JP5012709B2 - Bulk oil - Google Patents

Description

The present invention relates to a bulk oil containing an oil degradation inhibitor.

  Polyunsaturated fatty acids such as linoleic acid, linolenic acid, eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are important substances as precursors of essential fatty acids or prostaglandins, and recently have antithrombotic activity. In addition, it is also attracting attention from the viewpoint of physiological activities such as senile dementia prevention. These polyunsaturated fatty acids are used in foods and cosmetics in the form of fatty acids or fats.

However, since these polyunsaturated fatty acids have many unsaturated bonds, the oxidation proceeds rapidly. For this reason, harmful peroxides are generated and acid odor is produced, so it is necessary to take measures to prevent oxidation.
As conventional techniques related to prevention of deterioration of bulk oil, addition of an antioxidant, coating with a fatty acid or oil and fat, and powdering are known (for example, see Patent Document 1). However, this method has a problem that the effect is not sufficient. For example, although BHT (butylated hydroxytoluene), BHA (t-butylhydroxyanisole), tocopherol, etc. are currently approved as antioxidants in Japan, there are restrictions on the use of BHT and BHA, and safety The use was almost refrained from doubt. Furthermore, there is an optimum amount of tocopherol that gives the strongest antioxidant power, and there is a limit to the antioxidant power that can be expected. In addition, the technology of coating and powdering is effective to some extent, but this technology cannot completely block oil and air, and it is also disadvantageous in terms of the complexity of the process and cost. On the other hand, it was not a satisfactory method considering the restrictions on use resulting from the form.

Addition of a specific emulsifier is known as a conventional technique relating to prevention of deterioration of oil in an emulsion such as O / W or W / O emulsion (for example, see Non-Patent Document 1). However, this method has a problem that the effect is not sufficient. For example, Hara et al. Have reported the antioxidant behavior of phospholipids (lecithin) against highly unsaturated fatty acids in fish oil (see Non-Patent Document 2). According to the above report, although lecithin has an antioxidant power against fish oil, it needs to be added in an amount of 5-8% or more with respect to fish oil.
Japanese Patent Laid-Open No. 9-59669 Atsushi Aoyama, Takenori Maruyama, Hiroshi Kanematsu, Tsutomu Shintani, “Oil Chemistry”, Japan Oil Chemical Society, July 20, 1985, Vol. 34, no. 7, P554-557 Setsuko Hara, Norio Okada, Hidehiko Hibino, Yoichiro Toya, “Oil Chemistry”, Japan Oil Chemistry Association, February 20, 1992, Vol. 41, no. 2, P130-135

This invention was made paying attention to such a conventional problem, and the object is development of the bulk oil containing an oil degradation inhibitor .

Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that an oil deterioration inhibitor containing a specific active oxygen removing compound and a specific coating agent has an excellent effect in preventing oil deterioration. The inventors have found out that the present invention has been achieved and have reached the present invention.
That is, the gist of the present invention is that 0.1 to 20% by weight of a rosemary water-insoluble extract as a compound having an active oxygen removing ability having an IC50 value of 10,000 ppm or less, and dispersibility in water at 25 ° C. There resides a bulk oil, wherein the surface tension contains oil antidegradant you containing polyglycerol fatty acid ester 10 to 95% by weight of the following coating agent 40 mN / m.

The bulk oil containing the oil deterioration preventing agent of the present invention exhibits a very excellent effect for preventing oil deterioration.

The oil deterioration preventing agent of the present invention contains a compound having an IC50 value of 10,000 ppm or less and an active oxygen removing ability, and a film agent that is dispersible in water at 25 ° C. and has a surface tension of 40 mN / m or less. It is characterized by that.
[Oil deterioration inhibitor]
(1) Compounds having ability to remove active oxygen Active oxygen has recently attracted attention as having an adverse effect on the human body. Active oxygen is also called active oxygen radical or free radical. Generally, superoxide (· _{O 2} ^-), hydroxy radical (HO ·), hydrogen peroxide _{(H 2 O} 2), are called active oxygen refers to four of singlet oxygen (1O _2). In addition, hydroperoxy radicals (HOO.), Peroxy radicals (LOO.), Alkoxy radicals (LO.), And the like are considered active oxygen in a broad sense.
The active oxygen removal ability can be measured by the following method. The active oxygen removing ability (IC50 value) is preferably 10,000 ppm or less, more preferably 500 ppm or less, and further preferably 300 ppm or less.

