and moisture retention, and its usefulness as a functional material has attracted attention. Moreover, paying attention to these functions, α-D-DHPG is blended in various foods, seasonings, cosmetics, and the like.
Conventionally, an enzymatic method has been used as an industrial method for producing α-D-DHPG. For example, Patent Documents 1 to 3 disclose a method of introducing α-D-glucopyranosyl group into glycerin by allowing α-glucosidase to act on the saccharide in a solution in which the saccharide and glycerin are dissolved to obtain α-D-DHPG. It is disclosed. In addition, these documents disclose a method of recovering high-purity α-D-DHPG by separating α-D-DHPG in a reaction solution by chromatography.

Japanese Patent Laid-Open No. 11-222496 JP 2004-229668 A JP 2006-008703 A

α-D-DHPG has excellent moisture retention as described above, but a material that exhibits better moisture retention is required.
Further, α-D-DHPG has a problem that the conventional manufacturing method is not suitable for mass production because it takes time and effort to manufacture, and the cost increases. For example, in the production methods described in Patent Documents 1 to 3, it takes about 24 hours just to introduce the α-D-glucopyranosyl group. Furthermore, if separation by chromatography is performed in order to increase the purity, the process becomes complicated and the cost becomes high.
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a sugar composition having improved moisture retention and easy mass production and a method for producing the same, compared to the case of α-D-DHPG alone. And

As a result of extensive studies, the present inventors have determined that α-D-DHPG and its isomer β-D-dihydroxypropylglucopyranoside (hereinafter abbreviated as β-D-DHPG) have a predetermined ratio. It has been found that the composition contained in is superior in moisture retention as compared with the case of α-D-DHPG alone. Further, it has been found that such a composition can be produced by a simple organic synthesis method in which a glucose source such as glucose and glycerin formulated so as to have a predetermined molar ratio to the glucose source are reacted with an acidic catalyst. It was.
This invention which solves the said subject was made | formed based on these knowledge, and has the following aspects.
[1] A compound represented by the following formula (1) and a compound represented by the following formula (2) are contained at a mass ratio of 45 to 75:15 to 25, and the total sugar contained in the sugar composition The ratio of the compound represented by the formula (1) to the total amount is 58.4 to 65.3 mass%, and the ratio of the compound represented by the formula (2) is 21.6 to 24.5 mass% . A humectant comprising a sugar composition.

[2] A method for producing the humectant according to [1],
Reacting a glucose source with glycerin using an acidic catalyst ;
A step of removing the glycerin by distillation from a reaction product obtained by reacting the glucose source with the glycerin ;
The molar ratio of the charged amount and the charge amount of the glycerin in terms of glucose in the glucose source is 1: 4:00 to 1:16 der is,
A method for producing a moisturizing agent, wherein the distillation is performed within a range of pH (25 ° C.) 6.5 to 8.5 .
[3] The method for producing a humectant according to [2], wherein the reaction between the glucose source and the glycerin is performed under vacuum .
[ 4 ] The method for producing a humectant according to [ 2 ] or [3] , wherein hydrotalcites are used for controlling the pH during the distillation.

  According to the present invention, it is possible to provide a saccharide composition having improved moisture retention and easy mass production, and a method for producing the same, as compared with the case of α-D-DHPG alone.

2 is an HPLC chart of the sugar composition obtained in Example 2.

The sugar composition of the present invention comprises a compound represented by the following formula (1) and a compound represented by the following formula (2) in a mass ratio of 45 to 75:15 to 25, and the sugar composition is included in the sugar composition. The ratio of the total amount of the compound represented by the formula (1) and the compound represented by the formula (2) with respect to the total amount of all sugars contained is 60% by mass or more.
The compound represented by Formula (1) is α-D-DHPG, and the compound represented by Formula (2) is β-D-DHPG. Hereinafter, α-D-DHPG indicates a compound represented by Formula (1), and β-D-DHPG indicates a compound represented by Formula (2).
By containing α-D-DHPG and β-D-DHPG in the above ratio, the moisture retention is improved as compared with the case of α-D-DHPG alone. This is presumed to be due to some interaction between α-D-DHPG and β-D-DHPG.
Moreover, the saccharide | sugar composition of this invention can be manufactured with the simple synthesis method which makes a glucose source and glycerol react with a predetermined preparation ratio with an acidic catalyst so that it may mention later.

