WO2018199594A1 - Oil-in-water type emulsion composition containing emulsion particle clusters and preparation method therefor - Google Patents

Abstract

The present specification describes an oil-in-water (O/W) type emulsion cosmetic composition, wherein the oil-in-water (O/W) type composition contains: a branched-chain polymer having a lipophilic alkyl chain as a side branch or a carbomer; and a double-spheroid type polymer amphiphilic anisotropic powder having one side with hydrophilicity and the other side with hydrophobicity, wherein the powder has a structure in which the other side with hydrophobicity partially permeates into the one side with hydrophilicity to form a core of the one side with hydrophilicity, and wherein a shell of the one side with hydrophilicity comprises a functional group.

Description

Oil-in-water emulsion composition containing emulsion particle clusters and a method of manufacturing the same

The present specification describes an oil-in-water emulsion composition including an emulsion particle cluster and a method of manufacturing the same.

In the emulsion composition using the surfactant, when the size of the emulsion particles is small, the stability over time is relatively excellent, but oily (oily) in the feeling of use, it is difficult to give a fresh feeling. In addition, when the size of the emulsified particles is large, the water burst effect can be imparted to the feeling of use, but the stability of the emulsified particles is lowered.

Thus, there is a need for an emulsion composition that is excellent in both emulsion stability and usability.

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

In another aspect, the problem to be solved by the present invention is to provide an emulsified composition having a fine size of the emulsified particles, but excellent in the water bursting effect, a fresh feeling.

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

In another aspect, the problem to be solved by the present invention is to provide a stable emulsion composition without using an excessive amount of thickener.

In one aspect, the present invention provides a branched chain polymer or carbomer having a lipophilic alkyl chain; Into an oil-in-water (O / W) emulsion composition comprising; and a double spheroid type polymer amphiphilic anisotropic powder consisting of a hydrophilic one and a hydrophobic other.

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

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

a) adding a double spheroid type polymer amphiphilic anisotropic powder to an aqueous phase to form large emulsion particles;

b) adding a primary thickener to the resultant of a) to form fine emulsified particles; And

c) a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch to the resultant of b), and a polar organic solvent is added to the branched polymer or carbomer having a lipophilic alkyl chain as a branch to the fine emulsified particles. Forming a cluster of emulsion particles in which the adsorbed emulsion particle-polymer complexes are densely clustered;

Including,

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

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

In another aspect, the present invention can provide an emulsified composition having a fine size of the emulsified particles but having an excellent water burst effect and a neat feeling of use.

In another aspect, the present invention may provide an emulsion composition that exhibits good stability over a wide temperature range.

In another aspect, the present invention can provide a stable emulsion composition without the use of thickeners in excess.

1 is a schematic diagram schematically showing a method for preparing a composition according to an embodiment of the present invention.

2 is a schematic diagram of forming an amphipathic anisotropic powder.

3 is an optical micrograph immediately after the preparation of the emulsified particles of Example 1 and Comparative Examples 1-3 and after 10 weeks storage at 45 ° C.

4 is a graph showing changes in viscosity over time in Example 1 and Comparative Examples 1-3.

Hereinafter, with reference to the accompanying drawings, it will be described embodiments of the present application in more detail. However, the technology disclosed in the present application is not limited to the embodiments described herein and may be embodied in other forms. It is merely to be understood that the embodiments introduced herein are provided so that the disclosure can be made thorough and complete, and that the spirit of the present application can be fully conveyed to those skilled in the art. In order to clearly express each component in the drawings, the size, such as the width or thickness of the component, is shown to be somewhat enlarged. In addition, although only a part of the components are shown for convenience of description, those skilled in the art will be able to easily understand the rest of the components. In addition, one of ordinary skill in the art may implement the spirit of the present application in various other forms without departing from the technical spirit of the present application.

The particle size of the amphipathic anisotropic powder herein is a measure of the maximum length, which is the longest length of the powder particles. The particle size range of the amphipathic 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, an oil-in-water type (O / W) emulsion composition including a branched chain polymer or carbomer having a lipophilic alkyl chain as a side, and an amphiphilic anisotropic powder may be provided.

