Emulsion composition, compound, and method for producing the compound

Abstract

To provide an emulsion composition that can maintain a stable emulsion state independent of the type of an oil phase, a compound and a method for producing a compound.SOLUTION: An emulsion composition contains an oil phase, an aqueous phase, and a closed vesicle that is formed by an amphiphilic substance, which spontaneously a closed vesicle and is represented by the formula (1). (In the formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, R is H, an alkyl group, or a carboxylic acid group having a C1-6 alkylene group as a spacer, a phosphonic acid group, a phosphate group, a sulfonic acid group, a sulfate group or a salt of any of them).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an emulsion composition, a compound, and a method for producing the compound. [Background technology]

[0002] The hydrophilic nanoparticles used in three-phase emulsification include closed endoplasmic reticulum (vesicles) and monoparticles of polysaccharides, which stabilize the emulsion by adhering to the oil-water surface. Therefore, three-phase emulsification differs from conventional surfactant emulsification, which relies on a decrease in interfacial tension, and is possible regardless of the type of oil.

[0003] For example, Patent Document 1 describes an emulsifying dispersant whose main component is closed endoplasmic reticulum formed from a self-organizing amphiphilic substance. By using this emulsifying dispersant, it is possible to form an emulsifying dispersion system with excellent thermal stability at the interface between a functional oil base and water, or between functional granules and water, etc.

[0004] In such three-phase emulsification, maintaining a stable emulsion state over a long period of time requires that nanoparticles remain as particles without dissolving in either the oil or water phase. However, some oils used as solvents, such as fragrances and benzyl alcohol, dissolve the closed vesicles used in three-phase emulsification. In this case, even if the closed vesicles adhere to the oil phase surface, they gradually dissolve in the oil phase and cannot be maintained as particles. As a result, emulsion stability becomes insufficient over time. On the other hand, oils such as benzyl alcohol and fragrances are widely used as solvents for inks, paints, lacquers, epoxy resin coatings, and cosmetic ingredients. Due to their high versatility, there has been a demand in recent years for the development of emulsification technologies that can handle these solvents in emulsion systems. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 3855203 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide an emulsion composition, a compound, and a method for producing the compound, which can maintain a stable emulsion state regardless of the type of oil phase. [Means for solving the problem]

[0007] [1] An emulsion composition comprising an oil phase, an aqueous phase, and closed vesicles formed spontaneously from an amphiphilic substance represented by the following formula (1): [ka] (In the formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, and R is H, an alkyl group, or a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, a sulfate group, or a salt of any of these, with an alkylene group having 1 to 6 carbon atoms as a spacer.) [2] The emulsion composition according to [1] above, wherein the closed endoplasmic reticulum is present at the interface between the oil phase and the aqueous phase. [3] The emulsion composition according to [1] or [2] above, wherein in the formula (1), x is 17, m is 13.5 or more and 24 or less, n is 20 or more and 23 or less, and R is CH3. [4] The emulsion composition according to the above [1] or [2], wherein in the formula (1), x is 17, m is 23, n is 19, and R is CH2COOH or a salt thereof. [5] The emulsion composition according to [1] or [2] above, wherein in the formula (1), x is 17, m is 16 or more and 26 or less, n is 18, and R is CH2CH2PO(OH)2 or a salt thereof. [6] The emulsion composition according to the above [1] or [2], wherein in the formula (1), x is 17, m is 12 or more and 24 or less, n is 18 or more and 20 or less, and R is H. [7] A compound represented by the following formula (1) that spontaneously forms closed endoplasmic reticulum in water. [ka] (In the formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, and R is H, an alkyl group, or a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, a sulfate group, or a salt of any of these, with an alkylene group having 1 to 6 carbon atoms as a spacer.) [8] The compound according to [7] above, wherein in the formula (1), x is 17, m is 13.5 or more and 24 or less, n is 20 or more and 23 or less, and R is CH3. [9] The compound according to the above [7], wherein in the formula (1), x is 17, m is 23, n is 19, and R is CH2COOH or a salt thereof.

[10] The compound according to [7] above, wherein in the formula (1), x is 17, m is 16 or more and 26 or less, n is 18, and R is CH2CH2PO(OH)2 or a salt thereof.

[11] A method for producing a compound represented by the following formula (1), comprising: Step 1: carrying out anionic ring-opening polymerization of hexamethylcyclotrisiloxane using an alkyllithium obtained by reacting a bromoalkane with metallic lithium as an initiator, followed by reaction with chlorodimethylsilane as a terminator to synthesize a block copolymer of polydimethylsiloxane and an alkane having a Si-H bond at its terminal; Step 2: synthesizing an allyl ether of polyethylene glycol having an OR group at its terminal; and Step 3: carrying out an addition reaction between the Si-H bond of the block copolymer represented by the following formula (2) obtained in Step 1 and the carbon-carbon double bond of a compound represented by the following formula (3) obtained in Step 2. [ka] [ka] [ka] (In the formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, and R is H, an alkyl group, or a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, a sulfate group, or a salt of any of these, with an alkylene group having 1 to 6 carbon atoms as a spacer.) [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an emulsion composition, a compound, and a method for producing the compound that can maintain a stable emulsion state regardless of the type of oil phase. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 shows photographs of the appearance of the emulsion compositions of Examples 2 to 3, 6 to 8 and Comparative Example 2, in which benzyl alcohol is emulsified. [Figure 2] FIG. 2 is a photograph showing the appearance of emulsion compositions in which various oils are emulsified in closed endoplasmic reticulum prepared from the compound of Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, a detailed description will be given based on an embodiment.

[0011] As a result of extensive research, the present inventors have synthesized a new compound that is an ABC triblock copolymer, comprising a self-aggregating hydrocarbon moiety for forming vesicles, a lipophobic moiety that is incompatible with hydrocarbons and water and serves as a moiety that is insoluble in both the oil and aqueous phases, and a hydrophilic moiety that allows stable dispersion in water and prevents compatibility with the oil phase. The present inventors further noted that this compound can be used in three-phase emulsification as a novel closed endoplasmic reticulum-forming substance, and found that a three-phase emulsion composition using this compound can maintain a stable emulsified state regardless of the type of oil phase. The present invention was completed based on these findings.

[0012] The emulsion composition of the embodiment contains an oil phase, an aqueous phase, and closed vesicles (hereinafter simply referred to as closed vesicles) formed by an amphiphilic substance that spontaneously forms closed vesicles and is represented by the following formula (1):

[0013] [ka]

[0014] In the above formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, and R is H, an alkyl group, or a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, a sulfate group, or a salt of any of these, with an alkylene group having 1 to 6 carbon atoms as a spacer.

[0015] The emulsion composition of the embodiment is an emulsion composition produced by a so-called three-phase emulsification method using closed vesicles. The emulsion composition may be an oil-in-water (O / W) type or a water-in-oil (W / O) type.

[0016] When the emulsion composition is an O / W type, a plurality of closed vesicles are present around the oil phase, which is the internal phase, and an aqueous phase, which is the external phase, is present outside of the closed vesicles. That is, a plurality of closed vesicles are present at the interface between the oil phase and the aqueous phase, and the aqueous phase is the continuous phase.

[0017] The emulsion composition contains a large number of emulsion particles (three-phase emulsion particles) in which a large number of closed vesicles surround a particulate oil phase (oil droplets).The emulsion particles are surrounded by an aqueous phase, and a large number of emulsion particles are dispersed in the aqueous phase.

