JPH09208986A - Antioxidizing agent preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid antioxidizing agent preparation low in viscosity and capable of being easily compounded with food raw materials, etc., by dispersing an L-ascorbic acid fatty acid ester in an oily substance. SOLUTION: An L-ascorbic acid fatty acid ester is homogeneously dispersed in an oily substance such as rapeseed oil or soybean oil to obtain a liquid antioxidizing agent preparation low in viscosity. The liquid antioxidizing agent preparation does not require the addition of a large amount of lecithin for solubilization, is not browned at a temperature of approximately 180 deg.C, and can be added to fats and oils such as fats and oils for tempura (deep fried fish and vegetables) and foods containing the fats and the oils.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antioxidant preparation in which an L-ascorbic acid fatty acid ester is uniformly dispersed in an oily substance. More specifically, it is liquid,
Further, the present invention relates to an antioxidant formulation which is easy to handle because of its low viscosity and which can be easily incorporated into oils and fats and oil-containing foods or food materials. Furthermore, the present invention relates to an antioxidant formulation that does not brown under a high temperature of about 180 ° C.

[0002]

2. Description of the Related Art L-ascorbic acid (also known as vitamin C) has a strong reducing action, is added to many foods as a water-soluble antioxidant, and is safe and can be used as a nutrition enhancer. Was used by preference.

As a fatty acid ester of L-ascorbic acid, L-ascorbic acid palmitate has recently been newly added after L-ascorbic acid stearic acid ester, which was previously approved as a food additive in Japan. It can now be used as a food additive. L-ascorbic acid stearate and L-
Ascorbic acid palmitate is widely used in fats and oils and fat-containing foods as a fat-soluble antioxidant, and L-
Like ascorbic acid, it exerts an effective antioxidant function by its reducing action. The ester bond in L-ascorbic acid fatty acid ester is easily enzymatically decomposed in the body to form vitamin C and a fatty acid (palmitic acid or stearic acid), each of which acts as an active ingredient, and thus is highly evaluated for safety.

On the other hand, the above-mentioned L-ascorbic acid fatty acid ester can obtain a large synergistic effect when used in combination with other antioxidants. For example, tocopherol, which has been conventionally used as an oil-soluble antioxidant, has a low effect even when it is added to a vegetable oil that is usually derived from a raw material and contains tocopherol. However, when L-ascorbic acid fatty acid ester is added to the above vegetable oil, a synergistic antioxidant effect is exhibited. Therefore, L
-Ascorbic acid fatty acid ester is expected to be used more widely in the future in oils and fats, food materials, etc. alone or in combination with other antioxidant formulations, and it is also useful in this respect.

To use the above-mentioned ester as an antioxidant, white powdery L-ascorbyl palmitate and L-ascorbyl stearate are
It was carried out by directly adding it to fats and oils and dissolving it.

When added to various oils and fats, oil-and-fat-containing foods, food materials, etc., it is convenient to mix them as liquids rather than as powders because they are easier to handle. Therefore, L
-Liquefaction of ascorbic acid fatty acid ester is being investigated. At present, a liquefied preparation in which L-ascorbic acid fatty acid ester is solubilized using lecithin which is an oil-soluble natural surfactant is generally used. Furthermore, solubilization using a surfactant other than lecithin has also been investigated.

[0007]

Since L-ascorbic acid has poor stability over time and poor solubility in oils and fats, it is difficult to add L-ascorbic acid as an additive, and there are many problems in practical use. .

The fatty acid ester of L-ascorbic acid is
Although the stability over time is improved, the solubility in oils and fats remains unimproved and the temperature of oils and fats is kept at about 100 ° C.
It was dissolved in a state of being raised to a certain degree. Further, since the powder has a large bulk specific gravity, the powder is scattered in the air during the operation, and its handling is inconvenient. From this point of view, it was difficult to mix it with oils and fats.

Liquefaction was studied to facilitate blending,
It is possible to obtain a liquefied preparation by solubilizing L-ascorbic acid fatty acid ester, but this was because a large amount of lecithin was used during solubilization, so low temperature (about 5 ° C) When placed underneath, it solidified, lost fluidity and became difficult to handle. Moreover, this lecithin has a high temperature (for example, a heating temperature of 180 ° C. such as tempura).
When the lecithin-solubilized liquefied antioxidant formulation is added to frying oil, for example, the aforementioned properties of lecithin become prominent and the compounded oil browns at high temperatures. The phenomenon appears. Considering these points,
A method of solubilizing using other surfactants has also been investigated, but this results in a formulation having a very high viscosity, and L-
When the content of ascorbic acid fatty acid ester is increased, the fluidity is lost. As described above, in the past, no liquefied preparation has been found that is easy to handle and can be easily added to oils and fats and oil-containing foods or food materials in actual use.

