JPH08143513A - Production of polyglyceryl fatty acid ester - Google Patents

Abstract

PURPOSE: To obtain a surfactant capable of producing perfect dissolution products and stable emulsions in the fields of foods, cosmetics, medicines and other industries. CONSTITUTION: The method for producing the polyglyceryl fatty acid ester comprises the first process for obtaining a polyglycerol by removing the low molecular reaction products of the polyglycerol with a liquid chromatography using a column filled with the alkaline earth metal salt of a gel type ion exchange resin having a polystyrene skeleton having a cross-linking degree of 8-12%, and the second process containing the esterification reaction of the polyglycerol with a fatty acid. The method is suitable for producing perfect dissolution products and stable emulsions, and enables to produce products which have not been produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyglycerin fatty acid ester having a high ability to reduce surface tension. The polyglycerin fatty acid ester obtained by the present invention is emulsified, solubilized, dispersed, washed, anticorrosive, It can be used as a food additive, cosmetics, pharmaceutical and industrial surfactant for the purpose of lubrication, antistatic, wetting and the like.

[0002]

2. Description of the Related Art Conventionally, various compounds such as polyoxyethylene alkyl ether, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene alkylphenyl ether, and other ethylene oxide compounds have been used as emulsifying or solubilizing agents. Nonionic surfactants, sorbitan fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters (including polyglycerin condensed ricinoleic acid ester), and other food-grade surfactants are known. Among them, polyglycerin fatty acid ester is the most useful surfactant because it is safe to humans and the environment, and it is highly versatile because it can obtain various compositions. Polyglycerin fatty acid ester used as a raw material for polyglycerin fatty acid ester and polyglycerin condensed ricinoleic acid ester is a polymer obtained by polymerizing glycerin under high temperature conditions in the presence of an alkali catalyst such as caustic soda, and deodorizing and decolorizing. It was produced by an esterification reaction using glycerin and a fatty acid as raw materials. In addition, the reaction product obtained by chemical synthesis using epichlorohydrin, glycidol, glycerin or polyglycerin and epichlorohydrin, monochlorohydrin, dichlorohydrin or glycidol as it is, or if necessary, distilled , Polyglycerin obtained by purification by decolorization, deodorization, treatment with an ion exchange resin, etc. was used as a raw material for esterification.

[0003]

The polyglycerols on the market are called tetrameric polyglycerin, hexameric polyglycerin and decameric polyglycerin according to the average degree of polymerization calculated from the hydroxyl value. ing. However, it is actually a mixture of various glycerin polymers having a degree of polymerization of 1 to 10 or more. Generally, in the case of synthesizing an ester by esterification reaction of these polyglycerin and fatty acid, the reactivity is different depending on the degree of polymerization of glycerin, and polyglycerin having a low degree of polymerization is selectively esterified. As a result, the obtained ester is a mixture of a low degree of polymerization polyglycerin fatty acid ester having an ester bond with more fatty acids than the target and an unreacted high degree of polymerization polyglycerin having no ester bond. Therefore, the emulsifying and solubilizing power originally possessed cannot be exhibited. For example, when producing useful substances such as fat-soluble vitamins such as vitamin E and fat-soluble pigments such as carotene as beverages, existing food surface-active agents cannot be transparently solubilized and products with good storage stability should be prepared. It could not be manufactured. Further, other surfactants such as polyoxyethylene sorbitan ester can be used in the production of pharmaceuticals and cosmetics, but useful substances such as fat-soluble vitamins such as vitamin E and fat-soluble pigments such as carotene are produced as beverages. In this case, an auxiliary agent such as ethanol is required because it does not have sufficient solubilizing ability by itself. Therefore, when it is consumed in large quantities, it becomes drunk, which is a social problem especially for young people.

