KR20170062033A - Bi-continuous emulsion type composition comprising AMPHIPHILIC ANISOTROPIC PARTICLES - Google Patents

Abstract

The present disclosure relates to a Bi-continuous emulsion composition comprising an amphiphilic anisotropic powder, a non-polar oil and water, wherein the amphiphilic anisotropic powder comprises a first polymeric spheroid that is hydrophilic and a second polymeric spheroide that is hydrophobic Wherein the first polymer spolide and the second polymer spolide are at least partially bonded in a structure that penetrates the counterpart polymer spoloid, the first polymer spolide has a core-shell structure, and the shell has a functional group ≪ / RTI > with respect to the composition of the present invention.

Description

[0001] The present invention relates to a bi-continuous emulsion type composition comprising an amphiphilic anisotropic powder,

The present invention relates to a dual continuous phase emulsion composition comprising an amphiphilic anisotropic powder and a process for its preparation.

In an emulsification system using a surfactant, an oil-in-water (O / W) or water-in-oil (W / O) emulsified formulation is formed according to the HLB (Hydrophile-Lipophile Balance) value of the surfactant. In other words, the emulsion is formed by mixing the emulsion of water and oil phase, thereby forming a stable emulsion system that separates the internal phase and the external phase.

Bi-Continuous Emulsion (BCE) is a formulation in which two phases coexist without discrimination between the inner and outer phases, and is a formulation in which oil phase and water phase are mutually intersected and exist continuously. Fig. 1 shows a schematic view schematically showing an underwater type, a water-in-oil type and a dual-phase emulsion type emulsion. The dual emulsion emulsion is also referred to as a "soft solid" and is an emulsion formulation that is stabilized by wetting the particles on a continuous phase to cause spinodal decomposition. It is also called BIJEL (Bicontinuous Interfacially Jammed Emulsion Gel) according to these structural characteristics. The dual emulsion emulsion formulations are being applied in various fields such as catalysts, separation processes, cell engineering, fuel cells, solar cells, barrier materials and sensors due to their unique formulation properties.

It has been difficult to form a dual emulsion type emulsion using a conventional surfactant because it can be realized only at a composition ratio of a ternary system (water, oil, surfactant) and is difficult to stabilize due to the fluidity of emulsified interface film.

The size and shape of the spherical fine particles made of the polymer are controlled according to the manufacturing method, and thus the application possibility is expanded. One of its applications is Pickering emulsion which can form stabilized macroporous particles using micro spherical particles. O / W emulsified particles are formed at a contact angle of 90 ° or more, and W / O emulsion particles are formed at a temperature of 90 ° or less depending on the degree of hydrophilicity / hydrophobicity of the spherical particles.

Attempts have been made to produce new anisotropic powders by imparting amphiphilic properties, both hydrophilic and hydrophobic, to the microspheres. An example is the Janus spherical particles. However, due to the morphological limitations of these spheres, there is a limit to the chemical anisotropy. In other words, although it is morphologically anisotropic, it is totally hydrophobic or hydrophilic, so that there is a limit to chemical anisotropy.

It has been attempted to produce anisotropic powders having surface activity by imparting chemical anisotropy together with geometric shape control. However, despite the advantage of its applicability of amphiphilic anisotropic powder, up to now, Has not been specifically developed, and there is a problem that it is difficult to mass-produce uniformly in the industry, so that no practical industrial application has been made.

The prior art of the present invention is disclosed in Korean Patent Publication No. 1997-0025588.

From the viewpoint of one aspect, a problem to be solved by the present invention is to provide a dual smoke phase emulsion composition having excellent emulsion stability.

In another aspect, a problem to be solved by the present invention is to provide a dual smoke phase emulsion composition capable of simultaneously imparting water phase and oil phase characteristics.

In another aspect, a problem to be solved by the present invention is to provide a dual-phase emulsion composition in which formulations are stably maintained in various temperature ranges.

In another aspect, a problem to be solved by the present invention is to provide a dual-quench phase emulsion composition having excellent stability over time.

In another aspect, a problem to be solved by the present invention is to provide an emulsified composition of a characteristic gel-type formulation having no flowability.

A Bi-continuous emulsion composition comprising an amphiphilic anisotropic powder, a non-polar oil and water,

The amphiphilic anisotropic powder may be an amorphous powder,

A first polymeric spheroid that is hydrophilic and a second polymeric spheroid that is hydrophobic,

Wherein the first polymeric spheroids and the second polymeric spheroids are at least partially bound to a structure that penetrates the counterpart polymeric spheroids,

Wherein the first polymer spolide has a core-shell structure and the shell comprises a functional group.

In one aspect, the present invention can provide a dual-quench emulsion composition having excellent emulsion stability.

From another point of view, the present invention can provide a dual smoke phase emulsion composition capable of simultaneously imparting properties of water phase and oil phase.

In another aspect, the present invention can provide a dual-phase emulsion composition wherein the formulation remains stable over a wide temperature range.

