KR101515415B1 - Moisturizing patches comprising silica-containing complex nanoparticle - Google Patents

Abstract

The present invention relates to a moisturizing patch which consists of silica and a zwitterion high polymer thin film coated on the surface of the silica and contains complex nanoparticles, polysaccharides, and natural high polymer substances. The moisturizing patch of the present invention not only retains moisture for 120 hours with just one use on a user′s skin but also helps improve skin health by giving moisture and improving elasticity when continually used for a long time.

Description

[0001] MOISTURIZING PATCHES COMPRISING SILICA-CONTAINING COMPLEX NANOPARTICLE [0002]

The present invention relates to a water patch containing silica-containing composite nanoparticles.

Fine dust and heavy metals in the air can cause acne and various allergies as well as increase sebum secretion of the skin. Skin keratinization and drying phenomenon can be accelerated. Therefore, skin exposed to heavy metals is very sensitive, and special care is required for anti-inflammation, anti-allergy, etc., and skin care more than cleansing is necessary to remove foreign substances such as fine dust and heavy metal present on the skin. Skin care sheets or patches may be used for the skin care.

The skin care sheet or patch can adsorb a substance such as heavy metals including a fiber matrix, and can directly transmit an effective ingredient, a moisturizing ingredient, and the like, including a serum, to the skin. In addition, the moisture patch that can deliver moisturizing and moisturizing properties to the skin can be applied to the skin to replace the inherent skin protection performance of the stratum corneum. In particular, by allowing the outer layers of the skin to become saturated with water, it facilitates smooth skin regeneration within the skin (E. An, et al ., Langmuir , 28, 4095 (2012)).

Various types of moisture patches have been developed to date. A hydrogel patch based on a water-soluble polymer imparts a moisturizing feeling by hydrating the skin layers immediately upon application to the skin simultaneously with the application to the skin. However, in the absence of further system improvement, it is difficult to maintain the hydration state for a long period of time. In order to solve such a problem, a patch containing a fat-soluble patch or an emulsion has been developed (Korean Patent Registration No. 10-1399476).

Therefore, development of a moisture patch containing an artificial moisturizing factor capable of blocking the evaporation of water in the hydrogel system is steadily required.

Accordingly, an object of the present invention is to provide a moisture patch capable of imparting moisturizing feeling and moisture to the skin for a long time and improving skin elasticity.

In order to accomplish the above object, the present invention provides a composite nanoparticle comprising a silica and a bimetallic ion polymer thin-film coated on the surface of the silica particle; Polysaccharides; And a natural polymer material.

The moisture patch of the present invention not only shows a moisturizing and maintaining force for 120 hours even when applied once, but also provides effects of imparting moisture to the skin and improving elasticity when used continuously for a long period of time.

Fig. 1 is a graph showing moisture retention after using the water patch of the present invention.
FIGS. 2 and 3 are graphs showing changes in skin moisture content and skin elasticity after 2 weeks and 4 weeks of use of the water patch of the present invention, respectively.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a composite nanoparticle comprising silica and a bimetallic ion polymer thin-film coated on the surface of the silica particle; Polysaccharides; And a natural polymer material.

The moisture patch of the present invention may contain 0.001 to 10% by weight of the composite nanoparticles, 0.01 to 1% by weight of the polysaccharide and 0.1 to 3% by weight of the natural polymer material based on the total weight of the patch desirable.

The moisture patch of the present invention has an effect of minimizing the amount of percutaneous water loss by forming a moisture barrier film by containing an artificial moisturizing factor that exhibits a strong binding force with water to reduce the evaporation rate of water and maintain water retention and skin barrier function . In the present invention, the artificial moisturizing factor is a composite nanoparticle composed of silica and a bimetallic ion polymer thin-coated on the silica particle surface.

The moisture patch of the present invention is characterized by containing the composite nanoparticles in an amount of 0.001 to 10% by weight, preferably 0.01 to 1.00% by weight based on the total weight of the patch. When the content of the composite nanoparticles is 0.001% by weight or more, the moisture patch imparts an immediate moisturizing effect when applied to the skin, and the moisturizing effect can be maintained even for a long time. When the content is less than 10% by weight, Do.

