KR102088804B1 - Oil-in-water type emulsion composition comprising emulsion particle cluster and method preparing the same - Google Patents

Abstract

The present specification is a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch; And a double spheroid type polymer amphiphilic anisotropic powder composed of a hydrophilic one and a hydrophobic other; and an oil-in-water (O / W) emulsion composition comprising
The powder has a structure in which the hydrophobic other partially penetrates into the interior of the hydrophilic one to form a core of the hydrophilic one, and the shell of the hydrophilic one is described with respect to an oil-in-water emulsion cosmetic composition comprising a functional group.

Description

Oil-in-water type emulsion composition comprising emulsion particle cluster and method preparing the same}

The present specification describes an oil-in-water emulsifying composition comprising a cluster of emulsifying particles and a method of manufacturing the same.

In the emulsifying composition using a surfactant, when the size of the emulsifying particles is small, the stability over time is excellent, but it is oily in feeling of use, and it is difficult to impart a refreshing feeling. In addition, when the size of the emulsified particles is large, a water burst effect may be imparted to the feeling of use, but the stability of the emulsified particles is lowered.

Accordingly, there is a need for an emulsifying composition excellent in both emulsifying stability and usability.

The prior art of the present invention is described in Korean Patent Publication No. 10-2006-0009342.

In one aspect, the problem to be solved by the present invention is to provide an emulsion composition having a fine particle size and excellent stability.

In another aspect, the problem to be solved by the present invention is to provide an emulsifying composition having a fine size of an emulsifying particle but having an excellent water bursting effect and a refreshing feeling of use.

In another aspect, the problem to be solved by the present invention is to provide an emulsion composition exhibiting excellent stability over a wide temperature range.

In another aspect, the problem to be solved by the present invention is to provide a stable emulsifying composition without excessive use of a thickener.

In one aspect, the present invention is a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch; And a double spheroid type polymer amphiphilic anisotropic powder composed of a hydrophilic one and a hydrophobic other; and an oil-in-water (O / W) emulsifying composition comprising:

The powder has a structure in which the hydrophobic other partially penetrates into the interior of the hydrophilic one to form a core of the hydrophilic one, and the shell of the hydrophilic one provides a water-in-oil emulsion cosmetic composition comprising a functional group.

In another aspect, the present invention is a method for producing an oil-in-water (O / W) emulsifying composition comprising an emulsifying particle cluster.

a) adding double spheroid type polymer amphiphilic anisotropic powder to the water phase to form large emulsifying particles;

b) forming a fine emulsifying particle by adding a primary thickener to the product of a); And

c) a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch to the product of b), and a polar organic solvent is added to the branched chain polymer or carbomer having a lipophilic alkyl chain as a branch in the fine emulsion particles Forming an emulsifying particle cluster (cluster) formed of densely clustered adsorbed emulsifying particle-polymer complexes;

Including,

The powder has a structure in which the hydrophobic other partially penetrates into the interior of the hydrophilic one to form a core of the hydrophilic one, and the shell of the hydrophilic one includes a functional group, thereby providing a manufacturing method.

In one aspect, the present invention can provide an emulsion composition having a fine particle size and excellent stability.

In another aspect, the present invention can provide an emulsifying composition having a fine size of the emulsifying particles but having excellent water bursting effect and a refreshing feeling.

In another aspect, the present invention can provide an emulsion composition exhibiting excellent stability over a wide temperature range.

In another aspect, the present invention can provide a stable emulsifying composition without excessive use of a thickener.

1 is a schematic diagram schematically showing a method of manufacturing a composition according to an embodiment of the present invention.
2 is a schematic view of forming an amphipathic anisotropic powder.
FIG. 3 is an optical micrograph immediately after preparation of the emulsified particles of Example 1 and Comparative Examples 1-3 and after storage at 45 ° C. for 10 weeks.
4 is a graph showing viscosity change with time of Example 1 and Comparative Example 1-3.

Hereinafter, exemplary embodiments of the present application will be described in more detail with reference to the accompanying drawings. However, the technology disclosed in the present application is not limited to the embodiments described herein and may be embodied in other forms. However, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete and that the spirit of the present application is sufficiently conveyed to those skilled in the art. In order to clearly express each component in the drawings, the size of the component, such as width or thickness, is slightly enlarged. Also, for convenience of description, only some of the components are illustrated, but those skilled in the art will be able to easily grasp the rest of the components. In addition, a person having ordinary knowledge in the relevant field may implement the spirit of the present application in various other forms without departing from the technical spirit of the present application.

In this specification, the particle size of the amphiphilic anisotropic powder is a measurement of the longest length (maximum length), which is the longest length of the powder particles. In the present specification, the particle size range of the amphiphilic anisotropic powder means that at least 95% of the amphiphilic anisotropic powder present in the composition falls within the above range.

According to an embodiment of the present invention, an oil-in-water (O / W) emulsion composition comprising a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch, and an amphiphilic anisotropic powder can be provided.

