JPH09249615A - Polygrycerol monofatty acid ester and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyglycerol monofatty acid ester useful in order to provide a surfactant improvement in such tension, etc. SOLUTION: This polyglycerin monofatty acid ester has >=70% content of a polyglycerin monofatty and ester of formula I (R is a 6-21 alkyl, etc.; (n) is >=4 an average amount number) represented by peak area ratio when detected by using a ultraviolet absorption detector by a column chromatographic method. The polyglycerin monofatty acid ester containing a monofatty acid ester substance of formula I is obtained by reacting a fatty acid represented by formula II with glycidol in the presented of a phosphoric acid-base acidic catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyglycerin monofatty acid ester and a method for producing the same. The polyglycerin monofatty acid ester obtained by the present invention is useful as an emulsifier or base in the fields of food, cosmetics, medicine and the like.

[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 Application 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 disclosed technique, a high percentage of carboxylic acid-1-monoglyceride (n has an average value of 1 in the following chemical formula [1]) is produced in the presence of an inert solvent. In the method, 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 the hydrolysis reaction after the addition polymerization reaction of fatty acid and glycidol of Japanese Patent Publication No. 4-69621, the fatty acid used is a lower (C2-6) fatty acid, and , The purpose is the production of polyglycerin, and there is no mention 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. 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 the unsubstituted polyglycerin and the esterified product having two or more substituents remain, which are used as a surfactant or an emulsion stabilizer in the food field. When applied, it is feared that the surface tension will decrease, the dispersing power will decrease, the foaming power will decrease, and the 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 a number of problems in implementing it industrially,
The method of partitioning with an alkylsilylated silica gel described in JP-A-3-81252 has a high operating cost.
There is also a drawback that the operation is complicated. Further, these prior arts have a drawback in that unreacted polyglycerin can be removed, including the method described in JP-A-6-41007, but it is impossible to remove an ester compound having two or more substitutions.

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

[0012]

The present invention solves the above problems and provides a polyglycerin monofatty acid ester having a high monofatty acid ester content and a method for producing the same.

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] represented by the peak area ratio detected by an ultraviolet absorption detector in the column chromatographic analysis method. A polyglycerin monofatty acid ester having a ratio of 70% or more is provided.

[0014]

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According to a second aspect of the present invention, the general formula [2]
A method for producing a polyglycerin monofatty acid ester containing a monofatty acid ester represented by the following general formula [1], characterized in that a fatty acid represented by the formula (1) and glycidol are reacted in the presence of a phosphoric acid-based acidic catalyst is provided. To be done.

[0016]

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The polyglycerin monofatty acid ester having a peak area ratio of less than 70% has a reduced surface tension when applied to a surfactant or an emulsion stabilizer in the food field.
A decrease in dispersibility, a decrease in foaming power, and a decrease in emulsion stability are observed.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The fatty acid represented by the general formula [2] used in the addition polymerization reaction of glycidol with a fatty acid in the present invention is a fatty acid having 6 to 21 carbon atoms, and particularly preferably R Is a fatty acid having 7 to 21 carbon atoms. The fatty acid may be saturated fatty acid or unsaturated fatty acid,
Further, it may be a linear fatty acid, a fatty acid having a side chain, or a substituted fatty acid having a carbon chain substituted with a hydroxyl group. Examples of these fatty acids include caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid,
Palmitoleic acid, stearic acid, isostearic acid,
Examples include oleic acid, linoleic acid, behenic acid, erucic acid, ricinoleic acid and hydroxystearic acid. Among these, lauric acid or stearic acid is particularly preferable. These fatty acids may be used alone, or two or more kinds may be arbitrarily mixed and used in the reaction.

