Oil-type emulsion in phase D and method for producing the same

Abstract

This invention provides a method for dispersing oils and fats in water under a weak shear force when preparing an oil-in-water emulsion using protein materials. [Solution] A D-phase oil-in-D (O / D type) emulsion is prepared by dissolving a protein material having the properties (A) and (B) below in a D-phase composition with a moisture content of 50% by mass or less in a polyol, and then dispersing oils and fats in this composition. By further dispersing the D-phase oil-in-D emulsion in water, an oil-in-water emulsion can be obtained. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%.

Description

Technical Field

[0004]

[0001] The present invention relates to an oil-in-water-in-oil (O / W / O) emulsion and a method for producing the same.

Background Art

[0002] It is widely known to prepare oil-in-water emulsions using protein materials with high emulsifying power, such as isolated soy protein and milk protein, or these materials themselves. In addition, highly emulsified protein materials with enhanced emulsifying power through special preparation methods have also been developed. Patent Document 1 discloses an emulsified flavor using an oil-in-water emulsion with a highly emulsified soy protein material, and Patent Document 2 discloses an oil-in-water emulsion with a highly emulsified soy protein material and a further dried food, respectively. All of these oil-in-water emulsions are prepared using a strong shearing force. [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​When preparing oil-in-water emulsions using protein materials with emulsifying properties, strong shear force is required, and this is also true for the highly emulsifying protein materials used in the present invention. On the other hand, equipment that can apply strong shear force is limited, and manufacturers who wish to produce emulsions may not possess such equipment. The object of the present invention is to provide a method for dispersing oils and fats in water even under weak shear force when preparing oil-in-water emulsions using protein materials. [Means for solving the problem]

[0005] When preparing oil-in-water emulsions, the D-phase emulsion exemplified above can be dispersed under weak shear force. However, the emulsifiers used in the preparation of D-phase emulsions are low-molecular-weight fatty acid esters such as glycerol fatty acid esters, sugar esters, and lysolecithin. As a result of diligent research into the above-mentioned problems, the inventors of the present invention discovered that the highly emulsifiable protein material of the present invention is, quite unexpectedly, soluble in polyols, and that a D-phase composition can be prepared using this material. Furthermore, they discovered that oil-in-phase emulsions and oil-in-water emulsions can be prepared using this D-phase composition under weak shear forces, thus completing the present invention.

[0006] In other words, the present invention (1) A D-phase oil-type emulsion in which a protein material having the properties of (A) and (B) below is dissolved in a D-phase composition in a polyol with a moisture content of 50% by mass or less, and an oil is dispersed in it. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%. (2) The D-phase oil-type emulsion according to (1), wherein the polyol is glycerin or reduced starch syrup. (3) A D-phase oil-type emulsion according to (1) or (2), wherein the amount of polyol with a moisture content of 50% by mass or less is 15 parts by mass or less per 1 part by mass of protein material. (4) A method for producing an oil-in-D-phase emulsion, comprising the following steps [1] and [2]. [1] A step of obtaining a D-phase composition by dissolving a protein material having the properties of (A) and (B) below in a polyol with a moisture content of 50% by mass or less. [2] A step of dispersing oils and fats in the D-phase composition to prepare an oil-type emulsion in the D-phase. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%. (5) A method for producing an oil-in-D-phase emulsion according to (4), wherein the polyol is glycerin or reduced starch syrup. A method for producing an oil-in-water emulsion, comprising dispersing the oil-in-D-phase emulsion described in (6)(4) or (5) in water. (7) A method for dispersing oils and fats in water, comprising all of the following steps [1] to [3]. [1] A step of obtaining a D-phase composition by dissolving a protein material having the properties of (A) and (B) below in a polyol with a moisture content of 50% by mass or less. [2] A step of dispersing oils and fats in the D-phase composition to prepare an oil-type emulsion in the D-phase. [3] A step of dispersing the oil-type emulsion in water in phase D. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%. (8) The method for dispersing oils and fats in water according to (7), wherein the polyol is glycerin or reduced starch syrup. (9) A cosmetic product which is a D-phase oil-type emulsion or a water dilution thereof, in which a protein material having the properties of (A) and (B) below is dissolved in a D-phase composition in a polyol with a water content of 50% by mass or less, and an oil or fat is dispersed in the D-phase composition. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%. (10) Cosmetics as described in (9), wherein the cosmetic is a cleansing agent. (11) A food, which is an oil-in-D-phase emulsion in which an oil and fat is dispersed in a D-phase composition obtained by dissolving a protein material having the following properties (A) and (B) in a polyol having 50% by mass or less of water. (A) The viscosity measured at 25 ° C. after heating an aqueous solution containing 20% by mass of crude protein at 80 ° C. for 30 minutes is 10,000 mPa·s or less. (B) The TCA solubilization rate of 0.22 M is 30% to 95%. It relates to the above.