In the present invention, the composite nanoparticles may contain silica and a bion polymer at a ratio of 1: 0.5 to 1: 5 (w / w), preferably 1: 0.5 to 1: 3 (w / w).

The bionic ion polymer means a polymer synthesized by a single polymerization or copolymerization of a monomer containing a cation and an anion in the same molecule. The bi-ionic polymer may be a polymer monomer including a betaine group such as 2-methacryloyloxy ethyl phosphorylcholine (MPC), and MPC is preferable. The bion polymer may be thin-coated on silica in the form of a hydrogel, and may be coated on the silica particle surface in an amount of 12 to 20% by weight, preferably 15 to 18% by weight, based on the total weight of the silica particles .

The silica preferably has an average particle diameter (for example, 22 nm) of 20 to 25 nm, and the surface potential is negative. The silica may be dispersed in an aqueous phase.

In the present invention, the complex nanoparticles exhibit a diameter of 20 to 30 nm, preferably about 20 nm, in a dry state, and a diameter of 50 nm to 100 nm after being hydrated in water.

In the present invention, the composite nanoparticles are prepared by: 1) introducing an amine group to the surface of silica particles by coupling reaction of silica with a silane compound; 2) introducing a trichloroacetyl group onto the silica particle surface by condensation reaction of the silica particles obtained in the step 1) with trichloroacetyl isocyanate; And 3) polymerizing the silica particles obtained in the step 2) with a polymer monomer in the presence of a cross-linking agent to introduce a binary ionic polymer thin film layer on the silica particle surface.

In the above method, step 1) is a step of introducing an amine group to the silica particle surface by performing a silica-silane coupling reaction in order to increase the reactivity.

The silica is converted into a powder form by evaporating water and then irradiated with ultrasound or the like in an organic solvent to prepare a silica dispersion such that the silica is dispersed to 3 to 5% by weight, for example, about 3% by weight. The organic solvent may be selected from the group consisting of toluene, chloroform, methylene chloride, tetrahydrofuran, xylene, and mixtures thereof. Toluene is preferred.

Then, 1 to 300 parts by weight of a silane compound is added based on 100 parts by weight of the dispersed silica, and the silane coupling reaction is performed at 110 to 120 ° C for 8 to 9 hours to introduce an amine group into the surface of the silica particles. The silane compound may be selected from the group consisting of 3-aminopropyltriethoxysilane (APS), 3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, and mixtures thereof. APS .

Step 2) is a step of introducing a polymerization initiating site into the surface of the silica particles, and a trichloroacetyl group can be introduced to the surface of the silica particles by condensation reaction of the amine group of the silica particles obtained in the step 1) with a trichloroacetyl isocyanate group.

The silica particles obtained in the step 1) are dispersed by irradiation with an ultrasonic wave or the like in an organic solvent in the same manner as mentioned above to prepare a silica dispersion so as to be 3 to 5% by weight, for example, about 3% by weight. The organic solvent may be selected from the group consisting of toluene, chloroform, methylene chloride, tetrahydrofuran, xylene, and mixtures thereof. Toluene is preferred.

Then, 10 to 200 parts by weight of trichloroacetyl isocyanate based on 100 parts by weight of the dispersed silica is subjected to a condensation reaction at 80 to 90 DEG C for 8 to 9 hours in the presence of dibutyltin diaurate to obtain a silica particle surface A trichloroacetyl group can be introduced as a polymerization initiating site.

At this time, dibutyltin dilaurate can be used as a urethane reaction catalyst.

In step 3), a polymeric monomer and a cross-linking agent are added to the silica obtained in the step 2), and a polymerization reaction is carried out to introduce the polymeric thin film layer on the surface of the silica particles.

The silica particles obtained in step 2) are dispersed in a solvent to prepare a dispersion in an amount of 6 to 8% by weight, for example, about 6% by weight, and then a polymer monomer and a crosslinking agent are added. The solvent may be selected from the group consisting of ethanol, methanol, isopropanol, and a mixture of ethanol and water, preferably ethanol.