[0018] Closed vesicles formed by amphiphilic substances spontaneously form closed vesicles in aqueous components. Closed vesicles are known as particles with the so-called three-phase emulsification ability. Because the surfaces of closed vesicles are hydrophilic, repulsive forces are generated between the closed vesicles.

[0019] The presence of numerous closed endoplasmic reticulum on the surface of the oil phase, i.e., the surface of the oil phase is covered with numerous closed endoplasmic reticulum, generates a repulsive force between the oil phases. The repulsive force generated between the oil phases is greater than the attractive force generated between the oil phases. Therefore, aggregation of the oil phases in the aqueous phase, in other words, aggregation of the emulsified particles, is suppressed, and the dispersibility of the oil phase is maintained and improved.

[0020] When the emulsion composition is a W / O type, multiple closed endoplasmic reticulum are present around the aqueous phase, which is the internal phase, and an oil phase, which is the external phase, is present outside of the multiple closed endoplasmic reticulum. That is, multiple closed endoplasmic reticulum are present at the interface between the oil and aqueous phases, and the oil phase is the continuous phase.

[0021] The emulsion composition contains a large number of emulsion particles, each of which is composed of a large number of closed vesicles surrounding a particulate aqueous phase (a droplet-like aqueous phase).The emulsion particles are surrounded by an oil phase, and the large number of emulsion particles are dispersed in the oil phase.

[0022] The presence of numerous closed vesicles on the surface of the aqueous phase, i.e., the surface of the aqueous phase is covered with numerous closed vesicles, generates a repulsive force between the aqueous phases. The repulsive force generated between the aqueous phases is greater than the attractive force generated between the aqueous phases. Therefore, aggregation of the aqueous phase particles in the oil phase, in other words, aggregation of the emulsified particles, is suppressed, and the dispersibility of the aqueous phase is maintained and improved.

[0023] In this three-phase emulsification method, closed vesicles adhere to the internal phase by van der Waals forces, interposing themselves at the interface between the oil and aqueous phases (interface between the internal and external phases), enabling emulsification. The three-phase emulsification mechanism is completely different from the emulsification mechanism using surfactants, which maintains the emulsified state by directing the hydrophilic and hydrophobic portions toward the aqueous and oil phases, respectively, thereby lowering the interfacial tension between the oil and water (see, for example, Japanese Patent Publication No. 3855203).

[0024] As described above, the emulsion composition of the embodiment applies a three-phase emulsification technique that is completely different from the emulsification mechanism using a surfactant. Therefore, the emulsion composition can maintain a stable emulsion state even without containing a surfactant. In this way, the emulsion composition can significantly reduce the amount of surfactant compared to compositions that use conventional surfactants, and in some cases, can even not contain a surfactant.

[0025] The average particle size of the internal phase in the emulsion composition is appropriately selected depending on the intended use of the emulsion composition. Because the emulsion composition is a three-phase emulsion, the average particle size of the internal phase can be selected within a wider range than conventional emulsion compositions that use surfactants. For example, the average particle size of the internal phase is 0.1 μm or more. The average particle size of the internal phase is preferably 50.0 μm or less, more preferably 25.0 μm or less, and even more preferably 10.0 μm or less. The average particle size of the internal phase can be measured by dynamic light scattering using a particle size distribution analyzer FPAR (manufactured by Otsuka Electronics Co., Ltd.) and obtained by Contin analysis.

[0026] The oil contained in the oil phase constituting the emulsion composition may be either a solid oil or a liquid oil, and the oil may be selected appropriately depending on the intended use of the emulsion composition. A solid oil is an oil that is solid at room temperature (25°C), and a liquid oil is an oil that is liquid at room temperature. The oil contained in the oil phase may be only a solid oil, only a liquid oil, or a mixture of a solid oil and a liquid oil.

[0027] For example, solid oils include solid fats (hydrogenated palm oil, palm oil, hardened coconut oil, cocoa butter, peanut butter, lard, milk fat, etc.), solid paraffin, wax, higher alcohols (behenyl alcohol, stearyl alcohol, cetyl alcohol, batyl alcohol, octyldodecanol, oleyl alcohol, etc.), waxes (carnauba wax, beeswax, etc.), etc.

[0028] For example, liquid oils include vegetable oils (olive oil, avocado oil, camellia oil, macadamia nut oil, evening primrose oil, jojoba oil, rapeseed oil, egg yolk oil, sesame oil, castor oil, safflower oil, cottonseed oil, soybean oil, tea seed oil, rice bran oil, wheat germ oil, germ oil, peanut oil, sunflower oil, almond oil, turtle oil, corn oil, mink oil, persic oil, camellia oil, linseed oil, perilla oil, kaya oil, etc.), animal oils (beef tallow, lard, milk fat, etc.), medium-chain fatty acid triglycerides, hydrocarbon oils (squalene, squalane, liquid paraffin, etc.), ester oils (ethylhexyl methoxycinnamate, cetyl ethylhexanoate, diisostearyl malate, isopropyl myristate, ethylhexyl palmitate, octyl palmitate, octyl isopalmitate, isononyl isononanoate, Examples of suitable oils include isotridecyl isononanoate, methylheptyl laurate, hexyl laurate, caprylic / capric triglyceride, triethylhexanoin, neopentyl glycol dicaprate, cetyl octanoate, isocetyl stearate, isopropyl isostearate, isodecyl oleate, glyceryl tri-2-ethylhexanoate, pentaerythrityl tetra-2-ethylhexanoate, 2-ethylhexyl succinate, and diethyl sebacate, as well as silicone oils (cyclopentasiloxane, decamethylcyclopentasiloxane, methylpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, and dodecamethylcyclohexasiloxane).

[0029] Furthermore, in addition to the oils that can be emulsified by the conventional three-phase emulsification method mentioned above, examples include liquid oils that have high solubility in organic substances, such as benzyl alcohol, terpene-based oils (citronella oil, rose oil, lavender oil, thyme oil, turpentine, limonene, etc.), and perfluorocarbons.

[0030] The content of the oil phase relative to the total mass of the emulsion composition is appropriately selected depending on the intended use of the emulsion composition. Even if the content of the oil phase is high, the emulsion state of the emulsion composition can be stably maintained. For example, the content of the oil phase may be 1.0% by mass or more, 5.0% by mass or more, 10.0% by mass or more, 20.0% by mass or more, 30.0% by mass or more, 40.0% by mass or more, 50.0% by mass or more, 60.0% by mass or more, 70.0% by mass or more, or 80.0% by mass or more. Furthermore, the content of the oil phase may be, for example, 70.0% by mass or less, 60.0% by mass or less, 50.0% by mass or less, 40.0% by mass or less, 30.0% by mass or less, 20.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less.

[0031] The aqueous phase constituting the emulsion composition is an aqueous component and is immiscible with the oil phase. The aqueous phase is, for example, water. The content ratio of the aqueous phase relative to the total mass of the emulsion composition is appropriately selected depending on the intended use of the emulsion composition. For example, the content ratio of the aqueous phase may be 1.0% by mass or more, 5.0% by mass or more, 10.0% by mass or more, 20.0% by mass or more, 30.0% by mass or more, 40.0% by mass or more, 50.0% by mass or more, 60.0% by mass or more, 70.0% by mass or more, or 80.0% by mass or more. The content ratio of the aqueous phase may be, for example, 70.0% by mass or less, 60.0% by mass or less, 50.0% by mass or less, 40.0% by mass or less, 30.0% by mass or less, 20.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less.