The present invention has been made in view of the above-mentioned problems of the prior art,
A basic object of the present invention is to provide an antioxidant preparation of L-ascorbic acid fatty acid ester which can be easily blended with oils and fats and oil-containing foods or food materials. Another object of the present invention is to provide an antioxidant preparation which does not turn brown even when it is added to oils and fats used at high temperatures such as tempura oil.

[0011]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned object, by dispersing L-ascorbic acid fatty acid ester in an oily substance without using a large amount of lecithin for solubilization, The inventors have found that a liquid antioxidant formulation that does not turn brown at a high temperature of about 180 ° C. is prepared, and completed the present invention.

That is, the invention of claim 1 is an antioxidant preparation characterized in that the L-ascorbic acid fatty acid ester is uniformly dispersed in an oily substance. Since the L-ascorbic acid fatty acid ester is dispersed in an oily substance, the viscosity is low, and since it is not solubilized with a large amount of lecithin, a liquid antioxidant formulation that does not turn brown at high temperature is obtained. Obtainable. Claims 2-6
Indicates a preferred embodiment. That is, the invention of claim 2 is the invention of claim 1, wherein the L-ascorbic acid fatty acid ester is L-ascorbic acid palmitic acid ester and / or L-ascorbic acid stearic acid ester. As a result, an antioxidant preparation having a high antioxidant effect can be obtained. The invention according to claim 3 is the invention according to claim 1 or 2, wherein the oily substance is rapeseed oil, soybean oil, corn oil, rice oil, olive oil, sesame oil, safflower oil, sunflower oil, peanut oil, almond oil. , Cottonseed oil, fish oil, whale oil, shark oil, fish liver oil, mink oil, avocado oil, jojoba oil, lard, squalene,
It is one or more selected from the group consisting of medium-chain fatty acid triglycerides, vitamins A, D and E and derivatives thereof. The L-ascorbic acid fatty acid ester is uniformly dispersed in these oily substances. The invention according to claim 4 is the invention according to any one of claims 1 to 3, further comprising a surfactant. In the invention according to claim 5, in the invention according to claim 4, the surfactant is glycerin fatty acid ester, sucrose fatty acid ester, condensed resinolate, sorbitan fatty acid ester,
It is one or more selected from the group consisting of propylene glycol fatty acid ester, saponin and sterol. By adding these surfactants, a stable dispersion liquid in a dispersed state can be obtained. The invention according to claim 6 is the invention according to any one of claims 1 to 5, wherein the L-ascorbic acid fatty acid ester is 0.1 to 70% by weight based on the total weight of the antioxidant. .
With such a blending amount, a liquefied preparation in which L-ascorbic acid fatty acid ester is uniformly dispersed can be obtained.

In the present application, the description of the numerical range indicates an arbitrary value belonging to the range and is not limited to the values at both ends.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The antioxidant preparation of the present invention is a liquefied antioxidant preparation having a low viscosity in which an L-ascorbic acid fatty acid ester is uniformly dispersed in an oily substance. Therefore,
It is easy to handle and can be easily incorporated into fats and oils and fat-containing foods or food materials. Moreover, since it is not necessary to use a large amount of lecithin as a solubilizing agent, the browning phenomenon at high temperature (about 180 ° C.), which is a defect of lecithin, does not appear. Therefore, it can be safely blended with oils and fats such as frying oil used at high temperature.

The L-ascorbic acid fatty acid ester used in the present invention is a monoester, diester, triester or the like composed of L-ascorbic acid and a fatty acid, and examples of the acid moiety of the ester include lauric acid and myristic acid. , Palmitic acid, stearic acid, arachidonic acid, behenic acid, cerotic acid, oleic acid, linoleic acid, docosahexaenoic acid, eicosapentaenoic acid and the like. Among them, L-ascorbic acid palmitic acid ester and L-ascorbic acid stearic acid ester are particularly preferable, and L-ascorbic acid palmitic acid ester is most preferable. Since L-ascorbic acid palmitate has a small molecular weight, the effect of adding the same amount as L-ascorbic acid stearic acid is slightly higher than that of L-ascorbic acid stearic acid.

