JPH09117258A - Food additive composed of polyglycerol monofatty acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a food additive composed of a polyglycerol monofatty acid ester containing a prescribed amount of a specific monofatty acid ester, having high purity, exhibiting excellent surface tension, dispersibility, frothing performance and emulsion stability and useful e.g. as an emulsifier for an oil and fat composition for bakery and confectionery. SOLUTION: This food additive is composed of a polyglycerol monofatty acid ester containing a monofatty acid ester of the formula (R is a 6-21C alkyl, alkenyl or hydroxyl-substituted alkyl; (n) is >=4) in an amount of >=70% in terms of the peak area ratio measured by separating the fraction by a high- performance liquid chromatography with a silica gel column bonded with octadecylsilyl group and using an alcoholic solvent and/or distilled water as an eluting solution and determining the peak with an ultraviolet absorption detector. The monofatty acid ester can be produced by reacting a fatty acid of the formula RCOOH with glycidol in the presence of a phosphoric acid-type acidic catalyst (e.g. phosphoric acid). A polyglycerol monofatty acid ester containing the monofatty acid ester is preferably used as a food additive.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyglycerin monofatty acid ester and a food additive comprising the same. More specifically, it relates to a food additive comprising a polyglycerin monofatty acid ester containing a monofatty acid ester in a higher purity than conventional products.

[0002]

2. Description of the Related Art In recent years, polyglycerin fatty acid ester has been approved as a food additive, and its usage amount is gradually increasing. In general, this ester can be obtained as an ester having a wide range of HLB values by combining polyglycerin having a different degree of polymerization as a raw material with a fatty acid having a different chain length, and exhibits high stability in an acidic region. It is widely used as an emulsifier and a viscosity modifier in the food field. The method for producing this polyglycerin fatty acid ester includes (1) esterification reaction of polyglycerin and fatty acid,
(2) Transesterification reaction of polyglycerin and fatty acid ester, (3) Transesterification reaction of polyglycerin and oil and fat, (4) Addition polymerization reaction of glycidol and fatty acid monoglyceride, (5) Addition polymerization of glycidol and fatty acid There is a reaction. Among these, the methods (2) to (3) are methods that have many restrictions in terms of reactivity, quality and purity of the produced polyglycerin fatty acid ester.

The method (1) is based on JAOCS (Journal of A).
American 0il Chemists' Society) Vol. 58, No. 878
Page (1981), a method for obtaining a polyglycerin fatty acid ester by carrying out an esterification reaction of polyglycerin and a fatty acid in the presence of an alkali catalyst is disclosed. A similar method is disclosed in Japanese Patent Laid-Open No. 6-41007. For the method (4), refer to USP4.
515,775. Regarding the method (5), a monofatty acid ester of glycerin has been described so far in JP-A-51-65705. However, according to the technique disclosed in this publication, in the presence of an inert solvent, a high percentage of carboxylic acid-1-monoglyceride (in formula [1] below, n
The value of is 1 on average. ), The degree of polymerization of glycerin is 1 on average, and no mention is made of a monofatty acid ester of polyglycerin, and no actual study has been made.

As a technique using the addition polymerization reaction of glycidol, the addition polymerization reaction of glycerin and glycidol in producing polyglycerin used in the methods (1) to (3) (Japanese Patent Publication No. 1-55254). Japanese Patent Publication No. 4-11532, Japanese Patent Publication No. 5-1291) or a polyglycerin produced through a hydrolysis reaction after addition polymerization of fatty acid and glycidol (Japanese Patent Publication No. 4-6962).
No. 1), production of polyglycerin monoalkyl ether, polyglycerin monoalkyl thioether (USP
3,821,372, USP 3,966,398, US
P4,087,466) and the like are disclosed.

However, in the production of polyglycerin through a hydrolysis reaction after the addition polymerization reaction of a fatty acid and glycidol described in JP-B-4-69621, the fatty acid used is a lower fatty acid (having 2 to 6 carbon atoms). And the aim is the production of polyglycerin, no mention is made of polyglycerin fatty acid esters.

[0006]

[Problems to be Solved by the Invention] Conventionally, when a polyglycerin monofatty acid ester is produced, it is produced by the method (1). In this method, generally, as the raw material polyglycerin, the reaction active hydroxyl group is 4 to 4 on average.
Even if a mono-substituted fatty acid ester of 10 is used, the ratio of reactive hydroxyl groups is large relative to the equivalent of the fatty acid used, and the polyglycerin mono-fatty acid ester produced contains the desired mono- It has been pointed out that not only fatty acid ester compounds but also polyreacted ester compounds such as unreacted polyglycerin, diesters, triesters and tetraesters remain (N. Garti, et.
al, J. of Am. Oil Chem. Soc., 59, 317-319 (1982)).

Further, even when the glycidol is added to the fatty acid monoglyceride of (4) to carry out the addition polymerization reaction, the purity of the reaction product is greatly affected by the degree of purification of the raw material fatty acid monoglyceride. In particular, when a fatty acid monoglyceride obtained by the reaction of glycerin and a fatty acid is used as a raw material, the glycerin component remains in the raw material as in the above (1), and is obtained by an addition polymerization reaction of glycidol. The content of monofatty acid ester in the obtained polyglycerin monofatty acid ester is about 40%,
It is recognized that the remaining about 60% is unreacted glycerin and esters with 2 or more substitutions (Shigeru Tsuda, Monoglyceride, P67 (1985), Maki Shoten).

As described above, in the conventionally used polyglycerin monofatty acid ester, a large amount of unsubstituted polyglycerin and ester products of two or more substitutions remain, which are added to foods such as surfactants and emulsion stabilizers. When applied to agents, it is feared that the surface tension, dispersion power, foaming power, and emulsion stability will decrease.

On the other hand, as a method for removing unsubstituted polyglycerin, at least one selected from water-soluble organic solvents and water is used in combination with at least one selected from non-water-soluble organic solvents. To remove unreacted polyglycerin with the mixed solvent described above (JP-A-63-23837), and to remove unreacted polyglycerin by contacting and adsorbing a solution of an esterification reaction product with alkylsilylated silica gel. (JP-A-3-81252), a method of extracting and removing unreacted polyglycerin using a water-soluble organic solvent and an aqueous solution containing water or a salting-out agent (JP-A-6-41).
No. 007) has been proposed.

However, in the method described in JP-A-63-23837, aromatic hydrocarbons such as benzene and toluene, which are described as non-water-soluble organic solvents, have doubts about their safety, so There are problems with the use. Further, in this method, the reaction molar ratio of the fatty acid to the polyglycerin is limited to 1 or less, and the effectiveness in the case of the molar ratio exceeding 1 is not described. Even when the reaction molar ratio is 1 or less, toluene /
In methanol systems, etc., a considerable amount of high HLB polyglycerin fatty acid ester was found to migrate to the water-containing methanol phase, and in toluene / methanol systems, etc., unreacted polyglycerin was extremely insufficiently separated. There are several problems in industrial implementation.
Further, the method of partitioning with an alkylsilylated silica gel described in JP-A-3-81252 has the drawbacks that the operating cost is high and the operation is complicated. further,
These prior arts can remove unreacted polyglycerin, including the method described in JP-A-6-41007, but have a drawback in that it is impossible to remove an ester compound having two or more substitutions.

