JP4887351B2 - Isothiocyanate emulsion composition - Google Patents

Description

  The present invention relates to an emulsified composition of isothiocyanate such as horseradish essential oil, mustard essential oil or allyl isothiocyanate. More specifically, the present invention relates to an emulsion composition of an isothiocyanate ester that has good emulsion stability, is unlikely to decompose the isothiocyanate ester, and is easily dispersed uniformly in water.

  Wasabi and mustard have long been familiar as flavored spices such as sashimi, buckwheat, oden, tonkatsu and beef steak using their sharp spiciness. Wasabi and mustard spicy ingredients are isothiocyanate esters based on the highly volatile allyl isothiocyanate. It is used in various foods and beverages such as seasonings to be attached to the outside such as snacks and mustard-flavored snacks, and various irritating beverages. Moreover, it has been widely used as a volatile antibacterial agent utilizing its antibacterial property and volatility, and a freshness maintaining agent for fresh products. Isothiocyanates are also known as mustard oil, and are naturally found in the form of glycosides in wasabi, horseradish, mustard seeds, etc., and by grinding these tissues in the presence of water, β-glucosidase One type of myrosinase acts on glycosides and hydrolyzes them. Allyl isothiocyanate is also available as a synthetic product in addition to these naturally derived ones and is also designated as a food additive.

  On the other hand, since isothiocyanate is oil-soluble, when used in foods and drinks containing a lot of water, such as beverages and non-oil dressings, it is difficult to use unless it is emulsified and solubilized or dispersed in water. There are drawbacks.

  In order to obtain a stable O / W emulsion of an isothiocyanate, various emulsifiers and emulsification methods have been tried in the past. For example, 5% to 80% of isothiocyanates dissolved in oil, glycerin fatty acid 0.2% to 5.0% of edible emulsifier in which ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester and lecithin are appropriately combined, and 0% to 5.0 of emulsion stabilizer such as sticky substance % And water-in-water emulsion (Patent Document 1), oil-in-water type obtained by emulsifying oil and water containing 80% (W / W)% or more of allyl isothiocyanate with an emulsifier containing phospholipid Emulsion (Patent Document 2), allyl isothiocyanate 0.001% to 80% by weight, sorbitan fatty acid ester, polyoxyethylene sol It consists of a mixture of emulsifier and emulsifier such as tan fatty acid ester, polyoxyethylene polyoxypropylene glycol, polyoxyethylene hydrogenated castor oil, alkyl alkanolamide, polyglycerin fatty acid ester, sucrose fatty acid ester, and evenly in water Allyl isothiocyanate preparation characterized by being mixed (Patent Document 3), stable isothiocyanate emulsion composition obtained by emulsifying isothiocyanate ester with a specific decomposition product of cereal protein (patent) Reference 4), containing isothiocyanate compound and aliphatic carboxylic acid, tetraoleic acid polyoxyethylene sorbit, polyoxyethylene fatty acid ester, sorbitan mono, di or tri fatty acid ester, polyoxyethylene sorbitan fatty acid ester Disclosed is a gel composition emulsified with an emulsifier such as polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylenyl glycol, polyoxyethylene alkyl ether, glycerin fatty acid ester, and ethylene glycol fatty acid ester (Patent Document 5). ing.

Japanese Patent Publication No.58-2669 JP-A-6-47272 JP-A-6-303952 JP-A-9-308454 JP-A-10-276746

  However, it is difficult to say that an emulsion composition of an isothiocyanate ester that is sufficiently satisfactory in terms of the stability of the emulsion, the decomposition stability of the isothiocyanate ester, and the ease of dispersion in water is still undeveloped.

  The problem to be solved by the present invention is an emulsion composition of isothiocyanate ester, in which the emulsion stability is good, the decomposition of the isothiocyanate ester does not easily occur, and it is easy to uniformly disperse in water. It is to provide.

  In order to solve the above-mentioned problems, the present inventors have intensively studied particularly on selection of emulsifiers and combinations thereof. For example, we tried to emulsify isothiocyanate using polyglycerin fatty acid ester, which is generally excellent in emulsifying power, but polyglycerin fatty acid ester tends to be slightly alkaline, and alkaline and unstable isothiocyanate is decomposed. It turned out to be easy to emulsify and unsuitable for emulsification. Polyoxyethylene sorbitan fatty acid ester is also described in Patent Documents 3 and 5 as an emulsifier suitable for emulsification of isothiocyanate, but has a drawback that a large amount of alcohol or water is required for dissolution. It has been found. Furthermore, as described in Comparative Example 2 of the above-mentioned patent document, it was confirmed that Quillaja saponin is in a good state immediately after emulsification, but the emulsified particles become larger with time and are separated.

