KR20180024903A - Stably-suspended polymer composite nanoparticles containing organic sunscreen agents and preparing method thereof - Google Patents

Abstract

The present invention relates to a polymeric nanocomposite particle in which an organic ultraviolet (UV) blocking agent is dispersed and stabilized, and a production method thereof. The polymeric nanocomposite particles not only greatly increase dispersion stability of particles themselves but also have the size of 10 to 10000 nm, so that small size particles are evenly dispersed when applied to cosmetic formulations, thereby improving usability. By allowing UV blocking components (the UV blocking agent) to stay in an amorphous state rather than in a crystalline state, it is possible to remarkably increase UV blocking effects. By encapsulating the same with a polymer, it is possible to prevent skin irritation by suppressing penetration of the UV blocking agent directly to the skin when applied to the skin.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer nanocomposite particle dispersion stabilized with an organic UV blocking agent and a method for preparing the same,

The present invention relates to a polymer nanocomposite particle in which an organic ultraviolet blocking agent is dispersed and stabilized, and a method for producing the same.

As the amount of ultraviolet rays emitted from the surface of the ozone layer is steadily increasing, the market for UV-blocking products is growing every year. Organic sunscreen agents absorb ultraviolet rays and prevent ultraviolet rays from penetrating into skin. Most organic sunscreen agents are hardly dissolved in water, so it is difficult to disperse evenly in cosmetic formulations. have. In addition, if an ultraviolet screening agent is dispersed using a solvent such as oil to effectively block ultraviolet rays, skin irritation may be caused by skin absorption of a partially dissolved ultraviolet screening agent.

As a method for improving this point, raw materials using polymers such as PMMA (poly (methyl methacrylate)) to be used in various ultraviolet screening agents and water-based materials are also used, but generally, ultraviolet shielding raw materials are precipitated, there is a problem.

In addition, a patent has been filed for a polymer nanocomposite particle containing a UV blocking agent and a method for producing the same (Patent Document 1). However, since a UV blocking agent is directly bonded to a polymer by a method of producing a particle containing an ultraviolet blocking agent while polymerizing a monomer, So that the ultraviolet ray shielding effect as much as desired can not be exhibited.

Accordingly, it is required to develop an ultraviolet shielding high-efficacy particle having an excellent feeling in use when applied to cosmetics while being able to use the organic ultraviolet screening agent stably and efficiently.

Korean Patent Application No. 10-2013-0152001

Accordingly, the present inventors have made efforts to improve the above problems. As a result, the present inventors have found that an organic UV blocking agent, which is highly restricted in use, is encapsulated into amorphous nanoparticles by using an amphiphilic block copolymer (i.e., The present invention has been completed by developing a polymer nanocomposite particle which can minimize the irritation to the skin and improve the dispersibility and can be stably used, can be remarkably improved in application feeling when applied to cosmetics, and has excellent ultraviolet shielding effect .

Accordingly, an object of the present invention is to provide a polymer nanocomposite particle comprising an organic UV blocking agent, an amphiphilic block copolymer, and a hydrophobic core-forming polymer, and a method for producing the same.

Another object of the present invention is to provide a cosmetic composition for UV-screening which comprises the polymer nanocomposite particles as an active ingredient.

In order to solve the above problems, the present invention provides a polymer nanocomposite particle comprising an organic UV blocking agent, an amphiphilic block copolymer, and a hydrophobic core-forming polymer.

More specifically, the present invention relates to a polymer nanocomposite particle in which an organic UV blocking agent is encapsulated amorphously by an amphiphilic block copolymer and a hydrophobic core-forming polymer.

The organic UV-blocking agents that can be used in the present invention include bemotrizinol, derivatives thereof, bisoctrizole, derivatives thereof, ethyl hexyl triazone, derivatives thereof, iscotrizinol ), A derivative thereof, a p-aminobenzoic acid (PABA) derivative, a cinnamate derivative, a salicylic acid derivative, benzophenones, dibenzole methane and anthranilates And may preferably comprise at least one member selected from the group consisting of bemotrizinol and derivatives thereof.