Therefore, when it is applied to a food additive such as a surfactant or an emulsion stabilizer, it is expected to improve the surface tension, the dispersion power, the foaming power, and the emulsion stability. There has been a demand for a polyglycerin monofatty acid ester having a high fatty acid ester content and a method for producing the same.

[0012]

Means for Solving the Problems The present invention is intended to solve the above problems and is based on the finding that polyglycerol monofatty acid ester having a high monofatty acid ester content can be obtained by a specific method. The present invention provides a food additive comprising the polyglycerin monofatty acid ester obtained by the method. That is, according to the first aspect of the present invention, the content of the mono-fatty acid ester represented by the following general formula [1], which is eluted by the column chromatographic analysis method and is detected by using an ultraviolet absorption detector, in terms of peak area ratio Is 70%
A food additive comprising the above polyglycerol monofatty acid ester is provided.

[0013]

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According to a second aspect of the present invention, the general formula [2]
There is provided a food additive comprising a polyglycerin monofatty acid ester containing a monofatty acid ester body represented by the following general formula [1] obtained by reacting a fatty acid represented by the formula (4) with glycidol in the presence of a phosphoric acid-based acidic catalyst. It

[0015]

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When the polyglycerin monofatty acid ester having a peak area ratio of less than 70% is applied to a food additive such as a surfactant or an emulsion stabilizer, the surface tension is lowered, the dispersing power is lowered, and foaming is caused. A decrease in force and a decrease in emulsion stability are observed.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION When the polyglycerin monofatty acid ester used in the present invention is produced, the fatty acid represented by the general formula [2] used in the addition polymerization reaction of glycidol and fatty acid has 7 to 22 carbon atoms. The above fatty acid is preferably used, which has 8 or more carbon atoms, may be saturated fatty acid or unsaturated fatty acid, and may be a linear fatty acid or a fatty acid having a side chain, and further, a carbon chain substituted with a hydroxyl group. It may be a substituted fatty acid. Examples of these fatty acids include caproic acid, caprylic acid, 21-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid,
Examples include behenic acid, erucic acid, ricinoleic acid and hydroxystearic acid. These can be used alone,
Two or more kinds may be optionally mixed and used in the reaction. Among the above fatty acids, lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid are preferred.

The reaction between the fatty acid and glycidol must be carried out in the presence of a phosphoric acid-based acidic catalyst. The phosphoric acid-based acidic catalyst referred to here is phosphoric acid or an ester of phosphoric acid, and specifically, phosphoric acid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, Phosphoric acids such as tetraphosphoric acid or acidic phosphoric acid esters such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate and 2-ethylhexyl acid phosphate can be used. In addition, as these acidic phosphates, any of a monoester body, a diester body, and a mixture thereof can be used. Of the above, phosphoric acid and acidic phosphoric acid ester are preferably used.

The above catalysts may be used alone or in combination of two or more. The amount of the catalyst is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the fatty acid. If the amount is less than 0.01% by weight, the reaction rate is small, and if it exceeds 10% by weight, no improvement in the effect can be expected. Depending on the catalyst used, a large amount of a glycidol addition polymer in which the catalyst is used as an initiator is formed. Absent.

The reaction method is to take fatty acid in a reaction vessel,
The above catalyst is added to this, and the reaction is carried out while adding glycidol little by little. The reaction temperature is 50 to 180 ° C., preferably 70 to 160 ° C., more preferably 120.
~ 140 ° C. Below 50 ° C., the reaction rate is low,
On the other hand, if the temperature exceeds 180 ° C., coloring becomes intense. If the temperature is higher than 230 ° C., glycidol is decomposed to cause a side reaction, which is not preferable. In this case, a low boiling point compound that does not react with glycidol may be added to prevent the reaction temperature from rising. The reaction is desirably performed in a nitrogen gas atmosphere, and may be pressurized if necessary.

By the above reaction, glycidol is added and polymerized to the fatty acid to produce a polyglycerol monofatty acid ester having a higher degree of polymerization. The n of the mono-fatty acid ester represented by the general formula [1] contained in the produced polyglycerin mono-fatty acid ester at a high concentration is the average number of glycerin, which is approximately the same as the molar ratio of the fatty acid to be reacted and glycidol. Can be changed easily. The product is a polyglycerin monofatty acid ester having a high monofatty acid ester content. That is, the polyglycerin monofatty acid ester obtained by the above method and used in the present invention is a monofatty acid ester body represented by the above general formula [1] which is eluted by a column chromatographic analysis method and detected using an ultraviolet absorption detector. The content expressed by the peak area ratio is 70% or more. Here, the column chromatographic analysis method is a reversed-phase partition column analysis method using octadecylsilyl group as a functional group, octylsilyl group, butylsilyl group, trimethylsilyl group, and silica gel having phenylsilyl group bonded as a carrier,
Normal phase partitioning column analysis method using silica gel having cyanopropyl group and aminopropyl group as a functional group as a carrier, ion exchange column analysis method having quaternary ammonium group and phenylsulfonic acid group as a functional group, adsorption column of porous silica gel Analytical methods are included. In these analytical methods, a reversed phase partition column analytical method is preferably used in which silica gel having octadecylsilyl (ODS) groups bonded thereto is used as a carrier. Further, in order to improve the separation performance, the column size is preferably 4.6 mmφ × 250 mm or more, and it is more preferable to connect the columns in series because the separation ability can be improved. The peak area ratio of the mono-fatty acid ester is 70% or more, specifically, the following H
Under the analytical conditions of PLC (High Performance Liquid Chromatography), it means that the peak area ratio attributed to the monofatty acid ester is 70% or more based on the total peak area.

The case of analysis by the reversed-phase partition column analysis method will be described below. Since the developing solvent varies depending on the type of fatty acid of polyglycerin monofatty acid ester and the number of moles of glycidol added, it is preferable to determine the developing solvent from the solubility and separability of the analyte. Specifically, as a specific developing solvent having excellent solubility and separability of an analyte, an alcohol solvent and / or distilled water is preferable, and specifically, methanol is used as the polyglycerol monolaurate ester. It is preferable to use ethanol for polyglycerol monostearate.

The flow rate of the developing solvent is selected according to the pressure resistance of the column used and the degree of separation of the obtained chromatogram.
Usually, it is in the range of 0.05 to 1.0 ml / min, more preferably in the range of 0.1 to 0.8 ml / min. The column temperature is preferably in the range 30-60 ° C. The wavelength of the ultraviolet absorption detector is 210 nm.

As the sample to be subjected to HPLC, it is preferable to use the developing solution to be used as a solvent, and the concentration and injection amount are selected so as to be excellent in solubility and separability of the analyte. Specifically, the sample concentration is preferably 1 to 50%, and the injection volume is preferably 0.1 to 20 μl.

The content is measured as follows. In HPLC analysis using an ODS column, elution is generally performed in the order of polarity. Therefore, in the case of polyglycerins, unsubstituted polyglycerol having high polarity is eluted first, and then polyglycerin monofatty acid ester and polyglycerin difatty acid ester are detected. On the other hand, in the case of glycerin monofatty acid esters, polyglycerin monoester having high polarity is eluted first, and glycerin monoester is eluted last. Therefore, the standard products of polyglycerin and glycerin monofatty acid ester were analyzed by HPLC under the same conditions, the retention times of the standard product and the specimen were compared and examined, and those eluted after the elution of glycerin monoester were replaced with polysubstituted ester of diester or more. As an ingredient. The content rate (%) of the mono-fatty acid ester form is represented by the peak area ratio according to the following. From the analysis chart, the peak area of polyglycerin,
The peak area of polyglycerin monofatty acid ester (which is referred to as “polyglycerin”, but in the present invention, the glycerin portion includes polyglycerin to monoglycerin) and the peak area of polysubstituted ester components of diester or more were determined. . Then, it was calculated according to the following equation. In addition, the solvent whose peak position did not overlap with any of the peaks of polyglycerin, monofatty acid ester, and polysubstituted ester of diester or higher was selected. Also, the following formula
It is assumed that the retention time of the solvent is after the elution of the diester. Typical HPLC analytical conditions other than those used in the examples are as follows.

