Use of tocopheryl retinoate in cosmetics

Abstract

The present application relates to the technical field of cosmetic raw materials, and provides tocopheryl retinoate and application thereof in cosmetics and / or skin care products. The tocopheryl retinoate introduces a tocopherol group with antioxidant activity into the molecular structure of retinoic acid, significantly improves the light stability and thermal stability of the compound while maintaining the biological activity of vitamin A ingredients, and effectively reduces the irritation to the skin. The tocopheryl retinoate is suitable for the cosmetic and / or skin care product system used in the daytime, can improve the skin condition, repair the skin barrier and protect the skin, and has good safety and wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of cosmetic raw material technology, specifically to the application of tocopheryl retinyl esters in cosmetics and / or skin care products that improve product stability, enhance skin condition, repair the skin barrier, and protect the skin. Background Technology

[0002] Vitamin A derivatives (VA) are recognized as highly effective active ingredients in cosmetics and dermatology, with multiple benefits such as promoting epidermal renewal, stimulating collagen synthesis, and improving photoaging.

[0003] Retinol (Aleurone) is one of the most classic anti-aging active ingredients. Its anti-aging mechanism mainly includes promoting collagen synthesis and inducing the formation of dermal elastin and fibers, thereby reducing fine lines and wrinkles and improving skin firmness and elasticity. However, retinol molecules contain a large number of conjugated unsaturated double bonds and active hydroxyl groups, making them photosensitive, heat-sensitive, and easily oxidized and degraded, resulting in extremely poor chemical stability. When directly compounded into cosmetic formulations, it is highly susceptible to the influence of system moisture, acidity and alkalinity, dissolved oxygen, metal ions, emulsifiers, and conventional production processes, leading to overall instability of the formulation: on the one hand, retinol undergoes rapid oxidation, isomerization, and hydrolysis, causing loss of active ingredients and reduced efficacy; on the other hand, the organic acids and irritating impurities produced during degradation can disrupt the original balance of emulsions and creams, causing adverse phenomena such as yellowing and discoloration, off-odors, oil separation, flocculation and precipitation, abnormal system viscosity, and pH shift. Meanwhile, conventional water-in-oil and oil-in-water emulsion systems are unable to effectively protect retinol. Surfactants will exacerbate its molecular damage, and processing heating, air contact, and ordinary packaging and storage conditions will further amplify compatibility conflicts, ultimately leading to a shortened shelf life, poor batch consistency, and increased irritation of retinol-containing finished products, which seriously restricts the development and market launch of cosmetics with high retinol content.

[0004] To reduce irritation, various derivatives of retinol have been developed through side-chain modification, such as retinyl palmitate, retinyl acetate, and hydroxypinazone retinate. However, these derivatives generally suffer from insufficient stability, low biotransformation efficiency, or the need for additional antioxidant systems for protection. Furthermore, while achieving effective results, they still cannot completely eliminate irritation.

[0005] Therefore, it is particularly urgent to develop a new compound that is more stable, less irritating, and more effective, and to explore its applications. Summary of the Invention

[0006] Tocopherol retinate is a vitamin A derivative formed by chemically linking tocopherol groups to the retinoic acid molecule. This structure not only inherits the biological activity of vitamin A but also introduces the strong antioxidant properties of tocopherol, significantly improving the molecular photostability and thermal stability while reducing skin irritation. It is traditionally used as a skin protectant and antioxidant.

[0007] The present invention aims to explore the functions of tocopherol retinyl esters in depth, so that they can be applied to a wider range of functional products.

[0008] This invention discovers that tocopherol retinyl esters, while maintaining the biological activity of vitamin A derivatives, significantly improve system stability and reduce skin irritation. This allows for improved skin condition, skin barrier repair, and skin protection with lower application rates and higher skin tolerance. Specifically, it significantly increases the expression of a series of important proteins related to skin protection without cytotoxicity. Therefore, applying tocopherol retinyl esters to cosmetics and / or skincare products can achieve significant improvements in skin condition, skin barrier repair, and skin protection with lower application rates and less skin irritation.

[0009] The present invention provides a cosmetic / skin care product containing tocopherol retinyl ester, wherein the tocopherol retinyl ester accounts for 0.001% to 10% of the total material by mass, preferably 0.01% to 1%, and more preferably 0.1% to 0.5%.

[0010] Tocopherol retinate is dispersed as an additive in the matrix raw material, which is selected from one or more of the following: oily raw materials, powdery raw materials, gelatinous raw materials, fat raw materials, and solvent raw materials.

[0011] In addition, cosmetics and / or skin care products containing tocopheryl retinyl esters may also include one or more of the following: surfactants, fragrances and flavorings, pigments, moisturizers, preservatives, antioxidants, UV absorbers, chelating agents, astringents, penetration enhancers, pH adjusters, and nutritional additives.

[0012] The aforementioned cosmetics / skincare products may be one or more of the following: eye cream, face cream, serum, facial oil, lotion, and facial mask essence. Daytime use is preferred.

[0013] Compared with the prior art, the present invention has the following beneficial effects: (1) The tocopherol retinate exhibits unexpectedly high stability under light and high temperature conditions, effectively reducing the degradation risk of vitamin A components during storage and use; (2) It has good skin tolerance and its irritation is significantly lower than that of retinol and some existing retinol derivatives, and it is not likely to cause adverse reactions such as erythema or desquamation; (3) It does not have phototoxicity or photoallergenicity and can be safely applied to cosmetic systems used during the day; (4) While exerting the skin renewal effect of vitamin A, it not only does not weaken the skin barrier function, but also promotes the production of skin barrier-related proteins; (5) It also has the antioxidant effect of vitamin E, which works synergistically with the effects of vitamin A to comprehensively improve skin condition. Attached Figure Description

[0014] Figure 1 In a stability comparison study, the content changes of tocopherol retinate, retinol, retinaldehyde, hydroxypinazone retinate, and retinyl acetate were analyzed under light-protected, sealed conditions at 4°C for 8 months.