The branched chain polymer or carbomer having the lipophilic alkyl chain as a side can be adsorbed to the emulsifying particles due to the hydrophobic interaction with the amphiphilic anisotropic powder to form an emulsifying particle-polymer complex. These emulsifying particle-polymer composites can form a matrix of emulsifying particles by forming a network with each other.

The branched chain polymer having the lipophilic alkyl chain as a side is acrylate / C10-30 Alkyl Acrylate Crosspolymer, acrylate / C12-22 alkyl methacrylate copolymer (Acrylate / C12-22 Alkyl Metacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer or Acrylate / Ceteth-20 Metacrylate Copolymer ) Can be used.

The composition may include 0.01 wt% to 1 wt%, for example, 0.02 wt% to 0.08 wt%, of the branched chain polymer or carbomer having the lipophilic alkyl chain as a branch.

The composition may further include a polar organic solvent. The branched chain polymer or carbomer having the lipophilic alkyl chain as a branch reacts with a polar organic solvent to exhibit a shrinking phenomenon of the branched chain polymer or carbomer. When a polar organic solvent is added to the emulsifying particle matrix, the branched chain polymer or carbomer contained in the emulsifying particle matrix contracts, and the emulsifying particle-polymer complexes are clustered together. In this specification, the emulsified particle-polymer complexes are formed by densely clustered as an emulsified particle cluster.

The polar organic solvent may be ethanol, acetic acid, dimethylamide, methanol, pyridine, ethylene glycol, acetone, etc., but is not limited thereto. In one example, the polar organic solvent may be ethanol.

The composition may include the polar organic solvent in an amount of 5% to 40% by weight, for example, 10% to 30% by weight based on the total weight of the composition.

Since the emulsifying particle cluster maintains the ionicity of the particles, it can be stably maintained without fusion between emulsifying particles in the emulsifying particle cluster formed due to the repulsive force between charges.

The average particle size of the emulsified particle cluster may be 1 to 500 μm, for example, 30 to 300 μm. The average particle size of the emulsified particle cluster means the average diameter of the major axis and the minor axis, and means that 95% or more of the clusters present in the composition fall within the above range.

The composition may further include a primary thickener. The primary thickener increases the dosage form and serves as an auxiliary surfactant to serve to refine the size of the emulsified particles formed by the anisotropic powder.

In one example, the emulsifying particles formed before adding the primary thickener may be large emulsifying particles having an average particle diameter of 1 to 100 μm. The average particle diameter of the large emulsified particles means the average value of the diameter of a single particle. In the state of the large emulsifying particles, the particle size of the emulsifying particles is not uniform, and emulsifying particles having a wide range of particle diameters ranging from several µm to hundreds of µm coexist. The average particle diameter of the large emulsion particles may be, for example, 5 to 100 μm, 10 to 100 μm, 10 to 50 μm, or 25 μm. Specifically, the average particle diameter of the emulsified particles is 1 µm or more, 2 µm or more, 3 µm or more, 4 µm or more, 5 µm or more, 6 µm or more, 7 µm or more, 8 µm or more, 9 µm or more, 10 µm or more, 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, or 80 μm or more, 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, It may be 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, or 5 μm or less.

The hydrophobic part and the hydrophilic part of the amphiphilic anisotropic powder have different directionality with respect to the interface, thereby forming large emulsifying particles. While the interfacial film formed by the surfactant at the general molecular level forms a dynamic emulsification state, the emulsified particles formed by the amphiphilic anisotropic powder increase the thickness of the interfacial film to several hundred nm and form a strong interfacial film through strong bonding between the powders. Is done. The emulsion stability can be improved through the formation of the interfacial film.

In one example, the emulsified particles that are refined by adding the primary thickener may be fine emulsified particles having an average particle diameter of 1 μm to 20 μm. The average particle diameter of the fine emulsified particles means the average value of the diameter of a single particle. The average particle size range of the fine emulsified particles means that 95% or more, for example, 99% or more of the emulsified particles present in the composition fall within the above range, and the particle size may be uniform. For example, the average particle diameter of the fine emulsion particles is 1 μm or more, 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, 6 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, 10 μm or more , 11 µm or more, 12 µm or more, 13 µm or more, 14 µm or more, 15 µm or more, 16 µm or more, 17 µm or more, 18 µm or more, or 19 µm or more, 20 µm or less, 19 µm or less, 18 µm or less , 17 µm or less, 16 µm or less, 15 µm or less, 14 µm or less, 13 µm or less, 12 µm or less, 11 µm or less, 10 µm or less, 9 µm or less, 8 µm or less, 7 µm or less, 6 µm or less, or It may be 5 μm or less.

The primary thickener may be used without limitation as long as it is commonly used in the technical field as a thickener, but branched chain polymers and carbomers having the lipophilic alkyl chain included in the emulsifying particle cluster are excluded. For example, the primary thickener may be polyacrylate-13, polyisobutene, polysorbate 30, or the like.

The composition may include the primary thickener in an amount of 0.01% to 3% by weight, for example, 0.05% to 2% by weight relative to the total weight of the composition.

