KR20090021673A - Fat-soluble citric acid, a process for producing the oil and fat containing citric acid produced - Google Patents

Abstract

The present invention is a method for producing fat-soluble citric acid is a first step of mixing citric acid, propylene glycol, HLB 4-5 monoglycerides and polyglycerin fatty acid ester and the second step of reacting the mixture at 60 ℃ under reduced pressure Include. According to the present invention, it is possible to obtain a fat-soluble citric acid which is transparent and stable, suppresses thermal decomposition of the lactose oil and has a synergistic effect of an antioxidant, and is excellent in solubility in fat-soluble systems such as oils and fats while such fat-soluble citric acid is dissolved. It is possible to stabilize the quality of fats and oils and to greatly improve the oxidative stability of milk foods such as noodle and snacks.

Description

Fat soluble cirtic acid, the preparation method approximately and the oil containing the fat soluble citric acid}

The present invention relates to a process for producing fat-soluble citric acid by fat solubilizing citric acid, and a fat or oil containing the produced fat-soluble citric acid.

Since the oxidation of fats and oils changes its flavor and color and lowers the nutritional value, it is important for edible fats and oils to prevent the oxidation. The rancidity of edible oils and fats is due to hydrolysis and automatic oxidation. The change in flavor due to automatic oxidation is caused by decomposition products of hydrogen peroxide produced by oxidation, and for example, propionaldehyde, 2-pentenal, caproaldehyde, acetaldehyde, crotonaldehyde and the like can be obtained from the automatic oxidation of soybean oil.

Antioxidants are effective in prolonging the induction period of automatic oxidation of fats and oils, suppressing the increase in peroxide value of fats and oils, and improving the stability of AOM (active oxygen method). As such antioxidants, synergists such as phosphoric acid, citric acid and vitamin C are used.

Among them, citric acid is a metabolite of plants and animals in nature and is the most organic acid that can be obtained from citrus fruits. And, as one of the polybasic carboxylic acid having a hydroxyl group, it dissolves well in water and ethanol. When microorganisms are cultured using sugar as a substrate, citric acid (citric acid) accumulates in the culture solution, which is called citric acid fermentation. Several culture methods have been studied and now 90% of the world's total citric acid is produced by this fermentation method. As a microorganism causing citric acid fermentation, black mold is usually used. Citric acid can be obtained by fermenting at about 30 ° C. for 7 to 10 days in acid (pH 2 to 3). In addition, citric acid plays an important role in metabolism of higher animals as a component of the TCA circuit. It is also known to promote calcium absorption in the body. It is widely used in food, medicine, and industry as acidic agent, pH adjuster, antioxidant, detergent, astringent, etc., which has a refreshing sour taste, and is also used as analytical reagent. In addition, blood coagulation requires calcium ions, and citric acid is used as a blood coagulation inhibitor because it traps calcium ions.

Citric acid is divided into monohydrate and citric anhydride according to the presence of water molecules. More specifically, citric acid has a water content of 8.8% or less, a melting point of 100 ° C, and anhydrous citric acid has a water content of 0.5. Below%, melting | fusing point is 153 degreeC.

As mentioned above, citric acid is a hydrophilic substance, which is insoluble in oils and fats, and thus is used as an oxidative stabilizer because it is added only within about 3% at high temperature. That is, citric acid is insoluble in oil-soluble substances such as oil, so it is very difficult to use it in oil-soluble preparations, and if it is simply dissolved in alcohol and ethanol, citric acid precipitates and sinks over time, resulting in poor transparency and relatively poor storage stability. There is a disadvantage in use, and when the content of citric acid is increased to 3% or more, there is a problem that it is difficult to manufacture a transparent fat-soluble liquid material.

Therefore, until now, the technology has been citric acid is bound to fatty acids to produce an ester form and fat-soluble. However, the melting point is higher than 70 ℃, it is difficult to use in high-speed production line, the purity is low, it is difficult to expect the functionality of citric acid. Representatively, a technique of fat solubilization using a citric acid ester production method is disclosed in Korean Patent Publication No. 1986-0007192, 2004-083589, 2002-187870, 2001-048840, and the like.

That is, citric anhydride and hydrous citric acid have a melting point of 153 ° C. and 100 ° C., respectively, so that it is difficult to fat-soluble, and a widely used method is to prepare citric acid monoglyceride by chemically and enzymatically combining citric acid with fatty acid. Getting angry However, citric acid monoglycerides prepared by this method can be prepared only in the solid form melting point above 70 ℃ as an emulsifier, especially in the winter is very inconvenient to use in the factory and the purity of citric acid is very low. In addition, citric acid is combined with fatty acids may weaken the stabilization power by citric acid.