<Measurement method of active oxygen removal ability (IC50 value)>
Oxygen radical anions are generated in the system by adding xanthine-xanthine oxidase to each sample aqueous solution prepared at various concentrations of 0.001, 0.003, 0.01, 0.03, and 0.1% by weight. The sample removes this oxygen radical anion. This degree is calculated by taking the distilled water to which the sample has not been added as 100% and removing the ratio for each concentration. Plot the removal rate (enzyme inhibitory activity) obtained from each concentration, curve fit, and use the linear function (linear expression) where the linear relationship between concentration and enzyme inhibitory activity is established when the concentration is taken logarithmically. Thus, the sample concentration (IC50) when the enzyme inhibition activity was 50% was calculated as the ability to remove active oxygen.

  Examples of the compound having active oxygen removing ability include polyphenols. Among these, for example, flavonoids and their related components (catechin, quercetin, kaempferol, myricetin, rutin, anthocyanin, polyphenol, luteolin, etc.), phenylpropanoids (chlorogenic acid, ferulic acid, coumaric acid, quinic acid, Rosmarinic acid), polyphenol polymer, tannin, grape seeds and diterpenes (carnosol, carnosic acid, rosmanol, epirosmanols), saponins and vitamins. Of these, tea extract, grape seed extract, and rosemary extract are preferable. Regardless of bulk or emulsification system, rosemary water-insoluble extract that can be dissolved in oil is preferable for preventing deterioration of oil, and can be dissolved in water for preventing deterioration of oil in O / W and W / O emulsions. Rosemary water-soluble extract is preferred.

  Usually, rosemary extract is obtained by extraction from rosemary. This extract can be either water-soluble or water-insoluble depending on the method of treating the extraction solvent or the extract. A water-soluble extract is obtained by, for example, treating with ethanol having a water content of 40 to 60%, adding water to this extract to precipitate a water-insoluble component, and then distilling off the solvent component after removing the water-insoluble component. It is done. As with the water-soluble extract, the water-insoluble extract is treated with, for example, ethanol having a water content of 40 to 60%, water is added to the extract to precipitate water-insoluble components, and activated carbon is further added thereto. After stirring, the mixture of the water-insoluble component and the activated carbon component is filtered from the solution, this mixture is treated and extracted with ethanol, and the solvent is distilled off from the extract to obtain a powdery water-insoluble solution. Can be obtained (Japanese Patent Publication No. 59-4469). For the extraction, the whole plant of rosemary or its leaves, roots, stems, flowers, fruits and seeds may be used, but leaves are preferably used. It is preferable that the extraction is performed after chopping rosemary because the extraction efficiency is high.

(2) Coating agent that is dispersible in water at 25 ° C. and has a surface tension of 40 mN / m or less. A coating agent refers to one that can form a coating at the air-oil interface or water-oil interface. In the present invention, the dispersibility in water under the condition of 25 ° C. means that the coating agent is added to and stirred at 25 ° C. water so as to be 1% by weight, and after heating to 70 ° C., the coating agent becomes familiar with water. Then, it is left to cool, and when it reaches 25 ° C., it is allowed to stand and the appearance is observed. After 10 seconds, no precipitate is seen on the bottom.

The surface tension of the coating agent is measured by a plate method (Wilhelmy method) using a 1% by weight aqueous coating agent solution. The surface tension of the coating agent is 40 mN / m or less, preferably 35 mN / m or less, and usually 5 mN / m or more.
The coating agent preferably has 4 or more hydroxyl groups or an ionic group. More preferably, those having 6 or more hydroxyl groups or 2 or more ionic groups are preferred. Further, the hydrocarbon chain length is 6 to 22 carbon atoms, preferably 6 to 18 or 20 to 22 having one or more unsaturated groups.

  Examples of the film agent of the present invention include silicon and an emulsifier, but an emulsifier is preferable. The HLB of the emulsifier is preferably 11 or more, more preferably 15 or more, and usually 50 or less. Silicon is preferably hydrophilic silicon. Examples of the emulsifier include sucrose fatty acid ester, polyglycerin fatty acid ester, polysorbate, lecithin (excluding lecithin), organic acid monoglycerin ester, lactic acid fatty acid ester and the like. Among them, sucrose fatty acid ester, polyglycerin fatty acid Esters are preferred. Two or more of the above compounds may be used in combination as a coating agent.

