KR20180119499A - Oil-in-water type emulsion composition comprising emulsion particle cluster and method preparing the same - Google Patents

Abstract

The present specification discloses a branched polymer or carbomer having a lipophilic alkyl chain as a side chain; (O / W) emulsion composition comprising a hydrophilic one-side hydrophobic polymer and a hydrophilic one-side hydrophobic polymer and a bipolar type amphiphilic anisotropic powder comprising a hydrophobic one-side and a hydrophobic side.
Wherein the powder is a structure in which the hydrophobic part partially penetrates into the inside of the hydrophilic one to form a hydrophilic one of the cores, and the hydrophilic one shell comprises a functional group.

Description

[0001] The present invention relates to an oil-in-water emulsion composition comprising an oil-in-water type emulsion composition and a method for preparing the same,

This specification describes an oil-in-water type emulsion composition comprising an emulsion particle cluster and a method for producing the same.

In an emulsified composition using a surfactant, when the size of the emulsified particles is small, the stability with respect to time is comparatively excellent, but it is oily in feeling of use and hard to give a refreshing feeling. In addition, when the size of the emulsified particles is large, a water burst effect can be imparted to the feeling of use, but the stability of the emulsified particles is lowered.

Accordingly, there is a need for an emulsified composition which is excellent in both emulsion stability and feeling.

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

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

In another aspect, a problem to be solved by the present invention is to provide an emulsified composition having a fine emulsion particle size, excellent water jetting effect, and good feeling of use.

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

In another aspect, a problem to be solved by the present invention is to provide a stable emulsified composition without using an excess amount of the thickening agent.

In one aspect, the present invention relates to a branched polymer or carbomer having a lipophilic alkyl chain as a side chain; (O / W) emulsion composition comprising a hydrophilic one-side hydrophobic polymer and a hydrophilic one-side hydrophobic polymer and a bipolar type amphiphilic anisotropic powder comprising a hydrophobic one-side and a hydrophobic side.

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

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

a) adding a double spheroidal polymeric amphipathic anisotropic powder to the aqueous phase to form macroporous emulsion particles;

b) adding a primary thickening agent to the product of a) to form fine emulsified particles; And

c) adding a branched polymer or carbomer having a lipophilic alkyl chain as a side chain to the resulting product of b) and a polar organic solvent to prepare a branched polymer having a lipophilic alkyl chain as a side chain or a carbomer Forming emulsion particle clusters in which the adsorbed emulsion particle-polymer complexes are densely packed;

Lt; / RTI >

Wherein the powder partially penetrates into the inside of the hydrophilic one to form a hydrophilic one of the cores, and the hydrophilic one of the shells comprises a functional group.

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

In another aspect, the present invention can provide an emulsified composition having a minute size of emulsified particles but excellent water jetting effect and a fresh sensation.

In another aspect, the present invention can provide an emulsified composition that exhibits excellent stability over a wide temperature range.

In yet another aspect, the present invention can provide a stable emulsified composition without overdosage of the thickener.

1 is a schematic view schematically showing a method for producing a composition according to an embodiment of the present invention.
2 is a schematic diagram for forming an amphiphilic anisotropic powder.
3 is an optical microscope photograph of the emulsion particles of Example 1 and Comparative Example 1-3 immediately after preparation and after storage at 45 ° C for 10 weeks.
4 is a graph showing changes in viscosity with time in Example 1 and Comparative Example 1-3.

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

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

According to one embodiment of the present invention, it is possible to provide an oil-in-water (O / W) emulsified composition comprising a branched polymer or a carbomer having a lipophilic alkyl chain as a side chain, and an amphipathic anisotropic powder.

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

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

The composition may contain 0.01 to 1% by weight, for example, 0.02 to 0.08% by weight, based on the total weight of the composition, of a branched polymer or carbomer having the lipophilic alkyl chain as a side chain.

The composition may further comprise a polar organic solvent. The branched polymer or carbomer having the lipophilic alkyl chain as a side chain reacts with a polar organic solvent to exhibit a shrinking phenomenon of the branched polymer or carbomer. When the polar organic solvent is added to the emulsion particle matrix, the branched polymer or carbomer contained in the emulsion particle matrix shrinks and the emulsion particle-polymer complexes become clumped together. In this specification, it is referred to as an emulsion particle cluster in which the emulsion particle-polymer complexes are densely formed in a cluster.

