JP3312830B2 - Polyglycerin monofatty acid ester and method for producing the same - Google Patents

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 polyglycerol monofatty acid ester obtained according to 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 esters have been approved as food additives, and their use has been gradually increasing. In general, this ester is obtained by combining esters of polyglycerin having different degrees of polymerization with fatty acids having different chain lengths as raw materials to obtain an ester having a wide range of HLB values, and showing high stability in an acidic region. In the food field, it is widely used as an emulsifier and a viscosity modifier. The method for producing the polyglycerin fatty acid ester includes (1) an esterification reaction between polyglycerin and a fatty acid,
(2) transesterification reaction between polyglycerin and fatty acid ester, (3) transesterification reaction between polyglycerin and fat, (4) addition polymerization reaction between glycidol and fatty acid monoglyceride, (5) addition polymerization between glycidol and fatty acid There are reactions. Among them, the methods (2) and (3) have many restrictions in terms of reactivity, quality and purity of the produced polyglycerol fatty acid ester, and the like.

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

[0004] As a technique using the addition polymerization reaction of glycidol, there is known an addition polymerization reaction of glycerin and glycidol in producing polyglycerin used in the methods (1) to (3) (Japanese Patent Publication No. 1-55254). JP-B-4-11532, JP-B5-11291) or production of polyglycerin which is subjected to an addition polymerization reaction of a fatty acid and glycidol followed by a hydrolysis reaction (Japanese Patent Publication 4-6962).
No. 1), production of polyglycerin monoalkyl ether and polyglycerin monoalkylthioether (USP
3,821,372, USP 3,966,398, US
P4, 087, 466).

However, in the production of polyglycerin via a hydrolysis reaction after the addition polymerization reaction of a fatty acid and glycidol disclosed in Japanese Patent Publication No. 4-69621, the fatty acid used is a lower (2 to 6 carbon atoms) fatty acid, and The purpose is to produce polyglycerin, and there is no mention of polyglycerin fatty acid esters.

[0006]

Conventionally, when polyglycerin monofatty acid ester is produced, it is produced by the method (1). In this method, generally, as the raw material polyglycerin, the number of reactive hydroxyl groups is 4 to 4 on average.
Even if an attempt is made to produce a mono-substituted fatty acid ester, the ratio of the reactive hydroxyl group to the equivalent of the fatty acid used is large, and the polyglycerol monofatty acid ester produced contains It is pointed out that not only fatty acid esters but also unreacted polyglycerols, diesters, triesters, tetraesters, and other polysubstituted esterified compounds remain (N. Garti, et. Al.).
al, J. am. Oil Chem. Soc., 59, 317-319 (1982)).

[0007] Further, even in the case of the addition polymerization reaction of glycidol with the fatty acid monoglyceride of (4), the purity of the reaction product is greatly affected by the degree of purification of the raw material fatty acid monoglyceride. In particular, when fatty acid monoglyceride obtained by a reaction between glycerin and a fatty acid is used as a raw material, a glycerin component remains in the raw material as in (1) above, and the glycerol is obtained by an addition polymerization reaction of glycidol. The content of the monofatty acid ester in the obtained polyglycerol monofatty acid ester is about 40%,
It has been recognized that the remaining about 60% is unreacted glycerin and di- or higher-substituted ester (Shigeru Tsuda, monoglyceride, P67 (1985), Maki Shoten).

As described above, the polyglycerol monofatty acid ester conventionally used contains a large amount of unsubstituted polyglycerin and di- or more-substituted esterified products, which are used as surfactants and emulsion stabilizers in the food field. When applied, there is a concern that the surface tension, the dispersing power, the foaming power, and the emulsion stability may decrease.

On the other hand, as a method for removing unsubstituted polyglycerin, at least one selected from water-soluble organic solvents and water and at least one selected from non-water-soluble organic solvents are used in combination. (Japanese Unexamined Patent Publication (Kokai) No. 63-23837), a method of contacting and adsorbing a solution of an esterification reaction product with an alkylsilylated silica gel to remove unreacted polyglycerin. (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)
007 publication) has been proposed.