Another method of using citric acid in oil is to add it in the deodorization process during the oil refining process. The deodorization process is usually a process that volatilizes and removes odor at a high temperature of 250 ° C. It melts and mixes with oil during deodorization process and evaporates only distilled water instantly to dissolve citric acid in oil. In this way, citric acid cannot be used more than 30ppm because citric acid melts instantaneously but some precipitates, which requires additional filter equipment in the line. In addition, since 30 ppm of citric acid is dispersed in oil, distilled water must be used in a large amount to dissolve, thereby promoting hydrolysis of oil, thereby increasing the acid value of oil, thereby degrading quality.

In order to solve the above problems, the present invention is transparent and stable, does not precipitate citric acid, is not turbid by moisture, transformed into a fat-soluble as a dissolved state of citric acid as a dissolved state to inhibit thermal decomposition of oil and oil-soluble components and A fat-soluble citric acid having an effect of improving the oxidation stability of a milk product, a manufacturing method thereof, and an oil-containing fat-soluble citric acid are provided.

(1) The present invention is a method for producing fat-soluble hydrous citric acid 40-55% by weight of hydrous citric acid, 25-35% by weight of propylene glycol, 10-15% by weight of HLB 4-5 levels of monoglycerides and 10% by weight And a second step of mixing the polyglycerol fatty acid ester in% and reacting the mixed solution at 60 ° C. under reduced pressure.

(2) The present invention also provides a method for preparing a fat-soluble anhydrous citric acid, 40 to 60% by weight of citric anhydride, 25 to 35% by weight of propylene glycol, 5 to 15% by weight of HLB 4-5 monoglycerides and 10 And a second step of mixing the weight percent polyglycerin fatty acid ester and the second step of reacting the mixed solution at 60 ° C. under reduced pressure.

(3) Preferably, in another embodiment of the present invention, the first step and the second step are characterized in that they occur simultaneously.

(4) More preferably, in the method for producing fat-soluble citric acid of the present invention, the monoglyceride of the HLB 4-5 level is glycerin monostearate.

(5) Also preferably, in the method for producing fat-soluble citric acid of the present invention, the polyglycerol fatty acid ester is diglycerin monooleate.

(6) In the fat-soluble citric acid production method of the present invention, the reduced pressure is characterized in that 160 ~ 360mmHg.

(7) Provided is an oil-fat containing fat-soluble citric acid which adds 0.05 to 0.20% by weight of fat-soluble citric acid prepared in some embodiments of the present invention to fats and oils.

Decompression reaction is a method in which food ingredients are placed in a reaction tank, followed by continuous supply of heat under reduced pressure to maintain boiling state of water. The products produced after decompression reaction boil water even at low temperature due to the effect of decompression and sufficient reaction energy is transmitted. Can be. As mentioned above, the melting point of citric acid is very high at 153 ℃ for anhydrous citric acid and 100 ℃ for hydrous citric acid.It is difficult to dissolve citric acid and react at room temperature, and the reaction temperature of emulsifier required for fat solubilization of citric acid becomes very high to cause separation. do. In general, the emulsification reaction is usually carried out at 70 ℃ or less, when the emulsification reaction is carried out at 70 ℃ or more, the film is formed or the stability of the emulsion is a problem of precipitation of the emulsifier occurs or oil separation occurs.

In addition, in order to fatify citric acid, the water content of the reactants should be close to zero within 0.05%, but the water content of the reactants cannot be reduced to within 0.05% under normal temperature reaction conditions. If the water content is 0.05% or more, the phenomenon of clouding occurs within several hours. Due to the effect of decompression, the pressure-reducing tank boils water even at low temperatures, so that the emulsification process is generally performed at a relatively low temperature of 65 to 70 ° C. An irreversible reaction of citric acid may occur and the problem of precipitation may be solved.

It is preferable to use the pressure reduction reactor of 160-360 mmHg as a pressure reduction reactor. If it exceeds 360mmHg, the degree of vacuum is low to put a lot of citric acid, and the problem of precipitation and sinking or turbidity occurs. If it is less than 160mmHg, the viscosity is increased and flowability is notably reduced. The temperature was found to be suitable for 60 ℃ ~ 70 ℃.

According to the present invention, fats and oils containing fat-soluble citric acid can be obtained which is transparent and stable, suppresses thermal decomposition of lactose oil and has synergistic effect of antioxidant. In addition, the fat-soluble citric acid of the present invention is present in a state in which citric acid is dissolved, but excellent in solubility in fat-soluble systems such as lactose oil to stabilize the quality of the lactose oil and greatly improve the oxidation stability of the lactose foods such as the noodle and snacks.

The following examples are intended to illustrate the present invention in more detail, and these examples do not limit the technical scope of the present invention.

<Comparative Example 1-2>

After heating 175 g of alcohol and raising to 40 ° C., 200 g of hydrous citric acid and citric anhydride were added thereto, and the mixture was vigorously stirred at 80 ° C. for 20 minutes. Sunsoft-818 after stirring ^TM ) 125 g was added and stirred at 80 ° C. for 30 minutes to prepare fat-soluble citric acid. The prepared fat soluble citric acid was added to the fat or oil to produce a fat containing fat soluble citric acid. As a result of observing the prepared fats and oils, the separation of citric acid and fats and oils due to the emulsification problem and the foaming were not stable.

