WO2016108583A1 - Chemically asymmetric anisotropic powder and water-in-oil (w/o) emulsification composition containing same - Google Patents

Abstract

Disclosed are a chemically asymmetric anisotropic powder, a stabilized water-in-oil (W/O) emulsification composition containing the same, and a method for preparing the same. The composition contains a chemically asymmetric anisotropic powder that forms emulsification particles with a stabilized interface film and various sizes, thereby providing a stabilized W/O emulsification composition having a low-viscosity formulation, which has a significantly lighter feeling of use than existing W/O formulations.

Description

Chemically Asymmetric Anisotropic Powders and Water-in-Water (W / O) Emulsifying Compositions Containing the Same

Disclosed herein are chemically asymmetric anisotropic powders and stabilized water-in-oil (W / O) emulsion compositions containing them and methods for their preparation.

Various methods of manufacturing fine particles (nano, micro size) of various shapes and sizes have been reported, and in particular, spherical fine particles made of a polymer have been expanded as the size and shape are adjusted according to the manufacturing method thereof. One application is the Pickering emulsion, which can form stabilized large emulsion particles using fine spherical particles.

Pickering emulsions using spherical solid powders form w / o or o / w emulsions depending on the degree of wetting at the surface of the solid powder, ie lipophilic or hydrophilic. The contact angle is a factor that determines the directionality of the membrane. If the contact angle is smaller than 90 degrees, a large part of the surface of the particle exists as an aqueous phase to generate o / w. If the contact angle is larger than 90 degrees, it is present on the oil side to generate w / o. Create

In general, the water-in-oil (W / O) formulation is very limited in the emulsified composition to exhibit a variety of feelings due to the freezing stability of the emulsion particles. Although polyols / salts / alcohols and the like have been used in the inner phase to stabilize the W / O formulations, such inner phase compositions have a limit to affect the emulsifying interface and the thickening system to make only limited emulsion formulations. In addition, in order to stabilize the emulsion composition, an excessive amount of an inorganic thickener (for example, benton) or the like is used on the outer phase, which causes a problem of increasing the viscosity and showing a limited usability.

In one aspect, the present disclosure aims to provide a chemically asymmetric anisotropic powder imparting a chemical surfactant and a physical surfactant.

In another aspect, the present specification is to provide a water-in-oil emulsified composition that can be secured in the emulsion stability using a chemically asymmetric anisotropic powder rather than the existing underwater emulsifier and various emulsion composition ratios can be used to vary the feeling, such as viscosity control.

In another aspect, the present disclosure aims to provide a method for producing a chemically asymmetric anisotropic powder that is simple and maximizes yield and is capable of mass production.

In one aspect, the technology disclosed herein includes a first polymer spheroid and a second polymer spheroid, wherein the first polymer spheroid and the second polymer spheroid are at least partially infiltrating the relative polymer spheroid. In combination, the first polymeric spheroid has a core-shell structure and the shell provides a chemically asymmetric anisotropic powder comprising a functional group.

According to an exemplary embodiment, the core of the first polymer spheroid and the second polymer steroid include a vinyl polymer, and the shell of the first polymer spheroid includes a copolymer of a vinyl monomer and a monomer including a functional group. can do.

According to an exemplary embodiment, the vinyl polymer may be polystyrene.

According to one exemplary embodiment, the functional group may be a siloxane.

According to an exemplary embodiment, the chemically asymmetric anisotropic powder may be an asymmetric snowman shape or an asymmetric inverse snowman shape.

In another aspect, the techniques disclosed herein provide a water-in-oil (W / O) emulsion composition containing the chemically asymmetric anisotropic powder.

According to one exemplary embodiment, the chemically asymmetric anisotropic powder may be contained 1 to 15% by weight based on the total weight of the water-in-oil emulsion composition.

According to an exemplary embodiment, the water-in-oil emulsion composition may include an alcohol.

According to an exemplary embodiment, the water phase portion of the water-in-oil emulsion composition may include a salt.

According to an exemplary embodiment, the salt may be at least one selected from the group consisting of sodium chloride, potassium chloride, lithium chloride, calcium chloride and magnesium chloride.