However, in the method described in Japanese Patent Application Laid-Open No. 63-23837, aromatic hydrocarbons such as benzene and toluene described as water-insoluble organic solvents are questioned about their safety, There are problems with use. Further, in this method, the reaction molar ratio of the fatty acid to polyglycerin is limited to 1 or less, and the effectiveness in the case of a molar ratio exceeding 1 is not described. Even when the reaction molar ratio is 1 or less, toluene /
In the case of a methanol system, a considerable amount of high HLB polyglycerin fatty acid ester is observed to be transferred to the aqueous methanol phase, and in the case of the toluene / methanol system, separation of unreacted polyglycerin is extremely insufficient. There are a number of issues with industrial implementation,
The method of separating with an alkylsilylated silica gel described in JP-A-3-81252 has a high operating cost,
There is also a disadvantage that the operation is complicated. Further, these prior arts have the disadvantage that unreacted polyglycerin can be removed, including the method described in JP-A-6-41007, but it is impossible to remove di- or more-substituted esterified products.

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

[0012]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides a polyglycerol 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 peak area ratio of the monofatty acid ester represented by the following general formula [1], which is detected at a wavelength of 210 nm using an ultraviolet absorption detector by column chromatography, is represented. A polyglycerin monofatty acid ester having a content of 77.2 % or more is provided.

[0013]

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According to a second aspect of the present invention, the general formula [2]
Wherein glycidol is reacted with a fatty acid represented by the formula (I) in the presence of a phosphoric acid-based catalyst, and a method for producing a polyglycerol monofatty acid ester containing a monofatty acid ester represented by the following general formula [1] is provided: You.

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In the polyglycerol monofatty acid ester having a peak area ratio of less than 77.2% , a surfactant,
When applied to an emulsion stabilizer in the food field, a reduction in surface tension, a reduction in dispersing power, a reduction in foaming power, and a reduction in emulsion stability are observed.

As the fatty acid represented by the general formula [2] used in the addition polymerization reaction of glycidol and a fatty acid in the present invention, a fatty acid having 7 to 22 carbon atoms is used, and it may be a saturated fatty acid or an unsaturated fatty acid. 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, monoethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid,
Examples include stearic acid, isostearic acid, oleic acid, linoleic acid, behenic acid, erucic acid, ricinoleic acid, and hydroxystearic acid. Each of these may be used alone, or two or more of them may be arbitrarily mixed and used in the reaction.

The reaction between the fatty acid and glycidol needs to be performed in the presence of a phosphoric acid acidic catalyst. The phosphoric acid-based acidic catalyst referred to herein is a 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 phosphates such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, and the like can be used. In addition, as these acidic phosphates, any of a monoester body, a diester body, and a mixture thereof can be used. Among the above, it is preferable to use phosphoric acid and acidic phosphoric acid esters.

The above catalysts may be used alone or as a mixture 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, the effect cannot be expected to be improved. Absent.

The reaction method is to take fatty acids in a reaction vessel,
The above-mentioned catalyst is added thereto, and the reaction is carried out while adding glycidol little by little. The reaction temperature is 50-180 ° C, preferably 70-160 ° C, more preferably 120-180 ° C.
~ 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 compound that does not react with glycidol may be added to prevent an increase in the reaction temperature. The reaction is desirably performed in a nitrogen gas atmosphere, and may be pressurized if necessary.

By the above reaction, glycidol is addition-polymerized to the fatty acid to produce a polyglycerol monofatty acid ester having a higher polymerization degree. The product is a polyglycerin monofatty acid ester having a high monofatty acid ester content. That is, the polyglycerol monofatty acid ester obtained by the present invention was represented by the peak area ratio of the monofatty acid ester represented by the general formula [1], which was detected by column chromatography using an ultraviolet absorption detector. The content is 77.2 % or more. Here, column chromatography analysis means octadecyl group, octyl group,
Reversed-phase partition column analysis with butyl, trimethyl and phenyl groups, normal-phase partition column analysis with cyanopropyl and aminopropyl groups as functional groups, quaternary ammonium and phenylsulfonic acid groups as functional groups An ion exchange column analysis method and a porous silica gel adsorption column analysis method are mentioned. In these analytical methods, a reversed-phase partition column method is preferably used. When the peak area ratio of the monofatty acid ester is at least 77.2 %, specifically, under the following HPLC (high performance liquid chromatography) analysis conditions, the peak area ratio attributed to the monofatty acid ester corresponds to the total peak area. 77.2 % or more.