[0015] Figure 2 For stability comparison studies, the content changes of tocopherol retinate, retinol, retinaldehyde, hydroxypinazone retinate, and retinyl acetate were studied under light-protected, sealed, and room temperature conditions for 8 months.

[0016] Figure 3 For stability comparison studies, the content changes of tocopherol retinate, retinol, retinaldehyde, hydroxypinazone retinate, and retinyl acetate were investigated under light-protected, sealed conditions at 50°C for 8 months.

[0017] Figure 4 In a stability comparison study, the content changes of tocopherol retinate, retinol, retinaldehyde, hydroxypinazone retinate, and retinyl acetate were investigated under light, sealed, and room temperature conditions for 8 months.

[0018] Figure 5 The irritation results of tocopherol retinate, retinol, and hydroxypinazone retinate in an in vitro comparative irritation test of a recombinant human epidermal model.

[0019] Figure 6 This is a bar graph showing the results of measuring the moisture content of the stratum corneum before and after using 0.1% tocopheryl retinate serum in a clinical trial on human skin.

[0020] Figure 7 This is a bar graph showing the transepidermal water loss (TEWL) values ​​before and after use in a clinical trial on human skin using 0.1% tocopheryl retinate serum.

[0021] Figure 8 This is a bar graph showing the results of skin hemoglobin index testing before and after using 0.1% tocopherol retinyl ester essence oil in a clinical trial on human skin. Detailed Implementation

[0022] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. The instruments, reagent kits, cells, and reagents used in the experimental examples can all be purchased through publicly available commercial channels and are commonly used instruments, reagent kits, cells, and reagents in the art. The operation steps of the instruments and reagent kits are performed according to their instruction manuals.

[0023] Example 1. Stability study of tocopherol retinate Experimental Objective In accordance with the "Technical Guidelines for Stability Studies of Chemical Drugs (Active Pharmaceutical Ingredients)," a comparative stability study was conducted on tocopherol retinate and other vitamin A derivative samples.

[0024] Examination conditions Table 1 Examination Conditions condition Research Methods Sampling points Protect from light, seal, 4℃ Stability study of products after aluminum bottle packaging January, March, June, August Protect from light, seal, room temperature Stability study of products after aluminum bottle packaging January, March, June, August Protect from light, seal, 50℃ Stability study of products after aluminum bottle packaging January, March, June, August Light, sealed, room temperature Stability study of products packaged in transparent glass bottles January, March, June, August Examination method: Appearance: Changes in the appearance of the sample are observed visually. Odor: Assess changes in sample odor through olfaction; Content determination: The content of active ingredients in each sample was determined by high performance liquid chromatography (HPLC).

[0025] Results of the examination: Appearance and odor: As shown in Table 2, after being stored for 8 months under different conditions, the appearance, odor and color of tocopherol retinate did not change significantly under the following conditions: protected from light, sealed at 4°C, protected from light, sealed at room temperature, and exposed to light, sealed at room temperature. Under the following conditions: protected from light, sealed at 50°C, only a slight change in color to orange-yellow was observed. No precipitation, turbidity or off-odor was observed, indicating that the raw material still has good physical stability under high temperature conditions.

[0026] Table 2. Changes in appearance, odor, and color of tocopherol retinate under different conditions over 8 months .

[0027] Content, protected from light, sealed, 4℃: as shown in Table 3 / Figure 1 As shown, under these conditions, the content of tocopherol retinyl ester remained basically stable after 8 months of storage, and remained above 99% after 8 months, which is significantly better than retinol, retinaldehyde, hydroxypinazone retinyl ester and retinyl acetate.

[0028] Table 3. Content changes over 8 months under light-protected, sealed conditions at 4℃ Time (days) Retinol Retinaldehyde Hydroxypinazone retinyl ester Retinyl acetate Tocopheryl Retinyl Ester 0 100.00 100.00 100.00 100.00 100.00 30 99.52 99.71 99.78 99.61 99.99 60 99.33 99.62 99.77 99.71 99.82 90 99.21 99.69 99.65 99.45 99.42 120 99.0724 99.64 99.395 99.45 99.6 240 99.01 99.6 99.4 99.44 99.4 .

[0029] Light-proof, sealed, room temperature: as shown in Table 4 / Figure 2 As shown, under room temperature and light-protected conditions, tocopherol retinate still maintained a content of more than 95% after 8 months, while the contents of other control vitamin A derivatives decreased significantly under the same conditions, with some samples degrading by more than 50%, demonstrating that tocopherol retinate has a significant stability advantage under normal storage conditions.

[0030] Table 4. Content changes over 8 months under light-protected, sealed, and room-temperature conditions. Time (days) Retinol Retinaldehyde Hydroxypinazone retinyl ester Retinyl acetate Tocopheryl Retinyl Ester 0 100.00 100.00 100.00 100.00 100.00 30 82.38 84.23 91.96 87.32 98.9 60 70.19 72.87 82.64 78.22 98.77 90 61.36 65.44 78.37 70.43 98.71 120 50.94 56.02 64.84 60.35 96.1 240 32.71 35.11 41.01 39.62 95.27 Protect from light, seal tightly, 50℃: as shown in Table 5 / Figure 3 As shown, under high temperature conditions, tocopherol retinyl esters exhibited unexpectedly high stability, retaining more than 90% of their content after 8 months; in contrast, retinol, retinaldehyde and other retinol derivatives underwent severe degradation under the same conditions, with some samples becoming almost completely inactive after 120 days.