In the present invention, a polymer component such as MPC may be used as the polymer monomer, and divinylbenzene (DVB) is preferably used as the crosslinking agent.

The polymeric monomer and the cross-linking agent may be added in an amount of 1 to 500 parts by weight based on 100 parts by weight of silica, and may be polymerized with silica particles at 65 to 70 ° C for 12 to 13 hours. The crosslinking agent may be used in an amount of 0.1 to 50% by weight, for example, 10% by weight based on the total weight of the polymeric monomer and the crosslinking agent.

In step 3), a catalyst may be used to improve the reaction rate. The catalyst may be Mo (CO) ₆ and may be added in an amount of 0.01 to 5 wt%, for example 0.05 wt%, based on the total weight.

The moisture patch of the present invention is characterized in that the polysaccharide is contained in an amount of 0.01 to 1 wt%, preferably 0.1 to 0.5 wt%, based on the total weight of the patch.

The polysaccharide may be tamarind gum, and by containing tamarind gum, the skin may be moisturized and soft.

The moisture patch of the present invention is characterized by containing a natural polymer material in an amount of 0.1 to 3 wt%, preferably 1.0 to 2.0 wt%, based on the total weight of the patch.

The natural polymer material may be at least one member selected from the group consisting of carrageenan, carrageenan, mannan, cellulose gum, alginate, xanthan gum, and mixtures thereof, preferably a combination of carrageenan and carrageenan gum.

The moisture patch of the present invention may further comprise at least one component selected from the group consisting of chelating agents, emulsifiers, moisturizers, thickeners, softeners, preservatives, fragrances, skin conditioners and mixtures thereof in addition to the composite nanoparticles, polysaccharides, As shown in FIG.

The chelating agent may be at least one selected from the group consisting of ethylenediaminetetraacetic acid disodium salt (EDTA 2Na), ethylenediaminetetraacetic acid disodium salt (EDTA 3Na), and mixtures thereof, but is not limited thereto.

The emulsifier may be at least one selected from the group consisting of glycerin fatty ester, polyoxyethylene higher aliphatic alcohol, sorbitan fatty acid ester, and mixtures thereof, but is not limited thereto.

The moisturizing agent may be at least one selected from the group consisting of 1,3-butylene glycol, amino acid, glucose, urea, vitamin A, lecithin, riboflavin, tocopherol, glycerin, dipropylene glycol, But is not limited thereto.

The thickener may be at least one selected from the group consisting of sodium polyacrylate, polyacrylate-13, hydrogenated polydecene, trideceth-6, polyisobutene, and mixtures thereof. It is not.

The softening agent may be at least one selected from the group consisting of an ester component, a silicone oil, a heavy chain triglyceride oil, a mineral oil, and a mixture thereof, but is not limited thereto.

The preservative may be at least one selected from the group consisting of phenoxyethanol, clophenethine, methylparaben, ethylhexylglycerin, and mixtures thereof, but is not limited thereto.

The perfume may be at least one selected from the group consisting of natural essential oils, combination perfumes, and mixtures thereof, but is not limited thereto.

In the present invention, the term "moisture patch" means that a composition for moisture patch containing an artificial moisturizing factor component is prepared into a film, tape, or gel-type formulation. At this time, as a base of the patch, a gel-like water wrap or the like can be used.

The moisture patch according to the present invention can be applied directly to the skin and maintained for a certain period of time to impart an artificial moisturizing factor such as the silica / bimolecular polymer composite nanoparticles to the skin, thereby imparting moisture, moisturizing and elasticity.

According to one embodiment of the present invention, the water-based patch of the present invention exhibits a skin moisturizing retention ability for 120 hours even if it is applied only once to the skin (Test Example 1), and the skin moisture content and elasticity increase (Test Examples 2 and 3), it is useful for improving the skin condition.

The moisture patch of the present invention can be produced by the following manufacturing method.

