KR102591101B1 - Cosmetic composition comprising surface treated hollow glass microsphere - Google Patents

Abstract

The present invention relates to a cosmetic composition containing microscopic hollow glass spheres. Specifically, it relates to a cosmetic composition for blocking ultraviolet rays and/or improving wrinkles, including microscopic hollow glass spheres that are hydrophobically modified and applicable to an oil layer.

Description

Cosmetic composition comprising surface-modified hollow microscopic glass spheres {COSMETIC COMPOSITION COMPRISING SURFACE TREATED HOLLOW GLASS MICROSPHERE}

The present invention relates to a cosmetic composition containing hollow microscopic glass spheres. Specifically, it relates to a cosmetic composition for blocking ultraviolet rays and/or improving wrinkles, including microscopic hollow glass spheres that are hydrophobically modified and applicable to an oil layer.

Cosmetics gain functionality by adding various raw materials. In particular, in modern times, the demand for UV protection due to high temperatures caused by global warming and strong sunlight is increasing. At the same time, demand for environmental conservation and human safety is increasing.

Zinc oxide, a representative existing sunscreen, has a high UV blocking rate, but is not a good alternative for environmental pollution and human safety. In particular, it is not an alternative to the emerging concerns about human and environmental pollution from nanomaterials. Accordingly, a technology that provides a significant increase in UV protection and is a good alternative to safety concerns about nanomaterials is needed.

Korean Patent No. 10-1770835

The purpose of the present invention is to provide a cosmetic composition for blocking ultraviolet rays or improving skin wrinkles, including surface-modified hollow microscopic glass spheres.

Another object of the present invention is to provide a method for manufacturing the surface-modified hollow micro-glass spheres.

One aspect of the present invention relates to a cosmetic composition for blocking ultraviolet rays or improving skin wrinkles, including microscopic glass spheres treated with a surface modifier selected from the group consisting of alkyl silanes, fatty acids, alcohols, and silica.

In the present invention, the “micro-glass spheres” are generally made from a borosilicate-sodalime glass blend, and are a material that provides the advantages of low density, high heat and chemical resistance. The micro glass spheres are coated with silver, conductive nickel (Nickel-Plated), zinc oxide (ZnO), anatase, titanium dioxide (TiO ₂ ), etc. and have different properties and efficacy, and are used in biotechnology, It is used in a variety of ways, including medical devices and cosmetics.

The microglass spheres may include solid microspheres, hollow microspheres, or mixtures thereof. Specifically, the micro-glass spheres may be hollow micro-glass spheres.

In the present invention, “hollow glass microsphere” refers to a glass sphere with a diameter of 1 to 500 μm and a thickness of 1 to 20 μm. A preferable diameter is 10 to 100 μm, and a more preferable diameter is 10 to 40 μm. The most preferred diameter is 9 to 20 μm.

In the present invention, “surface modification” means changing the surface properties of microscopic glass spheres by treating them with a substance having hydrophilic or hydrophobic properties to suit the desired application.

The microscopic glass spheres can be treated with various surface treatment agents. For example, the surface treatment agent may be an alkyl silane, fatty acid, higher alcohol, silica, etc. commonly used in the industry, and may include dimethicone, glycerin, etc.

Specifically, the surface treatment agent may be an alkyl silane, and more specifically,

The alkyl silane may be triethoxycaprylysilane.

The triethoxycaprylysilane is a surface treatment agent that improves coating power and usability by adding an alkyl group to silicon. It has excellent dispersion ability, adsorption and lubrication properties, and is used as a nonionic surfactant, emulsifier, etc. It is being used. In particular, in cosmetics, it is often used as a raw material to help emulsify different ingredients that do not mix with each other.

In the present invention, it was confirmed that the effectiveness of hollow micro-glass spheres varies depending on the surface modifier, and among them, micro-glass spheres whose surface was treated with triethoxycaprylsilane showed excellent effects such as formulation stability, spreadability, and skin absorption. It was found that skin improvement effects such as UV protection and wrinkle improvement are improved accordingly.