The polyglycerol monofatty acid ester obtained in the present invention can be further purified through various purification steps, if necessary. Specific purification methods include (a) saturation under reduced pressure. There are a deodorizing method in which steam is deodorized by blowing heated steam, and (b) a decolorizing method such as bleaching with sodium hypophosphite or hydrogen peroxide.

As described above, according to the present invention, regarding the polyglycerol monofatty acid ester, in the addition polymerization reaction of glycidol and a fatty acid, the content of the monofatty acid ester represented by the peak area is 77.2 % or more. It is possible to obtain a certain polyglycerin monofatty acid ester, and when it is used as a surfactant, it has the effects of improving surface tension, improving dispersing power, improving foaming power, improving emulsion stability, and the like. .

Therefore, the polyglycerol monofatty acid ester obtained in the present invention is used for various applications in which polyglycerin monofatty acid ester and the like are conventionally used, and can sufficiently exhibit its intended function. . Hereinafter, these will be exemplified.

(1) The polyglycerol monofatty acid ester of the present invention can be used as an emulsifier for an oil or fat composition used in the production of bread, cake, and confectionery. For example, as described in JP-A-6-22690, when baking a bread dough made of flour or the like, each component in the flour undergoes physical, chemical, and biochemical reaction changes. It is necessary to strictly control the baking process for good bread production, and in order to obtain stable quality, it is composed of oils and fats such as soybean oil, cottonseed oil, rapeseed oil, and an aqueous phase containing a flavoring agent as needed An oil or fat composition is used. An emulsifier is used in the fat composition, and the polyglycerin monofatty acid ester of the present invention can be used as an emulsifier for such a fat composition for bread production. Similarly, Japanese Unexamined Patent Publication No. 6-53 describes a method of using a water-in-oil type fat or oil composition for producing butter cakes by an all-in-mix method. At that time, an emulsifier is used in an amount of 0.2 to 10% by weight based on the whole oil and fat composition, and the polyglycerin monofatty acid ester of the present invention is also used as an emulsifier for confectionery oil and fat compositions such as butter cakes. Useful. Also, JP-A-6-269244 discloses that
Sponge cake, snack cake, seafon cake,
In the production of cakes such as half-baked confectionery, to make dough stable, it is difficult for kettles to fall, and to make cakes with volume,
A foamable emulsified oil / fat composition in which an emulsifier, whey protein or the like is added to an aqueous phase such as water, sorbitol or liquid sugar is used.
As such an emulsifier, the polyglycerol monofatty acid ester of the present invention can be used. Furthermore, Japanese Patent Application Laid-Open No. 6-78672 discloses an oil-in-water emulsion containing water, oils and fats, saccharides, and an emulsifier, which imparts good flavor and texture with less stickiness of dough when applied to bread. In the composition, the fat content is 35 to 75% by weight,
Carbohydrate contains at least sorbitol 10-50% by weight
Wherein the content of the emulsifier is 5 to 25% by weight with respect to the aqueous phase. As the emulsifier, a 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 uses.

(2) JP-A-6-125711 discloses that
In order to prevent the floating of oils and fats and the precipitation of cocoa powder that occur when a cocoa beverage is stored, 1 to 25% by weight of sucrose oil and fatty acid ester, 3 to 36% by weight of glycerin fatty acid ester, 1 to 11% by weight of sorbitan fatty acid ester, 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, but the polyglycerin monofatty acid ester of the present invention is used instead of or together with the glycerin fatty acid ester. Can be used as an emulsion stabilizer compounding agent for cocoa beverages. JP-A-6-38682 discloses that a mixture of a cocoa component, a milk component, a sweetener and water contains 0.2 to 0.2 g of a lipophilic polyglycerin fatty acid ester with respect to the fat contained 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) JP-A-6-276972 discloses that
In order to make the noodles boil quickly, add 0.5 to 40 chicken eggs.
A noodle quality improving agent containing 0.01 to 0.5 parts by weight of lysoline oil is disclosed. In addition, it describes that 0.1 to 10 parts by weight of a surfactant for food may be added as necessary. The polyglycerin monofatty acid ester of the present invention can be used as a surfactant for blending such a noodle quality improving agent. Japanese Patent Application Laid-Open No. 6-197
No. 717 discloses that the use of mung bean-processed starch or an emulsifier in combination therewith when manufacturing boiled and steamed noodles makes the noodles extremely easy to loosen, and that a polyglycerin fatty acid ester or the like is used as an emulsifier. Have been. The emulsifier is used in an amount of 0.1 to 20% by weight based on the raw material for noodles, and the polyglycerin monofatty acid ester of the present invention can be used as such an emulsifier.