In the sugar composition of the present invention, the mass ratio of α-D-DHPG and β-D-DHPG is 45 to 75:15 to 25, and more preferably 55 to 65:18 to 22. This mass ratio is equal to the molar ratio.
Further, the ratio of the total amount of α-D-DHPG and β-D-DHPG to the total amount (100% by mass) of the total sugar contained in the sugar composition of the present invention is 60% by mass or more, and 75% by mass. The above is preferable, and 85 mass% or more is more preferable. The upper limit of the ratio is not particularly limited, and may be 100% by mass. That is, the sugar contained in the sugar composition of the present invention may be only α-D-DHPG and β-D-DHPG.
Hereinafter, simply referring to D-DHPG indicates both α-D-DHPG and β-D-DHPG.
The ratio of the total amount of α-D-DHPG and β-D-DHPG to the total solid content of the sugar composition of the present invention, that is, the purity as D-DHPG is preferably 65% by mass or more, and 75% by mass or more. Is more preferable, and may be 100% by mass.
In the present specification, the “total solid content” means the total of all components except for water contained in the sugar composition.

The sugar composition of the present invention may contain other sugars other than D-DHPG as long as the effects of the present invention are not impaired. The other sugar may be a monosaccharide other than glucose or a disaccharide or higher saccharide. Examples of the saccharide include those similar to the saccharides exemplified as the glucose source described later. The other sugar is derived from a raw material (for example, a glucose source such as glucose used as a raw material for producing a sugar composition, and when the glucose source is a saccharide of two or more sugars, Sugars produced as a by-product of the reaction of sugars, etc.) or separately formulated.
The glucose source will be described in detail in a later production method.

The sugar composition of the present invention may contain other components (hereinafter referred to as non-sugar components) other than sugar as long as the effects of the present invention are not impaired. Examples of the non-sugar component include alcohols such as glycerin, diglycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, and 1,2-pentanediol. The non-sugar component may be derived from a raw material or separately blended.
However, when glycerin is contained in the sugar composition, the blending amount into foods and drinks, seasonings, cosmetics, etc. may be limited. Therefore, the proportion of glycerin in the saccharide composition is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the saccharide composition.

The method for producing a saccharide composition of the present invention includes a step of reacting a glucose source with glycerin using an acidic catalyst (hereinafter referred to as a glucosylation step), and the glucose-based charge amount of the glucose source and the glycerin. The molar ratio to the charged amount is 1: 4 to 1:16. This production method is industrially useful because the sugar composition can be easily mass-produced.
The production method preferably further includes a step of removing glycerin by distillation from a reaction product obtained by reacting glycerin with a glucose source in the glucosylation step (hereinafter referred to as a distillation step). . In the reaction product obtained in the glucosylation step, glycerin as a raw material usually remains. Although it is not always necessary to remove this glycerin, the components blended in foods and drinks, seasonings, cosmetics and the like are often limited in the content of glycerin, and the sugar composition obtained by removing glycerin Improves usability. Further, the glycerin recovered at this time can be reused in the glucosylation step.
Hereinafter, each process will be described in more detail.

(Glucosylation process)
As the glucose source, at least one selected from saccharides and glucose containing glucose units and capable of decomposing under reaction conditions when reacting with glycerin to produce glucose is used.
The “unit” in the saccharide is a monosaccharide unit constituting a molecular chain of the saccharide by a glycosidic bond.
The saccharide used as a glucose source may be an oligosaccharide or a polysaccharide. In the present specification, “oligosaccharide” is assumed to be a combination of 2 to 10 monosaccharides, and “polysaccharide” is assumed to be a combination of 11 or more monosaccharides. Examples of the oligosaccharide include disaccharides such as maltose, sucrose, lactose and trehalose; trisaccharides such as maltotriose. Examples of the polysaccharide include starch and pullulan. These saccharides can be decomposed to produce glucose under the reaction conditions for reacting with glycerin (when a predetermined reaction temperature is set in the presence of an acidic catalyst). Even if it is a saccharide, for example, cellulose does not decompose under the reaction conditions when it is reacted with glycerin, and therefore does not fall under the “glucose source” in the present invention.
In the saccharide used as a glucose source, the ratio of the glucose unit to the total of all monosaccharide units constituting the saccharide is preferably 60 mol% or more, more preferably 80 mol% or more, and the ratio is It is particularly preferred that it consists only of 100 mol%, ie glucose units.