Further, although polyoxyethylene derivatives are used as hydrophilic emulsifiers in the cosmetics industry, there is a problem with safety such as skin irritation and alternatives are required, but conventional polyglycerin fatty acid esters are used. The performance of sucrose fatty acid ester and sucrose is insufficient and cannot be substituted. Japanese Unexamined Patent Publication No. 4-145046 discloses a method for producing a high-quality polyglycerin fatty acid ester using a metal oxide catalyst. In this method, ester decomposition and coloring are improved, but the molecular weight distribution of polyglycerin is improved. The obtained ester does not have a particularly improved surface-active ability because it cannot be controlled. JP 61
187795, JP 61-257191, JP 6
1-257191 and JP-A-3-151885 disclose a method of producing polyglycerin using a lipase when esterifying it, but this method also does not improve the surfactant activity. JP-A-63-23837 and JP-A-3-81252 attempt to improve the surface-active ability by removing unreacted polyglycerin by solvent fractionation after esterification, but this method complicates the process. Moreover, since the yield is low, it cannot be put to practical use.

Further, in JP-A-5-310625, polyglycerin, particularly glycerin, is heated at a high temperature under an alkali catalyst by chromatographic separation using a gel-type strongly acidic cation exchange resin having a polystyrene skeleton having a degree of crosslinking of 5 to 8%. Disclosed is a method of separating the polyglycerin composition produced by the method of polymerizing in, the reaction product polyglycerin is a polyglycerol produced by a method of polymerizing glycerin at a high temperature particularly under an alkaline catalyst. Since a large amount of acidic substances originating from acrolein-like substances produced as a by-product during the glycerin reaction are contained, ion exchange resins with a cross-linking degree of 6 or 8 that have been generally used conventionally have large swelling and shrinkage of the resin and easily break. It has the drawback that it cannot achieve the long-term stability that is most important for industrial production. It was.

[0006]

In view of the above points, the inventors of the present invention have made intensive studies and arrived at the present invention. That is, according to the present invention, the polyglycerin reaction product can be reduced by liquid chromatography using a column packed with an alkaline earth metal salt of a gel type cation exchange resin having a polystyrene skeleton having a cross-linking degree of more than 8% and 12% or less. The present invention relates to a method for producing a polyglycerin fatty acid ester obtained by a first step of removing a molecular reaction product to obtain polyglycerin and a second step including subsequent esterification with a fatty acid.
The present invention will be described in detail below. The surfactant referred to in the present invention is a substance added for the purpose of stabilization when mixing the lipophilic substance and the hydrophilic substance, and has a strong surfactant activity. These substances have both a lipophilic functional group and a hydrophilic functional group in the molecule, and reduce the surface tension of water. The polyglycerin referred to in the present invention is
A substance that has a hydroxyl group and an ether bond in the molecule obtained by dehydration condensation of glycerin, etc. and does not have any other functional group, and refers to all substances having an equivalent structure regardless of the raw material manufacturing method. It is a thing.

The polyglycerin reaction product referred to in the present invention is obtained by heating glycerin under normal pressure or reduced pressure in the presence of an alkali catalyst. Depending on the purpose of use, odorous components having a low boiling point, such as nitrogen and steam, can be removed. To remove
Purified by removing ion components such as catalysts used with ion exchange resins and ion exchange membranes, removing color components and odor components using adsorbents such as activated carbon, and reducing treatments such as hydrogenation. It Also, polyglycerin can be obtained by synthesizing and purifying glycidol, epichlorohydrin, monochlorohydrin and the like as raw materials. Further, it can be obtained by a dehalogenation alkali metal salt reaction using glycerin or a partial alcoholate of a polymer thereof and a halogenated hydrin such as dichlorohydrin or monochlorohydrin as raw materials. For example, by reacting 2 mol of monoalkoxyglycerol and 1 mol of dichlorohydrin, triglycerin and sodium chloride are obtained. But,
In this system, the viscosity becomes extremely high and the compatibility is poor, so it is actually preferable to add a solvent. The solvent used is preferably glycerin or a polymer thereof because of the simplicity of the purification step. More preferred are glycerin and diglycerin. These solvents can be easily removed by a liquid chromatography treatment in a later step, and can be reused as a raw material if necessary. Further, in the reaction, it is preferable to operate at a temperature as low as possible for the purpose of suppressing generation of by-products due to random reaction. The preferable condition is 150 ° C. or lower, more preferably 130 ° C. or lower.