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

The branched chain polymer having the lipophilic alkyl chain as an acrylate / C 10-30 alkyl acrylate crosspolymer (Acrylate / C 10-30 Alkyl Acrylate Crosspolymer), acrylate / C 12-22 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 a branched chain polymer or carbomer with the lipophilic alkyl chain as an amount of 0.01 wt% to 1 wt%, for example 0.02 wt% to 0.08 wt%, based on the total weight of the composition.

The composition may further comprise a polar organic solvent. The branched chain polymer or carbomer having the lipophilic alkyl chain as a side reacts with the polar organic solvent to exhibit shrinking of the branched chain polymer or carbomer. When the polar organic solvent is added to the emulsion particle matrix, the branched chain polymer or carbomer included in the emulsion particle matrix shrinks, and the emulsion particle-polymer complexes are entangled together in a group. In the present specification, the emulsion particle-polymer composites are densely clustered to form emulsified particle clusters.

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

The composition may comprise 5% to 40% by weight, for example 10% to 30% by weight, of the polar organic solvent relative to the total weight of the composition.

Since the emulsified particle cluster maintains the ionicity of the particles, the emulsified particle cluster can be stably maintained without the phenomenon of fusion between the emulsified particles in the formed emulsified particle cluster 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 clusters refers to the average diameter of the major axis and minor axis, and means that at least 95% of the clusters present in the composition fall within this range.

The composition may further comprise a primary thickener. The primary thickener increases the dosage form, and may serve as a secondary surfactant to refine the size of the emulsified particles formed by the anisotropic powder.

In one example, the emulsified particles formed before adding the primary thickener may be large emulsified particles having an average particle diameter of 1 to 100 μm. The average particle diameter of the said large emulsion particle means the average value of the diameter of a single particle. In the state of the said large emulsion particle | grains, the particle diameter of an emulsion particle is not uniform, and the emulsion particle of the particle size of the wide range of several micrometers to several hundred micrometers coexists. The average particle diameter of the macroemulsion 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 at least 1 μm, at least 2 μm, at least 3 μm, at least 4 μm, at least 5 μm, at least 6 μm, at least 7 μm, at least 8 μm, at least 9 μm, at least 10 μm, 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, 50 μm, 40 μm, 30 μm, 25 μm, 20 μm, 15 μm, 10 μm or 5 μm or less.

The hydrophobic portion and the hydrophilic portion of the amphiphilic anisotropic powder can form large emulsion particles by having different orientations to the interface. While the interfacial film formed by the general molecular level surfactant forms a dynamic emulsification state, the emulsified particles formed by the amphipathic 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. Done. Emulsification stability can be improved by forming such an interface film.

In one example, the emulsified particles to be refined by the addition of the primary thickener may be fine emulsified particles having an average particle diameter of 1 ㎛ to 20 ㎛. The average particle diameter of the fine emulsified particles means an average value of the diameters of the single particles. The average particle diameter 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 range, and the particle size may be uniform. For example, the average particle diameter of the fine emulsified particles is at least 1 μm, at least 2 μm, at least 3 μm, at least 4 μm, at least 5 μm, at least 6 μm, at least 7 μm, at least 8 μm, at least 9 μm, at least 10 μm. , 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 5 μm or less.

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

The composition may comprise from 0.01% to 3% by weight, for example from 0.05% to 2% by weight, based on the total weight of the composition.

The composition according to the present embodiment has a viscosity of at least 1000 cps, at least 1100 cps, at least 1200 cps, at least 1300 cps, at least 1400 cps, at least 1500 cps, at least 1600 cps, at least 1700 cps, and at least 1800 cps. Or more, 1900 cps or more, 2000 cps or more, 2100 cps or more, 2200 cps or more, 2300 cps or more, 2400 cps or more, 2500 cps or more, 20000 cps or less, 19000 cps or less, 18000 cps or less, 17000 cps or less, 16000 cps 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, 8300 cps or less, 8200 cps or less, 8100 cps or less, 8000 cps or less, 7900 cps or less, 7800 cps or less, 7700 cps or less, 7600 cps or less, 7500 cps or less, 7400 cps or less, 7300 cps or less, 7200 cps or less, 7100 cps 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 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 amphipathic anisotropic powder composed of hydrophilic one and hydrophobic other.