The reaction between the fatty acid and glycidol needs to 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 addition-polymerized with the fatty acid to produce a polyglycerin monofatty acid ester having a high 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 mono-fatty acid ester obtained by the above method is the peak area ratio of the mono-fatty 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 expressed content rate is 70% or more. Here, the column chromatographic analysis method is a reversed-phase partition column analysis method using silica gel having an octadecylsilyl group, an octylsilyl group, a butylsilyl group, a trimethylsilyl group, and a phenylsilyl group as a carrier as a functional group, and a cyanopropyl group as a functional group. The normal phase partitioning column analysis method using silica gel having an aminopropyl group as a carrier, the ion exchange column analysis method having a quaternary ammonium group or a phenylsulfonic acid group as a functional group, and the adsorption column analysis method of porous silica gel can be mentioned. 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 of 70% or more means that the peak area ratio attributed to the mono-fatty acid ester is 70% of the total peak area under the following HPLC (high performance liquid chromatography) analysis conditions. It means that it is more than%.

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, the developing solvent is determined from the solubility and separability of the analyte. Specifically, alcohol or a mixed solution of alcohol and water is preferable as a specific developing solvent having excellent solubility and separability of the analyte. Examples of alcohol include methanol, ethanol, isopropanol and the like. In addition, for example, it is preferable to use methanol for the polyglycerin monolaurate and ethanol for the polyglycerin 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.

It is preferable to use the developing solution used as a solvent for the sample to be subjected to HPLC, 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 are analyzed by HPLC under the same conditions, the retention times of the standard product and the specimen are compared and examined, and those eluted after the elution of glycerin monoester are diesters or higher polysubstituted esters. As an ingredient. The content (%) of the mono-fatty acid ester is represented by the peak area ratio according to the following. From the analysis chart, the peak area of polyglycerin, the monofatty acid ester of polyglycerin (which is referred to as “polyglycerin”, but in the present invention, the glycerin moiety includes from polyglycerin to monoglycerin.) The peak area of the polysubstituted ester component is determined. Then, it is calculated according to the following formula. The solvent is selected such that the peak position does not overlap with any peak of polyglycerin, monofatty acid ester, and polysubstituted ester of diester or more. The following formula assumes 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.

[0027]

## EQU1 ## Formula: Content rate of monoglyceride ester of polyglycerin (%) = {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 .: 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: 0.05 to
1.0 ml / min. , Column oven temperature: 30-6
0 ° C., detection method: ultraviolet absorption method (λ = 210 nm), sample concentration: 1 to 50% (solvent: methanol), injection amount:
0.1-20 μl. The retention time of each component is, for example, in the case of polyglycerin monolaurate, polyglycerin: 8 minutes or less, monolaurate ester:
8 to 12 minutes, dilaurate ester body or more: 12 minutes or later.

<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.
5 to 1.0 ml / min. , Column oven temperature: 30
~ 60 ° C, detection method: ultraviolet absorption method (λ = 210n
m), sample concentration: 1 to 50% (solvent: methanol), injection amount: 0.1 to 20 μl, retention time of each component is polyglycerin: 14 minutes or less, monoester body: 1
4 minutes to 16.5 minutes, diester or more: 16.5 minutes or later, 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:
0.05-1.0 ml / min. , Column oven temperature: 30-60 ° C., detection method: ultraviolet absorption method (λ = 21
0 nm), sample concentration: 1 to 50% (solvent: EtOH),
Injection volume: 0.1-20 μl. The retention time of each component is polyglycerin: 28.5 minutes or less, monoester form: 28.5 to 34 minutes, diester form or more: 34 minutes or more, ethanol component: 39 minutes.

Further, the polyglycerin monofatty acid ester obtained above can be further purified, if necessary, through various purification steps, and then used as a food additive, for example, and is 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 described above, in the present invention, the polyglycerin monofatty acid ester having a high purity, particularly, the content of the monofatty acid ester body represented by the above peak area ratio is 70% by the addition polymerization reaction of glycidol and fatty acid. The polyglycerin monofatty acid ester which is above is obtained.
Since such a polyglycerin monofatty acid ester is used as a food additive such as a surfactant or an emulsion stabilizer, the surface tension is improved, the dispersive power is improved, the foaming power is improved, and the emulsion stability is improved. effective.

Therefore, the polyglycerin monofatty acid ester obtained in the present invention is used in various applications in which polyglycerin monofatty acid ester and the like have been conventionally used, and can sufficiently exhibit its intended function. . These are exemplified below.