(3) Other components In addition to the above, as a component to be blended with the oil deterioration inhibitor, in the case of bulk fats and oils, an unsaturated fatty acid having a low HLB value is used as a constituent fatty acid in order to improve the solubility of the antioxidant in oil. Add the emulsifiers included as The HLB of the emulsifier is usually 5 or less, preferably 3 or less, and usually 1 or more. In the case of an emulsion, a pH adjuster or a polysaccharide is added in order to improve the emulsion stability.

(4) Content of each component in oil deterioration inhibitor The content of the compound having the ability to remove active oxygen in the oil deterioration inhibitor is usually 0.1 to 20% by weight, preferably 0.2 to 10%. % By weight. In addition, the content of the coating agent that is dispersible in water and has a surface tension of 40 mN / m or less in the oil deterioration preventing agent is usually 10 to 95% by weight, preferably 20 to 75% by weight. It is. The ratio (weight ratio) of the compound having the ability to remove active oxygen in the oil deterioration inhibitor and the dispersant is usually 1 to 500: 50 to 5000, preferably 3 to 500: 100 to 2000, and more preferably 5 to 300. : 100-1000.
The oil deterioration preventing agent of the present invention is added to emulsions such as the following bulk oil, O / W, and W / O emulsions to prevent oil deterioration (oxidation).

[Bulk oil]
Bulk oil is usually obtained by processing and refining vegetable oils such as safflower oil, olive oil, cottonseed oil, rapeseed oil, corn oil, soybean oil, palm oil, sunflower oil, sesame oil, and the like derived from natural products. , Lard, milk fat, and other animal oils, and oils and fats that are obtained by processing and purification from them, and that are said to deteriorate in the world. As other compounding components, there are lecithin and tocopherol originally present in fats and oils.

To these oils and fats, the above-mentioned oil deterioration preventing agent may be added, or a compound having an ability to remove active oxygen and a coating agent may be added separately.
The amount added to the oil is usually 10 to 5000 ppm, preferably 30 to 5000 ppm, more preferably 50 to 3000 ppm for a compound having an ability to remove active oxygen, and the coating agent is usually 0.05 to 5% by weight, preferably The content is preferably 0.1 to 2% by weight, more preferably 0.1 to 1% by weight. If the amount of the compound having active oxygen removing ability or the coating agent is too large, each of them will not dissolve in oil, and problems such as taste and smell will occur.

[Emulsions such as O / W and W / O emulsions]
The fats and oils used as the emulsion are usually the fats and oils exemplified for the bulk oil. The mixing ratio of water and oil varies depending on the form of food. Generally, when water> oil, an O / W emulsion is formed, and when oil> water, a W / O emulsion is formed.
Other compounding ingredients include lecithin and tocopherol originally present in vegetable oils. Moreover, in order to improve emulsification stability, a pH adjuster, a polysaccharide, and a specific gravity adjuster are added.
The emulsion stability may change dramatically depending on the pH, and a pH adjuster may be used for this purpose. Examples of pH adjusters include organic acids such as citric acid and DL-malic acid and salts thereof, carbonates such as sodium carbonate, and phosphoric acids such as phosphoric acid. Polysaccharides are used for viscosity adjustment and increase the emulsion stability. Examples of polysaccharides include pectin and sodium carboxymethylcellulose. The specific gravity adjusting agent suppresses that the emulsification becomes unstable due to different specific gravity of water and oil.

Preparation methods for emulsions such as O / W and W / O emulsions are described in detail in the book ("Emulsion Basics and Stabilization and Evaluation Technology", Technical Information Association, published on September 30, 1998). is described.
The oil deterioration preventing agent may be added to a mixture of oil and water before homogenization, or may be added to fat or water before homogenization. Moreover, you may add the compound which has active oxygen removal ability, and a film agent separately. It is preferable to add the water-soluble coating agent and the water-soluble active oxygen removing compound to water.