[0032] The closed vesicles constituting the emulsion composition spontaneously form closed vesicles and are formed by an amphiphilic substance represented by formula (1).

[0033] [ka]

[0034] In formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, and R is H, an alkyl group, or a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, a sulfate group, or a salt of any of these, with an alkylene group having 1 to 6 carbon atoms as a spacer.

[0035] The amphiphilic substance represented by formula (1) is insoluble not only in oily components that can be emulsified by conventional three-phase emulsification, but also in oily components that have high solubility in organic substances, such as benzyl alcohol. That is, the amphiphilic substance represented by formula (1) is insoluble in both the oil phase and the aqueous phase. Therefore, in the emulsion composition, the closed vesicles formed by the amphiphilic substance represented by formula (1) are not dissolved in the oil phase or the aqueous phase and remain stable as particles, so that the emulsion state of the emulsion composition is stably maintained over a long period of time.

[0036] The amphiphilic substance of formula (1) that spontaneously forms closed vesicles in water is an ABC triblock copolymer consisting of a hydrophobic alkyl chain self-aggregating unit, an oleophobic polydimethylsiloxane unit or a fluorocarbon unit that is insoluble in hydrocarbons, and a hydrophilic polyethylene glycol unit. Conventional amphiphilic substances that form closed vesicles used in three-phase emulsification are AB diblock copolymers that lack an oleophobic unit.

[0037] When x is 8 or more, the amphiphilic substance represented by formula (1) is more likely to form particulate vesicles; when x is 22 or less, the amphiphilic substance represented by formula (1) is more likely to disperse in water. When m is 9 or more, the amphiphilic substance represented by formula (1) is less likely to dissolve in oils; when m is 60 or less, the adhesive force of the closed vesicles formed by the amphiphilic substance represented by formula (1) to the internal phase can be maintained. Furthermore, when n is 10 or more, the amphiphilic substance represented by formula (1) is more likely to disperse in water; when n is 230 or less, the particle size of the closed vesicles formed by the amphiphilic substance represented by formula (1) can be maintained. Thus, when x, m, and n are within the above numerical ranges, the emulsion composition can stably maintain an emulsified state for a long period of time, regardless of the type of oil phase.

[0038] From the viewpoints of the insolubility of the amphiphilic substance represented by formula (1) in oil and aqueous phases and the ease of production of the amphiphilic substance represented by formula (1), the amphiphilic substance is preferably one of the following formulas (1-1) to (1-4). In the amphiphilic substance represented by formula (1-1), x is 17, m is 13.5 to 24, n is 20 to 23, and R is CH. In the amphiphilic substance represented by formula (1-2), x is 17, m is 23, n is 19, and R is CHCOOH or a salt thereof. In the amphiphilic substance represented by formula (1-3), x is 17, m is 16 to 26, n is 18, and R is CHCHPO(OH) or a salt thereof. In the amphiphilic substance represented by formula (1-4), x is 17, m is 12 to 24, n is 18 to 20, and R is H.

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] The content of closed vesicles relative to the total mass of the emulsion composition is appropriately selected depending on the intended use of the emulsion composition. Unlike conventional surfactants, even a small amount of closed vesicles constituting the emulsion composition can stably maintain the emulsified state of the emulsion composition. For example, the content of the closed vesicles may be 0.10% by mass or more, 0.30% by mass or more, 0.50% by mass or more, 1.00% by mass or more, or 2.00% by mass or more. Furthermore, the content of the closed vesicles may be, for example, 5.00% by mass or less, 4.00% by mass or less, 3.00% by mass or less, 2.00% by mass or less, 1.00% by mass or less, or 0.75% by mass or less. The above amounts are solid content.

[0044] The average particle size of the closed endoplasmic reticulum in the emulsion composition may be, for example, approximately 8 nm to 2000 nm, but smaller particle sizes improve emulsification. For this reason, the average particle size of the closed endoplasmic reticulum is preferably 8 nm to 800 nm, more preferably 8 nm to 500 nm. The average particle size of the closed endoplasmic reticulum is measured by dynamic light scattering using a particle size distribution analyzer FPAR (manufactured by Otsuka Electronics Co., Ltd.) and is a value determined by Contin analysis. The method for preparing closed endoplasmic reticulum formed from an amphiphilic substance represented by formula (1) and having an average particle size within the above numerical range is similar to known methods for preparing particles with three-phase emulsification ability, such as those described in Japanese Patent No. 3855203, and therefore will not be described here for convenience.

[0045] Furthermore, when light scattering measurement is performed on the emulsion composition described below and the average particle diameter of the closed vesicles present in the mixed solution is found to be, for example, 8 nm or more and 400 nm or less, it can be determined that the closed vesicles are capable of three-phase emulsification. Furthermore, this can be confirmed by observing the emulsified particles contained in the emulsion composition with an atomic force microscope (AFM) to confirm that the closed vesicles are attached to the surface of the internal phase.

[0046] Furthermore, the emulsion composition of the embodiment may further contain various functional components in addition to the oil phase, aqueous phase, and closed endoplasmic reticulum, as long as the functional components do not inhibit a stable emulsion state. The functional components are components that impart desired functions to the emulsion composition, for example, when the emulsion composition is used in foods, cosmetics, industrial products, etc.

[0047] Next, a method for producing the emulsion composition of the embodiment will be described.

[0048] The method for producing the emulsion composition includes a nanoparticle dispersion preparation step and an emulsification step.

[0049] In a method for producing an O / W emulsion composition, in the nanoparticle dispersion preparation step, a predetermined amount of an amphiphilic substance represented by formula (1) is added to an aqueous component such as water while stirring the aqueous component with a stirrer or the like, thereby forming multiple closed vesicles formed by the amphiphilic substance represented by formula (1), and the multiple closed vesicles are mixed with the aqueous component. In this mixed solution, multiple nanoparticle-shaped closed vesicles are dispersed in the aqueous component. When the aqueous component is water, the closed vesicles are stirred well when the water temperature is 60°C or higher.

[0050] The stirring speed of the aqueous component in the nanoparticle dispersion preparation step is preferably 1000 rpm or higher, which allows the closed vesicles to be thoroughly stirred into the aqueous component.

[0051] In order to maintain the dispersibility of the closed vesicles in the mixed solution, the mixed solution may be continuously stirred at a speed slower than the stirring speed in the nanoparticle dispersion preparation step until the emulsification step is carried out.

[0052] In the emulsification process performed after the nanoparticle dispersion preparation process, an oily component above its melting point is added to the mixed solution while stirring the mixed solution with a stirrer or the like, forming emulsified particles, thereby obtaining an emulsion composition containing a plurality of emulsified particles dispersed in an aqueous phase. The surface of the droplet-shaped oil phase of the emulsified particles is covered with a plurality of closed endoplasmic reticulum. When the functional component is contained in the oil phase, the oily component containing the functional component is added to the mixed solution while stirring, thereby obtaining emulsified particles containing the functional component in the oil phase. If the temperature of the oily component added to the mixed solution is below its melting point, it may be difficult to shear the oil. Therefore, if the temperature of the oily component added to the mixed solution is below its melting point, the oily component is heated to above its melting point, and an oily component above its melting point is added to the mixed solution.