<Comparative Example 3-4>

After heating 175 g of alcohol and raising to 40 ° C., 200 g of hydrous citric acid and citric anhydride were added thereto, and the mixture was vigorously stirred at 80 ° C. for 20 minutes. Sunsoft-818 after stirring 75 g of ^TM ) was added followed by 50 g of Arabic gum (Acasia gum-AA ^TM ) and stirred at 80 ° C. for 30 minutes to prepare fat-soluble citric acid. The prepared fat soluble citric acid was added to the fat or oil to produce a fat containing fat soluble citric acid. As a result of observing the prepared fats and oils, the separation of citric acid and fats and oils due to the emulsification problem and the foaming were not stable.

<Comparative Example 5-6>

After heating 175 g of alcohol and raising to 40 ° C., 200 g of hydrous citric acid and citric anhydride were added thereto, and the mixture was vigorously stirred at 80 ° C. for 20 minutes. Sunsoft-818 after stirring After adding 75 g of ^TM ), 50 g of soluble dextrin (emulstar-30A ^™ , Japan) was added and stirred at 80 ° C. for 30 minutes to prepare a fat-soluble citric acid. The prepared fat soluble citric acid was added to the fat or oil to produce a fat containing fat soluble citric acid. As a result of observing the prepared fats and oils, the separation of citric acid and fats and oils due to the emulsification problem and the foaming were not stable.

<Comparative Example 7-8>

After heating 175 g of alcohol and raising to 40 ° C., 200 g of hydrous citric acid and citric anhydride were added thereto, and the mixture was vigorously stirred at 80 ° C. for 20 minutes. Sunsoft-818 after stirring ^TM) followed by the addition of 75g were added to glycerol fatty acid ester (Almax-1800 ^TM) 50g and stirred at 80 ℃ for 30 minutes to prepare a fat soluble citric acid. The prepared fat soluble citric acid was added to the fat or oil to produce a fat containing fat soluble citric acid. As a result of observing the prepared fats and oils, foaming and citric acid precipitation occurred over time, and thus it was not stable. In addition, the phenomenon that the emulsifier solidified and agglomerated at 4 ℃ low temperature occurred. This was judged to be due to the characteristics of glycerin fatty acid ester having a high melting point.

<Comparative Example 9-10>

After heating 175 g of alcohol and raising to 40 ° C., 200 g of hydrous citric acid and citric anhydride were added thereto, and the mixture was vigorously stirred at 80 ° C. for 20 minutes. After stirring, 75 g of Sunsoft-818 (Sunsoft-818 ^TM ) was added, followed by 50 g of sorbitan fatty acid ester (Almax-3800 ^TM ), followed by stirring at 80 ° C. for 30 minutes to prepare a fat-soluble citric acid. The prepared fat soluble citric acid was added to the fat or oil to produce a fat containing fat soluble citric acid. As a result of observing the prepared fats and oils, foaming and citric acid precipitation occurred over time, and thus it was not stable.

<Comparative Example 11-12>

After heating 175 g of alcohol and raising to 40 ° C., 200 g of hydrous citric acid and citric anhydride were added thereto, and the mixture was vigorously stirred at 80 ° C. for 20 minutes. Sunsoft-818 after stirring ^TM) followed by the addition of 75g was added to an organic acid monoglyceride (Almax-5200 ^TM) 50g and stirred at 80 ℃ for 30 minutes to prepare a fat soluble citric acid. The prepared fat soluble citric acid was added to the fat or oil to produce a fat containing fat soluble citric acid. As a result of observing the prepared fats and oils, foaming and citric acid precipitation occurred over time, and thus it was not stable.

<Comparative Example 13-14>

After heating 175 g of alcohol and raising to 40 ° C., 200 g of hydrous citric acid and citric anhydride were added thereto, and the mixture was vigorously stirred at 80 ° C. for 20 minutes. Sunsoft-818 after stirring ^TM) followed by the addition of 75g was added to a sucrose fatty acid ester (F-50 ^TM) 50g and stirred at 80 ℃ for 30 minutes to prepare a fat soluble citric acid. The prepared fat soluble citric acid was added to the fat or oil to produce a fat containing fat soluble citric acid. As a result of observing the prepared fats and oils, foaming, citric acid precipitation and emulsion separation were not stable over time.

<Comparative Example 15-16>

After heating 175 g of alcohol and raising to 40 ° C., 200 g of hydrous citric acid and citric anhydride were added thereto, and the mixture was vigorously stirred at 80 ° C. for 20 minutes. After adding 125 g of polyglycerol fatty acid ester (Almax-9280 ^™ ) and stirring at 80 ° C. for 30 minutes, a fat-soluble citric acid was prepared. The prepared fat soluble citric acid was added to the fat or oil to produce a fat containing fat soluble citric acid. As a result of observing the prepared fats and oils, foaming, citric acid precipitation and emulsion separation were not stable over time.