(4) Japanese Patent Application Laid-Open No. 6-22730 discloses a method for producing a frozen surimi in which a quality improving agent containing a polyglycerin fatty acid ester is added to a seafood paste product. That is, it has been clarified that the frozen surimi has the effect of maintaining the reed forming ability and the effect of improving the whiteness. The addition amount is 1% by weight or less, preferably 0.1 to 0.5% by weight based on the surimi. Japanese Patent Application Laid-Open No. 6-9071
In Japanese Patent Publication No. 3 (1993), 0.1 to 2% by weight of a polyglycerol fatty acid ester emulsifier of HLB 13 or more is added to a surimi of seafood containing scallop ovaries and / or testes, together with water, oil and fat, and reduced starch saccharified product. And knead 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 fishery paste products instead of the polyglycerin fatty acid ester.

(5) JP-A-6-133735 discloses that
The granulated material containing lactic acid bacteria, coffee leaves or an extract thereof is (A) a layer containing fats and oils and a shaping agent, and (B) a layer containing a hydroalcoholic soluble protein such as zein.
Enteric lactic acid bacteria granules characterized by being coated with a layer are described. The layer (B) contains a polyglycerin fatty acid ester 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 a plasticizer for producing an enteric lactic acid bacteria granule such as the polyglycerin fatty acid ester.

(6) JP-A-6-209704 discloses that
Oil-in-water emulsified oil / fat composition containing no animal or vegetable fats and oils and a polyglycerin saturated fatty acid ester having a degree of esterification of 3 or less as an emulsifier without feathering or oil-off when added to coffee or tea. Is disclosed. It is disclosed that 0.1 to 1.5% by weight of an emulsifier is added to the dissolved fat or oil. The polyglycerin monofatty acid ester of the present invention can be used for the same purpose.

(7) JP-A-6-253718 discloses that
Bread made by medium- and long-time medium-type long-time breading by adding one kind selected from calcium carbonate of 0.1% by weight or less, glycerin fatty acid ester of 0.5% by weight or less, and egg white of 0.5% by weight or less to flour. Wheat flour formulations are described. It is stated 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) JP-A-6-14711 discloses that the sum of a phosphatidic acid (salt) or a lysophosphatidic acid (salt) in a fat or oil having a flavor or a fat or oil having a flavor component to which a flavor component is added is a total phospholipid. A fat / oil composition for cooking comprising 0.1 to 10% by weight of a phospholipid, which is 15% by weight or more, and 0.1 to 10% by weight of a food emulsifier is disclosed. A polyglycerin fatty acid ester is exemplified as one of the food emulsifiers.
The polyglycerol monofatty acid ester of the present invention can also be used as an emulsifier for such a fat or oil composition for cooking.

(10) JP-A-6-113799 discloses that
Lactic acid bacteria are inoculated into a cheese homogenous solution obtained by homogenizing natural cheese, water and skim milk powder, and fermented by lactic acid.
Lactic acid cheese fermented liquid of H3.6-4.5 was obtained, and about 5
Sour cheese beverages with ５０50% sugar added are described. Further, it is described that a surfactant such as glycerin fatty acid ester may be used as a fat dispersion / emulsification accelerator in addition to skim milk powder. The polyglycerin monofatty acid ester of the present invention can also be used as such a fat dispersion emulsifier for sour cheese beverages.

(11) JP-A-6-153888 discloses that
Disclosed is a freshness preserving agent for food, comprising persimmon leaf extract (flavonoids) and tocopherol, or persimmon leaf extract, tocopherol and gallic acid as active ingredients. It is convenient to use this freshness preserving agent in the form of a lipophilic emulsion. In this case, a polyglycerin fatty acid ester is exemplified as an emulsifying agent (surfactant). The polyglycerol monofatty acid ester provided in the present invention can also be used as this surfactant.