(1) The polyglycerin monofatty acid ester of the present invention can be used as an emulsifier of 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 polyglycerin monofatty acid ester of the present invention 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. At that time, the emulsifier is used in the range of 0.2 to 10% by weight with respect to the entire oil and fat composition, and the polyglycerin monofatty acid ester of the present invention is also used as an emulsifier for the oil and fat composition for confectionery such as butter cakes. It is useful. Further, in Japanese Patent Laid-Open No. 6-269244,
Sponge cake, snack cake, chiffon cake,
During the production of cakes such as semi-raw confectionery, the dough is stable, the kettle does not easily fall off, and the cake has a large volume.
A foamable emulsified oil / fat composition in which an emulsifier, whey protein and the like are added to an aqueous phase such as water, sorbitol and liquid sugar is used.
The polyglycerin monofatty acid ester of the present invention can also be used as such an emulsifier. 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, the content of fats and oils is 35 to 75% by weight,
Carbohydrate contains at least sorbitol 10 to 50% by weight
And a high oil content oil-in-water emulsion composition in which the content of the emulsifier is 5 to 25% by weight with respect to the aqueous phase. As the emulsifier, polyglycerin fatty acid ester having an HLB value of 7 to 16 is used. The polyglycerin monofatty acid ester of the present invention can be similarly used for such applications.

(2) Japanese Patent Application 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 Although an emulsion stabilizer for cocoa beverages comprising 26 to 90% by weight and 2 to 5% by weight of κ-carrageenan is disclosed, the polyglycerin monofatty acid ester of the present invention may be 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 Laid-Open No. 6-38682, a lipophilic polyglycerin fatty acid ester is added to a mixture containing a cocoa component, a milk component, a sweetener and water in an amount of 0.2 to 0.2% of lipophilic polyglycerin fatty acid ester with respect to the fat content in the mixture. A cocoa beverage added at a ratio of 5.0% by weight is disclosed. The polyglycerin monofatty acid ester of the present invention can be used in place of the lipophilic polyglycerin fatty acid ester.

(3) Japanese Patent Laid-Open No. 6-276972 discloses that
To make noodles that boil quickly, add 0.5 to 40 eggs.
A noodle quality improving agent containing 0.01 to 0.5 part by weight of a 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 polyglycerin monofatty acid ester of the present invention can be used as such a surfactant for blending noodle quality improving agents. In addition, JP-A-6-197
No. 717 describes that when the steamed noodles are boiled and used, mung bean modified starch or a combination thereof with an emulsifier makes the noodles extremely loose, and that polyglycerin fatty acid ester or the like is used as the emulsifier. Has been done. The emulsifier is used in an amount of 0.1 to 20% by weight based on the noodle raw material, and the polyglycerin monofatty acid ester of the present invention can be used as such an emulsifier.

(4) Japanese Unexamined Patent Publication No. 6-22730 discloses a method for producing a frozen surimi in which a quality improver containing a polyglycerin fatty acid ester is added 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-6-9071
No. 3, gazette of scallop ovary and / or fishmeat surimi containing testis was prepared by adding 0.1 to 2% by weight of polyglycerol fatty acid ester emulsifier with HLB of 13 or more together with water, oil and fat and reduced starch saccharified product. Kneading with salt,
A method for producing a kneaded product which is subjected to heat treatment after molding is described. The polyglycerin monofatty acid ester of the present invention can be used as an additive for such a fish paste product instead of the polyglycerin fatty acid ester.

(5) Japanese Patent Laid-Open No. 6-133735 discloses that
2) a layer containing a lactic acid bacterium, coffee leaves or an extract thereof containing (A) a layer containing fats and oils and an excipient, and (B) a layer containing a hydrous alcohol-soluble protein such as zein.
An enteric-coated lactic acid bacterium granule characterized by being coated with a layer is described. Further, in the layer (B), polyglycerin fatty acid ester is added as a plasticizer in an amount of 0.1% to improve the uniform dissolution and dispersibility of the hydrous alcohol-soluble protein.
It is described that about 8% by weight is used. The polyglycerin monofatty acid ester of the present invention can be used as a substitute for the plasticizer for producing enteric-coated lactic acid bacterium granules such as the polyglycerin fatty acid ester.