In another aspect, the present invention can provide a dual-quench emulsion composition having excellent stability over time.

In yet another aspect, the present invention can provide an emulsified composition of a characteristic gel-free formulation having no flowability.

FIG. 1 is a diagram illustrating an oil-in-water type (O / W), a water-in-oil type (W / O), and a dual-phase insole (BCE)
FIG. 2 is a photograph showing the results of an experiment to confirm the formation of a dual emulsion type emulsion by using the water-soluble and liposoluble dyes.
FIG. 3 is a graph showing changes in formulations and electrical conductivity characteristics according to the oil content of the examples and comparative formulations. FIG.
FIG. 4 is a photograph showing the gel formation and stability of the dual emulsion phase emulsion (BCE) formulation.

Embodiments of the present application will now be described in more detail with reference to the accompanying drawings. However, the techniques disclosed in the present application are not limited to the embodiments described herein but may be embodied in other forms. It should be understood, however, that the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the widths and thicknesses of components are slightly enlarged in order to clearly illustrate each component. In addition, although only a part of the components is shown for convenience of explanation, those skilled in the art can easily grasp the rest of the components. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention.

As used herein, unless otherwise defined, at least one hydrogen atom of the functional groups of the invention is optionally substituted with at least one substituent selected from the group consisting of halogen (F, Cl, Br or I), a hydroxy group, a nitro group, an imino group A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, May be substituted with a substituted heterocycloalkyl group having 2-30 carbon atoms.

As used herein, "(meth) acrylic" may mean acryl and / or methacryl.

The particle size of the amphiphilic anisotropic powder herein is the maximum length measured as the longest length of the powder particle. The particle size range of the amphiphilic anisotropic powder herein means that at least 95% of the amphipathic anisotropic powder present in the composition falls within this range.

According to one embodiment of the present invention, there is provided a Bi-continuous emulsion composition comprising an amphiphilic anisotropic powder. According to this embodiment, the interface film formed by the surfactant of general molecular level forms dynamic emulsification state, while the thickness of the emulsified interface film formed by the amphiphilic anisotropic powder increases to several hundred nm, An interface film is formed. Accordingly, the composition according to the present embodiment can contain an amphiphilic anisotropic powder to maintain a dense and stable continuous phase interface, and can form stable stable emulsion formulations.

In this embodiment, the dual emulsion phase emulsion composition may include an amphiphilic anisotropic powder and a non-polar oil.

The nonpolar oil may include 40 wt% to 65 wt%, for example, 56 wt% to 60 wt%, based on the total weight of the composition. The nonpolar oil may contain, for example, at least 40 wt%, at least 41 wt%, at least 42 wt%, at least 43 wt%, at least 44 wt%, at least 45 wt% of the total weight of the amphiphilic anisotropic powder, At least 46 wt%, at least 47 wt%, at least 48 wt%, at least 49 wt%, at least 50 wt%, at least 51 wt%, at least 52 wt%, at least 53 wt%, at least 54 wt% Or 56% by weight or more, 60% by weight or less, 59% by weight or less, 58% by weight or less, or 57% by weight or less. A stable dual emulsion phase emulsion can be formed within the above-mentioned range, and a stable formulation with a lapse of time can be maintained.

In the present embodiment, the amphiphilic anisotropic powder is present in an amount of at least 1.0 wt%, at least 1.5 wt%, at least 2.0 wt%, at least 2.5 wt%, at least 3.0 wt%, or at least 3.5 wt% Up to 7.5 wt%, up to 7.5 wt%, up to 7.0 wt%, up to 6.5 wt%, up to 6.0 wt%, up to 5.5 wt% up to 5.0 wt% up to 4.5 wt% up to 4.0 wt% 1% to 8% by weight, for example, 2% to 4% by weight. A stable dual emulsion phase emulsion can be formed within the above-mentioned range, and a stable formulation with a lapse of time can be maintained. The higher the amount of the amphiphilic anisotropic powder, the more dense the interface and the better the stability of the formulation.

In the present embodiment, the water may contain the amphiphilic anisotropic powder in an amount of 22 wt% to 59 wt%, for example, 36 wt% to 44 wt%, based on the total weight of the composition. A stable dual emulsion phase emulsion can be formed within the above-mentioned range, and a stable formulation with a lapse of time can be maintained.

In the present embodiment, the amphiphilic anisotropic powder and the nonpolar oil may be 1:15 to 30, for example, 1:25 by weight of the amphipathic anisotropic powder: nonpolar oil. A stable dual emulsion phase emulsion can be formed within the above-mentioned range, and a stable formulation with a lapse of time can be maintained.

In the present embodiment, the amphiphilic anisotropic powder and water may be, for example, 1: 2 to 20, 1: 4 to 15, or 1: 5 in terms of the weight ratio of the amphipathic anisotropic powder: water. A stable dual emulsion phase emulsion can be formed within the above-mentioned range, and a stable formulation with a lapse of time can be maintained.

