TW201735899A - Bi-continuous emulsion type composition comprising amphiphilic anisotropic particles - Google Patents

Abstract

Disclosed is a bi-continuous emulsion type composition including amphiphilic anisotropic powder, non-polar oil and water, wherein the amphiphilic anisotropic powder includes a first hydrophilic polymer spheroid and a second hydrophobic polymer spheroid, the first polymer spheroid and the second polymer spheroid are bound to each other with a structure in which one polymer spheroid at least partially penetrates into the other polymer spheroid, the first polymer spheroid has a core-shell structure, and the shell has a functional group.

Description

Bicontinuous emulsion composition comprising amphiphilic anisotropic particles

The present disclosure relates to a bicontinuous emulsion type composition comprising an amphiphilic anisotropic powder and a process for the preparation thereof.

In emulsion systems using surfactants, the formation of oil-in-water (O/W) or water-in-oil (W/O) emulsion formulations is dependent on interfacial activity. The hydrophilic-lipophile balance (HLB) value of the agent. In other words, the aqueous phase and the oil phase are mixed and emulsified with one another to form an emulsion system having an internal phase as well as an external phase that are distinguishable from each other and appear stable over time.

A bi-continuous emulsion (BCE) is a formulation in which two phases coexist and the internal phase and the external phase are indistinguishable from each other. In this BCE formulation, the oil phase and the aqueous phase are continuously present and span each other. 2 is a schematic view showing an oil-in-water emulsion, a water-in-oil emulsion, and a bicontinuous emulsion. Double continuous emulsions are also referred to as "soft solids" in which the particles are infiltrated in the continuous phase and stabilized by the creation of spinodal decomposition. Based on this structural property, the bicontinuous emulsion is also referred to as "bi-continuous interfacially jammed emulsion gel (BIJEL)". Through its unique formulation properties, this bicontinuous emulsion is used in a variety of industries including catalysts, separation processes, cell engineering, fuel cells, solar cells, barrier materials, and sensors.

According to the related art, the use of a surfactant to form a bicontinuous emulsion is limited by the composition ratio of the ternary system (water, oil, surfactant). Further, it has a problem in that it is difficult to be stabilized because of the flowability of the emulsion interface film layer.

The spherical particles containing the polymer have a controllable size and shape depending on the method of production, and thus have high applicability. For example, there is a Pickering emulsion that uses spherical particles to form stable macroemulsion particles. The contact angle (θ) between the aqueous phase and the oil phase changes with the hydrophilicity/hydrophobicity of the spherical particles. When the contact angle is greater than 90°, O/W emulsion particles are formed. Similarly, when the contact angle is less than 90°, W/O emulsion particles are formed.

In addition, there have been attempts to introduce amphiphilic properties (i.e., both hydrophilic and hydrophobic) into spherical microparticles to obtain novel anisotropic powders. This can be illustrated by Janus spherical particles. However, such spherical particles have a chemical anisotropy limitation due to their morphological limitations. In other words, although these particles are morphologically anisotropic, they may be hydrophobic or hydrophilic as a whole, and thus have limited chemical anisotropy.

Therefore, some attempts have been made to obtain surface-activated anisotropic powders by controlling the geometry and introducing chemical anisotropy. However, although this amphiphilic anisotropic powder exhibits high applicability, the mass production method of the amphiphilic anisotropic powder has not been developed so far. In addition, it is quite difficult to mass produce uniform amphiphilic anisotropic powders on an industrial scale, resulting in inability to practical use.

[Technical Problem] The technical problem to be solved by the present invention is to provide a bicontinuous emulsion type composition having excellent emulsion stability.

Another technical problem to be solved by the present disclosure is to provide a bicontinuous emulsion type composition which has both aqueous phase characteristics and oil phase characteristics.

Another technical problem to be solved by the present disclosure is to provide a bicontinuous emulsion type composition which maintains its formulation over a wide temperature range.

Another technical problem to be solved by the present disclosure is to provide a bicontinuous emulsion type composition which has excellent stability over time.

Another technical problem to be solved by the present disclosure is to provide a bicontinuous emulsion type composition having a specific non-flowable gel formulation.

[Technical Solution] In a general aspect, there is provided a bicontinuous emulsion type composition comprising an amphiphilic anisotropic powder, an apolar oil, and water, wherein the amphiphilic anisotropic powder comprises a first hydrophilic polymer sphere (hydrophilic polymer spheroid) and a second hydrophobic polymer spheroid, the structure of the first polymer sphere and the second polymer sphere system at least partially penetrating into another polymer sphere by a polymer sphere Linked to each other, the first polymer sphere has a core-shell structure, and the shell has a functional group.

[Advantageous Effects] In one aspect, the present disclosure provides a bicontinuous emulsion type composition which has excellent emulsion stability.

In another aspect, the present disclosure provides a bicontinuous emulsion type composition having both aqueous phase characteristics and oil phase characteristics.

In another aspect, the present disclosure provides a bicontinuous emulsion type composition that maintains its formulation over a wide temperature range.

In another aspect, the present disclosure provides a bicontinuous emulsion type composition that has excellent stability over time.

In another aspect, the present disclosure provides a bicontinuous emulsion type composition having a specific non-flowable gel formulation.

