KR101719811B1 - Oil-in-water type nano-particles emulsion cosmetic composition improved Skin-Absorption - Google Patents

Abstract

The present invention provides an oil-in-water-type nano-particle emulsion cosmetic composition having an improved skin absorption rate. The oil-in-water-type nano-particle emulsion cosmetic composition, on the basis of the total weigh thereof, comprises: 1-5 wt% of polyoxyethylene sorbitan ester of fatty acid; 1-5 wt% of PEG-5 rapeseed sterol; 1-5 wt% of polyglyceryl-3 diisostearate; 0.5-20 wt% of a block copolymer of poly-D,L-lactic acid-co-glycolic acid and polyacrylic acid substituted by ethylene diamine; 1-10 wt% of glyceryl monostearate; 1-10 wt% of carnauba wax; 1-10 wt% of ceteth-3 (CH_3(CH_2)_(14)CH_2(OCH_2CH_2)nOH); 1-10 wt% of cholesterol; 0.3-8.0 wt% of silicone oil; 0.3-8.0 wt% of macadamia nut oil; 0.01-20 wt% of oil soluble bioactive material; 0.01-20 wt% of water soluble bioactive material; and a remaining amount of water.

Description

[0001] The present invention relates to an underwater type nano-particle emulsion cosmetic composition,

The present invention relates to an underwater type nanoparticle emulsion cosmetic composition having improved skin absorption rate.

Emulsions are inhomogeneous systems in which an incompatible liquid is closely dispersed in the form of particles in other liquids, the particle diameter of which is generally greater than 0.1 micrometer ([mu] m). However, the diameters of the emulsified particles constituting the dispersed phase practically applied are in the range of about 0.5 μm to 100 μm. However, the emulsions have disadvantages that they are thermodynamically unstable due to their large particle size and also have a disadvantage in that their absorption of the active ingredients is limited.

However, since the composition of the nano emulsion is much smaller than that of the emulsion composition particle and the surface area per unit volume is much larger, the thermodynamic stability is remarkably improved as compared with the general emulsion composition and the skin absorbability of the active ingredient is improved. The particle size of a nano emulsion is generally defined as an emulsion having an average particle diameter of 20-500 nm.

Known methods for producing nano emulsions include a method of using a suitable surfactant such as a phospholipid and a co-surfactant while using a homogenizer at a high pressure (for example, about 800-1,500 atm) and a method of using a phase transition temperature There is a way to use the principle.

According to the method using the high-pressure homogenizer, it is difficult to mass-produce, and the productivity is deteriorated and the component is deteriorated due to heat generation since it is necessary to manufacture the water phase and the oil phase components in a momentary contact with each other through a thin nozzle under a high pressure condition . In addition, this method can only produce a nano emulsion having a low viscosity. Therefore, if the viscosity is high, the flowability of the image and the mixing property are deteriorated, so that the nano emulsion can not be uniformly produced. Thus, this method can not make cream-phase nano emulsion with high viscosity and particle diameter of about 200 nm.

The method of using the phase inversion temperature (PIT) principle is difficult to manufacture by adjusting the phase transition temperature in a mass production process, and it is more difficult to cool a mass produced product rapidly. In addition, there is a problem that the stability of the product is unstable because the produced product is easily transported at the phase transition temperature.

Korea Patent No. 10-0654841

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned disadvantages of the prior art,

Type nanoparticle emulsion cosmetic composition which is excellent in skin absorption rate and storage stability by containing stable nanoparticles of 50 m to 100 nm as an active ingredient.

Another object of the present invention is to provide a process for producing an effective cosmetic composition for nanoparticle emulsion.

