JP2701897B2 - Method for producing O / W emulsion containing natural tocopherol - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing an antioxidant emulsified product for use in foods and fats containing fats and oils and raw materials containing fats and oils, and more particularly, to an O / W type emulsion prepared by emulsifying natural tocopherol. The present invention relates to a method for producing an oxidized emulsion.

[Conventional technology]

Traditionally, ramen products, chocolate products, fried rice crackers, fried donuts, snacks, powdered soup, meat sauce, stewed hamburger, dressing, mayonnaise,
Various kinds of fats and oils components are added to these foods for the purpose of improving the texture of processed cheeses, margarine, various seafood minced fish, surimi of sea oysters and offshore and land surimi. An important issue for such fat-and-oil-based foods in general relates to suppression of oxidation (peroxide) of fats and oils. Selection and utilization of antioxidants are provided from each field as antioxidant measures for this oil and fat. Various antioxidants such as sperm extract sperm and other natural antioxidants have been used.As antioxidants, many antioxidants such as ascorbic acid and its preparation, sodium citrate have been developed. The γ (gamma-form) δ (delta-form) of natural tocopherol under excellent conditions has attracted attention. However, the disadvantages of natural tocopherols are
When the oxidizing condition of the fat or oil component itself starts (free radical reaction), the natural tocopherol itself can often become an oxidation promoter, and since it is a fat or oil component, it is difficult to provide it for the production of water-containing foods.

[Problems to be solved by the invention]

An object of the present invention is to provide a method for producing a natural tocopherol-rich O / W emulsion which can maintain long-term antioxidant stability of fats and oils, has good dispersibility, and is easy to use for foods. .

[Means for solving the problem]

The present invention, as a result of intensive research, to solve the above problems,
Dispersibility by utilizing edible oil-based medium-chain fatty acid triglyceride and polyglycerin fatty acid esters (such as hexaglycerin monolaurate), glycerin fatty acid ester or sorbitan fatty acid ester, which are one kind of hydrophilic nonionic surfactant. Further, it is based on the finding that it is possible to obtain an O / W emulsion having a high content of natural tocopherol with excellent antioxidant ability.

That is, the present invention relates to a method for producing a natural tocopherol-containing O / W emulsion, comprising: (i) 5 to 40 parts by weight of the natural tocopherol, and 5.75 to 14.60% by weight of an edible oil-based medium-chain fatty acid triglyceride (based on the natural tocopherol). And at least 3.0 to 9.8% by weight (based on the above-mentioned natural tocopherol) of at least one selected from polyglycerin fatty acid ester, glycerin fatty acid ester and sorbitan fatty acid ester, to obtain a mixed oil and fat solution. A step wherein the fatty acid of the edible oil-based medium-chain fatty acid triglyceride is a saturated fatty acid having 8 to 10 carbon atoms; (ii) 0.3 to 1.0% by weight of an emulsion stabilizer (based on the natural tocopherol); 1.9-4.8% by weight of sugar fatty acid ester (based on the above natural tocopherol) and 3.8-9.8% by weight of ethyl alcohol (Based on the above-mentioned natural tocopherol) and 22-40 parts by weight of sterilized purified water, and heating the mixture by boiling, wherein the emulsion stabilizer comprises xanthan gum, guar gum, locust bingham and gellan gum. And (iii) stirring the mixed liquid obtained in the step (ii) into the mixed oil and fat liquid obtained in the step (i) while heating. (Iv) preparing a mixed solution comprising: 29-55 parts by weight of at least one selected from the group consisting of D-sorbitol and starch-decomposed saccharified product; and the balance of the sterilized purified water. And mixing and stirring the mixture in the mixed solution obtained in the above step (iii) while maintaining the temperature at 40 ° C. or higher.

In the method of the present invention, vegetable oils may be added in an amount of 9.5 to 11.8% by weight based on the natural tocopherol, and in such a case, it is preferable to add them in the step (ii).

As the natural tocopherols, α, β, γ, ζ,
ε, η, and δ (alpha, beta, gamma, zeta, epsilon, eter, and delta) have seven types of vitamin homologues. Usually, four types, α, β, γ, and δ, are represented. Mixed tocopherol of seed mixture,
In addition, there are high-component tocopherols of γ and δ, and high-component tocopherol of δ-form, both of which can be used. With respect to the use of natural tocopherols, the latter two have a great effect as antioxidants. The amount of natural tocopherol used is 5 to 40 parts by weight based on all components. If the amount is less than 5 parts by weight, the amount of the natural tocopherol component becomes very small, which is not desirable, and if it exceeds 40 parts by weight, it becomes difficult to select the emulsifying conditions.