The exemplary embodiments will now be described more fully hereinafter with reference to the accompanying drawings of the exemplary embodiments. However, this disclosure may be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. In the drawings, the shapes, dimensions, regions, etc. of the drawings may be exaggerated for clarity. Further, although some constituent elements are shown for convenience of description, those skilled in the art can easily understand the remaining portions. In addition, those skilled in the art will appreciate that various changes in form and detail may be made without departing from the scope of the disclosure.

As used herein, "substituted" means that at least one of the hydrogen atoms of the functional groups described herein is via a halogen atom (F, Cl, Br or I), a hydroxyl group, a nitro group, an imine. Imino group (=NH, =NR, where R is a C1-C10 alkyl group), amidino group, hydrazine or hydrazone group, carboxyl group, substituted Or an unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C30 heteroaryl group, or a substituted or unsubstituted C2-C30 heterocycloalkyl group (heterocycloalkyl group) ) Replace unless otherwise stated.

As used herein, "(meth)acrylyl" means acryl and/or methacryl.

Herein, the particle size of the amphiphilic anisotropic powder is the maximum length measured, which is the maximum length of the powder particles. Herein, the particle size range of the amphiphilic anisotropic powder means that at least 95% of the composition of the amphiphilic anisotropic powder belongs to the corresponding range.

In one aspect, a bicontinuous emulsion type composition comprising an amphiphilic anisotropic powder is provided. According to an embodiment, when the interface film layer formed by the conventional molecular level surfactant forms a dynamic emulsion phase, the thickness of the emulsion particle interface film layer formed by the amphiphilic anisotropic powder is increased to several hundred nanometers, and The performance of a strong bond forms a stable interfacial film layer. Thus, for the composition comprising the amphiphilic anisotropic powder, a tight and stable continuous phase interface can be maintained and a stable bicontinuous emulsion formulation can be formed.

According to an embodiment of the present disclosure, the bicontinuous emulsion composition comprises an amphiphilic anisotropic powder and a non-polar oil.

According to another embodiment, the non-polar oil is used in an amount of from 40 to 65 weight percent (wt%), particularly from 56 to 60 wt%, based on the total weight of the composition. The amount of the non-polar oil used is 40 wt% or more, 41 wt% or more, 42 wt% or more, 43 wt% or more, 44 wt% based on the combined weight of the amphiphilic anisotropic powder, the nonpolar oil, and water. Above, 45 wt% or more, 46 wt% or more, 47 wt% or more, 48 wt% or more, 49 wt% or more, 50 wt% or more, 51 wt% or more, 52 wt% or more, 53 wt% or more, 54 wt% Above, 55 wt% or more, or 56 wt% or more, and 60 wt% or less, 59 wt% or less, 58 wt% or less, or 57 wt% or less. A stable bicontinuous emulsion formulation can be formed within the above defined range and a stable formulation is maintained over time.

According to another embodiment, the amphiphilic anisotropic powder is used in an amount of 1.0 wt% or more, 1.5 wt% or more, 2.0 wt% or more, 2.5 wt% or more, 3.0 wt% based on the total weight of the composition. Above or 3.5 wt% or more; and 8.0 wt% or less, 7.5 wt% or less, 7.0 wt% or less, 6.5 wt% or less, 6.0 wt% or less, 5.5 wt% or less, 5.0 wt% or less, 4.5 wt% or less, Or 4.0 wt% or less. For example, the amphiphilic anisotropic powder may be used in an amount of from 1 to 8 wt%, particularly from 2 to 4 wt%, based on the total weight of the composition. A stable bicontinuous emulsion formulation can be formed within the above defined range and a stable formulation is maintained over time. As the content of the amphiphilic anisotropic powder increases, a more intimate interfacial film layer is formed to provide higher formulation stability.

According to another embodiment, the amount of water used is from 22 to 59 wt%, especially from 36 to 44 wt%, based on the total weight of the composition. A stable bicontinuous emulsion formulation can be formed within the above defined range and a stable formulation is maintained over time.

According to another embodiment, the amphiphilic anisotropic powder and the non-polar oil are used in a weight ratio of 1:15 to 30, particularly 1:25 (amphiphilic anisotropic powder: apolar oil). A stable bicontinuous emulsion formulation can be formed within the above defined range and a stable formulation is maintained over time.

According to another embodiment, the amphiphilic anisotropic powder and water are used in a weight ratio of 1:2-20, 1:4-15 or 1:5 (amphiphilic anisotropic powder: water). A stable bicontinuous emulsion formulation can be formed within the above defined range and a stable formulation is maintained over time.

According to another embodiment, the amphiphilic anisotropic powder, non-polar oil and water are used in a weight ratio of 1:15 to 30:4-15 (amphiphilic anisotropic powder: apolar oil: water). A stable bicontinuous emulsion formulation can be formed within the above defined range and a stable formulation is maintained over time.

Specific examples of the non-polar oil may include a non-polar hydrocarbon oil such as hexane, octane, decane, dodecane, tetradecane, Hexadecane, mineral oil, liquid paraffin, isohexadecane, isododecane, ozokerite, hydrogenated poly(C6-C14 olefin) ), hydrogenated polydecene, squalane, squalene, paraffin, isoparaffin, ceresin, vaseline, polydimethyl Dimethicone, decamethyl cyclopentasiloxane, and hydrogenated polyisobutene, but are not limited thereto.