Advantages of the Invention

[0007] According to the present invention, by including the preparation of an oil-in-D-phase emulsion in the process, an oil-in-water emulsion using a protein material can be prepared even under a weak shearing force. Further, the obtained oil-in-D-phase emulsion can be used as a raw material for cosmetics or food of natural materials.

Brief Description of the Drawings

[0008] [Figure 1] It is a photograph substituting for a drawing in a state where various protein materials are dispersed in glycerin and centrifuged.

Modes for Carrying Out the Invention

[0009] ■ Polyol A polyol is a polyhydric alcohol having a plurality of hydroxyl groups. The polyol used in the present invention is an anhydride such as glycerin, ethylene glycol, propylene glycol, 1,3-butanediol, 1,2-pentanediol, sorbitol, reduced maltose, reduced starch syrup, etc. or a hydrate having 50% by mass or less of water, and is a liquid at normal temperature. Preferably, it is glycerin or reduced starch syrup, and most preferably glycerin.

[0010] ■ Oil and fat The fats and oils used in the present invention refer to substances that are insoluble or poorly soluble in water and easily soluble in neutral lipids. That is, triglycerides such as soybean oil, rapeseed oil, corn oil, safflower oil, rice oil, cottonseed oil, sunflower oil, sesame oil, olive oil, peanut oil, palm oil, palm kernel oil, coconut oil, cocoa butter, lard, beef tallow, fish oil, medium-chain fatty acid triglycerides, and those modified by transesterification, hydrogenation, etc., and fatty acids obtained by decomposing these. The fatty acids constituting the triglycerides also include polyunsaturated fatty acids (for example, eicosapentaenoic acid / EPA, docosahexaenoic acid / DHA, arachidonic acid, and γ-linolenic acid and / or ethyl ester). In addition, fatty acid esters of higher alcohols such as jojoba oil can also be used.

[0011] ■ Protein material The protein material used in the present invention needs to have a low viscosity after heating. That is, the viscosity of the protein material can be measured by preparing an aqueous solution with a crude protein content of 20% by mass, heating it at 80 ° C for 30 minutes, and then measuring the viscosity at 25 ° C. The viscosity after heating is 10,000 mPa·s or less, preferably 5,000 mPa·s or less, 1,000 mPa·s or less, 500 mPa·s or less, and more preferably 200 mPa·s or less, 100 mPa·s or less. In addition, this protein material requires a molecular weight of a certain size. The molecular weight is defined by the TCA solubilization rate. In the present invention, the TCA solubilization rate is defined as the ratio of the amount of crude protein dissolved in 0.22 M TCA to the total amount of crude protein. The TCA solubilization rate is 30 to 95%, preferably 35 to 90%, more preferably 40 to 85%, 50 to 80%. When the TCA solubilization rate is within this range, high emulsifying properties for forming an oil-in-D-phase emulsion can be obtained.

[0012] The protein material is preferably one with an NSI (Nitrogen Solubility Index) of 80 or higher, which is used as an indicator of protein solubility. More preferably, an NSI of 85 or higher, 90 or higher, 95 or higher, or 97 or higher can be used. A high NSI of the protein material indicates high dispersibility in water, which can contribute to the flavor deterioration suppression effect of the present invention. If the NSI is too low, precipitation is likely to occur. Furthermore, the crude protein content in the protein material is preferably 30% by mass or higher, more preferably 40% by mass or higher, more preferably 50% by mass or higher, and most preferably 60% by mass or higher, or 70% by mass or higher. A protein material with a higher crude protein content can produce its function in a smaller amount. Such protein materials can be obtained through denaturation and molecular weight adjustment processes, as described later. A commercially available example is "MIRA-MAP2.0" manufactured by Fuji Oil Co., Ltd. Commercially available soy protein materials, such as "Fujipro R," "Fujipro 748," "Fujipro CL," and "Highneut DC6" (all from Fuji Oil Co., Ltd.), do not meet these requirements.

[0013] The origin of the protein material to be prepared as described above is not particularly limited, but plant, animal, or microbial proteins can be used. Examples of plant proteins include those derived from legumes such as soybeans, peas, mung beans, lupin beans, chickpeas, kidney beans, flat beans, and cowpeas; seeds such as sesame, canola seeds, coconut seeds, and almond seeds; grains such as corn, buckwheat, wheat, and rice; vegetables; fruits; algae; and microalgae. As an example, in the case of soybean-derived protein material, it is prepared by further concentrating the protein from soybean raw materials such as defatted soybeans or whole soybeans, and conceptually includes isolated soy protein, concentrated soy protein, powdered soy milk, or various processed forms thereof. Furthermore, examples of animal proteins include egg proteins containing ovalbumin, milk proteins such as casein, whey, lactalbumin, blood-derived proteins such as plasma, serum albumin, and decolorized hemoglobin, livestock-derived proteins, and fish and shellfish-derived proteins. In addition, proteins derived from microorganisms such as yeast, mold, and bacteria can be used. Even proteins with poor water solubility can be prepared as protein materials usable in the present invention by the processing described later. Protein sources are preferably derived from plants, and more preferably from legumes. Among these, protein sources derived from soybeans and peas are the most preferred.