[0031] Table 5. Content changes over 8 months under light-protected, sealed conditions at 50℃ Time (days) Retinol Retinaldehyde Hydroxypinazone retinyl ester Retinyl acetate Tocopheryl Retinyl Ester 0 100.00 100.00 100.00 100.00 100.00 30 74.66 76.39 88.01 79.73 99.67 60 45.79 54.72 73.38 62.82 96.23 90 16.70 20.82 47.03 39.67 93.80 120 0.08 1.8137 24.86 15.59 92.50 240 0.02 0.05 3.03 2.01 90.57 Light exposure, sealing, room temperature: as shown in Table 6 / Figure 4 As shown, after 8 months of storage under light conditions, the content of tocopherol retinate remained above 90%, while other vitamin A derivatives showed varying degrees of photodegradation under light conditions, with a significant decrease in content, indicating that tocopherol retinate has excellent photostability.

[0032] Table 6. Content changes over 8 months under light, sealed, and room temperature conditions. Time (days) Retinol Retinaldehyde Hydroxypinazone retinyl ester Retinyl acetate Tocopheryl Retinyl Ester 0 100.00 100.00 100.00 100.00 100.00 30 86.33 90.62 96.80 94.81 99.39 60 63.29 76.61 93.77 90.21 98.11 90 51.75 65.36 91.89 82.91 96.88 120 30.11 57.74 84.82 71.17 93.30 240 5.01 26.76 66.73 43.73 90.66 in conclusion The stability study results indicate that tocopherol retinate exhibits significantly better stability than traditional vitamin A derivatives under various storage conditions, including low temperature, room temperature, high temperature, and light exposure. This stability advantage makes it less prone to inactivation during cosmetic storage, transportation, and actual use, which is beneficial for broadening the application scenarios of vitamin A derivatives in cosmetics, especially suitable for cosmetic systems that require high stability for daytime use and long-term storage.

[0033] Example 2. Human skin patch test of tocopherol retinyl esters 2.1 Materials and Methods: 2.1.1 Test substance: Prepared tocopherol retinate solutions of different concentrations.

[0034] 2.1.2 Negative control: filter.

[0035] 2.2.3 Subjects: A total of 90 subjects, who met the subject voluntary inclusion criteria.

[0036] 2.1.4 Patch test method: Select qualified patch test equipment and use the closed patch test method. Place about 0.020 mL to 0.025 mL of the test substance in the patch test device, apply it to the back of the subject with hypoallergenic adhesive tape, remove the test substance after 24 hours, and observe the skin reaction at 0.5, 24 and 48 hours after removal. Record the results according to the skin reaction grading standard in the current effective technical specifications.

[0037] 2.2 Test Results Table 7 Summary of Cosmetic Human Skin Patch Test Results .

[0038] 2.3 Conclusion Human skin patch tests showed that even at a concentration as high as 5% by mass, tocopheryl retinate did not cause irritation or sensitization to human skin, demonstrating good skin tolerance and safety. It is suitable for long-term use and daytime use in cosmetic systems, providing sufficient human safety evidence for its application in improving skin condition, repairing the skin barrier, and protecting the skin.

[0039] Example 3. Skin phototoxicity test of tocopherol retinate 3.1 Test method: Skin phototoxicity was scored according to the relevant provisions of Chapter 6 Toxicological Test Method 7 Skin Phototoxicity Test in the Cosmetic Safety Technical Specification (2015 Edition). The phototoxicity was determined based on the animal scores at each observation time point of 1h, 24h, 48h, and 72h.

[0040] 3.2 Experimental Results: No abnormal symptoms appeared on the skin during the experiment, and the skin reaction score at each observation time point was 0. According to the skin irritation reaction grading, no skin phototoxicity was observed in the test sample. The results of the positive control on skin phototoxicity test are shown in Table 7, and the results of the test sample on skin phototoxicity test are shown in Table 8.

[0041] Table 7 Results of skin phototoxicity test of positive control Table 8 Results of skin phototoxicity tests on the test samples

[0042] 3.3 Conclusion: Under the experimental conditions, tocopherol retinate did not cause any phototoxic skin reaction, indicating that it has good safety under light conditions, providing experimental evidence for its application in cosmetics used during the day.

[0043] Example 4. Skin photoallergy test of tocopherol retinate 4.1 Test Method: The test samples were tested according to Annex 2 of the "Skin Photoallergy Test Method" in Announcement No. 136 of 2017 issued by the State Food and Drug Administration. Skin reactions were observed 24 hours after ultraviolet irradiation in the photoinduction phase and 24 hours and 48 hours after ultraviolet irradiation in the photoexcitation phase, and skin reaction scores were determined.

[0044] 4.1 Control information: Positive control: tetrachlorosalicylic acid aniline; Negative control: distilled water.

[0045] 4.2 Experimental results: No abnormal symptoms were observed on the skin, and the photosensitive reaction rate of tocopherol retinate was 0%.

[0046] Table 9 Results of skin photoallergy

[0047] 4.3 Conclusion: The experimental results show that tocopherol retinate does not have the sensitizing effect of skin photosensitization and there is no risk of photosensitization under normal cosmetic use conditions, which further verifies its safety advantage as a vitamin A active ingredient that can be used during the day.

[0048] Example 5. Irritation test of in vitro recombinant human epidermal model of tocopherol retinate 5.1 Test Basis: The test was conducted in accordance with OECD TG439 In Vitro Skin Stimulation: Recombinant Human Epidermal Test.

[0049] 5.2 Test Grouping: Prepare the sample working solution according to the test groups in Table 10.

[0050] Table 10 Test Groups

[0051] Note: The active ingredient concentration of the tocopherol retinate, retinol, and hydroxypinazone retinate stock solution is 1.5% (v / v).

[0052] 5.3 Results Evaluation: The final irritation classification was determined with reference to OECD TG439, ​​and the judgment criteria are shown in Table 11.