  However, surprisingly, when emulsification of an isothiocyanate ester was attempted by using both polyoxyethylene sorbitan fatty acid ester and kiraya saponin as an emulsifier, the emulsion stability was good and the emulsion particles over time In addition, it was difficult to decompose the isothiocyanate, and it was possible to obtain an emulsified composition having very good dispersibility in water.

Thus, according to the present invention, (D) Quillaja saponin is mixed and dissolved in (D) water and / or an aqueous phase comprising a polyhydric alcohol. Separately, (A) isothiocyanate, (C) polyoxy The present invention provides a method for producing an O / W emulsion composition , comprising dissolving an ethylene sorbitan fatty acid ester, mixing both, and emulsifying the mixture .

The present invention also includes (A) 0.1 to 40% by mass of isothiocyanate ester, (B) 0.05 to 20% by mass of Quillaja saponin, and (C) 0 to polyoxyethylene sorbitan fatty acid ester. 0.005% by mass to 2% by mass and (D) 10% by mass to 90% by mass of water and / or polyhydric alcohol are provided, and the method for producing the O / W type emulsion composition is provided. It is.

  The isothiocyanate ester O / W emulsified composition of the present invention has good emulsification stability of the emulsion, and the emulsified particles do not increase over time or cause separation. In addition, since the decomposition of the isothiocyanate is unlikely to occur, the flavor is stable. Furthermore, since it is easy to disperse | distribute uniformly to water, it is easy to use for a drink or a non-oil dressing, and the temporal stability after addition is also favorable.

  The isothiocyanate used in the present invention may be a natural product or a synthetic product. For example, as natural products, plants such as a lot of cormorants, horseradish (horseradish), mustard seed (Brassicaceae), etc. are present in the presence of water. What was obtained by crushing or sliding down into a slurry, hydrolyzing the glycoside at 30 ° C. to 40 ° C. for about 1 to 4 hours, steam distillation, and separating the essential oil from the distillate, Moreover, what separated oil by pressing the hydrolyzate without steam distillation can be used. In these essential oils and oils, allyl isothiocyanate accounts for about 90% as a volatile component, but benzyl isothiocyanate, n-butyl isothiocyanate, 3-butenyl isothiocyanate, 4-pentenyl isothiocyanate, 5-isothiocyanate 5- It contains several percent of isothiocyanate such as hexenyl, 6-methylsulfinyl hexenyl isothiocyanate, 6-methylthiohexyl isothiocyanate, 2-phenylethyl isothiocyanate, and the like. It may also contain fatty acids such as palmitic acid, linolenic acid, and oleic acid. As preferred isothiocyanate esters, allyl isothiocyanate and benzyl isothiocyanate are preferred because they have a strong aroma and a pungent taste and are naturally present in large amounts.

  Moreover, the said isothiocyanic acid ester manufactured by the synthesis reaction can also be used. Since allyl isothiocyanate produced by a synthesis reaction is easily available, it is suitable as an isothiocyanate used in the present invention.

  The compounding amount of the isothiocyanate used in the present invention is 0.1 mass% to 40 mass%, preferably 0.5 mass% to 30 mass%, more preferably 1.0 mass% to 20 in the emulsion composition. A mass% can be illustrated. The amount of isothiocyanate ester is preferably as much as possible considering the cost of transporting the emulsion preparation and the storage location, etc., but when the amount of allyl isothiocyanate in the emulsion composition is more than 40% by mass, This is not preferable because the uniformity of emulsification and mixing tends to be insufficient. In addition, when the blending ratio of allyl isothiocyanate in the emulsion composition is less than 0.1% by mass, the amount of the emulsion composition added to blend the amount of isothiocyanate required for the final product increases. It is uneconomical.

  The emulsifier used in the present invention is characterized in that both quillaja saponin and polyoxyethylene sorbitan fatty acid ester are used. By using both in combination, the emulsion stability is good, the emulsified particles do not increase over time, do not cause separation, and the decomposition of the isothiocyanate does not easily occur. An emulsion that can be easily dispersed uniformly in water can be obtained.