In the present invention, as the L-ascorbic acid fatty acid ester, one kind selected from the above group may be used, or two or more kinds may be mixed and used. The content of the L-ascorbic acid fatty acid ester is preferably 0.1 to 70% by weight based on the total weight of the antioxidant preparation,
30% by weight is more preferred. 0.1 weight% or more is necessary to show an effective antioxidant effect, and 70 weight% or less is preferable in order to be manufactured as a fluid liquid.

The oily substance used in the present invention is an oily substance which is liquid at room temperature and includes animal and vegetable oils, hydrocarbons, vitamins, medium chain fatty acid triglycerides and the like. Specifically, as animal and vegetable oils and fats, rapeseed oil, soybean oil, corn oil, rice oil, olive oil, sesame oil, safflower oil, sunflower oil, peanut oil, almond oil, cottonseed oil, fish oil, whale oil, shark oil, fish liver oil, Mink oil, avocado oil, jojoba oil, lard and the like can be mentioned. Examples of the hydrocarbon include squalene. The medium-chain fatty acid triglyceride is a single or mixture of triglycerides having a fatty acid group having an arbitrary range of 6 to 24 carbon atoms. Examples of vitamins include vitamins A, D and E and their derivatives. Among these, rapeseed oil and medium-chain fatty acid triglyceride are particularly preferable.

Alternatively, instead of the oily substance, solvents such as glycerin and propylene glycol may be used.

In the present invention, as the oily substance, one kind selected from the above group may be selected and used, or two or more kinds may be mixed and used. The amount of the oily substance used is preferably 30 to 99.9% by weight, more preferably 60 to 98% by weight, based on the total weight of the antioxidant preparation. In order to uniformly disperse the L-ascorbic acid fatty acid ester, the amount of the oily substance used is preferably within the above range.

A surfactant may be added to the antioxidant preparation of the present invention. By adding a surfactant,
The dispersed state of the dispersion liquid can be stabilized. Preferred surfactants are nonionic and amphoteric surfactants. Specifically, as a nonionic surfactant,
Examples thereof include glycerin fatty acid ester, sucrose fatty acid ester, condensed resinolate, sorbitan fatty acid ester, propylene glycol fatty acid ester, saponin, and sterol. Among these, glycerin fatty acid ester, sucrose fatty acid ester and sorbitan fatty acid ester are particularly preferable. Lecithins such as lecithin, enzyme-treated lecithin and enzyme-decomposed lecithin are not affected by browning as long as a very small amount is blended, but it is preferable not to blend them.

In the present invention, as the surfactant, one kind selected from the above group may be selected and used, or two or more kinds may be mixed and used. The amount of the surfactant used is preferably 20% by weight or less based on the total weight of the antioxidant preparation,
1 to 10% by weight is more preferable. Even if it is used in an amount of more than 20% by weight, the effect as a dispersant is not increased by increasing the amount.

Next, the method for producing the L-ascorbic acid fatty acid ester dispersion according to the present invention will be described.
It is not limited to the following examples.

A surfactant is dissolved in an oily substance heated to 70 to 80 ° C., and the mixture is stirred with a homomixer and then L-
A fatty acid ester of ascorbic acid is mixed, stirred well for about 15 minutes, and cooled to obtain the antioxidant preparation of the present invention.

Alternatively, it can be manufactured by the following method.

A surfactant and L-ascorbic acid fatty acid ester are dissolved in an oily substance heated to 70 to 80 ° C., and the mixture is cooled with good stirring with a homomixer to obtain the antioxidant formulation of the present invention.

The antioxidant preparation of the present invention obtained by the above-mentioned production method has a viscosity of about 100, although it slightly changes depending on the concentration of the L-ascorbic acid fatty acid ester mixed therein.
It is a fluid cloudy liquid in the range of up to 3000 cp.

The antioxidant preparation of the present invention can be easily blended with fats and oils and fat-containing foods by mixing and stirring. Further, the antioxidant preparation of the present invention can also be blended by kneading it into a food material in the process of manufacturing food. A preferable blending amount is, for example, 0.1 to 0.5% by weight with respect to edible oil.

When the antioxidant preparation of the present invention is added alone to fats and oils and fat-containing foods or food materials,
If the finally added amount is the same, the same effect as when using a powdery fatty acid ester of L-ascorbic acid is obtained. Furthermore, when used in combination with other antioxidant formulations, its effect is synergistically increased.

The antioxidant preparation of the present invention does not solidify even when placed at a low temperature of about 0 ° C. and does not lose its fluidity. Further, when stored at room temperature in the dark, no disappearance of L-ascorbic acid fatty acid ester is observed for at least 6 months.

The antioxidant preparation according to the present invention can be added to cosmetics, medicines, feeds, etc. in addition to foods.