[0053] Table 11 Criteria for Judging Skin Irritation Relative activity average Skin irritation assessment results Relative activity average >50% Non-irritating (NI) The average relative activity is ≤50%. Irritating (I) 5.4 Test Results Table 12 Irritation Results of the In Vitro Recombinant Human Epidermal Model .

[0054] 5.5 Conclusion: The in vitro recombinant human epidermal irritation test results show that tocopherol retinate maintains good skin tolerance under high concentration conditions, and its irritation is significantly lower than that of traditional retinol and hydroxypinazone retinate, which further supports its application as a mild vitamin A active ingredient in cosmetics.

[0055] Example 6. In vitro recombinant human epidermal model experiment of tocopherol retinate 6.1 Experimental Objective: This test is based on a UVB irradiated 3D epidermal skin model (EpiKutis®). By detecting changes in the levels of inflammatory factors (IL-1α) and inflammatory mediators (PGE2), the test samples are evaluated to determine whether they have a soothing effect and ultimately achieve skin protection. By detecting changes in the levels of filaggrin (FLG) and lobelin (LOR), the test samples are evaluated to determine whether they have a repairing effect and ultimately achieve skin protection.

[0056] 6.2 Test Groups: Prepare sample working solutions according to the test groups in Table 13.

[0057] Table 13 Test Groups 6.3 Test Results 6.3.1 Inflammatory factor IL-1α: Compared with the BC group, the IL-1α level in the NC group was significantly increased, indicating that the stimulation conditions in this test were effective. Compared with the BC group, the IL-1α level in the SC group was significantly increased. Compared with the NC group, the IL-1α level in the PC group was significantly decreased, indicating that the positive control in this test was effective; compared with the NC group, the IL-1α level in the sample tocopherol retinate-0.1% group was significantly decreased, with an inhibition rate of 36.26%.

[0058] Table 14 Summary of IL-1α Immunofluorescence Analysis Results Note: When performing statistical analysis using the t-test method, significance compared with the BC group is indicated by #, with P-value < 0.05 indicated by # and P-value < 0.01 indicated by ##; significance compared with the NC group is indicated by *, with P-value < 0.05 indicated by * and P-value < 0.01 indicated by **; significance compared with the SC group is indicated by △, with P-value < 0.05 indicated by △ and P-value < 0.01 indicated by △△.

[0059] 6.3.2 Inflammatory mediator PGE2: Compared with the BC group, the PGE2 content in the NC group was significantly increased, indicating that the stimulation conditions in this test were effective. Compared with the BC group, the PGE2 content in the SC group was significantly increased. Compared with the NC group, the PGE2 content in the PC group was significantly decreased, indicating that the positive control in this test was effective; compared with the NC group, the PGE2 content in the sample tocopherol retinate-0.1% group was significantly decreased, with an inhibition rate of 40.97%.

[0060] Table 15 Summary of PGE2 Immunofluorescence Analysis Results Note: When performing statistical analysis using the t-test method, significance compared with the BC group is indicated by #, with P-value < 0.05 indicated by # and P-value < 0.01 indicated by ##; significance compared with the NC group is indicated by *, with P-value < 0.05 indicated by * and P-value < 0.01 indicated by **; significance compared with the SC group is indicated by △, with P-value < 0.05 indicated by △ and P-value < 0.01 indicated by △△.

[0061] 6.3.3 FLG (figrin): Compared with the BC group, the FLG content in the NC group was significantly lower, indicating that the stimulation conditions in this test were effective. Compared with the NC group, the FLG content in the SC group did not change significantly. Compared with the NC group, the FLG content in the PC1 group was significantly higher, indicating that the positive control in this test was effective. Compared with the NC group, the FLG content of tocopherol retinate in the sample at a concentration of 0.1% was significantly higher, with a promotion rate of 116.67%.

[0062] Table 16 Summary of FLG Immunofluorescence Analysis Results Note: The average relative integrated optical density (IOD) reflects the FLG content. When performing statistical analysis using the t-test method, significance compared to the BC group is indicated by # (P-value < 0.05 is indicated by #, P-value < 0.01 is indicated by ##); significance compared to the NC group is indicated by * (P-value < 0.05 is indicated by *, P-value < 0.01 is indicated by **); significance compared to the SC group is indicated by △ (P-value < 0.05 is indicated by △, P-value < 0.01 is indicated by △△).

[0063] 6.3.4 LOR of tocopheryl retinyl ester: Compared with the BC group, the LOR content in the NC group was significantly decreased, indicating that the stimulation conditions in this test were effective. Compared with the NC group, the LOR content in the SC group did not change significantly. Compared with the NC group, the LOR content in the PC1 group was significantly increased, indicating that the positive control in this test was effective. Compared with the NC group, the LOR content of tocopheryl retinyl ester in the sample was significantly increased at a concentration of 0.1%, with a promotion rate of 121.88%.

[0064] Table 17 Summary of LOR Immunofluorescence Analysis Results 6.4 Conclusion The above-mentioned in vitro three-dimensional recombinant human epidermal model experiments showed that tocopherol retinyl esters significantly inhibited the release of inflammatory cytokines IL-1α and inflammatory mediator PGE2 in a UVB-induced skin damage model, while significantly promoting the production of skin barrier-related proteins such as filaggrin and naegrin. These results fully demonstrate that tocopherol retinyl esters have good soothing and repairing effects, ultimately achieving skin protection. It is suitable for developing cosmetics with skin protection, barrier repair, and photodamage protection functions.

[0065] Example 7. Clinical trial of tocopherol retinyl esters in human skin 7.1 Experimental objective: To evaluate the skin protective effect of the samples by comparing the skin stratum corneum moisture content, transepidermal water loss (TEWL) value, and skin hemoglobin index before and after sample use using instrumental detection.

[0066] 7.2 Sample completion status: 32 participants were enrolled, 31 of whom completed the experiment, and 31 were included in the statistical analysis. There were 2 males and 29 females, with a mean age of 49 ± 7 years.