When the polymer nanocomposite particles according to the present invention (particles encapsulated with an organic ultraviolet screening agent) are impregnated into a cosmetic and applied to the skin, the dispersibility of the particles encapsulated with the organic ultraviolet screening agent is improved and the effect is improved The sunscreen absorbs the ultraviolet light and the particle has the effect of reflecting the ultraviolet rays, so that it can effectively shield the ultraviolet rays.

In particular, in the polymer nanocomposite particle according to the present invention, the polymer surrounding the organic UV blocking agent must be in an amorphous state, and in order to form the polymer, the hydrophobic core-forming polymer and the amphiphilic block copolymer for improving dispersibility may be used together . The hydrophobic part of the amphiphilic block copolymer and the ultraviolet screening agent (drug) are stabilized by hydrophobic interaction, and the hydrophobic core-forming polymer plays a role of strengthening and stabilizing the hydrophobic bond in the core part.

The term "amorphous state" as used in the present invention means a state in which a drug (organic sunscreen agent) is physically and uniformly dispersed in a hydrophobic core-forming polymer and an amphiphilic block copolymer

In the present invention, the material forming the particles together with the ultraviolet screening agent should be stably trapped so that the organic ultraviolet screening agent component does not precipitate in the process of making the particles (encapsulation).

The hydrophobic core-forming polymer can be used without limitation as long as it is a polymer capable of forming a hydrophobic core. Examples of the hydrophobic core-forming polymer include polycaprolactone, poly (lactide), poly (glycolide), poly (lactide-co-glycolide) , Biodegradable polymers such as polyanhydrides, polyorthoesters, polyether esters, polyester amides, poly (butyric acid), poly (valeric acid), polyurethanes, or copolymers thereof; And polyolefins such as polyacrylates, ethylene-vinyl acetate polymers, acrylic substituted cellulose acetates, non-degradable polyurethanes, polystyrenes, polyvinyl chlorides, polyvinyl fluorides, poly (vinylimidazoles), chlorosulphonate polyolefins, Non-biodegradable polymers such as polyethylene oxide and copolymers thereof may be used alone or in combination.

The hydrophobic core-forming polymer may be used in an amount of 50 to 1000 parts by weight, 50 to 500 parts by weight, or 60 to 300 parts by weight based on 100 parts by weight of the organic UV blocking agent. If the content is less than 50 parts by weight, there is a problem that the ultraviolet screening agent can not be efficiently encapsulated. If the content exceeds 1000 parts by weight, crystallinity increases and particles may be precipitated and physical properties may deteriorate.

Also, as the amphiphilic block copolymer, methoxy poly (ethyleneglycol) -b-poly (caprolactone), mPEG-PCL), methoxy poly (ethylene glycol) -b-poly (ethyleneglycol) -b-poly (D, L-lactide), methoxypoly (ethylene glycol) -b-poly (L-lactide) (ethylene glycol) -b-poly (ethyleneglycol) -b-poly (lactic-co-glycolic acid) methoxy poly (ethyleneglycol) -b-poly (caprolactone) -b-methoxy poly (ethylene glycol) -b-poly (ethyleneglycol) ), Methoxy poly (ethylene glycol) -b-poly (D, L-lactide) -b-methoxy poly (ethyleneglycol) methoxypoly (ethyleneglycol), methoxypoly (ethylene glycol) -b-poly (L-lactide) -b-methoxypoly b-poly (ethyleneglycol) -b-poly (L-lactide) -b-methoxy poly (ethyleneglycol)) and methoxypoly (ethylene glycol) At least one block copolymer selected from the group consisting of methoxy poly (ethyleneglycol) -b-poly (lactic-co-glycolic acid) -b-methoxy poly (ethyleneglycol) no.

The amphiphilic block copolymer is preferably used in an amount of 50 to 1000 parts by weight, 50 to 500 parts by weight, or 60 to 300 parts by weight based on 100 parts by weight of the organic UV blocking agent. If the content is less than 50 parts by weight, the dispersibility of the particles may be poor. If the content is more than 1,000 parts by weight, there is a problem that the physical properties such as viscosity and phase separation may deteriorate.