The water may contain distilled water as well as deionized water.

According to another embodiment, the amphiphilic anisotropic powder comprises a first hydrophilic polymer sphere and a second hydrophobic polymer sphere, wherein the first polymer sphere and the second polymer sphere system are at least one polymer sphere The structure partially penetrating to another polymer sphere has a core-shell structure, and the shell has a functional group.

As used herein, a sphere refers to a single individual formed by a polymer. For example, it may have a spherical, globoidal, oval shape, and a micro-scale or nanoscale long axis length depending on the largest length in the individual part.

According to an embodiment, the core of the second polymer sphere and the first polymer sphere may comprise vinyl polymers, and the shell of the first polymer sphere may comprise a vinyl monomer and a functional group-containing monomer. Copolymer.

According to another embodiment, the vinyl polymer may comprise a vinyl aromatic polymer, in particular polystyrene.

According to another embodiment, the vinyl monomer may comprise a vinyl aromatic monomer. For example, the vinyl monomer can be substituted or unsubstituted styrene.

According to another embodiment, the functional group may comprise a siloxane.

According to another embodiment, the functional group-containing monomer may be a siloxane-containing (meth)acrylate, in particular at least one selected from the group consisting of 3-(trimethoxydecyl)propyl. 3-(trimethoxysilyl) propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, vinyltriethoxysilane, and vinyl A group consisting of vinyltrimethoxysilane or a combination of the above.

According to another embodiment, the shell of the polymer sphere may have more hydrophilic functional groups attached thereto.

According to another embodiment, the hydrophilic functional group may be a negatively or positively functional functional group, or a polyethylene glycol (PEG) type functional group, and may include at least one selected from the group consisting of carboxylate groups ( Carboxyl group), sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group An ethnic group consisting of an acetate group, a polyethylene glycol group, and a hydroxyl group.

According to another embodiment, the shell of the first polymer sphere may further have a saccharide-containing functional group attached thereto.

According to another embodiment, the sugar-containing functional group may be derived from at least one selected from the group consisting of N{N-(3-triethoxymercaptopropyl)amine ethyl}glucosamine (N-{N-(3-triethoxysilylpropyl) )aminoethyl}gluconamide), N-(3-triethoxysilylpropyl) gluconamide, and N{N-(3-triethoxymercaptopropyl)amine Ethyl}-oligo-glucuronate amide. a group consisting of (N-{N-(3-triethoxysilylpropyl)aminoethyl}-oligo-hyaluronamide).

According to another embodiment, the amphiphilic anisotropic powder may have a symmetric shape, an asymmetric snowman shape, based on a joint where the first polymer sphere and the second polymer sphere are bonded to each other. Or asymmetric reverse snowman shape. The shape of the snowman means that the first polymer sphere and the second polymer sphere are bonded to each other and have different sizes.

According to another embodiment, the amphiphilic anisotropic powder may have a particle size of from 100 to 2500 nanometers (nm). In one variation, the amphiphilic anisotropic powder may have a particle size of 100-1500 nm, 100-500 nm, or 200-300 nm. In particular, the amphiphilic powder may have a particle size of 100 nm or more, 200 nm or more, 300 nm or more, 400 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, and 1000 nm. Above, above 1100 nm, above 1200 nm, above 1300 nm, above 1400 nm, or above 1500 nm; and below 2500 nm, below 2400 nm, below 2300 nm, below 2200 nm, below 2100 nm, below 2000 nm, at 1900 nm Hereinafter, below 1800 nm, below 1700 nm, below 1600 nm, below 1500 nm, below 1400 nm, below 1300 nm, below 1200 nm, below 1100 nm, below 1000 nm, below 900 nm, below 800 nm, below 700 nm, Below 600 nm, below 500 nm, below 400 nm, below 300 nm, or below 200 nm.

According to an embodiment, the amphiphilic anisotropic powder can be obtained by the method, comprising: polymerizing a first monomer to obtain a core of a first polymer sphere; coating the core of the first polymer sphere to obtain a first polymer sphere of a core-shell structure; and reacting the first polymer sphere having a core-shell structure with a second monomer to obtain an amphiphilic anisotropic powder, wherein the second polymer sphere is formed.

1 is a schematic view showing the formation of an amphiphilic anisotropic powder according to an embodiment of the present disclosure. The second polymer sphere is formed by allowing the core of the first polymer sphere to penetrate the shell of the first polymer sphere and grow outward toward the outside by the above method.

According to another embodiment, the method of preparing the amphiphilic anisotropic powder may include: (1) stirring the first monomer and the polymerization initiator to form a core of the first polymer sphere; (2) forming the first formed The core of the polymer sphere is agitated with the first monomer, the polymerization initiator, and the functional group-containing monomer to form a first polymer sphere having a coated core-shell structure; and (3) will be formed The first polymer sphere having a core-shell structure is stirred with a second monomer, a polymerization initiator to form an anisotropic powder, wherein a second polymer sphere is formed.

In the steps (1), (2) and (3), the stirring may be a rotary agitation. Rotary agitation is preferred because in-phase mechanical mixing must be accompanied by chemical modification to produce uniform particles. Spin stirring can be performed in a cylindrical reactor, but is not limited thereto.