[0053] In addition, in the method for producing a W / O emulsion composition, a plurality of closed endoplasmic reticulum and an aqueous component are mixed by carrying out the nanoparticle dispersion preparation step in the same manner as described above. When the functional component is to be contained in the aqueous phase, the functional component is further added to the mixed solution and mixed.

[0054] In the emulsification step performed after the nanoparticle dispersion preparation step, the nanoparticle dispersion is added to the oily component while stirring the oily component at or above its melting point using a stirrer or the like, thereby forming emulsified particles, and an emulsion composition containing a plurality of emulsified particles dispersed in the oil phase is obtained. The surfaces of the droplet-shaped aqueous phase of the emulsified particles are covered with a plurality of closed endoplasmic reticulum.

[0055] Next, the compound of the embodiment will be described. The compound of the embodiment is represented by formula (1) and spontaneously forms closed vesicles in water.

[0056] [ka]

[0057] In formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, and R is H, an alkyl group, or a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, a sulfate group, or a salt of any of these, with an alkylene group having 1 to 6 carbon atoms as a spacer.

[0058] The compound represented by formula (1) is suitable for use in an emulsion composition. The compound represented by formula (1) is an amphiphilic substance that spontaneously forms closed vesicles, and in the emulsion composition, it exists as closed vesicles at the interface between the oil phase and the aqueous phase (internal phase and external phase).

[0059] The compound represented by formula (1) is not dissolved in an aqueous phase. Furthermore, the compound represented by formula (1) is not dissolved in an oil phase containing not only common oily components but also oily components with high solvent properties, such as benzyl alcohol. Therefore, in an emulsion composition containing an oil phase, an aqueous phase, and closed vesicles formed by the compound represented by formula (1) (amphiphilic substance), the closed vesicles formed by the compound represented by formula (1) are stably present without being dissolved in the oil phase or the aqueous phase, so that the emulsion state of the emulsion composition is stably maintained for a long period of time. Thus, the compound represented by formula (1) is suitable as a compound for an emulsion composition.

[0060] The compound represented by formula (1) is an ABC triblock copolymer consisting of a hydrophobic alkyl chain portion of the self-aggregating portion, an oleophobic polydimethylsiloxane portion or a fluorocarbon portion that is insoluble in hydrocarbons, and a hydrophilic polyethylene glycol portion. Conventional amphiphilic substances that form closed vesicles used in three-phase emulsification are AB diblock copolymers that do not have an oleophobic portion.

[0061] When x is 8 or more, the amphiphilic substance represented by formula (1) is more likely to form particulate vesicles, and when x is 22 or less, the amphiphilic substance represented by formula (1) is more likely to disperse in water. When m is 9 or more, the compound represented by formula (1) is less soluble in oils, and when m is 60 or less, the adhesive strength of the closed vesicles formed by the amphiphilic substance represented by formula (1) to the internal phase can be maintained. Furthermore, when n is 10 or more, the compound represented by formula (1) is more likely to disperse in water, and when n is 230 or less, the particle size of the closed vesicles formed by the compound represented by formula (1) can be maintained. Therefore, when x, m, and n are within the above numerical ranges, the emulsion composition can stably maintain an emulsified state for a long period of time, regardless of the type of oil phase.

[0062] From the viewpoints of the insolubility of the compound represented by formula (1) in the oil phase and the aqueous phase in the emulsion composition and the ease of production of the compound represented by formula (1), the compound (amphiphilic substance) is preferably a compound represented by any one of the following formulas (1-1) to (1-4). In the compound represented by formula (1-1), x is 17, m is 13.5 or more and 24 or less, n is 20 or more and 23 or less, and R is CH. In the compound represented by formula (1-2), x is 17, m is 23, n is 19, and R is CHCOOH or a salt thereof. In the compound represented by formula (1-3), x is 17, m is 16 or more and 26 or less, n is 18, and R is CHCHPO(OH) or a salt thereof. In the compound represented by formula (1-4), x is 17, m is 12 or more and 24 or less, n is 18 or more and 20 or less, and R is H.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] Next, a method for producing the compound of the embodiment will be described. The method for producing the compound represented by formula (1) of the embodiment includes the following steps: Step 1: anionic ring-opening polymerization of hexamethylcyclotrisiloxane is performed using alkyllithium obtained by reacting bromoalkane with metallic lithium as an initiator, and the resulting polymerization is reacted with chlorodimethylsilane as a terminator to synthesize a block copolymer of polydimethylsiloxane and alkane having a Si-H bond at the terminal; Step 2: synthesizing an allyl ether of polyethylene glycol having an OR group at the terminal; and Step 3: addition reaction of the Si-H bond of the block copolymer obtained in Step 1 and represented by formula (2) below with the carbon-carbon double bond of the compound obtained in Step 2 and represented by formula (3) below.

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] In formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, and R is H, an alkyl group, or a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, a sulfate group, or a salt of any of these, with an alkylene group having 1 to 6 carbon atoms as a spacer.

[0072] This manufacturing method can produce the compound represented by formula (1), which is the ABC triblock copolymer. The terminal of the polyethylene glycol moiety is a carboxylic acid, phosphonic acid, alcohol, or ether that can be dissociated under acidic conditions. The hydrosilylation reaction, which is an addition reaction in the final step, step 3, generates bonds between blocks with different properties. Therefore, the compound represented by formula (1) can be easily purified by combining reprecipitation and column chromatography of the final product obtained in step 3.

[0073] The method for producing the compound represented by formula (1) above is the same for all four types of compounds with different R, and for the compounds represented by formulas (1-1) to (1-4). In steps 1-1-1, 1-2-1, 1-3-1, and 1-4-1, 1-bromooctadecane is used as the starting material, and the polysiloxane obtained by lithiation and ring-opening polymerization of hexamethylcyclotrisiloxane is capped at the ends with chlorodimethylsilane to obtain the compound represented by formula (21). The degree of polymerization m in formula (21) varies depending on the charge ratio of the hexamethylcyclotrisiloxane used, among other factors.

[0074] [ka]

[0075] The subsequent production method of the above formula (1-1) is as follows: In step 1-1-2, polyethylene glycol monomethyl ether (Mn: 1000) is reacted with NaH to form sodium alkoxide, which is then reacted with allyl bromide to obtain polyethylene glycol allyl ether in which the terminal R is methyl.

[0076] [ka]

[0077] Subsequently, in step 1-1-3, polyethylene glycol allyl ether is hydrosilylated using a compound represented by formula (21) in the presence of Karstedt's catalyst.

[0078] [ka]

[0079] Furthermore, among the compounds represented by the above formula (1), the compound in which R is CH2COOH or a salt thereof, as in the above formula (1-2), can be produced by the following method.

[0080] In step 1-2-1, the compound represented by formula (21) is obtained in the same manner as in step 1-1-1. Subsequently, in step 1-2-2, a carboxylic acid is introduced into polyethylene glycol allyl ether (Mn: 750) as a raw material to obtain a compound represented by formula (20). Then, in step 1-2-3, the compound represented by formula (21) is used to hydrosilylate the compound represented by formula (20), thereby obtaining the compound.

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] Among the compounds represented by the formula (1) above, the compound represented by the formula (1-3) in which R is CH2CH2PO(OH)2 or a salt thereof can be produced by the following method.