  The amount added to the oil is usually 10 to 5000 ppm, preferably 30 to 5000 ppm, more preferably 50 to 3000 ppm for a compound having an ability to remove active oxygen, and the coating agent is usually 0.05 to 5% by weight, preferably The content is preferably 0.1 to 2% by weight, more preferably 0.1 to 1% by weight. If the amount of the compound having active oxygen removing ability or the coating agent is too large, each of them will not dissolve in oil, and problems such as taste and smell will occur.

  The oil deterioration preventing agent of the present invention is added to foods and cosmetics composed of bulk oil or an emulsifying system, and prevents deterioration of foods and cosmetics. Examples of foods include processed fats and oils including edible oils, processed fast spread mayonnaise, processed processed fats and oils, and confectionery such as potato chips and karinto. In addition, beverages containing a small amount of oil contained in wheat, coffee beans, and the like, milk beverages such as cafe au lait and milk tea, and desserts such as pudding and ice cream are also included. Examples of cosmetics include emulsions of O / W and W / O emulsions, and whitening agents and humectants used for the purpose of suppressing oil deterioration on the body surface. Furthermore, the clothes used for health promotion etc. for the purpose of suppressing the oil deterioration of the body surface are mentioned. On the other hand, toiletries such as a sheet in which the oil content on the surface deteriorates due to oxides contained in the air and a fragrance containing an oily fragrance component are included.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited in particular to these.
<Production of rosemary-water-soluble extract>
10 kg of 50% water-containing ethanol was added to 1 kg of rosemary, heated under reflux for 3 hours, and filtered while warm to obtain a filtrate. The operation of extracting and treating the residual with 6 L of 50% aqueous ethanol in the same manner was further repeated twice to obtain a filtrate. When these filtrates were combined and 5 L of water was added, a precipitate was deposited. To this solution, 100 g of activated carbon was added, stirred for 1 hour, allowed to stand overnight in a cold place, and then filtered to obtain a filtrate. This was concentrated under reduced pressure to obtain 120 g of rosemary water extract.

<Production of Rosemary-water-insoluble extract>
10 kg of 50% aqueous ethanol was added to 1 kg of rosemary, heated under reflux for 3 hours, and filtered while warm to obtain a filtrate. The residue was similarly treated and extracted with 6 L of 50% aqueous ethanol in the same manner twice to obtain a filtrate. When these filtrates were combined and 5 L of water was added, a precipitate was deposited. To this filtrate, 100 g of activated carbon was added, stirred for 1 hour, allowed to stand overnight in a cool place, and then filtered to obtain a mixture of precipitate and activated carbon. 4 L of ethanol was added to this mixture, and the mixture was heated to reflux for 3 hours and filtered while warm to obtain a filtrate. An operation of treating and extracting the residue with 2.4 L of ethanol in the same manner was further repeated twice to obtain a filtrate. These filtrates were combined, concentrated under reduced pressure, and ethanol was distilled off to obtain a powdery rosemary water-insoluble extract.

<Measurement of active oxygen removal ability>
2.4 ml of 0.05 M Na ₂ CO ₃ buffer solution was taken into a test tube, and 0.1 ml each of 3 mM xanthine, 3 mM ethylenediaminetetraacetic acid, and 0.75 mM nitroblue tetrazolium was added. To this was added 0.1 ml of active oxygen eliminating compound (concentration 0.001, 0.003, 0.01, 0.03, 0.1%), left at 25 ° C. for 10 minutes, and then added 0.1 ml of xanthine oxidase solution. Stir quickly and start incubation at 25 ° C. After 20 minutes, 0.1 ml of 6 mM CuCl ₂ was added to stop the reaction, and the absorbance was measured at 560 nm. The blank was operated as described above using distilled water instead of the antioxidant. Enzyme inhibition using a linear function (linear expression) where a linear relationship is established between the concentration and enzyme inhibition activity when the enzyme inhibition activity obtained from each concentration is plotted, curve-fitted, and the concentration is taken logarithmically. The sample concentration (IC50) when the activity reached 50% was calculated. The results are shown in Table 1.

<Observation of water dispersibility>
The emulsifier of Table 2 was added to 25 ° C. water so as to be 1% by weight, stirred and heated to 70 ° C., confirmed that the emulsifier had become familiar with water, allowed to cool, and allowed to stand at 25 ° C. The appearance was observed. In this appearance observation, when the precipitate was seen at the bottom in 10 seconds, the dispersibility in water was evaluated by assuming that no precipitate was seen at the bottom in 10 seconds. The results are shown in Table 2.
<Surface tension measurement>
A 0.1% by weight aqueous solution of the emulsifier of Table 2 was prepared, and this was measured by a plate method (Wilhelmy method) at a measurement temperature of 25 ° C. The results are shown in Table 2.