[0067] 7.3 Sample usage: The sample group used 0.1% tocopherol retinate essence oil twice a day, morning and evening. The control group used base essence oil twice a day, morning and evening.

[0068] 7.3 Test Results 7.3.1 Results of skin stratum corneum moisture content test: Compared with before use, after using 0.1% tocopheryl retinyl ester essence oil for 2 weeks (T2) and 4 weeks (T4), the skin stratum corneum moisture content of the subjects was significantly increased, with an increase rate of 31.16% and 61.16%, respectively.

[0069] 7.3.2 Transdermal water loss (TEWL) value test results: Compared with before use, after using 0.1% tocopheryl retinyl ester essence oil for 2 weeks (T2) and 4 weeks (T4), the transdermal water loss (TEWL) values ​​of the subjects decreased significantly, with downregulation rates of 6.65% and 13.68%, respectively.

[0070] 7.3.3 Results of skin hemoglobin index test: Compared with before use, after using 0.1% tocopherol retinyl ester essence oil for 2 weeks (T2) and 4 weeks (T4), the skin hemoglobin index of the subjects decreased significantly, with a downregulation rate of 7.94% and 12.71%, respectively.

[0071] 7.4 Conclusion Cosmetics containing 0.1% tocopheryl retinate can effectively increase the moisture content of the stratum corneum, reduce transepidermal water loss, and reduce skin redness, demonstrating the good effects of tocopheryl retinate in improving skin barrier function and protecting skin health. Furthermore, no adverse skin reactions were observed in subjects who used 0.1% tocopheryl retinate serum oil for 28 consecutive days during the day, proving that this ingredient has good safety and tolerability for daytime use and is suitable for application in daily skincare products.

[0072] Example 8. Cosmetics / skincare products containing tocopherol retinyl esters The tocopherol retinate content in the total material is 0.001% to 10% by mass, preferably 0.01% to 1%, and more preferably 0.1% to 0.5%.

[0073] Tocopherol retinate is dispersed as an additive in the matrix raw material, which is selected from one or more of the following: oily raw materials, powdery raw materials, gelatinous raw materials, fat raw materials, and solvent raw materials.

[0074] The oily raw material can be any one or a combination of the following matrix raw materials: soybean oil, olive oil, almond oil, castor oil, peanut oil, cottonseed oil, tea seed oil, jojoba oil, avocado oil, coconut oil, palm oil, cocoa butter, rice bran oil, evening primrose oil, wheat germ oil, corn germ oil, palm wax, wood wax, mink oil, turtle oil, snake oil, egg yolk oil, beef tallow, horse tallow, lard, deer tallow, lecithin, lanolin, beeswax, cetacean wax, shellac wax, paraffin wax, petrolatum, microcrystalline wax, ceresin, squalane, lanolin wax, lanolin alcohol, lanolin alcohol. Esterified lanolin, acetylated lanolin alcohol, lanolin acid, lanolin esterified lanolin, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol ether, polyoxypropylene lanolin alcohol ether, hydrogenated lanolin, alkoxylated hydrogenated lanolin, silicone oil (e.g., dimethyl silicone oil, octamethyl silicone oil, methylphenyl polysiloxane), polysiloxane-polyoxyalkyl block copolymer, methyl hydrogen silicone oil, Cn fatty acids and their esters, Cn fatty alcohols and their esters; wherein n ≥ 10, preferably 10-24, more preferably 12-20, such as 14, 16, 17, 18; Cn fatty acids such as: lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, erucic acid, decanoic acid. Cn fatty alcohols such as: lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, cocoyl alcohol. Cn fatty acid esters and Cn fatty alcohol esters, such as: isopropyl myristate, myristyl myristate, tetradecyl lactate, hexadecyl lactate, isopropyl palmitate, palm isooctyl ester, butyl stearate, isooctyl stearate, monocotylene stearate, polyethylene glycol stearate, decyl oleate, octyl oleate, octyl oleate, glyceryl trioleate.

[0075] The powdered raw material can be any one or a combination of the following matrix raw materials: mica, magnesium carbonate, titanium dioxide, zinc dioxide, calcium hydroxide, calcium carbonate, kaolin, calcium stearate, zinc stearate, magnesium stearate, talc, silicon dioxide, aluminum hydroxide, calcium pyrophosphate, calcium bicarbonate, and bentonite.

[0076] Oil and fat raw materials can be any one or more of the following: vegetable oil, animal oil, mineral oil, synthetic oil, and semi-synthetic oil. Examples include: starch, cyclodextrin, xanthan gum, carrageenan, guar gum, gum arabic, astragalus gum, agar, shellac, sodium alginate, gelatin, methylcellulose, ethylcellulose, sodium carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropylcellulose, polycellulose ether quaternary ammonium salt, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, polyoxyethylene, vinylpyrrolidone / vinyl acetate copolymer, carbomer resin, magnesium aluminum silicate, and C12-15 benzoyl alcohol.

[0077] The solvent raw material can be any one or a combination of the following matrix raw materials: water, ethanol, propanol, isopropanol, isobutanol, ethylene glycol, 1,2-propanediol, cyclohexane, dichlorodifluoromethane, tetrafluorodichloroethane, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, amyl acetate, and dibutyl phthalate.

[0078] In addition, cosmetics and / or skin care products containing tocopheryl retinyl esters may also include one or more of the following: surfactants, fragrances and flavorings, pigments, moisturizers, preservatives, antioxidants, UV absorbers, chelating agents, astringents, penetration enhancers, pH adjusters, and nutritional additives.