[0085] In step 1-3-1, a compound represented by formula (21) is obtained in the same manner as in step 1-1-1. Subsequently, in step 1-3-2, a compound represented by formula (30) is obtained by a bromination reaction using polyethylene glycol allyl ether (PEG, Mn: 850) as a starting material, followed by a reaction with di-t-butyl phosphonate. Then, in step 1-3-3, a compound represented by formula (31) is obtained by a hydrosilylation reaction of formula (30) with formula (21). Finally, in step 1-3-4, a compound represented by formula (31) is obtained by deprotection of the compound represented by formula (32).

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] Among the compounds represented by the formula (1) above, the compound in which R is H, such as the compound represented by the formula (1-4), can be produced by the following method.

[0091] The allyl-PEG used in step 1-4-1 was freeze-dried with dry Benzene, and the synthetic zeolite was added for dehydration purposes. A 50 mL two-necked eggplant flask was charged with 1.05 g (1.23 mmol, 1.0 eq.) of allyl-PEG, 1.62 g (1.2 mmol, 1.2 eq.) of PDMS, and 2.1 g of synthetic zeolite A-3, and dried under vacuum. Then, 8 mL of dry THF was added and stirred at room temperature under a nitrogen atmosphere for 6 hours. Next, Karstedt's catalyst was added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 day. 1 The reaction was confirmed by H-NMR. Next, the synthetic zeolite was removed by suction filtration, and the residue was concentrated and vacuum dried to obtain 2.90 g of crude. This crude was dissolved in approximately 5 mL of chloroform and added dropwise to approximately 150 mL of hexane in an ice bath for reprecipitation, followed by centrifugation. The resulting filtrate was concentrated and vacuum dried to obtain the crude. This crude was dissolved in approximately 5 mL of chloroform and added dropwise to approximately 100 mL of methanol in an ice bath for reprecipitation. After centrifugation, the resulting filtrate was concentrated and vacuum dried to obtain 1.8 g. Next, the compound was isolated and purified by column chromatography (silica gel, h = 15 cm, φ = 3 cm, chloroform:methanol = 19:1) to obtain 428 mg of the compound (yellow viscous liquid).

[0092] [ka]

[0093] [ka]

[0094] According to the embodiment described above, by applying a three-phase emulsification method using closed vesicles formed from an amphiphilic substance that spontaneously forms closed vesicles and is represented by formula (1), the emulsion composition can maintain a stable emulsion state for a long period of time, regardless of the type of oil phase.In addition, a compound represented by formula (1) that is suitable for emulsion compositions can be provided. [Example]

[0095] Next, examples and comparative examples will be described, but the present invention is not limited to these examples. Below, first, the compounds produced in each example and each comparative example will be described. Next, the emulsion compositions produced using the compounds of each example and each comparative example will be described.

[0096] Example 1 A compound (amphiphile) represented by formula (1), where x is 17, m is 9, n is 22, and R is CH3, was prepared.

[0097] First, 2.58 g (11.6 mmol, 3.5 eq.) of hexamethylcyclotrisiloxane dissolved in dry THF in a 30 mL two-necked eggplant flask was added dropwise over 10 minutes to 5 mL (3.26 mmol, 1.0 eq.) of the reaction solution (2-4-1) taken from a 200 mL three-necked eggplant flask. The mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere. Next, 365 μL (3.29 mmol, 1.0 eq.) of chlorodimethylsilane was added and stirred for 30 minutes to terminate the reaction. 50 mL of saturated aqueous NH₄Cl was added to the reaction solution, which was then extracted three times with 50 mL of ethyl acetate. The resulting organic layer was washed twice with 50 mL of saturated aqueous NaCl, dried over anhydrous MgSO₄, filtered, concentrated, and evaporated under reduced pressure (150 °C) to obtain 2.73 g of a white liquid. The following reaction product was prepared: 1 The siloxane chain length (m) was calculated from H-NMR and found to be m = 16. However, the product also contains starting materials and by-products, and the NMR signal also contains the CH3Si from these, so it is presumed that the m = 16 calculated here is a larger value than that of the target product. These steps are shown below.

[0098] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1H-NMR (400 MHz, CDCl3): δ0.03-0.34 (107H, m), 0.52 (2H, t, J=8.0 Hz), 0.88 (6H, t, J=7.2 Hz), 1.03-1.26 (54H, m), 4.70 (1H, sept, J=2.8 Hz).

[0099] [ka]

[0100] Next, 6.03 g (6.03 mmol, 1.0 eq.) of polyethylene glycol monomethyl ether (Mn=1000) was placed in a 50 mL two-necked flask and dissolved in 28 mL of DMF. 6.45 g (1.90 × 10 -1 mol, 30 eq.), washed three times with dry hexane, concentrated, and dissolved PEG in a 50 mL two-necked flask. 23 The mixture was stirred for 1 hour. Furthermore, 7.30 g (0.60 mmol, 10 eq.) of allyl bromide and 40 mL of dry DMF were added. The solidified reaction mixture was broken up with a spatula, and after confirming that the stir bar was rotating, the mixture was refluxed at 80 °C for 17 hours. Then, 100 mL of water was added to the reaction solution, and the mixture was extracted three times with 100 mL of dichloromethane. The resulting organic layer was washed twice with 100 mL of saturated aqueous NaCl, dried over anhydrous MgSO4, filtered, concentrated, and evaporated under reduced pressure (80 °C) to yield 5.92 g of a yellow viscous solid. Two spots were confirmed by TLC, and the product was isolated and purified by column chromatography (hexane:ethyl acetate=2:1 → chloroform:methanol=9:1, Φ=4.2 cm, h=10 cm). The mixture was then concentrated and dried under vacuum to yield 6.09 g (5.86 mmol) of a light yellow viscous solid. The yield was 97%. These steps are shown below.

[0101] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1 H-NMR (400 MHz, CDCl3): δ 3.38 (3H, s), 3.45-3.83(91H, m), 4.02 (2H, dt, J=1.4, 5.7 Hz), 5.17 (1H, ddt, J=1.4, 1.7, 10.4 Hz), 5.27 (1H, ddt, J=1.7, 1.7, 17.3 Hz), 5.91 (1H, ddt, J= 5.7, 10.4, 17.3 Hz)

[0102] [ka]

[0103] Next, PEG was added to a 30 mL two-necked flask. 23 1.82 g (1.75 mmol, 1.0 eq.) of -Allyl was added, dried under vacuum, and then dissolved in 4.6 mL of dry THF. 2.73 g (1.74 mmol, 1.0 eq.) of PDMS-b-alkane dicopolymer dissolved in 8.7 mL of dry THF was added dropwise to this reaction solution over 5 minutes, followed by 10 drops of Karstedt's catalyst. The mixture was stirred at room temperature for 21 hours under a nitrogen atmosphere. The mixture was then concentrated and isolated and purified by column chromatography (hexane:ethyl acetate=2:1 → chloroform:methanol=9:1, Φ=4.2 cm, h=10 cm). After concentration and vacuum drying, 2.75 g of a pale yellow viscous solid was obtained. The yield was 54%. The following is a 54% yield: 1 The siloxane chain length of the product was determined from the H-NMR spectrum to be m = 9. These steps are shown below.

[0104] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1H-NMR (400 MHz, CDCl3): δ 0.01-0.22(91H,m), 0.49-0.53(4H,m), 0.88 (3H,t,J=7.2 Hz), 1.25-1.30(32H,m), 1.53-1.63 (13H,m), 3.38(5H,s), 3.41(3H,t, J=7.6 Hz), 3.45-3.89(147H,m)

[0105] [ka]

[0106] Thus, the compound of Example 1 was obtained.

