JP7260691B1 - Emulsion composition, oil-in-water (O/W type) emulsion composition, and cosmetic composition - Google Patents

Abstract

The present invention provides an emulsified composition having good emulsion dispersibility even when various oil-soluble substances are used. [Solution] An emulsified composition containing a polyhydric alcohol, a first aqueous medium, microbiomass, and an oil-soluble substance, wherein the content of the oil-soluble substance is 20% by mass or more, and the microbiomass The emulsion composition has a median diameter of 5 to 40 μm and a specific surface area of 5 to 100 m 2 /g. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to an emulsion composition, an oil-in-water (O/W) emulsion composition, and a cosmetic composition.

BACKGROUND ART Emulsions are used in many products such as various foods such as processed foods, luxury foods, and health foods, cosmetics, pharmaceuticals, paints, cooking/seasonings, various beverages, and feeds. Products containing these emulsified compositions are required to have a stable emulsifying ability with respect to oil agents in order to improve the stability of quality. Various methods are known for producing emulsion compositions. Among them, the D (detergent=surfactant) phase emulsification method that can obtain an emulsified composition of fine oil droplets has attracted attention (see, for example, Patent Documents 1 to 4).

In the phase D emulsification method, an emulsified composition is produced by first dissolving an emulsifier in a polyhydric alcohol or an aqueous polyhydric alcohol solution, adding an oil phase to the solution, and emulsifying the solution. Then, this emulsion composition is diluted with an aqueous medium to obtain a fine emulsion (see, for example, Non-Patent Document 1).

JP-A-7-59545 JP-A-2000-102356 JP-A-2000-83624 Japanese Patent Application Laid-Open No. 2004-290104

Fragrance Journal, 4, 34-41 (1993)

For example, in Patent Document 2, an oil-in-water phase emulsion obtained by adding eggs, vinegar and oil to an oil-in-D (O/D) emulsified composition containing an emulsifier with an HLB of 6 to 16 in the D-phase ( mayonnaise) is disclosed. The emulsion is described to be more stable than an oil-in-water emulsion (mayonnaise) obtained by simply mixing an emulsifier with an HLB of 6 to 16 with eggs, vinegar and oil. Patent Document 4 describes that an oil-in-D (O/D) emulsified composition containing an emulsifier with an HLB of 11 to 16 in the D phase has stable oil droplets even in acidic foods. In addition, in Example 2 of Patent Document 3, an oil-in-D phase (O/D type) containing diglyceryl monostearate (HLB 7.6) and decaglycerol distearate (HLB 11.7) in the D phase A whole egg liquid containing an emulsified composition is described to be stable even when frozen.

However, these oil-in-D phase (O/D type) emulsified compositions are poor in the stability of the oil droplets of the oil-in-water (O/W) emulsion obtained by mixing them with an aqueous medium, The stability of the oil droplets in hot conditions is still far from being satisfactory. In addition, in order to respond to the diversification of future products, it would be preferable from the viewpoint of versatility if an emulsified composition with high dispersibility in various oil-soluble substances could be obtained. has not yet been found.

Accordingly, it is an object of the present invention to provide an emulsified composition having good emulsion dispersibility even when various oil-soluble substances are used.

As a result of intensive studies in view of the above situation, the present inventors found that by combining a polyhydric alcohol and microbiomass when containing a high concentration of oil-soluble substances, fine oil droplets with high stability The present inventors have completed the present invention by finding that an emulsified composition that provides That is, the present invention is as follows.

[1] An emulsion composition containing a polyhydric alcohol, a first aqueous medium, microbiomass, and an oil-soluble substance, wherein the content of the oil-soluble substance is 20% by mass or more, and the median of the microbiomass An emulsion composition having a diameter of 5 to 40 μm and a specific surface area of 5 to 100 m ² /g.
[2] The emulsified composition according to [1], which is an oil-in-phase D type (O/D type).
[3] The emulsified composition according to [1] or [2], wherein the microbiomass is microbiomass particles and/or microbiomass fibers.
[4] The emulsified composition according to any one of [1] to [3], wherein the oil-soluble substance is at least one of saturated hydrocarbon oil, silicone oil and vegetable oil.
[5] An oil-in-water (O/W) emulsion composition comprising the emulsion composition according to any one of [1] to [4] and a second aqueous medium.
[6] A cosmetic composition comprising the emulsified composition according to any one of [1] to [4] or the oil-in-water (O/W) emulsified composition according to [5].

According to the present invention, it is possible to provide an emulsified composition having good emulsion dispersibility even when various oil-soluble substances are used.
In particular, when the emulsified composition of the present invention is an oil-in-D phase (O/D type) emulsified composition, it provides an emulsion with excellent oil droplet stability when further diluted with an aqueous medium. , cosmetics and the like.

[Emulsion composition]
An emulsified composition according to one embodiment (this embodiment) of the present invention contains a polyhydric alcohol, a first aqueous medium, microbiomass, and an oil-soluble substance. In this embodiment, the content of the oil-soluble substance is 20% by mass or more, the median diameter of the microbiomass is 5 to 40 μm, and the specific surface area is 5 to 100 m ² /g.