[0014] ■ Modification and molecular weight adjustment treatments The protein material used in the present invention is obtained by applying a combination of a "decomposition / denaturation treatment" that decomposes and / or denatures proteins and a "molecular weight distribution adjustment treatment" that adjusts the molecular weight distribution of proteins. Examples of the "decomposition / denaturation treatment" include enzyme treatment, pH adjustment treatment (e.g., acid treatment, alkali treatment), denaturant treatment, heat treatment, cooling treatment, high-pressure treatment, organic solvent treatment, mineral addition treatment, supercritical fluid treatment, ultrasonic treatment, electrolysis treatment, and combinations thereof. Examples of the "molecular weight distribution adjustment treatment" include filtration, gel filtration, chromatography, centrifugation, electrophoresis, dialysis, and combinations thereof. The order and number of times the "decomposition / denaturation treatment" and the "molecular weight distribution adjustment treatment" are performed are not particularly limited. The "decomposition / denaturation treatment" may be performed first and then the "molecular weight distribution adjustment treatment," or the "molecular weight distribution adjustment treatment" may be performed first and then the "decomposition / denaturation treatment," or both treatments may be performed simultaneously. Furthermore, it is possible to perform "decomposition / denaturation treatment" between two or more "molecular weight distribution adjustment treatments," or to perform "molecular weight distribution adjustment treatment" between two or more "decomposition / denaturation treatments," or to perform multiple treatments of each treatment in any order. Note that if the desired molecular weight distribution can be obtained by "decomposition / denaturation treatment," "molecular weight distribution adjustment treatment" does not need to be performed. When combining these treatments and performing them multiple times, all treatments may be performed consecutively from the raw material, or they may be performed with a time interval in between. For example, a commercially available product that has undergone one treatment may be used as a raw material for other treatments. Note that, as long as the above characteristics are met, a protein material that has undergone molecular weight distribution adjustment treatment and a protein material that has not undergone molecular weight distribution adjustment treatment may be mixed to form a specific protein material. In this case, the ratio of the two (treated protein material: untreated protein material) can be adjusted as appropriate within the range that satisfies the above characteristics, but examples of mass ratios include 1:99 to 99:1, 50:50 to 95:5, 75:25 to 90:10, etc. In one embodiment, the protein material used in this embodiment consists of a protein material that has undergone "decomposition / denaturation and molecular weight distribution adjustment treatment".

[0015] The conditions for the protein decomposition or denaturation process, such as the type and concentration of enzymes, pH, organic solvents, minerals, temperature, pressure, power output, current, and time, can be appropriately set by those skilled in the art. Examples of enzymes used include proteases classified as "metalloproteases," "acid proteases," "thiol proteases," and "serine proteases." The reaction can be carried out at a temperature of 20-80°C, preferably 40-60°C. For pH adjustment, the treatment can be performed within a pH range of, for example, pH 2-12, with any of the following values ​​as upper and lower limits: pH 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, and 12. For acid treatment, the method may involve adding acid or performing fermentation such as lactic acid fermentation. Examples of acids to be added include inorganic acids such as hydrochloric acid and phosphoric acid, and organic acids such as acetic acid, lactic acid, citric acid, gluconic acid, phytic acid, sorbic acid, adipic acid, succinic acid, tartaric acid, fumaric acid, malic acid, and ascorbic acid. Acids may also be added using acid-containing foods and beverages such as lemon juice, concentrated fruit juice, fermented milk, yogurt, and brewed vinegar. In the case of alkaline treatment, alkalis such as sodium hydroxide and potassium hydroxide may be added.

[0016] In the case of denaturing agent treatment, denaturing agents such as guanidine hydrochloride, urea, arginine, and PEG may be added. In the case of heating or cooling treatment, examples of heating temperatures include any temperature within the range of 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, and 150°C as upper and lower limits, for example, 60°C to 150°C. Examples of cooling temperatures include any temperature within the range of -10°C, -15°C, -20°C, -25°C, -30°C, -35°C, -40°C, -45°C, -50°C, -55°C, -60°C, -65°C, -70°C, and -75°C as upper and lower limits, for example, -10°C to -75°C. Examples of heating or cooling times include any time range with upper and lower limits of 5 seconds, 10 seconds, 30 seconds, 1 minute, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 120 minutes, 150 minutes, 180 minutes, and 200 minutes, for example, from 5 seconds to 200 minutes. For high-pressure processing, examples of pressure conditions include any pressure range with upper and lower limits of 100 MPa, 200 MPa, 300 MPa, 400 MPa, 500 MPa, 600 MPa, 700 MPa, 800 MPa, 900 MPa, and 1,000 MPa, for example, from 100 MPa to 1,000 MPa.