The polar organic solvent may include, but is not limited to, ethanol, acetic acid, dimethyl amide, methanol, pyridine, ethylene glycol, and acetone. In one example, the polar organic solvent may be ethanol.

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

Since the emulsion particle clusters maintain the ionicity of the particles, the emulsion particle clusters can be stably maintained without fusing phenomenon between the emulsion particles in the emulsion particle clusters formed due to the repulsive force between charges.

The emulsion particle clusters may have an average particle size of from 1 to 500 mu m, for example, from 30 to 300 mu m. The average particle size of the emulsion particle clusters means the average diameter of the long axis and short axis diameter, which means that 95% or more of the clusters present in the composition fall within the above range.

The composition may further comprise a primary thickening agent. The primary thickening agent increases the formulation and acts as a cosurfactant, thereby finely reducing the size of the emulsified particles formed by the anisotropic powder.

In one example, the emulsified particles formed prior to the addition of the primary thickener may be large emulsified particles having an average particle size of from 1 to 100 탆. The mean particle diameter of the macro emulsion particle means an average value of the diameter of a single particle. In the state of the large emulsified particles, the particle diameter of the emulsified particles is not uniform, and the emulsified particles having a particle diameter in a wide range of several 탆 to several hundred 탆 coexist. The mean particle diameter of the macro emulsion particles may be, for example, 5 to 100 mu m, 10 to 100 mu m, 10 to 50 mu m, or 25 mu m. Specifically, the average particle size 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, Not more than 100 占 퐉, not more than 90 占 퐉, not more than 80 占 퐉, not more than 70 占 퐉, not more than 60 占 퐉, not less than 20 占 퐉, not less than 20 占 퐉, not less than 25 占 퐉, not less than 30 占 퐉, not less than 40 占 퐉, Not more than 50 mu m, not more than 40 mu m, not more than 30 mu m, not more than 25 mu m, not more than 20 mu m, not more than 15 mu m, not more than 10 mu m, or not more than 5 mu m.

The hydrophobic portion and the hydrophilic portion of the amphipathic anisotropic powder have different orientations toward the interface, whereby the macro emulsion particles can be formed. While the interface film formed by a general molecular level surfactant forms a dynamic emulsification state, the emulsion particle formed by the amphiphilic anisotropic powder increases the thickness of the interfacial film to several hundreds nm and forms a solid interfacial film . The emulsion stability can be improved through the formation of the interfacial film.

In one example, the emulsified particles to be finely ground by adding the primary thickening agent may be fine emulsified particles having an average particle diameter of 1 to 20 μm. The average particle diameter of the fine emulsified particles means an average value of the diameter of a single particle. The average particle diameter of the fine emulsified particles means that at least 95%, 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 fine emulsified particles may have an average particle diameter of 1 탆 or more, 2 탆 or more, 3 탆 or more, 4 탆 or more, 5 탆 or more, 6 탆 or more, 7 탆 or more, 8 탆 or more, 9 탆 or more, At least 11 mu m, at least 12 mu m, at least 13 mu m, at least 14 mu m, at least 15 mu m, at least 16 mu m, at least 17 mu m, at least 18 mu m, at least 19 mu m, at most 20 mu m, at most 19 mu m, 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 or 6 μm or less 5 mu m or less.

The primary thickeners may be used without limitation as long as they are commonly used in the technical field in the art. However, branched chain polymers and carbomers having side chains of the lipophilic alkyl chains included in the emulsion particle clusters 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, such as from 0.05% to 2% by weight, based on the total weight of the composition of the primary thickeners.

The composition according to this embodiment may have a viscosity of greater than or equal to about 1000 cps, greater than about 1200 cps, greater than about 1300 cps, greater than about 1400 cps, greater than about 1500 cps, greater than about 1600 cps, greater than about 1700 cps, Or more, at least 1900 cps, at least 2000 cps, at least 2100 cps, at least 2200 cps, at least 2300 cps, at least 2400 cps, or at least 2500 cps, and no more than 20,000 cps, no more than 19,000 cps, no more than 18,000 cps, no more than 17,000 cps, no more than 16,000 cps Less than 15000 cps, less than 14000 cps, less than 13000 cps, less than 12000 cps, less than 11000 cps, less than 10,000 cps, less than 8900 cps, less than 8800 cps, less than 8700 cps, less than 8600 cps, less than 8500 cps, less than 8400 cps, 8,300 cps or less, 8,800 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 Less than 7000 cps, less than 6900 cps, less than 6800 cps, less than 6700 cps, less than 6600 cps, less than 6500 cps, less than 6400 cps Less than or equal to 6300 cps, less than or equal to 6200 cps, less than or equal to 6100 cps, or less than or equal to 6000 cps. For example, the viscosity may be 1,000 to 20,000 cps, 1,000 cps to 10,000 cps, 1,500 to 7,000 cps, or 2,000 to 6,000 cps.