Microbiomass are particles and/or fibers that are derived from biomass and are of the micro order in size. When the median diameter is 5 to 40 μm, it is possible to stabilize the dispersibility of the microbiomass in the preparation process of the emulsified composition when the emulsion composition is prepared, and the median diameter is 5 to 40 μm. can also impart a good tactile feel to the emulsified composition.
Further, as described above, the specific surface area of microbiomass is 5 to 100 m ² /g, but if the specific surface area is less than 5, microbiomass will precipitate. If the specific surface area exceeds 100 m ² /g, the viscosity increases, which affects handling properties in additional steps in the dispersion step and in subsequent steps. When the specific surface area is 5 to 100 m ² /g, it is assumed that only the particle surface becomes more fibrous and fluffy. As a result, it is considered that stable dispersion becomes possible when an emulsified composition is formed without increasing the viscosity.

Furthermore, since microbiomass is derived from biomass, there are hydrophilic and hydrophobic parts in its network. Due to this amphiphilicity, the polyhydric alcohol and the aqueous medium are well retained in the biomass network, and the emulsification stability of high-concentration oil-soluble substances of 20% by mass or more can be improved. It is speculated that
Here, the “micro” of microbiomass is the longest axis, which is the maximum length, the first short axis, which is the smallest length perpendicular to the long axis, and the shortest length, which is perpendicular to the long axis and the first short axis. Any of the second short axes of the thickness has a size of 1 to 1000 μm.

The emulsified composition according to the present embodiment can be obtained by adding an oil-soluble substance to a polyhydric alcohol containing microbiomass and an aqueous medium, or to an aqueous polyhydric alcohol solution containing microbiomass, followed by stirring. In particular, the inclusion of microbiomass facilitates the capture of oil-soluble substances by polyhydric alcohols in the network. As a result, unlike conventional emulsifiers, it becomes easier to obtain an emulsified composition having good emulsion dispersibility not only in a heated state but also at room temperature.

The emulsified composition according to the present embodiment is preferably an oil-in-D-phase type (O/D type) from the viewpoint of efficiently capturing oil-soluble substances in the microbiomass network.
Each component and the like will be described below, but the present invention is not limited to these.

(polyhydric alcohol)
As the polyhydric alcohol, it is preferable to use a water-soluble polyhydric alcohol, and among these, those having 3 or more hydroxyl groups in the molecule are preferable. For example, glycerin, diglycerin, triglycerin, polyglycerin such as tetraglycerin, sugars such as glucose, maltose, maltitol, sucrose, fructose, xylitol, inositol, pentaerythritol, sorbitol, maltotriose, starch-decomposing sugar, and these polyglycerin is preferred, and glycerin is more preferred. These may be used alone or in combination of two or more. Further, the polyhydric alcohol may be used as it is, or may be dissolved in water and used as an aqueous solution of about 50 to 99.9% by mass.

The proportion of the polyhydric alcohol in the emulsified composition (especially the D-phase oil-in-type (O/D type) emulsified composition) is preferably 7% by mass or more, more preferably 15% by mass or more. Moreover, it is preferably 50% by mass or less, more preferably 20% by mass or less.

(First aqueous medium)
Examples of the first aqueous medium include water, an aqueous solution containing a polar organic solvent, and the like. It is desirable that the concentration of the organic solvent is low, and water is particularly preferable. The proportion of the first aqueous medium in the emulsified composition (especially the oil-in-phase (O/D) emulsified composition in phase D) is preferably 1.0% by mass or more, and is 1.5% by mass or more. is more preferable. Also, it is preferably 8.0% by mass or less, more preferably 4.0% by mass or less.

(microbiomass)
Microbiomass is preferably microbiomass particles and/or microbiomass fibers. These are excellent in emulsifying performance, and can form stable emulsified compositions even when various oil-soluble substances are used.

Examples of microbiomass include plant microbiomass and animal microbiomass. Plant microbiomass includes cellulose, and animal microbiomass includes silk, chitin, chitosan, and the like. Any of the above-mentioned microbiomass can be used, but silk and cellulose are preferable in consideration of biocompatibility when used for cosmetics.

(1) Microbiomass Particles The microbiomass particles according to the present embodiment preferably have a unimodal particle size distribution. The phrase "the particle size distribution exhibits unimodality" means that the particle size distribution is in a monodisperse state and the histogram of the particle size distribution of the microbiomass particles exhibits only one peak. Being unimodal, it can be said that the microbiomass particles are particulate rather than fibrous. By being in the form of particles, entanglement unlike the fibrous form does not occur, and when it is made into a dispersion, the viscosity can be reduced compared to the fibrous form, and handling properties can be improved.
The particle size distribution of the microbiomass particles is preferably measured by the method described in Examples below, and the particle size range for measurement is preferably 0.1 to 500 μm.

As described above, the median diameter of the particle size distribution of the microbiomass particles is 5 to 40 μm, preferably 5 to 35 μm, more preferably 5 to 30 μm, more preferably 5 to 25 μm. preferable.

In addition, the half width of the unimodal peak described above is preferably 1 to 70 μm, more preferably 1 to 50 μm, even more preferably 1 to 15 μm, and particularly preferably 1 to 9 μm. , 1 to 7 μm. When the half width is in the narrow range of 1 to 70 μm, it can be said that the particle size is uniform, and it becomes easy to uniformly disperse the particles in the composition.
The half width can be measured as the width at half the height of the maximum frequency of the frequency distribution (unimodal peak top) in the particle size distribution curve.