In one embodiment of the present invention, the surface of the hollow micro-glass spheres was treated with alkali to generate abundant hydroxy groups, and then the surface was treated with alkyl silane to prepare hollow micro-glass spheres with a modified surface.

In one embodiment of the present invention, it was confirmed that the surface treatment of the hollow micro-glass spheres with alkyl silane improved spreadability and absorption, and significantly reduced feeling of stickiness, etc., which can be used as a cosmetic according to the surface treatment of the micro-glass spheres. It shows that it can be used in various formulations.

The micro glass spheres may be included in an amount of 3 to 12 parts by weight based on the total weight. Specifically, microscopic glass spheres may be included in a total weight of 3 to 10 parts by weight.

Additionally, the composition may further include titanium dioxide (TiO ₂ ) and powder. For example, the TiO ₂ powder may have been surface treated with aluminum hydroxide, isostearic acid, aluminum stearate, stearic acid, hydrated silica, alginic acid, etc.

More specifically, the TiO ₂ powder may be a TiO ₂ powder coated with aluminum hydroxide Al(OH) ₃ and stearic acid.

The composition may include microscopic glass spheres and TiO ₂ powder in a ratio of 1:1 to 1:3, and more specifically, in a ratio of 1:1 to 1:2.

In one example of the present invention, it was confirmed through SPF measurement that the composition containing surface-modified microscopic glass spheres had an excellent UV blocking effect, and that the addition of TiO ₂ powder significantly improved the UV blocking effect (Table 2).

In addition, in one embodiment of the present invention, the wrinkle-improving effect of microscopic glass spheres surface-modified with alkyl silane is excellent. In particular, the wrinkle-improving effect of TiO ₂ powder itself is somewhat weak, but a synergistic effect in wrinkle improvement is achieved depending on the combination of microglass spheres. It was confirmed that appeared (Table 3).

The cosmetic composition can be formulated by conventional methods. In formulating external skin preparations, reference can be made to the information disclosed in Remington's Pharmaceutical Science, Mack Publishing Company, Easton PA, and in formulating cosmetic compositions, International cosmetic ingredient dictionary, 6th ed (The cosmetic,

Toiletry and Fragrance Association, Inc., Washington, 1995).

Specifically, the cosmetic composition can be prepared in a general emulsified formulation and solubilized formulation. For example, lotion such as softening lotion or nourishing lotion; Emulsions such as facial lotion and body lotion; Creams such as nutritional cream, moisture cream, eye cream, etc.; essence; cosmetic ointment; spray; gel; pack; sunscreen; makeup base; Foundation, such as liquid type, solid type, or spray type; powder; Make-up removers such as cleansing creams, cleansing lotions, and cleansing oils; Alternatively, it may be formulated as a cleansing agent such as cleansing foam, soap, or body wash, but is not limited to this. Additionally, the skin external preparation may be formulated as an ointment, patch, gel, cream, or spray, but is not limited thereto.

In each formulation of the cosmetic composition, in addition to the essential ingredients, other ingredients may be appropriately mixed depending on the type of formulation or purpose of use, within the range that does not impair the purpose of the present invention.

The cosmetic composition may contain a generally acceptable carrier and may be appropriately mixed with, for example, oil, water, surfactant, moisturizer, lower alcohol, thickener, chelating agent, colorant, preservative, fragrance, etc., but is not limited thereto. no.

The acceptable carrier may vary depending on the formulation. For example, ointment, pay

When formulated as a cream or gel, animal oil, vegetable oil, wax, paraffin, starch, tracant, cellulose derivatives, polyethylene glycol, silicone, bentonite, silica, talc, zinc oxide or mixtures thereof may be used as carrier ingredients. there is.

When the cosmetic composition is formulated as a powder or spray, lactose, talc, silica, aluminum hydroxide, calcium silcate, polyamide powder, or mixtures thereof may be used as carrier ingredients, and in the case of a spray, chlorofluorohydride may be used. It may further include propellants such as carbon, propane, butane or dimethyl ether.

