KR102403135B1 - Organic-inorganic composite, manufacturing method thereof and cosmetic compositions using the same - Google Patents

Abstract

The organic-inorganic composite according to the present invention includes inorganic nanoparticles; and a polymer coating layer which is a polymer including a functional group capable of coordinating with the inorganic nanoparticles in a side branch and surrounds the inorganic nanoparticles. The organic-inorganic composite according to the present invention exhibits excellent dispersion stability and flowability in various media despite being contained in a high concentration, and thus can be widely used in various applications.

Description

Organic-inorganic composite, manufacturing method thereof, and cosmetic composition using same

The present invention relates to an organic-inorganic composite, and to an organic-inorganic composite having excellent dispersion stability and improved flowability even at high concentrations, a method for preparing the same, and a cosmetic composition using the same.

Nanopowders are being developed in various fields such as semiconductors, displays, machinery, automobiles, and household goods because they often have new or improved properties that could not be confirmed in existing micro-sized powders. Most of the surfaces of these nanopowders have high energy, and as they become unstable, oxidation tends to occur, and aggregation of particles easily occurs to reduce surface energy. Accordingly, not only the initial dispersion of the nano-powder is difficult, but also the re-agglomeration phenomenon occurs even after dispersion. Therefore, when dispersing at a high concentration in a solution, a rapid increase in viscosity (gelling) occurs, and phase separation occurs rapidly even after dispersion, so that 100% of the performance of the powder cannot be exhibited.

In the case of inorganic nanoparticles, which are one of the nanopowders, active oxygen (ROS) radicals generated by strong photocatalytic activity cause deterioration and oxidation of other raw materials in dispersed cosmetic, pharmaceutical, and food formulations, and cell membranes and cell nuclei. It is known to cause DNA damage, cancer, dementia, and aging by attacking

Since inorganic nanoparticles are not directly dispersed in a liquid phase in a solid state, they are provided in the form of a dispersion dispersed in a high concentration in a specific medium, and a certain amount of the high concentration dispersion is added to the liquid phase to be commercialized and used. However, inorganic nanoparticles typically have a high Hamaker constant and are very easily agglomerated in the dispersion. That is, inorganic nanoparticles easily agglomerate due to attraction between particles, making it difficult to disperse in a high concentration in a solvent, and when stored for a long period of time, agglomeration and phase separation occur in the formulation, making it difficult to apply them evenly to other surfaces.

In addition, due to the aggregation phenomenon of inorganic nanoparticles, when inorganic nanoparticles are dispersed at a high concentration, phase stability is very low, and gelation occurs due to a rapid increase in viscosity over time, and there is a limit to the concentration of inorganic nanoparticles used.

In order to solve this problem, various technologies such as a method of using a dispersion stabilizer together with inorganic nanoparticles or surface modification of chemically attaching functional groups to the surface of nanoparticles have been developed. Among these, the method using a dispersion stabilizer has the advantage that the process is relatively simple and the cost is low, but the usage of the dispersion stabilizer per unit volume inevitably increases in order to cover a very large surface area of the inorganic nanoparticles, This leads to the introduction of a larger volume of dispersant than the nanopowder, which has a disadvantage in that the ratio of the solid fraction of the nanopowder is significantly lowered.

KR 10-1648676 B1

The present invention relates to an organic-inorganic composite comprising inorganic nanoparticles, and an object of the present invention is to provide an organic-inorganic composite having excellent dispersion stability and improved flowability even at high concentration dispersion, a method for preparing the same, and a cosmetic composition using the same.

Another object of the present invention is to provide an organic-inorganic composite having UV blocking properties.

Another object of the present invention is to provide an organic-inorganic composite in which photocatalytic activity is suppressed.

Another object of the present invention is to provide an organic-inorganic composite dispersion having excellent flowability at a high concentration by eliminating strong cohesiveness of inorganic nanoparticles.

Another object of the present invention is to provide a cosmetic composition having excellent flowability while containing the organic-inorganic complex at a high concentration.

Another object of the present invention is to provide a cosmetic composition containing an organic-inorganic complex having suppressed photocatalytic activity while having a blocking effect of harmful visible light and ultraviolet light.

Another object of the present invention is to provide a method for producing an organic-inorganic composite capable of mass-producing the organic-inorganic composite in a short time through a low-cost, simple solution-phase batch-process.

The organic-inorganic composite according to the present invention includes inorganic nanoparticles; and a polymer coating layer that is a polymer including a functional group capable of coordinating with the inorganic nanoparticles in a side branch and surrounds the inorganic nanoparticles.

In the organic-inorganic composite according to an embodiment of the present invention, the polymer coating layer may include a polymer in which a monomer containing a functional group capable of coordinating with the inorganic nanoparticles is polymerized in-situ on the surface of the inorganic nanoparticles. can

In the organic-inorganic composite according to an embodiment of the present invention, the inorganic nanoparticles are titanium dioxide, zinc oxide, iron oxide, copper oxide, aluminum oxide, zirconium oxide, cerium oxide, barium oxide, cerium oxide, silica and composites thereof. One or more may be selected.

In the organic-inorganic composite according to an embodiment of the present invention, the average diameter of the inorganic nanoparticles may be 10 to 500 nm.

In the organic-inorganic composite according to an embodiment of the present invention, the polymer may include a repeating unit derived from an acrylic monomer including a functional group capable of coordinating.

In the organic-inorganic complex according to an embodiment of the present invention, the coordinating functional group may include a beta-ketoester functional group.

In the organic-inorganic composite according to an embodiment of the present invention, the polymer may include a repeating unit derived from a monomer represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ is hydrogen or an (C1-C4) alkyl group, L is (C1-C10) alkylene, -C(O)-NH-, -C(O)-O-, -O- and -NH-C(O)-O-, which is one or a combination of one or two divalent substituents selected from the group consisting of, R ₂ is a (C1-C6) alkyl group.

In the organic-inorganic composite according to an embodiment of the present invention, the polymer coating layer may be conformally coated on the surface of the inorganic nanoparticles to a thickness of 1 to 10 nm.

In the organic-inorganic composite according to an embodiment of the present invention, the organic-inorganic composite may have a photocatalytic activity represented by Equation 1 below.

[Equation 1]

Ac/Ao > 0.95

In Equation 1, Ao means absorbance measured at a reference wavelength after applying methylene blue to the organic-inorganic complex by applying ultrasonic waves and stirring to adsorb it to the organic-inorganic complex, and Ac is the organic-inorganic complex to which methylene blue is adsorbed. It means the absorbance measured at the reference wavelength after irradiating ultraviolet light of 254 nm for 1 hour.

In addition, the present invention provides a dispersion containing the above-described organic-inorganic complex and a medium.

In the dispersion according to an embodiment of the present invention, the organic-inorganic composite may be included in an amount of 40% by weight or more of the total weight of the dispersion and have flowability.

In the dispersion according to an embodiment of the present invention, the medium is an aqueous medium, and the surface of the organic-inorganic composite is negatively charged to be uniformly dispersed in the aqueous medium.

In addition, the present invention provides a cosmetic composition containing the above-described organic-inorganic complex.

The cosmetic composition according to an embodiment of the present invention may be a cosmetic composition for UV protection.

In the cosmetic composition according to an embodiment of the present invention, based on the total weight, 1 to 50% by weight of the organic-inorganic complex may be contained.

The method for preparing an organic-inorganic composite according to the present invention comprises the steps of (S1) dispersing inorganic nanoparticles in a polymerizable solution containing an acrylic monomer and a solvent including a coordinating functional group; (S2) coordinating the functional group of the acrylic monomer to the surface of the inorganic nanoparticles; and (S3) polymerizing the acrylic monomer to prepare a composite in which a polymer coating layer surrounding the inorganic nanoparticles is formed.