The specific surface area of the microbiomass particles according to the present embodiment is 5 to 100 m ² /g as described above, but is preferably 15 to 100 m ² /g, more preferably 40 to 100 m ² /g. Preferably, it is 60 to 100 m ² /g.
The specific surface area of microbiomass such as microbiomass particles and microbiomass fibers described later can be obtained by measuring by the method described in Examples described later.

The microbiomass particles according to this embodiment can be produced as follows. That is, the production method includes a high-pressure injection treatment step of performing a high-pressure injection treatment in which a raw material dispersion fluid containing a raw material of microbiomass particles is injected at a high pressure of 80 to 245 MPa to collide with a hard body for collision, and in the high-pressure injection treatment step , High-pressure injection treatment is performed until the median diameter of the particle size distribution of the resulting microbiomass particles reaches 5 to 40 μm.
The method for producing microbiomass particles will be described in detail below.

First, a slurry of cellulose particle raw material dispersed in water is prepared as a raw material dispersion fluid containing the microbiomass particle raw material. The raw material for microbiomass particles is, for example, fibers obtained by mechanically pulverizing cellulose. As the cellulose, wood pulp or the like having a crystalline form of I-type cellulose (cellulose I-type crystal structure) is used. The cellulose type I crystal structure is more resistant to molecular chain scission than cellulose type II, which has a lower molecular weight and crystallinity, and has higher heat resistance.

As a method for mechanically pulverizing the microbiomass particle raw material, the pulp is made to a predetermined length with a beater or refiner, and then mechanically pulverized by fibrillating or miniaturizing using a high-pressure homogenizer, grinder, impact crusher, bead mill, etc. method is known.

In the present embodiment, the raw material dispersion fluid is jetted at 80 to 245 MPa through a jet nozzle with a diameter of 0.1 to 0.8 mm, and is obtained by colliding with a hard body for collision and defibrating. It is preferable to be This fibrillation method is called a water jet method (WJ method), which utilizes shear force, impact force, and cavitation due to high-speed water jets. And, according to this method, like a commercially available high-pressure homogenizer, the raw material dispersion fluid is passed through a narrow channel at a predetermined pressure and speed, and not only the shear force that homogenizes it at the time of release, but also the impact hard body It is possible to perform continuous treatment using collision force and cavitation by colliding with .

In this embodiment, high-pressure injection treatment is performed to collide with a hard body for collision by high-pressure injection at 80 to 245 MPa, and the median diameter of the particle size distribution of the microbiomass particles obtained by the treatment is 5 to 40 μm. Microbiomass particles of the present embodiment are obtained by the treatment.

Here, when the microbiomass particles are cellulose particles, the pressure is preferably 80 to 245 MPa, more preferably 80 to 220 MPa, in order to make the median diameter of the particle size distribution 5 to 40 μm. It is more preferable to set the pressure to 200 MPa. In addition, in order to make the median diameter of the particle size distribution of the obtained cellulose particles 5 to 40 μm, performing high pressure injection treatment once in the above pressure range is regarded as 1 pass, preferably 1 to 15 passes, more preferably 1 to 15 passes. 10-pass iterative processing is performed.

It is preferable to decrease the number of passes when increasing the pressure of the high-pressure injection, and increase the number of passes when decreasing the pressure. For example, in the case of 150 MPa, the number of passes is 3 to 10 times, and in the case of 200 MPa, the number of passes is 1 to 3 times (preferably about 1 time), and the median diameter of the cellulose particles is 5 to 40 μm. of microbiomass particles can be obtained efficiently. In addition, by adjusting the pressure and/or the number of passes in this way, the median diameter, specific surface area, half-value width, etc. can also be adjusted within desired ranges.

Furthermore, in the WJ method, a high-concentration raw material dispersion fluid of up to 40% by mass is injected through an injection nozzle with a diameter of 0.1 to 0.8 mm at a high pressure of 100 to 245 MPa to impinge against a hard body for collision. Since the fiber can be defibrated at high pressure, the processing amount per solid content can be dramatically improved. As a result, it is possible to obtain microbiomass particles at low cost, low environmental load, and high efficiency.

(2) Microbiomass Fiber The microbiomass fiber according to the present embodiment refers to fibrous cellulose having an average fiber diameter of 0.1 to 20 μm and an average fiber length of 200 μm or more.
Since the microbiomass according to the present embodiment is a microbiomass fiber, it is possible to maintain the fiber shape with a lower viscosity than that of nanofibers, and it is possible to make the dispersibility better than that of nanofibers. .
The particle size distribution of the microbiomass fibers is also preferably measured by the method described in Examples below, and the particle size range for measurement is preferably 0.1 to 500 μm.

As described above, the median diameter of the particle size distribution of the microbiomass fibers is 5 to 40 μm, preferably 5 to 35 μm, more preferably 5 to 30 μm, and more preferably 5 to 25 μm. more preferred.

The specific surface area of the microbiomass fibers according to the present embodiment is 5 to 100 m ² /g as described above, preferably 15 to 100 m ² /g, more preferably 40 to 100 m ² /g. Preferably, it is 60 to 100 m2/g.

Here, when the microbiomass fibers according to the present embodiment are cellulose fibers, fibers derived from crystalline cellulose and fibers derived from powdered cellulose are preferable. These are preferable in terms of chemical stability and thermal stability.
A fiber derived from crystalline cellulose refers to a microfiber produced by subjecting known crystalline cellulose to a finer treatment. The crystalline cellulose used in the present embodiment is obtained by partially depolymerizing α-cellulose obtained as pulp from a fibrous plant with an acid and purifying it. As crystalline cellulose, for example, one described in the Japanese Standards of Food Additives (9th edition) is known.

