JP2000287631A - Polyglycerol fatty acid ester composition and emulsified composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having an excellent O/W type microemulsifying ability even under acidic conditions, excellent in flavor and useful for a food and drink, etc., by composing the composition of a constituent fatty acid which is a prescribed unsaturated fatty acid and providing a prescribed cloud point and a prescribed content of a fatty acid metal salt thereto. SOLUTION: This composition comprises a constituent fatty acid which is a 12-22C unsaturated fatty acid and has 65-90 deg.C cloud point of a 1 wt.% solution in an 8 wt.% aqueous solution of Na2SO4, <=0.2 wt.%, preferably <=0.05 wt.% content of a fatty acid alkali metal salt. Further, >=70% of the constituent fatty acid is preferably oleic acid. The polyglycerol fattyacid ester composition is preferably contained to prepare an emulsified composition in which an oil- soluble perfume, an oil-soluble coloring matter, an antioxidant or a functional fatty acid is emulsified.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyglycerin fatty acid ester (hereinafter abbreviated as "PoGE") composition having excellent O / W type fine emulsifying ability even under acidic conditions and having a good taste. And an emulsified composition containing the same.

[0002]

2. Description of the Related Art PoGE is known as a surfactant approved as a food additive, and is mainly used as an emulsifier for foods, and has recently been widely used for pharmaceuticals, cosmetics, and industrial uses. I have. By controlling the average degree of polymerization of polyglycerin, the chain length of the constituent fatty acids, and the degree of substitution of PoGE, PoGEs having a wide range of properties from hydrophilic to lipophilic can be obtained. Among them, carbon number 12-22
PoGE containing unsaturated fatty acids as constituents has excellent acid resistance, salt resistance, and heat resistance that are not found in other food emulsifiers.
It is effective for O / W emulsification under acidic or high salt concentration represented by sauce, dressing, mayonnaise and the like. When used alone, PoGE is used in combination with another emulsifier having a problem in acid resistance, whereby a stable emulsion can be obtained even under acidic conditions. Especially in 8 wt% Na ₂ SO ₄ aqueous solution, the cloud point of 1% by weight solution is preferred PoGE composition 65 to 90 ° C..

[0003]

However, a general method for producing PoGE is to directly esterify polyglycerin and a fatty acid in the presence of an alkali catalyst. Reacts to produce alkali metal salts (soap) of fatty acids, and the product P
Soap is mixed in the oGE composition. It is usually difficult to purify and remove the alkali metal salt (soap) of this fatty acid, and the soap content in a commercially available PoGE composition is usually about 1 to 4% by weight. Since this soap is an anionic surfactant having a high hydrophilicity, it is easily dissolved in water and exhibits bitterness, thereby affecting the flavor.

[0004]

The present invention has been studied variously with the aim of providing a PoGE which has solved the above-mentioned problems. As a result, 1 to 4% by weight was contained in the PoGE composition obtained by a usual method. It has been found that a good product having a good taste can be obtained by containing the alkali metal salt of a fatty acid in an amount of about 0.2% by weight or less. Specifically, the subject matter of the present invention is a constituent fatty acid is an unsaturated fatty acid having 12 to 22 carbon atoms, and the cloud point of a 1% by weight solution of 8 wt% Na ₂ SO ₄ aqueous solution is a 65 to 90 ° C. And a polyglycerin fatty acid ester composition having a fatty acid alkali metal salt content of 0.2% by weight or less, and an emulsified composition containing the same.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyglycerin fatty acid ester composition of the present invention is usually obtained by reacting polyglycerin with a fatty acid. The average degree of polymerization with polyglycerin is usually from 6 to 12, preferably from 10 to 12. The constituent fatty acid is selected from unsaturated fatty acids having 12 to 22 carbon atoms, and preferably has 18 to 22 carbon atoms. Examples of such fatty acids include oleic acid, linoleic acid, linolenic acid, erucic acid and the like, with oleic acid being preferred. These fatty acids can be used for two purposes.
Although a combination of more than one kind can be used, it is preferable that 70% or more of the constituent fatty acids is oleic acid.