As the glucose source, a solid source such as anhydrous crystalline glucose or hydrated crystalline glucose may be used, or liquid sugar containing 20 to 30% by mass of water may be used. Since the reactivity between the glucose source and glycerin improves as the amount of water in the reaction system decreases, it is preferable to use a solid material.
As the glucose source, among the above glucose and saccharides, glucose is preferable from the viewpoint of good reactivity. Among them, anhydrous crystalline glucose is preferable because it is low in water, inexpensive, and relatively low in color during the reaction. .
The glucose source used may be one type or two or more types.

Examples of glycerin include animal-derived ones, plant-derived ones, and synthetic products, and any of them can be used. From the viewpoint of safety and price, plant-derived glycerin is preferable.
In production, glycerin having a purity as high as possible is desired. However, for the purpose of reducing the viscosity in handling, one containing about 10 to 20% of water may be used.
As will be described later, when the reaction product is subjected to a distillation treatment for removing glycerin, the glycerin separated and recovered by the distillation treatment may be reused for the reaction with the glucose source.

In this step, the molar ratio of the glucose-sourced charge amount of the glucose source and the glycerin charge amount is within the range of 1: 4 to 1:16, and the glycerin and the glucose source are reacted. That is, the glucose source is reacted with 4 to 16 mol times the amount of glycerin with respect to the amount (mol) of the glucose source in terms of glucose. The molar ratio is preferably in the range of 1: 6 to 1:12.
If the molar ratio is outside the above range, it will be difficult to obtain the desired sugar composition. Furthermore, when the ratio of glycerol is too low, the purity of D-DHPG in the reaction product becomes low. When the purity is lowered, functions such as moisture retention are lowered, so that it is necessary to carry out a purification treatment such as distillation after this step, and the load is increased. If the ratio of glycerin is too high, the productivity is greatly reduced and it is not economical.
Here, when the glucose source is glucose, the charged amount (mol) of the glucose source is the charged amount (mol), and [the charged amount (g) as solid content of the glucose source / glucose source] Molecular weight].
When the glucose source is the saccharide, a value obtained by multiplying the charged amount (mol) by the number of glucose units contained in one molecule of the glucose source is “the charged amount (mol) of glucose of the glucose source”. . For example, when the glucose source is maltose, the number of glucose units contained in one molecule of the glucose source is 2, so that the amount of maltose charged (mol) × 2 is the amount of glucose converted (mol).

The acidic catalyst used when the glucose source and glycerin are reacted may be, for example, an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as paratoluenesulfonic acid or oxalic acid. May be.
0.05-5.0 mass% is preferable with respect to the total (100 mass%) of solid content of a glucose source, and glycerol, and, as for the usage-amount of an acidic catalyst, 0.07-0.15 mass% is more preferable. If the usage-amount of an acidic catalyst is 0.05 mass% or more, reaction will fully advance, and if it is 5.0 mass% or less, coloring of a reaction product can be suppressed.

90-140 degreeC is preferable and, as for the reaction temperature at the time of making a glucose source and glycerol react, 110-120 degreeC is more preferable. If reaction temperature is 90 degreeC or more, it can be made to fully react. If it is 140 degrees C or less, overdecomposition can be suppressed.
Although reaction time changes also with reaction temperature, 0.5-5 hours are preferable and 1-3 hours are more preferable. If the reaction time is 0.5 hours or longer, the glucose source can be sufficiently consumed, and the target sugar composition can be obtained in a high yield. If it is 5 hours or less, the productivity is good.

In the glucosylation step, the reaction between the glucose source and glycerin is preferably performed under vacuum.
When the glucose source reacts with glycerin, water is produced together with D-DHPG. When water is present in the reaction system, the reactivity between the glucose source and glycerin is deteriorated. Therefore, by performing the reaction under vacuum, the reaction can be performed while removing water in the reaction system, and the reactivity is greatly improved.
The degree of "vacuum" in this case, considering the moisture removal efficiency, preferably 15kPa (N / cm ²⁾ or less, 5kPa (N / cm ²⁾ or less is more preferable. The higher the moisture removal efficiency, the faster the reaction. The lower limit of the pressure is not particularly limited, but is practically about 1 kPa (N / cm ² ).

The glucosylation reaction can be stopped by adding an alkali and neutralizing the acidic catalyst.
Examples of the alkali used for neutralization include alkali metal hydroxides and alkaline earth metal hydroxides.
Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of the alkaline earth metal hydroxide include magnesium hydroxide and calcium hydroxide. Among these, sodium hydroxide is preferable from the viewpoint of economy.
What is necessary is just to set the usage-amount of an alkali suitably according to the regulation amount of the used acidic catalyst.