[0107] Example 2 A compound (amphiphile) represented by formula (1), where x is 17, m is 10, n is 22, and R is CH3, was prepared.

[0108] Specifically, the compound of Example 2 was obtained in the same manner as in Example 1, except that a small amount of high molecular weight components were separated and purified by column chromatography after the reaction.

[0109] Example 3 A compound (amphiphile) represented by formula (1), where x is 17, m is 13.5, n is 23, and R is CH3, was prepared.

[0110] Specifically, the compound of Example 3 was obtained in the same manner as in Example 1, except that silanes having different molecular weights were used in the reaction.

[0111] Example 4 A compound (amphiphile) represented by formula (1), where x is 17, m is 24, n is 20, and R is CH3, was prepared.

[0112] Specifically, the compound of Example 4 was obtained in the same manner as in Example 1, except that a silane having a different molecular weight was used in the reaction.

[0113] Example 5 A compound (amphiphile) represented by formula (1), where x is 17, m is 24, n is 23, and R is CH3, was prepared.

[0114] Specifically, the compound of Example 5 was obtained in the same manner as in Example 1, except that silanes having different molecular weights were used in the reaction.

[0115] Example 6 A compound (amphiphile) represented by formula (1), where x is 17, m is 23, n is 19, and R is CH2COOH, was prepared.

[0116] First, 3.39 g (3.79 mmol, 1.0 eq.) of Allyl-PEG750 in 50 mL of dry THF and 6.02 g (0.15 mol, 39.6 eq.) of 60% NaH in oil were added to a 300 mL two-necked flask and stirred at room temperature for two hours under a nitrogen atmosphere. 5.24 g (37.7 mmol, 9.9 eq.) of bromoacetic acid in 20 mL of dry THF was added dropwise using a syringe, and the mixture was stirred at 60°C under a nitrogen atmosphere for two days. 1 The reaction was confirmed by H-NMR. After stirring, the reaction mixture was dissolved in 200 mL of purified water and extracted three times with 100 mL of hexane. The resulting aqueous layer was extracted three times with 100 mL of chloroform. 90.0 mL of 2N HCl was added to the resulting aqueous layer, and extracted six times with 100 mL of chloroform. The organic layer was recovered, yielding a total of 600 mL of organic layer. The resulting organic layer was washed three times with 100 mL of saturated aqueous NaCl, dried over anhydrous MgSO4, filtered, concentrated, vacuum dried, and freeze-dried to yield 1.84 g of a yellow viscous liquid. These steps are shown below.

[0117] [ka]

[0118] Next, 0.693 g (32 mmol, 5.0 eq.) of the Li dispersion was placed in a 300 mL three-necked recovery flask and 15 mL of dry Et2O was added. 2.15 g (6.4 mmol, 1.0 eq.) of 1-bromooctadecane and 15 mL of Et2O were added to a 50 mL two-necked recovery flask and stirred. The mixture was then transferred to a dropping funnel and added dropwise over 30 minutes with stirring at 0 °C under a nitrogen atmosphere for a total of 1 hour. 8.67 g (39.0 mmol, 6.1 eq.) of hexamethylcyclotrisiloxane and 20 mL of dry THF were added to a 50 mL two-necked recovery flask and stirred. The mixture was then transferred to a dropping funnel and added dropwise. The mixture was then stirred at room temperature under a nitrogen atmosphere for one day. After stirring, 2.1 mL (19.2 mmol, 3.0 eq.) of chlorodimethylsilane was added and stirred for 2 hours. In an ice bath, 100 mL of saturated aqueous NH4Cl and 50 mL of ethyl acetate were added, followed by suction filtration and extraction. This was followed by two 100 mL portions of ethyl acetate. The resulting organic layer (300 mL) was washed with three 100 mL portions of saturated aqueous NaCl, dried over anhydrous MgSO4, filtered, and concentrated to dryness under vacuum, yielding 9.13 g of crude product. These steps are shown below.

[0119] [ka]

[0120] Next, 2.61 g (1.30 mmol, 1.5 eq.) of PDMS, 2 mL of dry THF, and 5 drops of Karstedt's catalyst were added to a 100 mL two-necked flask. 0.831 g (0.872 mmol, 1.0 eq.) of Allyl-PEG-CH2COOH in 2 mL of dry THF was added to the system, and the mixture was stirred at room temperature under a nitrogen atmosphere for one day. 1 The reaction was confirmed by H-NMR and TLC. 3.42 g of a brown viscous crude product was obtained. The steps are shown below. This crude product was then separated into [A], [B], and [C] and purified.

[0121] [ka]

[0122] [A] The crude product (482 mg) was dissolved in a small amount of chloroform and purified by column chromatography (silica gel washed with methanol, h = 15 cm, ψ = 3 cm, chloroform:methanol = 9:1). After concentration and lyophilization, 190 mg of a brown viscous substance was obtained.

[0123] [B] From the crude 1.02 g, 281 mg of a brown viscous substance was obtained by the same procedure as in [A] above.

[0124] [C] The crude 1.56g was filtered through Celite, concentrated, and dried in vacuo. 1 The product was confirmed by H-NMR. The crude was then dissolved in approximately 5 mL of chloroform and added dropwise to approximately 100 mL of methanol in an ice bath for reprecipitation. After centrifugation, the filtrate was concentrated and vacuum-dried to obtain a yellow viscous substance. This was then dissolved in approximately 5 mL of chloroform and added dropwise to approximately 100 mL of hexane in an ice bath for reprecipitation, followed by centrifugation. The resulting filtrate was concentrated and vacuum-dried to obtain a yellow viscous substance. The product was then isolated and purified by column chromatography (silica gel (washed with methanol), h = 15 cm, ψ = 3 cm, chloroform:methanol = 9:1). After concentration and lyophilization, 305 mg of yellow viscous substance F1 (first half) and 89 mg of F1 (second half) were obtained. The target product obtained from [A]-[C] was 3.50 g, with a yield of 74%.

[0125] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1H-NMR(400 MHz,CDCl3):δ =0.04 - 0.14(132H,m), 0.49 - 0.54(4H,m), 0.88(3H,t,J = 6.8 Hz), 1.25(32H,m), 1.56 - 1.64(2H,m), 3.39 - 3.43(2H,t,J = 7.1 Hz), 3.57-3.77(66H,m), 4.15(2H,s)

[0126] Thus, the compound of Example 6 was obtained.

[0127] Example 7 An emulsion composition was produced using a compound (amphiphilic substance) represented by formula (1), where x is 17, m is 26, n is 19, and R is CH2CH2PO(OH)2.

[0128] First, 3.78 g (4.2 mmol, 1.0 eq.) of allyl-PEG and dry Benzene were placed in a 300 mL two-necked flask (A) and freeze-dried. Then, 20 mL of dry THF was added. 4.58 g (17.5 mmol, 4.2 eq.) of triphenylphosphine was placed in a 50 mL two-necked flask (B), which was then degassed and placed under N2. 5.51 g (16.6 mmol, 4.0 eq.) of carbon tetrabromide was placed in a 50 mL two-necked flask (C), which was then degassed and placed under N2. Next, 10 mL of dry THF was added to each flask. (A) was placed in an ice bath, and the solutions (B) and (C) were added dropwise using a syringe. The ice bath was then removed. The mixture was stirred at room temperature under a N2 atmosphere for 20 hours. 1 The reaction was confirmed by H-NMR. After stirring, the solution was suction filtered, concentrated, and vacuum dried. The product was then isolated and purified by column chromatography (silica gel, h=6 cm, φ=4.5 cm, ethyl acetate:hexane=4:1→methanol) to obtain 3.37 g of a yellow viscous substance. The yield was 87%. These steps are shown below.