[0026]

## EQU1 ## Formula: Content of polyglycerin monofatty acid ester (%) = {peak area of polyglycerin monofatty acid ester / (peak area of polyglycerin + peak area of polyglycerin monofatty acid ester + diester The peak area of the above polysubstituted ester)} × 100
(%)

<HPLC analysis condition (1)> Column: Wakosil 5C18 × 2 (manufactured by Wako Pure Chemical Industries, Ltd .: a column having octadecylsilyl group as a functional group, which is a reverse phase distribution column, size: 4.6 mmφ × Two
50 mm), developing solvent: methanol, flow rate: 0.75 m
l / min. , Column oven temperature: 40 ° C., detection method: ultraviolet absorption method (λ = 210 nm), sample concentration: 10
% (Solvent: methanol), injection volume: 5 μl. For example, in the case of polyglycerin monolaurate, the retention time of each component is 8 minutes or less for polyglycerin, 8 to 12 minutes for monolaurate, and 12 minutes or more for dilaurate or more.

<HPLC analysis condition (2)> Column: Wakosil II 5C18HG (manufactured by Wako Pure Chemical Industries, Ltd .: a column having octadecylsilyl group as a functional group, which is a reverse phase distribution column, size: 4.6 mm)
φ × 250 mm), developing solvent: methanol, flow rate: 0.
2 ml / min. , Column oven temperature: 40 ° C., detection method: ultraviolet absorption method (λ = 210 nm), sample concentration: 5
% (Solvent: methanol), injection volume: 10 μl, retention time of each component was polyglycerin: before 14 minutes,
Monoester: 14 to 16.5 minutes, Diester and higher: 16.5 minutes and thereafter, methanol component: 18 minutes.

<HPLC analysis conditions (3)> Column: Wakosil 5C18 and Wakosil
II 5C18HG (all manufactured by Wako Pure Chemical Industries, Ltd .:
(A column having an octadecylsilyl group as a functional group, which is a reversed-phase distribution column, size: 4.6 mmφ × 250 mm)
Are connected in series. Developing solvent: ethanol, flow rate:
0.2 ml / min. , Column oven temperature: 40 ° C,
Detection method: UV absorption method (λ = 210 nm), sample concentration: 5% (solvent: EtOH), injection amount: 10 μl. The retention time of each component was as follows: polyglycerin: 28.5
Minutes before, the monoester compound: 28.5 minutes to 34 minutes, the diester compound or more: after 34 minutes, the ethanol component: 39 minutes.

Further, the polyglycerin monofatty acid ester obtained above can be used in the food additive of the present invention after further purification through various purification steps, if necessary, and is also preferable. Specific refining methods include (a) a deodorizing method in which saturated heated steam is blown under reduced pressure to deodorize steam, and (b) a decolorizing method such as bleaching with sodium hypophosphite or hydrogen peroxide. As another method (C), there is a method of adding water, heating and then dehydrating. The heating temperature is 60 to 200 ° C., and the heating time is 0.5 to 15 hours, particularly preferably 1 to 7 hours, depending on the temperature. Dehydration can be performed by distillation, azeotropic distillation, vacuum distillation, etc., and the heating temperature for distillation is 100
~ 200 ° C. The amount of water added is 0.1 to 20% by weight based on the polyglycerin monofatty acid ester,
It is preferably 1 to 10% by weight. For example, above (C)
When the method described above is carried out, the oxirane oxygen concentration in the polyglycerin monofatty acid ester is 500 ppm (0.05
%) To less than 100 ppm. In addition,
The oxirane oxygen concentration is as described in J. of Am. Oil Chem. Soc.
Cd. Using the titration method defined in 9-57, or proton NMR, the methylene and methine protons derived from polyglycerin were assigned 3.4 ppm and 4.4.
It can be measured by measuring the ratio of the peak area value of the chemical shift between 2.7 ppm and 2.8 ppm attributed to the methylene proton derived from the oxirane group to the peak area value of the chemical shift between ppm.

As described above, in the present invention, the polyglycerin monofatty acid ester having a high purity, in particular, the content of the monofatty acid ester body represented by the above peak area is 70% or more by the addition polymerization reaction of glycidol and fatty acid. Since polyglycerin monofatty acid ester is used as a food additive such as a surfactant and an emulsion stabilizer, it has the effects of improving surface tension, improving dispersive power, improving foaming power, and improving emulsion stability. is there.

Therefore, the polyglycerin monofatty acid ester represented by the general formula [1] having a high content of monofatty acid ester (hereinafter referred to as high-purity polyglycerin monofatty acid ester) used in the present invention is conventionally polyglycerin monofatty acid. It is used for various purposes as a food additive in which an ester or the like is used, and can sufficiently exhibit its intended function. These are exemplified below.

(1) The high-purity polyglycerin monofatty acid ester used in the present invention can be used as an emulsifier for an oil / fat composition used in the production of breads, cakes and confectioneries. For example, as described in JP-A-6-22690, when baking bread dough made of wheat flour or the like, each component in the wheat flour undergoes physical, chemical and biochemical reaction changes, but In order to obtain good bread, it is necessary to strictly control the baking process, and in order to obtain stable quality, it consists of soybean oil, cottonseed oil, rapeseed oil and other oils and fats, and if necessary, an aqueous phase containing a seasoning. A fat composition is used. An emulsifier is used in the oil / fat composition, and the high-purity polyglycerin monofatty acid ester can be used as an emulsifier in such an oil / fat composition for bread making. Similarly, JP-A-6-53 discloses a method of using a water-in-oil type oil / fat composition when producing butter cakes by an all-in-mix method. that time,
An emulsifier is used in the range of 0.2 to 10% by weight based on the total oil and fat composition, and the high-purity polyglycerin monofatty acid ester is also useful as an emulsifier for an oil and fat composition for confectionery such as butter cakes. . In addition, JP-A-6-2692
No. 44 gazette discloses water, sorbitol, liquid sugar, etc. in order to make cakes that are stable and do not easily fall in the pot when producing cakes such as sponge cakes, snack cakes, chiffon cakes, and semi-raw confections. A foamable emulsified oil / fat composition obtained by adding an emulsifier, whey protein, etc. to the aqueous phase of is used. Also as such an emulsifier, the high-purity polyglycerin monofatty acid ester can be used. Furthermore, JP-A-6-78672 discloses that when applied to bread, the dough gives less stickiness and gives a good flavor and texture, and an oil-in-water emulsion containing water, oils and fats, sugars and emulsifiers. In the composition, a high oil content in which the content of fats and oils is 35 to 75% by weight, the sugar is 10 to 50% by weight including at least sorbitol, and the content of the emulsifier is 5 to 25% by weight with respect to the aqueous phase. Oil-in-water emulsion compositions are described. And as the emulsifier, H
A polyglycerin fatty acid ester having an LB value of 7 to 16 is used. The high-purity polyglycerin monofatty acid ester can be similarly used for such applications.