In the present embodiment, the amphiphilic anisotropic powder, nonpolar oil, and water may be from 1:15 to 30: 4 to 15 by weight ratio of the amphipathic anisotropic powder: nonpolar oil: water. A stable dual emulsion phase emulsion can be formed within the above-mentioned range, and a stable formulation with a lapse of time can be maintained.

The nonpolar oil may be, for example, a nonpolar hydrocarbon-based oil, and may be, for example, hexane, octane, decane, dodecane, tetradecane, hexadecane, mineral oil, liquid paraffin, isohexadecane, isododecane, (C6-14 olefin), hydrogenated polydecene, squalane, squalane, paraffin, isoparaffin, ceresin, vaseline, dimethicone, decamethylcyclopentasiloxane, hydrogenated polyisobutene, etc. But are not limited thereto.

The water may be distilled water, deionized water or the like.

In the present embodiment, the amphiphilic anisotropic powder comprises a first polymeric spheroid which is hydrophilic and a second polymeric spheroid which is hydrophobic, and wherein the first polymeric spheroid and the second polymeric spheroid comprise at least partly spherical polymeric spheroids And the first polymer spolide has a core-shell structure, and the shell may include a functional group.

In this embodiment, the sphere is a body made of a polymer, for example, a spherical sphere, a globoid or an oval shape, and may have a micro- And may have a long axis length in units or nanometers.

In one embodiment, the core of the first polymer spolide and the second polymer spolide include a vinyl polymer, and the shell of the first polymer spolide may include a copolymer of a vinyl monomer and a monomer containing a functional group.

In one example, the vinyl polymer may be a vinyl aromatic polymer, and may be, for example, polystyrene.

In one example, the vinyl monomer may be vinyl aromatic. In one example, the vinyl monomer may be substituted or unsubstituted styrene.

In one example, the functional group may be a siloxane.

In one embodiment, the functional group-containing monomer may be a siloxane-containing (meth) acrylate, and specifically includes 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, vinyl Triethoxysilane, vinyltrimethoxysilane, or a mixture thereof.

In one embodiment, the shell of the first polymer spolide may additionally include a hydrophilic functional group.

For example, the hydrophilic functional group may be a functional group having a negative or positive charge or a polyethylene glycol (PEG) group, and may be a carboxylic acid group, a sulfonic group, a phosphate group, an amino group, an alkoxy group, an ester group, an acetate group, a polyethylene glycol group, And the like.

In one example, the shell of the first polymer spolide may further include a sugar-containing functional group.

In one embodiment, the functional group containing the sugar is selected from the group consisting of N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) - (3-triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide, and the like.

In one embodiment, the amphiphilic anisotropic powder may have a symmetrical shape, an asymmetric snowman shape, or an asymmetric inverse snowman shape based on the joint where the first polymer spoloid and the second polymer spoloid are combined. The shape of the snowman means that the first and second polymer spheroids having different sizes are combined.

In one example, the amphiphilic anisotropic powder may have a particle size of 100 to 2500 nm. In another aspect, the amphiphilic anisotropic powder may have a particle size of 100 to 1500 nm, 100 to 500 nm, or 200 to 300 nm. Specifically, the amphiphilic anisotropic powder preferably has 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, Or less, and 2500 nm or less, 2400 nm or less, 2300 nm or less, 2200 nm or less, 2100 nm or less, 2000 nm or less, 1900 nm or less Less than 1,100 nm, less than 1,100 nm, less than 1,000 nm, less than 900 nm, less than 800 nm, less than 700 nm, 600 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, or 200 nm or less.

In one embodiment of the present invention, the amphiphilic anisotropic powder may be prepared by polymerizing a first monomer to prepare a core of a first polymer spoloid, coating the core of the first polymer spoloid to form a core- And preparing an amphiphilic anisotropic powder in which the second polymer spolide is formed by reacting the first polymer spolide of the core-shell structure with the first monomer.

In one embodiment, the amphiphilic anisotropic powder is prepared by (1) stirring the first monomer and the polymerization initiator to prepare a core of the first polymer spolide; (2) stirring the prepared core of the first polymer spolide with a monomer containing a first monomer, a polymerization initiator and a functional group to prepare a first polymer spolide having a coated core-shell structure; (3) preparing an amphiphilic anisotropic powder in which the second polymer spolide is formed by stirring the first polymer spoloid of the prepared core-shell structure with the second monomer and the polymerization initiator.

In the above steps (1), (2) and (3), stirring may be rotary stirring. It is preferable to rotate and stir because chemical mechanical modification and homogeneous mechanical mixing are required for producing uniform particles. The rotational stirring may be performed in a cylindrical rotating reactor, but the rotational stirring method is not limited thereto.