  The reaction product obtained by the glucosylation step can be used as it is as the sugar composition of the present invention. Moreover, you may perform the refinement | purification processes (distillation etc. which are mentioned later) for removing impurities (residual glycerin, a residual glucose source, a by-product, etc.) and other arbitrary processes as needed.

(Distillation process)
In the distillation step, glycerin is removed from the reaction product obtained in the glucosylation step by distillation.
Removal of glycerin by distillation can be carried out, for example, by heating under vacuum. The degree of "vacuum" in this case, considering the removal efficiency of glycerin, preferably 7kPa (N / cm ²⁾ or less, 5kPa (N / cm ²⁾ or less is more preferable.
The heating is preferably performed so that the upper limit of the distillation temperature is 200 to 250 ° C. If the upper limit of the distillation temperature is 200 ° C. or higher, glycerin can be efficiently removed, and the glycerin remaining in the resulting sugar composition can be reduced to a level that does not affect its functionality. When the upper limit of the distillation temperature is 250 ° C. or less, coloring can be sufficiently suppressed, and the resulting sugar composition has a good hue.

When performing a distillation process, it is preferable to perform distillation of glycerol within the range of pH (25 degreeC) 5.0-10.0. The pH is more preferably 5.0 to 9.0, and even more preferably 6.5 to 8.5. Thereby, coloring by the heat | fever at the time of distillation is suppressed and the sugar composition obtained becomes the thing excellent in the hue.
If the pH is out of the above range, the thermal stability of D-DHPG is reduced for both α-type and β-type, and decomposes during distillation to lower the purity. Moreover, the hue of the sugar composition obtained also worsens. That is, D-DHPG has a hemiacetal structure peculiar to saccharides in both α-type and β-type, and is easily decomposed into glycerin and glucose under strong acidity. Further, under strong acidity, glucose liberated by decomposition is decomposed into caramel-like colored components and acidic components by heat history, and the hue is greatly deteriorated. Furthermore, this glucose falls into a vicious cycle, such as lowering the pH and inducing further degradation of D-DHPG. In addition, the sugar composition is easily colored under strong alkalinity.
On the other hand, when the pH is within the above range, D-DHPG is thermally stable, so that decomposition during distillation at a high temperature is sufficiently suppressed, and production of glucose which is a causative substance for coloring is suppressed. Moreover, since not only the sugar composition but also the hue of the collected glycerin is improved, it can be reused without requiring a new regeneration step (such as decoloring treatment).

Control of pH during glycerin distillation is, for example, at least one inorganic substance selected from alkali metal carbonates, alkaline earth metal carbonates, alkali metal oxides, alkaline earth metal oxides, and inorganic adsorbents. This can be done by adding a compound. These inorganic compounds neutralize or adsorb acidic components generated during distillation to suppress pH reduction.
Examples of the alkali metal carbonate include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like. Examples of the alkaline earth metal carbonate include magnesium carbonate, calcium carbonate, barium carbonate and the like. Examples of the alkali metal oxide include sodium oxide and potassium oxide. Examples of the alkaline earth metal oxide include magnesium oxide, calcium oxide, and barium oxide.
As the inorganic adsorbent, hydrotalcites are preferable. Hydrotalcite is a hydrotalcite (Mg ₆ Al ₆ (OH) ₁₆ · CO ₃ · nH ₂ O) and a compound having a structure similar thereto, a hydrotalcite-like compound, a layered double hydroxide (Layered) Also referred to as Double Hydroxide (LDH)), for example, a compound represented by the general formula [M ¹ _1-x M ² _x (OH) ₂ ] [A] _{x / n} · mH ₂ O, a fired product thereof, and the like can be given. .
In the general formula, M ¹ is a divalent metal ion (Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^2+, etc.), and M ² is a trivalent metal ion (Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , In ³⁺ etc.), and A is an n-valent anion. Examples of the anion include CO ₃ ²⁻ , halogen ion, NO ³⁻ , SO ₄ ²⁻ , Fe (CN) ₆ ³⁻ , CH ₃ CO ²⁻ , oxalate ion, and salicylate ion. The compound retains an anion (A) between layers of a double hydroxide layer ([M ¹ _1-x M ² _x (OH) ₂ ]) and exchanges the anion for another anion by intercalation. Has exchange ability. Further, when the compound is calcined, H ₂ O is desorbed, but when it is returned to water, H ₂ O is taken in and regenerated, and the same anion exchange ability is exhibited.
As the hydrotalcite, commercially available products can be used, and examples thereof include Kyoward (registered trademark) series manufactured by Kyowa Chemical Industry Co., Ltd. Specifically, the Kyoto word 500, the Kyoto word 1000, the Kyoto word 2000 (all are trade names), etc. are mentioned. Among these, KYOWARD 2000 is preferable because pH can be controlled with a small addition amount, and filtration separation is easy after dilution with water.
Among the inorganic compounds, hydrotalcites are preferable.
One or more inorganic compounds may be added.
The addition amount of the inorganic compound may be appropriately set according to the pH in the reaction system and the kind of the inorganic compound to be used, and is not particularly limited, but is usually the sum of the solid content of the glucose source and glycerin (100% by mass). ) In the range of 0.01 to 0.20 mass%. The addition of 0.01% by mass or more can sufficiently control the pH, and if it is 0.20% by mass or less, the influence of cost is small.