As a result of the experiments to Comparative Examples 1 to 16, the phenomenon of precipitation when citric acid was solubilized under normal temperature conditions could not be suppressed. In addition, the difference between anhydrous and hydrous citric acid was not seen, so the experiment was conducted on anhydrous citric acid, which is difficult to fatify because of its high melting point in an experiment using a vacuum reactor. This result is considered to have the same result even if the function citric acid experiment is conducted, and it is considered to be representative.

Comparative Example 17

For the decompression reaction, 175 g of alcohol was added to a high-pressure glass reactor (20 L) equipped with a double jacket, the heating bath was heated to 30 ° C., and 200 g of anhydrous citric acid was added to the stirring power under 160 mmHg pressure. Stir at 120 W at 1,200 rpm. Sunsoft-818 while maintaining the reduced pressure after stirring ^TM ) 125 g was added, followed by stirring at 1,200 rpm for 30 minutes at 30 ° C. to produce a fat-soluble anhydrous citric acid. The prepared fat soluble anhydrous citric acid was added to the fat or oil to produce a fat containing fat soluble anhydrous citric acid. As a result of observing the prepared fats and oils, the precipitation of citric acid did not occur, but the emulsion separation phenomenon was not stable.

Comparative Example 18

For the decompression reaction, 175 g of alcohol was added to a high-pressure glass reactor (20 L) equipped with a double jacket, the heating bath was heated to 30 ° C, and 200 g of anhydrous citric acid was added to stir the stirring power under 160 mmHg pressure. Stir at 120 W at 1,200 rpm. Sunsoft-818 while maintaining the reduced pressure after stirring ^TM ) 75 g and Arabian gum (Arabic gum (Acasia gum-AA ^TM )) was added thereto, followed by stirring at 1,200 rpm for 30 minutes at 30 ° C. to prepare a fat-soluble anhydrous citric acid. The prepared fat soluble anhydrous citric acid was added to the fat or oil to produce a fat containing fat soluble anhydrous citric acid. As a result of observing the prepared fats and oils, the precipitation of citric acid did not occur, but the emulsion separation phenomenon was not stable.

Comparative Example 19

For the decompression reaction, 175 g of alcohol was added to a high-pressure glass reactor (20 L) equipped with a double jacket, the heating bath was heated to 30 ° C, and 200 g of anhydrous citric acid was added to stir the stirring power under 160 mmHg pressure. Stir at 120 W at 1,200 rpm. Sunsoft-818 while maintaining the reduced pressure after stirring 75 g of ^TM ) and 50 g of soluble dextrin (emulstar-30A ^™ , Japan) were added, followed by stirring at 1,200 rpm for 30 minutes at 30 ° C. to prepare a fat-soluble anhydrous citric acid. The prepared fat soluble anhydrous citric acid was added to the fat or oil to produce a fat containing fat soluble anhydrous citric acid. As a result of observing the prepared fats and oils, the precipitation of citric acid did not occur, but the emulsion separation phenomenon was not stable.

Comparative Example 20

For the decompression reaction, 175 g of alcohol was added to a high-pressure glass reactor (20 L) equipped with a double jacket, the heating bath was heated to 30 ° C, and 200 g of anhydrous citric acid was added to stir the stirring power under 160 mmHg pressure. Stir at 120 W at 1,200 rpm. Sunsoft-818 while maintaining the reduced pressure after stirring ^TM ) 75 g and glycerin fatty acid ester (Almax-1800 ^TM ) were added thereto, followed by stirring at 1,200 rpm for 30 minutes at 30 ° C. to prepare a fat-soluble citric anhydride. The prepared fat soluble anhydrous citric acid was added to the fat or oil to produce a fat containing fat soluble anhydrous citric acid. As a result of observing the prepared fats and oils, the precipitation of citric acid did not occur, but the emulsion separation phenomenon was not stable.

Comparative Example 21

For the decompression reaction, 175 g of alcohol was added to a high-pressure glass reactor (20 L) equipped with a double jacket, the heating bath was heated to 30 ° C, and 200 g of anhydrous citric acid was added to stir the stirring power under 160 mmHg pressure. Stir at 120 W at 1,200 rpm. While stirring, while maintaining a reduced pressure, 75 g of Sunsoft-818 (Sunsoft-818 ^TM ) and 50 g of sorbitan fatty acid ester (Almax-3800 ^TM ) were added, followed by stirring at 1,200 rpm for 30 minutes at 30 ° C. to obtain fat-soluble anhydrous citric acid. Prepared. The prepared fat soluble anhydrous citric acid was added to the fat or oil to produce a fat containing fat soluble anhydrous citric acid. As a result of observing the prepared fats and oils, the precipitation of citric acid did not occur, but the emulsion separation phenomenon was not stable.