The present invention relates to a cosmetic composition,

1 to 5% by weight of a polyoxyethylene sorbitan ester of a fatty acid, 1 to 5% by weight of a PEG-5 rapeseed sterol and 1 to 5% by weight of polyglyceryl-3 diisostearate;

0.5 to 20% by weight of a block copolymer of poly-D, L-lactic acid-co-glycolic acid and polyacrylic acid substituted with ethylenediamine;

1 to 10% by weight of glyceryl monostearate, 1 to 10% by weight of carnauba wax, Ceteth-3: CH ₃ (CH ₂ ) ₁₄ CH ₂ (OCH ₂ CH ₂ ) 1 to 10% by weight of cholesterol, 1 to 10% by weight of cholesterol, 0.3 to 8.0% by weight of silicone oil, 0.3 to 8.0% by weight of macadamia nut oil,

0.01 to 20% by weight of an oil-soluble physiologically active substance;

0.01 to 20% by weight of a water-soluble physiologically active substance; And

Water balance, and provides an underwater type nanoparticle emulsion cosmetic composition made by a PIT system.

The block copolymer of the poly-D, L-lactic acid-co-glycolic acid and the polyacrylic acid substituted with ethylenediamine may be represented by the following Formula 1:

[Chemical Formula 1]

In this formula,

a and b are molar fractions, a is 0.5 and b is 0.5;

c and d are mole fractions, c is 0.05 to 0.2, d is 0.8 to 0.95, and c + d is 1.

Further, according to the present invention,

(a) 0.5 to 20% by weight of a block copolymer of polyacrylic acid substituted with poly-D, L-lactic acid-co-glycolic acid and ethylenediamine relative to the total weight of the cosmetic composition, polyoxyethylene sorbitan esters 1 to 5 1 to 5 wt% of PEG-5 rapeseed sterol and 1 to 5 wt% of polyglyceryl-3 diisostearate are dissolved in an organic solvent, (Ceteth-3: CH 3 (CH 2) 14 CH 2 (OCH 2 CH 2) 2) in an amount of from 0.01 to 20% by weight of physiologically active substance, from 1 to 10% by weight of glyceryl monostearate, from 1 to 10% by weight of carnauba wax, 1 to 10% by weight of cholesterol, 1 to 10% by weight of cholesterol, 0.3 to 8.0% by weight of silicone oil and 0.3 to 8.0% by weight of macadamia nut oil are mixed and mixed at 75 to 85 캜 Warming and preparing an oil phase;

 (b) 0.01 to 20% by weight of a water-soluble physiologically active substance and the balance of water, based on the total weight of the cosmetic composition, and heating the mixture to 75 to 85 캜 to prepare a water-

(c) stirring the water phase in an emulsification tank at 2,500 to 3,500 rpm, adding an oil phase to the emulsion and stirring the mixture at 2,500 to 3,500 rpm to form a micro-sized first emulsion phase;

(d) cooling the first emulsion phase to 37 to 50 占 폚; And

(e) introducing the first emulsion phase into a high-pressure emulsifier at a temperature of 37 to 50 DEG C and secondary-oiling the emulsion at a pressure of 600 to 1,500 bar two to three times. A method for producing an emulsion cosmetic composition is provided.

The water-in-oil type nanoparticulate emulsion cosmetic composition of the present invention is excellent in skin absorption rate and storage stability by containing stable nanoparticles of 50 m to 100 nm as an effective ingredient.

In addition, the method of producing the nanoparticulate emulsion cosmetic composition of the present invention can be carried out by introducing a block copolymer of polyacrylic acid substituted with poly-D, L-lactic acid-co-glycolic acid and ethylenediamine into the PIT system, Lt; / RTI >

Hereinafter, the present invention will be described in detail.

The present invention relates to a cosmetic composition,

1 to 5% by weight of a polyoxyethylene sorbitan ester of a fatty acid, 1 to 5% by weight of a PEG-5 rapeseed sterol and 1 to 5% by weight of polyglyceryl-3 diisostearate;

0.5 to 20% by weight of a block copolymer of poly-D, L-lactic acid-co-glycolic acid and polyacrylic acid substituted with ethylenediamine;

1 to 10% by weight of glyceryl monostearate, 1 to 10% by weight of carnauba wax, Ceteth-3: CH ₃ (CH ₂ ) ₁₄ CH ₂ (OCH ₂ CH ₂ ) 1 to 10% by weight of cholesterol, 1 to 10% by weight of cholesterol, 0.3 to 8.0% by weight of silicone oil, 0.3 to 8.0% by weight of macadamia nut oil,

0.01 to 20% by weight of an oil-soluble physiologically active substance;

0.01 to 20% by weight of a water-soluble physiologically active substance; And

Water residual amount, and which is manufactured by a PIT system.