According to one exemplary embodiment, the salt may be contained from 0.01 to 5% by weight based on the total weight of the water-in-oil emulsion composition.

According to an exemplary embodiment, the water-in-oil emulsion composition may be mixed in a ratio of 1 to 15: 50 to 80: 10 to 30 by weight of the chemically asymmetric anisotropic powder, oil phase and water phase.

According to an exemplary embodiment, the water-in-oil emulsion composition may have an emulsion particle of 5 to 200 ㎛ size.

According to one exemplary embodiment, the water-in-oil emulsion composition may have a low viscosity formulation of less than 10000 CPS.

In another aspect, the technology disclosed herein is a method for producing the chemically asymmetric anisotropic powder, comprising: (1) preparing a core of a first polymer spheroid by stirring a first monomer and a polymerization initiator; (2) preparing a first polymer spheroid having a core-shell structure coated with the first polymer spheroid prepared above by stirring the core with a compound containing a first monomer, a polymerization initiator, and a siloxane; And (3) preparing the anisotropic powder in which the second polymer spheroid is formed by stirring the prepared first polymer spheroid having a core-shell structure with a second monomer and a polymerization initiator. It provides a manufacturing method.

According to an exemplary embodiment, in the step (1), the first monomer and the polymerization initiator may be mixed in a weight ratio of 100 to 140: 1.

According to an exemplary embodiment, the second monomer content in the step (3) may be mixed to 40 to 100 parts by weight or 150 to 300 parts by weight when the weight of the first polymer spheroid of the core-shell structure is 100 parts by weight. .

In one aspect, the technique disclosed herein has the effect of providing a chemically asymmetric anisotropic powder that forms strong bonds between the powders to form a stabilized interfacial film due to the geometrically linear nature of the powder.

In another aspect, the techniques disclosed herein have the effect of providing stabilized water-in-oil emulsion compositions by including chemically asymmetric anisotropic powders, which are also stabilized for a variety of internal and external compositions.

In another aspect, the techniques disclosed herein include chemically asymmetric anisotropic powders that form emulsified particles of various sizes, thereby providing a water-in-oil emulsion composition having a low viscosity formulation having a much lighter feel compared to conventional W / O formulations. It works.

In another aspect, the technology disclosed herein aims to provide a method for producing a chemically asymmetric anisotropic powder that is simple and maximizes yield and is capable of mass production.

1 is a photograph of the viscosity comparison results of the water-in-oil emulsion composition according to Example 1 and Comparative Example 1. (a) is Comparative Example 1 which is a conventional W / O formulation, and (b) is Example 1 which is a W / O formulation containing anisotropic powder.

Figure 2 is to observe the emulsified particles of the water-in-oil emulsion composition according to this embodiment 1, (a) after storage for 2 months at room temperature, (b) frozen immediately after the preparation, (c) freezing and thawing is repeated four times After 2 months storage.

3 is a graph showing the results of changes in viscosity over time of the water-in-oil emulsion composition according to Example 1.

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.

As used herein, unless otherwise defined, "substituted" means that one or more hydrogen atoms of the functional groups of the present invention are halogen (F, Cl, Br or I), hydroxy, nitro, imino (= NH, = NR, R Is an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine or hydrazone group, carboxyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted It may mean substituted with a heterocycloalkyl group having 2 to 30 ring carbon atoms.

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

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.

In the present specification, the average particle diameter of the emulsified particles means an average value of the diameters of the single particles. In the present specification, the average particle diameter range of the emulsified particles means that at least 95% of the emulsified particles present in the composition fall within the range.

In one aspect, the technology disclosed herein includes a first polymer spheroid and a second polymer spheroid, wherein the first polymer spheroid and the second polymer spheroid are at least partially infiltrating the relative polymer spheroid. In combination, the first polymeric spheroid has a core-shell structure and the shell provides a chemically asymmetric anisotropic powder comprising a functional group.

In the present specification, the spheroid is a body composed of a polymer, for example, may be a spherical body or an ellipsoid, and may have a long axis length of micro units or nano units based on the longest length in the body cross section.

According to an exemplary embodiment, the core of the first polymer spheroid and the second polymer steroid include a vinyl polymer, and the shell of the first polymer spheroid includes a copolymer of a vinyl monomer and a monomer including a functional group. can do.