[0017] In the case of organic solvent treatment, examples of solvents used include alcohols and ketones, such as ethanol and acetone. In the case of mineral addition treatment, examples of minerals used include divalent metal ions such as calcium and magnesium. In the case of supercritical treatment, for example, treatment can be performed using supercritical carbon dioxide at a temperature of approximately 30°C or higher and a pressure of approximately 7 MPa or higher. In the case of ultrasonic treatment, for example, treatment can be performed by irradiating with a frequency of 100 kHz to 2 MHz and an output of 100 to 1,000 W. In the case of electrolysis treatment, for example, an aqueous protein solution can be treated by applying a voltage of 100 mV to 1,000 mV. In specific embodiments, the treatment for decomposing and / or denaturing proteins is selected from denaturant treatment, heat treatment, and combinations thereof.

[0018] The conditions for adjusting the molecular weight distribution of proteins, such as the type of filter media, the gel filtration support, the centrifugation speed, current, and time, can be appropriately set by those skilled in the art. Examples of filter media include filter paper, filter cloth, diatomaceous earth, ceramics, glass, and membranes. Examples of gel filtration supports include dextran and agarose. Examples of centrifugation conditions include 1,000 to 3,000 × g for 5 to 20 minutes.

[0019] ■D phase composition The "D" in phase D stands for detergent, indicating an emulsifier. The emulsifier used in this invention is the protein material described above. The phase D composition is a mixture in which the emulsifier is dissolved in a polyol or the like. In this invention, the protein material described above is dissolved in a polyol with a moisture content of 50% by mass or less. A polyol with a moisture content of 35% by mass or less is preferred, and a polyol with a moisture content of 28% by mass or less is more preferred. A polyol with a moisture content of 5% by mass or more is also preferred. If the moisture content in the polyol is within this range, the particle size of the final oil-in-water emulsion can be made finer. The mixing ratio of the emulsifier protein material to the polyol is preferably 15 parts by mass or less of polyol with a moisture content of 50% by mass or less per 1 part by mass of protein material. More preferably 12 parts by mass or less, 10 parts by mass or less, or 8 parts by mass or less, and most preferably 6 parts by mass or less. Also, 2 parts by mass or more is preferred. If the amount of polyol blended with the protein material is within this range, the particle size of the final oil-in-water emulsion can be made fine.

[0020] ■D-phase oil emulsion An oil-in-D (O / D) emulsion is an emulsion in which oils and fats are dispersed in a continuous phase D composition. It is sometimes also referred to as D-phase emulsification, D-phase emulsion, O / D emulsification, or O / D emulsion. The oil-in-D emulsion of the present invention is one in which oils and fats are dispersed in the aforementioned D-phase composition as a continuous phase. The mixing ratio of the D-phase composition and the oil / fat during the dispersion process largely depends on the protein material in the D-phase composition. Specifically, the amount of oil / fat per 1 part by mass of protein material is preferably 60 parts by mass or less, more preferably 35 parts by mass or less, and most preferably 25 parts by mass or less. If the ratio of fats and oils to protein materials falls within this range, the particle size of the final oil-in-water emulsion can be made finer.

[0021] ■ Preparation of Phase D Composition The oil-in-phase emulsion and oil-in-water emulsion of the present invention are prepared as follows. First, the D-phase composition is prepared by mixing the aforementioned protein material with a polyol containing 50% or less moisture. For mixing, a stirring device with low shear force, such as a propeller stirrer, colloid mill, disper mill, vacuum stepan, homomixer, or static mixer, can be used. A stirring device with high shear force, such as a high-pressure homogenizer or ultrasonic homogenizer, can also be used. The mixing ratio of the protein material to the polyol containing 50% or less moisture by mass is as described above, and the D-phase composition can be prepared in this way.

[0022] ■ Preparation of oil-based emulsion in phase D Next, an oil-in-water emulsion is prepared by mixing oil and fat into the D-phase composition. The mixing ratio depends on the protein material concentration in the D-phase composition, but the following ratios can be used as examples. The amount of oil and fat added per 1 part by mass of the D-phase composition is preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more. It is also preferably 4.0 parts by mass or less, more preferably 3.5 parts by mass or less, and most preferably 2.6 parts by mass or less. Within this range, it is often possible to make the particle size of the final oil-in-water emulsion finer. When the oil content of the oil-type emulsion in phase D is low, the amount of oil-type emulsion in phase D increases when preparing the oil-in-water emulsion. However, unless the oil content is extremely low, this does not affect the particle size of the resulting oil-in-water emulsion.