The polyglycerin reaction product thus obtained contains, as a main component, glycerin used as a solvent or its polymer and a theoretical reaction product, and a small amount of other polyglycerin having a higher degree of polymerization which is a by-product. Also includes. Among these polyglycerin reaction products, the polyglycerin reaction products obtained by the dehalogenation alkali metal salt reaction using glycerin or a partial alcoholate of the polymer and a halogenated hydrin as a raw material are compared with the polyglycerin reaction products obtained by the usual method. Most preferred is the narrow molecular weight distribution. Conventionally, the degree of polymerization of polyglycerin means that when 2 moles of glycerin are dehydrated and condensed, 2 moles of hydroxyl groups in the molecule have an ether bond of 1
Focusing on converting to moles, according to the standard oil and fat test method,
It has been understood as a measure of the hydroxyl value and calculation of its average degree of polymerization. This is because the polyglycerin conventionally supplied to the market has a wide molecular weight distribution from low molecular weight to high molecular weight, and it is complicated when the composition is expressed by a numerical value, and the molecular weight distribution is obtained as described in the present invention. This was because there were no findings focusing on the surface-active ability of the ester. However, the use of such a method for measuring the degree of polymerization is unsuitable for considering the characteristics of the polyglycerin fatty acid ester obtained from these polyglycerins.
Therefore, the degree of polymerization of polyglycerin in the present invention is determined by the area method by forming a polyglycerin derivative such as trimethylsilylated or acetylated, and then performing separation and quantification by the GC method (gas chromatography).

The analysis by the GC method can be easily carried out by conducting a temperature rising analysis from 100 ° C. to 250 ° C. at 10 ° C./min using a fused silica capillary tube in which a low polar liquid phase such as methyl silicon is chemically bonded. It can be carried out. Also,
The peak on the gas chromatogram can be identified by, for example, introducing a gas chromatograph into a double-focusing mass spectrograph, ionizing it by a method such as chemical ionization, and then measuring the peak on the gas chromatogram from the molecular weight of the parent ion. It can be easily carried out by obtaining the molecular weight of the above and further obtaining the degree of polymerization of glycerin from the chemical formula. The liquid chromatography referred to in the present invention refers to the difference in distribution coefficient between the solid particles packed in a column or the solid particles coated with a liquid layer on the surface and the two phases of the effluent and the partition coefficient. The separation device may be any known type of liquid chromatography. For example, a constant amount of raw material is supplied to a column filled with the effluent solvent, and then the effluent solvent is supplied in a single column system. It is possible to use a simulated moving bed type system or its improved type, which is continuously or intermittently supplied and withdraws a predetermined amount of effluent from a predetermined column at a fixed timing continuously or intermittently.

The solid particles packed in the column used in the liquid chromatography used in the present invention are ion exchange resins, more specifically gel type cation exchange resins having a polystyrene skeleton. This cation exchange resin uses styrene as the main raw material, divinylbenzene as the cross-linking agent, and in some cases 1,2,4-trivinylbenzene or 1,3,5-trivinylbenzene as the cross-linking agent. It can be obtained by carrying out suspension polymerization, then introducing a functional group by treatment with concentrated sulfuric acid, chlorosulfonic acid or sulfuric anhydride, and bringing it into contact with an aqueous solution of an alkaline earth metal salt. In this case, the degree of crosslinking is determined by the blending ratio of the crosslinking agent. For example, 90 parts of styrene and 1 part of divinylbenzene
A resin having a degree of crosslinking of 10 is produced when 0 parts are blended and subjected to suspension polymerization, or a resin having a degree of crosslinking of 12 is produced when 88 parts of styrene and 12 parts of divinylbenzene are blended and subjected to suspension polymerization.
In this case, when the amount of the crosslinking agent is increased, many chemical bonds are three-dimensionally generated during suspension polymerization, and both the physical strength and the chemical strength increase. When used for the purpose of the present invention, as described above, the resin is swelled and shrunk largely due to the acidic substance produced as a by-product during the reaction, and the resin is apt to be cracked. Therefore, it is difficult for a resin having a crosslinking degree of 6 or 8 which is usually used to be stable for a long period of time, and a crosslinking degree of more than 8 is required. However, it is not suitable to use a resin having a degree of cross-linking of more than 12 because the strength is sought too much, because the separation performance is extremely deteriorated. Further, in introducing the functional group, a substance having an exchange capacity of 0.5 to 3 meq / ml, preferably 1 to 2 meq / ml is preferable.