(2) Japanese Patent Laid-Open No. 6-125711 discloses that
To prevent the floating of oils and fats and the precipitation of cocoa powder that occur when storing cocoa beverages, sucrose oleic acid ester 1 to 25% by weight, glycerin fatty acid ester 3 to 36% by weight, sorbitan fatty acid ester 1 to 11% by weight, crystalline cellulose An emulsion stabilizer for cocoa beverages comprising 26 to 90% by weight and 2 to 5% by weight of κ-carrageenan is disclosed, wherein the high-purity polyglycerin monofatty acid ester is used in place of or together with the glycerin fatty acid ester. , It can be used as an emulsion stabilizer compounding agent for cocoa beverages. Further, in Japanese Patent Application Laid-Open No. 6-38682, a mixed solution consisting of a cocoa component, a milk component, a sweetener and water is added.
A cocoa beverage prepared by adding a lipophilic polyglycerin fatty acid ester in a proportion of 0.2 to 5.0% by weight with respect to the fat content contained in the mixed solution is disclosed. The high-purity polyglycerin monofatty acid ester can be used in place of the lipophilic polyglycerin fatty acid ester.

(3) The high-purity polyglycerin monofatty acid ester can be used as an additive for starch foods as follows. Japanese Patent Laid-Open No. 6-276972 discloses that chicken eggs should be added in an amount of 0.5 to 0.5 in order to make noodles that boil quickly.
A noodle quality improving agent containing 40 parts by weight and 0.01 to 0.5 part of lysolin oil quality is disclosed. It also describes that 0.1 to 10 parts by weight of a food-grade surfactant may be added, if necessary. The high-purity polyglycerin monofatty acid ester can be used as such a surfactant for blending noodle quality improving agents. In addition, Japanese Unexamined Patent Publication
In 197717 publication, it is described that when the steamed noodles are boiled, the unravelability of the noodles becomes extremely good by using mung bean modified starch or a combination thereof with an emulsifier, and that polyglycerin fatty acid ester or the like is used as the emulsifier. Has been done. The emulsifier is 0.1 to 2 with respect to noodle raw materials.
Although 0% by weight is used, the high-purity polyglycerol monofatty acid ester can be used as such an emulsifier. Further, in JP-A-6-225684, edible oil and fat 0 to 20% by weight, glycerin organic acid fatty acid ester and stearyl lactate 0.05 to 20% by weight, polyglycerin fatty acid ester and / or sucrose having HLB of 12 or more. Fatty acid ester 0.01-5% by weight, water content 50-
A 90% by weight composition for improving the quality of starch foods that is fluid at 10 ° C is disclosed. When this composition is used for foods such as bread, donuts, steamed buns, dumplings, noodles and spaghetti, it prevents adhesion of the dough to each other or a machine at the time of production, an increase in volume and an improvement in texture, and the time-lapse of starch after production. It is said that it exerts the effect of preventing the deterioration of the texture due to a change in taste. The high-purity polyglycerin monofatty acid ester can be used in place of the polyglycerin fatty acid ester as a blend of such a starch food quality improving composition.

(4) The high-purity polyglycerin monofatty acid ester can be used as an additive for fish paste products as follows. Japanese Unexamined Patent Publication (Kokai) No. 6-22730 discloses a method for producing a frozen surimi, which comprises adding a quality improving agent containing a polyglycerin fatty acid ester to a fish paste product. That is, it has been clarified that the frozen surimi has an effect of retaining the foot-forming ability and an effect of improving whiteness. The amount added is 1% by weight or less, preferably 0.1 to 0.5% by weight, based on the surimi. In addition, JP-A-6-907
No. 13, gazette contains 0.1 to 2% by weight of polyglycerin fatty acid ester emulsifier with HLB of 13 or more in addition to water, oil and fat, and reduced starch saccharified product, to the ground meat of seafood containing scallop ovary and / or testis. Then, a method for producing a kneaded product is described, in which the kneaded product is kneaded together with salt, and heat treatment is performed after molding. The high-purity polyglycerin monofatty acid ester can be used as an additive for such a fish paste product instead of the polyglycerin fatty acid ester. Further, JP-A-6-113727 describes a technique for improving the binding property between fish meat and fats and oils by injecting an oil-in-water emulsion containing egg white and carrageenan into fish meat. . It is described that this makes it possible to obtain a fish meat ham which has an appropriate texture without sacrificing the texture and flavor of the fish and has an excellent texture without being dry. Further, glycerin fatty acid ester is mentioned as one of the emulsifiers added to this emulsion. The high-purity polyglycerin monofatty acid ester can also be used as such an emulsifier for an oil-in-water emulsion for producing fish ham.

(5) Japanese Patent Laid-Open No. 6-209704 discloses that
Oil-in-water type emulsion oil composition which does not have feathering or oil-off when added to coffee or tea, or can be used for cooking, etc. and contains polyglycerin saturated fatty acid ester having an esterification degree of 3 or less as an emulsifier Is disclosed. It is disclosed that 0.1 to 1.5% by weight of an emulsifying agent is added to the dissolved oil and fat. The high-purity polyglycerin monofatty acid ester can be used for the same purpose.

(6) Japanese Patent Laid-Open No. 6-253718 discloses that
Bread made by adding at least 0.1% by weight of calcium carbonate, 0.5% by weight or less of glycerin fatty acid ester, and 0.5% by weight or less of egg white to wheat flour at room temperature for a long period of time in the medium seed method. Wheat flour formulations are described. It is said that this makes it possible to produce high-quality bread even if the fermentation time of the medium variety is extended. The high-purity polyglycerin monofatty acid ester can be used as an alternative to the glycerin fatty acid ester.

(7) Japanese Patent Laid-Open No. 6-113799 discloses that
Lactic acid bacteria are inoculated into a cheese homogeneous liquid obtained by homogenizing natural cheese, water, and skim milk powder, and lactic acid fermentation is performed.
H3.6-4.5 Lactic acid cheese fermented liquor was obtained, and about 5
Sour cheese beverages with ~ 50% sugar added are described. In addition to skimmed milk powder, it is described that a surfactant such as glycerin fatty acid ester may be used as a fat dispersion emulsification accelerator. The high-purity polyglycerin monofatty acid ester can also be used as such a fat dispersion emulsification accelerator for sour cheese beverages.

(8) Japanese Patent Laid-Open No. 6-153884 discloses that
Disclosed is a food freshness-retaining agent characterized by comprising persimmon leaf extract (flavonoids) and tocopherol, or persimmon leaf extract, tocopherol and gallic acid as active ingredients. It is convenient for use that this freshness-retaining agent is prepared as a lipophilic emulsion, and in that case, polyglycerin fatty acid ester is exemplified as an emulsifier (surfactant). The high-purity polyglycerin monofatty acid ester provided by the present invention can also be used as this surfactant.

(9) Japanese Unexamined Patent Publication (Kokai) No. 6-62734 discloses a fatty acid-containing sour milk beverage containing chitosan and polyglycerin fatty acid ester. Thereby, it is said that the stability of fat globules under acidic conditions, which is a preferable sour taste, is improved, but the high-purity polyglycerin monofatty acid ester is replaced with the polyglycerin fatty acid ester, and such a fat-containing material is contained. It can be used as an additive for lactic acid beverages.