[0023] Strong shear force is not essential in the preparation of oil-in-water emulsions, so the aforementioned equipment with weaker shear force can also be used. Furthermore, not only oil-in-water emulsions but also oil-in-water emulsions themselves can be circulated and then diluted before use.

[0024] ■ Preparation of oil-in-water emulsions If an oil-in-water emulsion is required, the oil-in-water emulsion in phase D is diluted and dispersed with water to obtain an oil-in-water emulsion of the desired concentration. Strong shear force is not essential in this preparation, and the aforementioned equipment with weaker shear force can also be used. The final concentration of the oil-in-water emulsion can be set arbitrarily.

[0025] ■Crude protein content The Kjeldahl method is used for measurement. Specifically, the mass of nitrogen measured by the Kjeldahl method relative to the mass of protein material is expressed as the crude protein content in the dry material as "mass %". The nitrogen conversion factor is 6.25. Basically, the value is obtained by rounding to two decimal places.

[0026] ■NSI Add 60 ml of water to 3 g of protein material sample, stir with a propeller at 37°C for 1 hour, then centrifuge at 1,400 × g for 10 minutes and collect the supernatant (I). Next, add another 100 ml of water to the remaining precipitate, stir with a propeller again at 37°C for 1 hour, then centrifuge and collect the supernatant (II). Combine solutions (I) and (II), and add water to the mixture to make 250 ml. Filter this mixture through filter paper (No. 5), and measure the nitrogen content of the filtrate using the Kjeldahl method. Simultaneously measure the amount of nitrogen in the sample using the Kjeldahl method, and the NSI is defined as the ratio of the amount of nitrogen recovered as filtrate (water-soluble nitrogen) to the total amount of nitrogen in the sample, expressed as mass %. Basically, it is obtained by rounding the value to two decimal places.

[0027] ■TCA solubility rate To a 2% by mass aqueous solution of the protein material sample, an equal volume of 0.44 M trichloroacetic acid (TCA) is added to prepare a 0.22 M TCA solution, and the percentage of soluble nitrogen is measured using the Kjeldahl method. Basically, the value is obtained by rounding to two decimal places.

[0028] ■Viscosity (viscosity after heating) The viscosity of protein materials is measured using a Type B viscometer (Toki Sangyo Co., Ltd., Type BM). An aqueous solution of the protein material is prepared so that the crude protein content is 20% by mass, filled into a measuring container, the rotor is set, and after sealing, it is heated in a water bath at 80°C for 30 minutes. Next, the viscosity is measured at 25°C at an arbitrary rotation speed, the pointer value is read, and the viscosity is calculated by multiplying it by the conversion multiplier corresponding to the rotor No. and rotation speed. (Unit: Pa·s) This is the measurement value after 1 minute. The rotation speed is basically set to 60 rpm. For high viscosity samples, the rotor No. is changed from 1 to 4 and the rotation speed is reduced to 6 rpm. The upper limit of viscosity that can be measured in this measurement is 100,000 mPa·s. If the measurement range is exceeded with rotor No. 4 and rotation speed of 6 rpm, the viscosity after heating is immediately judged to be 100,000 mPa·s or higher.

[0029] ■ Particle size The particle size of oil-in-water emulsions is measured using a laser diffraction particle size distribution analyzer (preferably one manufactured by Shimadzu Corporation), and the volume-based median diameter is defined as the emulsion particle size. In principle, it is expressed with three significant figures, rounded to the fourth decimal place.

[0030] ■Applications The D-phase oil-based emulsion of the present invention can be used as a novel D-phase oil-based emulsion that does not contain conventional emulsifiers mainly composed of fatty acid esters. D-phase oil-based emulsions have many examples of use in cosmetics and can also be used in oral care products such as toothpaste or in food products. In cosmetic applications, it can be used in cleansing agents, emulsions, creams, lotions, balms, foundations, sunscreens, etc. Use as a cleansing agent is particularly preferred. When used as a cleansing agent, a D-phase oil-type emulsion or its aqueous dilution with a high oil content is preferred. The oil content of the D-phase oil-type emulsion or its aqueous dilution is preferably 50% by mass or more, more preferably 60% by mass or more, and most preferably 65% ​​by mass or more. It is preferably 90% by mass or less, and more preferably 85% by mass or less. This cleansing agent is effective for removing lipstick, mascara, foundation, sunscreen, and other similar products. For low-polarity cosmetics such as lipstick, it is preferable that the water content is not too high. The water content of the oil-type emulsion in the D phase or its aqueous dilution is preferably 10% by mass or less, and more preferably 5% by mass or less. For cosmetics containing polar substances such as mascara, it may be preferable to contain a certain amount of water. The water content of the oil-type emulsion in the D phase or its aqueous dilution is preferably 5% to 20% by mass, and more preferably 10% to 15% by mass. For other cosmetics, it can be used primarily as an oil-in-water emulsion. In all cases, it is characterized by its formulation that does not contain conventional emulsifiers mainly composed of fatty acid esters, and that it can be prepared even under weak shear forces.