[0079] Among them, the surfactant can be: (1) anionic surfactant, such as: C12-14 fatty alcohol ammonium sulfate, C12-14 fatty alcohol polyoxyethylene ether carboxylate, diethanolamine dodecyl sulfate, C12-14 fatty alcohol polyoxyethylene ether ammonium sulfate, triethanolamine dodecyl sulfate, sodium monoethyl phthalate of alcohol ether, acylated peptide, sodium monoethanolamide laurate, n-octyl alcohol polyoxypropylene ether succinate monosulfonate, cetyl alcohol succinate monosulfonate, disodium sulfosuccinate monoester, disodium octadecyl succinate monoester, disodium sulfosuccinate monoester, disodium sulfosuccinate monoester, fatty alcohol polyoxyethylene ether (sodium) sulfosuccinate monoester ammonium salt, oleamide sulfosuccinate monoester disodium salt, potassium N-acylglutamate, sodium pyrrolidone carboxylate, sodium polyacrylate, fatty alcohol polyoxyethylene ether phosphate Esters, fatty alcohol polyoxyethylene ether phosphate monoesters and their salts, fatty alcohol polyoxyethylene ether phosphate monoester ethanolamine salts, alkylphenol polyoxyethylene ether phosphate monoesters and their salts, nonylphenol ether phosphate monoester ethanolamine salts, alkyl phosphate salts, phthalic acid monolaurate salts, zinc undecenoate, anionic amino acid surfactants, N-C12-18 acylglutamate sodium salt, N-lauroyl L-alanine sodium salt, N-stearoyl glutamate monosodium salt, N-cocoyl glutamate monosodium salt, N-mixed fatty acyl glutamate monosodium salt, long-chain alkyl aryl ether sulfonate sodium TH;(2) Nonionic surfactants, such as: oleyl alcohol polyoxyethylene ether (e.g., emulsifier VO series), alkylphenol polyoxyethylene ether (e.g., emulsifier OPE series), polyoxyethylene stearate, ethylene glycol monostearate, ethylene glycol distearate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol dilaurate, glyceryl distearate, glyceryl tristearate, sucrose stearate, polyoxyethylene glycerol ether monostearate, N-lauroyl glutamate dialkyl alcohol ester, benzoic acid fatty alcohol ester, sorbitan monofatty acid ester (Span, Sp (e.g., Span-20, Span-60, Span-65, Span-80, Span-83, Span-85), polyoxyethylene ether sorbitan monofatty acid esters (Tween, e.g., Tween-20, Tween-40, Tween-60, Tween-61, Tween-80), diethanolamine, triethanolamine, fatty acid monoethanolamides (e.g., coconut oil monoethanolamide, laurate monoethanolamide, palmitic acid monoethanolamide), coconut oil diethanolamide, laurate diethanolamide, methyl glucoside stearate, polyoxyethylene methyl glucoside Glycoside stearate, ethylene glycol glucoside stearate, propylene glycol glucoside stearate, C8-16 alkyl glucoside, eicosyl glucoside stearate, lauryl ether monoester of succinate, lauryl glycerol polyoxyethylene ether, mannitol stearate, polyoxyethylene mink oil, methyl mink oil, isopropyl mink oil; (3) cationic surfactants, such as chlorinated C12-18 alkyltrialkylammonium (e.g., hexadecyl dimethyl alkylammonium chloride, octadecyl trimethylammonium chloride, hexadecyl trimethylammonium chloride), chlorinated oleamide propyl dihydroxypropyl dimethyl alkylammonium, etc. Methylammonium, dihydroxypropyl dimethyl dodecylammonium chloride, dimethyl diallyl ammonium chloride / acrylamide copolymer, oleamidopropyl-2,3-dihydroxypropyl dimethylammonium chloride, ethyl oleamidopropyl dimethyl ethyl ammonium sulfate, bis(C12-18) dimethylammonium chloride, polyquaternium-11 conditioning agent, M-505 polyquaternium-7 conditioning agent, mink oleamidopropylamine-chitosan, mink oleamidopropylamine-hydrolyzed protein, cationic protein peptides, guar gum-hydroxypropyltrimethylammonium chloride, polycellulose ether quaternary ammonium salt, triethanolamine monooleate, DNP Series; (4) Amphoteric surfactants, such as C12-18 alkyl dihydroxyethyl betaine, N-C12-18 alkyl-N-(2-hydroxyethyl)-N-(2-formamidoethyl)ammonium acetate, C12-18 alkoxyhydroxypropyl betaine, oxidized cocamidopropylamine, sodium cocoyl hydroxyethyl sulfonate, oxidized octadecyl dimethylamine, cocoyl diethanolamine amine oxide, N-alkyl-β-aminopropionyl diethanolamine, oxidized lauroyl propylamine, N-C12-18 acylglutamic acid, hydroxyethyl decanoic acid imidazoline betaine, hydroxyethyl myristate imidazoline betaine, hydroxyethyl palmitic imidazoline betaine.