(10) Japanese Patent Laid-Open No. 6-189682 discloses that
A chocolate dough that has been rolled and conched, an aqueous component, a high-HLB polyglycerin fatty acid ester and a low-HLB polyglycerin fatty acid ester are mixed to emulsify into a water-in-oil type water content of 2% by weight or more and 50% by weight or less. Of water-containing chocolates are described. The low-HLB polyglycerin fatty acid ester is preferably HLB 2 to 4, and the high-HLB polyglycerin fatty acid ester is preferably HLB 11 to 13. The high-purity polyglycerin monofatty acid ester can be used as any of the polyglycerin fatty acid esters.

(11) JP-A-6-90663 discloses that the fat content is 10 to 40% by weight, the enzyme-treated lecithin containing lysolecithin as an emulsifier, and the monoglycerin fatty acid ester content is 50% by weight. To 70% by weight of medium purity monoglycerin fatty acid ester, succinic acid monoglyceride and lecithin are disclosed. It is described that, as a result, a coffee cream having a stable emulsion at room temperature and freezing resistance that does not cause emulsion destruction even if it is thawed after being stored at 0 ° C. or lower is described. Further, in the examples, 0.2 part of the intermediate-purity monoglyceride is used together with another emulsifier with respect to 25.5 parts by weight of palm kernel oil that constitutes the oil phase part. The high-purity polyglycerin monofatty acid ester can be used as an emulsifier for coffee cream as described above.

[0044]

EXAMPLES The production of high-purity polyglycerin monofatty acid ester used in the present invention and the effect of using the obtained high-purity polyglycerin monofatty acid ester as a food additive such as a surfactant and an emulsifier were evaluated below. The evaluation results will be specifically described by way of examples. The HPLC analysis conditions are as follows throughout the examples and comparative examples.

(Analysis conditions of HPLC) Column: Wakosil 5C18 × 2 (manufactured by Wako Pure Chemical Industries, Ltd .: column having octadecylsilyl group as a functional group which is a reverse phase distribution column, size: 4.6 mmφ × 2)
50 mm), developing solvent: methanol, flow rate: 0.75 m
l / min. , Column oven temperature: 40 ° C., detection method: ultraviolet absorption method (λ = 210 nm), sample concentration: 10
% (Solvent: methanol), injection volume: 5 μl. For example, in the case of polyglycerin monolaurate, the retention time of each component is 8 minutes or less for polyglycerin, 8 to 12 minutes for monolaurate, and 12 minutes or more for dilaurate or more.

Example 1 0.5 mol (100.1) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
6g) and 0.0622g of phosphoric acid (85% product)
Heated to 40 ° C. Then, 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours while maintaining the reaction temperature at 140 ° C., and the oxirane concentration in the system was 0.1%.
The reaction continued until less than. After cooling, the reaction product was taken out to obtain about 300 g of polyglycerin monolaurate (hexaglycerin monolaurate). The obtained polyglycerin monolaurate ester was added to the above H
It was evaluated under the analysis conditions of PLC. In addition, as a common and basic evaluation method for evaluating the effect of use as an additive such as an emulsifier or a surfactant in various food applications, a 10% aqueous solution of the obtained polyglycerin monolaurate ester is prepared, and then for 30 seconds. It was vibrated (manually) and the foamability and state were visually observed. The chart obtained by HPLC is shown in FIG. Furthermore, the results of the component analysis and the evaluation results of the foamability and the state by the analysis from HPLC are shown.
1 is shown.

(Example 2) 0.5 mol (100.1) of lauric acid was placed in a 1-liter 4-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
6g) and 0.0810g of phosphoric acid (85% product) were added, and 1
Heated to 40 ° C. Then, 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours while maintaining the reaction temperature at 140 ° C., and the oxirane concentration in the system was 0.1%.
The reaction continued until less than. After cooling, the reaction product was taken out to obtain about 300 g of polyglycerin monolaurate (hexaglycerin monolaurate). The obtained polyglycerin monolauric acid ester was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, shaken (manually) for 30 seconds, and the foamability and the state were visually observed. HP
The chart obtained by LC is shown in FIG. Also, H
Table 1 shows the result of the component analysis by the analysis from PLC and the evaluation result of the foamability and the state.

(Example 3) 0.5 mol (100.1) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller and a dropping cylinder.
6g) and 0.0810g of phosphoric acid (85% product) were added, and 1
Heated to 40 ° C. Next, while maintaining the reaction temperature at 140 ° C., 4.0 mol (296.32 g) of glycidol was added dropwise over 5 hours so that the oxirane concentration in the system was 0.1%.
The reaction continued until less than. After cooling, the reaction product was taken out to obtain about 400 g of polyglycerin monolaurate (octaglycerin monolaurate). The obtained polyglycerin monolauric acid ester was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, shaken (manually) for 30 seconds, and the foamability and the state were visually observed. HP
The chart obtained by LC is shown in FIG. Also, H
Table 1 shows the result of the component analysis by the analysis from PLC and the evaluation result of the foamability and the state.

(Example 4) 0.5 mol (100.1) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
6g) and 0.118g of phosphoric acid (85% product) were added,
Heated to 0 ° C. Then, while maintaining the reaction temperature at 140 ° C., 5.0 mol (370.40 g) of glycidol was mixed with 5 mol of glycidol.
The solution was added dropwise over time, and the reaction was continued until the oxirane concentration in the system became less than 0.1%. After cooling, remove the reaction product,
About 470 g of polyglycerin monolaurate (decaglycerin monolaurate) was obtained. The obtained polyglycerin monolauric acid ester was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, shaken (manually) for 30 seconds, and the foamability and the state were visually observed. The chart obtained by HPLC is shown in FIG. Also, HPLC
The results of the component analysis and the evaluation results of the foaming property and the state by the analysis from Table 1 are shown in Table-1.

Example 5 0.5 mol (100.1) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller and a dropping cylinder.
6 g) and EAP (a mixture of monoethyl acid phosphate and diethyl acid phosphate, manufactured by Nippon Kagaku Kogyo Co., Ltd.) (0.105 g) were added, and the mixture was heated to 140 ° C.
Next, 5.0 mol (370.40 g) of glycidol was added dropwise over 5 hours while maintaining the reaction temperature at 140 ° C., and the reaction was continued until the oxirane concentration in the system became less than 0.1%. After cooling, the reaction product was taken out to obtain about 470 g of polyglycerin monolaurate (decaglycerin monolaurate). The obtained polyglycerin monolauric acid ester was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, shaken (manually) for 30 seconds, and the foamability and the state were visually observed. The chart obtained by HPLC is shown in FIG. In addition, Table 1 shows the results of the component analysis by the analysis from HPLC and the evaluation results of the foamability and the state.
It was shown to.

(Comparative Example 1: When no catalyst is used) A 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder was charged with lauric acid of 0.1%.
5 mol (100.16 g) was added and heated to 140 ° C. Then, 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours while maintaining the reaction temperature at 140 ° C., and the reaction was continued until the oxirane concentration in the system became less than 0.1%. After cooling, the reaction product was taken out to obtain about 300 g of polyglycerin monolaurate. The obtained polyglycerin monolauric acid ester was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, shaken (manually) for 30 seconds, and the foamability and the state were visually observed. HP
The chart obtained by LC analysis is shown in FIG. Also, H
Table 1 shows the result of the component analysis and the evaluation result of the foamability and the state by the analysis from the PLC analysis.