Comparative Example 22

For the decompression reaction, 175 g of alcohol was added to a high-pressure glass reactor (20 L) equipped with a double jacket, the heating bath was heated to 30 ° C, and 200 g of anhydrous citric acid was added to stir the stirring power under 160 mmHg pressure. Stir at 120 W at 1,200 rpm. Sunsoft-818 while maintaining the reduced pressure after stirring ^TM ) 75 g and organic acid monoglyceride (Almax-5200 ^TM ) were added thereto, followed by stirring at 1,200 rpm for 30 minutes at 30 ° C. to prepare a fat-soluble citric anhydride. The prepared fat soluble anhydrous citric acid was added to the fat or oil to produce a fat containing fat soluble anhydrous citric acid. As a result of observing the prepared fats and oils, the precipitation of citric acid did not occur, but the emulsion separation phenomenon was not stable.

Comparative Example 23

For the decompression reaction, 175 g of alcohol was added to a high-pressure glass reactor (20 L) equipped with a double jacket, the heating bath was heated to 30 ° C, and 200 g of anhydrous citric acid was added to stir the stirring power under 160 mmHg pressure. Stir at 120 W at 1,200 rpm. While stirring under reduced pressure, 75 g of Sunsoft-818 (Sunsoft-818 ^TM ) and 50 g of sucrose fatty acid ester (F-50 ^TM ) were added thereto, followed by stirring at 1,200 rpm for 30 minutes at 30 ° C. to prepare a fat-soluble citric anhydride. It was. The prepared fat soluble anhydrous citric acid was added to the fat or oil to produce a fat containing fat soluble anhydrous citric acid. As a result of observing the prepared fats and oils, the precipitation of citric acid did not occur, but the emulsion separation phenomenon was not stable.

Comparative Example 24

For the decompression reaction, 175 g of alcohol was added to a high-pressure glass reactor (20 L) equipped with a double jacket, the heating bath was heated to 30 ° C, and 200 g of anhydrous citric acid was added to stir the stirring power under 160 mmHg pressure. Stir at 120 W at 1,200 rpm. After stirring, 125 g of polyglycerol fatty acid ester (Almax-9280 ^TM ) was added while maintaining a reduced pressure, followed by stirring at 1,200 rpm for 30 minutes at 30 ° C. to prepare a fat-soluble citric anhydride. The prepared fat soluble anhydrous citric acid was added to the fat or oil to produce a fat containing fat soluble anhydrous citric acid. As a result of observing the prepared fats and oils, the precipitation of citric acid did not occur, but the emulsion separation phenomenon was not stable.

In Comparative Examples 17 to 24, it was found that the vacuum condition was the largest reaction factor for the fat solubilization of citric acid by solving the problem of citric acid being precipitated by fatifying the citric acid using a reduced pressure reactor. In addition, it was found that the combination of emulsifiers also affected the fat solubilization of citric acid, which is highly water soluble. However, when the alcohol is used as a solvent as in the comparative examples there is a problem that the emulsion separation phenomenon occurs, it was inevitable to change the solvent.

<Examples 1-30>

To prepare a fat-soluble citric acid in the composition and content of Table 1.

[Table 1] Transformation conditions of citric acid

Vacuum degree (mmHg) Temperature (℃) PG ^{1 )} (wt%) Sunsoft-818 ^{TM 2)} (wt%) Almax-9280 ^{TM 3)} (wt%) Citric acid (% by weight) Example 1 80 60 35 15 10 40.0 Example  2 160 60 35 15 10 40.0 Example  3 360 60 35 15 10 40.0 Example 4 560 60 35 15 10 40.0 Example 5 760 60 35 15 10 40.0 Example 6 80 60 30 10 10 50.0 Example  7 160 60 30 10 10 50.0 Example  8 360 60 30 10 10 50.0 Example 9 560 60 30 10 10 50.0 Example 10 760 60 30 10 10 50.0 Example 11 80 60 25 10 10 55.0 Example  12 160 60 25 10 10 55.0 Example  13 360 60 25 10 10 55.0 Example 14 560 60 25 10 10 55.0 Example 15 760 60 25 10 10 55.0

Note ¹⁾ PG: Propylene Glycol

Note ²⁾ Sunsoft-818 ^TM: glycerin monostearate

Note ³⁾ Almax-9280 ^TM: diglycerol monooleate

As shown in the results of Table 1 above, it was possible to obtain a transparent fat-soluble citric acid of a certain content or more. However, the glycerin monostearate may be any monoglyceride as long as the HLB (Hydrophilic Lipophilic Balance) 4-5 level monoglycerides. The diglycerin monooleate can also be replaced with any polyglycerol fatty acid ester.

