KR20010068548A - Skin care composition containing Retinol and Tetradibutyl Pentaerithrityl Hydroxyhydrocinnamate - Google Patents

Abstract

PURPOSE: Provided is a composition of cosmetic material which has the maximizing effect of skin care such as wrinkle improvement by adding tetradibutyl pentaerythrityl hydroxyhydrocinnamate (TPH) so as to preserve and stabilize the activity of retinol for long time, protecting it from light, temperature and oxygen. CONSTITUTION: The composition is prepared by adding 0.001-10.0 parts by weight of retinol preferably 0.05-2.0 parts by weight based on the total weight of the cosmetic composition and 0.001-5.0 preferably 0.001-1.0 parts by weight of TPH based on the total weight of the composition.

Description

Cosmetic composition containing retinol and tetradibutyl pentaerythrityl hydroxyhydrocinnamate {Skin care composition containing Retinol and Tetradibutyl Pentaerithrityl Hydroxyhydrocinnamate}

The present invention relates to a cosmetic composition containing tetradibutyl pentaerithrityl Hydroxyhydrocinnamate (TPH) together with the existing cosmetic component retinol.

Short-term exposure to sunlight may cause sunburn, skin blackening, etc. In the long term, exposure to the skin may lead to photoaging of the skin, genetic mutations caused by DNA destruction, and effects on the Langerhans Cell. As described above, symptoms such as skin cancer may occur. In particular, the effect of ultraviolet rays during the daylight is very large, ultraviolet rays are classified into UVA (320-400nm), UVB (280-320nm), UVC (200-280nm) according to the effect on the living body. The UV rays that reach the surface are UVA and UVB, the amount of which is about 95 UVA and about 5 UVB. UVA has a longer wavelength than UVB and penetrates into the dermal layer of the skin and promotes skin aging due to protein denaturation, capillary expansion and DNA destruction in the dermal layer. On the other hand, UVB has a short wavelength and reaches only the epidermal layer of the skin, but has about 1000 times stronger energy than UVA, and mainly causes the destruction of skin tissues such as skin erythema and sunburn.

In most people's growing seasons, the skin responds easily to various sun protection systems, but as the age increases, the antioxidant system is destroyed by active oxygen species generated by ultraviolet rays, which lowers the defense ability and Under oxidative stress, damage to biological components such as lipid peroxidation, protein oxidation, chain breakdown and abnormal cross-linking of elastic fibers collagen and elastin, cleavage of hyaluronic acid chains, promotion of melanin production reactions, DNA oxidation, Accordingly, various skin aging phenomena such as wrinkle formation, thickening of the skin, blemishes, freckles, sagging of the skin, loss of skin elasticity, roughness of the skin, dryness of the skin, and skin stains appear. Therefore, in order to prevent skin aging, the development of an antioxidant system that protects the skin from ultraviolet rays, inhibits the generation of reactive oxygen species, and removes the generated active oxygen, and various antioxidants, such as It is necessary to delay or prevent skin aging by maintaining the activity of substances such as SOD, Vitamine E (㎗-α-tocopherol), Vitamine C, Catalase, and Ubiquinone.

As described above, a case for solving the photoaging problem of the skin caused by free radicals has also been reported (US Pat. No. 4603146, 4877805), and a representative material used therein may be a retinoid.

Retinoids used in skin care cosmetics include Retinol: Vitamin A alcohol, Retinal: Vitamin A aldehyde, Retinyl acetate, a retinyl ester, and Retinyl propionate. ), Retinyl linoleate and retinyl palmitate. Among these, retinol is an endogenous compound that exists naturally in the human body and is essential for differentiation and growth of epithelial tissue. In addition, retinol has a very high safety compared to retinoids such as retinoic acid, and can be said to be suitable as a raw material for skin improvement cosmetics.

However, retinol is effective in improving and preventing skin wrinkles and healing acne, but when it is prescribed in a product, discoloration or discoloration occurs due to light, heat, temperature, moisture, etc. It has a problem such as low titer as an active ingredient. Therefore, various studies have been conducted to stabilize retinol from light, heat, temperature, moisture, and time.