Silica, and composite nanoparticles, polysaccharides, and natural polymeric materials composed of a bimetallic ion polymer thin-coated on the surface of the silica particles, and chelating agents, emulsifiers, moisturizers, thickeners, softeners, preservatives, fragrances, skin conditioners, and mixtures thereof And at least one additive selected from the group consisting of As the solvent, ultrapure water, deep sea water, and plant extract water can be used. The mixture prepared above is heated at 70 to 90 ° C, for example, at 80 ° C to emulsify to prepare a gel composition for moisture patching. The prepared gel composition for moisture patch is subjected to vacuum, defoaming and filtration processes and is then patched according to a conventional beauty patch manufacturing method.

[Example]

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Preparation Example: Synthesis of Silica / Binary Ionic Polymer Composite Nanoparticles

Silica / bimolecular polymer composite nanoparticles composed of a bimetallic ion polymer thinly coated on the surface of silica and the silica particles were prepared as follows.

reagent

Silica (Ludox CL-X) was purchased from Aldrich. The average particle diameter of the silica was 22 nm, the surface potential of the silica was negative, and sodium was used as a stabilizing counter ion. The silica is in a form dispersed in an aqueous phase and has a concentration of 45% by weight.

(MPC), 3-aminopropyltriethoxysilane (APS), trichloroacetyl isocyanate, dibutyltin dilaurate and divinylbenzene (DVB) were all available from Sigma-Aldrich Dibutyltin dilaurate was used as a urethane reaction catalyst, and DVB was used as a crosslinking agent.

Step 1) Introduction of amine groups onto the surface of silica particles

An amine group was introduced by a silica-silane coupling reaction in order to increase the reactivity of the silica particle surface.

First, the moisture contained in the silica particles (Ludox CL-X) was evaporated under reduced pressure at room temperature to obtain a powder form. The silica powder thus obtained was put into toluene and redispersed by ultrasonic irradiation at 35 占 폚 for 10 minutes using a probe type ultrasonic wave irradiator (Sonics & Material Inc., VCX500, USA). The concentration of the silica particles was fixed at 3% by weight. Next, 150% APS was added to the silica particles in order to introduce the amine group, and the silica particles were reacted at 110 DEG C for 8 hours on the surface of the silica particles. The amine-introduced silica particles obtained through the above process were cleaned and recovered through 5 or more repetitive centrifugations at 5,000 rpm.

Step 2) Trichloroacetyl group introduction onto the silica particle surface

To introduce the polymerization initiating site into the silica particles, the silica particles obtained in the above step 1) and trichloroacetyl isocyanate were subjected to a condensation reaction.

First, the silica particles having the amine group introduced in the step 1) were introduced into toluene and redispersed by irradiation with ultrasound at 35 DEG C for 10 minutes using a probe type ultrasonic wave irradiator (Sonics & Material Inc., VCX500, USA) . The concentration of the silica particles was fixed at 3% by weight. Next, 80% by weight of the redispersed silica particles was added with 1% by weight of dibutyltin dilaurate based on the total weight, and the mixture was stirred at 80 DEG C for 8 hours to effect a condensation reaction. The silica particles having the trichloroacetyl group introduced through the above process were washed and recovered through 5 or more repetitive centrifugation at 5,000 rpm.

Step 3) Introduction of polymer thin film layer using surface polymerization

The silica particles having the trichloroacetyl group introduced in the step 2) were redispersed in ethanol. At this time, the concentration of the silica particles was fixed to 6% by weight. MPC and DVB were then added to the silica dispersion. At this time, the concentration of DVB was 10 wt% based on MPC, and Mo (CO) ₆ was added as a catalyst in an amount of 0.05 wt% based on the total weight. Finally, the content ratio of silica to MPC was adjusted to 1: 0.5 (w / w). After argon was injected into the reactor to remove oxygen, the polymer was polymerized at 70 DEG C for 12 hours to finally obtain poly (2-methacryloyloxy) ethyl-2- (trimethylammonio) ethylphosphate- Synthesis of silica / bimolecular polymer composite nanoparticles, in which a bidentate polymer, co - divinylbenzene, was coated on the surface of silica.