In the method of manufacturing an organic-inorganic composite according to an embodiment of the present invention, the polymerizable solution may contain 50 to 500 parts by weight of an acrylic monomer based on 100 parts by weight of the inorganic nanoparticles.

In the method of manufacturing an organic-inorganic composite according to an embodiment of the present invention, coordination may be accomplished by applying ultrasound.

The organic-inorganic composite according to the present invention includes a coating layer coated with a polymer (polymer) containing inorganic nanoparticles and a functional group capable of coordinating with the inorganic nanoparticles on the side branches, so that the polymer is strongly bonded to the inorganic nanoparticles and is very thin and uniform In the form of a single film, inorganic nanoparticles can be completely wrapped. Thereby, the organic-inorganic composite has the advantage of having excellent dispersion stability and flowability in various media, and can exhibit excellent flowability without gelling even in a high concentration aqueous dispersion.

The organic-inorganic composite according to the present invention has excellent dispersion stability and exhibits low viscosity even when dispersed in a high concentration in a liquid medium, so that it can be used for various purposes in various applications such as paints and composite materials.

In addition, according to one embodiment, when the inorganic nanoparticles are a material having photocatalytic activity, the polymer coating layer is coordinated with the inorganic nanoparticles, specifically, the inorganic components of the inorganic nanoparticles by the functional group of the side branch, and the inorganic nanoparticles are thin and without defects. Since it is completely wrapped in a uniform film form, the photocatalytic activity inherent in inorganic nanoparticles can be effectively suppressed.

The method for producing an organic-inorganic composite according to the present invention can produce an organic-inorganic composite having excellent dispersibility, and also, as it is based on a low-cost and simple solution-phase batch-process, the organic-inorganic composite can be prepared in a short time. It has the advantage of being able to mass-produce.

1 is an inorganic nanoparticle (FIG. 1 (a), (b)), an organic-inorganic composite prepared in Example 1 (FIG. 1 (c), (d)), an organic-inorganic composite prepared in Example 2 (FIG. 1 (e), (f)) and the organic-inorganic composite prepared in Example 3 (FIG. 1 (g), (h)) is a transmission scanning microscope image observed.
2 is a view showing the measurement of the polymer coating layer thickness (average thickness) of the organic-inorganic composite prepared according to an embodiment of the present invention.
3 is a view showing the results of Fourier transform integrative spectroscopic analysis of the organic-inorganic composite (solid line) and the monomer (dotted line) prepared according to an embodiment of the present invention.
4 is a view showing the photocatalytic activity inhibition test results of the organic-inorganic composite prepared according to an embodiment of the present invention.
5 is a diagram illustrating measurement of a particle size distribution change with time in an aqueous dispersion of an organic-inorganic composite prepared according to an embodiment of the present invention.
6 is an optical photograph observing the dispersibility of the organic-inorganic composite and inorganic nanoparticles prepared in Examples having similar zeta potential values.
7 is an optical photograph observing the dispersibility in the aqueous phase (FIG. 7(a)) and the oil phase (FIG. 7(b)) of the organic-inorganic composite prepared according to an embodiment of the present invention.
8 is an optical photograph of observing the color change of the organic-inorganic composite powder according to the thickness of the polymer coating layer in the organic-inorganic composite prepared according to an embodiment of the present invention.
9 is a diagram illustrating a diffuse reflectance spectrum of an organic-inorganic composite manufactured according to an embodiment of the present invention.
10 is a diagram illustrating measurement of changes in light transmittance and scattering intensity over time due to aggregation of particles in an aqueous dispersion of an organic-inorganic composite prepared according to an embodiment of the present invention.

Hereinafter, an organic-inorganic composite according to the present invention will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted. Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise. In this specification and the appended claims, the units used without special mention are based on weight, and in one example, the unit of % or ratio means weight % or weight ratio.

Hereinafter, the organic-inorganic composite according to the present invention will be described in detail. The organic-inorganic composite according to the present invention includes inorganic nanoparticles; and a polymer coating layer that is a polymer including a functional group capable of coordinating with the inorganic nanoparticles in a side branch and surrounds the inorganic nanoparticles. Hereinafter, the polymer coating layer is also referred to as a polymer film.

The organic-inorganic composite of the present invention is a polymer containing a functional group capable of coordinating with the inorganic nanoparticles as a side branch. As the inorganic nanoparticles are coated, the polymer is strongly bound to the inorganic nanoparticles and forms a thin and uniform film. can be completely covered. Accordingly, the organic-inorganic composite may have excellent dispersion stability and excellent flowability in various media.

Specifically, the polymer coating layer may be a polymer in which a monomer containing a functional group capable of coordinating with the inorganic nanoparticles is polymerized in-situ on the surface of the inorganic nanoparticles. As the coating layer of the organic-inorganic composite is formed by direct polymerization of the monomer coordinated with the inorganic nanoparticles on the surface of the inorganic nanoparticles, the coating layer is formed in the form of a thin, uniform film strongly chemically bonded to the entire surface of the inorganic nanoparticles. can A thin polymer film that is chemically bonded to the inorganic nanoparticles and completely covers the entire surface of the inorganic nanoparticles can significantly improve the dispersibility and flowability of the inorganic nanoparticles, and furthermore, it is possible to suppress the inherent catalytic ability of the inorganic nanoparticles.

In the organic-inorganic composite, inorganic nanoparticles are sufficient as long as they are conventionally used for the purpose in consideration of the specific use in the desired application field. For example, The inorganic nanoparticles may be oxides of metals or non-metals, and as a specific example, one of titanium dioxide, zinc oxide, iron oxide, copper oxide, aluminum oxide, zirconium oxide, cerium oxide, barium oxide, cerium oxide, silica, and complexes thereof The above may be selected, but is not limited thereto. As a practical example, When considering the use of UV protection in the cosmetic composition field, the inorganic nanoparticles may be titanium dioxide (TiO₂), zinc oxide, iron oxide, or a mixture thereof.

The size of the inorganic nanoparticles is also sufficient as long as it is a size commonly used for the purpose in consideration of the specific use in the intended application field. As is known, in the field of cosmetic compositions, the inorganic powder for UV protection is at the level of 10 to 200 nm, and the inorganic powder for pigments to scatter visible light and cover skin blemishes, freckles, erythema, blemishes, etc. is on the order of 200 to 400 nm. Accordingly, the average diameter of the inorganic nanoparticles may be 10 to 1000 nm, preferably 10 to 500 nm, more preferably 50 to 400 nm, 100 to 400 nm, or 150 to 350 nm, but must be limited thereto it is not going to be

The coordinating functional group included in the side branch of the polymer may be a beta-ketoester group. The functional group of the beta-ketoester group can not only coordinate with the inorganic component (inorganic atom) of the inorganic nanoparticles, but also does not require a chelating agent that helps to form a complex during bonding. That is, the beta-ketoester group can easily and stably coordinate with the inorganic component of the inorganic nanoparticles without the aid of a chelating agent.

To describe this in terms of a monomer, the monomer polymerized in-situ on the surface of the inorganic nanoparticles may be a monomer containing a beta-ketoester group as a functional group capable of coordinating with the inorganic nanoparticles. As the beta-ketoester group can be easily coordinated with the inorganic nanoparticles without the aid of a chelating agent, the organic monomer(s) can be co-coordinated and polymerized simultaneously and homogeneously on the surface of the inorganic nanoparticles. By such homogeneous and simultaneous bonding (binding to inorganic nanoparticles) and polymerization, an extremely thin film (polymer film) with a thickness of only 1 to 10 nm while completely covering the entire surface of the inorganic nanoparticles without defects can be formed. have.