[0080] Fragrances and flavorings may be selected from: natural flavorings, such as wormwood oil, eucalyptus oil, star anise oil, white lemon oil, white clove extract, clove oil, magnolia oil, magnolia extract, magnolia leaf oil, cypress oil, peppermint oil, atractylodes stearate, sweet osmanthus extract, orange leaf oil, clove basil oil, jasmine extract, wintergreen oil, angelica oil, angelica extract, lichenic acid, sandalwood oil, bitter orange flower oil, bitter orange leaf oil, hyacinth extract, sweetgum extract, linalool oil, sassafras oil, spikenard oil, osmanthus extract, mandarin orange oil, carrot seed oil, castor oil, and more. Okra oil, dandelion oil, patchouli oil, wormwood oil, Murraya paniculata extract, acacia extract, ginger oil, orange oil, peppermint oil, chrysanthemum extract, cumin oil, ambergris, spearmint oil, civet, wintersweet oil, lily of the valley extract, costus root oil, milan flower oil, rose leaf oil, rose oil, jasmine extract, oyster oil, marmalade extract, marmalade oil, lemon eucalyptus leaf oil, lemon oil, Murraya paniculata extract, nanmu leaf oil, celery seed oil, nutmeg oil, cinnamon oil, litsea cubeba oil, mink balsam tincture, narcissus extract, pine needle oil, tree moss extract, jasmine extract Ointment, Musk, Musk Ointment, Sweet Orange Oil, Sandalwood Oil, Tuberose Oil, Tuberose Extract, Marigold Essential Oil, Fennel Oil, Blood Cypress Oil, Citronella Oil, Bay Leaf Oil, Carnation Oil, Perilla Oil, Scented Perilla Oil, Cyperus Oil, Bergamot Peppermint Oil, Vetiver Oil, Elsholtzia Oil, Elsholtzia Extract, Rubus Rose Flower Oil, Rubus Rose Flower Extract, Lavender Oil, Bay Leaf Oil, Ylang Ylang Oil, Coriander Seed Oil, Fishgrass Oil, Rock Rose Extract, Cinnamon Oil, Grapefruit Peel Oil, Iris Oil, Tobacco Flower Oil, Citron Leaf Oil, Gardenia Flower Extract, Purple Spike Sophora japonica oil, violet leaf extract, guaiacol, 4-methylguaiacol, 4-ethylguaiacol, natural vanillin, camphor; synthetic fragrances, such as limonene, longifolene, beta-caryophyllene, isolongifolene, isolongifolene ketone, isolongifolene ketone, bromostyrene, diphenylmethane, diphenyl ether, m-methyl diphenyl ether, eugenol, isoeugenol, beta-caryophyllene methyl ether, beta-caryophyllene ethyl ether, p-methyl anisole, isocaryophyllene benzyl ether, rose ether, sandalwood ether, narcissus ether (or jasmine ether), ambergris ether, methyl cedarwood ether, epoxy cedarwood alkylene. Elintall, Elintall N, 3-Hexenol, Decanol, Lauryl alcohol, Benzyl alcohol, Phenylethanol, p-Methoxybenzyl alcohol, Cinnamyl alcohol, Dimethylbenzylmethanol, Geraniol, Nerol, Linalool, Rose alcohol, Terpineol, Citronellol, Racemic Menthol, Menthol, Borneol, Cedarwood alcohol, Cedarwood ketone, Methyl Cedarwood ketone, 3,4-Dioxomethylenebenzyl alcohol, α-Methyl-3,4-Dihydromethylenephenylpropanal, 2-tert-butyl-4-methylcyclohexanol, Perillyl alcohol, Santalol, 3-Methyl-5-(2',2',3'-Trimethylcyclopenten-1'-yl)-2-ol, Benzaldehyde, Acetophenone, Phenylacetic acid, p-Methylacetophenone, Benzophenone, Laural, Cinnamaldehyde, Cinnamic acid, α-Pentyl-β-phenylpropenal, α-Phenylacetal, Lily of the Valley Aldehyde, Neolily of the Valley Aldehyde, Raphanus aldehyde, 3,4-Dioxomethylenebenzaldehyde, 3,7-Dimethyl-6-octenal, 3,7-Dimethyl-7-hydroxyoctanal, citral, ethyl-cyclocitral, laval, citric acid, 4-hydroxy-3-methoxybenzaldehyde, α-dihydro-draconone, β-draconone, ionone, 6-methyl-ionone, nerone, carvone, piperylacetone, raspberry ketone, herbicide, cis-jasmone, heptanal ethylene glycol acetal, phenylacetaldehyde dimethyl acetal, octanal dimethyl acetal, α-pentylcinnamaldehyde dimethyl acetal, citral dimethyl acetal, citral diethyl acetal, anisaldehyde dimethyl acetal, mushroom aldehyde, chlorophyll Hyacin, apple ester, jeep ketal, geraniol formate, citronellol formate, averman ester, leaf alcohol acetate, benzyl acetate, phenethyl acetate, cinnamon ester, terpineol acetate, borneol acetate, linalyl acetate, geraniol acetate, p-tert-butylcyclohexyl acetate, o-tert-butylcyclohexyl acetate, vetiver acetate, succinate acetate, averman acetate, decahydrotheca acetate, cypress ester, geraniol propionate, trichloromethylbenzyl acetate, benzyl butyrate, leaf alcohol butyrate, geraniol butyrate, 2-methylvaleric acid phenylethyl Esters, p-cresol isobutyrate, methyl 2-nonenoate, ethyl benzoate, methyl benzoate, leaf benzoate, benzyl benzoate, ethyl phenylacetate, p-cresol phenylacetate, ethyl cinnamate, butyl salicylate, isobutyl salicylate, isoamyl salicylate, leaf benzoate, hexyl salicylate, benzyl salicylate, phenethyl salicylate, cyclohexyl salicylate, jasmine, jasmine ester, methyl 2-pentylcyclopentanone acetate, nerolidin, γ-nonanolide, γ-undecyl lactone, coumarin, indole, 3-methylindole, 3,7- Dimethyl-2,6-octadienonitrile, p-methoxybenzonitrile, xylene musk, ketone musk, 2,6-dinitro-3-methoxy-4-tert-butyltoluene, 1,1-dimethyl-4-acetyl-6-tert-butylindane, hexamethyltricycloisocyanuric musk, 1,1,2,3,3,6-hexamethyl-5-acetylindane, musk-T, musk-M, musk-L, musk-F, 11-oxacyclohexadecanolactone, tuna musk; (3) fragrances, rose fragrance, jasmine fragrance, sandalwood fragrance, magnolia fragrance.