The powder has a structure in which the hydrophobic other partially penetrates into the inside of the hydrophilic one to form a hydrophilic one core, 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 a shape in which two spheroids are combined, and a symmetrical shape and an asymmetrical snowman based on the combined part. snowman) shape or asymmetrical inverse snowman shape. The snowman shape means that the first and second polymer spheroids having different sizes are bonded to each other.

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

In one embodiment, the hydrophilic one side may have a core-shell structure in which the core is made of the same polymer as the hydrophobic other side, and the hydrophilic one side and the hydrophobic other side may form one spheroid shape each of the double spheroids. The coupling portion between the two spheroids of the double spheroid can be made into a structure that is continuous from the hydrophilic one core 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 embodiment, the vinyl polymer may be a vinyl aromatic polymer, for example, may be 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 embodiment, the functional group may be a siloxane.

In one embodiment, the monomer containing a 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 shell of the hydrophilic one side may be further introduced with a hydrophilic functional group.

In one embodiment, the hydrophilic functional group may be a negatively charged or positively charged functional group or polyethylene glycol (PEG) series, carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, polyethylene glycol group and hydride It may be at least one selected from the group consisting of a hydroxyl group.

In one example, the hydrophilic one shell may be further introduced with a functional group containing a sugar.

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

In one embodiment, the amphipathic anisotropic powder may have a particle size of 100 to 1500 nm. For example, the amphipathic 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 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 embodiment, the composition comprises the amphiphilic anisotropic powder, for example, based on the total weight of the composition, for example, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight or more , At least 0.7 wt%, at least 0.8 wt%, at least 0.9 wt%, or at least 1.0 wt%, at most 20 wt%, at most 19 wt%, at most 18 wt%, at most 17 wt%, at most 16 wt%, 15 wt% Or less, 14 or less, 13 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, 5 or less Or less than 4%, or less than or equal to 3% by weight. For example, the composition may include the amphiphilic 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 emulsion particles can be formed within the above range, and emulsion particles of appropriate size can be formed.

In one example, the amphipathic anisotropic powder comprises one hydrophilic one (first polymer spheroid) and the other hydrophobic (second polymer spheroid), the hydrophilic one has a core-shell structure, the other hydrophilic one is the hydrophilic one It is a structure which penetrates at least partially into the inside and forms one core of hydrophilicity, and the said hydrophilic one shell may contain a functional group.

In one embodiment of the present invention, the amphipathic anisotropic powder is prepared by polymerizing a first monomer to prepare a core of a first polymer spheroid, and coating a core of the first polymer spheroid to the first polymer sp of the core-shell structure It may be prepared to prepare the Lloyd, and reacting the first polymer spheroid and the first monomer of the core-shell structure to prepare an amphiphilic anisotropic powder in which the second polymer spheroid is formed.

Figure 2 is a schematic diagram showing the principle of formation of amphipathic anisotropic powder according to an embodiment of the present invention. According to the manufacturing method, the core of the first polymer spheroid may be penetrated through the shell of the first polymer spheroid, and then powdered to form a second polymer spheroid.

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

In the steps (1), (2) and (3), the stirring may be rotary stirring. Rotational agitation is preferred because uniform mechanical mixing is required along with chemical modification to produce uniform particles. The rotary stirring may be rotary stirring in a cylindrical rotary reactor, but the rotary stirring method is not limited thereto.

At this time, the design inside the reactor has a great influence on the powder formation. The size and location of the baffles in the cylindrical rotary reactor and the degree of spacing with the impeller greatly affect the uniformity of the particles produced. It is desirable to minimize the blade gap between the inner wing and the impeller to equalize the convective flow and its strength, and to supply the powder reaction liquid below the wing length and maintain the impeller rotation speed at a high speed. It may be rotated at a highway of 200 rpm or more, and the ratio of the length of the diameter and the 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 vary in proportion to the reaction capacity. In addition, the material of the cylindrical rotary reactor may be a ceramic, glass, and the like, the temperature of the stirring is preferably 50 to 90 ℃.