Accordingly , the polymer coating layer may be a polymer film conformally coated on the surface of the inorganic nanoparticles to a thickness (average thickness) of 1 to 10 nm, specifically, 2 to 9 nm, more specifically, 3 to 8 nm. Such an integrity conformal coating film (polymer film) at the several nanometer level is very effective in suppressing unwanted optical properties of inorganic nanoparticles while greatly improving the flowability of inorganic nanoparticles. Furthermore, the color of the organic-inorganic composite can be controlled by the polymer coating layer having a thickness of 1 to 10 nm.

In detail, the monomer containing the beta-ketoester group is simultaneously and homogeneously coordinated with the organic monomer(s) on the surface of the inorganic nanoparticles and polymerized at the same time, so that the polymer film formed from the monomer completely covers the surface of the inorganic nanoparticles and has no defects. can be wrapped without At this time, “wrap without defects” means a state in which a firm interface between the inorganic nanoparticles and the polymer film (polymer coating layer) is formed in the entire surface area of the inorganic nanoparticles, and the firm interface is experimentally observed with a high magnification transmission electron microscope (HRTEM) of the polymer. This means that the interface between the membrane and the inorganic nanoparticles is observed as a continuous line (unbroken line), and it means that substantially the same interface is observed regardless of the high-magnification transmission electron microscope observation position. In addition, the entire surface area of the nanoparticles means the entire surface of one nanoparticle when the nanoparticles are not aggregated and exist alone, but form a grain boundary between nanoparticles, and when two or more nanoparticles are aggregated, the grain boundary is excluded. It may mean the entire surface area of the aggregate.

The monomer containing a beta-ketoester group may preferably be an acrylic monomer containing a beta-ketoester group. As the polymerizable group of the monomer is an acrylic group, various initiators and polymerization methods can be used without limitation, and a polymer film can be effectively formed through a simple and economical polymerization method.

More specifically, the monomer containing a beta-ketoester group may be represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is hydrogen or an alkyl group of (C1-C4), L is an alkylene of (C1-C10), -C(O)-NH-, -C(O)-O-, -O - and -NH-C(O)-O- is one or a combination of one or two divalent substituents selected from the group consisting of, R ₂ is a (C1-C6) alkyl group.

Specifically, when R ₁ in Formula 1 is an alkyl group of (C1-C4), it may be a (C1-C4) straight-chain or branched alkyl group, and may be, for example, methyl, ethyl, propyl, butyl, or the like. Likewise, R ₂ may also be a (C1-C4) straight-chain or branched alkyl group. In Formula 1, L is a divalent substituent, and (C1-C10) alkylene may be specifically (C1-C7) alkylene, and more specifically, (C1-C4) alkylene. Preferably, the alkylene of (C1-C10) may be combined with -C(O)-NH-, -C(O)-O-, -O- or -NH-C(O)-O- , illustratively -C(O)-O-(C1-C10) alkylene-, -C(O)-NH-(C1-C10) alkylene- or -NH-C(O)-O- (C1-C10) alkylene-.

As a specific example of a monomer containing a beta-ketoester group, 2-(acetoacetoxy)methyl methacrylate (2-(acetoacetoxy)2-(acetoacetoxy) methylmethacrylate), 2-(acetoacetoxy)ethyl acrylate (2-(acetoacetoxy)ethyl acrylate, 2-(acetoacetoxy)ethyl ethylacrylate), 2-(acetoacetoxy)ethyl methacrylate, etc. may be included, but more preferably 2-(acetoacetoxy)ethyl methacrylate (acetoacetoxy)ethyl methacrylate) (2-(acetoacetoxy)ethyl methacrylate, AAEMA).

As a non-limiting example, a comonomer may be further included with a monomer containing a beta-ketoester group, and the copolymer may be included in the polymer coating layer. The comonomer is not limited as long as it is a monomer capable of radical polymerization, and as an example, a vinyl aromatic monomer, a vinyl cyanide monomer, a hydroxyl group-containing acrylic monomer, or a carboxylic acid group-containing acrylic monomer may be exemplified.

As a polymer film containing a polymer including a coordinating functional group in a side branch wraps the inorganic nanoparticles in an extremely thin and uniform order of several nanometers without defects, even when the inorganic nanoparticles have photocatalytic activity, a photocatalyst as shown in Equation 1 below may exhibit inhibitory properties.

(Equation 1)

Ac/Ao > 0.95

In Equation 1, Ao means absorbance measured at a reference wavelength after applying methylene blue to the organic-inorganic complex by applying ultrasonic waves and stirring to adsorb it to the organic-inorganic complex, and Ac is the organic-inorganic complex to which methylene blue is adsorbed. It refers to the absorbance measured at the reference wavelength after irradiation with ultraviolet light for 1 hour. At this time, of course, the same amount of methylene blue can be adsorbed to the organic-inorganic composite not irradiated with ultraviolet rays and the organic-inorganic complex irradiated with ultraviolet rays, and the amount of methylene blue adsorbed depends on the absorbance graph according to the concentration of methylene blue. It is enough to keep it within the range. For example, the adsorption amount of methylene blue may be 5 to 100 ppm (weight ppm), substantially 20 ppm, but is not necessarily limited thereto. In addition, the range of the ultraviolet wavelength may be 100 nm to 400 nm, for example, may be 254 nm, but is not limited thereto. The reference wavelength may be a wavelength belonging to a band of 400 nm to 800 nm, and may be, for example, 664 nm, but is not limited thereto. Ultraviolet rays may be irradiated with 5 to 10 W, for example, 8 W, but is not limited thereto.

When irradiated with ultraviolet light, methylene blue may be decomposed by the photocatalytic action of the inorganic nanoparticles, and Ac/Ao approaches 1 as the photocatalytic ability of the inorganic nanoparticles is suppressed by the polymer film. As shown in Equation 1, the organic-inorganic composite according to an embodiment may have an extremely excellent photocatalytic inhibition ability to the extent that methylene blue is not substantially decomposed even when irradiated with ultraviolet light for up to 1 hour.

Titanium dioxide (anatase structure), etc. is mentioned as a representative inorganic substance with strong photocatalytic activity. According to Equation 1, even when the inorganic nanoparticles of the organic-inorganic composite are titanium dioxide nanoparticles according to one embodiment, the photocatalytic ability of titanium dioxide itself is substantially completely suppressed, and generation of harmful radicals due to photocatalytic activity can be prevented. means

In addition, as described above, as the thickness of the polymer coating layer is controlled in the range of 1 to 10 nm, the color of the organic-inorganic composite can be adjusted. In detail, the thickness of the polymer coating layer becomes thicker in the range of 1 to 10 nm, and the color of the organic-inorganic composite is based on the CIE 1976 L*a*b* color space, and the a* value is 0.5 to 0.5 to the a* value of the inorganic nanoparticles themselves. 3.5 can be increased, and the b* value can be increased from 2 to 15 in the b* value of the inorganic nanoparticles themselves.

When the inorganic nanoparticles of the organic-inorganic composite are conventional white oxide-based nanoparticles, the increase in the a* value and the increase in the b* value in the range of 0.5 to 3.5, the thickness of the polymer coating layer is controlled in the range of 1 to 10 nm, and , which means that the color of the organic-inorganic complex can be adjusted from off-white to dark apricot. This off-white to dark apricot color range is similar to that of Asian skin. Accordingly, the organic-inorganic complex can be used very effectively in a cosmetic composition that requires a pigment to express a skin color, and can be used as a substitute for a pigment in a cosmetic composition for sensitivity that does not use a pigment.

