JPH0987231A - Method for producing organic acid monoglyceride with reduced free organic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organic acid monogyceride of reduced free organic acid content useful as an emulsifier for beverage and the like and a quality improver for food products by esterifying an organic acid with a monoglyceride, while keeping the water content of the reaction system lower than a specific level by dehydration under reduced pressure. SOLUTION: In the esterification reaction between (A) an organic acid and (B) a monoglyceride, or when an organic acid ester is prepared from the component A, (C) fatty acid and (D) glycerol, the water content in the reaction system is controlled lower than 0.1wt.%, preferably lower than 0.05wt.% to reduce the free organic acid lower than 1.5wt.%, preferably lower than 1.0wt.% to prepare the objective organic acid monoglyceride. The water content is most simply adjusted by setting the temperature conditions of 110-200 deg.C under reduced pressure, additionally blowing steam or an inert gas into the system to remove unreacting organic acid or organic acid anhydride.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for reducing free organic acids in ester compounds containing organic acid monoglycerides.

[0002]

BACKGROUND OF THE INVENTION An ester compound containing an organic acid monoglyceride is generally obtained by subjecting an organic acid and a monoglyceride to an esterification reaction or obtaining an esterified product of an organic acid from an organic acid, a fatty acid and glycerin. It is manufactured as a food additive, is used as a food additive, is used as many emulsified products, as a quality improver emulsifier used in bread making, and is used for shortening and the like. However, such an organic acid monoglyceride has a sour taste and an astringent taste, and there are problems that the use and the addition amount are limited. In particular, the expression of sourness when used as an emulsifier for coffee beverages, the expression of sourness when dissolved in oil itself, and the like are likely to be problems.

[0003]

The inventors of the present invention have analyzed the components responsible for the deterioration of the flavor of organic acid monoglycerides and found that the (free) organic acid contained in the reaction product is the main cause. Do you get it. That is, although several weight% of water is contained in the fatty acid monoglyceride as a reaction raw material, it has been considered that the water content is almost 1 weight% or less because it is dissolved at around 100 ° C. before the reaction. In fact, it was considered that there was no difference in the amount of free organic acid reacted under such a low water content, and almost no study was conducted. However, it was clarified that the amount of free organic acid after the reaction could be further reduced by reducing the water content of the reaction system to 0.1% by weight or less by the dehydration under reduced pressure, and the organic acid with a good flavor (reduced sourness and astringency) was obtained. It has been clarified that a monoglyceride composition can be obtained, and the inventors of the present invention industrially (in a free manner) by an inexpensive or convenient method.
The method of removing the organic acid was investigated and the present invention was completed. That is, the present invention, when performing an esterification reaction of an organic acid and a monoglyceride, or when producing an esterified product of an organic acid from an organic acid, a fatty acid, and glycerin, the water content in the reaction system is 0.1% by weight or less (preferably 0.05% by weight). (Below), the reaction is carried out, and it is contained in the reaction product (free).
A method for producing an organic acid monoglyceride characterized by reducing the amount of an organic acid to 1.5% by weight or less (preferably 1.0% by weight or less), an esterification reaction of an organic acid and a monoglyceride, or an organic acid, a fatty acid and glycerin An esterified product of an organic acid is prepared and then dried at 110 ° C to 200 ° C under reduced pressure.
Organic acid monoglyceride characterized by removing unreacted organic acid or organic acid anhydride compound under the temperature condition of ℃, and reducing the amount of free organic acid contained in the reaction product to 1.5% by weight or less. , An organic acid and a monoglyceride are subjected to an esterification reaction, or an esterified product of an organic acid is produced from an organic acid, a fatty acid and glycerin, and then steam or an inert gas is generated under reduced pressure at a temperature of 110 ° C to 200 ° C. Production of organic acid monoglyceride characterized by removing unreacted organic acid or organic acid anhydride compound while blowing a liquefied gas to reduce the amount of free organic acid contained in the reaction product to 1.5% by weight or less. Method, esterification reaction of organic acid and monoglyceride, or production of esterified product of organic acid from organic acid, fatty acid and glycerin, and then dispersing reaction product in water Or disperse or emulsify in water after dissolving in an organic solvent and distribute the free organic acid in water,
The amount of free organic acid contained in the reaction product is 1.5% by weight.
A method for producing an organic acid monoglyceride characterized by reducing the amount to the following. In the present invention, it is also possible to appropriately combine the above four methods. In the present invention, the organic acid monoglyceride also includes a polymerized derivative produced by an excessive reaction of the organic acid and the monoglyceride.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. As a method for producing an organic acid monoglyceride, it is common to carry out a condensation reaction from an acid anhydride of an organic acid and a monoglyceride, and the reaction apparatus is used to remove (free) organic acid or reduce the pressure. Below, it is considered that the method of blowing the water vapor or the inert gas to remove the (free) organic acid is the simplest. In the present invention, a condensation reaction between an acid anhydride of an organic acid and a monoglyceride is carried out,
Regarding the reaction molar ratio of acid anhydride / monoglyceride of organic acid at that time, when the molar ratio is small, that is, when the acid anhydride of organic acid is small relative to the monoglyceride, the amount of (free) organic acid after the condensation reaction is small. However, the purity of the target organic acid monoglyceride is lowered. On the other hand, if the molar ratio is increased, that is, the amount of the acid anhydride of the organic acid is larger than that of the monoglyceride, a large amount of unreacted organic acid remains, which is not preferable. From this, the reaction molar ratio of acid anhydride of organic acid / monoglyceride is preferably 0.7 / 1 to 1.1 / 1, and more preferably 0.85 / 1 to 1.05 / 1. In the present invention, the heating conditions under reduced pressure are preferably 110 to 200 ° C, more preferably 120 to 150 ° C. Further, the lower the degree of decompression, the higher the efficiency and the shorter the processing time. However, including the problem of the apparatus, it is preferably 50 torr or less, more preferably 30 torr or less, further preferably 5 torr or less. Of course, good results can be obtained by using a thin film deodorizer or the like. Examples of the organic acid of the organic acid monoglyceride referred to in the present invention include citric acid, succinic acid, tartaric acid, and diacetyltartaric acid, and particularly effective for succinic acid. Further, the fatty acid with monoglyceride has 2 to 24 carbon atoms, and particularly refers to a commonly used fatty acid having 12 to 24 carbon atoms.