According to an exemplary embodiment, the vinyl polymer may be a vinyl aromatic polymer, specifically, may be polystyrene.

According to one exemplary embodiment, the functional group may be a siloxane.

According to an exemplary embodiment, at least one of the first polymer spheroid and the second polymer spheroid may include an ionic vinyl polymer.

According to an exemplary embodiment, the ionic vinyl polymer may be a sodium 4-vinylbenzenesulfonate polymer.

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

In one embodiment, the shell of the first polymer spheroid may be further introduced with a hydrophilic functional group.

In one embodiment, the hydrophilic functional group may be a negative or positive charge 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.

The chemically asymmetric anisotropic powder having a geometrically dumbbell shape is capable of producing a stabilized water-in-oil emulsion composition due to its strong emulsification power. Chemically asymmetric anisotropic powders form large emulsion particles and physically harden the interface to produce larger emulsion particles compared to conventional W / O and W / S (silicon) formulations, enabling low viscosity and preventing unity. It is effective to prevent.

According to an exemplary embodiment, the chemically asymmetric anisotropic powder may be an asymmetric snowman shape or an asymmetric inverse snowman shape.

According to an exemplary embodiment, the chemically asymmetric anisotropic powder may have a particle size of 100 to 1500 nm. In another aspect, the chemically asymmetric anisotropic powder may have a particle size of 100 to 500 nm, or 200 to 300 nm. In this case, the particle size means the length of the longest portion of the chemically asymmetric anisotropic powder. Specifically, the chemically asymmetric 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 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 while being 1100 nm or more, 1200 nm or more, 1300 nm or more, or 1400 nm or more , 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 another aspect, the techniques disclosed herein provide a water-in-oil (W / O) emulsion composition containing the chemically asymmetric anisotropic powder.

According to one exemplary embodiment, the chemically asymmetric anisotropic powder may be contained 1 to 15% by weight based on the total weight of the water-in-oil emulsion composition. In another aspect, the chemically asymmetric anisotropic powder may be contained 0.5 to 5% by weight based on the total weight of the emulsion composition. Specifically, the chemically asymmetric anisotropic powder is at least 0.1% by weight, at least 0.5% by weight, at least 1% by weight, at least 2% by weight, at least 4% by weight, at least 6% by weight, at least 8% by weight, based on the total weight of the emulsion composition. 10 wt% or more or 12 wt% or more, but 15 wt% or less, 12 wt% or less, 10 wt% or less, 8 wt% or less, 6 wt% or less, 4 wt% or less, 2 wt% or less, 1 wt% or less Or 0.5 wt% or less. By adjusting the chemically asymmetric anisotropic powder content, the emulsified particle size can be adjusted from several μm to several tens or hundreds of μm.

According to an exemplary embodiment, the water-in-oil emulsion composition may include an alcohol. The chemically asymmetric anisotropic powder is dispersed in alcohol and then added together with the aqueous phase to prepare a water-in-oil emulsion composition. As the alcohol, lower alcohols having 1 to 4 carbon atoms, polyols or mixtures thereof can be used. By using lower alcohols, polyols or polyols having 1 to 4 carbon atoms, the freezing point of the water is lowered to prevent the phenomenon of freezing and thawing due to the formation of large emulsion particles, thereby improving stability.

The lower alcohol having 1 to 4 carbon atoms may be one or more selected from the group consisting of methanol, ethanol and butanol, and specifically, may be ethanol.

The polyol is a polyhydric alcohol, that is, an aliphatic compound having two or more hydroxyl groups (-OH), and having two hydroxyl groups is called glycol or diol, and has three hydroxyl groups. Four have pentaerythritol. Specifically, the polyol may be at least one selected from the group consisting of butylene glycol, propylene glycol, dipropylene glycol, erythritol, xylitol, sorbitol, polyethylene glycol, and isoprene glycol.

According to an exemplary embodiment, the water phase portion of the water-in-oil emulsion composition may include a salt. By containing a salt in the water phase part, it is possible to provide a stabilized water-in-oil emulsion composition by placing a chemically asymmetric anisotropic powder between water and oil and forming a stabilized interfacial film.