In addition, the present invention provides a dispersion comprising the organic-inorganic complex and a medium as described above.

The dispersion according to the present invention provides the technical advantage of having flowability despite the high solid content of the organic-inorganic complex in various media. When the organic-inorganic composite is included in a low content, the dispersion exhibits Newtonian fluid behavior, but when the organic-inorganic composite is included in a high content, it may exhibit pseudoplastic behavior.

The organic-inorganic composite may be included in 40 wt% or more of the total weight of the dispersion, specifically 50 wt% or more, and may be 70 wt% or less without limitation.

The medium may be an aqueous medium comprising water or an oily medium comprising oil.

Aqueous media include, but are not limited to, hydrophilic solvents. As a specific example, the hydrophilic solvent may be water, a polar protic solvent, a ketone-based solvent, or a combination thereof. The polar protic solvent may be an alcohol-based solvent or a glycol-based solvent, for example, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, or a combination thereof, but is limited thereto. do not receive Examples of the ketone-based solvent include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof.

Specific examples of the aqueous medium may include water, a mixed medium of water and ethanol, a mixed medium of water and ethylene glycol, or a mixed medium of water and butylene glycol.

In the case of oil, it may be an oil used in food, medical composition, or cosmetic composition, for example, hydrocarbon-based oil, ester-based oil, vegetable oil, or silicone-based oil, but this is only an example according to the field of application and is not limited thereto.

In general, in the case of a dispersion having a high solid content, gelation easily occurs, and thus exhibits the properties of a solid gel or paste without flow even when stress is applied. In particular, when inorganic nanoparticles with a high solid content are dispersed in a medium, gelation occurs more easily in an aqueous medium than in an oily medium, so a dispersion containing a high concentration of inorganic nanoparticles is a dispersion dispersed in an oily medium to inhibit gelation has been provided However, when inorganic nanoparticles are to be dispersed in an aqueous phase, the dispersion liquid dispersed in an oily medium has limitations in use, and thus, the development of a homogeneous and flowable high concentration inorganic nanoparticle dispersion in an aqueous medium has been continuously required. This is derived from the fact that most of the application fields of food, medical or cosmetic compositions are based on aqueous phase, but it was very difficult to implement a high-concentration aqueous dispersion. It was customary to include

However, the dispersion according to the present invention does not have gel properties even at high solids content, and as it exhibits a pseudoplastic behavior with flowability, it starts to flow when a stress is applied, and the resistance gradually decreases and flows. This has the advantage of being able to provide a base dispersion that can be mixed into compositions for a variety of applications.

According to the dispersion of the present invention, it has the characteristic of having excellent flowability even in an aqueous medium. According to an embodiment of the present invention, gelation does not occur even when the organic-inorganic composite in the aqueous medium accounts for 50% by weight of the total weight of the dispersion. In addition, the aqueous dispersion according to an embodiment shows dispersion stability as a homogeneous dispersion, has excellent flowability, and may have flowability even at a maximum of 70% by weight.

This is because the property of having a flowability of a dispersion containing inorganic nanoparticles having a high solid content is basically derived from the organic-inorganic composite according to the present invention, and the organic-inorganic composite has high dispersion stability without agglomeration in the medium.

The surface of the organic-inorganic composite may be negatively charged in the dispersion of the aqueous medium, and the surface potential basically depends on the polymer coating layer surrounding the inorganic nanoparticles, not depending on the properties of the inorganic nanoparticles. The beta-ketoester (β-ketoester) group of the polymer included in the polymer coating layer is negatively charged in an aqueous medium, and thus the surface potential of the organic-inorganic composite is negatively charged, so that it can have high dispersion stability in the dispersion. In this case, the surface potential may be defined as a zeta potential.

The surface potential of the aqueous dispersion of the organic-inorganic complex may be changed according to a change in pH. Even at weakly acidic pH, the surface potential has a negative value, but as the absolute value of the surface potential increases toward alkalinity, it has better dispersion stability and may be uniformly dispersed in an aqueous medium. Therefore, the organic-inorganic composite according to the present invention can have flowability while maintaining a low viscosity that could not be implemented in the past, despite the high concentration of inorganic nanoparticles in the liquid medium, so that cosmetics and pharmaceuticals, food, paints and composite materials It can have the advantage that it can be utilized in various application fields, such as a field.

In addition, the present invention provides a cosmetic composition comprising the organic-inorganic complex as described above. The cosmetic composition may be a single phase formulation, that is, an aqueous formulation or an oil phase formulation, or may be provided as an emulsion (emulsion) formulation. The emulsion formulation may be a water-in-oil (W/O) emulsion, an oil-in-water (O/W) emulsion, a water-in-oil-in-water (W/O/W) emulsion, or an oil-in-oil (O/W/O) emulsion formulation. .

In terms of products of the cosmetic composition, for example, lotion, nourishing cream, nourishing lotion, eye cream, essence, cleansing cream, cleansing lotion, pack, body lotion, body cream, body essence, makeup base, foundation, ointment, gel, It can be formulated as a cream, patch, etc.

The cosmetic composition may use ingredients commonly used in cosmetics without limitation, and may include, for example, an oil phase component, an aqueous phase component, a powder component, a surfactant, and the like, but is not limited thereto. In terms of ingredients included in addition to the organic-inorganic complex, specific examples include oils and fats, moisturizers, emollients, surfactants, organic pigments, inorganic pigments, organic powders, UV absorbers, preservatives, bactericides, antioxidants, plant extracts, pH adjusters, alcohol, colorants, fragrances, blood circulation promoters, cooling agents, limiting agents, purified water and the like may be mentioned, but these are only exemplary components, and thus are not limited thereto.

The organic-inorganic composite according to the present invention is included in the cosmetic composition, based on the total weight of the cosmetic composition, 0.1 to 70% by weight, specifically 1 to 50% by weight, more specifically 5 to 20% by weight of the organic-inorganic composite may include, but are not limited to. The organic-inorganic composite may be included in the form of a dispersion as described above, and may be included in the cosmetic composition by mixing a predetermined amount of the dispersion as a base.

Since the organic-inorganic composite according to the present invention has low viscosity and flowability in a medium, even if it is included in a cosmetic composition at a high concentration, it does not have a significant effect on the viscosity of the formulation, so there are few restrictions on the amount used. Furthermore, inorganic nanoparticles have a unique feeling of use of inorganic substances, but in the organic-inorganic composite according to the present invention, as the surface of the inorganic nanoparticles is completely and conformally coated with a polymer coating layer, the unique feeling of use of inorganic substances is not felt and spreadability and adhesion are excellent. It is excellent and it is desirable because the feeling of foreign substances due to friction is reduced.

The cosmetic composition according to an embodiment of the present invention may be a cosmetic composition for sunscreen, and as the organic-inorganic composite according to the present invention is included, it may be preferably used as a main component of the sunscreen.

For the analysis of the UV blocking effect of the UV blocking cosmetic composition, it may be measured using a UV transmittance analyzer. Specifically, the in vitro SPF can be measured according to the 'Ultraviolet blocking functional test method' among the 'Functional Cosmetics Standards and Test Methods' announced by the Ministry of Food and Drug Safety.

In addition, the present invention provides a method for economically and efficiently manufacturing an organic-inorganic composite.