The composition according to the present embodiment has a viscosity, and the composition has a viscosity of 1000 cps or more, 1100 cps or more, 1200 cps or more, 1300 cps or more, 1400 cps or more, 1500 cps or more, 1600 cps or more, 1700 cps or more, 1800 cps or more Above, above 1900 cps, above 2000 cps, above 2100 cps, above 2200 cps, above 2300 cps, above 2400 cps, or above 2500 cps, below 20000 cps, below 19000 cps, below 18000 cps, below 17000 cps, below 16000 cps Or less, 15000 cps or less, 14000 cps or less, 13000 cps or less, 12000 cps or less, 11000 cps or less, 10000 cps or less, 8900 cps or less, 8800 cps or less, 8700 cps or less, 8600 cps or less, 8500 cps or less, 8400 cps or less, Below 8300 cps, below 8200 cps, below 8100 cps, below 8000 cps, below 7900 cps, below 7800 cps, below 7700 cps, below 7600 cps, below 7500 cps, below 7400 cps, below 7300 cps, below 7200 cps, below 7100 cps Or less, 7000 cps or less, 6900 cps or less, 6800 cps or less, 6700 cps or less, 6600 cps or less, 6500 cps or less, 6400 cps Hereinafter, it may be 6300 cps or less, 6200 cps or less, 6100 cps or less, or 6000 cps or less. For example, the viscosity may be 1,000 to 20,000 cps, 1,000 cps to 10,000 cps, 1,500 cps to 7,000 cps, or 2,000 cps to 6,000 cps.

In this embodiment, the amphiphilic anisotropic powder may be a double spheroid type polymer amphiphilic anisotropic powder composed of a hydrophilic one and a hydrophobic other.

The powder has a structure in which the hydrophobic other partially penetrates into the interior of the hydrophilic one to form a core of the hydrophilic one, and the hydrophilic one may include a functional group.

The powder may be a double spheroid type, that is, a three-dimensional nephroid shape having two spheroids combined, and a symmetrical shape and an asymmetric snowman ( snowman) shape or asymmetric inverse snow man shape. The snowman shape means that the first and second polymer spheroids having different sizes are combined.

The spheroid may be, for example, a sphere, a globoid or an oval shape, and may have a long axis length in micro or nano units based on the longest length in the body section. have.

In one example, the hydrophilic one may have a core-shell structure in which the core is composed of the same polymer as the hydrophobic other, and the hydrophilic one and the hydrophobic one may form a spheroid shape of each of the double spheroids. The binding portion between the two spheroids of the double spheroid may be made of a structure that continues from the core of the hydrophilic one to the hydrophobic other.

In one example, the hydrophilic one core and the hydrophobic other include a vinyl polymer, and the hydrophilic one shell 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, 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 siloxane.

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

In one example, the hydrophilic one-sided shell may additionally introduce a hydrophilic functional group.

In one example, the hydrophilic functional group may be a functional group having a negative charge or a positive charge or a PEG (Polyethylene glycol) -based, carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, polyethylene glycol group and hydroxyl It may be one or more selected from the group consisting of roxyl groups.

In one example, the hydrophilic one-shell may further introduce a functional group containing sugar.

In one example, the functional group containing the sugar is N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) gluconamide and N- {N -(3-triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide may be derived from one or more selected from the group consisting of.

In one example, the amphiphilic anisotropic powder may have a particle size of 100 to 1500 nm. For example, the amphiphilic anisotropic powder may have a particle size of 100 to 500 nm, or 200 to 300 nm. Specifically, the amphiphilic anisotropic powder 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, 1000 nm Or more, 1100 nm or more, 1200 nm or more, 1300 nm or more, or 1400 nm or more, 1500 nm or less, 1400 nm or less, 1300 nm or less, 1200 nm or less, 1100 nm or less, 1000 nm or less, 900 nm or less, 800 nm or less , 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, or 200 nm or less.

In one example, the composition is based on the total weight of the amphiphilic anisotropic powder, for example, 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% or more, 0.6 wt% or more , 0.7% or more, 0.8% or more, 0.9% or more, or 1.0% or more, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or more % Or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less or 5% % Or less, 4 wt% or less, or 3 wt% or less. For example, the composition may include the amphipathic anisotropic powder in an amount of 0.1% to 20% by weight, for example, 1% to 3% based on the total weight of the composition. Stable emulsifying particles can be formed within the above range, and emulsifying particles of an appropriate size can be formed.

In one example, the amphiphilic anisotropic powder includes a hydrophilic one (first polymer spheroid) and a hydrophobic other (second polymer spheroid), wherein the hydrophilic one has a core-shell structure, and the hydrophobic one is the hydrophilic one It is a structure that penetrates at least partially into the inside to form a hydrophilic one core, and the hydrophilic one shell may include a functional group.

In one embodiment of the present invention, the amphipathic anisotropic powder polymerizes a first monomer to prepare a core of a first polymer spheroid, and coats the core of the first polymer spheroid to coat a core-shell structured first polymer spheroid. It may be prepared by manufacturing an Lloyd, and reacting the first polymer spheroid having the core-shell structure with the first monomer to produce an amphiphilic anisotropic powder having a second polymer spheroid.