According to an exemplary embodiment, the salt may be at least one selected from the group consisting of sodium chloride, potassium chloride, lithium chloride, calcium chloride and magnesium chloride.

According to one exemplary embodiment, the salt is 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 based on the total weight of the water-in-oil emulsion composition. At least 0.7%, at least 0.7%, at least 0.8%, at least 0.9%, at least 1%, at least 2%, at least 3%, at least 4%, or at least 5%, and at most 10%, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, or 5 wt% or less. For example, the salt may be contained in an amount of 0.1 to 10% by weight based on the total weight of the emulsion composition. It is possible to maintain the freeze thaw stability of the composition formulation within the above range, it may be excellent skin stability without irritation.

According to an exemplary embodiment, the water-in-oil emulsion composition may be mixed in a ratio of 1 to 15: 50 to 80: 10 to 30 by weight of the chemically asymmetric anisotropic powder, oil phase and water phase.

According to an exemplary embodiment, the water-in-oil emulsion composition may have an emulsified particle of 2 to 200 ㎛ size. In another aspect, the water-in-oil emulsion composition may have a large emulsion particle of 10 to 100 μm, 10 to 50 μm, or 25 μm. Specifically, the water-in-oil emulsified emulsion composition is at least 2 μm, at least 5 μm, at least 10 μm, at least 15 μm, at least 20 μm, at least 25 μm, at least 30 μm, at least 40 μm, at least 50 μm, at least 80 μm, 100 200 µm or less, 180 µm or less, 150 µm or less, 130 µm or less, 100 µm or less, 80 µm or less, 50 µm or less, 40 µm or less, 30 µm or more, 130 µm or more, 150 µm or more or 180 µm or more Or less, 25 µm or less, 20 µm or less, 15 µm or less, 10 µm or less, or 5 µm or less.

The chemically asymmetric anisotropic powder has a different orientation to the interface to form a large emulsified particles, it is possible to implement a formulation with excellent feeling. While it was difficult to make stabilized large emulsion particles having a particle diameter of several tens of micrometers with conventional molecular-level surfactants, and the surface thickness of the surfactant was about several nm, the thickness of the interface film in the case of the chemically asymmetric anisotropic powder disclosed herein Is increased to about several hundred nm and the emulsion stability can be greatly improved as the stabilized interfacial film is formed due to the strong bonding between the powders.

According to one exemplary embodiment, the water-in-oil emulsion composition may have a low viscosity formulation of less than 10000 CPS. In the case of conventional W / O and W / S (silicon) formulations, most of them can be prepared with a formulation having a viscosity of more than 10000 CPS, and formulation stability also has problems at viscosity below that, while the water-in-oil emulsion composition is chemically asymmetric. By containing the anisotropic powder, not only have a low viscosity formulation of 1000 CPS or less, but also a stable emulsion formulation can be prepared.

According to an exemplary embodiment, the chemically asymmetric anisotropic powder may be added together with the aqueous phase to prepare an emulsion cosmetic composition.

In another aspect, the technology disclosed herein is a method for producing the chemically asymmetric anisotropic powder, comprising: (1) preparing a core of a first polymer spheroid by stirring a first monomer and a polymerization initiator; (2) preparing a core-shell structured first polymer spheroid coated by stirring the core of the prepared first polymer spheroid with a monomer monomer including a monomer functional group including a first monomer, a polymerization initiator, and a functional group Doing; And (3) preparing the anisotropic powder in which the second polymer spheroid is formed by stirring the prepared first polymer spheroid having a core-shell structure with a second monomer and a polymerization initiator. It provides a manufacturing method.

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 the cylindrical 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 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 reactor may be ceramic, glass, etc., the temperature at the time of 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.

According to one exemplary 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 initiator used in each step may be the same or different.

According to an exemplary embodiment, the vinyl monomer may be a vinyl aromatic monomer. The vinyl aromatic monomer may be substituted or unsubstituted styrene, and may be, for example, one or more selected from the group consisting of styrene, alphamethylstyrene, alphaethylstyrene, and paramethylstyrene.