S1670: Sucrose fatty acid ester HLB16 Mitsubishi Chemical Corporation S570: Sucrose fatty acid ester HLB5 Mitsubishi Chemical Corporation L10D: Polyglycerol monolaurate ester Mitsubishi Chemical Corporation Er60D: Polyglycerol hexaerucate Made by Mitsubishi Chemical Corporation

<Oil degradation prevention test>
Example 1 , Reference Example 1 , Comparative Examples 1 and 2 Bulk oil and fat system 1 part by weight of the active oxygen removing agent shown in Table 3 and 10 parts by weight of the coating agent were mixed to prepare an oil deterioration preventing agent. This oil deterioration inhibitor 0.11% by weight was added to soybean oil, which was put into a predetermined container, blown with air, and kept at 100 ° C. In general, oil is an oxidative deterioration phenomenon, and after the start, a certain volatile component comes out with time, and thereafter, the volatile component rapidly increases with time due to oxidative deterioration. The time when the volatile component increased rapidly was defined as the oxidation induction time (Rancimat test method). When the oil and fat deterioration preventing agent was added, the increase ratio was evaluated as the oil deterioration preventing ability as compared with the case of the compound having the active oxygen removing ability alone. In addition, what improved 5% or more was judged to be effective.

Reference Examples 2-4 , Comparative Examples 3-4 O / W Emulsion System 1 part by weight of the active oxygen removing agent shown in Table 3 and 10 parts by weight of the coating agent were mixed to prepare an oil deterioration preventing agent. 30 parts by weight of pharmacopoeia soybean oil and 70 parts by weight of water are mixed, and an oil deterioration inhibitor is added to this so as to be 0.11% by weight with respect to pharmacopoeia soybean oil, and homogenized (6000 rpm, 10 minutes, 40 ° C.). did. The emulsion was placed in a container and incubated at 70 ° C. Sampling was performed after a certain time, and only the oil and fat were extracted, the amount of peroxide at wavelengths of 215 nm and 240 nm was measured, and the amount of peroxide in the oil after 20 hours was compared with the blank, and this was evaluated as the ability to prevent oil deterioration. In addition, what improved 5% or more was judged to be effective. The results are shown in Table 4.

Reference Examples 5-7 , Comparative Examples 5-6 W / O Emulsion System 1 part by weight of the active oxygen removing agent shown in Table 3 and 10 parts by weight of the coating agent were mixed to prepare an oil deterioration preventing agent. 70 parts by weight of pharmacopoeia soybean oil and 30 parts by weight of water are mixed, and an oil deterioration inhibitor is added to this so as to be 0.11% by weight with respect to the pharmacopoeia soybean oil, and homogenized (6000 rpm, 10 minutes, 40 ° C.). did. The emulsion was placed in a container and incubated at 70 ° C. Thereafter, the same treatment as in the O / W system was performed, and the oil deterioration prevention ability was evaluated. The results are shown in Table 5.

  From this, it can be seen that the oil deterioration preventing agent of the present invention greatly contributes to prevention of oil deterioration.

Claims (4)

Rosemary water-insoluble extract 0.1 to 20% by weight as a compound having an IC50 value of 10,000 ppm or less and an ability to remove active oxygen, dispersibility in water at 25 ° C., and surface tension of 40 mN / m The bulk oil characterized by containing the oil degradation inhibitor containing 10-95 weight% of polyglyceryl fatty acid esters as the following coating agents. The bulk oil according to claim 1, wherein the polyglycerin fatty acid ester as a film agent in the oil deterioration preventing agent has a hydrocarbon chain length of 6 to 18 carbon atoms. The bulk oil according to claim 1 or 2, wherein an addition amount of the rosemary water-insoluble extract as a compound having an ability to remove active oxygen in the oil deterioration inhibitor to the bulk oil is 10 to 5000 ppm. The bulk oil according to any one of claims 1 to 3, wherein an addition amount of the polyglycerin fatty acid ester as a film agent in the oil deterioration preventing agent to the bulk oil is 0.05 to 5% by weight.