Here, the internal design of the reactor significantly affects powder formation. The size and position of the cylindrical reactor baffles and the impeller distance have a significant effect on the uniformity of the particles to be produced. Preferably, the spacing between the inner baffle and the impeller blades is preferably reduced to create convection and uniform strength, the powdery reaction mixer is placed below the length of the baffle, and the impeller is maintained at a high rotational speed. . The revolutions per minute (rpm) of the rotational speed may be 200 rpm or more, and the ratio of the diameter to the height of the reactor may be 1-3:1-5. In particular, the reactor may have a diameter of 10-30 cm (cm) and a height of 10-50 cm. The reactor can be dimensionally changed in proportion to the reaction capacity. Further, the cylindrical reactor may be made of ceramic, glass, or the like. It is preferred to carry out the stirring at a temperature of 50 to 90 °C.

The simple mixing of the cylindrical rotary reactor produces uniform particles, requires low energy loss, and provides maximum reaction efficiency, and is therefore suitable for mass production. The conventional tumbling process involves the rotation of the reactor itself, causing the entire portion of the reactor to have a specific angle of inclination and rotating at high speeds, thus requiring high energy losses and limiting reactor size. Because of the size limitations of the reactor, the output is limited to a small amount of about tens of milligrams to several grams. Therefore, the conventional tumbling method is not suitable for mass production.

According to an embodiment, the first monomer and the second monomer may be the same or different, and are preferably a vinyl monomer. Further, the first monomer added in the step (2) may be the same as the first monomer used in the step (1), and the polymerization initiators used in each step may be the same or different.

According to another embodiment, the vinyl monomer can be a vinyl aromatic monomer. The vinyl aromatic monomer can be substituted or unsubstituted styrene.

According to another embodiment, the polymerization initiator may be a radical polymerization initiator. In particular, the polymerization initiator may be a peroxide-based or azo-based initiator or a combination thereof. In addition, ammonium persulfate, sodium persulfate or potassium persulfate may also be used.

According to another embodiment, in step (1), the weight ratio of the first monomer to the polymerization initiator may be from 100 to 1000:1. In one variation, the weight ratio of the first monomer to the polymerization initiator may be from 100 to 750:1, from 100 to 500:1, or from 100 to 250:1.

In a variation, in the step (1), the stabilizer may be added to the first single in a manner that the first monomer, the polymerization initiator, and the stabilizer are mixed in a weight ratio of 100-1000:1:0.001-5. In the body and in the polymerization initiator. The size and shape of the powder are determined by controlling the size of the first polymer sphere in step (1), and the size of the first polymer sphere can be controlled by the ratio of the first monomer, the polymerization initiator, and the stabilizer. Further, by mixing the first monomer, the polymerization initiator, and the stabilizer in the above defined ratio, the uniformity of the anisotropic powder can be increased.

According to an embodiment, the stabilizer may be an ionic vinyl monomer, and in particular sodium 4-vinylbenzene sulfonate may be used. The stabilizer prevents the particles from expanding and introduces a positive or negative charge to the surface of the powder, thus preventing the electrostatic particles from coalescing (linking).

When the amphiphilic anisotropic powder has a size of 200-250 nm, it can be obtained from the first polymer sphere, and the ratio of the first monomer, the polymerization initiator and the stabilizer is 110-130:1:2-4, especially 115-125: 1:2-4.

In addition, when the amphiphilic anisotropic powder has a size of 400-450 nm, which can be obtained from the first polymer sphere, the ratio of the first monomer, the polymerization initiator and the stabilizer is 225-240:1:1-3. Especially 230-235: 1:1-3.

In addition, when the amphiphilic anisotropic powder has a size of 1100-2500 nm, it can be obtained from the first polymer sphere by reacting the first monomer, the polymerization initiator and the stabilizer in a ratio of 110-130:1:0. Prepared, especially 115-125:1:0.

Further, an amphiphilic anisotropic powder having an asymmetrical snowman shape, which can be obtained from the first polymer sphere, by passing the first monomer, the polymerization initiator and the stabilizer in a ratio of 100-140:1:8-12 Prepared by reaction, especially 110-130:1:9-11.

Further, an amphiphilic anisotropic powder having an asymmetric inverted snowman shape, which is obtainable from the first polymer sphere, is a ratio of 100-140:1:1 through the first monomer, the polymerization initiator and the stabilizer. Prepared by the -5 reaction, especially 110-130:1:2-4.

According to another embodiment, the functional group-containing monomer in step (2) may be a siloxane-containing (meth)acrylate such as 3-(trimethoxydecyl)propyl 3-(trimethoxysilyl) propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, vinyl triethoxysilane, Vinyl trimethoxysilane or a combination thereof.