The alkaline earth metal salt used in the present invention is calcium, magnesium or the like, and its chloride is usually used. In this case, the selected salt is preferably one kind. When other metal ions such as alkali metal ions are used, the required strength cannot be obtained, and as a result, stable use for a long period of time is difficult. The contact between the resin and the alkaline earth metal salt solution is preferably carried out sufficiently until equilibrium is reached. After filling the column with the above ion-exchange resin and adding an aqueous solution of the polyglycerin reactant, elution with water may give an aqueous solution of polyglycerin having the desired degree of polymerization distribution, which is sequentially eluted depending on the degree of polymerization. I can. In this case, elute water with sodium chloride, sodium acetate,
Salts such as sodium sulfate, sodium phosphate and sodium citrate, or acidic substances such as acetic acid, phosphoric acid and citric acid may be added. Alternatively, a borate salt such as potassium borate may be used. At this time, any distribution of the degree of polymerization can be collected depending on the conditions. However, in order to carry out the appropriate esterification in the subsequent esterification reaction, the width of the distribution is preferably narrow, and the degree of polymerization is 3 or more. It is desirable to separate glycerin. It is more desirable to separate polyglycerin having a degree of polymerization of 3 or more and 10 or less. Most preferably, polyglycerin having a degree of polymerization of 4 or more and 10 or less is fractionated. The thus-obtained aqueous solution of polyglycerin is heated under reduced pressure to remove water, and then esterification with a fatty acid is carried out according to a conventional method to obtain the desired polyglycerin fatty acid ester.

The term "fatty acid" as used in the present invention is a general term for substances containing a carboxylic acid as a functional group, which is obtained by hydrolyzing oils and fats extracted from natural animals and plants, and separating or purifying without separation. It is not limited. The fatty acid of the present invention may be a fatty acid obtained by chemically synthesizing petroleum as a raw material, and may be obtained by reducing these fatty acids by hydrogenation or by polycondensing a fatty acid containing a hydroxyl group. It may be a condensed fatty acid or a polymerized fatty acid obtained by heat-polymerizing a fatty acid having an unsaturated bond. Oleic acid, isostearic acid, palmitic acid, lauric acid, capric acid, caprylic acid, ricinoleic acid, 12-hydroxystearic acid, condensed ricinoleic acid, condensed 12-hydroxystearic acid, caproic acid, heptyl acid, nonyl acid, undecanoic acid, Myristic acid, stearic acid, palmitooleic acid, behenic acid, linoleic acid, linolenic acid,
Elaidic acid, 2-ethylhexylic acid, or a mixture of these fatty acids can be exemplified. The selection of these fatty acids may be appropriately determined in consideration of the desired product effect. Natural fatty acids derived from plants and animals are preferable in consideration of environmental issues, and fatty acids having two or more unsaturated double bonds are preferable if stability over time is desired. In terms of fatty acid chain length, it preferably has 8 to 22 carbon atoms. Examples of preferred fatty acids include oleic acid, palmitic acid, lauric acid, capric acid, caprylic acid, ricinoleic acid, condensed ricinoleic acid, myristic acid, stearic acid, palmitooleic acid, behenic acid, or a mixture of these fatty acids. .

The polyglycerin and fatty acid referred to in the present invention are esterified by a known method. For example, esterification can be carried out under normal pressure or reduced pressure under an alkali catalyst, an acid catalyst, or a non-catalyst. Further, the amounts of polyglycerin and fatty acid charged must be appropriately selected depending on the purpose of the product. For example, in order to obtain a hydrophilic surfactant, it is sufficient to calculate the weight so as to be equimolar by calculating from the hydroxyl value of polyglycerin and the molecular weight of fatty acid, and to obtain a lipophilic surfactant. Then, the number of moles of fatty acid may be increased. The polyglycerin fatty acid ester obtained may be purified according to the usage requirements of the product. The purification method may be any known method and is not particularly limited. For example, purification by adsorption treatment with activated carbon or activated clay, reduced pressure treatment using water vapor, nitrogen, etc. as carrier gas, or washing with acid or alkali, or molecular distillation Alternatively, liquid-liquid distribution, an adsorbent, a resin, a molecular sieve, a loose reverse osmosis membrane, an ultrafiltration membrane or the like may be used to separate and remove unreacted polyglycerin and the like. Other components can be added to the polyglycerin fatty acid ester of the present invention to facilitate the handling of the product. For example, ethanol, propylene glycol, glycerin, polyglycerin, water, liquid sugar, to reduce the viscosity of the product,
You may melt | dissolve or emulsify by adding 1 type, or 2 or more types, such as fats and oils. Alternatively, a polysaccharide such as lactose or dextrin, or a protein such as caseinate may be added to obtain a powder.