When the cosmetic composition is formulated as a solution or emulsion, a solvent, solubilizing agent, or emulsifying agent may be used as a carrier component, such as water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl benzoate, propylene glycol, 1,3-Butylglycol oil may be used, in particular cottonseed oil, peanut oil, corn germ oil, olive oil, castor oil and sesame oil, glycerol aliphatic esters, polyethylene glycol or fatty acid esters of sorbitan.

When the cosmetic composition is formulated as a suspension, the carrier component includes water, a liquid diluent such as ethanol or propylene glycol, a suspending agent such as ethoxylated isostearyl alcohol, polyoxyethylene sorbitol ester, and polyoxyethylene sorbitan ester, Microcrystalline cellulose, aluminum metahydroxide, bentonite, agar, or tracant may be used.

When the cosmetic composition is formulated into soap, alkali metal salts of fatty acids, fatty acid hemiester salts, fatty acid protein hydrolyzates, isethionates, lanolin derivatives, fatty alcohols, vegetable oils, glycerol, sugars, etc. are used as carrier ingredients. can be used

The cosmetic composition may contain fatty substances, organic solvents, solubilizers, thickeners, gelling agents, softeners, antioxidants, suspending agents, stabilizers, foaming agents, fragrances, surfactants, etc. commonly used in the industry depending on the quality or function of the final product. Water, ionic or non-ionic emulsifiers, fillers, sequestering agents, chelating agents, preservatives, blocking agents, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic actives and any other ingredients customarily used in cosmetics. It may additionally contain adjuvants commonly used in the fields of cosmetology or dermatology, such as.

However, the auxiliaries and their mixing ratio may be appropriately selected so as not to affect the desirable properties of the cosmetic composition according to the present invention.

If the content deviation between each active ingredient constituting the composition containing the micro glass spheres is outside the above range, the synergistic effect due to the interaction between the active ingredients may not be properly realized, so the working environment and final product The mixing ratio can be appropriately controlled considering quality.

Another aspect of the present invention relates to a method for producing microscopic glass spheres, including the step of treating the microhollow glass spheres with any one surface modifier selected from the group consisting of alkyl silanes, fatty acids, alcohols, and silica.

Specifically, the alkyl silane may be triethoxycaprylysilane.

The hollow micro-glass spheres can be manufactured by various technologies. One approach is boric acid ?? After spray-drying a liquid precursor mixed with elements, the resulting raw material particles are formed into hollow spherical particles using flame, heating, plasma, laser, etc., but are not limited to this and are suitable for use in cosmetic purposes. Glass sphere manufacturing methods can be used without restrictions.

The cosmetic composition containing hollow micro-glass spheres surface-treated with a hydrophobic material such as alkyl silane of the present invention can increase skin adhesion and absorption by ensuring the dispersibility of the formulation. In addition, the composition improves the sticky feel of existing UV creams and can be used as a cosmetic raw material for UV protection and anti-wrinkle use with excellent spreadability.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings, but it is obvious that the present invention is not limited to the following examples.

Manufacturing example 1. Manufacturing of surface-modified hollow micro-glass spheres

1-1. Manufacturing of hollow micro-glass spheres

Boric acid (B ₂ O ₃ ) and urea were added to 200 to 250 g of distilled water heated to 50 to 60°C at a ratio of 1.5:1 to 3:1 and stirred vigorously to completely dissolve. The dissolved sample was slowly added to a completely mixed solution of water glass and distilled water and stirred with a stirrer for about 30 minutes to prepare a mixed liquid precursor. The mixed liquid precursor was used to prepare raw material powder using a fluid nozzle spray dryer (SD-1000, EYELA Co.), and then put into a furnace to prepare hollow micro-glass spheres.

1-2. Manufacturing of surface-modified hollow micro-glass spheres

In order to produce surface-modified hollow micro-glass spheres, the surface of the hollow micro-glass spheres prepared in Example 1-1 was treated with alkali to generate hydroxy groups, and then the microspheres were placed in a mixer and stirred. Afterwards, triethoxycaprylysilane was added and mixed. The mixed solution was dried at 80 to 90°C and heat treated at 110 to 160°C to complete surface treatment.