In the present embodiment, the amphiphilic anisotropic powder may be a double-sphere type polymeric amphipathic anisotropic powder consisting of a hydrophilic one-side and a hydrophobic one.

The powder may have a structure in which the hydrophobic other part partially penetrates into the inside of the hydrophilic one to form a hydrophilic one of the cores, and the hydrophilic one may include a functional group.

The powder may be in the form of a double sparoid, that is, a three-dimensional nephroid having a shape in which two spheroids are combined, and a symmetrical shape, asymmetric snowman snowman-shaped or asymmetric inverse snowman shape. The shape of the snowman 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 major axis length in microns or nanometers based on the longest length in the body cross-section. have.

In one embodiment, the hydrophilic one may be a core-shell structure in which the core is made of the same polymer as the hydrophobic base, and the hydrophilic one and the hydrophobic one may each take one spoloid shape of the double spoil. The binding portion between the two sphereoids of the double sphere may have a continuous structure from the hydrophilic core to the hydrophobic one.

In one embodiment, the hydrophilic one-side core and the hydrophobic one include a vinyl polymer, and the hydrophilic one-side 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, and may be, for example, polystyrene.

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

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

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

In one embodiment, the hydrophilic one-side shell may further include a hydrophilic functional group.

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

In one embodiment, the hydrophilic one-side shell may further include a sugar-containing functional group.

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

In one embodiment, the amphiphilic anisotropic powder may have a 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 preferably has a particle size of 100 nm or more, 200 nm or more, 300 nm or more, 400 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, 1200 nm or more, 1200 nm or more, 1300 nm or more or 1400 nm or more and 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 and 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 in an amount of, for example, at least 0.1%, at least 0.2%, at least 0.3%, at least 0.4%, at least 0.5%, at least 0.6% , Not less than 0.7 wt%, not less than 0.8 wt%, not less than 0.9 wt%, or not less than 1.0 wt%, not more than 20 wt%, not more than 19 wt%, not more than 18 wt%, not more than 17 wt% 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, 4 wt% or less, or 3 wt% or less. For example, the composition may comprise from 0.1% to 20% by weight, for example from 1% to 3%, of the amphipathic anisotropic powder relative to the total weight of the composition. Stable emulsion particles can be formed within the above range, and emulsion particles having an appropriate size can be formed.

In one example, the amphiphilic anisotropic powder includes a hydrophilic one (first polymer spoloid) and a hydrophobic other (second polymer spoloid), the hydrophilic one having a core-shell structure, the hydrophobic one having a hydrophilic one- At least partially penetrating into the inside of the hydrophilic core to form a hydrophilic one of the cores, and the hydrophilic one shell may contain a functional group.

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

2 is a schematic view showing a principle of forming an amphiphilic anisotropic powder according to an embodiment of the present invention. The core of the first polymer spolide may be formed through the shell of the first polymer spolide and may be grown to form a second polymer spoloid by the above manufacturing method.

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

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

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

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

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

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

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

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

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

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

The weight ratio of the first monomer, the polymerization initiator and the stabilizer is 80 to 135: 1: 1 to 5, specifically 95 to 120: 1: 2 to 4, when the amphiphilic anisotropic powder has a size of 200 to 250 nm. 1 < / RTI > polymer spolide.