In the present invention, the hydrophobic core-forming polymer may be polycaprolactone, poly (lactide), poly (glycolide), poly (lactide), or the like in consideration of the stable incorporation of the organic ultraviolet screening agent and the dispersibility in the formulation. And poly (lactide-co-glycolide), and the amphiphilic block copolymer may be mono-methoxypolyethylene glycol-polycaprolactone (MPEG-PCL).

In addition, the particles according to the present invention may further include a dispersion stabilizer, a surfactant, a preservative, an anti-inflammatory agent, etc. in addition to the above-mentioned components (polymer) for forming an organic ultraviolet screening agent and particles.

The average diameter of the polymer nanocomposite particles according to the present invention is 10 to 10,000 nm, 20 to 5,000 nm, 30 to 2,000 nm, or 50 to 1,000 nm. When the particle size is more than 10,000 nm, there is a problem that the dispersibility is reduced and the feeling of use is deteriorated when applied to cosmetic formulations.

The present invention also relates to a process for preparing nanoparticles of nanoparticles comprising the steps of: preparing a particle by applying a solvent evaporation method, and mixing an organic UV-ray blocking agent, an amphiphilic block copolymer, and a hydrophobic core-forming polymer; ≪ / RTI >

The method for preparing a polymer nanocomposite particle according to the present invention includes a first step of mixing a mixed solution of a hydrophobic core-forming polymer and an amphiphilic block copolymer and an organic UV blocking agent,

A second step of gradually introducing the mixed solution of the first step into an aqueous solution containing a dispersion stabilizer, and

And a third step of removing the solvent.

The mixed solution of the first step is prepared by mixing a hydrophobic core-forming polymer, an amphiphilic block copolymer and an organic solvent.

All of the above-mentioned contents relating to the polymer nanocomposite particles can be directly applied or applied to the production method of the polymer nanocomposite particles.

The organic solvent dissolves the polymer (amphiphilic block copolymer and the hydrophobic core-forming polymer) and the drug (sunscreen agent), and specifically includes methylene chloride, ethyl acetate, ethyl alcohol, isopropyl formate, isopropyl alcohol, and acetone. However, the present invention is not limited thereto. In addition, the amount thereof is preferably 200 to 2000 parts by weight based on 100 parts by weight of the ultraviolet screening agent. When the amount is less than 200 parts by weight, it is difficult to completely dissolve the polymer and the drug. When the amount is more than 2000 parts by weight, it is difficult to remove the solvent, which is inefficient.

The aqueous solution refers to a solution containing a dispersion stabilizer and purified water. Specific examples of the dispersion stabilizer include a water-soluble polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, and a cellulose derivative such as hydroxypropyl methylcellulose. But is not limited thereto. The amount of the aqueous solution containing the dispersion stabilizer is preferably 150 to 5000 parts by weight per 100 parts by weight of the ultraviolet screening agent. When the amount is less than 150 parts by weight, particles are difficult to be dispersed. When the amount is more than 2000 parts by weight, there is a problem that the content of the drug is too small.

In addition, the present invention provides a cosmetic composition for protecting ultraviolet rays comprising the polymer nanocomposite particles as an active ingredient.

The ultraviolet barrier cosmetic material according to the present invention preferably contains the polymer nanocomposite particles in an amount of 0.1 to 20 wt%, more preferably 1 to 10 wt%, based on the total weight of the cosmetic.

Meanwhile, the cosmetic composition according to the present invention can be manufactured in various formulations for cosmetics, make-up and hair products such as cosmetics, creams, powders, foundations, make-up bases and shampoos, A cream, a paste, a powder, a solid, or the like, and a conventional method for producing a cosmetic composition can be used. Particularly, the above-mentioned cosmetic composition is more preferably used for ultraviolet shielding of skin.

The cosmetic composition of the present invention may contain, in addition to the above polymer nanocomposite particles and other ultraviolet screening agents, a moisturizing agent, a thickener, a surfactant, a fatty base, a preservative, an antioxidant, an alcohol, Etc. may be further mixed.