In the cylindrical rotary reactor, the simple rotary method enables the production of uniform particles and is a low energy method that requires less energy, and has a characteristic of enabling mass production by maximizing reaction efficiency. The tumbling method in which the reactor itself rotates in the related art requires high energy and rotates the reactor at a predetermined angle, thus requiring high energy and restricting the size of the reactor. 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 embodiment, the first monomer and the second monomer may be the same or different, 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), 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, may be a peroxide-based, azo-based or a mixture thereof. Moreover, ammonium persulfate, sodium persulfate, potassium persulfate can also be used.

In one example, in step (1), the first monomer and the polymerization initiator 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), a stabilizer may be added together with the first monomer and 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 according to the size adjustment of the first polymer spheroid in the initial stage (1), and the first polymer spheroid size can be adjusted according to the weight ratio of the first monomer, the polymerization initiator and the stabilizer. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder. By mixing in the weight ratio in the above range, it is possible to 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 may be used. Stabilizers prevent swelling of the resulting particles and impart positive or negative charges to the surface of the powder to electrostatically prevent mutual coalescence (bonding) during particle generation.

When the amphipathic 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: 1 to 2-4 It can be prepared from 1 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 3 It can be prepared from the first polymeric 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: 0, specifically 115 to 125: 1: 0 It can be prepared from spheroids.

In addition, the amphipathic anisotropic powder of the asymmetrical snowman shape has 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 It can be prepared from polymeric spheroids.

In addition, the amphipathic anisotropic powder of the asymmetric inverse snowman shape is made of a weight ratio of the first monomer, the polymerization initiator, and the stabilizing agent is 100 to 140: 1: 1 to 5, specifically 110 to 130: 1: 1 to 2-4 It can be prepared from 1 polymer spheroid.

In one embodiment, the monomer containing a functional group in the 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, the monomer containing the first monomer, the polymerization initiator and the functional group in the step (2) 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: 6 to 40. The degree of coating can be adjusted according to the weight ratio, and the shape of the amphipathic anisotropic powder is subsequently determined according to the degree of coating, and when reacting with the weight ratio, the coating thickness increases to about 10-30%, specifically 20%, relative to the initial thickness. The coating is too thick so that powdering does not proceed or is too thin so that the powdering proceeds well without the problem of powdering in multiple directions. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.

By the step (3), a part of the core of the first polymer spheroid protrudes through the shell from one direction of the first polymer spheroid of the core-shell structure, and the protrusion grows by the polymer of the second monomer to form an anisotropic powder. It can form the form of.

In one 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 are 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 It can be mixed in a weight ratio of: 1, or 220 to 250: 1, or 230 to 250: 1, or 240 to 250: 1.

In another aspect, in step (3), the second monomer, the polymerization initiator and the stabilizer may be added together with the second monomer and the polymerization initiator to mix the second monomer, the polymerization initiator and the stabilizer in a weight ratio of 150 to 250: 1: 1: 0.001 to 5. The specific kind of stabilizer is as above-mentioned. By mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.

In one example, the second monomer content in the step (3) may be mixed to 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 of the core-shell structure is 100 parts by weight, an asymmetric snowman type powder is obtained, and 100 to 150 parts by weight, or 110 to 150 parts by weight. In the case of parts by weight, a symmetrical powder 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. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of 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 introducing a hydrophilic functional group into 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 regulator.

In one embodiment, 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 one 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 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 step (3). Hydrophilization can be suitably made within the said range.

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

In one example, the reaction regulator 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 can be suitably made within the said range.

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) introducing a functional group containing a sugar into 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 regulator.

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 regulator 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). Introduction of the functional group containing a sugar in the said range can be made suitably.

Amphiphilic anisotropic powder according to the above method does not use a crosslinking agent, there is no entanglement in production, the yield is high and uniform, and it is easy to mass-produce compared to the tumbling method using a simple stirring method. In particular, there is an advantage that can be mass-produced in the size of several tens g to several tens of kg nano size of 300 nm or less.

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 including an emulsified particle cluster.

1 is a schematic diagram schematically showing a method for preparing a composition according to an embodiment of the present invention. The production method comprises the addition of a double spheroid type polymer amphiphilic anisotropic powder to the aqueous phase to form large emulsion particles; A primary thickener is added to form fine emulsified particles, and a branched chain polymer or carbomer having a lipophilic alkyl chain as a side, and a polar organic solvent are added to add a lipophilic alkyl chain to the fine emulsified particles. Emulsified particle-polymer complexes adsorbed by branched chain polymers or carbomers having side chains can form clusters of emulsified particles that are densely clustered. In Figure 1, "polymer" refers to a branched chain polymer or carbomer with a lipophilic alkyl chain.