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

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

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

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

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

In one embodiment, the monomer containing the first monomer, the polymerization initiator and the functional group in the step (2) may be mixed in a weight ratio of 30 to 100: 0.2 to 1.0: 1 to 20. In another aspect, the monomer containing the first monomer, the polymerization initiator and the functional group may be mixed at a weight ratio of 150 to 300: 1: 6 to 40. The degree of coating can be controlled according to the weight ratio, and the shape of the amphipathic anisotropic powder is determined according to the degree of coating, and when the weight ratio is adjusted, the coating thickness is increased to about 10 to 30%, specifically about 20% And the coating is too thick, so that the pulverization does not proceed or the pulverization is proceeded well without the problem that the pulverization is too thin. In addition, by mixing at the weight ratio within the above range, there is an effect that the uniformity of the anisotropic powder can be increased.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

1 is a schematic view schematically showing a method for producing a composition according to an embodiment of the present invention. The method comprises the steps of: adding a double spheroidal polymer-amphiphilic anisotropic powder to a water phase to form macroporous emulsion particles; Adding a primary thickener to form fine emulsified particles and adding a branched chain polymer or carbomer having a lipophilic alkyl chain as a side chain and a polar organic solvent to form a lipophilic alkyl chain A branched chain polymer having side chains or an emulsion particle cluster in which the emulsion particle-polymer complex adsorbed by the carbomer is densely packed can be formed. In Fig. 1, " polymer " means a branched polymer or carbomer having a lipophilic alkyl chain as a side chain.

As shown in FIG. 1, when a polar organic solvent was added without addition of a polymer, that is, a branched polymer having a side chain of a lipophilic alkyl chain or a carbomer, after the addition of the incremental agent, But does not form a simple dispersion emulsion particle.

The amphiphilic anisotropic powder is as described in the composition according to one embodiment of the present invention described above, so the description of the anisotropic powder will be omitted.

In one embodiment, after the microemulsified particles are formed, a branched polymer or carbomer having a lipophilic alkyl chain as a side chain is added to the microemulsified particle, and a branched polymer having a lipophilic alkyl chain as a side chain or a carbomer The emulsion particle-polymer complex forms a network of emulsified particle matrices and a polar organic solvent is added thereto to shrink the branched polymer or carbomer having side chain lipophilic alkyl chains contained in the matrix, The particle-polymer complexes can be densely aggregated to form emulsion particle clusters.

Since the emulsion particles are present in the form of emulsion particle clusters and have high stability, the composition according to the present embodiment can provide a stable emulsion composition without using an excess amount of the thickener. Furthermore, since several emulsified particles exist densely gathered in a cluster form, the size of the emulsified particles is fine. However, when the emulsified particle interface is broken down due to friction during use, the water bursting effect is large and a feeling of fresh feeling can be exhibited.

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

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

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

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

[Production Examples 1 to 4]

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

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

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 bead)

CS: Coated first polymeric spheroid with core-shell structure

DB: Amphipathic anisotropic powder

TMSPA: Trimethoxysilyl propylacrylate (functional group)

AIBN: Azobisisobutyronitrile (polymerization initiator)

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

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

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

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

Manufacturing example  3. Amphipathic  Anisotropy Powder  (DB) manufacturing

40 g of styrene as a monomer, 0.35 g of sodium 4-vinylbenzenesulfonate as a stabilizer, and 0.35 g of azobisisobutyronitrile as a polymerization initiator were added to 240 g of the polystyrene core shell (PS-CS) water dispersion solution obtained as a result of the reaction, And 0.2 g of azobisisobutyronitrile (AIBN) were mixed and heated at 75 캜 for 8 hours. The reaction was stirred in a cylindrical rotating reactor to produce an amphiphilic anisotropic powder having an average particle size of 235 탆.

Manufacturing example  4. Hydrophilized Amphipathic  Anisotropy Powder  Produce

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

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

The underwater type emulsion compositions of Example 1 and Comparative Example 1 were prepared according to the compositions shown in Table 2 below.

All the processes were carried out at room temperature. After the water phase was prepared, the oil phase was added and mixed using a homomixer at 8000 rpm for 3 minutes. Then, a homogenizer was added to perform a homomixer process. Then, the polymer was added and further homomixer process . Finally, the ethanol portion was added and stirred with an agitator to prepare an emulsified composition.

Component (% by weight) Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Floating 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 nuuspera oil 1.5 1.5 1.5 1.5 Water top Deionized water Balance Balance Balance Balance Water-dispersed amphiphilic anisotropic powder (amphipathic anisotropic powder 10%) 10 10 10 - Glyceryl stearate - - - One Disodium ethylenediamine acetic acid 0.05 0.05 0.05 0.05 Floating Decamethylcyclopentasiloxane 6 6 6 6 Primary incrementer 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 fraction 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 emulsion particles prepared in Example 1 and Comparative Example 1-3 were stored immediately after the preparation and at 45 ° C for 10 weeks, and then observed with an optical microscope. An optical microscope photograph was shown in FIG. 3, The particle size is shown in Table 3.