Figure 2 is a schematic diagram showing the principle of formation of the amphipathic anisotropic powder according to an embodiment of the present invention. The core of the first polymer spheroid can be formed through the shell of the first polymer spheroid and grown outside to form a second polymer spheroid.

In one example, the amphipathic anisotropic powder comprises: (1) preparing a core of a first polymer spheroid by stirring the first monomer and the polymerization initiator; (2) preparing a first polymer spheroid having a core-shell structure coated by stirring the core of the prepared first polymer spheroid with a monomer containing a first monomer, a polymerization initiator, and a functional group; (3) stirring the prepared core-shell structured first polymer spheroid with a second monomer and a polymerization initiator to produce an amphiphilic anisotropic powder having a second polymer spheroid formed thereon.

Stirring in steps (1), (2) and (3) may be rotational stirring. Rotational stirring is preferred because chemical modification and uniform mechanical mixing are required for uniform particle generation. The rotational stirring may be rotationally stirred in a cylindrical rotational reactor, but the rotational stirring method is not limited thereto.

At this time, the reactor interior design has a great influence on the powder formation. The size and position of the baffles in the cylindrical rotating reactor, and the degree of distance from the impeller, have a great influence on the uniformity of the resulting particles. It is desirable to minimize the blade gap between the inner wing and the impeller to equalize the convection flow and its intensity, and the powder reaction solution is added to the length of the wing or less, and the impeller rotation speed is preferably maintained at high speed. It can be rotated at a speed of 200 rpm or more, and the ratio of the length of the diameter and height 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 changed in proportion to the reaction capacity. In addition, the material of the cylindrical rotary reactor may be ceramic, glass, etc., and the temperature when stirring is preferably 50 to 90 ° C.

In the cylindrical rotating reactor, the simple rotating method is a low-energy method that enables uniform particle generation and requires less energy, and has a feature that enables mass production by maximizing reaction efficiency. The tumbling method in which the reactor itself has been used in the prior art requires high energy and the size of the reactor is limited because the entire reactor must be inclined at a constant angle and rotated at a high speed. Due to the limitations of the reactor size, the amount produced is also limited to small amounts of about several hundred mg to several g, making it unsuitable for mass production.

In one example, the first monomer and the second monomer may be the same or different, and specifically may be a vinyl monomer. In addition, the first monomer added in step (2) is the same as the first monomer used in 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, peroxide-based, azo-based, or a mixture thereof. In addition, ammonium persulfate, sodium persulfate, and potassium persulfate can also be used.

In one example, the first monomer and the polymerization initiator in step (1) may be mixed in 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, in the step (1), the first monomer, the polymerization initiator, and the stabilizer may be added together with the polymerization initiator 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 by adjusting the size of the first polymer spheroid in the initial (1) step, and the size of the first polymer spheroid can be adjusted according to the weight ratio of the first monomer, polymerization initiator, and stabilizer. In addition, by mixing in a weight ratio in the above range, there is an effect that can increase the uniformity of the anisotropic powder. Mixing in the weight ratio of the above range can significantly increase the uniformity of the shape and size of the anisotropic powder.

In one example, the stabilizer may be an ionic vinyl monomer, specifically sodium 4-vinylbenzenesulfonate. The stabilizer prevents swelling of the resulting particles and electrostatically prevents mutual bonding (bonding) during particle formation by imparting a positive or negative charge to the powder surface.

When the amphiphilic anisotropic powder has a size of 200 to 250 nm, the weight ratio of the first monomer, the polymerization initiator, and the stabilizer is 80 to 135: 1: 1 to 5, specifically 95 to 120: 1: 2 to 4 1 It can be prepared from a polymer spheroid.

In addition, 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 225 to 240: 1: 1 to 3, specifically 230 to 235: 1: 1 to 1-3 Phosphorus may be prepared from a first polymer spheroid.

In addition, 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: 1, specifically 115 to 125: 1: 1. It can be prepared from spheroids.

In addition, the asymmetric snowman-like amphiphilic anisotropic powder has a first monomer, a polymerization initiator, and a stabilizer having a weight ratio of 100 to 140: 1: 8 to 12, specifically 110 to 130: 1: 9 to 11 It can be prepared from a polymer spheroid.

In addition, the amphiphilic anisotropic powder in the shape of an asymmetric reverse snowman has 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: 1 to 2-4. 1 It can be prepared from a polymer spheroid.

In one example, the monomer containing a functional group in step (2) may be a siloxane-containing (meth) acrylate, specifically, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl Methacrylate, vinyltriethoxysilane, vinyltrimethoxysilane, or mixtures thereof.