Conventionally, in order to prepare an organic-inorganic composite by coating the surface of inorganic nanoparticles, the sol-gel method, CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition), which is a chemical treatment technique for the surface of nanoparticles, is combined with The same deposition technique or special polymerization technique such as ATRP (Atom Transfer Radical Polymerization) has been used. In the case of the sol-gel method, although the process itself is simple, a high sintering temperature is required at a high temperature, and cracks in the coating thin film occur during drying and curing, so that the coating film is not conformally formed on the particle surface. Due to the non-uniform coating film on the surface of the nanoparticles, the cohesive force of the particles itself cannot be completely suppressed, so it may be very difficult to prepare a high-concentration dispersion of inorganic nanoparticles.

On the other hand, CVD or ALD technology has the advantage that the thickness of the thin film can be precisely controlled and conformal coating is possible.

The ATRP method has the advantage of forming a uniform thin film by growing a polymer thin film using a specific initiator in the graft-from method, but the process is complicated and the density of the polymer present on the surface is reduced to a certain density. There may be a disadvantage that it is difficult to increase more than that.

On the other hand, the method for producing an organic-inorganic composite according to the present invention can form a coating layer on the inorganic nanoparticles very economically and efficiently through solution-phase polymerization, as well as coordinating monomers with high density on the surface of the inorganic particles, By subsequent polymerization, a polymer coating layer having a very high polymer density can be formed. The method for producing an organic-inorganic composite according to the present invention having the above characteristics includes the steps of (S1) dispersing inorganic nanoparticles in a polymerizable solution containing an acrylic monomer and a solvent including a functional group capable of coordinating; (S2) coordinating the functional group of the acrylic monomer to the surface of the inorganic nanoparticles; and (S3) polymerizing the acrylic monomer to prepare a composite in which a polymer coating layer surrounding the inorganic nanoparticles is formed.

Specifically, in the step (S1), the solvent is not limited as long as it can promote the formation of a coordination bond. Examples of the solvent may be a polar protic solvent, a non-polar solvent, or a mixed solvent thereof. For example, water, a glycol-based solvent, a glycol ether-based solvent, an alcohol-based solvent, a ketone-based solvent, an ester-based solvent, an amide-based solvent, sulfoxide It may be a seed or sulfone solvent, a phenolic solvent, or a mixed solvent thereof. In this case, the glycol-based solvent may include ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, polyethylene glycol, ethoxydiglycol, dipropylene glycol, or a combination thereof, and the glycol ether-based solvent is methyl glycol ether, ethyl glycol ether, isopropyl glycol ether, or a combination thereof, and the like, and the alcoholic solvent may include methanol, ethanol, n-propanol, isopropanol, butanol, or a combination thereof. , the ketone-based solvent may include acetone, methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof, and the ester-based solvent is ethyl acetate, butyl acetate, diethylene glycol ether acetate, methoxypropyl acetate, ethylene carbonate, It may include propylene carbonate or a combination thereof, and the amide-based solvent may include dimethylformamide, dimethylacetamide, dimethylcaprylic/capric fatty acid amide, N-alkylpyrrolidone, or a combination thereof. In addition, the sulfoxide or sulfone-based solvent may include dimethyl sulfoxide (DMSO) or sulfolane, and the phenolic solvent may include toluene, xylene, and the like, but is not limited thereto. As a specific example, the organic solvent may be toluene, but is not limited thereto.

The polymerizable solution may contain 50 to 500 parts by weight of an acrylic monomer based on 100 parts by weight of the inorganic nanoparticles, specifically, 100 to 300 parts by weight of an organic monomer.

The amount of the solvent may be 300 to 800 parts by weight, specifically 400 to 500 parts by weight, based on 100 parts by weight of the acrylic monomer, but is not limited thereto.

Energy may be applied to disperse the inorganic nanoparticles in the polymerizable solution, and stirring or ultrasonic waves may be applied. Preferably, ultrasound may be applied, but may be applied for 5 to 30 minutes, but is not limited thereto. In this case, the temperature may be performed at room temperature.

In step (S2), the coordinating functional group of the acrylic monomer is coordinated to the surface of the inorganic nanoparticles dispersed in the polymerizable solution. In order to promote coordination bonding, ultrasound may be preferably applied, and may be performed for 20 minutes to 360 minutes, and specifically may be performed for 30 minutes to 120 minutes. At this time, the temperature may be carried out at room temperature to suppress the polymerization reaction.

After the coordination of the inorganic nanoparticles and the acrylic monomer is completed, the method may further include, optionally, stirring the dispersion. The stirring may be performed at 100 rpm to 1000 rpm, and may be performed for 30 minutes to 240 minutes, but is not limited thereto. The gas atmosphere may be an inert atmosphere.

In step (S3), a polymer coating layer is formed on the surface of the inorganic nanoparticles through a polymerization reaction. Polymerization can be initiated through the introduction of an initiator.

As the initiator, any initiator capable of generating radicals may be used without limitation. Specifically, for example, it may be a peroxide-based initiator, an azo-based initiator, or an oxidation-reduction-based initiator. The peroxide-based initiator may be exemplarily benzoyl peroxide or siliconyl peroxide, the azo-based initiator may be azodiisobutyronitrile (AIBN), and the oxidation-reduction-based initiator may be ammonium persulfate or potassium It may be a persulfate, but it is not limited thereto as this is only an example. Since the polymerization reaction conditions according to each initiator are known, detailed description is omitted.

After completion of the polymerization reaction, separation and purification steps may be further included. For separation of the organic-inorganic complex, alcohol may be added to the solution in which step (S3) is completed, and the organic-inorganic complex may be separated by centrifugation under low temperature conditions. Specifically, the alcohol may be, for example, methanol or ethanol, may be carried out at a low temperature condition of 0 to 8 ℃, centrifugation may be performed under the condition of 4000 to 10,000 rpm. The separation step may be performed multiple times to obtain a purified organic-inorganic complex. The organic-inorganic composite obtained through centrifugation may optionally be obtained as a solid phase through drying and pulverization processes at room temperature.

Hereinafter, the present invention will be described in detail with reference to Examples, but these are for describing the present invention in more detail, and the scope of the present invention is not limited by the Examples below.

<Production of organic-inorganic complex>

AAEMA (2-(acetoacetoxy)ethyl methacrylate) as a monomer capable of coordination bonding and polymer polymerization was added to toluene and ultrasonic wave was applied for 15 minutes. Thereafter, titanium dioxide nanoparticles (average size 100 nm) were added to prepare a mixed solution by adding titanium dioxide nanoparticles (average size 100 nm) so that the weight ratio of AAEMA: titanium dioxide was 1:1, and then AAEMA was coordinated to the titanium dioxide surface by stirring while applying ultrasonic waves for 1 hour. . Then, after stirring the ultrasonically applied mixture at 500 rpm and injecting nitrogen gas for 1 hour, azodiisobutyronitrile (AIBN), a polymerization initiator, was added so that the weight ratio of AAEMA: polymerization initiator was 1:0.2. , and reacted at 80° C. for 18 hours with stirring at 500 rpm, to prepare an organic-inorganic composite of titanium dioxide nanoparticles coated with p-AAEMA (poly(2-(acetoacetoxy)ethyl methacrylate)). Ethanol was added to the reaction solution at room temperature, followed by centrifugation at 8000 rpm and 4 ° C. for 20 minutes three times to recover the prepared organic-inorganic composite, and the recovered organic-inorganic composite was dried and pulverized at room temperature. Hereinafter, the organic-inorganic composite prepared in Example 1 may be collectively referred to as T1A1.

An organic-inorganic composite was prepared in the same manner as in Example 1, except that titanium dioxide: AAEMA was mixed in a weight ratio of 1: 2. Hereinafter, the organic-inorganic composite prepared in Example 2 may be collectively referred to as T1A2.