The polyoxyethylene sorbitan ester and the PEG-5 rapeseed sterol of fatty acids were included as a surfactant and the polyglyceryl-3 diisostearate was included as an auxiliary surfactant. When the above specific surfactant and co-surfactant are included in the above-mentioned range, formation of the nanoparticle emulsion is uniform and stable.

The glyceryl monostearate and carnauba wax are included as an emulsifier and the Ceteth-3: CH ₃ (CH ₂ ) ₁₄ CH ₂ (OCH ₂ CH ₂ ) nOH) . When the above-mentioned specific emulsifier and emulsion stabilizer are included in the above-mentioned range, formation of the nanoparticle emulsion is uniform and stable.

The block copolymer of the poly-D, L-lactic acid-co-glycolic acid and the polyacrylic acid substituted with ethylenediamine may be represented by the following formula (1)

[Chemical Formula 1]

In this formula,

a and b are molar fractions, a is 0.5 and b is 0.5;

c and d are mole fractions, c is 0.05 to 0.2, d is 0.8 to 0.95, and c + d is 1.

In the block copolymer of polyacrylic acid substituted with poly-D, L-lactic acid-co-glycolic acid and ethylenediamine, poly-D, L-lactic acid-co- glycolic acid is included as a hydrophobic part, Polyacrylic acid is included as a hydrophilic moiety.

Polyacrylic acid substituted by poly-D, L-lactic acid-co-glycolic acid (the following formula 2) and ethylenediamine in the above formula is reacted with poly-D, L-lactic acid- To form a block copolymer of polyacrylic acid substituted with a diamine.

(2)

(3)

The poly-D, L-lactic acid-co-glycolic acid preferably has a weight average molecular weight of 1,000 to 70,000, and the copolymer of polyacrylic acid substituted with ethylenediamine has a weight average molecular weight of 100 to 10,000 It is preferred for the formation of nanoparticle emulsions.

The average particle diameter of the copolymer is preferably from 10 to 100 nm. When such a particle size is used, penetration into the skin and collection of the active ingredient are excellent. The thus obtained copolymer is remarkably stable in an aqueous solution as compared with a low molecular weight micelle. This characteristic of the copolymer means that the water-in-oil type nanoparticulate emulsion cosmetic composition of the present invention can be stored in a stable state for a long period of time and can maintain its structure for a considerable period of time in the body.

The water-in-oil type nanoparticle emulsion cosmetic composition may further include 0.05 to 5% by weight of a tackifier, and may further include additives commonly used in this field.

In the above-mentioned water-in-oil type nano-particle emulsion cosmetic composition, the usable physiologically active ingredient means an active ingredient of the cosmetic which can be dissolved in the oily phase. The kind of the useful physiologically active ingredient is not particularly limited as long as it can be dissolved in the oily phase, and any physiologically active substance known in the field can be used.

The useful physiologically active ingredient may be selected from tocopherol, retinol, coenzyme Q10, oleanolic acid, uricolic acid, diacetylboline, useful licorice; Hydrocarbon-based substances such as paraffin oil, squalane and squalane; Synthetic triglycerides obtained by reacting with natural products such as caprylic capric triglyceride (Neobie M 5); Synthetic ester oils such as cetyl octanoate, octyldodecanol (utanol G), and isopropyl palmitate; Vegetable oils such as jojoba oil, olive oil, safflower oil, ragweed colostrum, colostrum, sesame oil, and perilla oil; Animal oils such as mink oil and shark oil; Fat-soluble vitamins such as vitamins A, E and F, and derivatives thereof, and they may be used singly or in combination of two or more. However, the present invention is not limited thereto.