(12) JP-A-6-225684 discloses that
0 to 20% by weight of edible oil and fat, 0.05 to 20% by weight of glycerin organic acid fatty acid ester and stearyl lactate, HL
B is 12 or more polyglycerin fatty acid ester and / or sucrose fatty acid ester 0.01 to 5% by weight, water 5
A composition for improving the quality of starch food which is fluid at 10 ° C. and comprises 0 to 90% by weight is disclosed. When this composition is used in foods such as bread, donuts, buns, dumplings, noodles, spaghetti, etc., it prevents adhesion to dough or machines during production, increases volume and improves texture, and ages of starch after production. It is said to exert an effect of preventing a decrease in texture due to a specific change. 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 in place of the polyglycerin fatty acid ester.

(13) JP-A-6-62734 discloses a fat-containing sour milk beverage using chitosan and polyglycerol fatty acid ester in a sour milk beverage containing fat. This is said to improve the stability of fat globules under acidic conditions, which is a preferable sour feeling, but the polyglycerin monofatty acid ester of the present invention replaces the polyglycerin fatty acid ester with such a fat-containing fatty acid. It can be used as an additive for lactic acid beverages.

(14) JP-A-6-189682 discloses that
Rolled and conched chocolate dough, aqueous component, high HLB polyglycerin fatty acid ester and low HLB polyglycerin fatty acid ester mixed to emulsify in water-in-oil type 2% by weight 50% by weight
The following hydrous chocolates are described: The low H
The LB polyglycerin fatty acid ester is preferably HLB2-4, and the high HLB is preferably HLB11-13 polyglycerin fatty acid ester. The polyglycerin monofatty acid ester of the present invention can be used as any of the above polyglycerin fatty acid esters.

(15) JP-A-6-90663 discloses that an oil-and-fat content is 10% by weight to 40% by weight, an enzyme-treated lecithin containing lysolecithin as an emulsifier, and a monoglycerin fatty acid ester content is 50% by weight. A coffee cream containing a medium-purity monoglycerin fatty acid ester, monoglyceride succinate, and lecithin of from about 70% to 70% by weight is disclosed. It is described that a coffee cream which maintains stable emulsification at room temperature and has freezing resistance which does not cause emulsification destruction even when thawed after storage at 0 ° C. or lower is described. In the examples, 0.2 part of the above-mentioned medium-purity monoglyceride was used together with other emulsifiers with respect to 25.5 parts by weight of palm kernel oil constituting the oil phase. The polyglycerol monofatty acid ester of the present invention can be used as an emulsifier for coffee cream as described above.

(16) JP-A-6-113727 discloses that
A technique is described in which an oil-in-water emulsion containing egg white and carrageenan is injected into fish meat to improve the binding property between the fish meat and the fat. It is described that a fish meat ham having an appropriate hardness can be obtained without impairing the texture and flavor of the fish, and the texture of the fish does not stick. Glycerin fatty acid esters are mentioned as one of emulsifiers to be 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 emulsion for producing fish ham.

[0039]

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

(Analysis conditions of HPLC) Column: Wakosil 5C18 ^* 2 (manufactured by Wako Pure Chemical Industries, Ltd ^. ; column having an octadecyl group as a functional group which is a reversed-phase distribution column), 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 amount: 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 mol) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen introducing pipe, a stirrer, a cooling pipe, a temperature controller, and a dropping cylinder.
6g) and 0.0622g of phosphoric acid (85% product)
Heated to 40 ° C. Then, while maintaining the reaction temperature at 140 ° C., 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours, and the oxirane concentration in the system was reduced to 0.1%.
The reaction was continued until less than. After cooling, take out the reaction product and add about 300 polyglycerin monolaurate.
g was obtained. The obtained polyglycerin monolaurate was evaluated under the above-described HPLC analysis conditions. Also, 10% of the obtained polyglycerin monolaurate was used.
The aqueous solution was prepared, vibrated (manually) for 30 seconds, and the foaming property and state were visually observed. The chart obtained by HPLC is shown in FIG. In addition, Table 1 shows the results of component analysis by HPLC analysis and the evaluation results of the foaming property and state.

