KR20190074787A - Development of core-shell microparticle - Google Patents

Abstract

In the present invention, microparticles in which an ultraviolet blocking agent and silica are hybridized are manufactured, and the microparticles are coated with a biocompatible polymer to manufacture composite microparticles. In addition to inherent characteristics of the ultraviolet blocking agent having a broad ultraviolet ray absorbing range, it is possible to provide the ultraviolet blocking agent with chemical stability and biocompatibility.

Description

Preparation of core-shell microparticles {Development of core-shell microparticle}

The present invention relates to a method for producing core-shell composite microparticles.

Generally, ultraviolet rays are classified into UV-C at a wavelength of 240 to 280 nm, UV-B at a wavelength of 280 to 320 nm, and UV-A at a wavelength of 320 to 400 nm, depending on the wavelength. UV-C passes through the ozone layer and disappears without reaching the surface. UV-B penetrates into the epidermis of the skin, causing erythema, freckles and edema. In addition, UV-A penetrates into the dermis of the skin, promoting skin cancer, wrinkles and melanin formation, and is known to cause skin aging and skin irritation.

Skin aging is closely related to increase of wrinkles, sagging and relaxation, and environmental factors such as physiological natural aging and exposure to ultraviolet rays are considered to cause such a phenomenon.

The ultraviolet rays emitted from the sunlight are a major cause of causing erythema, edema, freckles and skin cancer in the skin. Recently, many researches on various skin diseases caused by ultraviolet rays are actively conducted.

UV protection cosmetics is the fastest growth among the entire cosmetics market as a basic function in basic cosmetics and color cosmetics as well as single products.

In general, formulations of sunscreen cosmetics are oil-dispersed, i.e., water-in-oil (O / W) products, in which the aqueous system is a continuous phase. Therefore, these products have weak properties to sweat and water. UV cosmetic products are mainly used in environments where they are exposed to sweat and water, such as swimming, mountain climbing, skiing or bathing. Therefore, The effect can not be sufficiently exerted. In such an environment, tackiness may occur during coating several times, which may cause discomfort. In addition, conventional formulations have a short UV blocking effect, and when they are applied for more than 30 minutes after the application, the effect is less than 50%.

In order to solve such a problem, a technology relating to a cosmetic composition for protecting ultraviolet rays containing a mesoporous inorganic composite powder carrying a metal oxide in a pore and an organic UV-blocking agent is disclosed (Patent Document 1). However, the cosmetic composition for protecting ultraviolet rays containing the mesoporous inorganic composite powder carrying the metal oxide in the pores and the organic ultraviolet screening agent is characterized in that the pores of the mesoporous silica molecular sieve, which is substituted with a metal element such as titanium or zinc, Iron, or the like, which is yellow or red, and thus the skin is darkened, the skin defect cover effect is lowered, and the skin tone correction effect is reduced. In addition, the organic UV-blocking agent is merely mixed with the inorganic composite powder, causing skin troubles and skin allergies, and the sebum control effect is poor.

1. Korean Patent Publication No. 2008-0051830

The present invention relates to a process for preparing a microparticle in which a UV-blocking agent and silica are hybridized and coated with a biocompatible polymer to prepare a composite microparticle. In addition to the inherent characteristics of the UV-absorber having a broad ultraviolet absorption region, It is intended to give biocompatibility.

The present invention provides a method for producing microparticles comprising: preparing microparticles comprising an ultraviolet screening agent and silica; And

And forming a biocompatible polymer shell on the microparticles.

In addition, the present invention provides a cosmetic composition comprising the composite microparticles prepared by the production method.

In the present invention, microparticles in which an ultraviolet blocking agent and silica are hybridized are prepared and coated with a biocompatible polymer to prepare composite microparticles. In addition to the inherent characteristics of the ultraviolet screening agent having a broad ultraviolet ray absorbing region, the ultraviolet ray blocking agent can be given chemical stability and biocompatibility.

Particularly, the production process according to the present invention can easily and quickly produce core-shell particles containing two or more components, and can stably contain an active material, , Cosmetics, fragrance industry, and the like.