  Kirayasaponin is also called Kiraya extract and Kirayanin, and is listed as "Kiraya extract" in the 7th edition Food Additives Official Document. Quillaja saponin is a glycoside component contained in the bark of the Rosaceae plant Quillaia saponaria Molina, and is a natural interface composed mainly of several saponins consisting of triterpene saponins whose main component is aglycone. It is an active substance. Kiraya grows naturally in South America such as Chile, Bolivia, and Peru. Kirayasaponin not only has emulsifying power but also strong foaming ability, and locally, Kiraya is also called a soap tree, and its sap is used as a shampoo. Quillaja saponin is highly hydrophilic, has a strong surface tension reducing ability, and easily dissolves in water transparently. Therefore, it can be said that it is a surfactant having a high HLB. Moreover, since the emulsifying power is strong, it can also be used for transparent emulsification of oil-soluble substances (which appears transparent to the naked eye when finely emulsified).

  Quillaja saponin can be extracted from quinaya bark using water, lower alcohol, or a mixture thereof, but commercially available quillaja saponins can also be used. Examples of commercially available Kirayasaponins include Kirayanin S-100, Kirayanin C-100, and Kirayanin P-20 (manufactured by Maruzen Pharmaceutical Co., Ltd.).

  The amount of Kirayasaponin used in the present invention is 0.05 mass% to 20 mass%, preferably 0.2 mass% to 10 mass%, more preferably 1 mass% to 5 mass% in the emulsion composition. It can be illustrated. When the amount of Quillaja saponin is less than 0.05% by mass, a good emulsion may not be obtained, and even if it is used in an amount of more than 20% by mass, the emulsification effect is not so high.

  As described above, Kirayasaponin has a strong emulsifying power and can be used for transparent emulsification of oil-soluble substances, but it is not suitable for emulsification of isothiocyanate as a single emulsifier. When isothiocyanate is emulsified using Quillaja saponin alone as an emulsifier, the particle size of the emulsion increases with time and tends to separate.

  Polyoxyethylene sorbitan fatty acid ester, also called polysorbate, is a product in which polyoxyethylene is added to sorbitan fatty acid ester, and it exists in various combinations depending on the number of moles of polyoxyethylene added, the constituent fatty acid species of sorbitan fatty acid ester, and the degree of esterification To do. It has been used for a long time as an emulsifier for cosmetics and detergents, and as an emulsifier for foods overseas. In Japan, some polysorbates were approved as food additives in April 2008 and can be used for food. became.

  The polyoxyethylene sorbitan fatty acid ester that can be used in the present invention is not limited to the number of added moles, the type of fatty acid, and the degree of esterification, but the number of added ethylene units (degree of polymerization) is sorbitan fatty acid. The total number of oxyethylene units added to a plurality of hydroxyl groups of the ester is 1 to 100, more preferably 5 to 30, and still more preferably 15 to 25. The fatty acid species constituting the ester is preferably a saturated or unsaturated fatty acid having 8 to 22, more preferably 12 to 18, more preferably stearic acid, oleic acid, palmitic acid or lauric acid. The degree of esterification is not particularly limited and may be any of various ester forms such as monoesters, diesters, triesters, etc., but from the viewpoint of emulsion stability, safety to the environment, etc. Is particularly preferred. As preferable specific examples, the monoester type includes polysorbate 80 (polyoxyethylene sorbitan monooleate, 20EO), polysorbate 60 (polyoxyethylene sorbitan monostearate, 20EO), polysorbate 40 (polyoxyethylene sorbitan monopalmitate, 20EO). ), Polysorbate 20 (polyoxyethylene sorbitan monolaurate, 20EO), and the triester type is polysorbate 65 (polyoxyethylene sorbitan tristearate, 20EO).

  The blending amount of the polyoxyethylene sorbitan fatty acid ester used in the present invention is preferably 0.005% by mass to 2% by mass, preferably 0.04% by mass to 1% by mass, more preferably 0, in the emulsion composition. .1% by mass to 0.5% by mass can be exemplified. When the amount of the polyoxyethylene sorbitan fatty acid ester is less than 0.005% by mass, a good emulsion may not be obtained, and even if it is used more than 5% by mass, the emulsifying effect is not so high.

  Polyoxyethylene sorbitan fatty acid ester has a strong emulsifying power, but it is not suitable for emulsifying an isothiocyanate ester as a single emulsifier. When emulsifying isothiocyanate using polyoxyethylene sorbitan fatty acid ester alone as an emulsifier, a large amount of water or alcohol is required to dissolve polyoxyethylene sorbitan fatty acid ester. Can not be set high, and the obtained emulsion also has a relatively good emulsified state immediately after emulsification, but the particle size of the emulsion increases with time and tends to separate soon.