Example 1: Preparation of water patch

DI water, ethylenediaminetetraacetic acid disodium salt (EDTA 2Na) and glycerin were added in turn to the main kiln according to the content of each ingredient listed in Table 1 below, followed by mixing and heating at 80 ° C. Then, 1,3-butylene glycol (1.3 BG), carrageenan and carboplatin gum sludge, Flocare ET 76 and tamarind gum were separately dispersed, and then charged into a main kiln and dissolved at 80 캜 for primary emulsification.

(GMS 105), heavy chain triglyceride oil (MCT oil) and ester component (CEH) were charged into a separate dissolving tank, and the mixture was heated at 80 ° C and then put into the main kiln for secondary emulsification. To this, a preservative, a perfume, and the silica / bion-ion polymer composite nanoparticles obtained in the above-mentioned production example were added and subjected to tertiary emulsification. The emulsion thus obtained was vacuum-degassed, filtered and stored. Then, the emulsion was coated in accordance with a conventional method for producing a water patch, followed by a 10 ° C. cooling tunnel, followed by a press cutting process.

Raw material name (trade name) Availability Content (% by weight) Ultrapure water - 69.48 EDTA 2Na Hebei Methipharm 0.02 glycerin LG House Hold Health Care 12.00 1.3 BG Oxia Company 12.00 Carrageenan / Carp baking soda MSC 1.50 Flocare ET 76 SNF 0.20 Tamarind sword Dainippon Sumitomo Pharma 0.20 GMS 105 Kwang Il 1.00 MCT oil Greenwell 2.00 CEH  KCI 1.00 antiseptic Dow Corning 0.50 Spices - 0.05 Silica-containing composite nanoparticles Production Example 1 0.05

Test Example 1: Moisture persistence

In order to confirm the moisture holding performance of the water patch according to the present invention, the moisture patch prepared in Example 1 was applied to 22 healthy female subjects, and the water patch was applied for 30 minutes, , And skin moisture content were measured. The average age of the subjects was 44.41 years, and the skin condition consisted of 6 dry skin, 8 normal dry skin, 6 neutral skin, and 2 stopping skin . To the transfer of moisture patch 24 hours immediately after use, 72 hours, 96 hours, and a mean value measuring skin moisture content after 120 hours from the moisture meter (Corneometer ^®) are shown in Table 2 below.

The skin moisture content was measured by placing a probe on the skin to be tested and pressing the measuring terminal. The electrical conductivity of the skin was quantified through the sensor and the results were displayed on the screen. At this time, the skin moisture content in the case of not using the moisture patch as a control group was measured together, and the results are shown in Fig.

division Skin moisture content (A.U.) Before use 31.38 ± 6.03 Immediately after use 92.41 + - 9.85 After 24 hours of use 50.24 + - 6.43 After 72 hours of use 39.08 + - 6.49 After 96 hours of use 38.93 + - 5.39 After 120 hours of use 35.18 ± 5.23

As shown in Table 2 and FIG. 1, the moisture patch according to the present invention significantly increased the moisture content of the skin after use, and maintained moisture retention up to 120 hours. From these results, it can be seen that the moisture patch of the present invention can maintain the moisturizing power for a long time unlike the conventional moisture patch.

On the other hand, the skin moisture content was measured in the same manner as above using a conventional water patch (available from SAMPAR hydrogel mask), and the results are shown in Table 3 below.

division Skin moisture content (A.U.) Before use 31.46 + 5.05 Immediately after use 63.48 ± 9.78 After 3 hours of use 43.34 ± 6.25 After 6 hours of use 41.16 ± 5.79 After 12 hours of use 41.97 + - 6.42 After 24 hours of use 40.23 + - 4.11 After 30 hours of use 38.91 ± 2.91

As a result, the skin moisture content of the conventional moisture patch was 63.48 ± 9.78 immediately after use, which was much lower than the skin moisture content (92.41 ± 9.85) immediately after use of the water patch of the present invention. In addition, since the moisture content of the skin after 30 hours of use of the conventional moisture patch and the moisture content of the skin after 96 hours of use of the water patch of the present invention are similar to each other, the moisture patch of the present invention exhibits excellent moisture retention and moisture retention .

