Polypeptide moisturizing and repairing toner and preparation method thereof

Abstract

The invention discloses a polypeptide moisturizing and repairing toner and a preparation method thereof, and relates to the field of repairing toner. The preparation method comprises the following steps: carrying out dehydration grafting modification on an amino acid humectant NMF-50 by using dimercaptopropanol, and introducing dimercapto into molecules of the amino acid humectant, so as to prepare the amino acid moisturizing factor with efficient whitening and anti-blackening effects. Secondly, L-glutamic acid, D-amino acid, L-proline and L-arginine are subjected to carboxyl anhydride acidification and repolymerization to form small-molecular-weight oligopeptide with a repairing function, then the synthesized oligopeptide is used for modifying nano titanium dioxide and nano zinc dioxide, the nano titanium dioxide and the nano zinc dioxide are coated with the modified nano titanium dioxide and nano zinc dioxide, and the whitening repairing factor with the anti-ultraviolet and repairing effects is obtained. According to the polypeptide moisturizing and repairing toner prepared by the preparation method disclosed by the invention, on the basis of realizing a high moisturizing effect, the functions of whitening, resisting blackness, resisting oxidation and resisting ultraviolet repairing are effectively added.

Description

Technical Field

[0001] The invention relates to the technical field of toners, in particular to a polypeptide moisturizing and repairing toner and a preparation method thereof. Background Art

[0002] With the growing and diversified demand of consumers for skin care products, especially the pursuit of moisturizing, repairing and whitening skin care products, the research and development of peptide moisturizing and repairing toner can accurately meet the market gap and meet consumers' demand for high-quality skin care products, especially in anti-aging and moisturizing. The addition of peptides makes toner more competitive in the skin care market. As a protein fragment, peptides have extremely strong activity and diversity. Adding peptides to skin care products can promote cell growth and differentiation, stimulate collagen synthesis, and thus have an anti-aging effect. At the same time, peptides can also help the skin maintain moisture balance, enhance skin barrier function, improve moisture retention and relieve dryness symptoms. Therefore, the research and development of peptide moisturizing and repairing toner can significantly improve the skin care effect and better protect consumers' skin.

[0003] Currently, peptide toners on the market mainly have the effects of moisturizing and lightening spots, and there is still a lot of room for improvement in anti-ultraviolet function. Nano titanium dioxide and nano zinc dioxide are good anti-ultraviolet agents, but if they are directly added to toners and used on the skin, they will cause damage to the skin. Therefore, it is urgent to find an effective solution to improve the anti-ultraviolet performance of toners without causing damage to the skin. Summary of the invention

[0004] The purpose of the present invention is to provide a polypeptide moisturizing and repairing toner and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a polypeptide moisturizing and repairing toner, wherein the polypeptide moisturizing and repairing toner comprises an amino acid moisturizing factor, a whitening and repairing factor, ethanol, hydrosol, and deionized water.

[0006] Furthermore, the amino acid moisturizing factor is prepared by dehydration condensation of dimercaprol and amino acid moisturizer NMF-50.

[0007] Furthermore, the whitening and repairing factor is prepared by anhydrifying amino acids through carboxyl groups, further polymerizing to form small molecular weight oligopeptides, and then modifying nano titanium dioxide and nano zinc dioxide with the small molecular weight oligopeptides.

[0008] Furthermore, the amino acid is one or more of L-glutamic acid, D-amino acid, L-proline, and L-arginine.

[0009] Furthermore, the hydrosol is one or more of lavender hydrosol, tea tree hydrosol, jasmine hydrosol, and rose hydrosol.

[0010] Furthermore, a method for preparing a polypeptide moisturizing and repairing toner comprises the following preparation steps:

[0011] (1) Add dithiopropanol, amino acid moisturizing agent NMF-50, and 60% sulfuric acid by mass into anhydrous ethanol, place in an oil bath at 40-50°C, stir at a speed of 300-600 r / min for 12-24 hours under a nitrogen atmosphere, cool to room temperature, and remove the solvent from the clear liquid after the reaction by rotary evaporation to obtain a crude product. The crude product is redissolved in tetrahydrofuran to obtain solution A, and then solution A is added to n-hexane at a speed of 0.5-1 drop / s through a glass dropper. The volume ratio of n-hexane to solution A is 3:1. Let stand for 15-20 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran to obtain crystals. Then, the upper solvent is poured off, the product is dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization is repeated 4-6 times to finally obtain an amino acid moisturizing factor.