(6) 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 polyglycerin monofatty acid ester of the present invention can also be used for the same purpose.

(7) 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 polyglycerin monofatty acid ester of the present invention can be used as a substitute for the glycerin fatty acid ester.

(8) In Japanese Patent Laid-Open No. 6-14711, the sum of phosphatidic acid (salt) or lysophosphatidic acid (salt) is added to the flavored fats and oils or flavored fats and oils to which a flavor component is added. Disclosed is an oil and fat composition for cooking, which comprises 0.1 to 10% by weight of phospholipid, which is 15% by weight or more, and 0.1 to 10% by weight of a food emulsifier. And polyglycerin fatty acid ester is illustrated as one of the said food emulsifiers.
The polyglycerin monofatty acid ester of the present invention can also be used as an emulsifying agent for such an oil and fat composition for cooking.

(10) 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 polyglycerin monofatty acid ester of the present invention can also be used as such a fat dispersion emulsification accelerator for sour cheese beverages.

(11) 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 polyglycerin monofatty acid ester provided by the present invention can also be used as this surfactant.

(12) Japanese Patent Laid-Open No. 6-225684 discloses that
Edible oil and fat 0 to 20% by weight, glycerin organic acid fatty acid ester and stearyl lactate 0.05 to 20% by weight, HL
0.01 to 5% by weight of polyglycerin fatty acid ester and / or sucrose fatty acid ester having B of 12 or more, water content of 5
Disclosed is a composition for improving the quality of starch foods, which comprises 0 to 90% by weight and has fluidity at 10 ° C. 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 polyglycerin monofatty acid ester of the present invention can be used as a blend of such a composition for improving the quality of starch foods instead of the polyglycerin fatty acid ester.

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

(14) Japanese Patent Laid-Open No. 6-189682 discloses that
Rolled and conched chocolate dough, aqueous component, high HLB polyglycerin fatty acid ester and low HLB polyglycerin fatty acid ester are mixed and emulsified in water-in-oil type water content 2% by weight 50% by weight
The following hydrous chocolates are described. Low H
The polyglycerin fatty acid ester of LB is preferably HLB 2-4, and the high HLB is preferably polyglycerol fatty acid ester of HLB 11-13. The polyglycerin monofatty acid ester of the present invention can be used as any one of the above polyglycerin fatty acid esters.

(15) 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 polyglycerin monofatty acid ester of the present invention can be used as the emulsifier for coffee cream as described above.

(16) Japanese Patent Laid-Open No. 6-113727 discloses that
A technique for improving the binding property between fish meat and fats and oils by injecting an oil-in-water type emulsion containing egg white and carrageenan into fish meat is described. 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 polyglycerin monofatty acid ester of the present invention can also be used as such an emulsifier for an oil-in-water type emulsion for producing fish ham.

[0049]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. The HPLC analysis conditions are as follows throughout the examples and comparative examples.

(HPLC analysis conditions) Column: Wakosil 5C18 ^* 2 (manufactured by Wako Pure Chemical Industries, Ltd ^. ; column having octadecylsilyl group as a reverse phase distribution column as a functional group), developing solvent: methanol,
Flow rate: 0.75 ml / min. , Column oven temperature:
40 ° C., detection method: ultraviolet absorption method (λ = 210 nm),
Sample concentration: 10% (solvent: MeOH), injection volume: 5μ
l. The retention time of each component is, for example, in the case of polyglycerin monolaurate, polyglycerin:
Before 8 minutes, monolauric acid ester body: 8 minutes to 12 minutes,
Dilaurate ester or more: 12 minutes 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 and polyglycerin monolaurate ester was added to about 300
g was obtained. The obtained polyglycerin monolauric acid ester was evaluated under the above-mentioned HPLC analysis conditions. In addition, 10% of the obtained polyglycerin monolaurate ester
An aqueous solution was prepared, shaken (manually) for 30 seconds, and the foamability and state were visually observed. The chart obtained by HPLC 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.

(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 and polyglycerin monolaurate ester was added to about 300
g 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, and 3
It was vibrated for 0 seconds (manual), and the foamability and state were visually observed. The chart obtained by HPLC 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.