Test Example 2: Improved moisture

In order to confirm the effect of improving the water repellency of the water patch according to the present invention, the water patch prepared in Example 1 was applied to the same subjects as in Test Example 1, and the water patch after the cleansing was adhered for 20 minutes to absorb and remove , And skin moisture content were measured. The skin moisture content before, after 2 weeks, and 4 weeks after use of the water patch was measured in the same manner as in Test Example 1, and the results are shown in Table 4 and FIG.

division Skin moisture content (A.U.) Before use 71.86 +/- 7.11 After 2 weeks of use 79.25 + - 5.36 After 4 weeks of use 81.46 + 5.09

As shown in Table 4 and FIG. 2, the skin moisture content of the water patch according to the present invention was significantly increased after use compared with that before the patch use, and skin moisture content was about 11% And increased by more than 14% after 4 weeks of use. The percent change (%) was calculated as (skin moisture content after use - skin moisture content before use) / skin moisture content before use × 100.

Test Example  3: Improved skin elasticity

In order to confirm the skin elasticity improvement effect of the water patch according to the present invention, the water patch prepared in Example 1 was applied in the same manner as in Test Example 2, and the elasticity of the skin after 2 weeks and 4 weeks after use was measured by the elasticity measuring device (Cutometer ^® ), and the results are shown in Table 5 and FIG.

division Skin elasticity (A.U.) Before use 0.6051 + 0.0270 After 2 weeks of use 0.6388 + 0.0324 After 4 weeks of use 0.6824 + 0.0462

As shown in Table 5 and FIG. 3, the water patch according to the present invention showed an increase in skin elasticity after use compared to before patch use. Skin elasticity increased about 6% after 2 weeks of use, After the week, the rate of change was increased by about 13%. The change rate (%) was calculated as (skin elasticity before use-skin elasticity before use) / skin elasticity before use × 100.

Test Example 4: Preference Investigation

Surveys were conducted on the same subjects as those in Test Example 1, and the results of investigating the preferences of the subjects regarding the moisture, smoothness, degree of stickiness, absorbency, product smell and overall feel of the moisture patch of the present invention were examined. Respectively.

Likelihood score (mean ± standard deviation) Moistness lubricity Stickiness Absorbency Incense Overall feeling 3.48 ± 0.60 3.43 ± 0.75 3.00 0.63 3.24 ± 0.62 3.05 ± 0.59 3.38 + - 0.50 4: very good, 3: good, 2: slightly good, 1: moderate, 0: poor

As shown in Table 6, it can be seen that the moisture patch of the present invention exhibits a favorable overall acceptability.

Claims (11)

Composite nanoparticles composed of silica and 2-methacryloyloxy ethyl phosphorylcholine (MPC) thin-coated on the surface of the silica particles; Tamarind gum; And a natural polymeric material selected from the group consisting of carrageenan, carob bean gum, and mixtures thereof.
The method according to claim 1,
Wherein the composite nanoparticles are contained in an amount of 0.001 to 10 wt% based on the total weight of the patch.
delete delete The method according to claim 1,
Characterized in that the tamarind gum is included in an amount of 0.01 to 1% by weight based on the total weight of the patch.
The method according to claim 1,
Wherein the natural polymeric material is contained in an amount of 0.1 to 3% by weight based on the total weight of the patch.
The method according to claim 1,
Wherein the composite nanoparticle is contained in an amount of 0.001 to 10 wt%, the tamarind gum is contained in an amount of 0.01 to 1 wt%, and the natural polymer material is contained in an amount of 0.1 to 3 wt% based on the total weight of the moisture patch. Moisture patch to make.
The method according to claim 1,
Wherein the water patch further comprises at least one component selected from the group consisting of chelating agents, emulsifiers, moisturizers, thickeners, softeners, preservatives, fragrances, skin conditioners and mixtures thereof.
The method according to claim 1,
Wherein the composite nanoparticles comprise silica and 2-methacryloyloxyethylphosphoryl choline in a ratio of 1: 0.5 to 1: 5 (w / w).
The method according to claim 1,
Wherein the 2-methacryloyloxyethylphosphoryl choline is thin-coated on the surface of the silica particles in an amount of 12 to 20% by weight.
delete

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