From the results shown in Fig. 3, it can be seen that the emulsion particles formed in a fine size densely gathered together to form clusters in Example 1, and no additional aggregation or fusion was observed between the emulsion particle clusters. It is thought that this is because the anionicity of the emulsified particles is maintained and there is a repulsive force between the clusters. On the other hand, in the case of Comparative Example 1 in which a branched polymer having no lipophilic alkyl chain as a side chain or a carbomer was not used, the size of emulsified particles was similar to that of Example 1, but the same clusters as in Example 1 were not formed, As shown in FIG. In the case of Comparative Example 2 using the polymer different from the present invention, emulsion particle clusters are not formed, and small-sized emulsion particles exist in a dispersed state.

It can be confirmed that the composition of Example 1 is stably maintained without fusion of the emulsion particles and formation of additional aggregates among the emulsion particle clusters even when it is maintained at a high temperature for a long time. In the case of Comparative Examples 1 and 2, cluster particles can not be 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 particle pattern was different due to the progress of emulsification by the surfactant, and the aggregation phenomenon due to the instability of the formulation after 10 weeks occurred.

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

[Test Example 2] Viscosity evaluation

The viscosity of the composition prepared in Example 1 and Comparative Examples 1 to 3 was measured at 30 ° C through a 4-week viscometer (BROOKFIELD Viscometer, SPINDLE # 4, 12RPM, 2MIN.) And the measured viscosity is shown in FIG.

From the results of Fig. 4, it was confirmed that Example 1 exhibited a uniform stability even after four weeks. And Comparative Example 1 in which no branched chain polymer or carbomer having a lipophilic alkyl chain as a side chain and Comparative Example 2 in which different kinds of polymers were used can be confirmed to have lower viscosity than those of Examples. Also, in Comparative Example 3 using another surfactant, the viscosity could not be maintained and the viscosity drop was observed.

 [Test Example 3] Evaluation of use feeling

The composition used in Example 1 and Comparative Examples 1 to 3 was used in 20 women aged 25 to 40 years to evaluate the feeling of use. The results were rated on a 5-point scale (1 point: very poor to 5 points: very good), and the results were evaluated on a 5 point scale Are shown in Table 4 below.

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

From the results of Table 4, in Example 1 in which the emulsion particle clusters are formed, the size of the emulsion particles themselves is fine. However, the emulsion particles clusters form a cluster of emulsion particles and are excellent in the effect of water bursting and excellent oil repellency , And the compositions of Comparative Examples 1 to 3 in which clusters were not formed exhibit an oily feel.

Claims (25)