[0031] The oil-in-D-phase emulsion of the present invention can also be used as a food product. As described above, by using the oil-in-D-phase emulsion in the preparation process, it is possible to prepare an oil-in-water emulsion even under weak shear forces. Furthermore, for the purpose of distributing oil-in-water emulsions, the oil-in-D-phase emulsion can be distributed in its original form. Compared to oil-in-water emulsions, the oil-in-D-phase emulsion has a more stable emulsified state, and by setting a low water activity, its shelf life is improved, and it is easy to obtain an oil-in-water emulsion by subsequent dilution and stirring. It can be used in various creams, soups, seasonings, flavorings, etc. [Examples]

[0032] The present invention will be described below by the following examples. Unless otherwise specified, parts or percentages in the following descriptions refer to parts by mass or mass%. ■Ingredients The raw materials used in the examples and comparative examples are as follows:

[0033] ■ Protein material The following protein materials were used. The three materials that meet requirements (A) and (B) of the present invention are soy protein material A, milk whey protein material A, and pea protein material A. Soy protein material A: "MIRA-MAP2.0" - Fuji Oil Co., Ltd., Crude protein content 79.3%, TCA solubilization rate 61.8%, Viscosity after heating 28 mPa·s, NSI 98.1) Soy protein material B: "Fujipro F" - Fuji Oil Co., Ltd., Crude protein content 87.2%, TCA solubilization rate 3.2%, Viscosity after heating 100,000 mPa·s or higher, NSI 81.2) Soy protein material C: "Fujipro CL" - Fuji Oil Co., Ltd., Crude protein content 88.0%, TCA solubilization rate 23.0%, Viscosity after heating 100,000 mPa·s or higher, NSI 65.0) Soy peptide material: "HighNut DC6" - Fuji Oil Co., Ltd., Crude protein content 90.0%, TCA solubilization rate 100.0%, Viscosity after heating 17 mPa·s, NSI 100) Sodium caseinate: "Sodium Caseinate 180" - Fonterra, Crude protein content 92.3%, TCA solubilization rate 0.0%, Viscosity after heating ≥ 100,000 mPa·s, NSI 98.1) Milk whey protein material A: Decomposed / denatured and molecular weight distribution adjusted product of milk whey protein. (Test manufactured product of Fuji Oil Co., Ltd., moisture content 5.0%, crude protein content 72.9%, TCA solubilization rate 71.3%, viscosity after heating 9.7 mPa·s, NSI 100) Raw material "WPC80" (Agri-Mark, crude protein content 77.5%) Milk whey protein material B: "WPC392" - Fontera, crude protein content 81.2%, TCA solubilization rate 27.5%, viscosity after heating 100,000 mPa·s or higher, NSI 96.9) Pea protein material A: Pea protein decomposition / denaturation and molecular weight distribution adjustment processed product. (Test manufactured by Tianjin Fuji Protein Co., Ltd., moisture content 3.6%, crude protein content 81.7%, TCA solubilization rate 62.7%, viscosity after heating 16.2 mPa·s, NSI 97.8) Raw material: Pea protein: HYPP-B80 (manufactured by Hengyuan Biotechnology Co., Ltd., crude protein content 83.4%) Pea protein material B: "E86" - emsland, crude protein content 87.2%, TCA solubilization rate 3.5%, viscosity after heating 100,000 mPa·s or higher, NSI 29)

[0034] ■Other ingredients The following materials were used in addition to the above. Reduced starch syrup: "Amamiru" - Mitsubishi Corporation Life Sciences Co., Ltd., moisture content 30.2% Sunflower oil: "High-All 75B" - Fuji Oil Co., Ltd. Jojoba oil: "Jojoba oil" - Ryohin Keikaku Co., Ltd. Olive oil: "Olive Squalane Oil" - Ryohin Keikaku Co., Ltd. MCT (Medium-Chain Triglyceride): "MCT64" - Fuji Oil Co., Ltd. Cocoa butter: "Cocoa Butter 201" - Fuji Oil Co., Ltd.