An organic-inorganic composite was prepared in the same manner as in Example 1, except that titanium dioxide: AAEMA was mixed in a weight ratio of 1:3. Hereinafter, the organic-inorganic composite prepared in Example 3 may be collectively referred to as T1A3.

1 is a titanium dioxide nanoparticle before coating (FIGS. 1 (a), (b)), the organic-inorganic composite prepared in Example 1 (FIG. 1 (c), (d)), whether or not prepared in Example 2 It is a transmission scanning microscope image of the organic-inorganic composite (FIG. 1(g), (h)) prepared in Example 3 (FIG. 1(e), (f)) and the organic-inorganic composite. As a result of observation with a transmission scanning microscope, it can be seen that the polymer coating layer was formed with a uniform thickness of several nanometers, covering the entire surface of the nanoparticles without defects. In addition, even in the case of an extremely thin film of 1 nm level, it can be seen that a polymer coating layer surrounding the surface of the nanoparticles is formed in an intact continuous and uniform film form. In addition, it can be seen that even when nanoparticles are agglomerated forming grain boundaries with each other, a polymer coating layer is formed that completely seals even deep and sharp grooves created by aggregation without defects.

2 is a view showing the measurement of the polymer coating layer thickness (average thickness) of the organic-inorganic composites prepared in Examples 1 to 3 through transmission electron microscopy analysis. As can be seen from FIGS. 1 and 2 , it can be seen that the thickness of the film is controlled at the nm level by only controlling the amount of the monomer input compared to the inorganic nanoparticles.

3 is a view showing the results of Fourier transform integrative spectroscopy analysis of the surface (solid line) and AAEMA (dotted line) of the organic-inorganic composite (T1A3) prepared in Example 3; As can be seen in FIG. 3 , the double bond carbon of methacrylate was decreased on the surface of the prepared organic-inorganic composite, and it could be confirmed that the polymerization of AAEMA was made. Similarly, it can be confirmed that the beta-ketoester group is chemically bonded to titanium dioxide (titanium metal component) from the reduced peaks of the beta-ketoester groups of 1602 and 1509 cm ^-1 .

4 is a view showing the photocatalytic activity inhibition test result (T1A2 (anatase) of FIG. 3) of the organic-inorganic complex (T1A2) prepared in Example 2; During the photocatalytic activity inhibition test, ultrasonic waves were applied for 10 minutes to a mixture of 0.4 g of organic-inorganic complex and methylene blue to 20 ppm in 160 mL of distilled water, followed by stirring to adsorb methylene blue to the surface of the organic-inorganic complex, and then , UV (254 nm, 8 W) was continuously irradiated, and samples were collected at 15-minute intervals for up to 1 hour, and the collected samples were immediately centrifuged (12,000 rpm, 3 min) to measure absorbance (664 nm). At this time, the photocatalytic activity was evaluated by the ratio of the absorbance value (Ao) before UV irradiation and the absorbance value (Ac) according to the UV irradiation time. For comparison, methylin blue was adsorbed to titanium dioxide nanoparticles of anatase structure used as inorganic nanoparticles in Example 2 instead of organic-inorganic composites in the same manner and continuously irradiated with ultraviolet rays to induce photocatalytic activity of titanium dioxide (Non coating in FIG. 4 ). (anatase)) was evaluated as well.

As can be seen from FIG. 4 , in the case of uncoated titanium dioxide nanoparticles, it can be seen that about 8% of methylene blue was decomposed by the photocatalytic activity of titanium dioxide even when UV light was irradiated for only 15 minutes. However, in the case of the organic-inorganic composite prepared according to an embodiment of the present invention, the photocatalytic activity of titanium dioxide does not appear at all, so it can be seen that the absorbance of methylene blue is substantially the same as before ultraviolet irradiation even during continuous ultraviolet irradiation for 60 minutes. have. That is, it can be confirmed that the photocatalytic activity of the organic-inorganic composite prepared according to an embodiment of the present invention is completely suppressed close to 100% through FIG. 4 . The inhibition of photocatalytic activity up to 100% is possible because the polymer coating layer completely covers the surface of the inorganic nanoparticles without defects.

5 is a result of testing the dispersibility and dispersion stability of the organic-inorganic composites prepared in Examples 1 to 3, showing the particle size distribution and PDI (polydispersity index) analysis values according to time in the organic-inorganic composite aqueous dispersion to be. In the dispersion stability test, the organic-inorganic complex was dispersed in distilled water at 0.001 wt%, and the particle size distribution was measured after leaving it for 1 day, leaving it for 4 days, and leaving it for 7 days. In the superimposed particle size distribution graph, the black line indicates 1 day, the blue line indicates 4 days, and the red line indicates 7 days later. For comparison, the titanium dioxide nanoparticles having anatase structure used as inorganic nanoparticles in Examples instead of organic-inorganic composites were dispersed in distilled water to test dispersion stability in the same manner (Non coating in FIG. 5).

It can be seen that the uncoated titanium dioxide nanoparticles exhibit a polydispersion form, and the particle size change rate with time is large. However, it can be seen that Examples 1 to 3, T1A1, T1A2, and T1A3, each exhibit monodispersity, and little change in particle size distribution occurs even with time. This is a result proving that the aggregation of nanoparticles is suppressed and dispersion stability is improved by the polymer coating layer without defects.

The surface potential of the particles means the strength of the repulsive force between the particles, which is an indicator of dispersion stability. After dispersing the organic-inorganic complex (or titanium dioxide nanoparticles) at 0.0025 wt% in distilled water, the zeta potential was measured. As a result, at pH 10, the zeta potential of the titanium dioxide nanoparticles not coated with the polymer was -26.42 mV, the zeta potential of T1A1 was -37.82 mV, the zeta potential of T1A2 was -41.52 mV, and the zeta potential of T1A3 was - 45.37 mV. In addition, as a result of measuring the zeta potential by changing the pH for T1A1 prepared in Example 1, the zeta potential value was -4.81 mV at pH 4, -26.94 mV at pH 7, and -37.82 mV at pH 10.

Through the zeta potential measurement value, it can be seen that the organic-inorganic composite according to the present invention has a greater zeta potential than the inorganic nanoparticles, and thus has improved dispersibility and dispersion stability due to stronger interparticle repulsion. In addition, it can be seen that as the thickness of the coating layer increases, the surface potential increases as the dispersion medium approaches the base, resulting in improved dispersibility and dispersion stability.

These zeta potential measurement results prove that the organic-inorganic composite prepared according to an embodiment has improved dispersibility and dispersion stability by increasing the repulsive force between the organic-inorganic composites by the defect-free (integrity) and ionization of the polymer coating layer.

6 is an optical photograph observing the dispersibility of the organic-inorganic composite prepared in Examples and the dispersibility of titanium dioxide nanoparticles at similar zeta potential values. In detail, the optical photograph shown as non-coating in FIG. 6 is when titanium dioxide nanoparticles were mixed in distilled water at 50 wt% and pH was adjusted to 10, and T1A1 in FIG. 6 was 50 wt% in distilled water Example 1 This is a case where the organic-inorganic complex prepared in . was mixed and the pH was adjusted to 7.

In the previous zeta potential test, the zeta potential of titanium dioxide nanoparticles at pH 10 was -26.42 mV, and the T1A1 zeta potential at pH 7 was almost the same as -26.94 mV. This means that the titanium dioxide nanoparticles at pH 10 and T1A1 at pH 7 have almost the same surface charge state.

However, as can be seen from the results of FIG. 6 , despite having a similar zeta potential value, the titanium dioxide nanoparticles lost flowability due to gelation, but in the case of the organic-inorganic composite prepared according to an embodiment, smooth flowability can be seen to have Through this, it can be seen that the surface potential (ionization) can affect the dispersibility, but the integrity of the coating layer has a greater effect on the dispersibility than the surface potential (ionization).