A branched polymer or carbomer having a lipophilic alkyl chain as a side chain; (O / W) emulsion composition comprising a hydrophilic one-side hydrophobic polymer and a hydrophilic one-side hydrophobic polymer and a bipolar type amphiphilic anisotropic powder comprising a hydrophobic one-side and a hydrophobic side.
Wherein the powder has a structure in which the hydrophobic part partially penetrates into the interior of the hydrophilic one to form a hydrophilic one of the cores, and the hydrophilic one shell comprises a functional group. The method according to claim 1,
Wherein the composition comprises an emulsified particle cluster in which the emulsified particles and the emulsified particle-polymer complex adsorbed by the carbomer are densely packed together, with the branched polymer having lipophilic alkyl chains side-by-side or the carbomer adsorbed thereon. The method according to claim 1,
The branched polymer having the lipophilic alkyl chain as a side chain is an acrylate / C10-30 alkyl acrylate crosspolymer, an acrylate / C12-22 alkyl methacrylate copolymer, C12-22 Alkyl Methacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer, and Acrylate / Ceteth-20 Methacrylate Copolymer ). ≪ / RTI > The method according to claim 1,
Further comprising a polar organic solvent selected from the group consisting of ethanol, acetic acid, dimethyl amide, methanol, pyridine, ethylene glycol and acetone. The method according to claim 1,
Wherein the composition further comprises at least one primary thickener selected from the group consisting of polyacrylate-13, polyisobutene, and polysorbate 30. 3. The method of claim 2,
Wherein the emulsion particle clusters have an average particle size of from 1 to 500 mu m. The method according to claim 1,
Wherein the branched polymer or carbomer having the lipophilic alkyl chain as a side chain is contained in an amount of 0.01 to 1% by weight based on the total weight of the composition. The method according to claim 1,
Wherein the amphiphilic anisotropic powder comprises from 0.1 to 10% by weight based on the total weight of the composition. The method according to claim 1,
Wherein the functional group is a siloxane. The method according to claim 1,
The hydrophilic one side of the powder is a core-shell structure,
Wherein the hydrophilic one of the cores and the hydrophobic one include a vinyl aromatic polymer,
The hydrophilic one-side shell comprises a vinyl aromatic monomer; And a monomer containing a functional group. 11. The method of claim 10,
Wherein the functional group-containing monomer is a siloxane-containing (meth) acrylate. The method according to claim 1,
Wherein the amphiphilic anisotropic powder has a particle size of 100 to 2500 mm. The method according to claim 1,
Wherein the hydrophilic one-side shell is further introduced with a hydrophilic functional group or a functional group containing a sugar. 14. The method of claim 13,
Wherein the hydrophilic functional group is at least one selected from the group consisting of a carboxylic acid group, a sulfonic group, a phosphate group, an amino group, an alkoxy group, an ester group, an acetate group, a polyethylene glycol group and a hydroxyl group; The functional groups containing the sugar include N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) -Triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide. ≪ / RTI > A method for preparing an oil-in-water (O / W) emulsion composition comprising an emulsion particle cluster,
a) forming a large emulsion particle by adding an anisotropic powder of bi-sparoid type polymeric amphipathic anion having hydrophilic one-side and hydrophobic side to the aqueous phase;
b) adding a primary thickening agent to the product of a) to form fine emulsified particles; And
c) adding a branched polymer or carbomer having a lipophilic alkyl chain as a side chain to the resulting product of b) and a polar organic solvent to prepare a branched polymer having a lipophilic alkyl chain as a side chain or a carbomer Forming emulsion particle clusters in which the adsorbed emulsion particle-polymer complexes are densely packed;
Lt; / RTI >
Wherein the powder partially penetrates into the interior of the hydrophilic one of the hydrophobic parts to form a hydrophilic one of the cores, and the hydrophilic one of the shells comprises a functional group. 16. The method of claim 15,
The step c)
c-1) adding a branched polymer or carbomer having a lipophilic alkyl chain as a side chain to the result of the above step b), adding to the microemulsified particle a branched chain polymer having a lipophilic alkyl chain as a side chain or an oil- Forming a network of emulsion particles in which the particle-polymer complexes form a network; And
c-2) adding a polar organic solvent to the result of the step c-1) to shrink the branched polymer or carbomer having a lipophilic alkyl chain as a side chain contained in the matrix to form the emulsion particle- Forming a cluster of emulsified particle clusters;
≪ / RTI > 16. The method of claim 15,
The branched polymer having the lipophilic alkyl chain as a side chain is an acrylate / C10-30 alkyl acrylate crosspolymer, an acrylate / C12-22 alkyl methacrylate copolymer, C12-22 Alkyl Methacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer, and Acrylate / Ceteth-20 Methacrylate Copolymer ). ≪ / RTI > 16. The method of claim 15,
Wherein the primary thickener is at least one selected from the group consisting of polyacrylate-13, polyisobutene, and polysorbate 30. 16. The method of claim 15,
Wherein the polar organic solvent is selected from the group consisting of ethanol, acetic acid, dimethyl amide, methanol, pyridine, ethylene glycol and acetone. 16. The method of claim 15,
Wherein the emulsion particle clusters have an average particle size of 1 to 500 mu m. 16. The method of claim 15,
Wherein the functional group is a siloxane. 16. The method of claim 15,
The hydrophilic one side of the powder is a core-shell structure,
Wherein the hydrophilic one of the cores and the hydrophobic one include a vinyl aromatic polymer,
The hydrophilic one-side shell comprises a vinyl aromatic monomer; And a monomer containing a functional group. 23. The method of claim 22,
Wherein the functional group-containing monomer is a siloxane-containing (meth) acrylate. 16. The method of claim 15,
Wherein the macromolecular emulsion particle comprises emulsion particles of various sizes having an average particle size of from 1 탆 to 200 탆. 16. The method of claim 15,
Wherein the fine emulsified particles have an average particle size of 1 占 퐉 to 20 占 퐉.

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