In addition, the fiber derived from powdered cellulose refers to microfibers obtained by subjecting known powdered cellulose to a finer treatment. The powdered cellulose used in the present embodiment is obtained by treating α-cellulose obtained as pulp from a fibrous plant, refining it while leaving amorphous components such as hemicellulose and lignin, and mechanically pulverizing it. Powdered cellulose is known, for example, as described in the Japanese Code of Food Additives (9th edition).

The microbiomass fiber according to the present embodiment preferably has an average fiber diameter of 0.1 to 20 μm, more preferably 0.5 to 10 μm, from the viewpoint of maintaining the fiber network structure and stabilizing the emulsion. more preferred. From the same point of view, the average fiber length of the microbiomass fibers is preferably 200 μm or more, more preferably 200 to 500 μm. In particular, when the average fiber length is 200 to 500 μm, the increase in viscosity is suppressed, and the influence on handling properties in additional steps in the dispersing step and in subsequent steps can be reduced.
The average fiber diameter and average fiber length of the microbiomass fibers can be obtained by measuring 20 fiber diameters (fiber widths) and lengths of 20 fibers by transmission electron microscope observation, and calculating the average values thereof. .

Further, the aspect ratio (average fiber length/average fiber diameter) of the microbiomass fibers is preferably 20 to 10,000, more preferably 40 to 5,000, and more preferably 100 to 1,000.

For the microbiomass fibers according to the present embodiment, for example, when produced by the WJ method described above, the raw material concentration in the raw material dispersion fluid containing the microbiomass fiber raw material is 9% by mass or less, preferably 1 to 8% by mass. do. By making the raw material concentration relatively dilute, the microbiomass fibers obtained can have a specific surface area of 50 to 100 m ² /g and a median diameter of 5 to 40 μm.

When the microbiomass, such as microbiomass particles and microbiomass fibers, is cellulose (cellulose particles and cellulose fibers), it preferably has a cellulose type I crystal structure. The cellulose type I crystal structure tends to exhibit properties such as a low coefficient of linear expansion, a high elastic modulus, and high strength compared to the cellulose type II, III, and IV crystal structures. In addition, cellulose type II requires treatment of natural cellulose with a concentrated alkaline aqueous solution during production, cellulose type III requires liquid ammonia treatment, and cellulose type IV requires heat treatment at 280° C. in glycerol. On the other hand, cellulose type I, in which natural cellulose can be used as it is, has a lower environmental impact than other crystal structures.
The crystal structure of microbiomass can be measured by the method described in Examples below.

The microbiomas of the present embodiment is produced from microbiomass raw materials by various production methods, but mechanically fibrillated microbiomas produced by mechanical fibrillation is particularly preferable. Mechanical fibrillation microbiomass is obtained by fibrillating or pulverizing (mechanically pulverizing) microbiomass raw materials such as cellulose to a predetermined length using a beater or refiner and using a high-pressure homogenizer, grinder, impact crusher, bead mill, etc. can get.

On the other hand, there is a method in which the microbiomas raw material is chemically treated to facilitate miniaturization, and then mechanical fibrillation is performed to miniaturize the material. For example, if chemically modified cellulose such as TEMPO-oxidized is used, it is difficult to obtain a desired size due to accelerated refinement. Also, metal ions included during chemical processing may act as impurities. Metal ions are, for example, sodium, aluminum, copper, and silver.

In contrast, mechanically fibrillated microbiomas such as mechanically fibrillated cellulose does not undergo chemical modification during pulverization, and uses only an aqueous medium as a medium, so there are compounds that are likely to have some effect on microbiomass. It is chemically and thermally stable. Even if treated with a high-pressure homogenizer, the degree of polymerization of mechanically defibrated cellulose is unlikely to decrease.

Here, the mechanically defibrated microbiomass such as mechanically defibrated cellulose is any one of sodium, aluminum, copper, and silver (preferably any two, more preferably any three). The content is 0.1% by mass or less, preferably 0.01% by mass or less.
The content can be obtained by measuring by high-frequency inductively coupled plasma atomic emission spectrometry, EPMA method using an electron beam microanalyzer, and elemental analysis of fluorescent X-ray analysis. is 0.1% by mass or less, preferably 0.01% by mass or less.

The proportion of microbiomass in the emulsified composition (especially the oil-in-D phase (O/D type) emulsified composition) is diluted with an aqueous medium to form an oil-in-water (O/W type) emulsion. From the viewpoint of reducing the particle size, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and from the viewpoint of emulsion stability and flavor when used in foods and beverages. Therefore, it is preferably 10% by mass or less, more preferably 5% by mass or less.

In addition, in the emulsion composition (particularly the oil-in-D phase (O/D type) emulsion composition), the mass ratio of the microbiomass and the oil-soluble substance (oil-soluble substance/microbiomass) determines the dispersibility and stability of the emulsion. From the viewpoint of sexuality, it is preferably from 50 to 1,000, more preferably from 100 to 450, even more preferably from 100 to 350.

(Oil-soluble substance)
Any oil-soluble substance used in the fields of food, feed, cosmetics, pharmaceuticals and industry can be used as the oil-soluble substance. Examples include fatty acids, oils, waxes, hydrocarbons, silicone oils, higher alcohols, Terpenes, essential oils, fat-soluble vitamins, oil-soluble drugs, oil-soluble pigments, and the like.