[Table 2] Transformation Conditions of Anhydrous Citric Acid

Vacuum degree (mmHg) Temperature (℃) PG (% by weight) Sunsoft-818 ^TM (% by weight) Almax-9280 ^TM (% by weight) Citric anhydride (% by weight) Example 16 80 60 35 15 10 40.0 Example  17 160 60 35 15 10 40.0 Example  18 360 60 35 15 10 40.0 Example 19 560 60 35 15 10 40.0 Example 20 760 60 35 15 10 40.0 Example 21 80 60 30 10 10 50.0 Example  22 160 60 30 10 10 50.0 Example  23 360 60 30 10 10 50.0 Example 24 560 60 30 10 10 50.0 Example 25 760 60 30 10 10 50.0 Example 26 80 60 25 10 10 60.0 Example  27 160 60 25 5 10 60.0 Example  28 360 60 25 5 10 60.0 Example 29 560 60 25 10 10 60.0 Example 30 760 60 25 10 10 60.0

As shown in the results of Table 2, the transparent fat-soluble anhydrous citric acid more than a certain content was obtained. However, the glycerin monostearate may be any monoglyceride as long as the HLB (Hydrophilic Lipophilic Balance) 4-5 level monoglycerides. The diglycerin monooleate can also be replaced with any polyglycerol fatty acid ester.

Experimental Example 1 Turbidity and Viscosity Evaluation

The viscosity and turbidity observation experiment of the fats and oils containing the fat-soluble citric acid of the said Table 1 and Table 2 was performed by the following method. Turbidity accelerated at a low temperature of 4 ℃ to observe the emulsion stability and the degree of citric acid precipitation. Plasticity (viscosity) can be assessed by a viscometer and once again dispersed using an omni macro homogenizer (Model No. 17505, USA) to determine the viscosity. Viscosity after 30 seconds was measured using a Brookfield DV-III programmable rheometer with a # 3 LV spindle (Brookfield DV-III programmable rheometer, Brookfield Eng Labs. Inc., USA). Each viscosity was measured when the rotation speed of the spindle was 100 rpm.

TABLE 3 Turbidity and viscosity of fat-soluble citric acid

Example Turbidity Citric Acid Precipitation Viscosity (cps) Example Turbidity Citric Acid Precipitation Viscosity (cps) Example 1 Slightly turbid × 3,810 Example 16 Slightly turbid × 4,210 Example  2 Transparency × 2,130 Example  17 Transparency × 2,380 Example  3 Transparency × 2,080 Example  18 Transparency × 2,210 Example 4 muddiness × 2,320 Example 19 Slightly turbid × 2,370 Example 5 muddiness Precipitation 2,190 Example 20 Slightly turbid × 2,090 Example 6 muddiness Precipitation 3,920 Example 21 Slightly turbid Precipitation 4,880 Example  7 Transparency × 2,010 Example  22 Transparency × 2,210 Example  8 Transparency × 2,180 Example 23 Transparency × 2,310 Example 9 muddiness Precipitation 2,240 Example 24 Slightly turbid × 2,450 Example 10 muddiness Precipitation 2,580 Example 25 Slightly turbid Precipitation 2,210 Example 11 Slightly turbid × 4,010 Example 26 Slightly turbid × 4,510 Example  12 Transparency × 2,360 Example  27 Transparency × 2,560 Example  13 Transparency × 2,250 Example  28 Transparency × 2,420 Example 14 muddiness Precipitation 2,470 Example 29 Slightly turbid × 2,390 Example 15 muddiness Precipitation 2,220 Example 30 Slightly turbid Precipitation 2,470

As shown in the results of Table 3 above, in the case of hydrous citric acid, the desired conditions of Examples 17, 18, 22, 23, 27, and 28 of Examples 2, 3, 7, 8, 12, and 13, and A transparent fat or oil containing fat-soluble citric acid was obtained. In the case of hydrous citric acid, a mixture of monoglyceride (Sunsoft-818 ^TM ) and polyglycerin fatty acid ester (Almax-9280 ^TM ) with a certain amount or more is used at a vacuum degree of 160 to 360 mmHg. When the vacuum degree was lower than this condition, the viscosity increased too high and the usability was not good. When the vacuum degree was higher than this condition, there was no increase in viscosity, but the precipitation of citric acid was too severe. Anhydrous citric acid was also similar to hydrous citric acid, and anhydrous citric acid had less water content, so the turbidity was less severe than that of hydrous citric acid.

Experimental Example 2 Appearance Stability Evaluation

In order to evaluate the property stability of the examples in which the preparation of the transparent fats and oils of the above examples was observed after 4 weeks in thawing conditions after freezing at 60 ° C., 150 ° C. and in winter. As shown in Table 4, except that slightly turbid in Examples 12, 13, it was stable without change in properties.