At this time, the design inside the reactor has a great influence on powder formation. The size and location of the baffles in the cylindrical rotating reactor and the degree of spacing between the impeller and the baffles greatly influence the uniformity of the particles produced. It is desirable to minimize the interval between the blades of the inner wing and the impeller to equalize the convection flow and the strength thereof, and to feed the powder reaction liquid below the wing length and to maintain the impeller rotation speed at a high speed. 200 rpm, and the length to diameter ratio of the reactor may be 1 to 3: 1 to 5, more specifically 10 to 30 cm in diameter and 10 to 50 cm in height. The reactor size can be varied in proportion to the reaction capacity. The material of the cylindrical rotating reactor may be ceramics, glass, etc., and the temperature at the time of stirring is preferably 50 to 90 ° C.

In the cylindrical rotating reactor, the simple rotation method is capable of producing uniform particles, and is a low energy method requiring less energy and maximizing the reaction efficiency, enabling mass production. The conventional tumbling method in which the reactor itself rotates requires high energy and restricts the size of the reactor since the entire reactor must be tilted at a constant angle and rotated at high speed. The amount produced due to reactor size limitations was also limited to small quantities of the order of several hundreds of milligrams to several grams, making them unsuitable for mass production.

In one embodiment, the first monomer and the second monomer may be the same or different, and may be specifically vinyl monomers. The first monomer added in the step (2) is the same as the first monomer used in the step (1), and the polymerization initiator used in each step may be the same or different.

In one example, the vinyl monomer may be vinyl aromatic. In one example, the vinyl monomer may be substituted or unsubstituted styrene.

In one example, the polymerization initiator may be a radical polymerization initiator, specifically, a peroxide type, an azo type, or a mixture thereof. Ammonium persulfate, sodium persulfate and potassium persulfate may also be used.

In one example, in the step (1), the first monomer and the polymerization initiator may be mixed at a weight ratio of 100 to 1000: 1. In another aspect, the first monomer and the polymerization initiator may be mixed in a weight ratio of 100 to 750: 1, or 100 to 500: 1, or 100 to 250: 1.

In another aspect, a stabilizer may be added together with the first monomer and the polymerization initiator in the step (1) to mix the first monomer, the polymerization initiator, and the stabilizer in a weight ratio of 100 to 1000: 1: 0.001 to 5. The powder size and shape are determined according to the first polymer spoil size adjustment in the initial stage (1), and the first polymer spoil size can be adjusted according to the weight ratio of the first monomer, the polymerization initiator, and the stabilizer. In addition, by mixing at the weight ratio within the above range, there is an effect that the uniformity of the anisotropic powder can be increased.

In one example, the stabilizer may be an ionic vinyl monomer, and specifically sodium 4-vinylbenzene sulfonate may be used. Stabilizers prevent swelling of the resulting particles and provide positive or negative charge on the powder surface to electrostatically prevent interactions (bonds) during grain formation.

The weight ratio of the first monomer, the polymerization initiator and the stabilizer is 110 to 130: 1: 1 to 5, specifically 115 to 125: 1: 2 to 4, when the amphiphilic anisotropic powder has a size of 200 to 250 nm. 1 < / RTI > polymer spolide.

When the amphiphilic anisotropic powder has a size of 400 to 450 nm, the weight ratio of the first monomer, the polymerization initiator and the stabilizer is in the range of 225 to 240: 1: 1 to 3, specifically 230 to 235: 1: 1 to 3 , ≪ / RTI > the first polymeric spheroids.

When the amphiphilic anisotropic powder has a size of 1100 to 2500 nm, the first polymer having a weight ratio of the first monomer, the polymerization initiator and the stabilizer is 110 to 130: 1: 0, specifically 115 to 125: 1: 0 ≪ / RTI >

The amphiphilic anisotropic powder having an asymmetric snowman shape is preferably an amorphous powder having a weight ratio of the first monomer, the polymerization initiator and the stabilizer of 100 to 140: 1: 8 to 12, specifically 110 to 130: 1: 9 to 11 Can be prepared from polymeric sphereoids.

The amphiphilic anisotropic powder having an asymmetric reverse snowman shape is preferably an amphipathic powder having a weight ratio of the first monomer, the polymerization initiator and the stabilizer of 100 to 140: 1: 1 to 5, specifically 110 to 130: 1: 2 to 4 1 < / RTI > polymer spolide.

In one embodiment, the monomer containing a functional group in the step (2) may be a siloxane-containing (meth) acrylate. Specific examples thereof include 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) Methacrylate, vinyltriethoxysilane, vinyltrimethoxysilane, or a mixture thereof.

In one embodiment, the monomer containing the first monomer, the polymerization initiator and the functional group in the step (2) may be mixed at a weight ratio of 80 to 98: 0.2 to 1.0: 1 to 20. In another aspect, the first monomer, the polymerization initiator, and the monomer containing the functional group may be mixed at a weight ratio of 160 to 200: 1: 6 to 40. The degree of coating can be controlled according to the weight ratio, and the shape of the amphipathic anisotropic powder is determined according to the degree of coating, and when the weight ratio is adjusted, the coating thickness is increased to about 10 to 30%, specifically about 20% And the coating is too thick, so that the pulverization does not proceed or the pulverization is proceeded well without the problem that the pulverization is too thin. In addition, by mixing at the weight ratio within the above range, there is an effect that the uniformity of the anisotropic powder can be increased.