As the method of washing with water, the simplest method is to grind and wash with water (preferably with 5 times or more the weight of water) when the organic acid monoglyceride after reaction is solid. It is more efficient to raise the temperature during water washing to a temperature at which the organic acid does not dissolve. If the organic acid monoglyceride is a liquid or viscous substance, it is possible to wash it as it is, but since it is easily emulsified, it is dissolved in an organic solvent (water-insoluble) such as hexane and then washed with water. It is preferable to carry out. The organic acid monoglyceride in that case is 10 to 70% by weight in the organic solvent, and particularly preferably 20
It can be carried out in an amount of up to 40% by weight.

The organic acid monoglyceride composition thus obtained is used as a beverage, margarine, spread, butter cream, whipped cream, emulsifier of O / W or W / O emulsion of ice cream Tang, and bread. , Noodles, spaghetti, cake Tang protein, starch-based food properties and texture improver, shortening,
There are emulsifiers and the like that impart a defoaming effect and a releasing effect to fats and oils. Regarding the use of the organic acid monoglyceride composition in the food, the composition may be used as it is, but it is mixed with other powder such as starch, protein and cellulose to improve dispersibility and workability. Formulated products can also be used. Further, shortening or a form dispersed or dissolved in oil can also be used.

[0007]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 Monoglyceride (manufactured by Kao Corporation, trade name; T-95) 10
00 g was dissolved by heating at 80 ° C., dehydration treatment was performed under a reduced pressure of 5 Torr for 2 hours, and the water content was adjusted to 0.07 wt%. Next, succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name; RIKACID S)
252 g of A) was added, the temperature was raised from 80 ° C. to 110 ° C. at 10 ° C./hour, the esterification reaction was terminated, and the succinic acid monoglyceride composition of the present invention was obtained. As a result of the analysis, the amount of (free) succinic acid was 1.3% by weight. The amount of (free) succinic acid is measured by the following method.

[Method for Measuring Amount of (Free) Succinic Acid] A sample is dissolved in toluene (warming if necessary), transferred to a separating funnel, distilled water is added, and free succinic acid is extracted (when emulsifying). Was destroyed by heating), and this extraction operation was repeated twice. In addition, as a blank test, the same extraction operation was performed without adding the sample. The amount of (free) succinic acid was calculated by titrating the extract with phenolphthalein as an indicator and using 1/50 normal sodium hydroxide whose titer was calculated by standardizing with succinic acid in advance.

Example 2 Monoglyceride (Kao Corporation, trade name: O-95R)
1000 g was dissolved by heating at 80 ° C., and dehydration treatment was performed under a reduced pressure of 10 Torr for 2 hours to adjust the water content to 0.02% by weight. Next, succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name; RIKACID S)
280 g of A) was added and the temperature was raised from 80 ° C. to 120 ° C. at 10 ° C./hour to complete the esterification reaction. The obtained succinic acid monoglyceride composition was steam-deodorized for 3 hours under the conditions of 150 ° C., 5 Torr, and a steam amount of 1% by weight / hour (versus succinic acid monoglyceride) to obtain a succinic acid monoglyceride composition of the present invention. As a result of the analysis, the amount of (free) succinic acid was 0.6% by weight.