In one example, in the step (2), the first monomer, the polymerization initiator, and the monomer containing the functional group may be mixed in a weight ratio of 30 to 100: 0.2 to 1.0: 1 to 20. In another aspect, the first monomer, the polymerization initiator and the monomer containing a functional group may be mixed in a weight ratio of 150 to 300: 1: 1 to 6-40. The coating degree can be adjusted according to the weight ratio, and the shape of the amphiphilic anisotropic powder is subsequently determined according to the coating degree, and when reacted with the weight ratio, the coating thickness increases by about 10 to 30% compared to the initial thickness, specifically 20%. And the coating is too thick, so powdering does not proceed or is too thin, so powdering proceeds well without the problem of powdering in multiple directions. In addition, by mixing in a weight ratio in the above range, there is an effect that can increase the uniformity of the anisotropic powder.

By the step (3), a portion of the core of the first polymer spheroid is projected through the shell from one direction of the first polymer spheroid having the core-shell structure, and the protrusions are grown by the polymer of the second monomer, thereby anisotropic powder. Can form the shape of

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

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

In one example, the second monomer content in the step (3) may be mixed in 40 to 300 parts by weight when the weight of the first polymer spheroid 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 weight of the first polymer spheroid having the core-shell structure is 100 parts by weight, an asymmetric snowman type powder is obtained, 100 to 150 parts by weight, or 110 to 150 parts by weight In the case of parts by weight, a powder having a symmetrical shape is obtained, and in the case of 150 to 300 parts by weight, or in the case of 160 to 300 parts by weight, an asymmetric inverse snowman type powder is obtained. In addition, by mixing in a weight ratio in the above range, there is an effect that can increase the uniformity of the anisotropic powder.

In another embodiment of the present invention, when preparing the amphipathic anisotropic powder according to an embodiment of the present invention, after the step (3) (4) may further include the step of introducing a hydrophilic functional group to the prepared anisotropic powder have.

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

In one example, the silane coupling agent is (3-aminopropyl) trimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) propyl] ethylenedi Ammonium chloride, (N-succinyl-3-aminopropyl) trimethoxysilane, 1- [3- (trimethoxysilyl) propyl] urea and 3-[(trimethoxysilyl) propyloxy] -1,2 -It may be 1 or more selected from the group consisting of propanediol, specifically N- [3- (trimethoxysilyl) propyl] ethylenediamine.

In one example, the silane coupling agent may be mixed with 35 parts by weight to 65 parts by weight, for example, 40 parts by weight to 60 parts by weight with respect to 100 parts by weight of the anisotropic powder prepared in step (3). Hydrophilization may be appropriately performed within the above range.

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

In one example, the reaction modifier may be mixed in an amount of 85 parts by weight to 115 parts by weight, for example, 90 parts by weight to 110 parts by weight based on 100 parts by weight of the anisotropic powder prepared in step (3). Hydrophilization may be appropriately performed within the above range.

In another embodiment of the present invention, when preparing an amphipathic anisotropic powder according to an embodiment of the present invention, after the step (3) (4) introducing a functional group containing sugar to the prepared anisotropic powder It may further include.

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

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

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

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

The production of the amphiphilic anisotropic powder according to the above method does not use a crosslinking agent, so there is no entanglement in production, yield is high and uniform, and mass production is easy compared to the tumbling method using a simple stirring method. In particular, there is an advantage of mass production of nano sizes of 300 nm or less in units of tens of g to tens of kg.

According to an embodiment of the present invention, it is possible to provide a method for preparing an oil-in-water (O / W) emulsion composition comprising an emulsifying particle cluster.

1 is a schematic diagram schematically showing a method of manufacturing a composition according to an embodiment of the present invention. The manufacturing method comprises adding a double spheroid type polymer amphiphilic anisotropic powder to the water phase to form large emulsifying particles; A primary thickener is added thereto to form fine emulsified particles, and a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch is added, and a polar organic solvent is added to form a lipophilic alkyl chain to the fine emulsified particles. Emulsified particle-polymer complexes adsorbed by branched chain polymers or carbomers having side branches can form clusters of emulsified particles clustered densely. In FIG. 1, “polymer” refers to a branched chain polymer or carbomer having side chains of a lipophilic alkyl chain.

As shown in Fig. 1, after adding a thickener, when adding a polar organic solvent without adding a polymer, i.e. a branched chain polymer having a lipophilic alkyl chain or a carbomer, a cluster of emulsified particles as in the embodiments of the present invention It does not form, it will contain a simple dispersed emulsion particles.

The amphiphilic anisotropic powder is the same as described in the composition according to an embodiment of the present invention described above, and thus the technology is omitted.

In one example, after forming the fine emulsified particles, a branched chain polymer or carbomer having a lipophilic alkyl chain as a side is added, and the branched chain polymer or carbomer having a lipophilic alkyl chain as a side is adsorbed to the fine emulsified particle. The emulsifying particle-polymer complexes form a matrix of emulsifying particles forming a network, and by adding a polar organic solvent thereto, the branched chain polymer or carbomer having a lipophilic alkyl chain included in the matrix is constricted to emulsify the emulsification. Particle-polymer complexes can be densely clustered to form an emulsifying particle cluster.