The edible oil-based medium-chain fatty acid triglyceride refers to a fatty acid component composed of a saturated fatty acid having 8 to 10 carbon atoms, and is a liquid oil generally called medium chain triglyceride (MCT).

The amount of the edible oil-based medium-chain fatty acid triglyceride to be added is preferably 5.75 to 14.60% by weight based on the amount of the natural tocopherol. If the amount is less than the lower limit, it becomes difficult to produce good emulsification, and the amount exceeds the upper limit. And the fat / oil content ratio becomes excessive, which is not preferable.

The polyglycerin fatty acid ester is an ester of a glycerin polymer (preferably 2 to 10 polymers) and a fatty acid, such as hexaglycerin monolaurate, hexaglycerin monostearate, hexaglycerin monooleate, and decaglycerin monocaprin. Acid esters, decaglycerin monolaurate, decaglycerin monostearate, decaglycerin monooleate, tetraglycerin condensed ricinoleate, hexaglycerin condensed ricinoleate, and the like can be used. Of these, generally, hexaglycerin monolaurate (HLB13.8) hexaglycerin monostearate (HLB12.2) decaglycerin monostearate (HLB14.5) hexaglycerin monooleate (HLB12.2) Decaglycerin monooleate (HLB14.5) and the like are preferably used.

As the glycerin fatty acid ester, those generally used as food additives can be appropriately used. For example, stearic acid monoglyceride and the like can be used.

As the sorbitan fatty acid ester, those generally used as food additives can be appropriately used, and for example, sorbitan monooleate and the like can be used.

It is preferable to use 3.0 to 9.8% by weight of these natural tocopherols. If the amount is less than the lower limit, good emulsification cannot be obtained.

Xanthan gum, guar gum,
Natural products such as locust bingham and gellan gum are preferred. The preferred amount of addition is 0.3 to 1% by weight (based on natural tocopherol). When the amount is less than the lower limit, the viscosity is insufficient, and when the amount is more than the upper limit, the emulsion viscosity is increased and the emulsification fluidity during production is inhibited. But not preferred.

As the sucrose fatty acid ester, those commonly used as food additives can be appropriately selected. For example, an esterified product of sucrose with stearic acid, palmitic acid, or the like can be used. Its preferred use range is from 1.9 to 4.8% by weight. When the amount is below the lower limit, a good emulsion cannot be obtained, and when the amount exceeds the upper limit, a good emulsion cannot be obtained in relation to the amount of added water.

As ethyl alcohol, modified ethyl alcohol having an alcohol purity of 95% or more is particularly preferred. This denatured ethyl alcohol can be used which corresponds to the use name: No. 11 for food preservation, flavor classification flavor H-No. 9 (alcohol 200 / flavor 1.5 kg) in the list of uses approved by the Ministry of International Trade and Industry.

This ethyl alcohol is used as the above-mentioned natural emulsion stabilizer and dispersant for the sucrose fatty acid ester.
The preferred range of use is 3.8 to 9.8% by weight. Below the lower limit, the dispersing effect becomes insufficient, and if it exceeds the upper limit, no further improvement in the dispersing effect is seen, and it is useless.

D-sorbitol and starch-decomposed saccharified product (for example, maltose starch syrup, isomerized syrup, hydrogenated starch syrup, etc.) are used in an amount of 29 to 55 parts by weight based on 5 to 40 parts by weight of natural tocopherol. If the amount is less than 29 parts by weight, the taste and the like are often undesirably lost. Exceeding 55 parts by weight is not preferred because of excessive sweetness. As vegetable oils, corn oil, rapeseed oil, soybean oil, palm kernel oil, and the like can be used arbitrarily for the purpose of improving aromaticity and taste. The amount is from 9.5% to 12% with respect to the natural tocopherol compounding amount, and if it is less than 9.5%, it lacks aroma and taste. If it is 12% or more, an excessive amount of fats and oils is caused, which is not preferable.

Further, the amount of water used in the present invention is preferably from 22 to 40 parts by weight based on the total amount of the components. The aromatic water-dispersible natural tocopherol-rich emulsion obtained in this manner is excellent in isomerized sugar solution, D-sorbitol solution, reduced starch saccharified product, and soy sauce-based seasoning, which is a kind of starch degradation product. For example, 70% by weight of reduced starch saccharified product and 30% by weight of natural tocopherol-rich O / W emulsion are primarily dispersed at a ratio of 30% by weight to easily produce various edible oil / fat-based foods for antioxidant purposes. Available to

In order to maximize the antioxidant ability of the natural tocopherol-rich O / W emulsion, a complex of natural phytic acid, ascorbic acid, ascorbic acid stearate, and sodium citrate was used as a metal chelating agent. The body can be used in combination for the production of the natural tocopherol-rich O / W emulsion.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention.