According to the above step (3), a part of the core of the first polymer spolide is protruded from the one side of the first polymer spolide of the core-shell structure through the shell and the protrusions are grown by the polymer of the second monomer, Can be formed.

For example, in the step (3), the second monomer and the polymerization initiator may be mixed in a weight ratio of 150 to 250: 1. In another aspect, the second monomer and the polymerization initiator may be present in an amount of from 160 to 250: 1, or from 170 to 250: 1, or from 180 to 250: 1, or from 190 to 250: 1, or from 200 to 250: : 1, or 220 to 250: 1, or 230 to 250: 1, or 240 to 250: 1.

In another aspect, the second monomer, the polymerization initiator and the stabilizer may be mixed in a weight ratio of 150: 250: 1: 0.001 to 5 by adding the second monomer and the polymerization initiator together with the stabilizer in the step (3). Specific types of stabilizers are as described above. By mixing at a weight ratio within the above range, uniformity of the anisotropic powder can be enhanced.

In one embodiment, in the step (3), the second monomer content may be 40 to 300 parts by weight when the weight of the first polymer spoil of the core-shell structure is 100 parts by weight. Specifically, when the second monomer content is 40 to 100 parts by weight when the first polymer spoil weight of the core-shell structure is 100 parts by weight, the asymmetric snowman type powder is obtained, and 100 to 150 parts by weight, or 110 to 150 parts by weight, When the weight is in the range of 150 to 300 parts by weight or in the range of 160 to 300 parts by weight, an asymmetric reverse snowman type powder is obtained. In addition, by mixing at the weight ratio within the above range, there is an effect that the uniformity of the anisotropic powder can be increased.

In another embodiment of the present invention, in the production of an amphiphilic anisotropic powder according to an embodiment of the present invention, the step (3) may further include the step of (4) introducing a hydrophilic functional group into the produced anisotropic powder have.

In one embodiment, the hydrophilic functional group in step (4) is not limited thereto, but may be introduced using a silane coupling agent and a reaction control agent.

In one embodiment, the silane coupling agent is selected from the group consisting of (3-aminopropyl) trimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) (Trimethoxysilyl) propyl] urea and 3 - [(trimethoxysilyl) propyloxy] -1,2 (trimethylsilyl) Propanediol, and specifically may be at least one selected from the group consisting of N- [3- (trimethoxysilyl) propyl] ethylenediamine.

For example, the silane coupling agent may be added in an amount of 35 to 65 parts by weight, for example, 40 to 60 parts by weight based on 100 parts by weight of the anisotropic powder prepared in the step (3). Within this range, hydrophilization can be appropriately performed.

In one example, the reaction modifier may be ammonium hydroxide.

For example, the reaction modifier may be added in an amount of 85 to 115 parts by weight, for example, 90 to 110 parts by weight based on 100 parts by weight of the anisotropic powder prepared in the step (3). Within this range, hydrophilization can be appropriately performed.

In another embodiment of the present invention, in the production of the amphiphilic anisotropic powder according to one embodiment of the present invention, the step (3) is followed by (4) a step of introducing a sugar-containing functional group into the produced anisotropic powder .

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

According to one exemplary embodiment, the sugar-containing silane coupling agent is selected from the group consisting of N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) And N- {N- (3-triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide.

According to one exemplary embodiment, the reaction modifier may be ammonium hydroxide.

For example, the reaction modifier may be added in an amount of 85 to 115 parts by weight, for example, 90 to 110 parts by weight based on 100 parts by weight of the anisotropic powder prepared in the step (3). The introduction of a sugar-containing functional group within the above range can be suitably performed.

The preparation of the amphiphilic anisotropic powder according to the above method does not use a cross-linking agent, so there is no production entanglement. Thus, the yield is high and uniform, and mass production is easier than the tumbling method using a simple agitation method. In particular, there is an advantage that a nano size of 300 nm or less can be mass-produced in a unit of tens g to several tens of kg.

The composition according to this embodiment may be a composition having a dual-layer emulsion formulation. Since the formulation is a formulation in which the oil phase and the water phase cross each other continuously, it can exhibit a unique effect of simultaneously imparting the characteristics of the oil phase component and the characteristics of the water phase component.

The composition according to this embodiment may have a hardness of 7 to 60 (mN). It is possible to provide a feeling of use peculiar to the twin-screw knife while being stable within the above range.

The composition according to this embodiment is capable of forming a flow-free gel formulation due to the characteristics of the dual emulsion formulations.

The compositions according to this embodiment may exhibit aging emulsion stability over a wide temperature range, for example, from -15 占 폚 to 60 占 폚.