[Table 4] Property stability results of fat-soluble citric acid by temperature

Example Change of appearance Example Change of appearance 60 ℃ 150 ℃ Thaw after freezing 60 ℃ 150 ℃ Thaw after freezing Example 2 Transparency Transparency Transparency Example 17 Transparency Transparency Transparency Example 3 Transparency Transparency Transparency Example 18 Transparency Transparency Transparency Example 7 Transparency Transparency Transparency Example 22 Transparency Transparency Transparency Example 8 Transparency Transparency Transparency Example 23 Transparency Transparency Transparency Example 12 Transparency Transparency Slightly turbid Example 27 Transparency Transparency Transparency Example 13 Transparency Transparency Slightly turbid Example 28 Transparency Transparency Transparency

Experimental Example 3 Evaluation of Citric Acid Degradation Rate According to Storage Period

The content stability of the transparent fats and oils containing fat-soluble citric acid prepared in Example 7 was evaluated and the results of the residual content (%) compared to the content before the start of the stability evaluation experiment are shown in Table 5.

[Table 5] Content stability results of fat-soluble citric acid

Item Condition 4 Weeks 8 Weeks 12 Weeks 16 Weeks content (%) Room temperature 94 95 93 92 60 ℃ 95 94 96 95 150 ℃ 97 93 92 94 Thaw after freezing 97 94 95 95 Constellation Transparency Transparency Transparency Transparency

As can be seen from the results of Table 5, the citric acid-containing transparent liquid formulation of the present invention can be seen that citric acid is protected from the external environment and stable.

Experimental Example 4 Oxidation Stability Evaluation Using a Rancimat Device

In order to evaluate the degree of oxidation stability improvement of palm oil of the fat-soluble citric acid of Table 1 and Table 2 was used in the rancimat 743 (Rancimat 743, Metrohm AG, CH-9100 Herisau, Switzerland). In other words, take 3.0 g of palm oil in the reaction vessel, add oil-soluble citric acid to the reaction vessel so that it contains 0.15% of the palm oil, and then disperse it sufficiently in palm oil using a voltex mixer (3 minutes) to obtain aluminum of 120 ± 0.1 ° C. 20 L of air per hour was injected on an aluminum heating block to oxidize. The resulting volatile oxidized product is transferred to an adsorption vessel containing 60 ml of distilled water, and the conductivity is measured and recorded by a double platinum foli electrode and a recorder. In the chart, the degree of antioxidant activity of each extract was measured by calculating the induction period (IP) from the conductivity of the initiation of the reaction to the time when the conductivity was rapidly increased. At the same time, fat-soluble citric acid was added. Antioxidant activity was compared and expressed as AI (antioxdiant index) as a control.

AI = duration of induction of antioxidants (hours) / duration of standard maintenance (hours)

[Table 6] Oxidative Stability Improvement Effect of Fat-Soluble Citric Acid on Palm Oil

Example Temperature (℃) Induction period (IP) Example Temperature (℃) Induction period (IP) Control group (no addition) 120 12.45 Control group (no addition) 120 12.24 Example 2 120 16.89 Example 17 120 17.04 Example 3 120 16.95 Example 18 120 16.91 Example 7 120 17.23 Example 22 120 16.88 Example 8 120 16.90 Example 23 120 16.65 Example 12 120 16.35 Example 27 120 16.43 Example 13 120 16.12 Example 28 120 16.78

As can be seen from the results of Table 6, the fat-soluble citric acid of the present invention can greatly improve the oxidation stability by inhibiting the thermal decomposition of the milk.

Experimental Example 5 Evaluation of Oxidative Stability of Yutang Noodles

In order to measure the oxidative stability effect of the noodle using the fat-soluble citric acid prepared in the present invention, the noodle was prepared in a pilot room. In order to prepare steamed noodles, flour and starch were mixed at a predetermined ratio, mixed with water, kneaded, and then stirred in a multi-function machine. After forming a straw through a seven-stage roller, a 1.8ⅹ1.2mm ring was passed. The lactose prescription for lacquering the prepared cotton pad was prepared by adding 0.05%, 0.1%, 0.15%, and 0.20% of the oil-soluble citric acid of the present invention to palm oil, respectively, to prepare the milk-containing oil containing fat-soluble citric acid. After steaming under steam pressure, exactly 130 g was taken and put into lead molds, and each of the prepared lactose oil was simmered at 150 ° C. to 153 ° C. for 60 seconds.

After cooling the milked samples at room temperature, accelerated oxidation was performed for 9, 12, 15, 18, 21, 24, 27, 30, 33, 36, 39, 42 days in a 60 ℃ thermostat to measure the effect of improving oxidation stability. Used as a sample. A control was prepared as above without adding fat soluble citric acid to palm oil.

[Comparison of Peroxide Values in Fats and Oils Containing Fat-Soluble Citric Acid]

In this experiment, 5.0 g of fat or oil containing fat-soluble citric acid was dissolved in 35 ml of an acetic acid: chloroform (3: 2) solvent and dissolved in 1 ml of saturated KI solution. The mixture was shaken for 1 minute and then titrated with 0.01N Na ₂ S ₂ O ₃ solution to determine the peroxide value. The values were compared with the control without the addition of fat-soluble citric acid. The calculation of the peroxide value was as follows.