[0035] ■Preparation of oil-in-water emulsion (Example 1) A D-phase composition was prepared by mixing and dissolving 1 part by mass of soy protein material A, which is an emulsifier (D), with 4 parts by mass of glycerin as a polyol (P) using a mechanical stirrer HIDDON BL1200 (Shinto Kagaku Co., Ltd.) while stirring with a propeller (1,000 rpm). Subsequently, an oil-in-D-phase emulsion was prepared by gradually mixing and dispersing 10 parts by mass of sunflower oil, which is the oil phase (O), with the D-phase composition while stirring with a propeller (1,000 rpm). Furthermore, an oil-in-water emulsion was prepared by gradually mixing 85 parts by mass of water with the D-phase oil-in-phase emulsion while stirring with a propeller (1,000 rpm). The prepared oil-in-water emulsions were measured for median diameter immediately after preparation (Day 1) and on day 7 (Day 7) using a laser diffraction particle size distribution analyzer (Shimadzu Corporation), and this was used as the emulsion particle size. Based on the smaller of the two emulsion particle sizes (Day 1 or Day 7), particles less than 1.0 μm were rated as particularly good (++), 1.0 μm to less than 1.6 μm as good (+), 1.6 μm to less than 2 μm as usable (±), and 2 μm or larger as unacceptable (-).

[0036] ■ Investigation of variations in the moisture content of polyols (Examples 2-5) The following was carried out using the same procedure as in Example 1. D-phase compositions were prepared by mixing and dissolving 1 part by mass of soy protein material, which is an emulsifier (D), into a polyol (P) made by adding 0.4 to 2 parts by mass of water to 3.6 to 2 parts by mass of glycerin, according to the formulations shown in Table 1 (Examples 2 to 4). In addition, a D-phase composition was prepared by mixing and dissolving 1 part by mass of soy protein material, which is an emulsifier (D), into 10 parts by mass of reduced starch syrup with a water content of 30% as polyol (P) (Example 5). An oil-in-D-phase emulsion was prepared by dispersing 10 parts by mass of sunflower oil, which is an oil phase (O), in each D-phase composition. Furthermore, an oil-in-water emulsion was prepared by dispersing the oil-in-D-phase emulsion in 85 parts by mass of water (Examples 2 to 4) or 79 parts by mass of water (Example 5).

[0037] ■Table 1: Experiments with different moisture content of polyols TIFF2026076476000001.tif134144

[0038] The results for Examples 1-5 are shown in the lower part of Table 1. The emulsion particle size was particularly good in Examples 2 and 3, and good in Examples 1, 4, and 5. In all cases, the D-phase composition, oil-in-D-phase emulsion, and oil-in-water emulsion could be prepared using a weak shear force, which is propeller stirring. No significant change in the emulsion particle size was observed in these emulsions even after 7 days.

[0039] ■ Investigations with varying amounts of polyol (Examples 6-12) The following was carried out using the same procedure as in Example 1. D-phase compositions, D-phase oil-in-phase emulsions, and oil-in-water emulsions were prepared using glycerin, soy protein material, and sunflower oil according to the formulations shown in Table 2. The results are shown in the lower part of Table 2. Example 12, which had the highest proportion of oil and fat relative to the emulsifier, soy protein material A, had a particle size exceeding 1.6 μm and was therefore evaluated as usable (±). In addition, Example 8, which used 10 parts by mass of oil and fat to 7 parts by mass of the D phase composition, had the finest particle size and was able to prepare a stable emulsion.

[0040] ■Table 2: Experiments with different amounts of polyol TIFF2026076476000002.tif104145

[0041] ■ Investigation with different types of oils and fats (Examples 13-17) The following was carried out using the same procedure as in Example 1. According to the formulations shown in Table 3, sunflower oil was replaced with various fats and oils to prepare the D-phase composition, the D-phase oil-in-phase emulsion, and the oil-in-water emulsion. In Example 17, which used cocoa butter, all operations were carried out at 60°C or higher using heated raw materials. The results are shown in the lower section of Table 3. There was no difference even when the type of oil was changed, and good oil-in-water emulsions were prepared in all cases.

[0042] ■Table 3: Examination with different types of oils and fats TIFF2026076476000003.tif146144

[0043] ■D-phase compositions using other protein materials (Examples 18, 19, Comparative Examples 1-6) The following procedures were carried out in the same manner as in Example 1. D-phase compositions, oil-in-D-phase emulsions, and oil-in-water emulsions were prepared by substituting soy protein material with various protein materials according to the formulations shown in Table 4. Emulsified particle size was measured on Day 3 and Day 7. Each protein material used in Examples 9, 10, 18, and 19 possessed requirements (A) and (B) of the present invention, and all had emulsifying properties, allowing for the preparation of D-phase compositions, oil-in-D-phase emulsions, and oil-in-water emulsions. On the other hand, Comparative Examples 1, 2, 4-6 failed to form dissolved D-phase compositions. Furthermore, while Comparative Example 3 was able to form a D-phase composition, it was a low-molecular-weight material with a TCA solubilization rate of 100.0% and lacked emulsifying properties, thus failing to produce oil-in-D-phase emulsions and oil-in-water emulsions. Each prepared D-phase composition was placed in a 1 ml test tube and centrifuged at 20,000 × g for 30 minutes (25°C). The state after centrifugation is shown in Figure 1. Protein materials other than those in Examples 10, 18, 19 and Comparative Example 3 did not dissolve in glycerin and precipitated. Similar results were obtained for Comparative Examples 5 and 6, although they are not shown here. Table 4, lower section, shows the particle size of the oil-in-water emulsion on Day 3. Examples 18 and 19, which used materials possessing properties (A) and (B) of the present invention, were both able to prepare oil-in-phase D emulsions and oil-in-water emulsions. Example 19, in particular, which used peas as a raw material, showed a good emulsion particle size. On the other hand, the comparative examples all showed extremely large emulsion particle sizes and were unsuitable as oil-in-water emulsions. Measurements on Day 7 were not performed because the emulsification state was already poor on Day 3.