The composition according to the embodiments of the present invention has a unique stem structure that supports the interface of the continuous phase and can be used for a cosmetic material, a catalyst, a separation process, a cell engineering, a fuel cell, a solar battery, And the like.

For example, when the composition is used in a cosmetic composition, it is possible to provide a cosmetic for cleansing which simultaneously imparts cleansing power of oil and freshness of water.

The cosmetic composition according to embodiments of the present invention may be formulated containing a cosmetically or dermatologically acceptable medium or base. It may be in the form of a suspension, a microemulsion, a microcapsule, a microgranule or an ionic (liposome) and a non-ionic follicular dispersion, or a cream, a skin, a lotion, a powder, an ointment, a spray, May be provided in the form of a stick. It can also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions may be prepared according to conventional methods in the art.

In addition, the cosmetic composition according to embodiments of the present invention may be in the form of powders, fatty substances, organic solvents, solubilizers, thickeners, gelling agents, softeners, antioxidants, suspending agents, stabilizers, foaming agents, , Water, ionic or nonionic emulsifiers, fillers, sequestering agents, chelating agents, preservatives, vitamins, barrier agents, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or cosmetics And any other ingredients used, such as cosmetics or adjuvants commonly used in the field of dermatology. Such adjuvants are introduced in amounts commonly used in the cosmetics or dermatological fields. The cosmetic composition according to the embodiments of the present invention may further contain a skin absorption promoting substance to increase the skin improving effect.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

[Production Examples 1 to 4]

Production Examples 1 to 4 were prepared according to the compositions shown in Table 1 below. Specific methods are described below.

The components used in the following Production Examples are as follows.

MeOH: Methanol cosolvent

KPS: Potassium persulfate (initiator)

SVBS: Sodium vinyl benzene sulfonate (stabilizer)

PS: Polystyrene (polymer bead)

TMSPA: Trimethoxysilyl propylacrylate (functional group)

AIBN: Azobisisobutyronitrile (polymerization initiator)

Manufacturing example  1. Polystyrene (PS) First polymer Speroid  Produce

50 g of styrene as a monomer, 1.0 g of sodium 4-vinylbenzenesulfonate as a stabilizer and 0.5 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were mixed in a water bath at 75 DEG C For 8 hours. The reaction was stirred in a cylindrical rotating reactor. The cylindrical rotating reactor was 11 cm in diameter, 17 cm in height, made of glass, and rotated at a speed of 200 rpm.

Manufacturing example  2. Coated first polymer of core-shell (CS) structure Speroid  Produce

(Styrene), 6 g of TMSPA (3- (trimethoxysilyl) propylacrylate) as a monomer, and 0.2 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were added to 300 g of the obtained first polymeric spolide of polystyrene ) Were mixed and reacted at 75 DEG C for 8 hours. The reaction was stirred in a cylindrical rotating reactor.

Manufacturing example  3. Amphipathic  Anisotropy Powder  (DB) manufacturing

40 g of styrene as a monomer, 0.35 g of sodium 4-vinylbenzenesulfonate as a stabilizer, and 0.35 g of azobisisobutyronitrile as a polymerization initiator were added to 240 g of the polystyrene core shell (PS-CS) water dispersion solution obtained as a result of the reaction, And 0.2 g of azobisisobutyronitrile (AIBN) were mixed and heated at 75 캜 for 8 hours. The reaction was stirred in a cylindrical rotating reactor to produce an amphiphilic anisotropic powder.

Manufacturing example  4. Hydrophilized Amphipathic  Anisotropy Powder  Produce

30 g of N- [3- (trimethoxysilyl) propyl] ethylenediamine as a silane coupling agent and 30 g of N- [3- (trimethoxysilyl) propyl] ethylenediamine were added to 600 g of the aqueous dispersion solution of the obtained anisotropic powder, (Ammmonium hydroxide) were mixed and reacted at 25 DEG C for 24 hours to introduce a hydrophilic functional group. The reaction was stirred in a cylindrical rotating reactor to prepare a hydrophilized amphipathic anisotropic powder.

[ Test Example 1] Confirmation of emulsification of a dual smell

Using the anisotropic powder, deionized water and squalane according to Preparation Example 3, they were homomixed in a beaker at a composition of the following Table 2 at 7500 rpm for 3 minutes to prepare three compositions of Formulation Examples 1 to 3 . The water-soluble dyes were prepared by mixing for 3 minutes in an agitator according to the composition shown in Table 3, and the oil-soluble dyes were mixed with an agitation mixer for 3 minutes while heating at 70 ° C according to the composition shown in Table 3.