According to one exemplary embodiment, the polymerization initiator may be a radical polymerization initiator, specifically, at least one of a peroxide-based and azo-based. Moreover, ammonium persulfate, sodium persulfate, potassium persulfate can also be used. The peroxide radical polymerization initiator is benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t- butyl hydroperoxide, o-chlorobenzoyl peroxide, o- methoxy benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and t-butylperoxyisobutyrate may be one or more selected from the group consisting of, the azo radical polymerization initiator is 2,2'- azobisisobutyronitrile, 2,2'-azobis (2-methylisobutyronitrile) and 2,2'-zobis (2,4-dimethylvaleronitrile).

According to an exemplary embodiment, in the step (1), the first monomer and the polymerization initiator may be mixed in a weight ratio of 100 to 250: 1.

In another aspect, in step (1), the first monomer, the polymerization initiator and the stabilizer may be added together to mix the first monomer, the polymerization initiator, and the stabilizer in a weight ratio of 100 to 250: 1: 1: 0.001 to 5. The powder size and shape are determined according to the first polymer spheroid size control in the initial step (1), and the first polymer spheroid size can be adjusted according to the reaction ratio of the first monomer, initiator and stabilizer. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.

According to an exemplary embodiment, 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 chemically anisotropic powder has a size of 200 to 250 nm, the ratio of the first monomer, the initiator and the stabilizer is 110 to 130: 1: 2 to 4, specifically 115 to 125: 1: 2 to 4, more specifically 120 It can be prepared from a first polymer spheroid of 1: 3.

In addition, when the chemically anisotropic powder has a size of 400 to 450 nm, the ratio of the first monomer, the initiator and the stabilizer is 225 to 240: 1: 1 to 3, specifically 230 to 235: 1: 1 to 3, more specifically 235: 1: 2 can be prepared from the first polymer spheroid.

In addition, when the chemically anisotropic powder has a size of 1100 to 1500 nm, the ratio of the first monomer, the initiator and the stabilizer is 110 to 130: 1: 0, specifically 115 to 125: 1: 0, more specifically 120: 1 : Can be prepared from a first polymer spheroid that is zero.

In addition, the chemically anisotropic powder in the form of an asymmetric snowman has a ratio of the first monomer, the initiator, and the stabilizer 100 to 140: 1: 8 to 12, specifically 110 to 130: 1: 9 to 11, and more specifically 120: 1: It may be prepared from the first polymer spheroid prepared at a reaction ratio of 10.

In addition, the chemically anisotropic powder in the form of an asymmetric inverse snowman has a ratio of the first monomer, the initiator and the stabilizer of 100 to 140: 1: 1 to 5, specifically 110 to 130: 1: 1 to 4, more specifically 120: 1. It can be prepared from the first polymer spheroid prepared at a reaction ratio of 3 :.

According to an exemplary embodiment, the monomer monomer including a monomer functional group including a functional group in the step (2) may be a compound containing a siloxane. Specifically it may be a siloxane-containing (meth) acrylate polymer, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, vinyltriethoxysilane and vinyltrimethoxysilane It may be one or more selected from the group consisting of.

According to an exemplary embodiment, in the step (2), the monomer monomer including the monomer functional group including the first monomer, the polymerization initiator and the functional group may be mixed in a weight ratio of 80 to 98: 0.2 to 0.8: 2 to 20. have. In another aspect, the monomer including a monomer functional group including the first monomer, a polymerization initiator, and a functional group may be mixed in a monomer ratio of 160 to 200: 1: 6 to 40 by weight. The degree of coating can be adjusted according to the reaction ratio, and then the shape of the chemically anisotropic powder is made according to the degree of coating. When reacting with the reaction 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.

According to an exemplary embodiment, in the step (3), the second monomer and the polymerization initiator may be mixed in a weight ratio of 200 to 250: 1.

In another aspect, in step (3), 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 200 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.

According to an exemplary embodiment, the second monomer content in the step (3) may be mixed to 40 to 100 parts by weight or 150 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% by weight of the weight of the first polymer spheroid of the core-shell structure, an asymmetrical snowman type powder is obtained, and when it is 100 to 150%, or 110 to 150%, a symmetrical shape The powder of is obtained, and when it is 150 to 300% or 160 to 300%, 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.