After the glucosylation step or after the distillation step, water may be added to the obtained sugar composition as necessary to obtain an aqueous solution. It is preferable to use an aqueous solution because the viscosity is lowered and handling properties are improved.
In this case, the aqueous solution has a sufficiently good hue, but may be subjected to a decoloring treatment in order to further improve the hue. The decoloring treatment can be performed by using a known method used for decoloring a sugar solution, for example, by adding activated carbon to the aqueous solution and heating it. The added activated carbon can be removed by filtration or the like.
Moreover, you may perform pH adjustment, solid content concentration adjustment, etc. as needed.
The pH of the aqueous solution is preferably 4 to 7 and more preferably 5.5 to 6.5 at 25 ° C. in consideration of applications (food and cosmetics).
The solid content concentration of the aqueous solution is preferably 60 to 90% by mass, more preferably 70 to 80% by mass in consideration of ease of handling (handling).

In the production method of the present invention, the mass ratio (= molar ratio) of α-D-DHPG and β-D-DHPG in the obtained sugar composition can be adjusted, for example, by the following method.
(1) A method of adjusting the molar ratio between the glucose-converted charge amount of the glucose source and the glycerin charge amount.
As described above, in the glucosylation step, the reaction is performed within the range of the molar ratio of the glucose-sourced amount of glucose source and the amount of glycerin charged. Within this range, the higher the ratio of glycerin, the more α The ratio of β-D-DHPG to the sum of -D-DHPG and β-D-DHPG tends to be high. Therefore, the ratio of α-D-DHPG and β-D-DHPG can be adjusted by adjusting this molar ratio.
(2) A method of adjusting the reaction temperature in the glucosylation step.
There exists a tendency for the ratio of (beta) -D-DHPG with respect to the sum total of (alpha) -D-DHPG and (beta) -D-DHPG to become high, so that the reaction temperature in a glucosylation process is low. Therefore, the ratio of α-D-DHPG and β-D-DHPG can be adjusted by adjusting the reaction temperature.
(3) A method of adjusting the amount of acidic catalyst used in the glucosylation step.
The smaller the amount of acidic catalyst used in the glucosylation step, the higher the ratio of β-D-DHPG to the sum of α-D-DHPG and β-D-DHPG tends to increase. Therefore, the ratio of α-D-DHPG and β-D-DHPG can be adjusted by adjusting the amount of the acidic catalyst.
Moreover, the mass ratio of (alpha) -D-DHPG and (beta) -D-DHPG in a saccharide | sugar composition and the purity of D-DHPG can be adjusted by performing a refinement | purification process suitably after a glucosylation process or a distillation process.

As described above, the sugar composition of the present invention is of high quality with improved moisture retention compared to α-D-DHPG alone, and is useful as a moisturizing agent blended in cosmetics, for example. In addition, β-D-DHPG is a non-reducing saccharide like α-D-DHPG, and therefore the sugar composition of the present invention is expected to have non-cariogenic and indigestible functions in food applications. .
In addition, the sugar composition of the present invention is easy to mass-produce and has a low production cost as compared with α-D-DHPG produced using an enzymatic method. Therefore, it can be provided at a lower cost than α-D-DHPG.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The measurement methods and evaluation methods used in the following examples and comparative examples are as follows.
[PH]
The pH at 25 ° C. of each of the crude sugar composition after neutralization and the purified sugar composition after distillation was measured by the following procedure.
The crude sugar composition or the purified sugar composition was diluted with water so that the solid content concentration was 50% by mass, and the pH (25 ° C.) of this diluted solution was measured with an electrode-type pH meter.