According to another embodiment, in the step (2), the first monomer, the polymerization initiator, and the functional group-containing compound may be mixed in a weight ratio of 80 to 98: 0.2 to 1.0: 1 to 20. In one variation, the first monomer, polymerization initiator, and functional group-containing compound may be mixed in a weight ratio of 160-200:1:6-40. The degree of coating can be controlled according to the reaction ratio, and the degree of coating determines the shape of the amphiphilic anisotropic powder. On the basis of the initial thickness, when the first monomer, the polymerization initiator and the functional group-containing compound are used in the above defined proportions, the coating thickness is increased by about 10 to 30%, particularly about 20%. In this case, the powder was smoothly formed without the following problems, such as excessively thick coating causing the powder to fail to form, or too thin coating to cause powdery omnidirectional formation. Further, the uniformity of the anisotropic powder can be increased within the above weight ratio.

In step (3), the core of the first polymer sphere penetrates through the housing from the direction of the first polymer sphere having the core-shell structure and projects outwardly from the housing. This protrusion can then be enlarged by the polymer of the second monomer to form an anisotropic powder shape.

According to another embodiment, in the step (3), the second monomer and the polymerization initiator may be mixed in a weight ratio of 150 to 250:1. In a variation, the mixing weight ratio of the second monomer to the polymerization initiator may be 160-250:1, 170-250:1, 180-250:1, 190-250:1, 200-250:1. 210-250: 1, 220-250: 1, 230-250: 1, or 240-250: 1.

In a variation, in the step (3), the stabilizer may be added to the second single in a manner of mixing the second monomer, the polymerization initiator and the stabilizer in a weight ratio of 150-250:1:0.001-5. In the body and in the polymerization initiator. Specific examples of the stabilizer are the same as described above. Within the above weight ratio, the uniformity of the anisotropic powder can be increased.

According to another embodiment, in the step (3), the weight of the first polymer sphere having a core-shell structure is 100 parts by weight, and the mixed weight of the second monomer is about 40 to 300 parts by weight. Specifically, the base of the first polymer sphere is 100 parts by weight, and when the content of the second monomer is 40-100 parts by weight, an asymmetric snow-like powder is obtained. When the content of the second monomer is from 100 to 150 parts by weight or from 110 to 150 parts by weight, a symmetric powder is obtained. Further, when the content of the second monomer is 150-300 parts by weight or 160-300 parts by weight, an asymmetric inverted snow-like powder is obtained. The uniformity of the anisotropic powder can be increased within the above weight ratio.

According to another embodiment, the method of preparing the amphiphilic anisotropic powder may be followed by the step (3), further comprising the step (4) of introducing a hydrophilic functional group to the anisotropic powder.

According to another embodiment, the hydrophilic functional group of step (4) can be accessed by using a silane coupling agent and a reaction modifier, but is not limited thereto.

According to another embodiment, the decane coupling agent may be at least one selected from the group consisting of N-[(3-(trimethoxysilyl)propyl)ethylenediamine), N- [3-(trimethoxysilyl)propyl]ethylene diammonium chloride), (N-Ambermethyl-3-aminopropyl)triethoxy (N-succinyl-3-aminopropyl) trimethoxysilane, 1-[3-(trimethoxysilyl)propyl]urea (1-[3-(trimethoxysilyl)propyl]urea) and 3-[(trimethoxy) a group consisting of alkoxy)-1,2-propanediol (3-[(trimethoxysilyl)propyloxy]-1,2-propanediol). In particular, the decane coupling agent may be N-[(3-(trimethoxydecyl)propyl)ethylenediamine.

According to another embodiment, the amount of the decane coupling agent may be 35 to 65 parts by weight, particularly 40 to 60 parts by weight, based on 100 parts by weight of the anisotropic powder obtained in the step (3). Hydrophilization can be suitably achieved within the above defined range.

According to another embodiment, the reaction modifier can be ammonium hydroxide.

According to another embodiment, the reaction modifier may be blended in an amount of from 85 to 115 parts by weight, particularly from 90 to 110 parts by weight, based on 100 parts by weight of the anisotropic powder obtained in the step (3). Hydrophilization can be suitably achieved within the above defined range.

According to another embodiment, the method of preparing the amphiphilic anisotropic powder may be followed by the step (3), and further comprising the step (4) of introducing a saccharide-containing functional group into the anisotropic powder.

In the step (4), the sugar-containing functional group may be introduced by a sugar-containing decane coupling agent and a reaction modifier, but is not limited thereto.

According to another embodiment, the sugar-containing decane coupling agent may be at least one selected from the group consisting of N{N-(3-triethoxymercaptopropyl)amine ethyl}glucosamine, N-(3-triethoxyindolyl) A group consisting of propyl)glucamine and N{N-(3-triethoxymercaptopropyl)amineethyl}-oligo-glucuronate.

According to another embodiment, the reaction modifier can be ammonium hydroxide.

According to another embodiment, the reaction modifier may be blended in an amount of from 85 to 115 parts by weight, particularly from 90 to 110 parts by weight, based on 100 parts by weight of the anisotropic powder obtained in the step (3). The sugar-containing functional group can be appropriately incorporated within the above defined range.

The preparation method of the amphiphilic anisotropic powder disclosed herein does not require the use of a crosslinking agent, and thus does not cause agglomeration, and provides high yield and uniformity. In addition, the method disclosed herein uses a simple agitation process and is therefore easier to mass produce than a tumbling process. In particular, the method disclosed herein is quite good, so it is capable of mass producing tens of grams to several tens of kilograms of nano-sized particles having a size of 300 nm or less.