Examples and Comparative Examples

Example and comparative example compositions containing the surface-modified hollow micro-glass spheres prepared in Preparation Example 1 are shown in Table 1 below.

award Raw material name Comparison example 1 Comparison example 2 Comparative Example 3 Example 1 Example 2 paid
(content%) O.M.C. 6.5 6.5 6.5 6.5 6.5 H.M.S. 5.5 5.5 5.5 5.5 5.5 aracel 165 2.5 2.5 2.5 2.5 2.5 twenty 60 2 2 2 2 2 alkylbenzoate 16 11 11 11 11 Altevo GS60 CS - - - 5 3 Ti-al1100sa - 5 5 - 5 Awards
(content%) water 57.48 57.48 54.48 57.48 54.48 EDTA 2na 0.02 0.02 0.02 0.02 0.02 1,3-BG 7 7 7 7 7 1,2-HD 2 2 2 2 2 Aristoflex AVC One One One One One Altevo GS60 - - 3 - - Sum 100 100 100 100 100

* Ti-al 1100sa: TiO ₂ powder surface treated with aluminum hydroxide Al(OH) ₃ and stearic acid * Altevo GS60: Hollow micro-glass sphere

* Altevo GS60 CS: Hollow micro-glass spheres surface treated with triethoxycaprylysilane

Experimental Example 1. Evaluation of UV blocking efficacy

In order to confirm the UV blocking efficacy of Examples 1 and 2 and Comparative Examples 1 to 3, 10 adult men and women were selected for each composition.

The amount of ultraviolet rays emitted from the solar simulator (ORIEL ^Solar Simulator 81293, Minimal erythema dose (MED) was confirmed 24 hours after irradiation with ultraviolet rays. Thereafter, in order to confirm the UV blocking effect of the composition of the present invention, a sample was uniformly applied to the test subject's back at a thickness of 2 μl/cm ² and left for 15 minutes to dry. An ultraviolet irradiation window is attached and fixed to the area where each composition is applied, and areas other than the irradiation window are blocked from ultraviolet rays using leather and a towel, then irradiated with ultraviolet rays, and then the irradiation amount is measured using a light meter (IL1700 Radiometer, SED 240 probe). Measured.

Based on the subject's MED, the UV irradiation dose was gradually increased starting from SPF 15-40 for the sample expected to be SPF 50 and SPF 40-65 for the sample expected to be SPF 100. The minimum amount of erythema was determined 24 hours after UV irradiation, and the UV blocking effect of the sample was calculated according to the general formula below.

[Equation 1]

UV protection effect (SPF) = MED on the area where the sample was applied/MED on the area where the sample was not applied

Here, MED stands for Minimal Erythemal Dose (Minimum Ultraviolet Radiation Dose that causes erythema on the skin; hereinafter “MED”).

The SPF value for each composition is shown in Table 2 below, and the value represents the average SPF value for 10 people.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 SPF 40.1 58.1 75.2 43.2 88.1

As shown in Table 2, compared to the composition containing only hollow microglass spheres and/or TiO ₂ powder (Comparative Examples 1 to 3), the ultraviolet ray blocking effect of the hollow microglass spheres surface-modified with alkyl silane is You can tell it's excellent. In particular, when TiO ₂ powder was treated with a hollow microscopic glass sphere composition modified with triethoxycaprylylsilane, the UV blocking effect was significantly improved, confirming an unexpected synergy effect in UV blocking, which was confirmed by the present invention. This shows that the composition can be used as a composition for blocking ultraviolet rays.

Experimental Example 2. Wrinkle improvement efficacy evaluation

100 adult men and women were selected, and the compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were divided into 20 people each to evaluate the wrinkle improvement efficacy. First, the selected test subjects rested for 30 minutes in a waiting room under constant temperature and humidity conditions (24-26℃, relative humidity 40-50%) to adjust their skin surface temperature and humidity to the environment of the measurement space. Water intake was limited. For objective measurement, measurements were made by one researcher, and the same area was measured for each measurement.