In the water-in-oil type nano-particle emulsion cosmetic composition, the water-soluble physiologically active ingredient means the active ingredient of the cosmetic which can be dissolved in the aqueous phase. The kind of the water-soluble physiologically active ingredient is not particularly limited as long as it can be dissolved in the aqueous phase, and any known physiologically active substance in the field can be used.

Examples of the water-soluble physiologically active ingredient include adenosine, arbutin, Centella asiatica extract, yeast, a fermentation product obtained by fermenting lactic acid bacteria, a hydrophilic peptide, a polyol such as propylene glycol, butylene glycol, glycerin, and polyethylene glycol Ryu; Mucopolysaccharides such as hyaluronic acid, chondroitin sulfate, and glucosamine; Water-soluble vitamins such as vitamin C and panthenol, and derivatives thereof, and they may be used singly or in combination of two or more kinds. However, the present invention is not limited thereto.

The underwater type nano-particle emulsion cosmetic composition may be at least one selected from the group consisting of a hair tonic, a scarf treatment, a hair cream, a general ointment, a softening longevity, a convergent lotion, a nutritional lotion, an eye cream, a nutrition cream, a massage cream, a cleansing cream, a cleansing foam, , Body lotion, body cream, body oil, body essence, makeup base, foundation, hair dye, shampoo, rinse, body cleanser, toothpaste, or mouthwash.

The active ingredients used in this field for preparing such cosmetic compositions may be included in the water-in-oil type nanoparticle emulsion cosmetic composition of the present invention without limitation.

The nanoparticles contained in the underwater type nanoparticle emulsion cosmetic composition may be from 50 nm to 100 nm.

Further, according to the present invention,

(a) 0.5 to 20% by weight of a block copolymer of polyacrylic acid substituted with poly-D, L-lactic acid-co-glycolic acid and ethylenediamine relative to the total weight of the cosmetic composition, polyoxyethylene sorbitan esters 1 to 5 1 to 5 wt% of PEG-5 rapeseed sterol and 1 to 5 wt% of polyglyceryl-3 diisostearate are dissolved in an organic solvent, (Ceteth-3: CH ₃ (CH ₂ ) ₁₄ CH (CH ₂ ) ₂ CH ₃ CH ₂ CH ₂ CH ₂ ) _{2 (OCH 2 CH 2) nOH} ) 1 ~ 10 % by weight, cholesterol (cholesterol) 1 ~ 10% by weight, the silicone oil 0.3 ~ 8.0% by weight, and macadamia nut oil (Macadamia nut Oil) 0.3 ~ 8.0% by weight; put Mixing and heating to 75 to 85 캜 to prepare an oily portion;

(b) 0.01 to 20% by weight of water-soluble physiologically active substance and the balance of water are mixed with the total weight of the cosmetic composition, and the mixture is heated to 75 to 85 캜 to prepare a water-

(c) stirring the water phase in an emulsification tank at 2,500 to 3,500 rpm, adding an oil phase to the emulsion and stirring the mixture at 2,500 to 3,500 rpm to form a micro-sized first emulsion phase;

(d) cooling the first emulsion phase to 37 to 50 占 폚; And

(e) introducing the first emulsion phase into a high-pressure emulsifier at a temperature of 37 to 50 DEG C and secondary-oiling the emulsion at a pressure of 600 to 1,500 bar two to three times. To a process for producing an emulsion cosmetic composition.

In the step (a), the organic solvent may include acetone, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, dioxane, tetrahydrofuran, ethyl acetate, acetonitrile, methyl ethyl ketone, methylene chloride, chloroform, methanol, A solvent selected from the group consisting of ethanol, ethyl ether, diethyl ether, hexane and petroleum ether, or a mixture thereof may be used.

The content of each component described above can be applied to all of the components described in the water-in-oil type nano-particle emulsion cosmetic composition. Therefore, redundant description is omitted.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Manufacturing example  1: substituted with ethylenediamine Of polyacrylic acid  Produce

40 g of acrylic acid was added to a 1 L reactor equipped with a cooling device so that the nitrogen gas was refluxed and the temperature thereof was easily controlled. 60 g of ethyl acetate (EAc) was poured into the solvent and the nitrogen gas was purged for 30 minutes. The temperature was maintained at 60 占 폚, 0.1 g of AIBN (azobisisobutyronitrile) as a reaction initiator was added, and the reaction was carried out for 3 hours to prepare a polyacrylic acid polymer.