Depending on the purpose of use, the polyglycerol fatty acid ester of the present invention may be mixed with another surfactant to prepare a surfactant preparation. Usable surfactants are soybean lecithin, egg yolk lecithin, lecithin such as rapeseed lecithin or a partial hydrolyzate thereof, caprylic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, myristic acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride,
Behenic acid monoglyceride, oleic acid monoglyceride, elaidic acid monoglyceride, ricinoleic acid monoglyceride, condensed ricinoleic acid monoglyceride and other monoglycerides, or a mixture of these monoglycerides, or organic acids such as acetic acid, citric acid, succinic acid, malic acid, tartaric acid of these monoglycerides. Organic acid monoglyceride, caprylic acid sorbitan ester, capric acid sorbitan ester, lauric acid sorbitan ester, myristic acid sorbitan ester, palmitic acid sorbitan ester, stearic acid sorbitan ester, behenic acid sorbitan ester, oleic acid sorbitan ester, elaidin Acid sorbitan ester, ricinoleic acid sorbitan ester, condensed ricinoleic acid sorbitan ester Sorbitan fatty acid ester such as tellurium, caprylic acid propylene glycol ester, capric acid propylene glycol ester, lauric acid propylene glycol ester, myristic acid propylene glycol ester, palmitic acid propylene glycol ester, stearic acid propylene glycol ester, behenic acid propylene glycol ester, olein Acid propylene glycol ester, elaidic acid propylene glycol ester, ricinoleic acid propylene glycol ester, condensed ricinoleic acid propylene glycol ester and other propylene glycol fatty acid esters, caprylic acid sucrose ester, capric acid sucrose ester, lauric acid sucrose ester, Myristic acid sucrose ester, palmitic acid sucrose ester, Tea sucrose ester, behenate sucrose ester, oleic acid sucrose ester, elaidic acid sucrose ester, ricinoleic acid sucrose ester, condensed ricinoleic acid sucrose ester and other sucrose fatty acid esters, soybean lecithin, egg yolk lecithin or its Nonionic surfactants such as lysolecithin, phosphatidic acid, lysophosphatidic acid, which is an enzymatic degradation product, phosphatidylglycerol, lysophosphatidylglycerol, which is an enzymatically treated product, or phospholipids such as hydrogenated products and fractions thereof, or nonionics thereof. Examples thereof include ethylene oxide adducts of surfactants, amphoteric surfactants, anionic surfactants, and cationic surfactants. From the viewpoint of safety to the human body and the environment, nonionic surfactants such as glycerin fatty acid ester, organic acid monoglyceride, sorbitan fatty acid ester, propylene glycol, fatty acid ester, sucrose fatty acid ester and phospholipid are preferred. The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[0015]

【Example】

Polyglycerin Reaction Example 1 3000 g of glycerin and 30 g of 50% sodium hydroxide aqueous solution were put into a 5 liter four-necked flask, heated to 240 ° C. while removing water under a nitrogen stream at a pressure of 100 torr, and kept for 20 hours. Thus, 1870 g of a polyglycerin reaction product was obtained. The composition of the resulting polyglycerin reaction product is shown in Table 1.