(Unit: wt%) Formulation Example 1
(O / W) Formulation Example 2
(W / O) Formulation Example 3
(BCE) Anisotropic powder aqueous solution
(Anisotropic powder content in aqueous solution: 8% by weight) 30 30 30 Deionized water 40 0 10 Squalane 30 70 60

(Unit: wt%) Water-soluble dye Oil-soluble dye Deionized water 99.999 0 TPP blue 0.001 0 Squalane 0 99.999 Nile red 0 0.001

0.5 g of each of the compositions of Formulation Examples 1 to 3 prepared in accordance with Table 2 was placed on a glass plate and 0.5 ml of each of the water-soluble dyes and liposoluble dyes was added to each composition and mixed with a spatula. Respectively. A photograph confirming the dispersed state is shown in Fig.

2, Formulation Example 1, which is an O / W formulation, is well mixed with water but not mixed with oil, so that when the water-soluble dye is dropped, the blue color of TPP blue is uniformly mixed with the composition, while Nile red The red color and the formulation are separated. Formulation Example 2, which is a W / O formulation, reversely mixes with oil but does not mix with water, so that when the water-soluble dye is dropped, the composition and the dye are separated without mixing, and when the oil-soluble dye is dropped, the dye is uniformly mixed in the formulation. On the other hand, in the case of Formulation Example 3, which is a dual emulsion phase emulsion, it is confirmed that both water-soluble dyes and oil-soluble dyes are evenly mixed. In the case of W / O using liposoluble dyes, it was confirmed that they were well mixed in oil but not in water. This property indicates that the BCE is a mixture of oil and water, indicating two continuous phases, Bi-continuous.

The components used in the following examples and comparative examples are as follows.

(a) Amphiphilic Anisotropic Powder (ASP): An amphiphilic anisotropic powder prepared in Preparation Example 3 was dissolved in deionized water in an aqueous solution of 20% by weight based on the total weight of the aqueous solution

(b) Nonpolar oil: Squalane (Neosance squalane, Amyris)

(c) Ion control agent: EDTA (Ethylenediaminetetraacetic acid, E.D.T.A.-2NA, Neod)

(d) Surfactant: Glyceryl Stearate and PEG-100 Stearate, Arlacel 170-PA- (SG), Uniquema)

[ Example  1 to 4 and Comparative Example  One]

The emulsion compositions of Examples 1 to 4 and Comparative Example 1 were prepared according to the compositions shown in Table 4 below. The preparation method was prepared by homomixing the ingredients according to the composition at 7500 rpm for 3 minutes.

Unit: wt% Comparative Example 1 Example 1 Example 2 Example 3 Example 4 ASP solution 2.5 5 7.5 10 20 (ASP content) (0.5) (One) (1.5) (2) (4) Deionized water 37.45 34.95 32.45 29.95 19.95 Ion modifier 0.05 0.05 0.05 0.05 0.05 Nonpolar oil 60 60 60 60 60

[ Example  5 to 7, Comparative Example  2 ~ 3]

The emulsion compositions of Examples 5 to 7 and Comparative Example 2 were prepared according to the compositions shown in Table 5 below. The preparation method was prepared by homomixing the ingredients according to the composition at 7500 rpm for 3 minutes.

Unit: wt% Example 5 Example 6 Example 7 Comparative Example 2 Comparative Example 3 ASP solution 20 20 20 20 - (ASP content) (4) (4) (4) (4) - Surfactants - - - - 4 Deionized water Balance Balance Balance Balance Balance Ion modifier 0.05 0.05 0.05 0.05 0.05 Nonpolar oil 56 58 60 64 60

[Property evaluation]

The properties of Examples 1 to 7 and Comparative Examples 1 and 2 prepared above were evaluated as follows, and the results are shown in Tables 6 and 7.

(1) Whether the formulations were formed: Whether or not the emulsion of the double-layered emulsion was formed was confirmed in the same manner as in Test Example 1 by mixing the water-soluble dyes with the oil-soluble dyes. ○ indicates that the emulsion of the dual emulsion phase is formed, △ indicates that the emulsion of the double emulsion is formed, but the oil seeps into the upper emulsion layer after production, and ⅹ indicates that the water and oil are separated without forming a double continuous phase.

(2) Hardness (mN): The hardness of the compositions of the above Examples and Comparative Examples was measured at 30 占 폚 using a Rheometer (compact-100II, Sun scientific co., LTD).

(3) Temperature Stability: The compositions of the above-mentioned examples and comparative examples were stored at -15 ° C to 60 ° C for 4 weeks. Whether or not the initial state and the surface state were the same, whether surface oil was leaking out, And the temperature stability was evaluated by comparing with a sample at room temperature. ∘ is the same as the room temperature state △ indicates that the instability confirmation ⅹ is not possible to maintain the dosage form as compared with the room temperature state.