[0129] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1H-NMR (400 MHz, CDCl3): δ3.48(2H,t,J =6.4 Hz), 3.60-3.67(92 H,m), 3.81(2H, t,J=6.4 Hz), 4.03(2H,d,J =5.7 Hz), 5.16 - 5.19 (1H,dd,J=1.4 and 10.4 Hz), 5.25-5.29(1H,dd,J=1.4 and 17.4 Hz), 5.87-5.97(1H,m)

[0130] [ka]

[0131] Next, 2 mL of dry DMF (A), 210 μL of di-tert-butyl phosphate (1.03 mmol, 3.0 eq.), and 22 mg of 60% NaH in oil (0.55 mmol, 1.6 eq.) were added to a 30 mL two-necked recovery flask (A) and stirred at room temperature under nitrogen for 1 hour. After stirring, 0.330 g of Allyl-PEG-Br (0.344 mmol, 1.0 eq.) was dissolved in 1 mL of dry DMF in a 20 mL two-necked recovery flask (B). The solution was then transferred to recovery flask (A) and stirred overnight at room temperature under nitrogen. After evaporation under reduced pressure at 70 °C, the mixture was extracted with 20 mL of chloroform and 20 mL of purified water, followed by two additional extractions with 20 mL of chloroform. The resulting organic layer was washed with saturated aqueous NaCl, dried over anhydrous MgSO4, filtered, concentrated, and vacuum dried to yield 291 mg of a yellow viscous liquid. The yield was 73%. These steps are shown below.

[0132] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1H-NMR (400 MHz, CDCl3): δ1.49 (18H, s), 2.06 (2H), 3.59 - 3.66 (82H, m), 4.02 (2H, d, J = 5.7 Hz), 5.18 (1H, dd, J = 1.6, 10.5 Hz), 5.25 (1H, dd, J = 1.6, 17.3 Hz), 5.88 - 5.96 (1H, m) 31 P{ 1 H}-NMR(160 MHz, CDCl3 / 85% H3PO4):δ29.6

[0133] [ka]

[0134] Next, Allyl-PEG-PO(O) was added to a 30 mL two-necked flask. t Allyl-PEG-PO(O t Bu)2 was freeze-dried with dry benzene before use, and synthetic zeolite was added for dehydration purposes. 3 mL of dry THF was then added and the mixture was stirred overnight at room temperature under a nitrogen atmosphere (dehydration). Karstedt's catalyst was then added and the mixture was stirred overnight at room temperature under a nitrogen atmosphere. 1The reaction was confirmed by H-NMR. Next, zeolite filtration, concentration, and vacuum drying yielded 982 mg of crude. This was dissolved in 5 mL of chloroform and added to 100 mL of methanol in an ice bath for reprecipitation. Centrifuged, the resulting filtrate was concentrated and vacuum dried to yield a crude product. The crude product was then dissolved in 5 mL of chloroform and added to 100 mL of hexane in an ice bath for reprecipitation. Centrifuged, the resulting filtrate was concentrated and vacuum dried to yield 549 mg of crude. Column chromatography (silica gel, h = 18 cm, φ = 3 cm, chloroform:methanol = 15:1) yielded 359 mg of a yellow viscous product. Lyophilization with dry benzene yielded 339 mg of the desired product. The yield was 68%. These steps are shown below.

[0135] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1 H-NMR(400 MHz,CDCl3)δ:0.04 - 0.14(160H, m), 0.49 - 0.54(4H,m), 0.87(12H, t), 1.25 (64H, m), 1.49(18H, s), 1.56-1.64(2H, m), 2.01 - 2.10(2H), 3.40(2H, t), 3.64(72H, m) 31 P{ 1 H}-NMR(160 MHz,CDCl3 / 85% H3PO4)δ: 19.2

[0136] [ka]

[0137] Next, 2399 mg (0.150 mmol, 1.0 eq.) of C18-PDMS-PEG-P(=O)(OtBu) was placed in a 20 mL two-necked flask, 2 mL of dry 1,4-dioxane, and 135 μL (0.536 mmol, 3.6 eq.) of 4 N HCl / dioxane were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. After 4 and 8 hours, the reaction was monitored by NMR, revealing the presence of starting material. 33.5 μL (0.134 mmol, 0.9 eq.) of 4 N HCl / dioxane was added, and the mixture was stirred overnight. The mixture was then concentrated and lyophilized with dry 1,4-dioxane to yield 320 mg of a yellow viscous liquid. The yield was 88%. These steps are shown below.

[0138] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1 H-NMR (400MHz, CDCl3): δ0.04-0.14(161H,m), 0.49 -0.54(4H,m), 0.87(11H,t), 1.25(67H,m), 1.56- 1.64(2H, m), 2.01-2.10(3H), 3.41(2H,t,J=7.1 Hz), 3.64-3.84(76H,m)

[0139] [ka]

[0140] Thus, the compound of Example 7 was obtained.

[0141] Example 8 A compound (amphiphile) represented by formula (1), in which x is 17, m is 12, n is 18, and R is H, was prepared.

[0142] The allyl-PEG used here was freeze-dried with dry Benzene, and the synthetic zeolite was added for dehydration purposes. A 50 mL two-necked flask was charged with 1.05 g (1.23 mmol, 1.0 eq) of allyl-PEG, 1.62 g (1.2 mmol, 1.2 eq) of PDMS (3-2), and 2.1 g of synthetic zeolite A-3, and the mixture was dried under vacuum. Then, 8 mL of dry THF was added and the mixture was stirred at room temperature under a nitrogen atmosphere for 6 hours. Next, Karstedt's catalyst was added and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 day. 1 The reaction was confirmed by H-NMR. The synthetic zeolite was then removed by suction filtration, followed by concentration and vacuum drying to yield 2.90 g of crude. This crude was dissolved in approximately 5 mL of chloroform and added dropwise to approximately 150 mL of hexane in an ice bath for reprecipitation, followed by centrifugation. The resulting filtrate was concentrated and vacuum dried to yield the crude. This crude was dissolved in approximately 5 mL of chloroform and added dropwise to approximately 100 mL of methanol in an ice bath for reprecipitation. After centrifugation, the resulting filtrate was concentrated and vacuum dried to yield 1.8 g. Next, the product was purified by column chromatography (silica gel, h = 15 cm, φ = 3 cm, chloroform:methanol = 19:1) to yield 428 mg of a yellow viscous substance. The yield was 15%.

[0143] 1 The results of H-NMR (JEOL Ltd., 400 MHz) measurement are shown below. 1 H-NMR(400 MHz,CDCl3):δ 0.04 - 0.14 (77H,m), 0.49 - 0.54 (4H,m), 0.87(3H,t,J = 6.6 Hz), 1.25(35H,m), 1.56 - 1.64(2H,m), 3.41(2H,t,J = 7.2Hz), 3.59-3.72(91H,m)

[0144] [ka]

[0145] Thus, the compound of Example 8 was obtained.

[0146] (Comparative Example 1) A compound (amphiphile) represented by formula (1), where x is 3, m is 7, n is 22, and R is CH3, was prepared.