Examples 1 to 5 Five types of natural tocopherol-rich O / W emulsions having the composition ratios shown in Table 1 were prepared, and were primarily dispersed as shown in Table 2 at the following four types of compounding ratios. 100 of the dispersion
Indirect heating was performed at 2 ° C. for 2 hours, and the heat-resistant emulsification stability was evaluated. The results are shown in Table 5.

The order of each seasoning in which Examples 1 to 5 were dispersed into four types of seasonings was classified into A, B, C, and D as shown in Table 2.

Seasoning categories B and C of the primary dispersion emulsion shown in Table 2
Was picked up and secondary-dispersed in the following five compounding ratios as shown in Table 3, and the secondary dispersion emulsification stability was evaluated and the results are shown in Table 5.

Then the total amount of natural tocopherol in the secondary dispersion is
It is as shown in the following equation.

As is clear from Table 4, the secondary dispersion results in Table 3,
It can be used in various food fields.

The propylene glycol fatty acid ester and the sorbitan fatty acid ester used in Example 5 and Comparative Examples 1 and 2 have high emulsifying performance when used in combination with polyglycerin fatty acid esters, but the foaming conditions are limited. It is not preferable for dispersion or the like.

TABLE 1 Non-dispersed natural tocopherol O / W emulsions of Examples 1 to 5 obtained in Table 1 and Examples 1 to 5 of Examples 1 to 5 obtained in Table 2.
The primary dispersion of each of the seasoning dispersion examples A, B, C, and D was subjected to a heat-durable emulsification stability test. The emulsion was stored in a thermostat set at 50 ° C. for 20 days, and the emulsion stability was measured. The results are shown in Table 5.

The evaluation method of the emulsification stability test of the non-dispersed natural tocopherol O / W emulsion and the primary dispersion was performed as follows.

(1) Direct heating method In a Erlenmeyer flask or a beaker, a heat test was carried out for 2 hours at 100 ° C. in Table 2 of the non-dispersed natural tocopherol O / W emulsions 1 to 5 obtained in Examples of Table 1 and primary dispersion. The primary dispersion emulsion was put in the flask and heated to 80 ° C to 100 ° C in an open flame or in a boiling water bath to determine the presence or absence of phase separation between the natural tocopherol and the oil component.

(2) Indirect heating method The heating durability test was performed by the direct heating method of (1). Each emulsion was placed in a thermostat set at 50 ° C for 10 days (24 hours).
0 hour) The presence or absence of phase separation between the natural tocopherol and the fat component contained in the severe test was determined.

Next, the emulsification stability of the secondary dispersed natural tocopherol emulsion obtained at the five compounding ratios shown in Table 3 was measured.

(1) Emulsification stability visual test The emulsified material dispersed secondarily was placed in a graduated cylinder, stored in a thermostat set at 25 ° C for 10 days, and then visually separated and observed. The graduated cylinder was wrapped.

The particles of the secondary dispersed emulsion visually observed in (1) were observed.

(2) Microscopic Inspection Method The emulsion stability colloid formation of the secondary dispersion emulsion was observed with a microscope, emulsification stable dispersion state and micron scale were attached, and the micron numerical value was enlarged by 600 times. Was observed.

Microscopic examination of the secondary dispersion emulsion revealed the following.

Dispersion material conditions Dispersion material to be used for secondary dispersion, for example, sterilized purified water or normal tap water, acidity 4.5% edible rice vinegar, alcohol purity 5
Secondary dispersion of 0% denatured ethyl alcohol, 17.8% salt soy sauce, 1% sodium salt solution (1% trisodium phosphate solution) secondary dispersion material, primary dispersion natural tocopherol emulsion obtained by primary dispersion respectively The present invention has also revealed that the micron value at the time differs. Next, Table 4 shows the results of the microscopic microscopic case inspection.

As a result of the micron-scale inspection of the microscope shown in Table 4, the secondary dispersion emulsified in each of the five types of dispersing materials was 0.1%.
It was a very small micron of 8 μm to 3.0 μm or less. Especially in sterilized purified water and ordinary tap water, alkaline salt water, denatured ethyl alcohol, etc., Brownian movement is observed by microscopic examination, and natural tocopherol, which is extremely difficult to emulsify, is used in the present invention to develop ultra-small particles. , From microns to Angstroms.

Emulsification stability of Examples and Comparative Examples in Table 1 and primary,
The evaluation criteria of the emulsion stability of the secondary dispersion emulsion are as follows.