(Comparative Example 2: Using paratoluenesulfonic acid (PTS) as a catalyst) Lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen introducing tube, a stirrer, a cooling tube, a temperature controller and a dropping cylinder. 0.5 mol (100.
16 g) and PTS 0.371 g were added, and the mixture was heated to 140 ° C. Then, 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours while maintaining the reaction temperature at 140 ° C., and the reaction was continued until the oxirane concentration in the system became less than 0.1%. After cooling, the reaction product was taken out to obtain about 300 g of polyglycerin monolaurate. The obtained polyglycerin monolauric acid ester was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, shaken (manually) for 30 seconds, and the foamability and the state were visually observed. HP
The chart obtained by LC is shown in FIG. 7. In addition, HPL
Table 1 shows the result of the component analysis by the analysis from C and the evaluation result of the foamability and the state.

(Comparative Example 3: In case of reaction of fatty acid monoglyceride and glycidol) Nitrogen introduction tube, stirrer, cooling tube,
0.5 mol of lauric acid monoglyceride was added to a 1-liter 4-necked flask equipped with a temperature controller and a dropping cylinder.
(137 g) was added, and 0.45 g of sodium methylate (NaOCH ₃ : 28% methanol solution) as a catalyst was added.
Was added and heated to 90 ° C. Then, the reaction temperature is set to 90.
2.5 mol of glycidol (185.2
g) was added dropwise over 5 hours, and the reaction was continued until the oxirane concentration in the system became less than 0.1%. After cooling, the reaction product was taken out to obtain about 300 g of polyglycerin monolaurate. The obtained polyglycerin monolauric acid ester was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, shaken (manually) for 30 seconds, and the foamability and the state were visually observed. The chart obtained by HPLC analysis is shown in FIG. In addition, Table 1 shows the results of component analysis and the results of evaluation of foamability and state by analysis from HPLC.

(Comparative Example 4: In the case of reaction of fatty acid and polyglycerin) Polyglycerin (Daicel Chemical Industry) was placed in a 1-liter 4-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder. PGL Co., Ltd.
06: hexaglycerin, hydroxyl value 960) 175.3
g (0.5 mol) and heated to 80 ° C., while maintaining the reaction temperature at 80 ° C., 0.5 mol (10 mol) of lauric acid.
0.16 g) was added and dissolved. Next, 0.75 g of sodium carbonate and 0.25 g of sodium bisulfite were added, and an esterification reaction was performed at 210 ° C. After 2 hours of reaction, the acid value became 0.89. After cooling to 100 ° C., the reaction product was taken out. The obtained polyglycerin monolauric acid ester was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, shaken (manually) for 30 seconds, and the foamability and the state were visually observed. The chart obtained by HPLC analysis is shown in FIG. In addition, Table 1 shows the results of component analysis and the results of evaluation of foamability and state by analysis from HPLC.

[0055]

[Table 1]

Comparative Examples 5 to 14: Evaluation Results of Commercially Available Polyglycerin Fatty Acid Ester As commercially available polyglycerin fatty acid ester produced by reaction of polyglycerin and fatty acid, SY Glister (manufactured by Sakamoto Yakuhin Kogyo) No. 5 ( MO-310, MO-750, ML-310, ML-
500, ML-750), 2 product numbers (J-6021, J-0021) of Poem (manufactured by Riken Vitamin), 2 product numbers (GO-106, GL-106) of Uniguri (manufactured by NOF Corporation) and Sunsoft Q12S (Taiyo). (Manufactured by Kagaku Co., Ltd.) was selected to prepare a 10% aqueous solution of each polyglycerin fatty acid ester, which was vibrated (manually) for 30 seconds, and the foamability and state were visually observed. The charts obtained by HPLC analysis are shown in FIGS. 10 to 19. In addition, HPL
The results of the component analysis by the analysis from C and the evaluation results of the foamability and the state are shown in Table-2.

[0057]

[Table 2]

Production Example 1: Production Example of Hexaglycerin Monostearate 0.5 mol of stearic acid was added to a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder. 142 g) and 0.3 g of phosphoric acid (85% product) were added and heated to 140 ° C. Then, while maintaining the reaction temperature at 140 ° C, glycidol 3.
0 mol (222 g) was added dropwise over 5 hours, and the reaction was continued until the oxirane concentration in the system became less than 0.1%. After cooling, the reaction product was taken out to obtain hexaglycerin monostearate. When the monoester content of the obtained hexaglycerin monostearate was measured using the above-mentioned HPLC, it was 75%.

(Production Example 2: Production example of decaglycerin monopalmitate) 0.5 mol of palmitic acid was placed in a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller and a dropping cylinder. (128 g) and 0.2 g of phosphoric acid (85% product) were added and heated to 140 ° C. Then, while maintaining the reaction temperature at 140 ° C., glycidol 5.
0 mol (370 g) was added dropwise over 7 hours, and the reaction was continued until the oxirane concentration in the system became less than 0.1%. After cooling, the reaction product was taken out to obtain decaglycerin monopalmitate. When the monoester content of the obtained decaglycerin monopalmitate was measured using the above-mentioned HPLC, it was 72%.

(Production Example 3: Production example of decaglycerin monooleate) Nitrogen introduction pipe, stirrer, cooling pipe, temperature controller,
In a 1-liter four-necked flask equipped with a dropping cylinder, 0.5 mol (141 g) of oleic acid and phosphoric acid (8
0.3% of 5% product) was added and heated to 140 ° C. Then, while maintaining the reaction temperature at 140 ° C, 5.0 g of glycidol
ol (370 g) was added dropwise over 7 hours, and the reaction was continued until the oxirane concentration in the system became less than 0.1%. After cooling, the reaction product was taken out to obtain decaglycerin monooleate.
The obtained decaglycerin monooleate was added to the above-mentioned HPL.
When the monoester content was measured using C, it was 75
%Met.

(Production Example 4: Production Example of Hexaglycerin Monostearate) 3000 g of glycerin and 30 g of sodium hydroxide were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, and a temperature controller. , While removing the generated water under a reduced pressure of 150 mmHg under a nitrogen stream 24
The mixture was heated to 0 ° C. and kept for 24 hours to obtain a reaction product of hexaglycerin. The obtained hexaglycerin was subjected to NaOH removal using an ion exchange resin. The hydroxyl value of the obtained product was 970. Hexaglycerin obtained above was charged with 0.5 mol (142 g) of stearic acid and 0.4 g of sodium hydroxide in a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, and a temperature controller. 0.
Hexaglycerin monostearate was obtained by charging 5 mol (231 g) and reacting at 250 ° C. while removing generated water under a nitrogen stream. When the monoester content of the obtained hexaglycerin monostearate was measured by the above-mentioned HPLC, it was 56%.

(Production Example 5: Production example of decaglycerin monopalmitate) Glycerin 3 was added to a 5 liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, and a temperature controller.
000 g and 30 g of sodium hydroxide were put in, and while removing the generated water under a reduced pressure of 150 mmHg under nitrogen stream, 240
The mixture was heated to ℃ and held for 35 hours to obtain a reaction product of decaglycerin. The resulting decaglycerin was subjected to NaOH removal using an ion exchange resin. The hydroxyl value of the obtained product is 8
It was 90. Into a 1-liter four-necked flask, 0.6 mol (153.6 g) of palmitic acid was added, 0.4 g of sodium hydroxide was added, and decaglycerin (0.1 g) obtained above was added.
6 mol (454.8 g) was charged and the produced water was removed under a nitrogen stream while reacting at 250 ° C. to obtain decaglycerin monopalmitate. When the monoester body content of the obtained decaglycerin monopalmitate was measured using the above-mentioned HPLC, it was 63%.