[Hue]
The hue of the purified sugar composition after distillation was evaluated by the following procedure.
The purified sugar composition was diluted with water so that the solid content concentration was 50% by mass, and the hue (APHA (also referred to as Hazen color number)) of the diluted solution was measured in accordance with JIS K3331.

[Sugar composition, free glycerin content]
The sugar composition of the finally obtained decolorized and purified sugar composition (aqueous solution having a solid content of 50% by mass) and the amount of free glycerin (% by mass) in the decolorized and purified sugar composition were measured by the following procedure.
In addition, a saccharide | sugar composition is a ratio (mass%) of each saccharide | sugar with respect to the sum total (100 mass%) of all the saccharides contained in this decoloring refinement | purification saccharide | sugar composition. In addition, since the decolorized and purified sugar compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 did not contain components other than sugar and free glycerin, respectively, (100-free glycerin amount) was decolorized. It is the ratio (mass%) of the total of all the sugars with respect to the total solid of a refined sugar composition.
The decolorized and purified sugar composition was analyzed by high performance liquid chromatography (hereinafter referred to as HPLC) under the following measurement conditions.
(Measurement condition)
Column: Shim-Pack SCR-101 (inner diameter 7.9 mm × length 30 cm, manufactured by Shimadzu Corporation)
-Column temperature: 60 ° C
・ Eluent: Water ・ Flow rate: 0.6 ml / min
・ Detector: Differential refractometer ・ Sample concentration: 5%

An HPLC chart of the decolorized and purified sugar composition of Example 2 analyzed under the above measurement conditions is shown in FIG. In FIG. 1, the assignment of each peak marked with circled numbers 1 to 5 (each confirmed by NMR) is as follows.
1 (retention time 9.728 minutes): α-D-DHPG.
2 (retention time 9.100 minutes): β-D-DHPG.
3 (retention time 7.960 minutes): disaccharide.
4 (retention time 7.059 minutes): More than trisaccharide.
5 (retention time 13.233 minutes): free glycerin.

[Moisturizing]
The moisture retention of the finally obtained decolorized and purified sugar composition (an aqueous solution having a solid content of 50% by mass) was evaluated by the following procedure.
Place 2 g of decolorized and purified sugar composition in an aluminum petri dish, put the aluminum petri dish in a thermostat / humidifier at a temperature of 25 ° C. and a humidity of 60%, and immediately change the humidity to 35%. Maintained for hours. From the mass of the decolorized and purified sugar composition before and after the treatment, the mass reduction rate (%) was determined by the following formula.

[Example 1]
Glycerin: 552 g (6 mol), anhydrous crystalline glucose: 180 g (1 mol), and paratoluenesulfonic acid: 0.73 g were charged into a 1 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. The pressure in the reaction system was 5 kPa (N / cm ² ), and a vacuum dehydration reaction was performed at a reaction temperature of 115 ° C. for 2 hours. Thereafter, 0.15 g of sodium hydroxide dissolved in a small amount of water was added for neutralization, and 0.5 g of hydrotalcite (trade name “KYOWARD 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added. . At this time, a part of the reaction product (crude sugar composition) was taken out, diluted with an equal amount of pure water, and its pH was measured as an aqueous solution having a solid content concentration of 50% by mass, which was 7.8.
Thereafter, the temperature was raised to 230 ° C. under 5 kPa (N / cm ² ), and excess glycerin was distilled off from the crude sugar composition. As a result, 259.2 g of a purified sugar composition was obtained, and 450.4 g of glycerin was separately collected. The purified sugar composition obtained was dissolved by adding an equal amount of pure water to obtain an aqueous solution having a solid concentration of 50% by mass. The pH at this time was 7.6, and the hue was APHA300.
To the aqueous solution of the purified sugar composition, 6.5 g of activated carbon was added and heated at 80 ° C. for 30 minutes, and then the activated carbon was removed by filtration to obtain a decolorized and purified sugar composition.
Table 1 shows the sugar composition, the amount of free glycerin, the hue, and the moisture retention of the obtained decolorized and purified sugar composition.