(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 and polyglycerin monolaurate ester was added to about 400
g 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, and 3
It was vibrated for 0 seconds (manual), and the foamability and state were visually observed. The chart obtained by HPLC 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.

Example 4 0.5 mol (100.1) of lauric acid was placed in a 1-liter 4-necked flask equipped with a nitrogen introducing 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 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. In addition, Table 1 shows the results of component analysis and the results of evaluation of foamability and state by analysis from HPLC.

Example 5 0.5 mol (100.1) of lauric acid was placed in a 1-liter 4-necked flask equipped with a nitrogen introducing 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. The obtained polyglycerin monolauric acid ester was evaluated by HPLC. Also, prepare a 10% aqueous solution of the obtained polyglycerin monolaurate and shake for 30 seconds (manual).
The foamability and condition were visually observed. HPLC
The chart obtained in 1. 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 1: When no catalyst is used) A 1-liter four-necked flask equipped with a nitrogen introduction 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: When paratoluenesulfonic acid (PTS) was used 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, 0.45 g of sodium methylate (NaOCH3: 28% methanol solution) was added as a catalyst, and the mixture was heated to 90 ° C. Then, the reaction temperature is 90 ℃
Glycidol 2.5 mol (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 with polyglycerin Polyglycerin (Daicel Chemical Industries) 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.

[0060]

[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 Glyster (manufactured by Sakamoto Yakuhin Kogyo) 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.

[0062]

[Table 2]

[0063]

EFFECTS OF THE INVENTION As is clear from the detailed description of the examples and comparative examples, the polyglycerin monofatty acid ester having a high content of monofatty acid ester compound provided by the present invention is used as a surfactant or an emulsifier in the food field. When applied to a stabilizer, the surface tension, the dispersive power, the foaming power, and the emulsion stability are remarkably improved.

[Brief description of 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.

Claims (11)

[Claims] 1. The content of the mono-fatty acid ester represented by the following general formula [1], which is detected by an ultraviolet absorption detector in a column chromatographic analysis, in a peak area ratio of 7:
Polyglycerin monofatty acid ester which is 0% or more. Embedded image 2. The following general formula [1] which is detected by an ultraviolet absorption detector after separation by high performance liquid chromatography using an octadecylsilyl group-containing silica gel column with an alcohol or a mixed solution of alcohol and water as an eluent. The polyglycerin monofatty acid ester having a content of 70% or more represented by the peak area ratio of the monofatty acid ester body represented by. Embedded image 3. The polyglycerin monofatty acid ester according to claim 2, wherein the alcohol or a mixed solution of alcohol and water is methanol or a mixed solution of methanol and water. 4. The polyglycerin monofatty acid ester according to claim 2, wherein the alcohol or a mixed solution of alcohol and water is ethanol or a mixed solution of ethanol and water. 5. The carbon number of R in the general formula [1] is 7 to.
21. The polyglycerol monofatty acid ester according to any one of claims 1 to 4, which is 21. 6. The alkyl group represented by R in the general formula [1] is an undecyl group.
4. The polyglycerin monofatty acid ester according to any of 4 to 4. 7. The polyglycerin monofatty acid ester according to any one of claims 1 to 4, wherein the alkyl group represented by R in the general formula [1] is a heptadecyl group. 8. A monofatty acid ester represented by the following general formula [1], which comprises reacting a fatty acid represented by the general formula [2] with glycidol in the presence of a phosphoric acid-based acidic catalyst. A method for producing a polyglycerin monofatty acid ester. Embedded image 9. The carbon number of R in the general formula [2] is 7 to.
21. The fatty acid of 21 is made to react, The manufacturing method of the poly glycerol mono fatty acid ester of Claim 8 characterized by the above-mentioned. 10. The method for producing a polyglycerin monofatty acid ester according to claim 8, wherein the fatty acid represented by the general formula [2] is either lauric acid or stearic acid. 11. The method for producing a polyglycerin monofatty acid ester according to claim 8, wherein the phosphoric acid-based acidic catalyst is phosphoric acid or an acidic phosphoric acid ester.