50 ml of dimethylformamide and 145 mg of N, N-carbonyldiimidazole (CDI) were added to a 1 L reactor equipped with a cooling device so that nitrogen gas was refluxed and temperature was easily controlled. 100 g of the polyacrylic acid polymer solid prepared above and 2 g of ethylenediamine were added and reacted for 2 hours under stirring at 1 atm and room temperature, to prepare polyacrylic acid substituted with ethylenediamine (number average molecular weight 1,500).

Manufacturing example  2: Poly - D, L - lactic acid-co- Glycolic acid  Ethylenediamine Of polyacrylic acid  Preparation of block copolymers

100 ml of dimethylformamide and 290 mg of N, N-carbonyldiimidazole (CDI) were added to the reaction vessel and stirred. To this was added 20 g of poly-D, L-lactic acid-co-glycolic acid (RG502, Boehringer Ingelheim, Germany) having a number average molecular weight of 11,000 to obtain a hydroxyaldehyde group of poly-D, L-lactic acid- Lt; / RTI > To the solution was added 25 g of polyacrylic acid substituted with ethylenediamine having a number average molecular weight of 1,500 prepared in Preparation Example 1, and the mixture was stirred at 1 atm and room temperature. The mixture was reacted for 12 hours, filtered through a nylon filter having a pore size of 0.45 micrometer, dispersed in tertiary distilled water, and dialyzed to remove unreacted materials and reaction reagents to prepare a block copolymer.

Example  1: Underwater type nano particle emulsion Cosmetics  Preparation of composition

10 parts by weight of a block copolymer of polyacrylic acid substituted with poly-D, L-lactic acid-co-glycolic acid and ethylenediamine prepared in Preparation Example 2, 3 parts by weight of polyoxyethylene sorbitan ester of fatty acid, 3 parts by weight of seed sterol (PEG-5 rapeseed sterol) and 3 parts by weight of polyglyceryl-3 diisostearate were dissolved in 30 parts by weight of ethanol. To the above solution, 2 parts by weight of coenzyme Q10 as a useful physiologically active substance and 2 parts by weight of squalane 2 5 parts by weight of glyceryl monostearate, 3 parts by weight of carnauba wax, Ceteth-3: CH ₃ (CH ₂ ) ₁₄ CH ₂ (OCH ₂ CH ₂ ) nOH 2 , 3 parts by weight of cholesterol, 0.5 part by weight of silicone oil and 0.5 part by weight of Macadamia Nut Oil were mixed and heated to 70 캜 to prepare an oily portion.

2 parts by weight of arbutin, 1 part by weight of preservative and 65 parts by weight of purified water were mixed as a water-soluble physiologically active substance, and heated to 70 캜 to prepare a water-soluble part.

The water phase was stirred in a vacuum emulsification tank at 3,000 rpm, and an oil phase was added thereto. The oil phase was stirred at 3,000 rpm and emulsified to form a micro-sized first emulsion phase. The first emulsion phase was cooled to 40 占 폚, put into a high-pressure emulsifier and secondary emulsified three times at a pressure of 1,000 bar to prepare an underwater type nano-particle emulsion cosmetic composition.

Example  2: Underwater type nanoparticle emulsion Cosmetics  Preparation of composition

2 parts by weight of coenzyme Q10 used as an oil-soluble physiologically active ingredient in Example 1 and 2 parts by weight of tocopherol and 2 parts by weight of retinol were used instead of 2 parts by weight of squalane and 2 parts by weight of vitamin C was used instead of 2 parts by weight of arbutin as a water- , An underwater type nano-particle emulsion cosmetic composition was prepared.