Since the composition according to the present embodiment has very high stability because the emulsifying particles exist in the form of an emulsifying particle cluster, it is possible to provide a stable emulsifying composition without using an excessive amount of a thickener. Furthermore, since several emulsified particles are densely gathered in a cluster form, the size of the emulsified particles is fine, but when used, the interface of the emulsified particles collapses due to friction, and thus a large bursting effect can be exhibited.

The composition according to this embodiment may exhibit emulsion stability over time in a wide temperature range, and the temperature may be, for example, -15 ° C to 60 ° C.

The composition according to embodiments of the present invention may be a cosmetic composition. The cosmetic composition may be formulated to contain a cosmetic or dermatologically acceptable medium or base. These are all formulations suitable for topical application, in the form of suspensions, microemulsions, microcapsules, microgranules or ionic (liposomal) and nonionic vesicle dispersants, or as creams, skins, lotions, powders, ointments, sprays or cones. It can 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 can be prepared according to conventional methods in the art.

In addition, the cosmetic composition according to the embodiments of the present invention is a powder, fatty substance, organic solvent, solubilizer, thickening agent, gelling agent, softening agent, antioxidant, suspending agent, stabilizer, foaming agent, fragrance, surfactant , Water, ionic or nonionic emulsifiers, fillers, metal ion blockers, chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic actives, lipid vesicles or cosmetic products It may contain adjuvants commonly used in the cosmetic or dermatological field, such as any other ingredients used. The adjuvant is introduced in an amount commonly used in the cosmetic or dermatological field. The cosmetic composition according to embodiments of the present invention may further contain a skin absorption promoting material in order to increase the skin improvement effect.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as limited by these examples.

[Production Examples 1 to 4]

Preparation Examples 1 to 4 were prepared according to the composition of Table 1 below. The specific method is divided below.

The components used in the following preparation examples are as follows.

PS
(1L shaking type reaction tank) CS DB Water 300 PS 300 CS 240 MeOH 40 Water 250 Water 350 Styrene 50 TMSPA 6 AIBN 0.2 KPS 0.5 Styrene 50 Styrene 40 SVBS 1.0 AIBN 0.2 SVBS 0.35

MeOH: Methanol cosolvent KPS: Potassium persulfate (initiator)

SVBS: Sodium vinyl benzene sulfonate (stabilizer)

PS: Polystyrene (polymer beads)

CS: Core-shell structured first polymer spheroid coated

DB: Amphiphilic anisotropic powder

TMSPA: Trimethoxysilyl propylacrylate (functional group)

AIBN: Azobisisobutyronitrile (polymerization initiator)

Manufacturing example  1. Polystyrene (PS) first polymer Spheroid  Produce

50 g of styrene as a monomer in the aqueous phase, 1.0 g of sodium 4-vinylbenzenesulfonate as a stabilizer, 0.5 g of azobisisobutyronitrile (AIBN) as a polymerization initiator, and mixed at 75 ° C Was reacted for 8 hours. The reaction was stirred in a cylindrical rotating reactor, and the cylindrical rotating reactor was 11 cm in diameter, 17 cm in height, glass material, and rotated at a speed of 200 rpm.

Preparation Example 2. Preparation of a first polymer spheroid coated with a core-shell (CS) structure

To the obtained polystyrene (PS) first polymer spheroid 300g, styrene (Styrene) 50g, TMSPA (3- (trimethoxysilyl) propylacrylate) 6g, azobisisobutyronitrile 0.2g (Azobisisobutyronitrile, AIBN) as a polymerization initiator ) And reacted at 75 ° C. for 8 hours. The reaction was stirred in a cylindrical rotating reactor.

Manufacturing example  3. Amphipathy  Anisotropy Powder  (DB) Manufacturing

As a result of the reaction, 240 g of a polystyrene-core shell (PS-CS) aqueous dispersion solution, 40 g of styrene as a monomer, 0.35 g of sodium 4-vinylbenzenesulfonate as a stabilizer, and azo as a polymerization initiator 0.2 g of bisisobutyronitrile (Azobisisobutyronitrile, AIBN) was mixed and heated to 75 ° C. for 8 hours. The reaction was stirred in a cylindrical rotary reactor to produce amphiphilic anisotropic powders having an average particle size of 235 μm.

Manufacturing example  4. Hydrophilic Amphipathy  Anisotropy Powder  Produce

30 g of N- [3- (trimethoxysilyl) propyl] ethylenediamine (N- [3- (Trimethoxysilyl) propyl] ethylenediamine) as a silane coupling agent to 600 g of the aqueous dispersion of the obtained anisotropic powder and ammonium hydroxide as a reaction regulator A side (Ammmonium hydroxide) 60g was mixed and reacted at 25 ° C for 24 hours to introduce a hydrophilic functional group. The reaction was stirred in a cylindrical rotating reactor to produce hydrophilized amphiphilic anisotropic powder.

[Example 1 and Comparative Example 1] Preparation of emulsion composition

According to the composition of Table 2, an oil-in-water emulsifying composition of Example 1 and Comparative Example 1 was prepared.