So far, examples of attempts to stabilize retinol include patents on oil-in-water (O / W) emulsifiers that stabilize the retinoic acid using oil-soluble oxidants BHT, dl-α-tocopherol and chelating agent EDTA. U.S. Patent No. 3,906,108, and a patent for an oil-in-water type emulsifier that stabilizes retinol using oil soluble tocopherol and citric acid (US Patent 4,247,547), and retinol, retinyl acetate using oil soluble oxidants BHT, BHA. And patent for water-in-oil emulsifier type stabilized retinyl palmitate (US Patent 4,826,828), water-in-oil type stabilized retinol using antioxidants BHA, ascorbic acid, tocopherinoleate (US Patent 4,720,353, one or more types of water soluble antioxidants, one or more types to improve the chemical stability of the retinoid An oil-in-water emulsion composition containing oil-soluble antioxidants and chelating agents (European Patent 0440,398 BI) has been published.European patent 1568106A1 discloses chelating and oil-soluble antioxidants, chelating agents and water-soluble antioxidants, and emulsions as a system for stabilizing retinoids. Oil-in-water emulsion compositions containing antioxidants and free-based imidazoles simultaneously present in the oil phase and the water phase have been reported.

In the case of the various patents described above, it can be seen that oils, water-soluble antioxidants or chelating agents are used depending on the type of emulsion to stabilize the retinol or derivatives thereof.

As such, various antioxidants are used for stabilization of retinol, and among them, BHT (Butylated hydroxytoluene) and BHA (Butylated hydroxyanisole) are most commonly used. These are radical scavengers, which strongly inhibit radical chain reactions, which have antioxidant activity. Substances. In general, the generation of radicals that cause discoloration, discoloration of cosmetics, lowering the potency of active ingredients (decreasing potency), lowering emulsification stability, and the like are promoted by metal ions. It will increase the efficacy of antioxidants.

However, most of the antioxidants including BHT used in cosmetics have many problems in terms of stability. In general, the ideal antioxidant should be stable and effective over a wide range of pH (pH), no discoloration or odor caused by any reaction, and good compatibility with other cosmetic ingredients without irritation to the skin. . In addition, such as retinol, it must have an effective antioxidant ability against a material that is very unstable and easily oxidized in light, temperature, heat, oxygen, and the like.

The most widely used antioxidants under these ideal antioxidant conditions are BHT, but BHT also has the same disadvantages. First, when a formulation containing BHT is prepared by a process of 75 ° C. or more, the titer of BHT decreases, so that it is difficult to play a role as an antioxidant when the product is used for a long time. This is because BHT has a low molecular weight and high volatility. In addition, since BHT itself is very inferior in photo-oxidative stability, exposure to light, oxygen, etc. may cause a chemical reaction and discoloration to yellow. This is because BHT is photooxidized and converted to Stilbenquinone, which is yellow in color. Therefore, there are many limitations in using BHT to secure the stability of the product for a long time.

It is an object of the present invention to stabilize the retinol, the existing antioxidants contained in the cosmetics, in particular, BHT instability at high temperatures, poor antioxidant capacity, its own discoloration and odor phenomenon, lowering the potency over time, By solving problems such as instability against photooxidation, there is no lowering of titer and discoloration during long-term storage, and effectively maintains retinol activity from light, temperature and oxygen, thereby maximizing skin beauty effects such as wrinkle improvement with retinol It is to provide a cosmetic composition.

In order to achieve the above object, the present invention overcomes the problems of BHT and uses tetraphenyl pentaerithrityl hydroxyhydrocinnamate (TPH), a phenolic antioxidants such as BHT, with retinol. It consists of providing the cosmetic composition contained together.

The inventors of the present invention for the treatment of tetradibutyl pentaerithrityl hydroxyhydrocinnamate (TPH) for the prevention of skin aging, improvement of pigmentation such as blemishes, freckles, black mushrooms, treatment of damaged skin, sun protection, etc. To overcome the problems of high temperature stability and discoloration due to photooxidation of BHT, which is most commonly used as an antioxidant for the prevention of oxidation of physiologically active substances including retinol widely used in external preparations and cosmetics, by maintaining the activity of retinol for a long time, the effect of retinol The present invention has been completed by discovering that it improves and increases the stability of the product such as discoloration.