[0044] ■Table 4 Examination using other protein materials TIFF2026076476000004.tif118146

[0045] ■ Prototype of cleansing agent A cleansing agent was prototyped using the oil-based emulsion in phase D of the present invention. Following the formulations in Table 5, soy protein material A was added to glycerin (Prototype Example 1) or reduced starch syrup (Prototype Example 3) to prepare a phase D composition in the same manner as in Example 1. Sunflower oil was added to the phase D composition and stirred in the same manner to obtain a cleansing agent (Prototype Example 1, Prototype Example 3), which is an oil-based emulsion in phase D. Prototype 2 was obtained by adding 10 parts by mass of water to 90 parts by mass of prototype 1 and stirring. Similarly, prototype 4 was obtained by adding 5 parts by mass of water to 95 parts by mass of prototype 3. When these prototypes were used to wash away cosmetics adhering to the skin, prototypes 1 and 3 showed particularly good cleansing effects for lipstick, while prototypes 2 and 4 showed particularly good cleansing effects for mascara.

[0046] ■Table 5 Cleansing agent formulation TIFF2026076476000005.tif77143 [Industrial applicability]

[0047] By using the present invention, oil-in-water emulsions using protein materials can be easily prepared even with equipment that has low shear force, significantly increasing the number of facilities that can prepare emulsions. Furthermore, it becomes possible to manufacture highly safe cosmetics using this emulsion.

Claims

1. A D-phase oil-in-phase emulsion in which a protein material having the properties of (A) and (B) below is dissolved in a D-phase composition containing oil or fat dispersed in a polyol with a moisture content of 50% by mass or less. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%.

2. The D-phase oil-type emulsion according to claim 1, wherein the polyol is glycerin or reduced starch syrup.

3. A D-phase oil-type emulsion according to claim 1 or claim 2, wherein the amount of polyol with a moisture content of 50% by mass or less is 15 parts by mass or less per 1 part by mass of protein material.

4. A method for producing an oil-in-D-phase emulsion, comprising the following steps [1] and [2]. [1] A step of obtaining a D-phase composition by dissolving a protein material having the properties of (A) and (B) below in a polyol with a moisture content of 50% by mass or less. [2] A step of dispersing oil and fat in the D-phase composition to prepare an oil-type emulsion in the D-phase. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%.

5. A method for producing an oil-in-D-phase emulsion according to claim 4, wherein the polyol is glycerin or reduced starch syrup.

6. A method for producing an oil-in-water emulsion, comprising dispersing the oil-in-D-phase emulsion described in claim 4 or claim 5 in water.

7. A method for dispersing oil and fat in water, comprising all of the following steps [1] to [3]. [1] A step of obtaining a D-phase composition by dissolving a protein material having the properties of (A) and (B) below in a polyol with a moisture content of 50% by mass or less. [2] A step of dispersing oil and fat in the D-phase composition to prepare an oil-type emulsion in the D-phase. [3] A step of dispersing the oil-type emulsion in water in the D phase. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%.

8. A method for dispersing oils and fats in water according to claim 7, wherein the polyol is glycerin or reduced starch syrup.

9. A cosmetic product comprising a D-phase composition in which a protein material having the properties of (A) and (B) below is dissolved in a polyol with a water content of 50% by mass or less, wherein oils and fats are dispersed in the D-phase composition, and is an oil-in-D-phase emulsion or a water-diluted thereof. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%.

10. The cosmetic according to claim 9, wherein the cosmetic is a cleansing agent.

11. A food product that is an oil-in-D phase emulsion in which a protein material having the properties of (A) and (B) below is dissolved in a polyol with a water content of 50% by mass or less, and an oil is dispersed in a D phase composition. (A) An aqueous solution containing 20% ​​by mass of crude protein is heated at 80°C for 30 minutes, and the viscosity measured at 25°C is 10,000 mPa·s or less. (B) The solubilization rate of 0.22M TCA is 30% to 95%.

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