  The present invention is characterized in that both of these, alone, are not necessarily suitable for emulsification of an isothiocyanate ester, but are both kirayasaponin and polyoxyethylene sorbitan fatty acid ester. In the present invention, the emulsion stability of the emulsion is good only by using both of these in combination, the emulsified particles do not increase over time, do not cause separation, and the decomposition of the isothiocyanate hardly occurs, Furthermore, an emulsion that can be easily dispersed uniformly in water could be obtained. The ratio of Quillaja saponin and polyoxyethylene sorbitan fatty acid ester is, for example, in the range of 50: 1 to 1: 5, preferably 20: 1 to 1: 2, more preferably 5: 1 to 1: 1 in terms of mass. It can be illustrated.

  In this invention, 1 or more types chosen from water and / or a polyhydric alcohol are used in an emulsion composition. Polyoxyethylene sorbitan fatty acid ester has a high HLB and is mixed with an isothiocyanate ester in an arbitrary ratio. However, as described above, Kirayasaponin is a surfactant having a high hydrophilicity and a high HLB. It is difficult to mix with esters, and a water-soluble medium is required to dissolve them. However, since monohydric alcohols such as ethanol easily react with isothiocyanate to produce insoluble allyl thiourethane, dihydric or higher alcohols are preferred. Examples of the polyhydric alcohol that can be used in the present invention include saccharides such as propylene glycol, glycerin, sorbitol, maltitol, starch syrup, reduced starch syrup, glucose, fructose, sucrose, maltose, liquid sugar, and these two types. The above mixture can be illustrated. The compounding quantity of 1 or more types chosen from the water and / or polyhydric alcohol used by this invention is 10 mass%-90 mass% in an emulsion composition, Preferably it is 20 mass%-80 mass%, More preferably, it is 30 mass. % -70 mass% can be illustrated.

  In the present invention, other oil-soluble or water-soluble raw materials can be blended as long as emulsification is not hindered. Examples of other components include animal and vegetable oils and fats, fragrances, pigments, functional substances, antioxidants, emulsifiers other than those described above, thickeners, stabilizers, and the like.

If the preparation method of the O / W type emulsion composition of this invention is illustrated, for example, Quillaja saponin is mixed and dissolved in an aqueous phase such as a sugar solution, and separately from this, polyoxyethylene sorbitan fatty acid is added to an isothiocyanate ester. Dissolve the ester, mix both, and emulsify using an emulsifier such as TK-Homomixer (made by Tokushu Kika Kogyo Co., Ltd.) at a rotational speed of about 5000 rpm to about 10,000 rpm for about 5 minutes to about 20 minutes. . Further, in place of the TK-homomixer (made by Tokushu Kika Kogyo Co., Ltd.), any emulsifier such as a conventionally known high-pressure homogenizer or colloid mill can be used as long as it has an equal or higher emulsifying capacity. It may be processed .

  The thus obtained isothiocyanate ester O / W emulsion composition has good emulsion stability, and the emulsion particles do not increase over time or cause separation. In addition, since the decomposition of the isothiocyanate is unlikely to occur, the flavor is stable. Furthermore, since it is easy to disperse | distribute uniformly to water, it is easy to use for a drink or a non-oil dressing, and the temporal stability after addition is also favorable.

According to the present invention, the O / W type emulsion composition obtained as described above can be used, for example, kneaded mustard, kneaded wasabi, arabiki mustard, dressing, mayonnaise, soy sauce, sashimi sauce, sprinkle, wasabi pickles, rice crackers, By blending, for example, about 0.02% by mass to about 2% by mass with snacks, ice cream, various irritating beverages, etc., foods and drinks having a pungency characteristic of isothiocyanate are obtained. Moreover, it can also be used as a microorganism growth inhibitor and a freshness preserving agent by spraying the OW type emulsified composition of the present invention on fresh food or processed food, or by including it in a packaging container.
The following examples further illustrate the present invention.

Example 1 (using Kirayasaponin and polysorbate as emulsifiers)
50 g of Kirayanin C-100 (manufactured by Maruzen Pharmaceutical Co., Ltd .: containing 25% Kiraya extract) is mixed and dissolved in 845 g of isomerized liquid sugar (Bx75 °) to obtain an aqueous phase part. Separately from this, 5 g of Emazole L-120V (polysorbate 20, manufactured by Kao Corporation) is mixed and dissolved in 100 g of allyl isothiocyanate to obtain an oil phase part. The water phase part and the oil phase part were mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (Invention product 1). : Allyl isothiocyanate 10.0% contained).

Example 2
In Example 1, except that 5 g of Emazole S-120V (Polysorbate 60, manufactured by Kao Corporation) was used instead of 5 g of Emazole L-120V (Polysorbate 20, manufactured by Kao Corporation), the same operation as in Example 1 was performed. An emulsion composition of allyl isothiocyanate (1000 g) was obtained (product of the present invention 2: containing 10.0% allyl isothiocyanate).