[Example 2]
Glycerin: 1104 g (12 mol), anhydrous crystalline glucose: 180 g (1 mol), paratoluenesulfonic acid: 1.28 g were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. The pressure in the reaction system was 5 kPa (N / cm ² ), and a vacuum dehydration reaction was performed at a reaction temperature of 115 ° C. for 2 hours. Thereafter, 0.27 g of sodium hydroxide dissolved in a small amount of water was added for neutralization, and 1.0 g of hydrotalcite (trade name “KYOWARD 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added. . At this time, a part of the reaction product (crude sugar composition) was taken out, diluted with an equal amount of pure water, and its pH was measured as an aqueous solution having a solid content concentration of 50% by mass, which was 7.7.
Thereafter, the temperature was raised to 230 ° C. under 5 kPa (N / cm ² ), and excess glycerin was distilled off from the crude sugar composition. As a result, 277.6 g of a purified sugar composition was obtained, and 982.6 g of glycerin was separately collected. The purified sugar composition obtained was dissolved by adding an equal amount of pure water to obtain an aqueous solution having a solid concentration of 50% by mass. The pH at this time was 7.3, and the hue was APHA250.
To the aqueous solution of the purified sugar composition, 7.0 g of activated carbon was added and heated at 80 ° C. for 30 minutes, and then the activated carbon was removed by filtration to obtain a decolorized and purified sugar composition.
Table 1 shows the sugar composition, the amount of free glycerin, the hue, and the moisture retention of the obtained decolorized and purified sugar composition.

[Example 3]
In a three-necked flask with an internal volume of 2 L equipped with a thermometer, a stirrer and a cooling tube, glycerin: 1104 g (12 mol), water candy (trade name “KM55”, manufactured by Gunei Chemical Industry Co., Ltd., mainly maltose, water content is 25% water candy): 228 g (1 mol) and paratoluenesulfonic acid: 1.28 g were charged. The pressure in the reaction system was 5 kPa (N / cm ² ), and a vacuum dehydration reaction was performed at a reaction temperature of 115 ° C. for 2 hours. Thereafter, 0.27 g of sodium hydroxide dissolved in a small amount of water was added for neutralization, and 1.0 g of hydrotalcite (trade name “KYOWARD 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added. . At this time, a part of the reaction product (crude sugar composition) was taken out, diluted with an equal amount of pure water, and its pH was measured as an aqueous solution with a solid content concentration of 50% by mass, which was 8.0.
Thereafter, the temperature was raised to 230 ° C. under 5 kPa (N / cm ² ), and excess glycerin was distilled off from the crude sugar composition. As a result, 270.2 g of a purified sugar composition was obtained, and 977.0 g of glycerin was separately collected. The purified sugar composition obtained was dissolved by adding an equal amount of pure water to obtain an aqueous solution having a solid concentration of 50% by mass. The pH at this time was 7.8, and the hue was APHA350.
To the aqueous solution of the purified sugar composition, 7.0 g of activated carbon was added and heated at 80 ° C. for 30 minutes, and then the activated carbon was removed by filtration to obtain a decolorized and purified sugar composition.
Table 1 shows the sugar composition, the amount of free glycerin, the hue, and the moisture retention of the obtained decolorized and purified sugar composition.

[Comparative Example 1]
Glycerin: 276 g (3 mol), anhydrous crystalline glucose: 180 g (1 mol), and paratoluenesulfonic acid: 0.46 g were charged into a 0.5 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. The pressure in the reaction system was 5 kPa (N / cm ² ), and a vacuum dehydration reaction was performed at a reaction temperature of 115 ° C. for 2 hours. Thereafter, 0.10 g of sodium hydroxide dissolved in a small amount of water was added for neutralization, and 0.4 g of hydrotalcite (trade name “KYOWARD 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added. . At this time, a part of the reaction product (crude sugar composition) was taken out, diluted with an equal amount of pure water, and its pH was measured as an aqueous solution with a solid content concentration of 50 mass%, which was 7.6.
Thereafter, the temperature was raised to 230 ° C. under 5 kPa (N / cm ² ), and excess glycerin was distilled off from the crude sugar composition. As a result, 220.3 g of a purified sugar composition was obtained, and 193.2 g of glycerin was separately collected. The purified sugar composition obtained was dissolved by adding an equal amount of pure water to obtain an aqueous solution having a solid concentration of 50% by mass. The pH at this time was 7.2, and the hue was APHA350.
To the aqueous solution of the purified sugar composition, 6.5 g of activated carbon was added and heated at 80 ° C. for 30 minutes, and then the activated carbon was removed by filtration to obtain a decolorized and purified sugar composition.
Table 1 shows the sugar composition, the amount of free glycerin, the hue, and the moisture retention of the obtained decolorized and purified sugar composition.