1 is a schematic view of a composite microparticle according to the present invention.
2 is a SEM (Scanning Electronic Microscope) photograph of the microparticles prepared in the step 1) of the present invention and the composite microparticles prepared in the step 3).

Hereinafter, the configuration of the present invention will be described in detail.

The present invention relates to a process for preparing microparticles comprising an ultraviolet screening agent and silica; And

And forming a biocompatible polymer shell on the microparticles.

In the present invention, microparticles in which an ultraviolet screening agent and silica are hybridized are prepared and then coated with a biocompatible polymer to prepare composite microparticles. In addition to the inherent characteristics of the ultraviolet screening agent having a wide ultraviolet ray absorbing region, And biocompatibility.

The first step in the present invention is the step of producing microparticles.

In the present invention, the microparticles can be prepared by emulsion polymerization of a mixture of an ultraviolet screening agent, a silica precursor and a surfactant.

The type of the ultraviolet screening agent is not particularly limited, and an organic ultraviolet screening agent generally used in the art can be used. Specifically, examples of the ultraviolet light blocking agent include bemotrizinol, avobenzone, p-aminobenzoic acid, benzophenone-9, bexophenome-3, Bis-triol, bis-triol, bis-triol, bis-triol, bis-triol, bis-ortho-triol, bis-ortho-triol, biso-ctrizole, 3- (4- methylbenzylidene) -camphor, cinoxate, diethylaminohydroxybenzoyl hexoyl benzoate, dioxybenzone, drometrizole trisiloxane, ecamsule, ethylhexyl triazone, homosalate, menthyl anthranilate, and the like. Octocrylene, octyl salicylate, iscotrizinol, isopentenyl-4-methoxycinnamate, octyl-dimethyl-p-amino Octyl-dimethyl-p-aminobenzoic acid, octyl-methine oxycinnamate, oxybenzone, polysilicone-15, and trolamine salicylate may be used.

In one embodiment of the present invention, bamotrigizinol may be used as a sunscreen. The bamotriginol has a relatively wide ultraviolet absorption region and has the advantage of absorbing and blocking the ultraviolet ray A and the ultraviolet ray B at the same time. In particular, when the bamotrigizinol absorbs ultraviolet rays, energy conversion that is released as heat harmless to the human body occurs, and the state returns to a state where the UV can be absorbed again. This reaction has an advantage that it is harmless to the human body because there is no chemical side reaction due to a very rapid reaction occurring in 10 ^-12 seconds.

In the present invention, the silica serves to stabilize the ultraviolet screening agent.

Sunscreen agents are unstable in their efficacy and therefore require a suitable carrier. In the present invention, silica which is chemically stable and thermally stable can be used for stabilizing the ultraviolet screening agent.

In one embodiment of the present invention, the silica is prepared from a silica precursor and the silica precursor is selected from the group consisting of tetramethylorthosilicate (TMOS), tetraethylortho silicate (TEOS), tetrapropylorthosilicate, tetraethylorthosilicate At least one selected from the group consisting of tetrabutylorthosilicate and trimethoxymethylsilane (TMOMS) can be used.

Also, in the present invention, a surfactant such as sodium dodecyl sulfate (SDS), cetrimonium bromide (CTAB), and polyvinylpyrrolidone (PVP) .

In one embodiment of the present invention, sodium dodecyl sulfate may be used as a surfactant. The sodium dodecyl sulfate is an amphipathic anionic surfactant containing a hydrophilic group and a hydrophilic group in the structure.

In the present invention, a reaction catalyst may be further used, and acetic acid may be used as the reaction catalyst.

In the present invention, emulsion polymerization for the production of microparticles can be carried out for 1 to 5 hours, for 2 to 3 hours. By the polymerization, the silica precursor is hydrolyzed, and condensation reaction is carried out, whereby microparticles in the form of (hybridized) the silica with an ultraviolet blocking agent contained therein can be produced.

Since the ultraviolet screening agent is dispersed evenly in the mixture, the ultraviolet screening agent is dispersed in the silica in the course of polymerizing the silica precursor into the silica, As shown in FIG.