The composition according to embodiments of the present disclosure may be a bicontinuous emulsion type composition. In the bicontinuous emulsion, a formulation in which an oil phase and an aqueous phase are continuously present and span each other. Therefore, the composition can have a unique effect of providing both the characteristics of the oil phase and the characteristics of the water phase.

The composition according to the embodiment of the present disclosure may have a hardness of 7 to 60 (mN). It provides a unique sense of use of the dual continuous phase and maintains stability over the above range.

Compositions in accordance with embodiments of the present disclosure may form a non-flowable gel formulation based on the characteristics of a bicontinuous emulsion.

The composition according to the embodiments of the present disclosure can exhibit emulsion stability over time over a wide temperature range, particularly from -15 ° C to 60 ° C.

The composition according to the disclosed embodiments has a unique backbone structure to support the interface of the continuous phase, and thus can be used in many industrial fields, including cosmetics, catalysts, separation processes, cell engineering, fuel cells, through its unique properties. Solar cells, barrier materials, and sensors.

For example, when the composition is used in a cosmetic composition, a cosmetic agent for cleaning can be provided which has both the cleaning ability of the oil and the refreshing feeling of water.

Formulation of the cosmetic composition according to embodiments of the present disclosure may incorporate a cosmetic or dermatologically acceptable medium or substrate therein. This formulation contains any formulation for topical application and can be suspension, microemulsion, microcapsules, microgranules or ionic (liposome) and non-ionic porous The form of a vesicular dispersant is provided as a cream, a skin, a lotion, a powder, an ointment, a spray or a concealer. The form of (conceal stick) is provided. Further, the composition may be used in the form of a foam or an aerosol composition comprising a pressurized propellant. Such compositions can be obtained by methods known to those skilled in the art.

Compositions according to embodiments of the present disclosure may comprise supplemental materials conventionally used in the field of cosmetics or dermatology, such as powders, fat materals, organic solvents (solubilizers, concentrating agents, gums) Gelling agent, softening agent, antioxidant, suspending agent, stabilizer, foaming agent, perfuming agent, surfactant, water, ion Type or nonionic emulsifier, filler, metal ion chelating agent, chelating agent, preservative, vitamin, protective agent, wetting agent, essential oil, dye, pigment, hydrophilic or lipophilic activator, Lipid vesicles or any other material conventionally used in cosmetics. These supplemental materials are added in amounts generally used in the field of cosmetics or dermatology. The composition according to embodiments of the present disclosure may further comprise a skin absorption enhancer. Increase the effect of improving skin condition. [Invention mode]

The examples will now be described to illustrate the disclosure in detail. Those skilled in the art will understand that the following examples are for illustrative purposes only and are not intended to limit the scope of the disclosure.

[ Preparation Examples 1-4] Preparation Examples 1-4 were obtained according to the compositions of Table 1 below. The preparation method will be explained later.

The materials used in Preparation Examples 1-4 are shown below. [Table 1] MeOH: Methanol (cosolvent) KPS: Potassium persulfate (starter) SVBS: Sodium vinyl benzene sulfonate (stabilizer) PS: Polystyrene (Polymer particles) CS: Coated first polymer sphere DB having a core-shell structure: Amphiphilic anisotropic powder TMSPA: Trimethoxysilyl propylacrylate (functional group) AIBN : Azobisisobutyronitrile (polymerization initiator)

Preparation Example 1 Preparation of Polystyrene (PS) First Polymer Sphere First, 50 g of styrene as a monomer, 1.0 g of sodium 4-vinylbenzene sulfonate as a stabilizer, and 0.5 g of azobisisobutyronitrile (AIBN) as a polymerization initiator was mixed in the aqueous phase and reacted at 75 ° C for 8 hours. The reaction was carried out by stirring the reaction mixture at a speed of 200 rpm in a cylindrical reactor having a diameter of 11 cm and a height of 17 cm.

Preparation Example 2 : Preparation of coated first polymer sphere having a core - shell (CS) structure First, 300 g of the above obtained polystyrene (PS) first polymer sphere particles, and 50 g as a monomer Styrene, 6 g of trimethoxydecyl propyl acrylate (TMSPA), and 0.2 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were mixed, and the reaction mixture was reacted at 75 ° C for 8 hours. The reaction was carried out by stirring the reaction mixture in a cylindrical reactor.

Preparation Example 3 Preparation of Amphiphilic Anisotropic Powder (DB) First, 240 g of the aqueous phase dispersant of the above-obtained polystyrene-core shell (PC-CS) dispersant, and 40 g of styrene as a monomer, 0.35 g of sodium 4-vinylbenzenesulfonate as a stabilizer and 0.2 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were mixed, and the reaction mixture was heated to 75 ° C for 8 hours. The reaction was carried out by stirring the reaction mixture in a cylindrical reactor. In this method, an amphiphilic anisotropic powder is obtained.

Preparation Example 4 Preparation of Hydrophilized Amphiphilic Anisotropic Powder First, 600 g of the aqueous phase dispersant of the anisotropic powder obtained above, and 30 g of N-[(3-(trimethoxydecyl)alkyl group as a decane coupling agent) Ethyl)diamine, and 60 g of ammonium hydroxide as a reaction modifier were mixed, and the reaction mixture was reacted at 25 ° C for 24 hours to access a hydrophilic functional group. The reaction was carried out by stirring the reaction mixture in a cylindrical reactor to obtain a hydrophilized amphiphilic anisotropic powder.