Production Example 6: Production Example of Decaglycerin Monooleate In a 1-liter four-necked flask, 0.6 mol (153.6 g) of oleic acid was placed, and 0.5 g of sodium hydroxide was placed. 0.6 mol (454.8 g) of the obtained decaglycerin was charged and reacted at 250 ° C. while removing generated water under a nitrogen stream to obtain decaglycerin monooleate. When the monoester content of the obtained decaglycerin monooleate was measured using the above-mentioned HPLC, it was 59%.

Example 6 Production of Oil and Fat Composition for Butter Cakes 60 parts by weight of hydrogenated fish oil having a melting point of 35 ° C., 15 parts by weight of refined soybean oil, 5 parts by weight of monoglyceride stearate (monoester content 90%). Was melted by heating to obtain an oil phase part. Next, 6 parts by weight of hexaglycerin monostearate obtained in Production Example 1 was added and dispersed in 14 parts by weight of water and heated to obtain an aqueous phase part. While stirring the oil phase portion, the water phase portion was gradually added to emulsify and mix, and then the mixture was passed through a quenching plasticizer (combinator) to obtain an oil and fat composition.

Comparative Example 15 Fish oil hydrogenated oil 6 having a melting point of 35 ° C.
0 parts by weight, 15 parts by weight of purified soybean oil, and 5 parts by weight of monoglyceride stearate (monoester content 90%) were heated and dissolved to obtain an oil phase part. Next, 6 parts by weight of a commercially available polyglycerin lauric acid ester was added and dispersed in 14 parts by weight of water and heated to obtain an aqueous phase part. While stirring the oil phase portion, the water phase portion was gradually added to emulsify and mix, and then the mixture was passed through a quenching plasticizer (combinator) to obtain an oil and fat composition.

(Test Example 1) Using the oil and fat compositions obtained in Example 6 and Comparative Example 15, butter cake dough was blended as shown in Table 3 by an all-in-mix method, and the dough specific gravity was 0.8. After whipped until obtained, 400 obtained
g was baked in a 180 ° C. oven. The obtained butter cake was sensory-evaluated for the dough state and texture. The results are shown in Table-4.

[0067]

[Table 3]

[0068]

[Table 4]

As shown in Table 4, the butter cake obtained in Example 6 had better dough condition and texture than those obtained in Comparative Example 15.

(Example 7: Cocoa drink) 1 part by weight of cocoa powder (containing 10% by weight of cocoa butter), 15 parts by weight of milk, 5 parts by weight of sucrose, 1 part by weight of decaglycerin monopalmitate obtained from Production Example 2. Parts and 78 parts by weight of warm water were mixed, heated to 70 ° C., stirred with a high-speed mixer for 5 minutes, homogenized with a homogenizer, and then filled in a can.

(Comparative Example 16) 1 part by weight of cocoa powder (containing 10% by weight of cocoa butter), 15 parts by weight of milk, 5 parts by weight of sucrose, 1 part by weight of decaglycerin monopalmitate obtained from Production Example 5 and 78 parts by weight of warm water was mixed, heated to 70 ° C., stirred with a high-speed mixer for 5 minutes, homogenized with a homogenizer, and then charged.

(Test Example 2) The cans prepared in Example 7 and Comparative Example 16 were allowed to stand at room temperature, and 10 cans were opened with time, and the presence or absence of floating substances was observed. The results are shown in Table-5.

[0073]

[Table 5]

The cocoa drink obtained in Example 7 had no suspended solids observed on the 5th day, and the cocoa drink obtained in Comparative Example 16 had suspended solids recognized on the 5th day.

(Example 8) For 1000 g of semi-strong powder,
3 g of decaglycerin monooleate obtained from Production Example 3
7g of powder cans, 10g of salt, and 300g of water are mixed, mixed for 15 minutes with a mixer, rolled by a standard method, cut out (final noodle band 1.5mm, cutting teeth # 20 square), and steamed the abalone obtained with a steamer. It was steamed for 7 minutes and washed with running water for 30 seconds. After draining, 170 g of steamed noodle was filled in a polyethylene bag and sealed.

Comparative Example 17 To 1000 g of semi-strong powder, 3 g of decaglycerin monooleate obtained in Production Example 6 was mixed with 7 g of powder kansen, 10 g of salt and 300 g of water, mixed for 15 minutes with a mixer, and rolled by a standard method. After cutting out (final noodle band 1.5 mm, cutting teeth # 20 square), the resulting noodles were steamed for 7 minutes in a steamer and washed with running water for 30 seconds. After draining, 170 g of steamed noodle was filled in a polyethylene bag and sealed.

Test Example 3 The steamed noodles prepared in Example 8 and Comparative Example 17 were stored in a refrigerator at 5 ° C. for 5 days,
Oil in a frying pan, fry steamed noodles, panelist 20
The noodles were evaluated for their unraveling property, taste and texture by name. As for the evaluation of the unraveling of the noodles, when tasting with chopsticks, the tenths of the unraveling of the noodles are extremely good,
A 10-point evaluation was carried out with 1 being extremely bad, and the average value of 20 panelists was shown. Evaluation of taste and texture is 10 points for extremely good and 1 point for extremely bad
A graded evaluation was performed and the average value of 20 panelists was shown. The results are shown in Table-6.

[0078]

[Table 6]

The steamed noodles obtained in Example 8 were the same as Comparative Example 1
As compared with the steamed noodles obtained in No. 7, the looseness, texture and taste were good.

(Example 9) 1 part of 750 g of sorbit powder was added.
The mixture was heated to 05 ° C. to be melted, 100 g of decaglycerin monooleate obtained in Production Example 3 was heated to 80 ° C., and the mixture was vigorously stirred with a homomixer for 5 minutes while maintaining the temperature at 90 ° C. or higher. The dispersion was transferred to a kneader with a jacket kept at about 80 ° C., 130 g of sorbit fine powder having a particle size of 80 mesh or less was added, and mixed for 10 minutes. The mixture was cooled, then ground, and passed through a 16-mesh sieve to obtain a powdered quality improver for addition of frozen surimi.

Comparative Example 18 750 g of sorbit powder was heated to 105 ° C. and melted, and 100 g of decaglycerin monooleate obtained in Production Example 6 heated to 80 ° C. was added thereto and kept at 90 ° C. or higher. While vigorously stirring with a homomixer for 5 minutes. The dispersion was transferred to a kneader with a jacket kept at about 80 ° C., 130 g of sorbit fine powder having a particle size of 80 mesh or less was added, and mixed for 10 minutes.
The mixture was cooled, then ground, and passed through a 16-mesh sieve to obtain a powdered quality improver for addition of frozen surimi.

(Test Example 4) To 5 kg of dehydrated meat obtained from Alaska pollack by a conventional method, 125 g of the improving agent of Example 9 or Comparative Example 18 and 200 g of sucrose, 5 g of pyrophosphoric acid and sodium polyphosphate each were added, and 5 Mix for minutes to make uniform. After filling this bag with 2.5 kg each in a polyethylene bag, freeze at -30 ° C,
After 3 weeks, it was left in a refrigerator (5 ° C.) overnight and naturally thawed.
Put 2kg of this surimi into a silent cutter, add 3% salt and 5% potato starch to the surimi and add 1
The mixture was kneaded for 3 minutes, filled in a film made of vinylidene chloride having a folded diameter of 48 mm, knotted, and then heated in hot water at 90 ° C. for 30 minutes to produce a kamaboko. The whiteness of the hunter and the elasticity of the kamaboko were measured. The results are shown in Table-7.