In the present invention, it is possible to further include a step of separating the prepared microparticles after carrying out the reaction. Separation of the microparticles can be carried out using a filtering or centrifugal separator.

In one embodiment, the first step comprises dissolving the surfactant in distilled water to produce a 1 wt% surfactant solution; Stirring the solution with an ultraviolet screening agent; Adding a silica precursor and a catalyst, and then reacting for 2 hours; And recovering the prepared microspheres by a filtering or centrifugal method.

In the present invention, the second step is a step of preparing the composite microparticles. The composite microparticles can be prepared by forming a biocompatible polymer shell on the microparticles prepared in the first step.

In this step, a biocompatible polymer shell is formed on the microparticles, thereby improving the biocompatibility and imparting high applicability to the skin when applied to cosmetics. Further, the stability of the ultraviolet light source can be further improved.

In particular, when bemotriginol is used as an ultraviolet screening agent, there is concern that the blocking agent component may be released through the pores of the microparticles. Therefore, in the present invention, the above problem can be prevented by forming a shell.

In one embodiment, the composite microparticles can be prepared by emulsion polymerization of a microparticle, a biocompatible monomer, a cross-linker, and a surfactant mixture.

The formation of the polymer shell on the conventional silica particles was carried out by modifying the surface of silica with a silane coupling agent and then using a radical polymerization method. However, the method has a problem that the manufacturing time is long and the manufacturing process is complicated. In the present invention, a biocompatible polymer shell is formed on the microparticles through emulsion polymerization, thereby simplifying the manufacturing process and forming the shell more quickly.

In the present invention, the kind of the biocompatible monomer is not particularly limited, and at least one selected from the group consisting of methyl methacrylate, styrene and acrylonitrile can be used.

As the crosslinking agent, divinylbenzene may be used.

Also, at least one selected from the group consisting of sodium dodecyl sulfate (SDS) and polyvinyl alcohol (PVA) may be used as the surfactant.

In the present invention, a reaction initiator and a buffer may be additionally used to facilitate the reaction, and potassium sulfate and sodium hydrogencarbonate may be used as the reaction initiator and buffer, respectively.

The emulsion polymerization in the present invention can be carried out at 50 to 100 캜, or at 70 to 90 캜, for 8 to 24 hours, or for 10 to 15 hours.

In the present invention, it is possible to further include a step of separating the prepared composite microparticles after performing the reaction. Separation of the composite microparticles can be performed using a centrifuge.

The microparticles are stabilized in aqueous solution by electrostatic stabilization by a surfactant and negatively charged. The reaction is initiated by adding a biocompatible monomer, a buffer and a crosslinking agent, adding an initiator, stirring the mixture, and raising the temperature. Radicals are formed by the initiator, monomers are polymerized singly, and polymerization is formed with the polymer.

In one embodiment, the second step comprises dissolving the surfactant in distilled water to produce a 0.02% wt% surfactant solution; Adding microparticles in a powder state to a solution; Adding a buffer to the solution; Adding a biocompatible monomer to the solution; Adding a crosslinking agent to the solution; Adding the solution to a three-necked flask and stirring at 80 DEG C; And recovering the prepared microparticles by a centrifugal separation method.

In one embodiment, biocompatible monomers and cross-linking agents are stored in the presence of inhibitors as monomers and can therefore be purified and used through the column prior to application to the process.

The present invention also relates to composite microparticles prepared by the above-mentioned production method.

The composite microparticles have a core / shell structure, the core is a particle in which an ultraviolet blocking agent and silica are hybridized, and the shell includes a biocompatible polymer.

The present invention also relates to a cosmetic composition comprising the composite microparticles prepared by the above-mentioned production method.

The present invention will be described in more detail with reference to the following examples. It will be apparent to those skilled in the art, however, that the scope of the present invention is not limited to the following embodiments, and that various changes, modifications, and / or other applications may be made without departing from the spirit and scope of the invention, will be.