Unit: wt% Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Whether the formulation is formed X ○ ○ ○ ○ Hardness (mN) X 7 9 17 24 Temperature stability X △ △ ○ ○

Unit: wt% Example 5 Example 6 Example 7 Comparative Example 2 Comparative Example 3 Whether the formulation is formed ○ ○ ○ X (WO creation) Ⅹ (OW generation) Hardness (mN) 17 23 27 X X Temperature stability ○ ○ ○ △ X

The compositions of Examples 1 to 7 stably form a dual emulsion phase emulsion and have a high hardness and do not cause problems such as oil seeping and separation of formulations for about 4 weeks in the temperature range of -5 to 60 ° C, Whereas in Comparative Example 1 in which the amphipathic anisotropic powder content was less than 1% by weight, no double sheath formulation was formed, and in the case of Comparative Example 2 in which the non-polar oil exceeded 60% by weight, the dual- Non-W / O formulations were produced, and hardness can not be measured due to the nature of the formulation. In the case of Comparative Example 3, O / W formulations were produced using a general surfactant, and it was impossible to measure the hardness by a flowable formulation. It was difficult to maintain the emulsified formulations due to the high oil content, As shown in FIG.

[ Test Example  2] Evaluation of electrical conductivity

An emulsion formulation was prepared in the same composition as in Example 5 except that the non-polar oil content was changed to 0 to 80% by weight, and electric conductivity was evaluated to confirm formation of a twinning phase.

When an underwater type emulsion is formed, the electric conductivity is measured to be high because the water part is increased. When the water type emulsion is formed, the electric conductivity is low. In the case of the double continuous type, the electric conductivity value It is measured irregularly.

3 shows the electric conductivity value according to the non-polar oil content. In FIG. 3, the electric conductivity did not change with time. However, when the non-polar oil content was in the range of 40 wt% to 60 wt%, the electric conductivity was irregularly measured.

[ Test Example  3] Evaluation of the stability of the formulation over time

The compositions of Examples 3 to 6 were placed in a beaker and turned upside down with the inlet facing downward and held at -15 to 60 ° C for 180 days.

All of the compositions of Examples 3 to 6 maintained the stability over time in the whole temperature range and maintained a stable formulation without flowing out.

Fig. 4 shows the appearance and hardness of the composition of Example 4 after the composition was prepared, maintained at 30 캜, and the next day and after 180 days. It can be confirmed that the composition forms a flow-free gel formulation and maintains a stable formulation without falling down even after 180 days without change in hardness.

Claims (17)

A Bi-continuous emulsion composition comprising an amphiphilic anisotropic powder, a non-polar oil and water,
The amphiphilic anisotropic powder may be an amorphous powder,
A first polymeric spheroid that is hydrophilic and a second polymeric spheroid that is hydrophobic,
Wherein the first polymeric spheroids and the second polymeric spheroids are at least partially bound to a structure that penetrates the counterpart polymeric spheroids,
Wherein the first polymer spolide has a core-shell structure and the shell comprises a functional group. The method according to claim 1,
Wherein the composition comprises from 1% to 8% by weight of the amphiphilic anisotropic powder relative to the total weight of the composition. The method according to claim 1,
Wherein the composition comprises 40% to 60% by weight of the non-polar oil based on the total weight of the composition. The method according to claim 1,
Wherein the amphipathic anisotropic powder and the nonpolar oil are contained in a weight ratio of 1: 15 to 30 of an amphiphilic anisotropic powder: nonpolar oil. The method according to claim 1,
Wherein the amphipathic anisotropic powder, the nonpolar oil and the water are contained in an amount of 1: 4 to 15 in terms of the weight ratio of the amphipathic anisotropic powder: the nonpolar oil: water. The method according to claim 1,
Wherein the non-polar oil is a hydrocarbon-based oil. The method according to claim 1,
Wherein the functional group is a siloxane. The method according to claim 1,
Wherein the core of the first polymer spolide and the second polymer spolide comprise a vinyl polymer,
The shell of the first polymer spolide may comprise a vinyl monomer; And a monomer containing a functional group. 9. The method of claim 8,
Wherein the vinyl polymer is a vinyl aromatic polymer. 9. The method of claim 8,
Wherein the vinyl monomer is a vinyl aromatic monomer. 9. The method of claim 8,
Wherein the functional group-containing monomer is a siloxane-containing (meth) acrylate. The method according to claim 1,
Wherein the amphipathic anisotropic powder has a symmetrical shape, an asymmetric snowman shape or an asymmetric inverted snowman shape with respect to the joint where the first polymeric spheroid and the second polymeric spheroid are bonded. The method according to claim 1,
Wherein the amphiphilic anisotropic powder has a particle size of 100 to 2500 nm. The method according to claim 1,
Wherein the shell of the first polymer spolide is further introduced with a hydrophilic functional group. 15. The method of claim 14,
Wherein the hydrophilic functional group is at least one selected from the group consisting of a carboxylic acid group, a sulfonic group, a phosphate group, an amino group, an alkoxy group, an ester group, an acetate group, a polyethylene glycol group and a hydroxyl group. The method according to claim 1,
Wherein the shell of the first polymer spolide is further introduced with a sugar-containing functional group. 17. The method of claim 16,
The functional groups containing the sugar include N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) -Triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide. ≪ / RTI >

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