[0006] The polyglycerin fatty acid ester group of the present invention
The cloud point of the product is 8% by weight Na_Two SO _Four Single in aqueous solution
The cloud point of the solution is 65-90 ° C. Cloud point
Sets the cloud point of polyglycerin fatty acid ester
The method used for processing is disclosed in Japanese Patent Application Laid-Open No. 9-157386.
And the benefits are explained as follows:
You. Various chemical analysis methods have been used for PoGE analysis.
Has been used. For example, the degree of esterification and residual fatty acids
The acid value, ester value and hydroxyl value are often
The amount of soap or residual catalyst used is often used.
Evaluation method by analysis of ignition residue for
Was.

The PoG skeleton of the hydrophilic portion in PoGE is a composition having a distribution of the degree of polymerization because it is a polycondensate of glycerin. Not only linear polymers but also branched polymers and cyclic polymers can be used. include. In general, PoG increases in viscosity with an increase in the degree of polymerization, and it is very difficult to purify such as separating a cyclic polymer from a polycondensate. Therefore, a reaction product obtained by esterifying a hydroxyl group of PoG with fatty acids is used. The product PoGE is usually a composition comprising PoGE of various esterification degrees having different PoG skeletons and unreacted PoG.
Further, the esterification reaction product has soaps as by-products generated in the reaction between the alkali catalyst used in the reaction and the fatty acids as the raw materials, and when the esterification reaction is insufficient and when the stoichiometric amount is exceeded. When fatty acids are used in excess, unreacted fatty acids may be included. PoG like this
Since E is a complex mixture, for example, even if the average esterification degree of PoGE is similar or the same, physical properties such as emulsification stability may be remarkably different, and conventional esterification degree such as average esterification degree and unreacted PoG However, physical properties could not be sufficiently grasped only by the chemical analysis method described above, and inconvenience occurred in the physical property evaluation method.

As a method for evaluating the physical properties of a surfactant other than the above-mentioned chemical analysis, for example, a method using a cloud point in a polyoxyethylene-based nonionic surfactant derived from ethylene oxide or the like is known (Oil Glossary Dictionary). : Japan Oil Chemistry Association (ed by Koshobo). Generally, the cloud point is defined as the temperature at which a nonionic surfactant aqueous solution derived from ethylene oxide separates into two phases due to an increase in temperature and becomes inhomogeneous. When the temperature decreases, the system becomes homogeneous again. (Fat and Glossary Dictionary). In polyoxyethylene surfactants, there is a correlation between the cloud point and the average degree of polymerization of the polyoxyethylene chain that is a hydrophilic group, and the average degree of polymerization of polyoxyethylene ethylene oxide increases and the hydrophilicity increases. It is known that the cloud point increases as it becomes. When producing the desired surfactant, the cloud point was measured and the reaction conditions were selected so that the degree of addition polymerization of ethylene oxide was within an appropriate range. It has been described that such a manufacturing operation was possible because the hydrophilicity of the ether groups present in the ethylene oxide polymer of such surfactants decreased with increasing temperature.

On the other hand, in PoGE, since the hydrophilic portion is a polycondensate of glycerin, unlike the polyoxyethylene chain, not only a hydroxyl group and an ether group are present at the same time, but also the presence of the hydroxyl group causes branch condensation and cyclic condensation. Polycondensation has occurred and the composition is extremely complicated.
Although it was difficult to measure the cloud point of GE, it is difficult to prepare a homogeneous aqueous solution by adding salts and / or polyhydric alcohols to PoGE and raise the temperature of the aqueous solution to form a heterogeneous aqueous solution. The cloud point of PoGE can be measured. Even in the case of PoGE in which a difference does not appear clearly by a chemical analysis method such as the analysis of the acid value, ester value, hydroxyl value, and residue on ignition, the difference can be made clear in the cloud point. In addition, since there is a strong correlation between the functions such as emulsifying ability and solubilizing ability and the cloud point, it is very useful to use the cloud point for PoGE product management (Toshiya Katsuragi, NEWSLETTER, 23 (1), 10 (199
8)).