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

The amphipathic anisotropic powder is omitted as it is described in the above-described composition according to an embodiment of the present invention.

In one embodiment, after forming the fine emulsified particles, a branched chain polymer or carbomer is added to the fine emulsified particles, and the branched polymer or carbomer adsorbed to the microemulsified particles is adsorbed. The emulsion particle-polymer complexes form a network of emulsion particle matrix in which a network is formed, and a polar organic solvent is added thereto so that the branched polymer or carbomer having a lipophilic alkyl chain included in the matrix shrinks, thereby emulsifying the emulsion. Particle-polymer complexes may be densely clustered to form emulsified particle clusters.

Since the composition according to the present embodiment has a very high stability because the emulsion particles exist in the form of emulsion particle clusters, it is possible to provide a stable emulsion composition without using an excessive amount of a thickener. Furthermore, since a large number of emulsified particles exist in a clustered state, the size of the emulsified particles is fine, but the water burst effect generated when the emulsified particle interface collapses due to friction during use can provide a fresh feeling.

The composition according to the present 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 the embodiments of the present invention may be a cosmetic composition. The cosmetic composition may be formulated containing a cosmetically or dermatologically acceptable medium or base. It is any formulation suitable for topical application, in the form of suspensions, microemulsions, microcapsules, microgranules or ionic (liposomal) and nonionic vesicle dispersants or creams, skins, lotions, powders, ointments, sprays or concealers. It may be provided in the form of a stick. It may 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 may be a powder, a fatty substance, an organic solvent, a dissolving agent, a thickening agent, a gelling agent, a softening agent, an antioxidant, a suspending agent, a stabilizer, a foaming agent, a fragrance, a surfactant. Commonly used in water, ionic or nonionic emulsifiers, fillers, metal ion sequestrants, chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or cosmetics It may contain adjuvants conventionally used in the cosmetic or dermatological fields, such as any other ingredients used. Such adjuvants are introduced in amounts generally used in the cosmetic or dermatological arts. 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. 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.

[Manufacture example 1-4]

According to the composition of Table 1, Preparation Examples 1 to 4 were prepared. Specific methods are described below.

The component used by the following preparation example is as follows.

PS (1L shake reactor) 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

CS: coated first polymer spheroid of core-shell structure

DB: Amphiphilic Anisotropic Powder

TMSPA: Trimethoxysilyl propylacrylate (functional group)

AIBN: Azobisisobutyronitrile (polymerization initiator)

Preparation Example 1 Preparation of Polystyrene (PS) First Polymer Spheroid

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 an aqueous phase to 75 ° C. The reaction was carried out for 8 hours. The reaction was stirred in a cylindrical rotary reactor, the cylindrical rotary reactor was 11 cm in diameter, 17 cm in height, glass, and was rotated at a speed of 200 rpm.

Preparation Example 2 Preparation of Coated First Polymer Spheroid of Core-Shell (CS) Structure

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

Preparation Example 3 Preparation of Amphiphilic Anisotropic Powder (DB)

To 240 g of polystyrene-coreshell (PS-CS) aqueous dispersion solution obtained as a result of the reaction, 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 an amphipathic anisotropic powder with an average particle size of 235 μm.

Preparation Example 4 Preparation of Hydrophilized Amphiphilic Anisotropic Powder

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

Example 1 and Comparative Example 1 Preparation of Emulsifying Composition

To prepare an oil-in-water emulsion composition of Example 1 and Comparative Example 1 according to the composition of Table 2.

All processes were carried out at room temperature, after the aqueous phase was prepared, the oil phase was added and the mixture was mixed at 8000 rpm for 3 minutes using a homo mixer, followed by the addition of the first thickener, followed by the homo mixer. Proceeded. Finally, the ethanol part was added and stirred with an azimixer to prepare an emulsion composition.