Fatty acids are, for example, myristic acid, palmitic acid, isopalmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, 12-hydroxystearic acid, 10-hydroxystearic acid, behenic acid, hexadecatrienoic acid, Octadecatrienoic acid, eicosatetraenoic acid, docosatetraenoic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, tetrahexaenoic acid, geometric isomers thereof, and the like. Examples of fatty acid esters include esters of the above-described fatty acids such as ethyl myristate.

Fats and oils are glycerol esters of fatty acids and glycerol esters of the fatty acid mixtures mentioned above. For example, animal oils such as fish oil, beef tallow, lard, milk fat, horse oil, snake oil, egg oil, egg yolk oil, turtle oil, mink oil; soybean oil, corn oil, cottonseed oil, rapeseed oil, sesame oil, perilla oil, Rice germ oil, sunflower oil, peanut oil, olive oil, palm oil, palm kernel oil, rice germ oil, wheat germ oil, brown rice germ oil, adlay oil, garlic oil, macadamia nut oil, avocado oil, evening primrose oil, flower oil, vegetable oils and fats such as camellia oil, coconut oil, castor oil, linseed oil and cacao oil; hydrogenated or transesterified products thereof; and medium-chain fatty acid triglycerides.

Waxes are esters of fatty acids and higher monohydric or dihydric alcohols. Examples thereof include jojoba oil, rice wax, propolis, beeswax, bleached beeswax, candelilla wax, carnauba wax, Japan wax, and spermaceti.

Hydrocarbons include, for example, liquid paraffins such as light liquid paraffin, heavy liquid paraffin, liquid isoparaffin, and light liquid isoparaffin, paraffin, petrolatum, microcrystalline wax, ceresin, squalane, squalene, etc. Among them, saturated hydrocarbons system oils are preferred.

Silicone-based oils are, for example, modified dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and aminosilicones, fatty acid silicones, alcohol silicones, polyether silicones, epoxy silicones, fluorine silicones, glycoside silicones and/or alkyl silicones. silicone compounds and the like.

Examples of higher alcohols include saturated or unsaturated alcohols having 8 to 44 carbon atoms such as lauryl alcohol, myristyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, laurin alcohol, isostearyl alcohol, 2-octyldodecanol octacosanol, etc. .
Terpenes include, for example, eugenol, geraniol, menthol, citral, citronellal, borneol and the like.

Essential oils are, for example, ambrette seed oil, mustard oil, saffron oil, citronella oil, vetiver oil, valerian oil, mugwort oil, chamomile oil, camphor oil, sassafras oil, pepper oil, rosewood oil, clary sage oil, thyme oil. , basil oil, carnation oil, cedarwood oil, cypress oil, cedar oil, clove oil, turpentine oil, pine oil, orange oil, lemongrass oil, tarragon oil, laurel leaf oil, cassia oil, cinnamon oil, pepper oil, calamus oil , sage oil, peppermint oil, peppermint oil, spearmint oil, patchouli oil, rosemary oil, lavandin oil, lavender oil, curcuma oil, cardamom oil, ginger oil, angelica oil, anise oil, fennel oil, parsley oil, celery oil , carbanum oil, cumin oil, coriander oil, dill oil, carrot oil, killaway oil, wintergreen oil, nutmeg oil, rose oil, cypress oil, sandalwood oil, allspice oil, grapefruit oil, neroli oil, lemon oil, lime oil , bergamot oil, mandarin oil, onion oil, garlic oil, bitter almond oil, geranium oil, mimosa oil, jasmine oil, osmanthus oil, star anise oil, cananga oil, ylang-ylang oil, eucalyptus oil; Oleoresins or resinoids such as ginger, parsley, coriander, licorice, pimenta, vanilla, celery, clove, nutmeg, paprika, iris resinoid, and frankincense.

Fat-soluble vitamins include, for example, vitamins A, D, E, K and derivatives thereof.
Oil-soluble drugs include, for example, coenzyme Q10, α-lipoic acid, rutin, lutein and the like.
Oil-soluble pigments include, for example, annatto pigment, paprika pigment, β-carotene, chlorophyll, monascus pigment, turmeric pigment and the like. These may be used alone or in combination of two or more.

The oil-soluble substance is preferably at least one of saturated hydrocarbon-based oil, silicone-based oil, and vegetable oil, from the viewpoint of good complementation to the microbiomass network.

When the oil-soluble substance is solid at the temperature for producing the oil-in-D phase (O/D type) emulsified composition, it may be used by dissolving it in the oil-soluble substance which is liquid at that temperature.

The proportion of the oil-soluble substance in the emulsified composition (especially the oil-in-D phase (O/D type) emulsified composition) is 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, 50% by mass or more is more preferable. If it is less than 20% by mass, the concentration of the oil-soluble substance will relatively decrease when diluted with an aqueous medium in a later step, and versatility will also decrease. The proportion of the oil-soluble substance is preferably 90% by mass or less, more preferably 80% by mass or less, preferably 70% by mass or less, and preferably 65% by mass or less.