As a method of measuring the cloud point, it is usually necessary to measure the polyglycerin fatty acid ester after dissolving it in a 1 to 30% by weight sodium chloride or sodium sulfate solution. The conditions depend on the solubility of the target sample. Although different, in the case of the present invention, first, the polyglycerin fatty acid ester composition is dispersed in an 8% by weight aqueous solution of sodium sulfate so as to be 1% by weight, and stirred while heating to obtain a uniform aqueous solution. Then, the obtained aqueous solution of polyglycerol fatty acid ester is heated to 2 to 5 ° C at an arbitrary temperature of 0 ° C or more and 100 ° C or less.
The mixture is shaken and agitated, and the polyglycerol fatty acid ester is separated as an oil or a gel. This non-uniform state is called "cloud point"
In the present invention, the temperature at that time is obtained. If the temperature is lower than 0 ° C., the temperature is lower than the melting point of ice, and if it is higher than 100 ° C., the temperature is higher than the boiling point of water.

The polyglycerol fatty acid ester composition of the present invention has a 1% by weight solution in an 8% by weight aqueous sodium sulfate solution having a cloud point of 65 to 90 ° C. Cloud point 6
It was found that when the temperature is lower than 5 ° C., the hydrophobicity becomes high, it is difficult to form a stable fine emulsion composition, and the transmittance of the emulsion composition decreases. In addition, PoGE having a cloud point of more than 90 ° C. cannot be obtained unless POG having a very high degree of polymerization is used as a raw material unless synthesized with a very small ratio of fatty acid to PoG charged. In such PoGE, the amount of residual PoG in the product increases, the net PoGE amount decreases, and the emulsifying ability may decrease. The content of the fatty acid alkali metal salt (soap) in the polyglycerin fatty acid ester composition of the present invention is 0.1%.
It is 2% by weight or less, preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and 0.001% by weight or more. If the soap content is large, it is not possible to obtain a flavorful O / W (oil-in-water) fine emulsion.

The specific POGE composition of the present invention can be produced by suppressing the amount of the sodium catalyst during the esterification reaction to a small amount and reacting at a relatively high temperature for a long time.
Specifically, in a direct esterification reaction between polyglycerin and a fatty acid, 0.001 to 0.025
A very small amount of alkali catalyst is used at a reaction temperature of 200 to 300 ° C., preferably a reaction temperature of 200 to 240 until the conversion of fatty acids reaches at least 70%.
C., and the reaction temperature is further raised by 20 to 60 ° C. to carry out the reaction. The amount of the alkali catalyst used in the present invention is 0.001 to 0.025% by weight, preferably 0.002 to 0.02% by weight, based on the sum of the raw materials, polyglycerin and fatty acid. When the amount of the alkali catalyst used is less than the above range, the esterification reaction does not easily proceed. If the amount used exceeds the above range, problems such as coloring of the product and polymerization of the raw material PoG occur. Examples of the alkali catalyst include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide and the like. The reaction is usually carried out while charging a polyglycerin, a fatty acid, and a catalyst in a stirred tank type reactor, heating the mixture to a predetermined temperature while stirring, and distilling the generated water out of the reaction system. During a series of reactions, it is preferable to pass an inert gas such as nitrogen through the gas phase of the reactor.

The polyglycerin fatty acid ester composition of the present invention can maintain a high transmittance even under acidic conditions in an emulsifying use, and can produce a fine flavored fine emulsion composition. The polyglycerin fatty acid ester composition of the present invention comprises an oil-soluble flavor, oil-soluble pigments, animal and vegetable oils and fats, medium-chain saturated fatty acid triglycerides, oil-soluble vitamins, antioxidants, and edible properties of functional fatty acids such as DHA. It can be used to emulsify oily materials in water.