A detailed description will be given below with reference to examples. However, the present invention is not limited to these. Unless otherwise specified,% means% by weight.

[0032]

【Example】

<Example 1> Dispersibility (Prototype of Antioxidant Formulation) An antioxidant formulation was prototyped with the following formulation. L-ascorbic acid palmitate 10% sucrose palmitate 2% rapeseed oil 88% rapeseed oil was heated to 70-80 ° C, and sucrose palmitate was added and dissolved therein. While stirring the solution with a homomixer at about 6000 rpm, L-ascorbic acid palmitate was mixed and stirring was continued for 15 minutes. After stirring, the solution was cooled to obtain the antioxidant formulation of the present invention.

(Comparison of dispersion state) Rapeseed oil 1 at room temperature
The prototype antioxidant preparation was added so that the amount of L-ascorbic acid palmitate ester was 0.02% with respect to 00 g, and the mixture was thoroughly mixed and stirred, and then L in rapeseed oil was added.
-The state of dispersion of ascorbyl palmitate was observed visually and by an optical microscope.

(Results) Visual observation revealed that L-ascorbic acid palmitate was uniformly dispersed throughout the rapeseed oil, and the rapeseed oil was opaque. Under the microscope, needle-like crystals with a length of 25 to 50 μm were observed,
No aggregates were observed.

<Comparative Example 1> 100 g of rapeseed oil at room temperature
In addition, L-ascorbic acid palmitate is 0.0
The powder was directly added so as to be 2% and well mixed and stirred, and the dispersed state was observed in the same manner as in Example 1.

(Results) Visual observation of lumps of L-ascorbyl palmitate ester in the rapeseed oil showed a floating state and precipitation, and the rapeseed oil was transparent. 30 under the microscope
Needle-like crystals with a length of -80 μm and their aggregates (diameter about 5
00 μm) was observed.

Example 2 Measurement of Antioxidant Effect on Vegetable Oil (Antioxidant Effect Test by Auto Oxidation (AOM) Test)
At room temperature, the antioxidant formulation trial-produced in Example 1 was added so that L-ascorbic acid palmitate would be 0.02% with respect to 100 g of rice oil.

According to the AOM test method of the standard oil and fat analysis method, the rice oil to which the antioxidant formulation was added was allowed to stand in a thermostat at 180 ° C. for 2 hours and then placed in an AOM tester prepared at 70 ° C. Then, the peroxide value was measured.

Table 1 shows the results.

[0040]

[Table 1]

Comparative Example 2 Using 100 g of rice oil without any additive, an AOM test was conducted in the same manner as in Example 2 above to measure the peroxide value. The results are shown in Table 1 above.

<Comparative Example 3> Powdered L-ascorbic acid palmitate was added directly to 100 g of rice oil so that the amount thereof was 0.02%, and the mixture was stirred well in the same manner as in Example 2 above. An AOM test was performed to measure the peroxide number. The results are shown in Table 1 above.

From Example 1, since the antioxidant preparation of the present invention is liquid, it can be easily added to oils and fats and can be easily blended, and L-ascorbic acid palmitate is an oil and fat. It was evenly dispersed in the compound. On the other hand, in Comparative Example 1, the powder is easily scattered in the air due to wind or the like and is inconvenient to handle, and when it is blended with fats and oils, it needs to be considerably mixed and stirred, which is troublesome. However, lumps still remained, and sedimentation with time occurred.

Furthermore, in Example 2, the antioxidant preparation according to the present invention, when the final addition concentration is the same,
The powder of Comparative Example 3 exhibited an antioxidant effect equivalent to that of L-ascorbic acid palmitate. Therefore, it was shown that the product of the present invention is easy to mix and has the same antioxidant effect as the powder.

<Example 3> Browning by heating (Gardner method and visual evaluation of browning) At room temperature, L-ascorbic acid palmitate is 0.02% based on 100 g of rapeseed oil. The antioxidant formulation prepared in Example 1 was added to and mixed well.

The rapeseed oil was allowed to stand in a constant temperature bath prepared at 180 ° C., and the color of the solution after 0 minutes, 30 minutes, 90 minutes, and 120 minutes was visually observed and the oil and fat analysis test method according to the Gadner method was used. It was measured.

Table 2 shows the results.