Example 3 Monoglyceride (manufactured by Kao Corporation, trade name: T-95) 10
00 g was dissolved by heating at 80 ° C. and dehydrated under reduced pressure of 10 Torr for 3 hours to adjust the water content to 0.05% by weight. Next, succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name; RIKACID S)
280 g of A) was added and the temperature was raised from 80 ° C. to 120 ° C. at 10 ° C./hour to complete the esterification reaction. The obtained succinic acid monoglyceride composition was subjected to steam deodorization for 5 hours under the conditions of 120 ° C., 15 Torr and a water vapor amount of 1% by weight / hour (vs. succinic acid monoglyceride) to obtain a succinic acid monoglyceride composition of the present invention. As a result of the analysis, the amount of (free) succinic acid was 0.9% by weight.

Example 4 Monoglyceride (Kao Corporation, trade name: O-95) 10
00 g was dissolved by heating at 80 ° C. and dehydrated under reduced pressure of 10 Torr for 3 hours to adjust the water content to 0.04% by weight. Next, succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name; RIKACID S)
280 g of A) was added and the temperature was raised from 80 ° C. to 120 ° C. at 10 ° C./hour to complete the esterification reaction. Nitrogen gas was blown into the obtained succinic acid monoglyceride composition while maintaining 120 ° C. and 5 Torr to obtain a succinic acid monoglyceride composition of the present invention. As a result of the analysis, the amount of (free) succinic acid was 0.8% by weight.

Example 5 Monoglyceride (trade name; T-95, manufactured by Kao Corporation) 10
00 g was dissolved by heating at 80 ° C. and dehydrated under reduced pressure of 10 Torr for 3 hours to adjust the water content to 0.04% by weight. Next, succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name; RIKACID S)
280 g of A) was added and the temperature was raised from 80 ° C. to 110 ° C. at 10 ° C./hour to complete the esterification reaction. The obtained succinic acid monoglyceride composition was solidified by cooling, crushed to 300 μm or less, and the crushed product was washed 3 times with 5 times amount of water and then dried to obtain the succinic acid monoglyceride composition of the present invention. It was As a result of the analysis, the amount of (free) succinic acid was 0.6% by weight.

Comparative Example 1 Monoglyceride (Kao Corporation, trade name: O-95R)
1000 g was melted by heating at 80 ° C. This water content is 0.3% by weight
Met. Next, add 280 g of succinic anhydride (Shin-Nippon Rika Co., Ltd., trade name: RIKACID SA), and add from 80 ° C to 10 ° C.
The temperature is raised to 110 ° C per hour / hour to complete the esterification reaction,
A succinic acid monoglyceride composition was obtained. The amount of (free) succinic acid in this product was 2.8% by weight.

Comparative Example 2 Monoglyceride (trade name; T-95, manufactured by Kao Corporation) 10
00 g was melted by heating at 80 ° C. The water content was 0.5% by weight. Next, 252 g of succinic anhydride (manufactured by Shin-Nippon Rika Co., Ltd., trade name: RIKACID SA) was added, and 80 ° C to 10 ° C /
The temperature was raised to 120 ° C. over time, the esterification reaction was completed, and a succinic acid monoglyceride composition was obtained. The amount of free succinic acid in this product was 3.0% by weight.

Example 6 Using the succinic acid monoglycerides obtained in Examples 1-5 and Comparative Examples 1-2, a coffee whitener was prepared according to the formulation shown in Table 1 and the production method shown in FIG. A sensory test and stability evaluation were performed. Table 2 shows the results. The sensory test of the coffee whitener was performed as follows. [Sensory test of coffee whitener] A sensory test of the flavor and sourness of the coffee whitener was conducted by 20 panelists. Regarding the flavor, the number of people who answered that the flavor was good among the 20 people and the sourness were 20 The number of people who answered that they felt sour in their name was shown. The stability was evaluated by storing the product at 40 ° C. for 24 hours, observing the emulsified state, and if no change was observed in comparison with the state immediately after the production, it was judged as acceptable.