[0016]

[Table 1]

Polyglycerin Reaction Example 2 3300 g of diglycerin was placed in a 5-liter four-necked flask.
Then, 800 g of a 50% aqueous sodium hydroxide solution was added, and the mixture was heated to 140 ° C. while removing water under a nitrogen stream. After the distillation of water was completed, 640 g of dichlorohydrin was added dropwise over 2 hours, and the salt produced as a by-product was removed by filtration, electrodialysis, and ion exchange column treatment, and 324 polyglycerol reaction products were removed.
0 g was obtained. The composition of the obtained polyglycerin reaction product is shown in Table 1.
It was as follows. Polyglycerin Production Example 1 Polyglycerin of Polyglycerin Reaction Example 1 (10 g) was added to a column filled with 12% of cross-linking degree and 50 ml of calcium type cation exchange resin, and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 1. Polyglycerin Production Example 2 Polyglycerin of Polyglycerin Reaction Example 1 (10 g) was added to a column packed with a crosslinking degree of 10% and 50 ml of a calcium-type cation exchange resin, and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 1.

Polyglycerin Production Example 3 Polyglycerin 10 g of polyglycerin of Reaction Example 1 was added to a column packed with a crosslinking degree of 9% and 50 ml of a calcium type cation exchange resin, and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 1. Polyglycerin Production Comparative Example 1 Polyglycerin 10 g of polyglycerin of Reaction Example 1 was added to a column packed with a crosslinking degree of 8% and 50 ml of a calcium-type cation exchange resin, and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 2.

[0019]

[Table 2]

Polyglycerin Production Comparative Example 2 Polyglycerin 10 g of the polyglycerin of Reaction Example 1 was added to a column filled with 50 ml of calcium type cation exchange resin with a crosslinking degree of 6% and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 1. Polyglycerin Production Example 4 Polyglycerin of Polyglycerin Reaction Example 2 (10 g) was added to a column packed with 12% of cross-linking degree and 50 ml of calcium type cation exchange resin, and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 2. Polyglycerin Production Example 5 Polyglycerin of Polyglycerin Reaction Example 2 (10 g) was added to a column filled with 10% of cross-linking degree and 50 ml of calcium type cation exchange resin, and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 2. Polyglycerin Production Example 6 Polyglycerin of Polyglycerin Reaction Example 2 (10 g) was added to a column filled with a crosslinking degree of 8% and 50 ml of calcium type cation exchange resin, and the mixture was allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The yield and composition of the obtained polyglycerin are shown in Table 3.

[0021]

[Table 3]

Polyglycerin Production Comparative Example 3 Polyglycerin 10 g of the polyglycerin obtained in Reaction Example 2 was added to a column filled with 50 ml of a calcium type cation exchange resin having a crosslinking degree of 8% and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 3. Polyglycerin Production Comparative Example 4 Polyglycerin 10 g of the polyglycerin reaction example 2 was added to a column packed with a crosslinking degree of 6% and 50 ml of a calcium type cation exchange resin, and allowed to flow out with water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer. This operation was repeated 100 times. All polyglycerin solutions were collected and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 3. Polyglycerin Production Example 7 Polyglycerin 1000 g of polyglycerin of Reaction Example 1 was added to a simulated moving bed type chromatographic apparatus composed of 8 columns packed with 12% of crosslinking degree and 10 ml of calcium type cation exchange resin, and added to water. And let it flow out. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 3. Polyglycerin Production Example 8 Polyglycerin of the reaction example 1 (1000 g) was added to a simulated moving bed chromatograph apparatus composed of 8 columns filled with 10% of crosslinking degree and 10 ml of calcium type cation exchange resin, and added to water. And let it flow out. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 4.

[0023]

[Table 4]

Polyglycerin Production Example 9 Polyglycerin 1000 g of polyglycerin of Reaction Example 1 was added to a simulated moving bed type chromatograph apparatus composed of 8 columns packed with a crosslinking degree of 9% and 10 ml of calcium type cation exchange resin. , With water. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 4.
It was as follows. Polyglycerin Production Comparative Example 5 Polyglycerin of Reaction Example 1 (1000 g) was added to a simulated moving bed chromatograph apparatus composed of 8 columns filled with 10% of a calcium type cation exchange resin and a crosslinking degree of 8%, and water. It was drained at. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 4.
It was as follows. Polyglycerin Production Comparative Example 6 Polyglycerin of Reaction Example 1 (1000 g) was added to a simulated moving bed type chromatographic apparatus composed of 8 columns filled with 10% of a calcium type cation exchange resin and a crosslinking degree of 6%, and water was added. It was drained at. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 4.
It was as follows. Polyglycerin Production Example 10 1000 g of polyglycerin of Polyglycerin Reaction Example 2 was added to a simulated moving bed type chromatograph apparatus composed of 4 columns filled with 10% of a calcium type cation exchange resin and having a crosslinking degree of 12%, and added to water. And let it flow out. However, the ratio of supply / outflow time and circulation time was 2: 1. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 5.