The polymer nanocomposite particle according to the present invention is encapsulated with an organic UV-blocking agent, which is highly restricted in use, by using a hydrophobic core-forming polymer and an amphiphilic block copolymer to minimize irritation to the skin and improve dispersibility, In particular, when applied to a cosmetic composition, the feeling of use is remarkably improved and the ultraviolet ray shielding effect is excellent.

FIG. 1 is a schematic diagram of Example 1 and Comparative Example 1. FIG.
FIG. 2 is a graph showing the DSC curve of the polymer nanocomposite particle blend prepared in Preparation Example 1 and the drug bemotrizinol.
3 is a microscope image of the cream containing polymer nanocomposite particles containing the ultraviolet screening agent prepared according to Example 1 of the present invention and the cream containing the ultraviolet screening agent prepared according to Comparative Example 1. Fig.

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

Manufacturing example  One: bemotrizinol  Of polymer nanocomposite particles

15 parts by weight of an amphiphilic block copolymer methoxy poly (ethylene glycol) -b-poly (caprolactone), mPEG-PCL, 5k-5k) and 15 parts by weight of polycaprolactone (ethylene glycol) polycaprolactone) in 60 parts by weight of methylene chloride was added 20 parts by weight of bemotrizinol as an ultraviolet blocking component. 0.2 part by weight of polyvinyl alcohol, 1 part by weight of 1,2-hexanediol and 48.8 parts by weight of purified water was added dropwise with stirring at 700 rpm while stirring the solution dropwise. The solvent was left to stir for 24 hours at 700 rpm to evaporate the methylene chloride solvent. The remaining solvent was removed using a rotary evaporator to prepare a blend containing the polymer nanocomposite particles so that the bemotrizinol content was 20% by weight (See Figs. 1 and 2).

Analysis by liquid chromatography revealed that the content of bemotrizinol was 20 wt%, and the average size of the particles was 600 nm by a laser light scattering (LLS) method (Malvern Zetasizer 2000 ^TM ).

FIG. 2 is a graph showing DSC curves of the polymer nanocomposite particle mixture prepared in Production Example 1 and the drug bemotrizinol (second heating run, heating rate: 10 ° C./min). This result shows that the drug has a sharp melting point peak because it is in the crystalline state when the drug is in the state of drug, and that the drug - impregnated particle is amorphous and the peak is almost flat.

Comparative Example  1 and Example  1: o / w emulsion  UV protection Cosmetics  Produce

An oil in water formulation containing bemotrizinol, an organic sunscreen, was prepared according to the preparation method of a conventional emulsion cosmetic by the ingredients and contents of Table 1 below.

ingredient Example 1 Comparative Example 1 Cetyl hexanoate 2.5 2.5 VEPI / Eikosenkopolymer 0.2 0.2 Cetearyl alcohol 2.0 2.0 Glyceryl stearate 1.5 1.5 Cyclopentasiloxane 4.0 4.0 Magnesium aluminum silicate 0.5 0.5 To a solution of < RTI ID = 0.0 & 7.0 7.0 Potassium cetyl phosphate 2.0 2.0 Acrylate / C10-30 alkyl acrylate crosspolymer 0.2 0.2 Tromethamine 1.6 1.6 Dipropylene glycol 2.0 2.0 1,2-hexanediol 2.0 2.0 Tree sodium 0.02 0.02 The blend of the polymer nanocomposite particles of Production Example 1 10 0 Bemotrizinol 0 2 Purified water To 100 To 100

Comparative Example  2 and Example  2: w / o emulsion  UV protection Cosmetics  Produce

Water in oil formulations containing bemotrizinol, an organic sunscreen, were prepared according to the preparation of conventional emulsion cosmetic compositions with the ingredients and contents shown in Table 2 below.

ingredient Example 2 Comparative Example 2 Three tilipies / piperazine-10/1 dimethicone 3.0 3.0 Dimethicone, dimethicone / phage-10/15 crosspolymer 5.0 5.0 Caprylylmethicone 5.0 5.0 Sorbitan sesquioleate 0.5 0.5 Cyclopentasiloxane, distearmonium hectorite, propylene carbonate (77: 18: 5) 2.0 2.0 To a solution of < RTI ID = 0.0 & 7.0 7.0 Caprylic / capric triglyceride 3.0 3.0 Hydrogenated polydecene 10.0 10.0 Dextrin palmitate 1.0 1.0 Sorbitan sesquioleate 0.5 0.5 Dipropylene glycol 2.0 2.0 1,2-hexanediol 2.0 2.0 Tree sodium 0.02 0.02 The blend of the polymer nanocomposite particles of Production Example 1 10 0 Bemotrizinol 0 2 Purified water To 100 To 100