All processes were carried out at room temperature, after the water phase was prepared, the oil phase was added, and after mixing for 3 minutes at 8000 rpm using a homomixer, the first thickener was added to perform the homomixer process, and then the polymer was added to the additional homomixer process. Proceeded. Finally, an ethanol part was added and stirred with an agitator to prepare an emulsion composition.

Ingredient (% by weight) Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Yusangbu Butylene glycol / dicaprylate dicaprate 0.5 0.5 0.5 0.5 Cetyl Octanoate One One One One Diethoxyethyl succinate One One One One Cocos Nuspera Oil 1.5 1.5 1.5 1.5 Prime Minister Deionized water Balance Balance Balance Balance Water dispersion amphiphilic anisotropic powder (10% amphiphilic anisotropic powder) 10 10 10 - Glyceryl stearate - - - One Disodium ethylenediamine acetic acid 0.05 0.05 0.05 0.05 Yusangbu Decamethylcyclopentasiloxane 6 6 6 6 Primary thickener Polyacrylate-13 & polyisobutene & polysorbate 20 One One One One Polymer Acrylate / C10-30 alkyl acrylate crosspolymer 0.05 - - 0.05 Xanthan gum - - 0.05 - Ethanol part ethanol 30 30 30 30 Spices 0.7 0.7 0.7 0.7

[Test Example 1] observation of the formed emulsion particles

In order to compare the emulsifying particles, the emulsifying particles prepared in Example 1 and Comparative Examples 1-3 were observed immediately after production and stored at 45 ° C. for 10 weeks, and observed with an optical microscope. Table 3 shows the particle size.

In the results of FIG. 3, it can be seen that in Example 1, the emulsion particles formed in a fine size were densely gathered together to form a cluster, and no additional aggregation or fusion was observed between the emulsion particle clusters. This is considered to be because the anionic property of the emulsified particles is maintained and repulsion between clusters exists. On the other hand, in Comparative Example 1 without using a branched chain polymer or carbomer having a lipophilic alkyl chain as a side, the size of the emulsified particles is similar to that of Example 1, but the clusters of Example 1 are not formed and dispersed. It can be confirmed that it exists in a state. In the case of Comparative Example 2 using a polymer different from the present application, the emulsifying particle cluster is not formed, and the emulsifying particles of a small size exist in a dispersed state.

In the case of the composition of Example 1, it can be seen that even when maintained at a high temperature for a long time, it remains stable without fusion of the emulsifying particles and without further aggregation between the emulsifying particle clusters. In Comparative Examples 1 and 2, cluster particles were not formed even after a lapse of time. In the case of Comparative Example 3, it was confirmed that the initial particle size was small and the pattern of the particles was different by emulsifying with a surfactant, and aggregation occurred due to instability of the formulation after 10 weeks.

Particle size (unit: μm) Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Emulsifying particles 13.7 15.8 14.4 3.7 Emulsion particle cluster 39.5 none none none

[Test Example 2] Viscosity evaluation

The compositions prepared in Example 1 and Comparative Examples 1 to 3 were measured for viscosity through a viscosity meter (BROOKFIELD Viscometer, SPINDLE # 4,12RPM, 2MIN.) At 30 ° C for 4 weeks, and the measured viscosity is shown in FIG. 4.

From the results of FIG. 4, it was confirmed that Example 1 showed uniform stability even after 4 weeks had elapsed. And it can be seen that Comparative Example 1 without branched chain polymer or carbomer having a lipophilic alkyl chain and Comparative Example 2 with other types of polymers have lower viscosity than the Examples. In addition, in the case of Comparative Example 3 using another surfactant, it was confirmed that a viscosity drop phenomenon occurred because stability was not maintained.

 [Test Example 3] Evaluation of usability

The composition prepared in Example 1 and Comparative Examples 1 to 3 was used for 20 females aged 25 to 40 to evaluate the feeling of use. As for the items of freshness, water breakage, and oiliness (please describe the excellent usability evaluation items due to cluster particles), the results were evaluated on a 5-point scale (1 point: very poor to 5 points: very good), and the results were evaluated. It is shown in Table 4 below.

Evaluation items Example 1 Comparative Example 1 Comparative Example 2 Neatness 5 3 3 Burst 4 3 2 Oily 5 3 3

In the results of Table 4, in Example 1 of forming the emulsion particle cluster, the size of the emulsion particle itself is fine, but when used by the formation of the emulsion particle cluster, it shows excellent freshness, water bursting effect, and does not feel oily. , It can be seen that in the case of the compositions of Comparative Examples 1 to 3 in which no cluster was formed, results indicating an oily feeling of use were shown.