D-phase oil-in-type (O / D type) emulsion composition is an aqueous solution of polyhydric alcohol in which microbiomass is dispersed, at a temperature of 10 to 80 ° C., 500 to 20,000 rpm, preferably 500 to 10,000 rpm. To this, an oil-soluble substance in which a lipophilic emulsifier is dissolved is added little by little, and then, while maintaining the temperature, the mixture is stirred at 500 to 20,000 rpm, preferably 500 to 10,000 rpm for 1 to 60 minutes, preferably 5 minutes. It can be obtained by further stirring for ~30 minutes. The microbiomass may be added to the polyhydric alcohol in the form of either an aqueous dispersion or a dry form.

(emulsifier)
The emulsion composition according to this embodiment may contain an emulsifier. Usable emulsifiers include polyglycerin having a degree of polymerization of 4 or more, preferably 4 to 12, such as decaglycerin monomyristate, decaglycerin monopalmitate, decaglycerin monostearate, and decaglycerin monooleate. Fatty acid esters; sucrose fatty acid esters such as sucrose monomyristate, sucrose monopalmitate, sucrose monostearate, sucrose monooleate; water-soluble phospholipids such as lecithin partial hydrolyzate and lysolecithin emulsifiers having an HLB of 10 or more, such as glycolipids; saponins; proteins such as soybean protein and sodium caseinate, and modified products thereof. These may be used alone or in combination of two or more.

The emulsified composition according to the present embodiment (in particular, the oil-in-D (O/D type) emulsified composition) is used for cosmetics, paints, pharmaceuticals, retort foods, instant foods, instant noodles, dry foods, processed milk, and the like. Foods such as processed foods, luxury foods, supplements, functional foods, foods for special dietary uses, foods for the sick, foods for the elderly, infant formula, health foods such as specified health foods, self-emulsifying fats and oils, ketchup, mayonnaise , tartar sauce, Worcestershire sauce, chili oil, spices, herbs, oils and fats, cooking and seasonings such as salad dressing, and beverages such as sake, coffee and tea.

[Oil-in-water type (O/W type) emulsion composition]
The oil-in-water (O/W) emulsion composition of the present embodiment contains the emulsified composition of the present embodiment described above and a second aqueous medium. Examples of the second aqueous medium include those similar to those of the first aqueous medium, and the first aqueous medium and the second aqueous medium may be the same or different.

The oil-in-D phase (O/D type) emulsion composition according to the present embodiment has an oil-in-D phase (O/D type) emulsion composition of, for example, 0.01 to 50% by mass, preferably 0.1 to 20 An oil-in-aqueous (O/W) emulsified composition is obtained by mixing with a second aqueous medium so as to make the mass %.
The D-phase oil-in-type (O/D type) emulsified composition according to the present embodiment is used as a cosmetic composition such as a lotion or beauty essence by diluting a water-soluble active ingredient or additive added. can do. Further, the oil-in-water type (O / W type) emulsion composition of the present embodiment obtained from the D-phase oil-in type (O / D type) emulsion composition according to the present embodiment has stability at high temperature (60 ° C.) It is also suitable for warming foods such as instant soups, and warming beverages such as hot milk coffee and hot milk tea.

[Cosmetic composition]
The cosmetic composition of the present embodiment includes the emulsified composition of the present embodiment or the oil-in-water (O/W) emulsified composition of the present embodiment. Then, the product to which a water-soluble active ingredient or additive is added can be appropriately diluted and used as a cosmetic composition such as a lotion or beauty essence.

Additives include, for example, water-soluble vitamins such as ascorbic acid, nicotinamide, and nicotinic acid; Animal and plant extracts such as placenta extract, seaweed extract, horse chestnut extract, yuzu extract, eucalyptus extract, asunaro extract; salts such as potassium hydroxide, sodium hydroxide, triethanolamine, sodium carbonate; citrate, tartrate, pH adjusters such as lactate, phosphate, succinate, and adipate; thickeners such as carboxyvinyl polymer, sodium alginate, carrageenan, carboxymethylcellulose, hydroxyethylcellulose, guar gum, xanthan gum, carboxymethylchitosan, and sodium hyaluronate agents and the like.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples do not limit or limit the present invention in any way.
The dispersibility in each example was evaluated as follows.

<Dispersion stability>
Dispersion stability (dispersibility) was evaluated by standing at room temperature after final stirring and evaluating the appearance of the emulsified composition after 72 hours. “There is clear separation between the water layer and the oil layer” is D, “There seems to be some separation but it can be said that it is in an emulsified state” is C, “Clear separation can hardly be confirmed, that is, in an emulsified state B was assigned to those in which clear separation was not confirmed at all;

[Example 1]
Using 5 g of silicone oil as an oil-soluble substance, an emulsified composition (an oil-in-D-phase (O/D type) emulsified composition) was prepared by the following procedure.

(1) To 10 g of glycerin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same applies to the following examples), 5 g each of cellulose particle A aqueous dispersion (cellulose particle A: 15% by mass) and ion-exchanged water were added. and stirred for 10 minutes to prepare a uniform mixture.
(2) Add silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name KF-96A-100CS, the same applies to the following examples) with a three-one motor stirrer to the mixture prepared in (1) at a rate of 5 ml / min. bottom.
(3) After completion of the addition, the mixture was stirred at 500 rpm for 15 minutes to obtain an oil-in-D phase (O/D type) emulsified composition. Dispersion stability was evaluated for the prepared emulsified composition. Table 1 shows the evaluation results together with the ratio of each component in the emulsified composition (parts by mass, the same applies to other tables).