Test Example  1: ultraviolet ray Blocking ability  exam

The ultraviolet blocking effect of Examples 1 and 2 and Comparative Examples 1 and 2 prepared from the o / w or w / o type emulsion was confirmed.

The SPF 290 (Sun Protection Factor) analyzer showed very high PF (Protection Factor) and SPF (Sun Protection Factor).

The results are shown in Table 3 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 SPF 32.2 29.8 11.3 13.5 UVA PF 7.1 6.9 3.2 3.5

As shown in Table 3 above, the ultraviolet screening effect was 2 to 3 times better than that in the formulations containing bemotrizinol (Examples 1 and 2), compared with the formulations containing bemotrizinol (Comparative Examples 1 and 2) It was confirmed that bemotrizinol, which is an organic UV blocking agent, was encapsulated in an amorphous state, effectively absorbing ultraviolet rays from the skin surface, and exhibited a high UV blocking effect.

Test Example  2: Skin irritation test

Twenty test subjects were subjected to skin patch test using the UV-screening cosmetics of Example 1 and Comparative Example 1 to test skin irritation.

The results are shown in Table 4 below.

division Example 1 Comparative Example 1 +++ 0 0 ++ 0 One + One 3 ± 12 14 - 7 2 Total number of people 20 20 * Criteria
+++: Strong trouble, ++: Weak trouble,
+: Slight trouble, ±: normal, -: negative

As can be seen from Table 4, in Example 1, only one subject showed slight trouble, whereas in Comparative Example 1, four subjects showed slight irritation and abnormal irritation. In the case of Example 1 containing particles containing an organic UV blocking agent, the UV blocking agent was hardly directly absorbed by the skin, whereas in the case of Comparative Example 1, the UV blocking agent component was dissolved or dispersed in the oil phase, It may be absorbed by the skin and cause irritation.

Test Example  3: Feeling  Confirmation test

In order to evaluate the feeling of use of the ultraviolet barrier cosmetic composition giving the feeling of use improvement effect according to the present invention, the human body experiment was carried out as follows.

A total of 20 subjects were each provided with the cosmetic composition prepared in Example 1 and Comparative Example 1, and the feeling was evaluated.

Table 5 shows the evaluation results of feeling for Example 1 and Comparative Example 1.

division Feeling persons % Example 1 Very good (5) 5 25 Good (4) 9 45 Usually (3) 4 20 Poor (2) 2 10 Very bad (1) - - Comparative Example 1 Very good (5) - - Good (4) 3 15 Usually (3) 9 45 Poor (2) 6 30 Very bad (1) 2 10

As shown in Table 5, 70% or more of the subjects of the cosmetic composition according to Example 1 of the present invention gave 4 points or more, whereas only 15% of Comparative Example 1 was given 4 points, Was significantly higher than that of Comparative Example 1. < tb > < TABLE >

Claims (18)