Ingredient (wt%) Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 The upper part Butylene Glycol / Dicaprylate Dicaprate 0.5 0.5 0.5 0.5 Cetyloctanoate One One One One Diethoxyethyl succinate One One One One Cocos Nouspera Oil 1.5 1.5 1.5 1.5 Award Deionized water Remaining amount Remaining amount Remaining amount Remaining amount Water Dispersion Amphipathic Anisotropic Powder (10% Amphipathic Anisotropic Powder) 10 10 10 - Glyceryl Stearate - - - One Disodium Ethylenediamine Acetic Acid 0.05 0.05 0.05 0.05 The upper part Decamethylcyclopentasiloxane 6 6 6 6 1st increment 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 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 emulsified particles, the emulsified particles prepared in Example 1 and Comparative Examples 1-3 were stored immediately after the preparation and at 45 ° C. for 10 weeks, and then observed with an optical microscope. An optical micrograph is shown in FIG. The size of the particles is shown in Table 3.

In the results of FIG. 3, it can be seen that in Example 1, emulsified particles formed in fine sizes dense together to form clusters, and no further aggregation or fusion was observed between the emulsified particle clusters. This is considered to be because the anionicity of the emulsified particles is maintained so that a repulsion force exists between the clusters. On the other hand, in Comparative Example 1 without a branched chain polymer or carbomer with a lipophilic alkyl chain, the size of the emulsified particles is similar to Example 1, but the same cluster as in Example 1 is dispersed without forming You can see that it exists in a state. In the case of Comparative Example 2 using a different polymer from the present invention, no emulsion particle clusters are formed, and the emulsion particles of a small size are present in a dispersed state.

In the case of the composition of Example 1, it can be confirmed that even after being kept at a high temperature for a long time, it is stably maintained without fusion of emulsified particles and without further aggregation of emulsified particle clusters. In Comparative Examples 1 and 2, cluster particles cannot be formed even after elapse of time. In the case of Comparative Example 3, the initial particle size was small and the pattern of the particles was different by emulsification with the surfactant, and after 10 weeks, it was confirmed that the aggregation phenomenon was caused by the instability of the formulation.

Particle Size (Unit: μm) Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Emulsified particles 13.7 15.8 14.4 3.7 Emulsified 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 4 weeks at 30 ° C. using a viscosity meter (BROOKFIELD Viscometer, SPINDLE # 4, 12 RPM, 2MIN.) And the measured viscosity is shown in FIG. 4.

In the result of FIG. 4, it was confirmed that Example 1 shows uniform stability even after 4 weeks. And it can be seen that the comparative example 1 without the branched chain polymer or carbomer with a lipophilic alkyl chain side and Comparative Example 2 used a different type of polymer has a lower viscosity than the example. In addition, in the case of Comparative Example 3 using a different surfactant it can be confirmed that the viscosity drop phenomenon does not maintain stability.

 Test Example 3 Evaluation

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

Evaluation item Example 1 Comparative Example 1 Comparative Example 2 Freshness 5 3 3 Water burst 4 3 2 Oily 5 3 3

In the results of Table 4, in Example 1 forming the emulsified particle cluster, although the size of the emulsified particle itself is fine, when used by the emulsified particle cluster formation, the freshness, water bursting effect is excellent, and it shows excellent feeling of not feeling oily. In the case of the compositions of Comparative Examples 1 to 3, which do not form clusters, it can be seen that the results exhibit an oily feeling.

Claims (25)