An emulsified composition obtained by emulsifying an edible oily material with the polyglycerol fatty acid ester composition of the present invention (usually, the edible oily material is 4 to 20% by weight, and if the final emulsified composition needs to be transparent, 4-5% by weight, PoGE
Foods and beverages such as soft drinks, protein drinks, fruit juice drinks, soy milk drinks, fermented milk drinks, energy drinks, etc .; mousses, cakes, chocolates, candy, chewing gum and the like. Sweets;
Fruit jams and preserves; fish paste products such as kamaboko, hampan, chikuwa, fish meat ham and sausage; meat products such as ham, bacon, corn beef; pickles, tsukudani, delicacy foods; sauces; This makes it possible to produce a food or drink (final emulsified composition) having a long-term stable flavor and appearance such as aroma, flavor, and color tone. Usually, the PoGE composition in the final emulsified composition is 0.004 to 0.040% by weight.

[0015]

EXAMPLES Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. The fatty acid alkali metal salt content and the cloud point of the polyglycerin fatty acid ester composition used in this example were measured by the following methods. [Content of fatty acid alkali metal salt (soap) in PoGE]
It was measured according to the following method in accordance with the standard method for analyzing fats and oils (established by Japan Oil Chemicals Agreement). 1) About 10 g of the reaction product was precisely weighed in a tall beaker, and T
HF / ethanol / water = 10/2/1 VOL% solution 10
Dissolve in 0 ml. 2) Titrate with an automatic titrator (GT-05, manufactured by Mitsubishi Chemical Corporation). First, an ethanolic solution of N / 10 hydrochloric acid is excessively titrated, and then a back titration is performed with an ethanolic solution of N / 10 sodium hydroxide, and the equivalent point is determined from the inflection point of the titration value-potential curve. 3) Calculate the total acid / total alkali amount in the sample from the following formula based on both titration values, and confirm that all alkali metals in the product are fatty acid salts from total acid> total alkali. Total alkali amount (mol / g) = titration (ml) x
0.1 × titer × 1000 × sample (g) Total acid amount (mol / g) = (second titer−first titer) (ml) × 0.1 × titer × 1000 × sample (g) 4) Calculate the soap content from the total alkali content. Soap content (wt%) = total alkali amount (mol / g) x
Soap molecular weight x 100

[Measurement of Cloud Point of PoGE] PoGE was dissolved in a previously prepared 8% by weight aqueous sodium sulfate solution so that the PoGE concentration became 1% by weight, and the solution was sealed in a glass tube. After heating and stirring the glass tube to make the solution uniform, the glass tube is immersed in a constant temperature bath set at a predetermined temperature, left for several minutes to 1 hour, and then visually observed for the separation of the solution in the glass tube. went. The temperature of the constant temperature bath was raised in increments of 5 ° C., and the above method was repeated.
The cloud point was defined as the intermediate temperature between the temperature at which the GE separated and the solution became cloudy and the maximum temperature at which the solution was uniform.

Production Example 1 Production Example of PoGE-A First, PoG (average degree of polymerization: 10) was placed in a 2-liter reaction vessel equipped with a stirrer, thermometer, heating jacket, gas inlet, and raw material inlet. 1200g was charged.
Then, the same reaction vessel was charged with oleic acid (purity 82%) and a 10% aqueous sodium hydroxide solution. The amount of oleic acid charged was such that the oleic acid / PoG molar ratio was 0.7 / 1. The amount of sodium hydroxide is P
0.0025% by weight based on the total amount of oG and oleic acid
And The internal temperature was raised to 240 ° C. at normal pressure under a nitrogen stream, and the reaction was carried out at this temperature for 3 hours.
The temperature was raised to 0 ° C., and the reaction was carried out at this temperature for 4 hours. After completion of the reaction, the internal temperature was cooled to room temperature to obtain a liquid polyglycerin oleate (PoGE-A). About the obtained reaction product, the cloud point and the soap content were measured by the above methods. The results are shown in Table 1.