In addition, the cellulose particle A water dispersion was prepared as follows.
Powdered cellulose (particle size: 5 to 45 μm) was used as a raw material for cellulose particles, and a dispersion liquid was prepared with ion-exchanged water so that the concentration of the cellulose would be 25% by mass. This dispersion was subjected to high-pressure injection treatment once at 200 MPa using a wet atomization device (Starburst, WJ method, manufactured by Sugino Machine Co., Ltd.) to form an aqueous dispersion of cellulose particles A (cellulose particle A aqueous dispersion). body) was produced.

Regarding the cellulose particles A in the prepared aqueous dispersion of cellulose particles A, the median diameter, specific surface area and crystal structure were measured as follows (other examples were similarly measured). Table 1 shows the results.

・Median diameter The median diameter of cellulose particles and cellulose fibers (the particle diameter at which the cumulative volume-based frequency is 50%) is determined by a laser diffraction/scattering particle size distribution measurement method (manufactured by Horiba, Ltd., device name: LA-960). I asked for it. The resulting aqueous dispersion of cellulose particles and cellulose fibers was adjusted with ion-exchanged water to a final concentration of 0.5% by mass, and blended in a Waring blender (manufactured by WARING, device name: 7012S) at 3400 rpm for 5 minutes. After the treatment under the conditions of , an ultrasonic dispersion treatment was performed for 1 minute before the measurement, and the particle size distribution was measured. The half-value width was defined as the width obtained by taking the half value of the maximum frequency obtained with respect to the mountain-shaped peak obtained by the particle size distribution measurement. The measurement range of particle size was 0.1 to 500 μm.

・Specific surface area A dry powder sample was obtained by freezing at a freezing temperature of -20°C after replacing the solvent of the aqueous dispersion of cellulose particles and cellulose fibers with t-butanol, and then freeze-drying at a pressure of 0.05 kPa or less. . Using this dry powder, the specific surface area was measured. The specific surface area was measured by the BET multipoint method using an automatic specific surface area/pore size distribution measuring device (manufactured by micromeritics, device name: Tristar II).

・Crystal structure After replacing the solvent with t-butanol, an aqueous dispersion of cellulose particles and cellulose fibers was frozen at a freezing temperature of -20°C, and then freeze-dried at a pressure of 0.05 kPa or less to obtain a dry powder sample. .
Crystal structures of cellulose particles and cellulose fibers were investigated using dry powder samples. A fully automatic horizontal multi-purpose X-ray diffractometer "Smart Lab" manufactured by Rigaku Corporation was used as a measuring device. The fact that it has a cellulose type I crystal structure is that in the diffraction profile obtained from an X-ray diffraction photograph using CuKα (λ = 1.542184 Å), 2θ = 15 to 17° and 2θ = 22 to 23°. can be identified by having typical peaks at two positions of . In addition, having a cellulose II type crystal structure is a diffraction profile obtained from an X-ray diffraction photograph using CuKα (λ = 1.542184 Å). It can be identified by having typical peaks at three positions near 20° and 2θ=21-23°.

[Examples 2 to 6]
An oil-in-phase D (O/D type) emulsified composition was prepared in the same manner as in Example 1 except that the composition was as shown in Table 1, and the dispersion stability was evaluated. Table 1 shows the results.

[Examples 7 to 12]
Oil-in-phase D (O/D type) emulsification was carried out in the same manner as in Example 1, except that the aqueous dispersion of cellulose particles B was used instead of the aqueous dispersion of cellulose particles A and the composition shown in Table 1 was obtained. A composition was prepared and evaluated for dispersion stability. Table 1 shows the results.

The cellulose particle B aqueous dispersion was prepared as follows.
Powdered cellulose (particle size: 5 to 45 μm) was used as a raw material for cellulose particles, and a dispersion liquid was prepared with ion-exchanged water so that the concentration of the cellulose would be 2% by mass. This dispersion is subjected to high-pressure injection treatment once at 150 MPa using a wet atomization device (Starburst, WJ method, manufactured by Sugino Machine Co., Ltd.) to form an aqueous dispersion of cellulose particles A (cellulose particle A aqueous dispersion). body) was produced.

[Comparative Examples 1 to 5]
Oil-in-phase D (O/D type) emulsification was carried out in the same manner as in Example 1, except that the aqueous dispersion of cellulose particles X was used instead of the aqueous dispersion of cellulose particles A, and the composition was as shown in Table 2. A composition was prepared and evaluated for dispersion stability. Table 2 shows the results.

The cellulose particle X aqueous dispersion was prepared as follows.
α-cellulose obtained as pulp from a fibrous plant is treated with a mineral acid, purified while leaving amorphous components such as hemicellulose and lignin, and mechanically pulverized to produce cellulose particles X, which are added to water. By dispersing, an aqueous dispersion of cellulose particles X (cellulose particle X dispersion) was produced.

[Examples 13 to 18]
In the same manner as in Example 1, except that olive oil was used instead of silicone oil and the composition was as shown in Table 3, an oil-in-D (O / D type) emulsified composition was prepared and dispersion stability was improved. was evaluated. Table 3 shows the results.

[Examples 19 to 41]
The procedure of Example 1 was repeated except that the aqueous dispersion of cellulose particles C was used instead of the aqueous dispersion of cellulose particles A, and the type of oil was changed so that the compositions shown in Tables 4 to 6 were obtained. , an oil-in-D phase (O/D type) emulsified composition was prepared and dispersion stability was evaluated. The results are shown in Tables 4-6.