Example 2 0.5 mol (100.1 mol) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
6g) and 0.0810 g of phosphoric acid (85% product)
Heated to 40 ° C. Then, while maintaining the reaction temperature at 140 ° C., 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours, and the oxirane concentration in the system was reduced to 0.1%.
The reaction was continued until less than. After cooling, take out the reaction product and add about 300 polyglycerin monolaurate.
g was obtained. The obtained polyglycerin monolaurate was evaluated by HPLC. Further, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, and
It was vibrated (manually) for 0 seconds, and the foaming property and state were visually observed. The chart obtained by HPLC is shown in FIG. In addition, Table 1 shows the results of component analysis by HPLC analysis and the evaluation results of the foaming property and state.

Example 3 0.5 mol (100.1 mol) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
6g) and 0.0810 g of phosphoric acid (85% product)
Heated to 40 ° C. Then, 4.0 mol (296.32 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 reduced to 0.1%.
The reaction was continued until less than. After cooling, the reaction product was taken out, and polyglycerin monolaurate was added for about 400 hours.
g was obtained. The obtained polyglycerin monolaurate was evaluated by HPLC. Further, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, and
It was vibrated (manually) for 0 seconds, and the foaming property and state were visually observed. The chart obtained by HPLC is shown in FIG. In addition, Table 1 shows the results of component analysis by HPLC analysis and the evaluation results of the foaming property and state.

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

Example 5 0.5 mol (100.1 mol) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
6g) and 0.105 g of EAP (a mixture of monoethyl acid phosphate and diethyl acid phosphate, manufactured by Nippon Chemical Industry Co., Ltd.), and heated to 140 ° C.
Then, while maintaining the reaction temperature at 140 ° C., 5.0 mol (370.40 g) of glycidol 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 470 g of polyglycerin monolaurate. The obtained polyglycerin monolaurate was evaluated by HPLC. In addition, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, and vibrated for 30 seconds (manual).
The foaming property and the state were visually observed. HPLC
5 is shown in FIG. In addition, Table 1 shows the results of component analysis by HPLC analysis and the evaluation results of the foaming property and state.

(Comparative Example 1: When no catalyst is used) Lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
5 mol (100.16 g) was added, and the mixture was heated to 140 ° C. Then, while maintaining the reaction temperature at 140 ° C., 3.0 mol (222.24 g) of glycidol 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 monolaurate was evaluated by HPLC. Further, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, vibrated (manually) for 30 seconds, and the foaming property and state were visually observed. HP
The chart obtained by the LC analysis is shown in FIG. Also, H
Table 1 shows the results of the component analysis and the evaluation results of the foaming property and the state by the analysis from the PLC analysis.

Comparative Example 2: When p-toluenesulfonic acid (PTS) was used as the catalyst Lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder. 0.5 mol (100.
16g) and 0.371 g of PTS were added, and heated to 140 ° C. Then, while maintaining the reaction temperature at 140 ° C., 3.0 mol (222.24 g) of glycidol 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 monolaurate was evaluated by HPLC. Further, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, vibrated (manually) for 30 seconds, and the foaming property and state were visually observed. HP
The chart obtained by LC is shown in FIG. Also, HPL
Table 1 shows the component analysis results and the evaluation results of the foaming property and state by analysis from C.

(Comparative Example 13: Reaction of fatty acid monoglyceride with glycidol) 0.5 mol of lauric acid monoglyceride was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
of sodium methylate (NaOCH3: 28% methanol solution) 0.45
g was added and heated to 90 ° C. Then, the reaction temperature was increased to 9
While maintaining the temperature at 0 ° C, 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 monolaurate was evaluated by HPLC. Further, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, vibrated (manually) for 30 seconds, and the foaming property and state were visually observed. The chart obtained by HPLC analysis is shown in FIG. In addition, Table 1 shows the results of component analysis by HPLC analysis and the evaluation results of the foaming property and state.