[0025]

[Table 5]

Polyglycerin Production Example 11 Polyglycerin 1000 g of polyglycerin of Reaction Example 2 was added to a simulated moving bed type chromatographic apparatus composed of four columns filled with 10% of crosslinking degree and 10 ml of calcium type cation exchange resin. , With water. However, the ratio of supply / outflow time and circulation time was 2: 1. Polyglycerin having a degree of polymerization of 3 or more was collected while measuring the flow-out liquid with a refractometer and dehydrated and concentrated by a rotary evaporator to obtain polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 5. Polyglycerin Production Example 12 The polyglycerin of 1000 g of polyglycerin reaction example 2 was added to a simulated moving bed type chromatographic apparatus composed of four columns filled with 10% of a calcium type cation exchange resin and a crosslinking degree of 9%, and added to water. And let it flow out. However, supply,
The ratio of outflow time to circulation time was 2: 1. While measuring the flow-out liquid with a refractometer, polyglycerin with a degree of polymerization of 3 or more is collected, dehydrated and concentrated by a rotary evaporator,
Obtained polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 5.

Comparative Example 7 of Polyglycerin Production A poly-glycerin reaction example 1 was used in a simulated moving bed type chromatograph apparatus composed of four columns filled with 1000 g of polyglycerin of 8% cross-linking degree and 10 ml of calcium type cation exchange resin. In addition, it was made to flow out with water. However, supply,
The ratio of outflow time to circulation time was 2: 1. While measuring the flow-out liquid with a refractometer, polyglycerin with a degree of polymerization of 3 or more is collected, dehydrated and concentrated by a rotary evaporator,
Obtained polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 5. Polyglycerin Production Comparative Example 8 Polyglycerin of Reaction Example 2 (1000 g) was added to a simulated moving bed chromatograph apparatus composed of four columns filled with 10% of calcium-type cation exchange resin and having a crosslinking degree of 6%, and water. It was drained at. However, supply,
The ratio of outflow time to circulation time was 2: 1. While measuring the flow-out liquid with a refractometer, polyglycerin with a degree of polymerization of 3 or more is collected, dehydrated and concentrated by a rotary evaporator,
Obtained polyglycerin. The same operation was repeated 4 times using the same column. The composition of the obtained polyglycerin is shown in Table 5.

Examples 1 to 12 500 g of ricinoleic acid and 0.8 g of sodium hydroxide were placed in a 1-liter four-necked flask and reacted at 210 ° C. while removing the produced water under a nitrogen stream to obtain condensed ricinoleic acid. It was The acid value of this condensate was 33.8. Polyglycerin (1) obtained in Production Examples 1 to 12
60.5 g of the mixture of the 4th time-the 4th time) was added, and it was made to react at 250 degreeC, removing the produced water under nitrogen stream, and polyglycerol condensed ricinoleic acid ester was obtained. Examples 13 to 24 In a 500 ml four-necked flask, 210 g of polyglycerin (mixture of the first to fourth times) obtained in Polyglycerin Production Examples 1 to 12, 90 g of isostearic acid and 0.1 g of tripotassium phosphate were placed, The reaction was carried out at 250 ° C. while removing generated water under a nitrogen stream, and 0.3 ml of phosphoric acid was added after the reaction to obtain polyglycerin isostearic acid ester. Examples 25 to 36 Polyglycerin 225.2 g of the polyglycerin (mixture of the 1st to 4th times) obtained in Production Examples 1 to 12 and 74.2 g of stearic acid were prepared from polyglycerin stearin by exactly the same process as in Examples 13 to 24. An acid ester was obtained.