[0083]

[Table 7]

Example 9 was superior to Comparative Example 18 in whiteness and elasticity.

Example 10 Salad oil 40 parts by weight, acetic acid 15 parts by weight, salt 2.0 parts by weight, xanthan gum 0.2
Parts by weight, 41.8 parts by weight of water, and 1 part by weight of hexaglycerin monostearate obtained in Production Example 1 were added, and a homomixer was used to emulsify at 10000 rpm for 2 minutes to prepare a dressing. The pH of the resulting dressing was 4.0.

Comparative Example 19 Salad oil 40 parts by weight, acetic acid 15 parts by weight, salt 2.0 parts by weight, xanthan gum 0.2
Parts by weight, 41.8 parts by weight of water, and 1 part by weight of hexaglycerin monostearate obtained in Production Example 4 were added, and the mixture was emulsified at 10000 rpm for 2 minutes using a homomixer to prepare a dressing. The pH of the resulting dressing was 4.0.

(Test Example 5) The emulsified dressings obtained in Example 10 and Comparative Example 19 were stored at 40 ° C for 10 days. As a result, in Example 10, no oil layer separation was observed, whereas in the emulsified dressing obtained in Comparative Example 19, 10% by weight of the salad oil caused separation.

(Example 11) To 88.8 parts by weight of soy sauce, 10 parts by weight of salad oil, and 0.2 parts by weight of xanthan gum, 1 part by weight of hexaglycerin monostearate obtained in Production Example 1 was added, and a homomixer was used. Then 10,000 rp
The emulsion was prepared by emulsification for 2 minutes.

(Comparative Example 20) To 88.8 parts by weight of soy sauce, 10 parts by weight of salad oil, and 0.2 parts by weight of xanthan gum, 1 part by weight of hexaglycerin monostearate obtained in Production Example 4 was added, and a homomixer was used. Using 10,000 rp
The emulsion was prepared by emulsification for 2 minutes.

Test Example 6 The sauce obtained in Example 11 or Comparative Example 20 was stored at 40 ° C. for 4 days. As a result, the sauce of Example 11 did not cause oil layer separation, whereas
In the sauce of Comparative Example 20, 20% by weight of the salad oil caused separation.

(Example 12) Hardened coconut oil 20.0 parts by weight, skim milk powder 2.5 parts by weight, sodium caseinate 2.5
To 1 part by weight of water and 74 parts by weight of water, 1 part by weight of hexaglycerin monosterate obtained in Production Example 1 was added, and emulsified at 10,000 rpm for 2 minutes using a homomixer to prepare a coffee cream.

Comparative Example 21 Hardened coconut oil 20.0 parts by weight, skim milk powder 2.5 parts by weight, sodium caseinate 2.5
To 1 part by weight of water and 74 parts by weight of water, 1 part by weight of hexaglycerin monostearate obtained in Production Example 4 was added, and the mixture was emulsified at 10,000 rpm for 2 minutes using a homomixer to prepare a coffee cream. .

Test Example 7 The coffee creams obtained in Example 12 and Comparative Example 21 were stored at 40 ° C. for 4 days. Table 8 shows the changes in the state visually.

[0094]

[Table 8]

The coffee cream obtained in Example 12 was more stable in emulsification than the coffee cream obtained in Comparative Example 21.

[0096]

As is apparent from the specific description of the examples, comparative examples, test examples, etc., the present invention
When a polyglycerin monofatty acid ester having a high content of monofatty acid ester is applied to a food additive such as a surfactant and an emulsion stabilizer, the surface tension is improved and the dispersibility is improved.
The foaming power and the emulsion stability are remarkably improved.

[Brief description of the drawings]

FIG. 1 is a HPLC chart of polyglycerin monolaurate obtained in Example 1.

FIG. 2 is a HPLC chart of polyglycerin monolaurate obtained in Example 2.

FIG. 3 is a HPLC chart for the polyglycerin monolaurate obtained in Example 3.

FIG. 4 is a HPLC chart of the polyglycerin monolaurate obtained in Example 4.

FIG. 5 is a HPLC chart of the polyglycerin monolaurate obtained in Example 5.

FIG. 6 is an HPLC chart of the polyglycerin monolaurate obtained in Comparative Example 1.

FIG. 7 is an HPLC chart of the polyglycerin monolaurate obtained in Comparative Example 2.

FIG. 8 is a HPLC chart of the polyglycerin monolaurate obtained in Comparative Example 3.

9 is a HPLC chart for the polyglycerin monolaurate ester obtained in Comparative Example 4. FIG.

FIG. 10 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 5.

FIG. 11 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 6.

FIG. 12 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 7.

FIG. 13 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 8.

FIG. 14 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 9.

FIG. 15 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 10.

16 is a HPLC chart for a commercially available polyglycerin fatty acid ester used in Comparative Example 11. FIG.

FIG. 17 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 12.

18 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 13. FIG.

FIG. 19 is an HPLC chart of a commercially available polyglycerin fatty acid ester used in Comparative Example 14.

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Claims (13)

[Claims] 1. The content of the mono-fatty acid ester represented by the following general formula [1], which is eluted by a column chromatographic analysis method and detected by an ultraviolet absorption detector, in a peak area ratio of 70% or more. A food additive consisting of a certain polyglycerin monofatty acid ester. Embedded image 2. A compound represented by the general formula [1], which is separated by high performance liquid chromatography using an octadecylsilyl group-bonded silica gel column using an alcohol solvent and / or distilled water as an eluent and detected by an ultraviolet absorption detector. Content of mono fatty acid ester is 7
A food additive consisting of 0% or more of polyglycerin monofatty acid ester. Embedded image 3. A polyglycerin monocomprising a monofatty acid ester represented by the following general formula [1] obtained by reacting a fatty acid represented by the general formula [2] with glycidol in the presence of a phosphoric acid-based acidic catalyst. Food additive consisting of fatty acid ester. Embedded image 4. The carbon number of R is 7 or more.
A food additive comprising the polyglycerin monofatty acid ester according to any one of 1. 5. The food additive according to claim 1, wherein the food additive is an emulsifier for an oil and fat composition for bread making and confectionery. 6. The food additive according to claim 1, wherein the food additive is an emulsion stabilizer for cocoa drinks. 7. The food additive according to claim 1, wherein the food additive is a starch food additive. 8. The food additive according to any one of claims 1 to 4, wherein the food additive is an additive for a fish paste product. 9. The food additive according to claim 1, wherein the food additive is an emulsifier for an oil-in-water emulsion oil / fat composition. 10. The food additive according to any one of claims 1 to 4, wherein the food additive is a wheat flour mixture for bread making at room temperature for a long time. 11. The food additive according to any one of claims 1 to 4, wherein the food additive is a fat dispersion emulsification accelerator for sour cheese beverages. 12. The food additive according to claim 1, wherein the food additive is an emulsifier for a food freshness preserving agent. 13. The food additive according to claim 1, wherein the food additive is an emulsifier for coffee cream.