[0048]

[Table 2]

<Comparative Example 4> An antioxidant formulation having the following composition was prepared. L-Ascorbic acid palmitate 10% Lecithin 75% Rapeseed oil 15% The obtained antioxidant was dark brown and transparent in appearance, and was a viscous liquid. The antioxidant obtained as described above was added to 100 g of rapeseed oil at room temperature to obtain L
-Ascorbic acid palmitate was added so as to be 0.02% and mixed well, and then the color of the solution was observed in the same manner as in Example 3. The results are shown in Table 2 above.

The vegetable oil blended with the dispersion of the present invention did not show any browning phenomenon even at high temperatures. On the other hand, in the oil containing the lecithin preparation of Comparative Example 4, browning was observed 30 minutes after the high temperature treatment was started, and it was observed that browning occurred promptly in response to the high temperature treatment. Therefore, it was shown that the product of the present invention does not use a large amount of lecithin as a solubilizing agent, so that the browning phenomenon can be avoided.

Example 4 Measurement of Viscosity (Preparation of Antioxidant Formulations at Various Concentrations) Dispersions of L-ascorbic acid palmitate at various concentrations were trial-produced with the compositions shown in Table 3 below.

[0052]

[Table 3]

(Measurement of Viscosity) According to the standard fat and oil analysis method,
The viscosity of the antioxidant formulation at each concentration was measured.

The results are shown in Table 4.

[0055]

[Table 4]

<Comparative Example 5> A solubilizing solution of L-ascorbic acid palmitic acid ester having each composition having the composition shown in Table 3 above was experimentally produced, and the viscosity of each solution was measured in the same manner as in Example 4. The results are shown in Table 4 above.

In the solubilized liquid of Comparative Example 5, a 10% solution of L-ascorbyl palmitate has a considerably high viscosity, and if the concentration is further increased, the fluidity disappears.
The dispersion according to the present invention maintained fluidity even in a 30% solution. Therefore, it was shown that the dispersion liquid of the present invention can contain a high concentration of L-ascorbyl palmitate ester while maintaining fluidity as compared with the solubilization liquid. .

[0058]

INDUSTRIAL APPLICABILITY The antioxidant preparation of the present invention is a liquid in which a fatty acid ester of L-ascorbic acid is uniformly dispersed in an oily substance. Compared to conventional powdered L-ascorbic acid fatty acid ester, since it is a liquid, it can be easily added and blended into fats and oils and foods containing fats and oils, food materials, and the like, and the viscosity of the liquid is also low, which makes it easy to handle. It is a thing. Moreover, when the final amount of the L-ascorbic acid fatty acid ester added is the same with respect to the total weight of the added fat or oil, the antioxidant effect is the same as when the powder is directly added. Further, since it is easy to mix, it can be easily used in combination with other antioxidant preparations, and the combined use increases the effect synergistically. Further, since it is not necessary to use a large amount of lecithin having a property of browning at high temperature as a solubilizing agent, it does not show browning phenomenon even at high temperature. Therefore, it can be safely added to, for example, fats and oils used at high temperatures, especially edible oils such as frying oil.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahiro Atsumi 2-7-1, Nishishinjuku, Shinjuku-ku, Tokyo Tama Seikagaku Co., Ltd. (72) Inventor, Yarichika Riko 1 Minami-Asamacho, Nishi-ku, Yokohama-shi, Kanagawa No. 1 Yokohama Oil & Fat Industry Co., Ltd.

Claims (6)

[Claims] 1. An antioxidant preparation, wherein L-ascorbic acid fatty acid ester is uniformly dispersed in an oily substance. 2. The antioxidant preparation according to claim 1, wherein the L-ascorbic acid fatty acid ester is L-ascorbic acid palmitic acid ester and / or L-ascorbic acid stearic acid ester. 3. The oily substance is rapeseed oil, soybean oil, corn oil, rice oil, olive oil, sesame oil, safflower oil, sunflower oil, peanut oil, almond oil, cottonseed oil, fish oil, whale oil, shark oil, fish liver oil, mink. The oil, avocado oil, jojoba oil, lard, squalene, medium-chain fatty acid triglyceride, vitamins A, D and E, and one or more selected from the group consisting of derivatives thereof. Antioxidant formulation. 4. The antioxidant preparation according to any one of claims 1 to 3, further comprising a surfactant. 5. The surfactant is one or more selected from the group consisting of glycerin fatty acid ester, sucrose fatty acid ester, condensed resinolate, sorbitan fatty acid ester, propylene glycol fatty acid ester, saponin and sterol. The antioxidant preparation according to claim 4. 6. The antioxidant preparation according to any one of claims 1 to 5, wherein the L-ascorbic acid fatty acid ester is 0.1 to 70% by weight based on the total weight of the antioxidant preparation.