The cellulose particle C aqueous dispersion was prepared as follows.
Powdered cellulose (particle size: 10 to 250 μm) was used as a raw material for cellulose particles, and a dispersion liquid was prepared with ion-exchanged water so that the concentration of the cellulose would be 30% by mass. This dispersion is subjected to high-pressure injection treatment once at 200 MPa using a wet atomization device (Starburst manufactured by Sugino Machine Co., Ltd., WJ method) to form an aqueous dispersion of cellulose particles C (aqueous dispersion of cellulose particles C). body) was produced.

[Examples 42 to 49]
An oil-in-phase D (O/D type) emulsification was carried out in the same manner as in Example 1 except that the aqueous dispersion of cellulose particles D was used instead of the aqueous dispersion of cellulose particles A and the composition was as shown in Table 7. A composition was prepared and evaluated for dispersion stability. Table 7 shows the results.

In addition, the cellulose particle D aqueous dispersion was prepared as follows.
Powdered cellulose (particle size: 10 to 250 μm) was used as a raw material for cellulose particles, and a dispersion was prepared with ion-exchanged water so that the concentration of the cellulose would be 2% by mass. This dispersion is subjected to high-pressure injection treatment 10 times at 150 MPa using a wet atomization device (Starburst, manufactured by Sugino Machine Co., Ltd., WJ method) to form an aqueous dispersion of cellulose particles D (aqueous dispersion of cellulose particles D). body) was produced.

[Comparative Examples 7 to 14]
An oil-in-phase D (O/D type) emulsification was carried out in the same manner as in Example 1, except that the aqueous dispersion of cellulose particles Z was used instead of the aqueous dispersion of cellulose particles A, and the composition was as shown in Table 8. A composition was prepared and evaluated for dispersion stability. Table 7 shows the results.

The cellulose particle Z aqueous dispersion was prepared as follows.
α-cellulose obtained as pulp from a fibrous plant was partially depolymerized with a strong mineral acid, purified, and dispersed in water to prepare an aqueous dispersion of cellulose particles Z (cellulose particle Z dispersion). .

[Examples 50-61]
Oil-in-phase D type (O/D type) was prepared in the same manner as in Example 1 except that the cellulose fiber fiber A aqueous dispersion was used instead of the cellulose particle A aqueous dispersion and the composition was as shown in Table 9. An emulsified composition was prepared and evaluated for dispersion stability. Table 9 shows the results.

The cellulose fiber A aqueous dispersion was prepared as follows.
A dispersion containing 8% by mass of cotton powder-like cellulose as a cellulose fiber raw material was prepared. This dispersion was subjected to high pressure injection treatment 10 times at 200 MPa using a wet atomization device (Starburst manufactured by Sugino Machine Co., Ltd., WJ method) to form an aqueous dispersion of cellulose fiber A (cellulose fiber A aqueous dispersion body) was produced.

Regarding cellulose fiber A and cellulose fiber X, which will be described later, the average fiber diameter and average fiber length were determined as follows. These are also shown in each table.

・Average fiber diameter and average fiber length After replacing the solvent of the aqueous dispersion of cellulose fibers with t-butanol, freezing at a freezing temperature of -20 ° C., and then freeze-drying at a pressure of 0.05 kPa or less to obtain a dry sample. Obtained. The fiber diameter of the dry sample was measured using an electron microscope (manufactured by JEOL Ltd., device name: JCM-5700). Twenty of each fiber were observed, and the average values of the fiber diameter and length were taken as the average fiber diameter and average fiber length.

[Comparative Examples 15 to 20]
Oil-in-phase D (O/D type) emulsification was carried out in the same manner as in Example 1 except that the cellulose fiber X aqueous dispersion was used instead of the cellulose particle A aqueous dispersion and the composition was as shown in Table 10. A composition was prepared and evaluated for dispersion stability. Table 9 shows the results.

The cellulose fiber X aqueous dispersion was prepared as follows.
First, a cellulose fibrous raw material was pulverized with a cutting mill (Pulverisette 15 manufactured by Fritsch) to obtain cotton powder-like cellulose. An aqueous dispersion of cellulose fibers X (aqueous dispersion of cellulose fibers X) was prepared by preparing a dispersion of the obtained cotton powder-like cellulose with ion-exchanged water so as to have a concentration of 8% by mass.

Claims (5)

An emulsified composition containing a polyhydric alcohol, a first aqueous medium, microbiomass, and an oil-soluble substance,
The microbiomass is either cellulose, silk, chitin, or chitosan,
The content of the oil-soluble substance is 20% by mass or more,
The microbiomass has a median diameter of 5 to 40 μm and a specific surface area of 5 to 100 m ² /g,
An emulsified composition that is an oil-in-D phase type (O/D type). 2. The emulsified composition according to claim 1, wherein said microbiomass is microbiomass particles and/or microbiomass fibers. 3. The emulsified composition according to claim 1, wherein said oil-soluble substance is at least one of saturated hydrocarbon oil, silicone oil and vegetable oil. An oil-in-water (O/W) emulsion composition comprising the emulsion composition according to claim 1 and a second aqueous medium. A cosmetic composition comprising the emulsified composition according to claim 1 or 2 or the oil-in-water type (O/W type) emulsified composition according to claim 4.