Examples 37 to 48 Polyglycerin 225.2 g of the polyglycerin (mixture of the first to fourth times) obtained in Production Examples 1 to 12 and 74.2 g of oleic acid were prepared by the same steps as in Examples 13 to 24. Polyglycerin oleic acid was obtained. Test Example 1 Polyglycerin ester obtained in Production Examples 1 to 12 was added to 100 g of commercially available bitter chocolate.
% Was added and the viscosity was measured at 50 ° C. with a B type viscometer. Further, as a comparison, the same test was performed on commercially available tetraglycerin condensed ricinoleic acid ester, hexaglycerin condensed ricinoleic acid ester, and decaglycerin condensed ricinoleic acid ester. The results are shown in Table 6.

[0030]

[Table 6]

Test Example 2 Example 1 was added to 0.13 part by weight of commercially available 80% pure vitamin E.
Polyglycerin fatty acid ester obtained in 3-24.
4 parts by weight was added and heated to mix well. Part of it is 0.
Take 063 parts by weight, add 100 ml of warm water and stir well, and measure its turbidity with a spectrophotometer at a wavelength of 650.
It was measured as the absorbance at nm. Further, as a comparison, the same test was carried out on commercially available tetraglycerin isostearic acid ester, hexaglycerin isostearic acid ester, and decaglycerin isostearic acid ester. The results are shown in Table 7.

[0032]

[Table 7]

Test Example 3 1.2 parts by weight of the polyglycerol fatty acid ester obtained in Examples 25 to 36 was dissolved in 280 parts by weight of soybean white squeezing oil, and 280 parts by weight of a 10% sodium chloride solution was stirred with a homomixer at 5000 rpm. And then 10,000 rpm
And stirred for 2 minutes to obtain a W / O emulsion. The emulsion was statically stored at 60 ° C. for 3 days, and the separation of the aqueous layer was observed by visual observation. Further, as a comparison, the same test was performed on commercially available tetraglycerin stearic acid ester, hexaglycerin stearic acid ester, and decaglycerin stearic acid ester. Table 8 shows the results.

[0034]

[Table 8]

Test Example 4 To 100 parts by weight of water, 1 part by weight of the polyglycerin fatty acid ester obtained in Examples 37 to 48 was added and dissolved by heating at 60 ° C. While stirring with a homomixer at 5000 rpm, 100 parts by weight of soybean white squeezing oil heated to 60 ° C. was added,
Then, the mixture was stirred at 10,000 rpm for 2 minutes to obtain an O / W emulsion. The obtained two emulsions were placed in an autoclave for 12
After treatment at 0 ° C. for 30 minutes, the separation of the aqueous layer was observed by visual observation. Further, as a comparison, commercially available tetraglycerin oleic acid ester, hexaglycerin oleic acid ester,
A similar test was conducted for decaglycerin oleic acid ester. The results are shown in Table 9.

[0036]

[Table 9]

[0037]

According to the present invention as proved in the above Examples, the polyglycerin fatty acid ester of the present invention has a strong viscosity lowering power, solubilization, salt emulsification resistance, acid emulsification resistance, heat emulsification capacity, It is clear that it will be possible to manufacture completely solubilized products and stable emulsions, which have been impossible in the fields of foods, pharmaceuticals and cosmetics.

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Claims (3)

[Claims] 1. A polyglycerin reaction product obtained by liquid chromatography using a column packed with an alkaline earth metal salt of a gel-type cation exchange resin having a polystyrene skeleton having a cross-linking degree of more than 8% and 12% or less. A first step of removing the low molecular weight reactant to obtain polyglycerin;
Process for producing polyglycerin fatty acid ester obtained by the second step, which comprises subsequent esterification with fatty acid 2. A simulated moving bed liquid chromatography using a column packed with an alkaline earth metal salt of a gel-type cation exchange resin having a polystyrene skeleton having a degree of cross-linking of more than 8% and not more than 12%. The method for producing a polyglycerin fatty acid ester according to claim 1, wherein a low molecular weight reactant of the glycerin reactant is removed. 3. The polyglycerin reaction product is a polyglycerin reaction product obtained by a dehalogenation alkali metal salt reaction using glycerin or a partial alcoholate of a glycerin polymer and a halogenated hydrin as raw materials. A method for producing the polyglycerin fatty acid ester according to claim 1.