Attempts have been made to increase the interfacial activity by imparting interfacial activity to the spherical powder particles used in the conventional pickling. Examples include Janus spherical particles, but the geometrical limitations and the difficulty of uniform mass production make practical applications. This was not done. On the other hand, the method of producing the chemically anisotropic powder disclosed in the present specification does not use a cross-linking agent, there is no entanglement in production, the yield is high and uniform, and mass production is easier than 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.

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.

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.

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

Styrene as a monomer, sodium 4-vinylbenzenesulfonate as a stabilizer, and azobisisobutyronitrile (AIBN) as an initiator were mixed and reacted at 75 ° C. for 8 hours. . The reaction was stirred in a cylindrical reactor, which was 11 cm in diameter, 17 cm in height, glass, and was rotated at a speed of 200 rpm.

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

Styrene, TMSPA (3- (trimethoxysilyl) propylacrylate) as a monomer, and azobisisobutyronitrile (AIBN) as an initiator were mixed and reacted with the obtained polystyrene (PS) first polymer spherical particles. . The reaction was stirred in a cylindrical reactor.

Preparation Example 3 Preparation of Anisotropic Powder

Styrene as a monomer, sodium 4-vinylbenzenesulfonate as a stabilizer, and azobisisobutyronitrile as an initiator in a polystyrene-coreshell (PS-CS) aqueous dispersion solution obtained as a result of the reaction. (Azobisisobutyronitrile, AIBN) was mixed and heated to 75 ° C to proceed with the reaction. The reaction was stirred in a cylindrical reactor to obtain an amphipathic anisotropic powder.

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.

Examples and Comparative Examples.

The water-in-oil emulsion composition of Table 1 was prepared using the anisotropic powder prepared in Preparation Example 3.

(Unit: weight%)	Example 1	Example 2	Comparative Example 1
Silicone Cyclopentasiloxane	30	0	15
Oil Squalane	0	30	5
Inorganic thickener Disteardimonium Hectorite	0.2	0.2	0.5
OIL DIETHOXYETHYL SUCCINATE	2	2	0
Silicone Oil PCA Dimethicone	5	5	0
Purified water D.I.Water	to 100	to 100	to 100
Salt NaCl	2	2	One
Anisotropic Powder Dispersion (20% by Weight in ethanol)	15	15	0
Surfactants Cyclopentasiloxane * PEG-10 Dimethicone * Disteardimonium Hectorite	0	0	4
Surfactant PEG-10 Dimethicone	0	0	2
Surfactants Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone	0	0	0.5

Test Example 1. Comparison of Viscosity of Emulsifying Composition

In order to confirm the stability of the emulsion composition containing the anisotropic powder, about 1.5 g of the emulsion composition of Example 1 and the conventional emulsion composition of Comparative Example 1 were put on a black square plastic plate and placed at 45 degrees from the ground for 15 minutes. Hold to compare the viscosity. The results are shown in the photograph of FIG.

As shown in FIG. 1, Example 1, which is a W / O formulation containing anisotropic powder, is capable of implementing low viscosity by controlling the size of the emulsified particles and the viscosity of an external phase, unlike Comparative Example 1, which is a conventional W / O formulation. Could know. This is a viscosity that is difficult to implement due to emulsion stability in conventional water-in-oil formulations. On the contrary, in the case of the example composition, even if the emulsion particles meet each other, coalescence does not occur and thus a stable emulsion state may be maintained.

Test Example 2 Evaluation of Temperature Stability of Emulsifying Composition

The composition of Example 1 was stored at -15 ° C. to -25 ° C. for 2 months and kept at -20 ° C. or lower for at least 1 week. Stability was observed and the observed optical micrograph is shown in FIG. 2.

In addition, as shown in Figure 2, the water-in-oil emulsified emulsion composition is stored at room temperature (25 ℃) immediately after the manufacture (Fig. 2 (a)), as well as frozen for two months (Fig. 2 (b)) and frozen And when the thawing was repeated four times (Fig. 2 (c)) it showed stable emulsion particles.

Test Example 3 Evaluation of Stability of Emulsifying Composition Over Time

The viscosity change of the composition was measured using a Viscometer (LVDV-II + PRO, BROOKFIELD, USA) while maintaining the composition of Example 1 at 30 ° C. for 12 weeks, and the results are shown in FIG. 3.