Production Example 2 Production Example of PoGE-B Polyglycerin oleate (PoGE-B) was obtained in the same manner as in Production Example 1 except that the oleic acid / PoG molar ratio was changed to 1/1. About the obtained reaction product, the cloud point and the soap content were measured by the above methods. The results are shown in Table 1. [Production Example 3] Production Example of PoGE-C To PoGE-A obtained in Production Example 1, 1% of sodium oleate was added and melt-mixed to obtain polyglycerin oleate (PoGE-C). Obtained.
About the obtained reaction product, the cloud point and the soap content were measured by the above methods. Table 1 shows the results.

Example 1 To 120 g of glycerin was added and dissolved 8 g of PoGE-A as a polyglycerin fatty acid ester, and 8 g of MCT (middle chain triglyceride) was added.
Stir at 000 rpm for 30 minutes, 136 g of emulsified composition
I got 0.17 g of this emulsified composition was mixed with 19.83 g of a 0.1% aqueous citric acid solution. The transmittance of the diluted solution was measured at 650 nm at room temperature using UV-1200 manufactured by Shimadzu. In addition, three expert panelists performed a sensory evaluation test on the diluted solution.

Comparative Example 1 An emulsified composition was prepared in the same manner as in Example 1 except that PoGE-B was used as the polyglycerin fatty acid ester, and a diluted solution of an aqueous citric acid solution was prepared. The measurement and the sensory evaluation test were performed. Comparative Example 2 Po as a polyglycerin fatty acid ester
After preparing an emulsified composition in the same manner as in Example 1 except that GE-C was used, a diluted solution of a citric acid aqueous solution was prepared, and a transmittance measurement and a sensory evaluation test were similarly performed. Table 1 shows the results of Example 1 and Comparative Examples 1 and 2.

[0021]

[Table 1]

From the results shown in Table 1, it can be seen that the diluent of Example 1 has a high transmittance and no problem in flavor. On the other hand, it can be seen that the diluted solution of Comparative Example 1 has no problem in flavor, but has a low transmittance. It can be seen that the diluent of Comparative Example 2 has a high transmittance, but exhibits bitterness that is considered to be derived from the soap component and has a problem in flavor.

[0023]

Industrial Applicability The polyglycerin fatty acid ester composition of the present invention has an excellent effect of excellent O / W type fine emulsification even under acidic conditions and provides a flavorful emulsion composition.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4B026 DC01 DG20 DK01 4B035 LC01 LG07 LG09 LG12 LK02 LK11 LK13 4D077 AB08 AB11 AB12 AC03 BA01 BA03 BA07 CA03 CA13 CA15 DC02Z DC16Z DC27Z DD08Y DD36Y DE02Y DE07Y DE08Y BB03 BA034 BC03 BC10 BC13 BC23 DA02 DA09 DA24 DA30 EA11 EA40

Claims (5)

[Claims] A constituent fatty acid is an unsaturated fatty acid having 12 to 22 carbon atoms, a 1% by weight solution in an 8% by weight aqueous solution of Na ₂ SO ₄ has a cloud point of 65 to 90 ° C., and a fatty acid alkali. A polyglycerin fatty acid ester composition having a metal salt content of 0.2% by weight or less. 2. The method according to claim 1, wherein the content of the alkali metal salt of fatty acid is 0.1%.
The polyglycerin fatty acid ester composition according to claim 1, wherein the content is not more than 05% by weight. 3. The polyglycerol fatty acid ester composition according to claim 1, wherein 70% or more of the constituent fatty acids is oleic acid. 4. An emulsified composition comprising the polyglycerin fatty acid ester composition according to claim 1. Description: 5. The emulsified composition according to claim 4, wherein the emulsified composition is obtained by emulsifying an oil-soluble flavor, an oil-soluble pigment, an antioxidant or a functional fatty acid.