[Comparative Example 2]
Glycerin: 1104 g (12 mol), anhydrous crystalline glucose: 180 g (1 mol), paratoluenesulfonic acid: 1.28 g were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. The pressure in the reaction system was 5 kPa (N / cm ² ), and a vacuum dehydration reaction was performed at a reaction temperature of 115 ° C. for 2 hours. Thereafter, 0.27 g of sodium hydroxide dissolved in a small amount of water was added for neutralization. At this time, a part of the reaction product (crude sugar composition) was taken out, diluted with an equal amount of pure water, and its pH was measured as an aqueous solution having a solid content concentration of 50% by mass.
Thereafter, the temperature was raised to 230 ° C. under 5 kPa (N / cm ² ), and excess glycerin was distilled off from the crude sugar composition. As a result, 243.7 g of a purified sugar composition was obtained, and 1015.7 g of glycerin was separately collected. The purified sugar composition obtained was dissolved by adding an equal amount of pure water to obtain an aqueous solution having a solid concentration of 50% by mass. The pH at this time was 4.2, and the hue was APHA 500 or more (dark brown).
To the aqueous solution of the purified sugar composition, 10.0 g of activated carbon was added, heated at 80 ° C. for 30 minutes, and filtered to obtain a decolorized and purified sugar composition.
Table 1 shows the sugar composition, the amount of free glycerin, the hue, and the moisture retention of the obtained decolorized and purified sugar composition.

[Comparative Example 3]
Decolorized and purified saccharide composition obtained in Example 2: Using 100 g, α-D-DHPG was separated by chromatography using an ion exchange resin, and decolorized and purified saccharide composition containing α-D-DHPG in high purity ( 20 g of an aqueous solution having a solid concentration of 50% by mass was obtained.
Table 1 shows the sugar composition, the amount of free glycerin, the hue, and the moisture retention of the obtained decolorized and purified sugar composition.

As shown in the above results, the decolorized and purified sugar compositions of Examples 1 to 3 had a lower mass reduction rate and higher moisture retention than the decolorized and purified sugar compositions of Comparative Examples 1 to 3. The hue (APHA) was also good.
On the other hand, Comparative Example 1 having a low feed molar ratio of glycerin as a raw material has a ratio of the total content of α-D-DHPG and β-D-DHPG to the total of all sugars in the obtained decolorized and purified sugar composition. Less than 60%. In addition, the decolorized and purified sugar composition had low moisture retention and poor hue.
Moreover, the comparative example 2 whose pH fell to 4.2 at the time of distillation is the ratio of the total content of α-D-DHPG and β-D-DHPG with respect to the total of all sugars in the obtained decolorized and purified sugar composition. Was less than 60%. In addition, the decolorized and purified sugar composition had low moisture retention and poor hue. This is considered to be because α-D-DHPG and β-D-DHPG were decomposed by pH reduction, the purity was lowered, and browning was caused by the produced glucose.
Moreover, although the decoloration refinement | purification sugar composition of the comparative example 3 contains (alpha) -D-DHPG in high purity, the moisture retention was lower than Examples 1-3.

Claims (4)

The compound represented by the following formula (1) and the compound represented by the following formula (2) are included at a mass ratio of 45 to 75:15 to 25, and the total amount of all the sugars contained in the sugar composition. The sugar composition in which the ratio of the compound represented by the formula (1) is 58.4 to 65.3 mass% and the ratio of the compound represented by the formula (2) is 21.6 to 24.5 mass%. A moisturizer consisting of things.

A method for producing a humectant according to claim 1, comprising:
Reacting a glucose source with glycerin using an acidic catalyst ;
A step of removing the glycerin by distillation from a reaction product obtained by reacting the glucose source with the glycerin ;
The molar ratio of the charged amount and the charge amount of the glycerin in terms of glucose in the glucose source is 1: 4:00 to 1:16 der is,
A method for producing a moisturizing agent, wherein the distillation is performed within a range of pH (25 ° C.) 6.5 to 8.5 . The method for producing a humectant according to claim 2, wherein the reaction between the glucose source and the glycerin is performed under vacuum. The method for producing a humectant according to claim 2 or 3 , wherein hydrotalcites are used for controlling the pH during the distillation.

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