Figure 7 is an aqueous phase (distilled water, Figure 7 (a)) and an oil phase (squalene, Figure 7 (b)), the organic-inorganic complex (T1A1) prepared according to an embodiment under a high concentration condition (50 wt%) dispersibility of is an optical photograph of the observation. For comparison, a photograph observing the dispersibility of titanium dioxide nanoparticles (Non coating, TiO ₂ ) without a polymer coating layer instead of an organic-inorganic composite is also shown.

As can be seen from FIG. 7 , the titanium dioxide nanoparticles do not have flowability due to gelation, but a coating layer of the thinnest thickness among the organic-inorganic composites prepared in Examples is formed, resulting in a relatively small (small absolute value) negative It can be seen that, despite T1A1 having a zeta potential, it has flowability in both the aqueous phase and the oil phase even at an extremely high content of 50 wt%.

8 is an optical photograph of observing the color change of the organic-inorganic composite powder according to the thickness of the polymer coating layer in the organic-inorganic composite prepared according to an embodiment, and for comparison, titanium dioxide nanoparticles without a polymer coating layer (Non coating) The color of the powder was also observed. Table 1 below is a summary of the colors measured according to the CIE 1976 L*a*b* color space of titanium dioxide nanoparticles, T1A1, T1A2, and T1A3 powder, respectively.

As can be seen in Figure 8 and Table 1, as the thickness of the polymer coating layer increases from 1 to 2 nm to 7 to 8 nm, the red and yellow darkens, and it can be seen that the color similar to the skin color of Asians is shown. .

In addition, as the thickness of the polymer coating layer becomes thicker, the color changes from light off-white to light apricot and dark apricot, indicating that it has a wide color spectrum, and the color of the organic-inorganic composite can be controlled only by controlling the thickness of the polymer coating layer. It can be seen that there is

This indicates that when the organic-inorganic composite according to the present invention is used, a desired color can be realized in a cosmetic composition without adding a separate pigment, and thus it can be very effectively applied to makeup products without a pigment.

The color change of the organic-inorganic composite powder according to the thickness of the polymer coating layer means that the visible light absorption (or reflection) characteristics of the organic-inorganic composite vary according to the thickness of the polymer coating layer.

9 is a view showing the diffuse reflectance spectra of Examples 1 to 3 and titanium dioxide nanoparticles (non coating) powder, respectively.

In the color change of FIG. 8, as the thickness of the polymer coating layer increases, red and yellow colors increase, so it can be predicted that the absorption rates of green light (520 to 570 nm) and blue light (380 to 500 nm) increase. .

The diffuse reflection spectrum of FIG. 9 corresponds to that predicted by this color change, and it was confirmed that as the thickness of the polymer coating layer increased, the light absorption in the vicinity of 380 nm to 500 nm increased significantly.

This blue light blocking ability indicates that the organic-inorganic composite according to the present invention can be very effectively applied to products for the purpose of blocking blue light, and furthermore, that it is a high-functional material capable of blocking UV light and blocking blue light at the same time. is to direct

10 is a view showing the water dispersion stability results of the organic-inorganic composite T1A1 aqueous dispersion prepared according to Example 1 of the present invention and the control (Non coating) aqueous dispersion without surface treatment.

An aqueous dispersion of organic-inorganic complex T1A1 containing 50% by weight and an aqueous dispersion of non-coating containing 50% by weight were dispersed in distilled water at 1% by weight, respectively, and stirred, and dispersion stability was measured for 24 hours. compared.

The dispersion stability was analyzed by Turbiscan. Specifically, the water-dispersed sample was analyzed by measuring transmittance (T) and back scattering (BS) intensity at a wavelength of 880 nm at one hour intervals for 24 hours at 25 °C. The measurement sample was shaken and stirred immediately before measurement and dispersed by applying ultrasonic waves for 3 minutes, and then transmittance and scattering intensity were measured. When aggregation of particles occurs over time in the particle dispersion phase, a change in the transmittance (T) of the sample appears, and a gradient of the scattering intensity is generated with respect to the height difference of the sample container due to sedimentation of the agglomerated particles.

Referring to FIG. 10 , the X axis means the height from the bottom to the upper layer of the sample container, and the left to right direction means the height direction from the bottom to the upper layer. 10 (a) is the dispersion stability measurement result of the control (Non-coating), the upper figure is the transmittance result, the lower figure is the scattering result. In each figure, blue indicates results measured at time 0, and red indicates results measured over time.

As can be seen in (a) of FIG. 10, the control group without surface treatment showed a large change in transmittance over time, and even in the scattering results, Mie scattering (particle size of 0.6 μm or more) increased in the entire region (global backscattering) appeared very quickly and clearly. This suggests that the dispersion stability of the control sample greatly decreased over time and aggregation phenomenon occurred significantly. In contrast, in the case of the organic-inorganic complex T1A1 aqueous dispersion, the transmittance was almost constant over time, and Mie scattering was observed gradually over time in the scattering results, but the overall dispersion stability of the sample was significantly higher than that of the control. showed

<Preparation of cosmetic composition of W/O emulsion formulation containing organic-inorganic complex>

As a specific application example of the complexes of Examples 1 to 3, formulations of cosmetic compositions were prepared according to Table 2 below. Formulation used a conventional method known in the cosmetic composition of the W / O emulsion formulation. In detail, according to the composition of Table 2, the oil phase component and the powder component were uniformly mixed at 75 °C, and separately, the aqueous phase component was uniformly mixed at 75 °C. Thereafter, while maintaining the temperature of 75 ℃ while stirring the aqueous phase component mixture, the mixture of the oil phase component and the powder component was added to prepare a W/O emulsion.

(Unit: % by weight) division ingredient Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Comparative Example 1 oily ingredients Butylene Glycol Dicaprylate/Dicaprate 6 6 6 6 Oily component triisononanoin 4 4 4 4 Oily component octyl methoxycinnamate 5 5 5 5 Oily component cyclopentasiloxane/cyclohexasiloxane 15 15 15 15 Oily component tridecyl trimellitate 3 3 3 3 Oil phase component dimethicone/vinyldimethicone crosspolymer/cyclopentasiloxane/cyclohexasilicone 2 2 2 2 Oily Ingredients Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 7.5 7.5 7.5 7.5 Oily component disteadimonium hectorite 1.1 1.1 1.1 1.1 Oily ingredient paraoxybenzoate ester appropriate amount appropriate amount appropriate amount appropriate amount Oil-based purified water To 100 To 100 To 100 To 100 award-winning ingredients butylene glycol 5.0 5.0 5.0 5.0 Aqueous ingredient disodium EDTA appropriate amount appropriate amount appropriate amount appropriate amount Award-winning TEA appropriate amount appropriate amount appropriate amount appropriate amount Aqueous ingredient imidazolidinyl urea appropriate amount appropriate amount appropriate amount appropriate amount powder component T1A1 5 - - - T1A2 - 5 - - T1A3 - - 5 - titanium dioxide nanoparticles - - - 5

<Preparation of cosmetic composition of face powder formulation containing organic-inorganic complex>

A cosmetic composition of a face powder formulation was prepared using a conventional method with the composition shown in Table 3 below. In detail, according to the composition of Table 3, the powder components were mixed with a Henschel mixer for 30 minutes, and the oily components were uniformly dissolved by heating to 80 °C. While mixing the powder components, the oily component lysate was added by spray spraying, mixed for 30 minutes, and pulverized and filtered with a grinder to prepare a powdery cosmetic composition.