[0147] Specifically, the compound of Comparative Example 1 was obtained in the same manner as in Example 1, except that the commercially available x and m were changed to 3 and 12. The compound obtained had x=3, m=7, and n=22.

[0148] (Comparative Example 2) The compound of Comparative Example 2 was polyoxyethylene hydrogenated castor oil (HCO-40) represented by the following formula (l+m+n+x+y+z=40).

[0149] [ka]

[0150] Next, the compounds of Example 1 and Comparative Example 1 were used to prepare O / W emulsion compositions.

[0151] First, the above compound was added to water and stirred to convert the compound into nanoparticle-shaped closed vesicles, preparing a 0.5 wt% closed vesicle dispersion. Next, hexadecane (Wako Pure Chemical Industries, Ltd.) above the melting point was added to the closed vesicle dispersion to a concentration of 20 wt%, and the mixture was stirred for 3 minutes using an ultrasonic mixer (OHTAKE WORKS Sonicator) to produce an O / W emulsion composition. The results are shown in Table 1.

[0152] The emulsion stability shown in Table 1 was ranked as follows: 〇: Stable emulsification △: Part of the oil and water is separated ×: Oil and water are separated

[0153] A dispersion of closed vesicles was prepared using the compounds of Example 1 and Comparative Example 1, which have different chain lengths for the alkyl chain (x) serving as the self-aggregation portion and the polydimethylsiloxane portion (m) serving as the lipophobic portion. As a result, the average particle diameter of the closed vesicles was 20.5 nm in Example 1 and 31.1 nm in Comparative Example 1, and both closed vesicles were nanoparticles.

[0154] Furthermore, visual observation of the resulting emulsion compositions revealed that the emulsion state was stable in the emulsion composition of Example 1. On the other hand, with the lapse of time, the oil phase partly separated in the emulsion composition of Comparative Example 1. In Comparative Example 1, it is believed that the compound used had a small self-aggregation portion (x) and thus had poor adhesion to the oil phase of the closed endoplasmic reticulum, and furthermore, had a small lipophobic portion (m), which resulted in dissolution in the oil agent, resulting in destabilization of the emulsion.

[0155] Therefore, it is generally believed that if the hydrocarbon number is less than 8, the hydrocarbons do not exhibit cohesive force and micelles cannot be formed. Therefore, for the compound represented by formula (1), if x is 8 or more in the sense that the hydrocarbons can maintain cohesive force, and if m is 9 or more in the sense that the solubility in oils is low, the emulsion stability of the emulsion composition is considered to be good.

[0156] [Table 1]

[0157] Next, the compounds of Examples 1 to 8 and Comparative Example 2 were used to produce O / W emulsion compositions.

[0158] First, the above compound was added to water and stirred to convert the compound into nanoparticle-shaped closed vesicles, preparing a 0.5 wt% closed vesicle dispersion. Next, benzyl alcohol above the melting point was added to the closed vesicle dispersion to a concentration of 20 wt%, and the mixture was stirred for 3 minutes using an ultrasonic mixer (OHTAKE WORKS Sonicator) to produce an O / W emulsion composition. The results are shown in Table 2.

[0159] The emulsion stability shown in Table 2 was ranked as follows: 〇: Stable emulsification △: Part of the oil and water is separated ×: Oil and water are separated

[0160] As shown in Table 2, the closed vesicles of Examples 1 to 8 and Comparative Example 2 were all nanoparticles.

[0161] FIG. 1 shows photographs of the appearance of the emulsion compositions of Examples 2 to 3, 6 to 8 and Comparative Example 2 in which benzyl alcohol is emulsified.

[0162] As shown in Figure 1 and Table 2, some of the emulsion compositions of Examples 1 to 8 exhibited separation of oil droplets, but compared to the emulsion composition of Comparative Example 2, the emulsion compositions of Examples 1 to 8 exhibited superior emulsifying properties. On the other hand, oil-water separation occurred in the emulsion composition of Comparative Example 2, and emulsification was not possible. It is believed that the closed vesicles obtained with the compound used in Comparative Example 2 were unable to dissolve in benzyl alcohol and maintain nanoparticles, and therefore the closed vesicles of Comparative Example 2 were unable to emulsify.

[0163] The closed vesicles obtained with the compounds used in Examples 1 to 8 were able to be emulsified because they maintained a nanoparticle state due to the lipophobic and hydrophilic portions that were insoluble in benzyl alcohol. Furthermore, the compounds used in Examples 1 to 8 had long lipophobic portions, and even though ionic functional groups were added to the hydrophilic portions, they were able to form nanoparticles in water, and their insolubility in benzyl alcohol was increased, improving emulsification properties.

[0164] [Table 2]

[0165] Next, O / W emulsion compositions were produced using the compounds of Examples 3 to 6 and various types of oils.

[0166] First, the above compound was added to water and stirred to convert the compound into nanoparticle-shaped closed vesicles, preparing a 0.5 wt% closed vesicle dispersion. Next, oils with melting points above those shown in Table 3 were added to the closed vesicle dispersion to a concentration of 20 wt%, and the mixture was stirred for 3 minutes using an ultrasonic mixer (OHTAKE WORKS Sonicator) to produce an O / W emulsion composition. The oils used were hexadecane (Wako Pure Chemical Industries), citronella oil, silicone oil (Toray Dow Corning, SH200 2CS), and olive oil (EXTRA VIRGIN OLIVE OIL, Spain). The results are shown in Table 3.

[0167] The emulsion stability shown in Table 3 was ranked as follows: 〇: Stable emulsification △: Part of the oil and water is separated ×: Oil and water are separated -: Not implemented

[0168] FIG. 2 is a photograph of the appearance of an emulsion composition in which various oils were emulsified with closed vesicles prepared from the compound of Example 3. As shown in FIG. 2 and Table 3, the emulsion composition of Example 3 in which various oils were emulsified all exhibited excellent emulsifying properties. Furthermore, the emulsion compositions of Examples 4 to 6 in which various oils were emulsified also exhibited excellent emulsifying properties. This demonstrates that stable emulsification is possible regardless of the type of oil, such as hydrocarbon oil, terpene oil, silicone oil, or vegetable oil.

[0169] [Table 3]

Claims

1. an oil phase; An aqueous phase; The closed endoplasmic reticulum spontaneously forms, and the closed endoplasmic reticulum is formed by an amphiphilic substance represented by the following formula (1): Including, The closed vesicles are present at the interface between the oil phase and the aqueous phase in an emulsion composition. 【Chemistry 1】 (In the formula (1), x is 8 or more and 22 or less, m is 9 or more and 60 or less, n is 10 or more and 230 or less, and R is H, CH3, CH2COOH, or CH2CH2PO(OH)2.)

2. In the formula (1), x is 17, m is 13.5 or more and 24 or less, n is 20 or more and 23 or less, and R is CH ３ The emulsion composition according to claim 1, wherein

3. In the formula (1), x is 17, m is 23, n is 19, and R is CH ２ The emulsion composition according to claim 1 , wherein the hydroxyl group is COOH.

4. In the formula (1), x is 17, m is 16 or more and 26 or less, n is 18, and R is CH ２ CH ２ The emulsion composition according to claim 1, which is PO(OH)2.

5. The emulsion composition according to claim 1, wherein in the formula (1), x is 17, m is 12 or more and 24 or less, n is 18 or more and 20 or less, and R is H.

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