The area to measure the degree of wrinkles was the area around the test subject's eyes, and the left and right sides were measured at a point 2 cm away from the corner of the eye. Measurements were made using a 3D skin imaging device (PRIMOS premium) before and after using the product, and the skin Ra (Average Roughness) value of the saved image was analyzed after measurement. This means that as the Ra value decreases, the roughness decreases, indicating a wrinkle improvement effect.

division Period of use Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Ra Before use 24.411 23.994 24.075 25.358 25.361 After 4 weeks of use 24.393 23.837 23.793 23.436 25.008 After 8 weeks of use 24.146 23.589 23.789 23.522 23.966 After 12 weeks of use 23.988 23.796 23.699 22.541 22.771

As shown in Table 3, it was confirmed that the decrease in Ra value increased as the period of use increased in the compositions of Examples 1 and 2 containing hollow micro-glass spheres surface-modified with alkyl silane, which was confirmed by the hollow micro-sphere of the present invention. It shows that the wrinkle improvement effect of the cosmetic composition containing shaped micro glass spheres is excellent.

Experimental Example 3. Sensory evaluation

Regarding the compositions of Examples 1 to 3, which were confirmed to be excellent in UV blocking and wrinkle improvement efficacy in Experimental Examples 1 and 2, 50 adult men and women in their 20s to 40s were selected and a sensory evaluation was conducted on each product. Sensory evaluation scores were expressed as the average value for each product.

The judgment criteria are as follows: 2 points - good, 1 point - average, 0 points - poor.

division Sensory evaluation feeling of use Spreadability incense absorptivity Comparative Example 1 0.8 1.3 1.1 1.4 Comparative Example 2 0.8 1.4 One 1.3 Comparative Example 3 0.9 1.2 One 1.5 Example 1 1.3 1.8 1.2 1.6 Example 2 1.4 1.8 One 1.7

As shown in Table 4, in the sensory evaluation of the examples, the feeling of use, spreadability, scent, and absorption power are all excellent. In particular, by using surface-modified micro glass spheres, the problem of sticky feeling due to high oil absorption can be improved, and skin absorption ability It was confirmed that as this increases, it can have a higher UV blocking ability. The above description of the present invention is for illustrative purposes, and those skilled in the art will understand the technical idea or essential features of the present invention. You will understand that it can be easily transformed into another specific form without changing it. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims described below, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention.

Claims (7)

Hollow microscopic glass spheres treated with triethoxycaprylysilane and titanium dioxide (TiO ₂ ) surface treated with aluminum hydroxide Al(OH) ₃ and stearic acid. A cosmetic composition for improving skin wrinkles that has a UV blocking effect, comprising powder as an active ingredient. delete delete According to paragraph 1,
The hollow micro-glass spheres treated with triethoxycaprylysilane,
A cosmetic composition comprising 3 to 10 parts by weight based on the total weight. delete According to paragraph 1,
The hollow microscopic glass spheres and titanium dioxide powder,
A cosmetic composition mixed in a ratio of 1:1 to 1:2. (1) manufacturing hollow micro-glass spheres;
(2) generating hydroxyl groups by treating the surface of the hollow micro-glass spheres in step 1 with alkali;
(3) adding and mixing triethoxycaprylysilane to the hollow micro-glass spheres of the second step;
(4) drying the mixture of steps 3 at 80 to 90°C and surface treating it by heat treatment at 110 to 160°C to produce surface-treated hollow micro-glass spheres;
(5) TiO ₂ powder surface-treated with aluminum hydroxide Al(OH) ₃ and stearic acid was added to the four-step surface-treated hollow micro-glass spheres at a ratio of 1:1 to 1:3. A method of manufacturing micro-glass spheres for improving skin wrinkles having an ultraviolet ray blocking effect, comprising: mixing.