POV (meq / kg) = (A-B) × 0.01 × F / S × 100

A: Appropriate consumption amount of the sample 0.01N Na ₂ S ₂ O ₃ solution (ml)

B: titration consumption (mL) of 0.01 N Na ₂ S ₂ O ₃ solution of the control group

F: Factor of 0.01N Na ₂ S ₂ O ₃

S: sampling amount (g)

[Comparison of hexanal concentration change]

In this experiment, the concentration of hexanal, the causative agent of bad odor, was measured by the following method. 15.0 g of fat-soluble citric acid was placed in a clavenger trap, and 5 mL of hexane prepared at a concentration of 30 ppm of internal standard (ethylbenzene) was added after adding 360 mL of water. To prevent boiling, 1 ml of antifoam (antifoam A, Sigma) was added and distilled for 90 minutes. The supernatant was taken, concentrated to 2 ml and analyzed by GC.

Figures 1 and 2 formulated fat-soluble citric acid according to the present invention to the blended water by the concentration of the preparation of the noodle noodle and peroxide value (peroxide value) and off-flavor (off off) This graph shows the analysis of hexanal, a component of -flavor. As can be seen from the graph, it can be seen that both the rate of increase of the content of the peroxide as the primary oxide and the rate of increase of the hexanal as the secondary oxide decrease with increasing concentration of the fat-soluble citric acid. In particular, the effect was excellent at more than 0.10% (1,000ppm), and it can be seen that the addition of 0.05% improves the stability of the existing noodle. This suggests that when oil-soluble citric acid is prescribed for lactose oil, the shelf life can be extended and the freshness of the noodle can be maintained longer by guaranteeing the shelf life of noodles under the usual high temperature and summer high temperature conditions. I think you can.

Figure 1 is a graph of peroxide value (peroxide value) according to the concentration of the fat-soluble citric acid of the present invention.

Figure 2 is a graph analyzing the hexanal (off-flavor) component of the present invention fat-soluble citric acid according to the addition concentration (off-flavor).

Claims (13)

40 to 55% by weight of hydrous citric acid, 25 to 35% by weight of propylene glycol, 10 to 15% by weight of HLB (Hydrophilic Lipophilic Balance) 4-5 levels of monoglycerides and 10% by weight of polyglycerin fatty acid esters A first step of mixing; And And a second step of reacting the mixed solution at 60 ° C. under reduced pressure. The method of claim 1, The first step and the second step of producing a fat-soluble citric acid, characterized in that at the same time. The method according to claim 1 or 2, The HLB (Hydrophilic Lipophilic Balance) 4-5 levels of monoglycerides are glycerin monostearate, characterized in that the production method of fat-soluble hydrous citric acid. The method according to claim 1 or 2, The polyglycerol fatty acid ester is a method for producing fat-soluble hydrous citric acid, characterized in that diglycerin monooleate. The method according to claim 1 or 2, The decompression condition is a method for producing fat-soluble citric acid, characterized in that 160 ~ 360mmHg. 40 to 60% by weight of citric anhydride, 25 to 35% by weight of propylene glycol, 5 to 15% by weight of HLB (Hydrophilic Lipophilic Balance) 4-5 levels of monoglycerides and 10% by weight of polyglycerin fatty acid esters A first step of mixing; And And a second step of reacting the mixed solution at 60 ° C. under reduced pressure. The method of claim 6, The first step and the second step of producing a fat-soluble citric anhydride, characterized in that at the same time. The method according to claim 6 or 7, The HLB (Hydrophilic Lipophilic Balance) 4-5 levels of monoglycerides are glycerin monostearate, characterized in that the production method of fat-soluble citric anhydride. The method according to claim 6 or 7, The polyglycerol fatty acid ester is a method for producing fat-soluble citric anhydride, characterized in that diglycerol monooleate. The method according to claim 6 or 7, The decompression condition is a method for producing fat-soluble citric anhydride, characterized in that 160 ~ 360mmHg. 40 to 55% by weight of hydrous citric acid, 25 to 35% by weight of propylene glycol, 10 to 15% by weight of HLB (Hydrophilic Lipophilic Balance) 4-5 levels of monoglycerides and 10% by weight of polyglycerin fatty acid esters Fat-soluble function citric acid, characterized in that it comprises. 40 to 60% by weight of citric anhydride, 25 to 35% by weight of propylene glycol, 5 to 15% by weight of HLB (Hydrophilic Lipophilic Balance) 4-5 levels of monoglycerides and 10% by weight of polyglycerin fatty acid esters Fat-soluble citric anhydride, characterized in that it comprises. Fat-soluble citric acid or fat-soluble citric acid of Claim 11 or 12, and fat-soluble citric acid containing fats and oils, Comprising: It consists of 0.05-0.20 weight% of fats and oils.

Images