[0081] The pigment may be selected from one or more of the following components: zirconium dioxide, lead acetate, silver nitrate, chlorophyll, copper chlorophyll, ferrous ferrocyanide, guanine, fast red, food red I, reduced red I, carmine, edible bayberry red, edible cherry red, food red 17, amaranth red, fast green, food yellow 3, edible tartrazine, edible Sudan yellow, edible indigo, food blue 2, fluorescent pink, β-carotene, henna, gardenia red, gardenia green, gardenia blue, gardenia yellow, titanium mica pearlescent pigment, iron oxide red, iron oxide yellow, iron oxide black, chromium oxide green, bismuth oxychloride, basic pink, cinnabar R, quinoline yellow, lithospermum erythrorhizon, shellac red, ultramarine, acid red 87, acid green 25, acid fluorescent yellow, acid orange 7, golden red 53, Litholite BK, Litholite 2R, permanent orange.

[0082] Preservatives may be selected from one or more of the following components: sorbic acid and its salts, propionate, p-hydroxybenzoate, benzyl alcohol, benzoic acid and its salts, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, Kathon, imidazolidinyl urea, dehydroacetic acid and its salts, sodium sulfite, sodium bisulfite, sodium metabisulfite, 2,2-bromo-2-nitro-1,3-propanediol (Bropol), isoascorbic acid and its salts, kojic acid and its esters, azelaic acid, usnic acid, and resorcinol.

[0083] Antioxidants may be selected from one or more of the following components: SOD, butylated hydroxyanisole, gallate, ascorbic acid and its salts, isoascorbic acid and its salts, sitosterol, rutin, and tocopherol.

[0084] The moisturizer may be selected from one or more of the following components: 1,2-butanediol, sorbitol, xylitol, glycerin, lactate, polyethylene glycol, DL-pyrrolidone carboxylate, D-glucose, kojic acid and its esters, uric acid, orotic acid, pectic acid, laminine, collagen, trehalose, 12-hydroxystearic acid cholesterol ester.

[0085] The ultraviolet absorber may be selected from one or more of the following components: pyridoxine hydrochloride, kojic acid and its esters, rutin, aloe-emodin, caffeine, hesperidin, 2-ethylhexyl salicylate, 2-ethylhexyl p-dimethylaminobenzoate, 2-ethylhexyl p-methoxycinnamate, phenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-octyloxybenzophenone.

[0086] The chelating agent may be one or a combination of the following components: disodium EDTA, zinc dipyridylthione, and sodium thiosulfate.

[0087] Astringents may be one or a combination of the following components: zinc phenol-p-sulfonate, aluminum hydroxychloride, aluminum sulfate, potassium aluminum sulfate, zinc sulfate, aluminum chloride, zinc chloride, and carmine.

[0088] The penetration enhancer may be one or a combination of the following components: isosorbide dimethyl ether, dimethyl sulfoxide, 1-n-dodecylazine-2-one, 2-aminoethanol.

[0089] pH adjusters can be selected from one or more of the following components: potassium hydroxide, aminopropanol, citric acid, sodium citrate, tartaric acid, lactic acid, boric acid, and succinic acid.

[0090] Nutritional additives may be selected from one or more of the following components: chitosan, chitosan, silk peptides, silk fibroin, lecithin, epidermal growth factor, trehalose, lactose, pearl powder, collagen, collagen hydrolysate, hyaluronic acid and its salts, egg membrane, phytosterols, lysozyme chloride, sodium chondroitin sulfate, royal jelly, propolis, honey, glycyrrhizic acid, glycyrrhetinic acid, gamma-linolenic acid, kojic acid and its esters, gibberellic acid, glycine, L-aspartic acid and its salts, L-cysteine ​​and its salts, DL-alanine, L-serine, DL-serine L-methionine, DL-methionine, L-lysine hydrochloride, L-threonine, inositol, maltol, pantothenate, D-panthenol, retinyl acetate, allantoin, pyridoxine hydrochloride, cortisone, nicotinamide, vitamins, estrogen, hematoxylin, uric acid, orotic acid, aloe-emodin, azelaic acid, rosin acid, usnic acid, laminarin, thymosin, alizarin, limonene, baicalin, deoxycholic acid, guaiac wood, hesperidin, tannic acid, selenium disulfide, tea saponins, triethyl citrate, butylated hydroxytoluene, phytic acid, dimethyl diallyl ammonium chloride.

[0091] The cosmetic / skincare product can be one or more of the following: eye cream, face cream, serum, facial oil, lotion, and facial mask essence.

Claims

1. Application of tocopheryl retinyl esters in improving the stability of cosmetics and / or skin care products.

2. Application of tocopherol retinates in the preparation of highly stable cosmetics and / or skin care products for improving skin condition, repairing the skin barrier and / or protecting the skin.

3. The application as described in claim 2, characterized in that: The cosmetics and / or skincare products are also used to soothe and / or repair the skin.

4. Application of tocopherol retinate in the preparation of formulations that downregulate interleukin-1α and / or prostaglandin E2.

5. Application of tocopherol retinate in the preparation of formulations that upregulate the expression of filaggrin and / or pachyrhizin in the skin.

6. Application of tocopherol retinate in the preparation of formulations that increase the moisture content of the stratum corneum and / or reduce transepidermal water loss.

7. A cosmetic and / or skincare product, characterized in that: Contains tocopheryl retinyl esters; The tocopherol retinate content in cosmetics and / or skin care products is 0.001% to 10% by mass.

8. A cosmetic and / or skincare product as described in claim 7, characterized in that: The tocopherol retinate is dispersed in a matrix material, which is selected from one or more of oily materials, powdery materials, gel-like materials and / or solvent materials.

9. A cosmetic and / or skincare product as described in claim 7, characterized in that: The cosmetics and / or skincare products also contain one or more of the following: surfactants, fragrances or flavorings, colorants, moisturizers, preservatives, antioxidants, UV absorbers, chelating agents, astringents, penetration enhancers, pH adjusters, and / or nutritional additives.

10. A cosmetic and / or skincare product as described in claim 7, characterized in that: It is a daily-use product.

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