Polymer nanocomposite particles comprising an organic UV blocking agent, an amphiphilic block copolymer and a hydrophobic core forming polymer.
Wherein the organic UV blocking agent is encapsulated in an amorphous state by an amphiphilic block copolymer and a hydrophobic core forming polymer.
3. The method according to claim 1 or 2,
The organic UV blocking agent may be selected from the group consisting of bemotrizinol, derivatives thereof, bisoctrizole, derivatives thereof, ethyl hexyl triazone, derivatives thereof, iscotrizinol, derivatives thereof, At least one selected from the group consisting of PABA (p-aminobenzoic acid) derivatives, cinnamate derivatives, salicylic acid derivatives, benzophenones, dibenzole methane and anthranilates. Polymer nanocomposite particles.
3. The method according to claim 1 or 2,
Wherein the organic UV blocking agent is at least one selected from the group consisting of bemotrizinol and derivatives thereof.
3. The method according to claim 1 or 2,
The amphiphilic block copolymer may be selected from the group consisting of methoxy poly (ethyleneglycol) -b-poly (caprolactone), mPEG-PCL), methoxypoly (ethylene glycol) -b - methoxy poly (ethyleneglycol) -b-poly (D, L-lactide), methoxy poly (ethylene glycol) -b-poly (L-lactide) (ethylene glycol) -b-poly (ethyleneglycol) -b-poly (lactic-co-glycolic acid) ), Methoxy poly (ethylene glycol) -b-poly (caprolactone) -b-methoxy poly (ethyleneglycol) -b-poly (caprolactone) -b-methoxy poly (ethyleneglycol) Methoxy poly (ethylene glycol) -b-poly (D, L-lactide) -b-methoxy poly (ethyleneglycol) poly (ethyleneglycol), methoxy poly (ethylene glycol) -b-poly (L-lactide) -b-methoxy poly (ethylene glycol) (ethylene glycol) -b-poly (lactic-co-glycolic acid) -b-methoxypoly (ethyleneglycol) -bis- poly (ethyleneglycol) -b-poly (lactic-co-glycolic acid) -b-methoxy poly (ethyleneglycol)).
3. The method according to claim 1 or 2,
Wherein the amphiphilic block copolymer is methoxy poly (ethylene glycol) -b-poly (ethyleneglycol) -b-poly (caprolactone), mPEG-PCL).
3. The method according to claim 1 or 2,
The hydrophobic core-forming polymer may be selected from the group consisting of poly (lactide), poly (glycolide), poly (lactide-co-glycolid), polyanhydride, polyorthoesters, polyether esters, polycaprolactones, , Poly (butyric acid), poly (valeric acid), polyurethane, polyacrylate, ethylene-vinyl acetate polymer, acrylic substituted cellulose acetate, non-degradable polyurethane, polystyrene, polyvinyl chloride, polyvinyl fluoride , Poly (vinyl imidazole), chlorosulphonate polyolefins, polyethylene oxide, and copolymers thereof. The polymer nanocomposite particles according to claim 1,
3. The method according to claim 1 or 2,
Wherein the hydrophobic core-forming polymer is at least one selected from the group consisting of polycaprolactone, poly (lactide), poly (glycolide), and poly (lactide-co-glycolide).
3. The method according to claim 1 or 2,
Wherein the average particle diameter of the polymer nanocomposite particles is 10 to 10,000 nm.
3. The method according to claim 1 or 2,
Wherein the amphiphilic block copolymer is 50 to 1000 parts by weight based on 100 parts by weight of the organic UV blocking agent.
3. The method according to claim 1 or 2,
Wherein the hydrophobic core-forming polymer is 50 to 1000 parts by weight based on 100 parts by weight of the organic UV blocking agent.
3. The method of claim 2,
Wherein the amorphous state is a state in which the organic UV blocking agent is physically and uniformly dispersed in the hydrophobic core forming polymer and the amphiphilic block copolymer.
A cosmetic composition for protecting ultraviolet rays comprising the polymer nanocomposite particles according to claim 1 or 2 as an active ingredient.
14. The method of claim 13,
Wherein the polymer nanocomposite particles comprise 0.1 to 20% by weight based on the total weight of the cosmetic composition.
An organic peritectin blocker, an amphiphilic block copolymer, and a hydrophobic core-forming polymer.
16. The method of claim 15,
A first step of mixing the mixed solution of the hydrophobic core-forming polymer and the amphiphilic block copolymer and the organic UV blocking agent,
A second step of gradually introducing the mixed solution of the first step into an aqueous solution containing a dispersion stabilizer, and
The third step of removing the solvent
Wherein the polymer nanocomposite particles have an average particle diameter of not more than 100 nm.
17. The method of claim 16,
Wherein the mixed solution of the first step is prepared by mixing a hydrophobic core-forming polymer, an amphiphilic block copolymer, and an organic solvent.
16. The polymer nanocomposite particle produced by the manufacturing method according to claim 15.

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