[0016]

[Table 1]

* 1 Hardened palm olein IV = 52 * 2 Hardened rapeseed IV = 80

[0018]

[Table 2]

Example 7 Using the succinic acid monoglyceride compositions obtained in Examples 1, 3, 5 and Comparative Example 2, bread was produced by the following method, and a sensory test of its flavor was conducted. The results are shown in Table 3. (Preparation of medium-sized dough) Medium-sized mixed material (strong flour 1400 parts by weight, yeast 40 parts by weight, yeast food 2 parts by weight, water 80
0 part by weight and 6 parts by weight of each succinic acid monoglyceride composition pulverized to 200 μm or less) were put into a ball, and the materials were kneaded using a vertical mixer (10 coats, hook, manufactured by Kanto Mixer Co., Ltd.). (Low speed 2 minutes, medium high speed 1 minute) to prepare a medium seed dough. The kneading temperature of the medium-sized dough was set to 24 ° C. Next, the obtained intermediate dough was fermented for 4 hours and 30 minutes under the conditions of a temperature of 27.5 ° C. and a relative humidity of 75% (final fermentation product temperature: 29.5
° C). (Preparation of main kneaded dough) Next, this kneaded dough compounding material (600 parts by weight of strong wheat flour, 40 parts by weight of salt, 40 parts by weight of sugar, 40 parts by weight of skim milk powder, 500 parts by weight of water) was added to the medium-type fermentation dough. Then, the obtained mixture was kneaded (low speed 3 minutes, medium high speed 4 minutes). Then, 100 parts by weight of shortening was added thereto, and the obtained mixture was kneaded (low speed 2 minutes, medium high speed 3 minutes) to obtain a final kneaded dough (dough temperature: about 27.5 ° C.). (Baking of bread) Next, the floor time was set at 27.5 ° C for 20 minutes to recover the dough damaged by the kneading. Then, the dough was divided into pieces, each weighing 450 g. In order to recover the dough that was damaged by the division, a bench time was taken at room temperature for 20 minutes, and then the divided dough was shaped with a moulder. Next, the shaped product was put into a one loaf pan type, put into a proofer set to a temperature of 37.5 ° C. and a relative humidity of 80%, and fermented for 40 minutes. The bread dough thus prepared was baked in an oven at 210 ° C. for 40 minutes to obtain a loaf of bread. still,
The sensory evaluation (flavor, texture) of the bread was performed as follows. [Sensory Evaluation of Bread] Flavor: A total of 20 panelists conducted a sensory evaluation of the flavor and sourness, and the number of those who answered that the flavor was good was shown. Texture: The number of people who answered that the bread was soft among the 20 panelists was shown.

[0020]

[Table 3]

[Brief description of drawings]

FIG. 1 is a process chart showing a method for producing a coffee whitener used in Examples.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsutomu Nishide 20 Kao Stock Company Research Institute, Kamisu-cho, Kashima-gun, Ibaraki Prefecture (72) Inventor Tatsuya Tokunaga 20 Higashi-Fukashi Kabushi-cho, Kashima-gun, Ibaraki Prefecture Kao Stock Company Research Institute

Claims (6)

[Claims] 1. When the organic acid and the monoglyceride are subjected to an esterification reaction, or when an esterified product of the organic acid is produced from the organic acid, the fatty acid and glycerin, the water content in the reaction system is reduced.
A method for producing an organic acid monoglyceride, which comprises reducing the content of free organic acid contained in a reaction product to 1.5% by weight or less by controlling the reaction to be 0.1% by weight or less. 2. An esterification reaction of an organic acid and a monoglyceride, or an esterified product of an organic acid is prepared from an organic acid, a fatty acid and glycerin, and then 110 ° C. to 200 ° C. under reduced pressure.
Organic acid monoglyceride characterized by removing unreacted organic acid or organic acid anhydride compound under the temperature condition of ℃, and reducing the amount of free organic acid contained in the reaction product to 1.5% by weight or less. Manufacturing method. 3. An esterification reaction of an organic acid and a monoglyceride, or an esterified product of an organic acid is produced from an organic acid, a fatty acid and glycerin, and then 110 ° C. to 200 ° C. under reduced pressure.
Under the temperature condition of ° C, unreacted organic acid or anhydrous organic acid compound is removed by blowing steam or an inert gas, and the amount of free organic acid contained in the reaction product is reduced to 1.5.
A method for producing an organic acid monoglyceride, which comprises reducing the content to less than or equal to% by weight. 4. An organic acid and a monoglyceride are subjected to an esterification reaction, or an esterified product of an organic acid is produced from an organic acid, a fatty acid and glycerin, and then the reaction product is dispersed in water or dissolved in an organic solvent and then dissolved in water. A method for producing an organic acid monoglyceride, which comprises dispersing or emulsifying, distributing a free organic acid in water, and reducing the amount of the free organic acid contained in the reaction product to 1.5% by weight or less. 5. The method for producing an organic acid monoglyceride according to claim 1, wherein the organic acid is succinic acid. 6. An emulsifier or a food quality improving agent containing an organic acid monoglyceride and its derivative as a main component, which are produced by the method according to any one of claims 1 to 5.