Claims (25)

Polar organic solvents; Primary thickener; Branched chain polymers or carbomers with side-by-side lipophilic alkyl chains; And a double spheroid type polymer amphiphilic anisotropic powder consisting of a hydrophilic one and a hydrophobic one; in an oil-in-water (O / W) emulsifying composition,
The powder is a structure in which the hydrophobic other partially penetrates into the interior of the hydrophilic one to form a core of the hydrophilic one, and the shell of the hydrophilic one includes a functional group,
The composition includes an emulsifying particle cluster (cluster) formed by densely clustering an emulsifying particle-polymer complex adsorbed by a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch on the emulsifying particles,
The emulsion particle cluster is formed by the polar organic solvent,
The polar organic solvent is selected from ethanol, acetic acid, dimethylamide, methanol, pyridine, ethylene glycol and acetone,
The primary thickener is at least one selected from the group consisting of polyacrylate-13, polyisobutene and polysorbate 20, oil-in-water emulsion cosmetic composition. delete According to claim 1,
The branched chain polymer having the lipophilic alkyl chain as a side is acrylate / C10-30 Alkyl Acrylate Crosspolymer, acrylate / C12-22 alkyl methacrylate copolymer (Acrylate / C12-22 Alkyl Metacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer and Acrylate / Cetheth-20 Metacrylate Copolymer ) Is selected from the group consisting of. delete delete According to claim 1,
The average particle size of the emulsion particle cluster is 1 to 500 ㎛, composition. According to claim 1,
The branched chain polymer or carbomer having the lipophilic alkyl chain as a branch contains 0.01 to 1% by weight based on the total weight of the composition. According to claim 1,
The amphipathic anisotropic powder comprises 0.1 to 10% by weight based on the total weight of the composition. According to claim 1,
The functional group is a siloxane composition. According to claim 1,
The hydrophilic one side of the powder is a core-shell structure,
The hydrophilic one core and the hydrophobic other include a vinyl aromatic polymer,
The hydrophilic one-sided shell is a vinyl aromatic monomer; And a monomer containing a functional group. The method of claim 10,
The composition containing the functional group is a siloxane-containing (meth) acrylate, composition. According to claim 1,
The amphiphilic anisotropic powder has a particle size of 100 to 1500nm, composition. According to claim 1,
The hydrophilic one-sided shell is a composition in which a hydrophilic functional group or a functional group containing a sugar is additionally introduced. The method of claim 13,
The hydrophilic functional group is at least one selected from the group consisting of carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, polyethylene glycol group and hydroxyl group; The functional group containing the sugar is N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) gluconamide and N- {N- (3 -Triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide. A method for preparing an oil-in-water (O / W) emulsion composition comprising an emulsifying particle cluster (cluster),
a) forming a large emulsifying particle by adding a double spheroid type polymer amphiphilic anisotropic powder composed of a hydrophilic one and a hydrophobic other to the water phase;
b) forming fine emulsified particles by adding at least one primary thickener selected from the group consisting of polyacrylate-13, polyisobutene and polysorbate 20 to the resultant a); And
c) a branched chain polymer or carbomer having a lipophilic alkyl chain as a side branch, and a polar organic solvent, and a branched chain polymer or carbomer having a lipophilic alkyl chain as a side branch in the fine emulsified particles Forming an emulsifying particle cluster (cluster) formed of densely clustered adsorbed emulsifying particle-polymer complexes;
Including,
The powder has a structure in which the hydrophobic other partially penetrates into the interior of the hydrophilic one to form a core of the hydrophilic one, and the shell of the hydrophilic one includes a functional group. The method of claim 15,
Step c),
c-1) Emulsion adsorbed by a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch by adding a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch to the product of b). Forming a matrix of emulsified particles in which particle-polymer composites form a network; And
c-2) By adding a polar organic solvent to the product of c-1), the branched chain polymer or carbomer having the lipophilic alkyl chain included in the matrix is contracted, so that the emulsified particle-polymer complexes are densely packed. Forming a cluster of emulsified particle clusters;
Manufacturing method comprising a. The method of claim 15,
The branched chain polymer having the lipophilic alkyl chain as a side is acrylate / C10-30 Alkyl Acrylate Crosspolymer, acrylate / C12-22 alkyl methacrylate copolymer (Acrylate / C12-22 Alkyl Metacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer and Acrylate / Cetheth-20 Metacrylate Copolymer ) Is selected from the group consisting of. delete The method of claim 15,
The polar organic solvent is selected from ethanol, acetic acid, dimethylamide, methanol, pyridine, ethylene glycol and acetone. The method of claim 15,
The average particle size of the emulsion particle cluster is 1 to 500 ㎛, the production method. The method of claim 15,
The functional group is a siloxane, production method. The method of claim 15,
The hydrophilic one side of the powder is a core-shell structure,
The hydrophilic one core and the hydrophobic other include a vinyl aromatic polymer,
The hydrophilic one-sided shell is a vinyl aromatic monomer; And a monomer containing a functional group. The method of claim 22,
The monomer containing the functional group is a siloxane-containing (meth) acrylate, the production method. The method of claim 15,
The large emulsified particles, the average particle size of 1㎛ to 100㎛ containing the emulsified particles of various sizes, the production method. The method of claim 15,
The fine emulsion particles, the average particle size is 1㎛ to 20㎛, the production method.

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