Example 3
In Example 1, except that 5 g of Emazole O-120V (Polysorbate 80, manufactured by Kao Corporation) was used instead of 5 g of Emazole L-120V (Polysorbate 20, manufactured by Kao Corporation), the same operation as in Example 1 was performed. An emulsion composition of 1000 g of allyl isothiocyanate was obtained (Product 3 of the present invention: 10.0% allyl isothiocyanate contained).

Comparative Example 1 (using Kirayasaponin as an emulsifier)
50 g of Kirayanin C-100 (manufactured by Maruzen Pharmaceutical Co., Ltd .: containing 25% Kiraya extract) is mixed and dissolved in 850 g of isomerized liquid sugar (Bx75 °) to obtain an aqueous phase part. This was mixed with 100 g of allyl isothiocyanate and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion (Comparative product 1: isothiocyanate). Acid allyl 10.0%).

Comparative Example 2 (using polysorbate as an emulsifier)
20 g of Emazole O-120V (polysorbate 80, manufactured by Kao Corporation) is mixed and dissolved in 100 g of allyl isothiocyanate to obtain an oil phase part. This was mixed with 880 g of isomerized liquid sugar (Bx75 °) and stirred for 10 minutes at 6000 rpm using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (comparison). Product 2: Allyl isothiocyanate 10.0% contained).

Comparative Example 3 (using polyglycerol fatty acid ester as an emulsifier)
50 g of decaglycerin monooleate (trade name: Decaglyn 1-OLV, manufactured by Nikko Chemicals) is mixed and dissolved in 850 g of isomerized liquid sugar (Bx75 °) to obtain an aqueous phase part. To this, 100 g of allyl isothiocyanate was mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (Comparative product 3: isothiocyanate). Contains 10.0% allyl acid, pH 8.5 of the formulation.

Comparative Example 4 (pH adjusted using polyglycerol fatty acid ester as an emulsifier)
In Comparative Example 3, since the pH of the preparation was 8.5, which was on the alkali side, an acid was added to adjust the pH.
To 815 g of isomerized liquid sugar (Bx75 °), 35 g of 2% citric acid aqueous solution and 50 g of decaglycerin monooleate (trade name: Decaglyn 1-OLV, manufactured by Nikko Chemicals) are mixed and dissolved to obtain an aqueous phase part. To this, 100 g of allyl isothiocyanate was mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (Comparative product 4: isothiocyanate). Contains allyl acid 10.0%, pH of the formulation 5.5).

Comparative Example 5 (using sucrose fatty acid ester as an emulsifier)
To 880 g of isomerized liquid sugar (Bx75 °), 20 g of sucrose stearate (trade name: Sugar Ester DK-SS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added and dissolved to obtain an aqueous phase part. This was mixed with 100 g of allyl isothiocyanate and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion (Comparative product 5: isothiocyanate). Acid allyl 10.0%, formulation pH 7.0).

Comparative Example 6 (using gum arabic as an emulsifier)
500 g of gum arabic aqueous solution (concentration 30%) is sterilized at 85 ° C. to 95 ° C. for 15 minutes, cooled to 40 ° C. or less, dissolved by adding 400 g of glycerin to obtain an aqueous phase part. This was mixed with 100 g of allyl isothiocyanate and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (Comparative product 6: isothiocyanate). Acid allyl 10.0%, formulation pH 4.5).

Comparative Example 7 (using polyglycerin fatty acid ester and polysorbate as an emulsifier)
50 g of decaglycerin monooleate (trade name: Decaglyn 1-OLV, manufactured by Nikko Chemicals) is mixed and dissolved in 845 g of isomerized liquid sugar (Bx75 °) to obtain an aqueous phase part. Separately from this, 5 g of Emazole O-120V (polysorbate 80, manufactured by Kao Corporation) is mixed and dissolved in 100 g of allyl isothiocyanate to obtain an oil phase part. The water phase part and the oil phase part were mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (made by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (Comparative product 7: Containing 10.0% allyl isothiocyanate).

Comparative Example 8 (using gum arabic and polysorbate as emulsifier)
495 g of gum arabic aqueous solution (concentration 30%) is sterilized at 85 ° C. to 95 ° C. for 15 minutes, cooled to 40 ° C. or less, dissolved by adding 400 g of glycerin to obtain an aqueous phase part. Separately from this, 5 g of Emazole O-120V (polysorbate 80, manufactured by Kao Corporation) is mixed and dissolved in 100 g of allyl isothiocyanate to obtain an oil phase part. The water phase part and the oil phase part were mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (made by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (Comparative product 8: Containing 10.0% allyl isothiocyanate).