(Unit: % by weight) division ingredient Formulation Example 4 Formulation Example 5 Formulation Example 6 Formulation Comparative Example 2 oily ingredients Polyglyceryl-2 triisostearate 4 4 4 4 Oily component dimethicone 5 5 5 5 Oily component polyoxyethylene hydrogenated castor oil 2 2 2 2 Oily ingredient paraoxybenzoate ester appropriate amount appropriate amount appropriate amount appropriate amount powder component Talc (dimethicone treatment) To 100 To 100 To 100 To 100 Powder mica (dimethicone treatment) 30 30 30 30 Powder component sericite (dimethicone treatment) 25 25 25 25 powdery silica 5 5 5 5 T1A1 5 - - - T1A2 - 5 - - T1A3 - - 5 - titanium dioxide nanoparticles - - - 5

<Evaluation of UV protection index>

The UV protection factor (in vistro SPF) of the formulations prepared in Example 4 was measured according to the “UV protection functional test method” among the “Functional Cosmetic Standards and Test Methods” announced by the Ministry of Food and Drug Safety. As for the measurement method, the sample was coated on a polymethylmethacrylate (PMMA; Polymethylmethacrylate) plate at a level of 2 mg/cm², dried for 15 minutes, and the UV-blocking effect was measured using a UV Transmittance Analyzer (Labsphere). The UV protection factor was measured repeatedly 5 times and was taken as an average value, and the results are shown in Table 4 below. As can be seen in Table 4, it was confirmed that Formulation Examples 1 to 3 containing the organic-inorganic composite prepared according to one embodiment had better UV blocking effect than Formulation Comparative Example 1 containing titanium dioxide nanoparticles. In addition, it can be seen that the thicker the polymer layer in Examples 1 to 3, the higher the UV blocking coefficient.

division Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Comparative Example 1 In vitro SPF 14.1 17.4 21.6 10.3 standard error 1.25 1.37 1.51 1.36

<Sensory evaluation>

In order to measure the feeling of use of the formulations prepared in Example 4, a blind test was conducted on 30 women aged 25 to 35, and evaluation of spreadability, adhesion, and particle agglomeration at the time of application was evaluated in Table 5 below. Sensory evaluation was carried out according to the standard, and the average value is shown in Table 6 below.

Sensory evaluation criteria Evaluation standard One very bad 2 bad 3 usually 4 Great 5 very good

Evaluation results division Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Comparative Example 1 spreadability 5 5 4 3 adhesion 4 4 4 3 particle agglomeration 5 4 4 2

As shown in Table 6, in the case of Formulation Comparative Example 1, the average score of about 2.7 points in spreadability, adhesion, and particle agglomeration was poor. On the other hand, in the case of Formulation Examples 1 to 3 containing the organic-inorganic complex prepared according to one embodiment, it was confirmed that the excellent results of about 4 points or more were averaged in all items.

<Frictional force evaluation>

Friction force during skin application was measured for the face powders prepared in Example 5. In the friction test, the same amount of face powder is put on the puff and applied on the artificial skin at a uniform speed of 540 mm/min, and the friction force in each section is measured (measurement device: SUN RHEOMETER CR500DS), and the results are shown in the table below. 7 is shown. In Table 7, in the case of Formulation Examples 4 to 6, which are face powders containing organic-inorganic complexes, frictional force was significantly reduced compared to Formulation Comparative Example 2 in all sections from the initial application to 5 cm. That is, it can be confirmed that the solid cosmetic composition containing the organic-inorganic complex also exhibits a very soft feeling and excellent spreadability.

(Unit of friction force measurement: N) division Formulation Example 4 Formulation Example 5 Formulation Example 6 Formulation Comparative Example 2 initial friction force 25.38 25.71 25.20 38.12 1 cm application 22.70 23.01 23.55 31.45 3 cm application 18.83 19.31 19.36 23.66 5 cm application 15.61 15.95 16.41 18.07

As described above, the present invention has been described with specific details and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims described below, but also all of the claims and all equivalents or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (18)

inorganic nanoparticles; and a polymer comprising a functional group capable of coordinating with the inorganic nanoparticles in a side branch, and a polymer coating layer surrounding the inorganic nanoparticles, wherein the polymer coating layer is conformally coated on the surface of the inorganic nanoparticles to a thickness of 1 to 10 nm organic-inorganic complex. The method of claim 1,
The polymer coating layer is an organic-inorganic composite in which a monomer containing a functional group capable of coordinating with the inorganic nanoparticles is polymerized in-situ on the surface of the inorganic nanoparticles. The method of claim 1,
The inorganic nanoparticles are organic-inorganic composites selected from titanium dioxide, zinc oxide, iron oxide, copper oxide, aluminum oxide, zirconium oxide, cerium oxide, barium oxide, cerium oxide, silica, and complexes thereof. The method of claim 1,
The inorganic nanoparticles have an average diameter of 10 to 500 nm. The method of claim 1,
The polymer is an organic-inorganic composite including a repeating unit derived from an acrylic monomer including a coordination-bondable functional group. The method of claim 1,
The coordinating functional group is a beta-ketoester (β-ketoester) group organic-inorganic complex. The method of claim 1,
The polymer is an organic-inorganic composite comprising a repeating unit derived from a monomer represented by the following formula (1).
[Formula 1]

(R ₁ is hydrogen or an alkyl group of (C1-C4), L is an alkylene of (C1-C10), -C(O)-NH-, -C(O)-O-, -O- and -NH -C(O)-O- is one or a combination of one or two divalent substituents selected from the group consisting of, R ₂ is a (C1-C6) alkyl group) delete According to claim 1,
The organic-inorganic composite is an organic-inorganic composite having a photocatalytic activity represented by the following formula (1).
[Equation 1]
Ac/Ao > 0.95
(Ao is the absorbance measured at the reference wavelength after applying methylene blue to the organic/inorganic complex with ultrasonic waves and stirring it to adsorb it to the organic/inorganic complex, and Ac is the methylene blue adsorbed organic/inorganic complex at 254 nm. It refers to the absorbance measured at the reference wavelength after irradiating ultraviolet light for 1 hour) 10. A dispersion comprising the organic-inorganic complex according to any one of claims 1 to 7 and 9 and a medium. 11. The method of claim 10,
The organic-inorganic composite is included in 40% by weight or more of the total weight of the dispersion and has flowability, the dispersion. 11. The method of claim 10,
The medium is an aqueous medium, and the surface of the organic-inorganic composite is negatively charged and uniformly dispersed in the aqueous medium. 10. A cosmetic composition containing the organic-inorganic complex according to any one of claims 1 to 7 and 9. 14. The method of claim 13
The cosmetic composition is a cosmetic composition for UV protection. 14. The method of claim 13
The cosmetic composition is a cosmetic composition containing an organic-inorganic complex in an amount of 1 to 50% by weight, based on the total weight of inorganic substances in the composition. (S1) dispersing the inorganic nanoparticles in a polymerizable solution containing an acrylic monomer and a solvent including a coordinating functional group;
(S2) coordinating the functional group of the acrylic monomer to the surface of the inorganic nanoparticles; and
(S3) polymerizing the acrylic monomer to prepare a composite in which a polymer coating layer surrounding the inorganic nanoparticles is formed;
The polymer coating layer is a method of manufacturing an organic-inorganic composite conformally coated on the surface of the inorganic nanoparticles to a thickness of 1 to 10 nm. 17. The method of claim 16,
The polymerizable solution is a method for producing a composite comprising 50 to 500 parts by weight of an acrylic monomer based on 100 parts by weight of the inorganic nanoparticles. 17. The method of claim 16,
The coordination bond is a method for producing a complex made by applying ultrasonic waves.

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