[ Test Example 1] Determination of a double continuous emulsion According to the compositions listed in Table 2 below, an anisotropic powder according to Preparation Example 3, deionized water, and squalane were poured into a beaker, and homogenous mixing was performed (homo- Mixing), maintained at 7500 rpm for 3 minutes to obtain three types of compositions according to Formulation Examples 1-3. Further, materials of the compositions listed in Table 3 below were mixed for 3 minutes using an agi-mixer to prepare a water-soluble dye. The materials of the compositions listed in Table 3 below were mixed using an agi-mixer for 3 minutes and heated to 70 ° C to prepare an oil-soluble dye. [Table 2] [table 3]

0.5 g of each of the compositions of Formulation Examples 1-3 according to Table 2 was placed on a glass plate, and 0.5 ml (mL) of a water-soluble dye and an oil-soluble dye were each dropped into each of the compositions. Then mix with a spatula. Then, the dispersion state of each composition was confirmed. Fig. 3 is a photograph showing the state of dispersion.

As can be seen from Fig. 3, Formulation Example 1 (O/W formulation) was well mixed with water but could not be mixed with oil, and the water-soluble dye was dropped into the composition to exhibit a blue color of TPP blue and uniformity of the composition. mixing. However, in the case of Formulation Example 1, the composition could not be mixed with the oil-soluble dye, and separation of the formulation was produced from the red color of Nile Red. Conversely, Formulation Example 2 (W/O Formulation) was mixed with oil but not mixed with water, and thus dropping a water-soluble dye into the composition caused the composition to be separated from the dye, and the oil-soluble dye was dropped into the composition. The product showed uniform mixing of the dye with the formulation. However, it can be seen that Formulation Example 3 (bicontinuous emulsion) is uniformly mixed with both the water-soluble dye and the oil-soluble dye. In the case of W/O using oil-soluble dyes, it can be seen that the formulation mixes well with the oil but does not mix with water. This property represents the binding of BCE to the oil phase as well as the aqueous phase and both phases are continuous to provide a bicontinuous emulsion.

The materials used in the following examples and comparative examples are shown below.

(a) Amphiphilic anisotropic powder: The amphiphilic anisotropic powder of Preparation Example 3 was dissolved in deionized water to 20 wt% to obtain a solution. (b) Apolar oil: squalane (Amyris) (c) Ethylene diamine tetraacetic acid (EDTA) (EDTA-2NA, Neord Co., Ltd.) (d) Glyceryl stearate / PEG-100 stearate (Arlacel 170-PA-(SG), Uniquema).

[ Examples 1-4 and Comparative Example 1] The emulsion compositions of Examples 1-4 and Comparative Example 1 were prepared according to the following Table 4. The raw material of each composition was kept at 7500 rpm for 3 minutes for homo-mixing. [Table 4]

[ Examples 5-7 and Comparative Example 2-3] The emulsion compositions of Examples 5-7 and Comparative Examples 2-3 were prepared according to the following Table 5. The raw material of each composition was kept at 7500 rpm for 3 minutes for homo-mixing. [table 5] [ Physical property evaluation ]

The physical properties of each of the compositions of Examples 1-7 and Comparative Examples 1-3 were evaluated as follows, and the results are presented in Tables 6 and 7.

(1) Formulation formation: Whether or not the two-continuous emulsion was formed was measured by the same method as in Test Example 1, by mixing with a water-soluble dye and an oil-soluble dye. "○" indicates formation of a bicontinuous emulsion, "△" indicates formation of a bicontinuous emulsion, but oil was dripped in the upper portion, and "x" indicates that a bicontinuous emulsion was not formed, but water and oil were separated from each other.

(2) Hardness (mN): Each composition of the examples and comparative examples was measured at 30 ° C using a Rheometer (compact-100II, Sun scientific Cp., Ltd.). hardness.

(3) Temperature stability: Each of the components of the examples and comparative examples was stored at -15 ° C to 60 ° C for 4 weeks. Then, it was evaluated whether the appearance of each composition showed the surface state as in the initial preparation, whether the oil dripped from the surface, and whether the formulation collapsed. These results were compared to the results for each sample under the greenhouse. "○" indicates that the same result as the room temperature result was obtained. "△" indicates that the sample is unstable compared to the sample at room temperature. "x" indicates that the sample cannot maintain its formulation. [Table 6] [Table 7]

Each of the compositions of Examples 1 to 7 stably formed a bicontinuous emulsion having a high hardness, no oil precipitation and separation of the formulation, and maintaining the shape as in the initial preparation state. On the other hand, Comparative Example 1 in which the content of the amphiphilic anisotropic powder was less than 1% by weight did not form a bicontinuous emulsion. Comparative Example 2, in which the nonpolar oil content was more than 60% by weight, formed a water-in-oil (W/O) emulsion instead of a bicontinuous emulsion, and the hardness could not be detected because of the formulation characteristics. Comparative Example 3 using a conventional surfactant formed an oil-in-water (O/W) emulsion having a flowable formulation that could not detect hardness, which was a formulation with high oil content and no thickener, and it was difficult to maintain the emulsion formulation. And provides a fairly low stability. [ Test Example 2] Conductivity evaluation

An emulsion formulation was prepared in the same manner as in Example 5 except that the amount of non-polar oil used was 0-80 wt%. Then, a conductivity test was performed to determine whether or not the two-continuous emulsion was formed.