Comparative Example 9 (using polyglycerin fatty acid ester and Quillaja saponin as an emulsifier)
800 g of isomerized liquid sugar (Bx75 °) mixed with 50 g of decaglycerin monooleate (trade name: Decaglyn 1-OLV, manufactured by Nikko Chemicals) and 50 g of kirayanin C-100 (manufactured by Maruzen Pharmaceutical Co., Ltd .: 25% kiraya extract) Dissolve to make the aqueous phase. This was mixed with 100 g of allyl isothiocyanate and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (Comparative product 9: isothiocyanate). Acid allyl 10.0%).

Example 4
Inventive products 1 to 3 and comparative products 1 to 9 were subdivided into 30 ml sample bottles by 30 g and subjected to a storage test at 5 ° C., 20 ° C. and 50 ° C. for 1 week, and the browning and emulsification states were observed with the naked eye. Further, the emulsified state was further observed with an electron microscope, and the emulsified state was determined. The results are shown in Table 1.

  As shown in Table 1, the products 1 to 3 of the present invention, in which Kirayasaponin and polysorbate are used together as an emulsifier, give a stable emulsion immediately after emulsification, and the emulsion state is stable without browning even after storage at 50 ° C. for 1 week. Met.

  On the other hand, Comparative Product 1 using Kirayasaponin alone, which is one of the two types of emulsifiers used in the present invention, appeared to be in a good emulsified state immediately after emulsification, but was observed with an optical microscope. However, aggregates were observed. In addition, the particles increased even at 5 ° C. by storage for 1 week, oil separation was observed at 20 ° C. and 50 ° C., and it was observed that the emulsification was broken.

  Comparative product 2 using polysorbate, which is the other emulsifier of the two types of emulsifiers used in the present invention, was in an emulsified state immediately after emulsification, but at 5 ° C and 20 ° C after storage for 1 week. Particles increased, oil separation was seen at 50 ° C., and the emulsification was broken.

  Comparative product 3 uses polyglycerin fatty acid ester, which is a widely used emulsifier because of its excellent emulsifying power, but is slightly browned immediately after emulsification, and browning after storage. Was larger than other emulsifiers. In addition, the particles increased even at 5 ° C. by storage for 1 week, oil separation was observed at 20 ° C. and 50 ° C., and it was observed that the emulsification was broken.

  Allyl isothiocyanate has the property of being easily decomposed on the alkaline side, but the browning may be caused by the inclination of polyglycerol fatty acid ester to alkalinity. Then, the comparative product 4 which made the emulsified preparation weakly acidic using citric acid was prepared. However, Comparative Product 4 was less brown than Comparative Product 3 in terms of browning, but the stability of emulsification was comparable to Comparative Product 4.

  Sugar ester and gum arabic are also emulsifiers commonly used in the same way as polyglycerin fatty acid ester, and the liquidity at the time of dissolution is also neutral to weakly acidic, but the stability test results of comparative product 5 and comparative product 6 are As shown in Table 1, it was inferior to the product 1 of the present invention.

  Moreover, the comparison product 7 combining polysorbate and polyglycerin fatty acid ester which is another emulsifier, the comparison product 8 combining gum arabic, and the combination using the product of the present invention, which are related to the combination of the product of the present invention. On the other hand, as shown in Table 1, the stability of the comparative product 9 combining Kirayasaponin and polyglycerin fatty acid ester, which is one of the above, was inferior to that of the product 1 of the present invention.

Example 5
About this invention products 1-3 which were good in the emulsification state in Example 4, the storage period was further extended and the preservation | save was performed at 50 degreeC for 1 month (starting immediately after emulsification). As a result, browning progressed slightly, and aroma deterioration was observed, but the emulsified state was good, and no condensation or increase of particles was observed even by observation with an optical microscope, maintaining an extremely stable emulsified state. It was.

Reference example 1
To 150 kg of the defatted yellow mustard pulverized product, 900 kg of hot water at 40 ° C. was added, mixed well, and allowed to stand at 40 ° C. with occasional stirring for 3 hours (about 1 minute in 30 minutes). Thereafter, steam distillation was performed under reduced pressure (40 ° C., 0.04 Mpa) to obtain 300 kg of a distillate. 30 kg of sodium chloride was mixed and dissolved in the distillate, salted out, allowed to stand for 1 hour, the essential oil floating in the upper layer was separated by decantation, dehydrated and filtered with anhydrous sodium sulfate, and 1.15 kg of eggplant essential oil ( Reference product 1) was obtained.
Composition of isothiocyanate esters of Reference product 1 (Gas chromatography method,% by peak area ratio)
Ingredient Content Allyl isothiocyanate 71.5%
N-Butyl isothiocyanate 12.8%
3-Butenyl isothiocyanate 6.5%
4-pentenyl isothiocyanate 2.2%
2-phenylethyl isothiocyanate 1.1%
Other aromatic components 5.9%