Comparative Example 4 Reaction of Fatty Acid with Polyglycerin Polyglycerin (Daicel Chemical Industries, Ltd.) was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder. PGL manufactured by
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 monolaurate was evaluated by HPLC. Further, a 10% aqueous solution of the obtained polyglycerin monolaurate was prepared, vibrated (manually) for 30 seconds, and the foaming property and state were visually observed. The chart obtained by the HPLC analysis is shown in FIG. In addition, Table 1 shows the results of component analysis by HPLC analysis and the evaluation results of the foaming property and state.

[0050]

[Table 1]

(Comparative Examples 5 to 14: Evaluation results of commercially available polyglycerin fatty acid esters) As commercial polyglycerin fatty acid esters produced from the reaction of polyglycerin and fatty acids, 5 products of SY Glister (manufactured by Sakamoto Yakuhin Kogyo) MO-310, MO-750, ML-310, ML-
500, ML-750), Poem (manufactured by Riken Vitamin), two parts (J-6021, J-0021), Unigri (manufactured by Nippon Oil & Fats), two parts (GO-106, GL-106) and Sunsoft Q12S (sun) (Manufactured by Kagaku) was selected, and a 10% aqueous solution was prepared for each polyglycerin fatty acid ester. Charts obtained by HPLC analysis are shown in FIGS. Also, HPL
Table 2 shows the component analysis results and the evaluation results of the foaming property and the state by analysis from C.

[0052]

[Table 2]

[0053]

As described above, as is apparent from the concrete description of the examples and comparative examples, the polyglycerin monofatty acid ester having a high content of monofatty acid ester provided by the present invention can be used as a surfactant and an emulsifier in the food field. When applied to a stabilizer, an improvement in surface tension, an improvement in dispersing power, an improvement in foaming power, and a marked improvement in emulsion stability are achieved.

[Brief description of the drawings]

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

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

FIG. 3 is a chart by HPLC of polyglycerin monolaurate obtained in Example 3.

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

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

FIG. 6 is a chart by HPLC of polyglycerin monolaurate obtained in Comparative Example 1.

FIG. 7 is a chart by HPLC of polyglycerin monolaurate obtained in Comparative Example 2.

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

9 is a chart by HPLC of polyglycerin monolaurate obtained in Comparative Example 4. FIG.

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

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

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

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

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

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

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

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

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

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

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 69/33 C07C 67/26 C07C 69/533 C07C 69/58 C07C 69/675

Claims (7)

(57) [Claims] 1. A content of a monofatty acid ester represented by the following general formula [1], which is detected at a wavelength of 210 nm by a column chromatography analysis method using an ultraviolet absorption detector and represented by a peak area ratio of 77. 2 % or more of polyglycerin mono fatty acid ester. Embedded image 2. Separation by high performance liquid chromatography using an octadecyl group-containing silica gel column using methanol as an eluent, and using an ultraviolet absorption detector , a wavelength of 210
The content represented by the peak area ratio of the monofatty acid ester represented by the following general formula [1] and detected in nm is 77.2.
% Polyglycerol monofatty acid ester. Embedded image 3. The polyglycerol monofatty acid ester according to claim 1, wherein R has 7 or more carbon atoms. 4. An octadecyl group-containing polyglycerol monofatty acid ester or polyglycerol difatty acid ester represented by the general formula [1] described in claim 1 and polyglycerin, wherein methanol is used as an eluent. Separation by high performance liquid chromatography using a silica gel column, and using an ultraviolet absorption detector, a wavelength of 210 nm
A surfactant whose content, expressed in terms of peak area ratio, is 77.2 % or more for polyglycerin monofatty acid ester and 15 % or less for polyglycerin. 5. A fatty acid represented by the following general formula [2]:
Glycidol is reacted in the presence of a phosphoric acid-based catalyst, separated by high performance liquid chromatography, and detected using an ultraviolet absorption detector at a wavelength of 210 nm to obtain a monofatty acid ester represented by the following general formula [1]. A method for producing a polyglycerol monofatty acid ester having a content expressed as a peak area ratio of 77.2 % or more. Embedded image 6. The method for producing a polyglycerol monofatty acid ester according to claim 5, wherein a fatty acid having 7 or more carbon atoms of R is reacted. 7. The method for producing a polyglycerol monofatty acid ester according to claim 5, wherein the phosphoric acid-based acidic catalyst is phosphoric acid or an acidic phosphoric acid ester.