Tetradibutyl pentaerythryl hydroxyhydrocinnamate, a phenolic antioxidant used in the present invention, has a structure similar to that of BHT, but has a high molecular weight of 1178, which is much higher than BHT (molecular weight: 220), and thus has low volatility at high temperature. Unlike BHT, which has excellent stability and converts into Stilbenquinones during the photooxidation process, it is converted into a non-covalent Bisquinonemethide which has almost no color even when photooxidation occurs. Therefore, unlike Stilbenquinones, the oxidation of the product is released by slowly releasing the energy increased by oxygen or light during the photooxidation process. It has the effect of preventing and preventing discoloration.

The cosmetic composition of the present invention containing tetradibutyl pentaerythryl hydroxyhydrocinnamate is not particularly limited in the formulation, for example, softening longevity, astringent longevity, nourishing longevity, eye cream, nutrition cream, massage It may have a formulation such as cream, cleansing cream, cleansing foam, cleansing water, powder, essence, pack, and the like.

In addition, in the cosmetic composition of each formulation, ingredients other than retinol or tetradibutyl pentaerythryl hydroxyhydrocinnamate as skin raw materials including retinol and tetradibutyl pentaerythritol hydroxyhydrocinnamate described above Depending on the formulation or purpose of use can be appropriately selected and formulated by the skilled person without difficulty.

Hereinafter, one or more test examples will be described in detail the configuration and effects of the present invention, but the present invention is not intended to be limited to these test examples.

For the test examples, a composition containing tetradibutyl pentaerythryl hydroxyhydrocinnamate with retinol (Example) and a composition containing Retinol and BHT (Comparative Example) were prepared according to the present invention as shown in Table 1 below. It became.

The raw materials of phases A and B in Table 1 were uniformly mixed, heated to 75 ° C., and then emulsified in two phases. After cooling to 45 ° C., retinol, fragrance, and preservatives were added and mixed in order to obtain a final product.

Table 1. Examples and Comparative Examples

Unit: weight ingredient Example Comparative Example Delta-tocopherol 0.2 0.2 Retinol 0.3 0.3 A Cetostearyl alcohol 2.0 2.0 Glyceryl Stearate 1.5 1.5 Microcrystallin 0.7 0.7 Squalane 5.0 5.0 Liquid paraffin 3.0 3.0 Trioctanoine 5.0 5.0 Polysorbate 60 1.2 1.2 Sorbitan stearate 0.5 0.5 Cyclomethicone 3.0 3.0 Tocopheryl Acetate 0.2 0.2 TPH 0.05 - BHT - 0.05 B Purified water Remaining amount Remaining amount Concentrated glycerin 4.0 4.0 1,3-butylene glycol 2.0 2.0 Xanthan Gum 0.1 0.1 EDTA-2Na 0.05 0.05 Incense, preservative Quantity Quantity system 100 100

In Table 1, TPH represents tetradibutyl pentaerythryl hydroxyhydrocinnamate used in the present invention.

[Test Example 1] Product discoloration test

The Examples and Comparative Examples of Table 1 were stored in an opaque glass container in a constant temperature bath maintained at 45 ° C. and stored for 8 weeks, and then the degree of separation and discoloration were measured, and the results are shown in Table 2 below. At this time, product separation and discoloration were evaluated by classifying into the following six grades.

Product discoloration evaluation criteria:

0: no change 1: very little separation (discoloration)

2: Separate slightly (discolored) 3: Separate slightly (discolored)

4: severely separated (discolored) 5: extremely severely separated (discolored)

Table 2. Stability of Examples and Comparative Examples

Elapsed time (weeks) Example Comparative Example 2 0 0.5 4 0 1.0 6 0.5 2.0 8 0.5 2.5

As a result of the test, the Example showed only a slight discoloration which is hard to be distinguished by the naked eye even after 8 weeks, whereas the Comparative Example showed a discoloration phenomenon that could be visually recognized after 4 weeks, compared to the Comparative Example. It can be seen that the stability is very high. This indicates that the TPH of the Example effectively stabilizes by inhibiting the oxidation of retinol when used longer than BHT. That is, BHT is low in high temperature stability, it can be seen that the discoloration occurs when used for a long time because the titer drops under the heating conditions (70 ℃ or more) of the general cosmetic emulsion formulation.

Test Example 2 Activity Test of Retinol

After the compositions of Examples and Comparative Examples were stored at 45 ° C. for 4 weeks, the retinol content in each content was analyzed by high performance liquid chromatography. Each content was diluted to a concentration of 20 mg / mL in a mixed solution of methanol and ethyl acetate (50 weights each), and then eluted with tetrahydrofuran / acetonitrile (5:95) and 0.05N ammonium acetate solution. A reversed phase column (C-8) was used and the content of retinol was analyzed at 340 nm. The retinol content after storage for 1 week and 4 weeks was calculated based on the retinol content of 100 immediately after the preparation of each content. The test results are shown in Table 3 below.