Example

Example  1. Composite microparticle manufacturing

Step 1: Preparation of microparticles comprising an ultraviolet screening agent and silica

0.6 g of bemotrizinol (Kolon Life Science) was added to a solution of 0.045 g of sodium dodecyl sulfate (TCI) in 4.5 g of distilled water and stirred. After 2-3 hours, 2.5 g of tetraethoxysilane (Sigma-Aldrich) and 15 g of acetic acid (JUNSEI) as a catalyst for hydrolysis and condensation reaction were added and stirred for 2 hours to form microparticles.

Thereafter, the formed microparticles were collected by filtration or centrifugal separation to prepare silica microparticles containing the ultraviolet blocking agent.

Step 2: Methyl methacrylate  And Divinylbenzene  refine

Potassium persulfate (Sigma-Aldrich), a initiator used in the formation of the shell, divinylbenzene (Sigma-Aldrich), and methyl methacrylate, which are crosslinking agents, were dissolved in a column (inhibitor remover disposable column, Sigma) Lt; / RTI >

Step 3: Preparation of composite microparticles

0.019 g of sodium dodecyl sulfate (TCI) and 100 g of distilled water were added to a three neck flask to prepare a solution.

In a three neck flask, 0.24 g of the microparticles obtained in the above step 1, sodium bicarbonate (Sigma-Aldrich) as a buffer, methyl methacrylate (Sigma) 4 g, and 0.16 g of divinylbenzene were put in order with stirring. Finally, 0.04 g of potassium sulfate was placed in a three-necked flask, and the temperature was adjusted to 80 DEG C, followed by initiating the emulsion polymerization reaction. The reaction was continued for 10 hours.

Thereafter, the prepared composite microparticles were collected by centrifugation.

2 is a SEM (Scanning Electronic Microscope) photograph of the microparticles (coating untreated) prepared in step 1) of the present invention and the composite microparticles (coated) prepared in step 3).

As shown in FIG. 2, the left photograph (coated untreated) is a microparticle in which an ultraviolet screening agent and silica are hybridized. The particle size is about 10 μm, which is suitable for application to cosmetics and has a smooth surface by silica . The photograph on the right side (coating treatment) shows that the biocompatible polymer shell was formed on the microparticles, and shells were formed on the smooth surface before forming the shell.

Claims (8)

Preparing microparticles comprising an ultraviolet screening agent and silica; And
And forming a biocompatible polymer shell on the microparticles.
The method according to claim 1,
The microparticles are prepared by emulsion polymerization of a mixture of an ultraviolet screening agent, a silica precursor and a surfactant.
3. The method of claim 2,
The ultraviolet light blocking agent may be selected from the group consisting of bemotrizinol, avobenzone, p-aminobenzoic acid, benzophenone-9, bexophenome-3, (4-methylbenzylidene) -camphor, cinoxate, diethylaminohydroxybenzoyl hexyl benzoate, di (4-methylbenzylidene) But are not limited to, dioxybenzone, drometrizole trisiloxane, ecamsule, ethylhexyl triazone, homosalate, menthyl anthranilate, octocrylene, octylacrylene, octyl salicylate, iscotrizinol, isopentenyl-4-methoxycinnamate, octyl-dimethyl-p-aminobenzoic acid, dimethyl-p-aminobenzoic acid, octyl-methoxycinnamate, Wherein the at least one compound is at least one selected from the group consisting of oxybenzone, polysilicone-15, and trollamine salicylate.
3. The method of claim 2,
The silica precursor may be selected from the group consisting of tetramethylorthosilicate (TMOS), tetraethylortho silicate (TEOS), tetrapropylorthosilicate, tetrabutylorthosilicate and trimethoxymethylsilane (TMOMS) ≪ RTI ID = 0.0 > 1, < / RTI >
The method according to claim 1,
A biocompatible polymer shell is prepared by emulsion polymerization of a mixture of microparticles, biocompatible monomers, crosslinking agents and surfactants.
6. The method of claim 5,
Wherein the biocompatible monomer comprises at least one selected from the group consisting of methyl methacrylate, styrene, and acrylonitrile.
6. The method of claim 5,
Wherein the cross-linking agent is divinylbenzene.
A cosmetic composition comprising the composite microparticles prepared by the manufacturing method according to claim 1.

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