Example 6 (using Kirayasaponin and polysorbate as emulsifiers)
50 g of Kirayanin C-100 (manufactured by Maruzen Pharmaceutical Co., Ltd .: containing 25% Kiraya extract) is mixed and dissolved in 845 g of isomerized liquid sugar (Bx75 °) to obtain an aqueous phase part. Separately from this, 5 g of Emazole L-120V (Polysorbate 20, manufactured by Kao Corporation) is mixed and dissolved in 100 g of Reference Product 1 (Zushi Essential Oil) to obtain an oil phase part. The water phase part and the oil phase part were mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an emulsion composition of coconut essential oil (Invention product 4: Contains eggplant essential oil 10.0%).

Example 7
In Example 6, except that 5 g of Emazole S-120V (Polysorbate 60, manufactured by Kao Corporation) was used instead of 5 g of Emazole L-120V (Polysorbate 20, manufactured by Kao Corporation), the same operation as in Example 6 was performed, An emulsion composition of eggplant essential oil (1000 g) was obtained (Product 5 of the present invention: containing eggplant essential oil 10.0%).

Example 8
In Example 6, except that 5 g of Emazole O-120V (Polysorbate 80, manufactured by Kao Corporation) was used instead of 5 g of Emazole L-120V (Polysorbate 20, manufactured by Kao Corporation), the same operation as in Example 6 was performed, An emulsion composition of eggplant essential oil (1000 g) was obtained (Product 6 of the present invention: 10.0% eggplant essential oil contained).

Comparative Example 10 (using Kirayasaponin as an emulsifier)
50 g of Kirayanin C-100 (manufactured by Maruzen Pharmaceutical Co., Ltd .: containing 25% Kiraya extract) is mixed and dissolved in 850 g of isomerized liquid sugar (Bx75 °) to obtain an aqueous phase part. To this, 100 g of Reference Product 1 (Zushi Essential Oil) was mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an emulsion composition of Zushi Essential Oil (Comparative Product). 10: Contains coconut essential oil 10.0%).

Comparative Example 11 (using polysorbate as an emulsifier)
20 g of Emazole O-120V (Polysorbate 80, manufactured by Kao Corporation) is mixed and dissolved in 100 g of Reference Product 1 (Zushi Essential Oil) to obtain an oil phase part. This was mixed with 880 g of isomerized liquid sugar (Bx75 °) and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an emulsion composition of coconut essential oil (comparative product) 11: Contains coconut essential oil 10.0%).

Comparative Example 12 (using polyglycerol fatty acid ester as an emulsifier)
50 g of decaglycerin monooleate (trade name: Decaglyn 1-OLV, manufactured by Nikko Chemicals) is mixed and dissolved in 850 g of isomerized liquid sugar (Bx75 °) to obtain an aqueous phase part. To this, 100 g of Reference Product 1 (Zushi Essential Oil) was mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an emulsion composition of Zushi Essential Oil (Comparative Product). 12: Contains coconut essential oil 10.0%).

Comparative Example 13 (polyglycerin fatty acid ester was used as an emulsifier and pH was adjusted)
In Comparative Example 12, since the pH of the preparation was 8.5 and the alkali side, an acid was added to lower the pH.
815 g of isomerized liquid sugar (Bx75 °) with 35 g of 2% citric acid aqueous solution and 50 g of decaglycerin monooleate (trade name: Decaglyn 1-OLV, manufactured by Nikko Chemicals) (using polyglycerin fatty acid ester as an emulsifier) Mix and dissolve to make the aqueous phase part. To this, 100 g of Reference Product 1 (Zushi Essential Oil) was mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an emulsion composition of Zushi Essential Oil (Comparative Product). 13: Contains coconut essential oil 10.0%).

Comparative Example 14 (using sucrose fatty acid ester as emulsifier)
To 880 g of isomerized liquid sugar (Bx75 °), 20 g of sucrose stearate (trade name: Sugar Ester DK-SS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added and dissolved to obtain an aqueous phase part. To this, 100 g of Reference Product 1 (Zushi Essential Oil) was mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an emulsion composition of Zushi Essential Oil (Comparative Product). 14: Contains coconut essential oil 10.0%).