Table 3. Changes in Retinol Content

Elapsed time (weeks) Retinol content after storage at 45 ° C Example Comparative Example One 97 92 2 99 86 3 95 75 4 93 69

As a result of the test, the retinol content of the Example was almost unchanged for 2 weeks and dropped slightly after 4 weeks, but the Comparative Example fell to the level after 4 weeks of Example after 1 week and rapidly dropped after 4 weeks. Can be seen. From this, it can be seen that TPH preserves the titer by inhibiting the oxidation of retinol very effectively compared to BTH.

Test Example 3 Skin Wrinkle Improvement

Twenty women aged 30 years or older (mean age 37.5 years) were divided into two groups (A and B), and the examples for group A and the comparative examples for group B were formulated according to Table 1 above. After applying for 12 weeks on the area of 2X2 cm2 of the upper arm (2 times / day, 0.2g / time), the replica of the skin wrinkles is floated using a transparent silicone solution (SKIN VISIOMETER SV400, C + K Electronics GmbH. 3D analysis of the replica image with a CCD camera, and the wrinkle improvement effect by the average wrinkle roughness (R _z ) of the following formula, which is the sum of the roughness of each wrinkle (R _m : m is an integer of 1 or more) divided by the number of wrinkles. Was analyzed. The test results are shown in Table 4 below.

Table 4. Skin wrinkle improvement effect (12 weeks)

Average wrinkle roughness (R _z, ㎛) Example Comparative Example T0 T12 ΔR _z T0 T12 ΔR _z Subject 1 110 95 -15 124 95 -29 Subject 2 140 100 -40 123 100 -23 Subject 3 125 80 -45 132 109 -23 Subject 4 137 95 -42 127 110 -17 Subject 5 125 93 -32 135 108 -27 Subject 6 111 93 -18 142 115 -27 Subject 7 140 88 -52 131 113 -18 Subject 8 121 91 -30 129 112 -17 Subject 9 115 77 -38 120 100 -20 Subject 10 123 89 -34 147 135 -12 Average -34.6 -21.3

As a result of the test, after 12 weeks, the Example was lowered by 34.6 μm (p <0.01), and the wrinkles were further improved by about 62.4 or more compared with the Comparative Example. Therefore, it can be seen that TPH effectively preserves the titer of retinol, thereby effectively improving the wrinkle improvement effect of retinol compared to the comparative example.

Test Example 4 Skin Safety Test

Thirty subjects (mean age 25.9 years, age distribution 18-33 years) were divided into two groups (A, B), and the examples for group A and the comparative examples for group B, respectively. Formulation according to 1 was carried out for 2 months at room temperature using a Haye's Test Chamber skin patch test (Patch Test) was performed. Psoriasis, Eczema, and other skin lesion holders, or those who are pregnant, nursing or contraceptives, or antihistamines, are excluded from this study.

The test site was wiped with 70 ethanol and dried, and the Examples were added dropwise to the A group, and the Comparative Example was added to the B group by 15 µg, respectively, and then fixed on the upper arm. The patch is applied for 24 hours, and after removing the patch, the test site is marked with a marking pen, and the test site is observed after 24 hours, 48 hours, and 72 hours, respectively.

Determination was performed 24 hours, 48 hours, 72 hours after patch removal, and skin reactions were determined according to the regulations of the International Contact Dermatitis Research Group (ICDRG) shown in Table 5 below. The test results are shown in Table 6 below.

Table 5. Criteria for international contact dermatitis meeting

sign Criteria evaluation Mean score ± ++++++- Doubtful or slight reaction and erythemaErythema + IndurationErythema + Induration + VesicleErythema + Induration + Bullae Stimulus stimulus non stimulus 0 to 0.91.0 to 2.93.0 to 4.95.0 or more

Table 6. Skin Safety

Elapsed time Example Comparative Example 24 hours 0.5 1.0 48 hours 0 0.5 72 hours 0 0.0

As a result of the skin safety test, it can be seen that the Example is a safe cosmetic having no skin irritation with an average irritation degree of 0. In the Comparative Example, the mild irritation after 24 hours and the mild irritation after 48 hours remained. This means that in the formulation of this test containing retinol and antioxidants, TPH effectively inhibited the oxidation of retinol in the Examples, showing little skin irritation, whereas in the Comparative Example, retinol was oxidized over time causing skin irritation. It can be seen.