(1) Examples and Comparative Examples and Evaluation Standards for Evaluating Emulsion Stability of Primary Dispersion Emulsions…: Extremely Stable…: Draft △: Unstable (2) Evaluation Criteria for Emulsion Stability of Secondary Dispersion Emulsions Incidentally, the emulsion stability evaluation criteria of Examples and Comparative Examples and the primary dispersion emulsion of the above (1), evaluation by microscopic inspection results, when the particle size is 5 μm or less, it is extremely stable, When it was more than 5 μm and less than 10 μm, it was regarded as stable, and when it was 10 μm or more, it was regarded as unstable. Evaluation criteria of emulsion stability of secondary dispersion, evaluation by microscopic inspection results, the particle size is 2.5μm or less that the Brownian motion develops in general is ultra-stable, 2.5μm or more to 5μ
In the case of m or less, the development of Brownian motion is partly inspected.
Those having a size of not less than μm and not more than 10 μm were regarded as stable. Also, 10μ
Those with m or more were regarded as unstable.

Further, the numbers of the dispersant seasonings in Table 5 showing the results of the evaluation of the emulsion stability are shown based on the order of use of the dispersion seasonings in Tables 2 and 3.

As can be seen from Table 5, Examples 1 to 5 having the compositions shown in Table 1 show excellent emulsification stability at ultra-micron numerical values.

Further, the natural tocopherol-rich O / W emulsions obtained in Examples 1 to 5 were dispersed by the primary dispersion method in Table 2, and the compositions shown in Tables 6 and 7 were obtained using the dispersed emulsions. And soy sauce soup for powdered rice crackers, powdered soups and dry sausages, iriko boiled water, frozen fish immersion liquid, sourdough surimi, small fish surimi, etc. were manufactured. The stability of the emulsion in the food was evaluated by microscopy, and the antioxidant stability as an antioxidant was evaluated for peroxide value (POV) using the Wheeler heating method. The degrees are shown in Table 8. (The seasoning category C of the primary dispersion method in Table 2 was used as a reference.) The evaluation criteria of the emulsion stability and antioxidant stability in the foods manufactured in the examples of Table 8 are as follows.

◎ …… Extremely stable ○ …… Predicted △ …… Unstable Light mouth soy sauce for fried rice crackers, powdered soups and dry sausages, iriko (Jako) boiling water, frozen fish immersion liquid,
Surimi and other surimi are rich in natural tocopherol
As a result of using the O / W emulsion, there was no taste and no inhibition, the taste was good, and as is clear from Table 8, the emulsion stability and antioxidant stability were good. Was. Particularly good results were obtained when a dispersant in the field of starch degradation products was used in the primary dispersion method.

〔The invention's effect〕

The O / W emulsion having a high content of natural tocopherol produced by the method of the present invention has a very small dispersed particle size of 3 μm or less, and is particularly excellent in dispersibility, and is particularly suitable for water, alcohols, acids, alkalis, salts, and hot water. And the like, and the emulsion stability is extremely good, and good antioxidant stability can be maintained for a long period of time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location A23L 1/24 A23L 1/24 A 1/31 1/31 A 1/325 1/325 A 101 101D 1/40 1/40

Claims (2)

(57) [Claims] 1. A method for producing an O / W emulsion containing natural tocopherol, comprising: (i) 5 to 40 parts by weight of the natural tocopherol, 5.75 to 14.60% by weight of edible oil-based medium-chain fatty acid triglyceride (based on the natural tocopherol) ) And at least 3.0 to 9.8% by weight (based on the natural tocopherol) selected from the group consisting of polyglycerol fatty acid ester, glycerin fatty acid ester and sorbitan fatty acid ester, to obtain a mixed oil and fat solution. A step wherein the fatty acid of the edible oil-based medium-chain fatty acid triglyceride is a saturated fatty acid having 8 to 10 carbon atoms; (ii) 0.3 to 1.0% by weight of an emulsion stabilizer (based on the natural tocopherol); 1.9-4.8% by weight of fatty acid ester (based on the natural tocopherol) and 3.8-9.8% by weight of ethyl alcohol ( A mixture of 22-40 parts by weight of sterilized purified water) and heating the mixture by boiling, wherein the emulsion stabilizer comprises xanthan gum, guar gum, locust bingham and gellan gum. And (iii) stirring the mixed solution obtained in the step (ii) into the mixed oil and fat liquid obtained in the step (i) under heating. (Iv) preparing a mixed solution comprising: 29-55 parts by weight of at least one selected from the group consisting of D-sorbitol and starch-decomposed saccharified product; Mixing and stirring the mixture in the mixture obtained in the step (iii) while maintaining the temperature at 40 ° C. or higher. 2. The method according to claim 1, wherein 9.5 to 11.8% by weight of vegetable oil (based on the natural tocopherol) is added and mixed in the step (ii).