In the results of FIG. 3, it can be seen that the composition viscosity converges to a constant viscosity without significant change over time, and thus excellent stability over time.

As described above, specific portions of the present disclosure have been described in detail, and for those skilled in the art, these specific techniques are merely preferred embodiments, and the scope of the present disclosure is not limited thereto. Will be obvious. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (17)

1. A first polymer spheroid and a second polymer spheroid,

   The first polymer spheroid and the second polymer spheroid are combined at least partially in a structure that penetrates the relative polymer spheroid,

   The first polymeric spheroid has a core-shell structure and the shell comprises a functional group, chemically asymmetric anisotropic powder.
2. The method of claim 1,

   The core and the second polymer steroid of the first polymer spheroid includes a vinyl polymer,

   The shell of the first polymer spheroid chemically asymmetric anisotropic powder, characterized in that it comprises a copolymer of a monomer containing a vinyl monomer and a functional group.
3. The method of claim 2,

   Chemically asymmetric anisotropic powder, characterized in that the vinyl polymer is polystyrene or polymethyl methacrylate.
4. The method of claim 1,

   Chemically asymmetric anisotropic powder, characterized in that the functional group is a siloxane.
5. The method of claim 1,

   The chemically asymmetric anisotropic powder is characterized in that the chemically asymmetrical snowman (symmetrical snowman) or asymmetrical inverse snowman shape.
6. A water-in-oil (W / O) emulsion composition containing the chemically asymmetric anisotropic powder according to any one of claims 1 to 5.
7. The method of claim 6,

   The chemically asymmetric anisotropic powder is water-in-oil (W / O) emulsion composition, characterized in that contained 1 to 15% by weight based on the total weight of the water-in-oil emulsion composition.
8. The method of claim 6,

   The water-in-oil emulsion composition is water-in-oil (W / O) emulsion composition, characterized in that it comprises an alcohol.
9. The method of claim 6,

   The water-in-oil emulsion composition, characterized in that the water phase portion of the water-in-oil emulsion composition.
10. The method of claim 9,

    The salt is a water-in-oil (W / O) emulsion composition, characterized in that at least one selected from the group consisting of sodium chloride, potassium chloride, lithium chloride, calcium chloride and magnesium chloride.
11. The method of claim 9,

    The salt is a water-in-oil emulsion composition, characterized in that containing 0.1 to 10% by weight based on the total weight of the water-in-oil emulsion composition.
12. The method of claim 6,

    The water-in-oil emulsion composition is a water-in-oil emulsion composition, characterized in that the chemically asymmetric anisotropic powder, oil phase portion and the water phase portion are mixed in a ratio of 1 to 15:50 to 80:10 to 30 by weight.
13. The method of claim 6,

    The water-in-oil emulsion composition is water-in-oil (W / O) emulsion composition, characterized in that it has an emulsion particles of 2 to 200 ㎛ size.
14. The method of claim 6,

    The water-in-oil emulsion composition is a water-in-oil emulsion composition, characterized in that it has a low viscosity formulation of less than 10000 CPS.
15. As a method for producing a chemically asymmetric anisotropic powder according to any one of claims 1 to 5,

    (1) stirring the first monomer and the polymerization initiator to prepare a core of the first polymer spheroid;

    (2) stirring the core of the prepared first polymer spheroid with a compound containing a first monomer, a polymerization initiator, and a siloxane to prepare a coated core-shell structured first polymer spheroid; And

    (3) preparing the anisotropic powder in which the second polymer spheroid is formed by stirring the first polymer spheroid having the prepared core-shell structure with a second monomer and a polymerization initiator. Way.
16. The method of claim 15,

    The method of producing a chemically asymmetric anisotropic powder, characterized in that in the step (1) the first monomer and the polymerization initiator are mixed in a weight ratio of 100 to 140: 1.
17. The method of claim 15,

    In the step (3), the second monomer content is prepared from 40 to 100 parts by weight or 150 to 300 parts by weight when the weight of the first polymer spheroid of the core-shell structure is 100 parts by weight. Way.

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