Branched polymers or carbomers having lipophilic alkyl chains; Into an oil-in-water (O / W) emulsion composition comprising; and a double spheroid type polymer amphiphilic anisotropic powder consisting of a hydrophilic one and a hydrophobic other. The said powder is a structure which the said hydrophobic other partially penetrates into the inside of the said hydrophilic one, and forms the hydrophilic one core, The said hydrophilic one shell contains a functional group, The oil-in-water type emulsion cosmetic composition. The method of claim 1, The composition comprises an emulsified particle cluster (cluster) formed in a densely clustered emulsified particle-polymer complex adsorbed by a branched chain polymer or carbomer having a lipophilic alkyl chain side to the emulsified particles. The method of claim 1, The branched chain polymer having the lipophilic alkyl chain as an acrylate / C 10-30 alkyl acrylate crosspolymer (Acrylate / C 10-30 Alkyl Acrylate Crosspolymer), acrylate / C 12-22 alkyl methacrylate copolymer (Acrylate / C12-22 Alkyl Metacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer, and Acrylate / Ceteth-20 Metacrylate Copolymer ) Is selected from the group consisting of. The method of claim 1, It further comprises a polar organic solvent selected from ethanol, acetic acid, dimethylamide, methanol, pyridine, ethylene glycol and acetone. The method of claim 1, A composition further comprising at least one primary thickener selected from the group consisting of polyacrylate-13, polyisobutene and polysorbate 30. The method of claim 2, The composition of claim 1, wherein the emulsified particle cluster has an average particle size of 1 to 500 μm. The method of claim 1, The branched chain polymer or carbomer having the lipophilic alkyl chain as a side comprises 0.01 to 1% by weight based on the total weight of the composition. The method of claim 1, The amphipathic anisotropic powder comprises 0.1 to 10% by weight based on the total weight of the composition. The method of claim 1, Wherein said functional group is a siloxane. The method of claim 1, 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 said hydrophilic one shell is a vinyl aromatic monomer; And a monomer containing a functional group. The method of claim 10, The monomer containing the said functional group is a siloxane containing (meth) acrylate. The method of claim 1, The amphipathic anisotropic powder has a particle size of 100 to 2500mm. The method of claim 1, The said hydrophilic one shell is a composition which the hydrophilic functional group or the functional group containing sugar was further introduced. The method of claim 13, The hydrophilic functional group is at least one selected from the group consisting of a carboxylic acid group, a sulfone 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 sugar-containing functional groups are N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) gluconamide and N- {N- (3 -Triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide, wherein the composition is derived from one or more selected from the group consisting of. In the method of producing an oil-in-water (O / W) emulsion composition comprising an emulsion particle cluster (cluster), a) adding a double spheroid type polymer amphiphilic anisotropic powder composed of hydrophilic one and hydrophobic other to the aqueous phase to form large emulsion particles; b) adding a primary thickener to the resultant of a) to form fine emulsified particles; And c) a branched chain polymer or carbomer having a lipophilic alkyl chain as a branch to the resultant of b), and a polar organic solvent is added to the branched polymer or carbomer having a lipophilic alkyl chain as a branch to the fine emulsified particles. Forming a cluster of emulsion particles in which the adsorbed emulsion particle-polymer complexes are densely clustered; Including, The said powder is a structure in which the said hydrophobic other partially penetrates into the inside of the said hydrophilic one, and forms a hydrophilic one core, The said hydrophilic one shell contains a functional group. The method of claim 15, C), c-1) Emulsified by branched polymers or carbomers having lipophilic alkyl chains to the fine emulsified particles by adding branched polymers or carbomers having lipophilic alkyl chains to the product of b). Forming the emulsion particle matrix in which the particle-polymer complexes form a network; And c-2) By adding a polar organic solvent to the resultant of c-1), branched polymers or carbomers having lipophilic alkyl chains included in the matrix shrink and contract the densified particle-polymer complexes. Clustering emulsified particle clusters; It includes, a manufacturing method. The method of claim 15, The branched chain polymer having the lipophilic alkyl chain as an acrylate / C 10-30 alkyl acrylate crosspolymer (Acrylate / C 10-30 Alkyl Acrylate Crosspolymer), acrylate / C 12-22 alkyl methacrylate copolymer (Acrylate / C12-22 Alkyl Metacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer, and Acrylate / Ceteth-20 Metacrylate Copolymer ) Is selected from the group consisting of, manufacturing method. The method of claim 15, The primary thickener is one or more selected from the group consisting of polyacrylate-13, polyisobutene and polysorbate 30, the production method. 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 emulsified particle cluster is 1 to 500 ㎛. The method of claim 15, The functional group is a siloxane. The method of claim 15, 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 said hydrophilic one shell is a vinyl aromatic monomer; And a monomer containing a functional group. The method of claim 22, The monomer containing the said functional group is siloxane containing (meth) acrylate, The manufacturing method. The method of claim 15, The macro-emulsified particles, the average particle size of 1 ㎛ to 200 ㎛ will include a variety of size of the emulsified particles. The method of claim 15, The fine emulsified particles will have an average particle size of 1㎛ to 20㎛, manufacturing method.

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