Based on the results of the above test examples, a cosmetic composition containing retinol and tetradibutyl pentaerythryl hydroxyhydrocinnamate is presented. However, the composition of the present invention is not intended to be limited to the following formulation examples.

Formulation Example 1 Softening Cosmetic (Skin Lotion)

Ingredient Parts by weight Retinol 0.01 1,3-butylene glycol 6.0 glycerin 4.0 Oleyl alcohol 0.1 Polysorbate 20 0.5 ethanol 15.0 TPH 0.01 Benzophenone-9 0.05 Incense, preservative a very small amount Purified water to 100

Formulation Example 2. Nutrients (Milk Lotion)

Ingredient Parts by weight Retinol 0.06 TPH 0.02 Propylene glycol 6.0 glycerin 4.0 Triethanolamine 1.2 Tocopheryl Acetate 3.0 Floating paraffin 5.0 Squalane 3.0 Macadamia Nut Oil 2.0 Polysorbate 60 1.5 Sorbitan sesquioleate 1.0 Carboxyvinyl Polymer 1.0 IDT-2N 0.01 Incense, preservative a very small amount Purified water to 100

Formulation Example 3. Nutrition Cream

Ingredient Parts by weight Retinol 0.3 TPH 0.05 Cetostearyl alcohol 2.0 Glyceryl Stearate 1.5 Trioctanoine 5.0 Polysorbate 60 1.2 Sorbitan stearate 0.5 Squalane 5.0 Liquid paraffin 3.0 Cyclomethicone 3.0 Delta-tocopherol 0.2 Concentrated glycerin 4.0 1,3-butylene glycol 2.0 Xanthan Gum 0.1 IDT-2N 0.05 Incense, preservative a very small amount Purified water to 100

Formulation Example 4 Massage Cream

Ingredient Parts by weight Retinol 0.03 TPH 0.01 Propylene glycol 6.0 glycerin 4.0 Triethanolamine 0.5 Beeswax 2.0 Tocopheryl Acetate 0.1 Polysorbate 60 3.0 Sorbitan sesquioleate 2.5 Cetearyl Alcohol 2.0 Liquid paraffin 30.0 Carboxy Vinyl Polymer 0.5 Incense, preservative a very small amount Purified water to 100

Formulation Example 5 Pack

Ingredient Parts by weight Retinol 0.06 TPH 0.02 Propylene glycol 2.0 glycerin 4.0 Carboxyvinyl Polymer 0.3 ethanol 7.0 Fiji-40 Hydrogenated Castor Oil 0.8 Triethanolamine 0.3 IDT-2N 0.01 Incense, preservative a very small amount Purified water to 100

As described above, the cosmetic composition of the present invention contains tetradibutyl pentaerythryl hydroxyhydrocinnamate together with retinol, which is a conventional cosmetic component, and thus the existing antioxidant contained in the cosmetic to stabilize retinol. Among them, in particular, it was possible to solve problems such as instability at high temperatures, poor antioxidant activity, discoloration and odor of itself, lowering of titer over time, and instability of photooxidation.

Accordingly, by completing the present invention, there is no reverse effect and discoloration phenomenon during long-term storage and effectively maintains the activity of retinol from light, temperature, oxygen, etc. It could be provided.

Claims (4)

Cosmetic composition, characterized in that it contains tetradibutyl pentaerithrityl Hydroxyhydrocinnamate (TPH) together with retinol. The method of claim 1, Tetradibutyl pentaerythryl hydroxyhydrocinnamate is contained in an amount of 0.001 to 5.0% by weight based on the total weight of the cosmetic, cosmetic composition. The method of claim 1, Tetradibutyl pentaerythryl hydroxyhydrocinnamate is contained in an amount of 0.005 to 1.0 weight based on the total weight of the cosmetic composition, cosmetic composition. A method for stabilizing retinol in a cosmetic composition, comprising stabilizing retinol by containing tetradibutyl pentaerythryl hydroxyhydrocinnamate together with a conventional cosmetic component retinol. .