Comparative Example 15 (using gum arabic as an emulsifier)
500 g of gum arabic aqueous solution (concentration 30%) is sterilized at 85 ° C. to 95 ° C. for 15 minutes, cooled to 40 ° C. or less, dissolved by adding 400 g of glycerin to obtain an aqueous phase part. To this, 100 g of Reference Product 1 (Zushi Essential Oil) was mixed and stirred at 6000 rpm for 10 minutes using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an emulsion composition of Zushi Essential Oil (Comparative Product). 15: Contains coconut essential oil 10.0%).

Comparative Example 16 (using polyglycerin fatty acid ester and polysorbate as an emulsifier)
50 g of decaglycerin monooleate (trade name: Decaglyn 1-OLV, manufactured by Nikko Chemicals) is mixed and dissolved in 845 g of isomerized liquid sugar (Bx75 °) to obtain an aqueous phase part. Separately from this, 5 g of Emazole O-120V (Polysorbate 80, manufactured by Kao Corporation) is mixed and dissolved in 100 g of Reference Product 1 (Zushi Essential Oil) to obtain an oil phase part. The water phase part and the oil phase part were mixed and stirred for 10 minutes at 6000 rpm using a TK-homomixer (made by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an essential oil emulsion composition (Comparative product 16: Isogo Contains essential oil 10.0%).

Comparative Example 17 (using gum arabic and polysorbate as emulsifier)
495 g of gum arabic aqueous solution (concentration 30%) is sterilized at 85 ° C. to 95 ° C. for 15 minutes, cooled to 40 ° C. or less, dissolved by adding 400 g of glycerin to obtain an aqueous phase part. Separately from this, 5 g of Emazole O-120V (Polysorbate 80, manufactured by Kao Corporation) is mixed and dissolved in 100 g of Reference Product 1 (Zushi Essential Oil) to obtain an oil phase part. The water phase part and the oil phase part were mixed and stirred for 10 minutes at 6000 rpm using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (Comparative Product 17: Contains eggplant essential oil 10.0%).

Comparative Example 18 (using polyglycerin fatty acid ester and Quillaja saponin as an emulsifier)
800 g of isomerized liquid sugar (Bx75 °) mixed with 50 g of decaglycerin monooleate (trade name: Decaglyn 1-OLV, manufactured by Nikko Chemicals) and 50 g of kirayanin C-100 (manufactured by Maruzen Pharmaceutical Co., Ltd .: 25% kiraya extract) Dissolve to make the aqueous phase. To this, 100 g of Reference product 1 (Zushi essential oil) was mixed and stirred for 10 minutes at 6000 rpm using a TK-homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1000 g of an allyl isothiocyanate emulsion composition (comparison). Product 18: Contains coconut essential oil 10.0%).

Example 9
Invention products 4 to 6 and comparative products 10 to 18 were subdivided into 30 ml sample bottles by 30 g, and a storage test was conducted at 5 ° C., 20 ° C. and 50 ° C. for 1 week, and browning and emulsification were observed with the naked eye. Further, the emulsified state was further observed with an electron microscope, and the emulsified state was determined. The results are shown in Table 2.

  As shown in Table 2, the same results as those shown in Table 1 were obtained when coconut essential oil was used instead of rill isothiocyanate. That is, the products 4 to 6 of the present invention in which Kirayasaponin and polysorbate were used in combination obtained a stable emulsion immediately after emulsification, and even after storage at 50 ° C. for 1 week, the emulsion state was stable without browning. On the other hand, in Comparative Examples 10-18 using other emulsifiers or combinations thereof, an emulsion having good stability could not be obtained.

Example 10
About the invention products 4-6 which were good in the emulsified state in Example 9, the storage period was further extended, and storage was performed at 50 ° C. for 1 month (starting immediately after emulsification). As a result, browning progressed slightly, and aroma deterioration was observed, but the emulsified state was good, and no condensation or increase of particles was observed even by observation with an optical microscope, maintaining an extremely stable emulsified state. It was.

Claims (2)

(D) In a water phase part composed of water and / or polyhydric alcohol, (B) Kirayasaponin is mixed and dissolved. Separately, (A) isothiocyanate ester, (C) polyoxyethylene sorbitan fatty acid ester A method for producing an O / W type emulsified composition comprising dissolving, mixing both, and emulsifying .
(A) 0.1 mass% to 40 mass% of isothiocyanate ester, (B) 0.05 mass% to 20 mass% of Kirayasaponin, (C) 0.005 mass% to 2 of polyoxyethylene sorbitan fatty acid ester 2. The method for producing an O / W emulsion composition according to claim 1, further comprising 10% by mass to 90% by mass of (D) water and / or polyhydric alcohol.