Test Example  1: Measurement of emulsion particle size and evaluation of stability of nano emulsion by particle size change

The particle size of the water-in-oil type nanoparticle emulsion cosmetic compositions of the present invention obtained according to the above Examples 1 and 2 was measured using mastersizer 2000 (Mastersizer 2000, Malvern Instrument, UK) by the dynamic light scattering principle, The results are shown in Table 1 below. At this time, the measurement of the particle size was carried out under the following conditions by diluting the nano emulsion diluted solution with purified water to have a turbidity of 10-20%.

Measurement time: 2 minutes, number of measurements per second: 5 占 103, temperature: 20 占 폚, viscosity: 0.89 centipoise, particle refractive index: 1.4, dispersion medium refractive index: 1.33

Particle size measurements were made after one day of manufacture and after storage for 6 months at 40 ° C for two times to evaluate the thermodynamic stability of the nanoemulsion after long term storage at high temperature.

Test Example  2. Stability of emulsification by visual observation

The emulsion stability of the underwater type nano-emulsion cosmetic compositions obtained in Examples 1 and 2 was evaluated by observing the naked eye with the particle size as follows. The results are shown in Table 1 below.

The emulsified state of the compositions of Example 1-2 after storage at room temperature (about 25 ° C) and at 40 ° C for 6 months was compared with the state immediately after preparation. The unstable state was observed by visual observation as sedimentation, separation, drainage, creaming, and union. The emulsion stability is evaluated as a percentage (%) of the stable part excluding the unstable part as a whole.

Emulsion stability (%) = [(total - unstable part) / total] × 100%

Nanoparticle emulsion
Cosmetic composition Particle Size (nm) Increase in particle size (%) Stability of emulsification by visual observation (%) After the preparation, storage at room temperature for 1 day After storage for 6 months at 40 ° C Example 1 82 86 4.6 95 Example 2 79 83 4.8 96

As shown in Table 1, the average diameter of the emulsified particles of the submerged-type nano-particle emulsion cosmetic compositions of Examples 1 and 2 of the present invention was very good at 83 nm and 86 nm after 1 day of preparation. In addition, in the stability evaluation by the particle size measurement after storage at 40 占 폚 for 6 months, the increase of the average particle size of the composition of Examples 1 and 2 of the present invention was found to be about 4.7%, and the stability was excellent. It was also confirmed that the result of evaluation of emulsion stability by visual observation after storage at 40 占 폚 for 6 months was also excellent at not less than 95%.

Claims (1)

Based on the total weight of the cosmetic composition,
1 to 5% by weight of a polyoxyethylene sorbitan ester of a fatty acid, 1 to 5% by weight of a PEG-5 rapeseed sterol and 1 to 5% by weight of polyglyceryl-3 diisostearate;
0.5 to 20% by weight of a block copolymer of poly-D, L-lactic acid-co-glycolic acid and polyacrylic acid substituted with ethylenediamine;
1 to 10% by weight of glyceryl monostearate, 1 to 10% by weight of carnauba wax, Ceteth-3: CH ₃ (CH ₂ ) ₁₄ CH ₂ (OCH ₂ CH ₂ ) 1 to 10% by weight of cholesterol, 1 to 10% by weight of cholesterol, 0.3 to 8.0% by weight of silicone oil, 0.3 to 8.0% by weight of macadamia nut oil,
0.01 to 20% by weight of an oil-soluble physiologically active substance;
0.01 to 20% by weight of a water-soluble physiologically active substance; And
Water balance,
The above-mentioned oil-soluble physiologically active ingredient is,
Derived derivatives of tocopherol, retinol, coenzyme Q10, oleanolic acid, uricolic acid, diacetylboline, useful licorice, paraffin oil, squalane, squalene, synthetic triglyceride, synthetic ester oil, vegetable oil, animal oil, fat soluble vitamin, and fat soluble vitamin ≪ RTI ID = 0.0 > 1, < / RTI >
Wherein the block copolymer of poly-D, L-lactic acid-co-glycolic acid and polyacrylic acid substituted with ethylenediamine is represented by the following formula (1):
[Chemical Formula 1]

In this formula,
a and b are molar fractions, a is 0.5 and b is 0.5;
c and d are mole fractions, c is 0.05 to 0.2, d is 0.8 to 0.95, and c + d is 1.