When the oil-in-water emulsion is formed, the proportion of the aqueous phase is increased, resulting in high electrical conductivity. When the water-in-oil emulsion is formed, the conductivity is low. In the case of a bicontinuous emulsion, an irregular conductivity value is caused because of the presence of the aqueous phase as well as the continuous phase of the oil phase.

Figure 4 is a graph illustrating the conductivity value depending on the non-polar oil content. In Figure 4, the change in conductivity over time is not presented. However, when the amount of the non-polar oil was changed from 40% by weight to 60% by weight, an irregular conductivity value was measured. This illustrates the formation of a bicontinuous emulsion. [ Test Example 3] Evaluating formulation stability over time

Each of the compositions according to Examples 3-6 was poured into a beaker and the beaker was inverted so that the opening faced the ground and was maintained at -15 to 60 °C for 180 days.

Each of the compositions of Examples 3-6 maintained stability over the entire temperature range without dripping and maintaining a stable formulation.

Figure 5 is a photograph showing the appearance and hardness of the composition according to Example 4 after the day after preparation and after maintaining at 30 ° C for 180 days. It can be seen that the composition forms a non-flowable gel formulation which does not cause dripping and does not change in hardness even after 180 days, and maintains a stable formulation.

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BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the formation of an amphiphilic anisotropic powder according to an embodiment of the present disclosure. 2 is a schematic diagram showing an oil-in-water (O/W) type emulsion, a water-in-oil (W/O) type emulsion, and a double continuous emulsion (BCE). Figure 3 is a graph showing the results of a two-continuous emulsion type formulation based on the dye affinity of a water-soluble dye and an oil-soluble dye. Figure 4 is a graph illustrating formulation changes and conductivity changes depending on the oil content of the examples and comparative examples. Figure 5 is a photograph illustrating the gel formability and stability of a bicontinuous emulsion (BCE).

Claims (17)

A bicontinuous emulsion type composition comprising an amphiphilic anisotropic powder, a non-polar oil, and water, wherein the amphiphilic anisotropic powder comprises a first hydrophilic polymer sphere and a second hydrophobic polymer sphere, the first The polymer sphere and the second polymer sphere system are linked to each other with a structure in which at least a polymer sphere penetrates at least partially to another polymer sphere, and the first polymer sphere has a core-shell structure, and the shell has a function base. The composition according to claim 1, wherein the composition comprises the amphiphilic anisotropic powder in an amount of from 1 to 8 wt% based on the total weight of the composition. The composition of claim 1, wherein the composition comprises the non-polar oil in an amount of from 40 to 60% by weight based on the total weight of the composition. The composition according to claim 1, wherein the amphiphilic anisotropic powder and the non-polar oil exhibit a weight ratio of 1:15 to 30 (amphiphilic anisotropic powder: apolar oil). The composition of claim 1, wherein the amphiphilic anisotropic powder, the non-polar oil, and the water exhibit a weight ratio of 1:4-15 (amphiphilic anisotropic powder: apolar oil: water). The composition of claim 1, wherein the non-polar oil is a hydrocarbon oil. The composition of claim 1 wherein the functional group is a decane. The composition of claim 1, wherein the second polymer sphere and the core of the first polymer sphere comprise a vinyl polymer, and the shell of the first polymer sphere comprises a vinyl monomer and a copolymer of functional monomer. The composition of claim 8 wherein the vinyl polymer is a vinyl aromatic polymer. The composition of claim 8 wherein the vinyl monomer is a vinyl aromatic monomer. The composition of claim 8, wherein the functional group-containing monomer is a decyloxy (meth) acrylate. The composition of claim 1, wherein the amphiphilic anisotropic powder has a symmetrical shape and an asymmetric snowman shape based on a joint where the first polymer sphere and the second polymer sphere are bonded to each other. Or asymmetrically reverse the shape of the snowman. The composition of claim 1, wherein the amphiphilic anisotropic powder has a particle size of from 100 to 2500 nm. The composition of claim 1, wherein the shell of the first polymer sphere comprises a hydrophilic functional group additionally attached thereto. The composition of claim 14, wherein the hydrophilic functional group is at least one selected from the group consisting of a carboxylate group, a sulfone group, a phosphate group, and an amine group. (amino group), alkoxy group, ester group, acetate group, polyethylene glycol group, and hydroxyl group (hydroxyl group) Group) The group of people. The composition of claim 1, wherein the shell of the first polymer sphere comprises an accharide-containing functional group additionally attached thereto. The composition of claim 16, wherein the sugar-containing functional group is derived from at least one selected from the group consisting of N{N-(3-triethoxymercaptopropyl)amine ethyl}glucosamine (N-{ N-(3-triethoxysilylpropyl)aminoethyl}gluconamide), N-(3-triethoxysilylpropyl) gluconamide, and N{N-(3-triethoxy) A group consisting of N-{N-(3-triethoxysilylpropylamino)-oligo-hyaluronamide.