[0012] (2) Add the amino acid to a clean Shrek bottle, evacuate with an oil pump for 20 to 60 minutes, add tetrahydrofuran and triphosgene under a nitrogen atmosphere, place in an oil bath at 40 to 50°C, stir at a speed of 200 to 400 r / min for 5 to 10 hours, and perform rotary evaporation to remove the solvent and part of the generated HCl after the reaction. Then, introduce the crude product into a glove box, redissolve the crude product with tetrahydrofuran to obtain solution B, and then add solution B to n-hexane at a speed of 1 to 2 drops / s through a glass dropper. The volume ratio of n-hexane to solution B is 3:1. After complete addition, place in a -20°C refrigerator and stand for 24 to 36 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran to obtain crystals. Then, pour off the upper solvent, evacuate with a vacuum pump, and then dissolve with tetrahydrofuran. Repeat the crystallization 2 to 5 times to obtain carboxylic anhydride amino acids.

[0013] (3) taking 5 to 10 parts of nano titanium dioxide with a particle size of 50 to 100 nm and 5 to 10 parts of nano zinc dioxide with a particle size of 50 to 100 nm, placing them in 60 to 100 parts of a sodium hydroxide solution with a concentration of 0.1 to 0.4 mol / L, stirring them at 60 to 90° C. and 200 to 400 r / min for 1 to 3 hours, cooling them to room temperature, washing them with deionized water until the pH value is 6.8 to 7.2, filtering them, and drying them at 90 to 120° C. for 1 to 4 hours to obtain pretreated nano titanium dioxide and nano zinc dioxide;

[0014] (4) In a glove box, weigh the carboxylic anhydride amino acid obtained in step (2) and add it to N,N-dimethylformamide. After dissolving, add the pretreated nano-titanium dioxide, nano-zinc dioxide and hexamethyldisilazane. Stir the mixture at a rate of 200 to 400 r / min at room temperature for 8 to 12 hours, pour it into ether twice the volume of the reaction solution, let it stand for 10 to 30 minutes, filter it, and dry the filtrate at 25 to 40° C. for 6 to 8 hours to obtain a whitening repair factor;

[0015] (5) Stir the amino acid moisturizing factor, whitening repair factor, ethanol, hydrosol, and deionized water at a speed of 200 to 400 r / min for 30 to 60 minutes to obtain a polypeptide moisturizing repair toner.

[0016] Furthermore, in the step (1), the mass ratio of dimercaprol, amino acid moisturizer NMF-50, sulfuric acid and anhydrous ethanol is 20-40:20-40:5-10:60-90.

[0017] Furthermore, in the step (2), the mass ratio of amino acid, tetrahydrofuran and triphosgene is 10-20:100-150:60-100.

[0018] Furthermore, in the step (4), the mass ratio of carboxylic anhydride amino acid, N,N-dimethylformamide, pretreated nano titanium dioxide and nano zinc dioxide, and hexamethyldisilazane is 10-20:50-100:1-5:1-5.

[0019] Furthermore, in step (5), the mass ratio of the amino acid moisturizing factor, the whitening repair factor, ethanol, the polysaccharide compound, the hydrosol, and the deionized water is 1-2:1-2:2-4:2-4:10-20:70-90.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] The polypeptide moisturizing and repairing toner prepared by the present invention not only achieves a high moisturizing effect, but also effectively increases the functions of whitening, anti-darkening, anti-oxidation and anti-ultraviolet repair.

[0022] First, the amino acid moisturizer NMF-50 was dehydrated and grafted with dithiol propanol to introduce dithiol groups into the amino acid moisturizer molecules to prepare an amino acid moisturizing factor with high whitening and anti-melanin effects. The generated amino acid moisturizing factor has a small molecular weight and can quickly enter the dermis. The introduced dithiol groups can form a complex with the copper ions in tyrosinase, making the tyrosinase inactive, thereby inhibiting the formation of melanin and achieving a whitening effect.

[0023] Secondly, L-glutamic acid, D-amino acid, L-proline and L-arginine are used to form small molecular weight oligopeptides with repairing functions through carboxyl internal anhydride and repolymerization. The synthesized oligopeptides are then used to modify nano-titanium dioxide and nano-zinc dioxide and encapsulate them to obtain whitening and repairing factors with anti-ultraviolet and repairing effects. The generated whitening and repairing factors can effectively participate in the cell repair project due to the presence of a large number of active groups such as hydroxyl, carboxyl, guanidine, and amide bonds. The combined use of nano-titanium dioxide and nano-zinc dioxide effectively broadens the wavelength range of ultraviolet absorption and enhances the anti-ultraviolet effect. The charged particles formed after absorbing ultraviolet rays neutralize various active groups in the whitening and repairing factors, effectively reducing the damage caused to the skin by nano-titanium dioxide and nano-zinc dioxide due to absorbing ultraviolet rays, and plays an early protective role on the skin. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the polypeptide moisturizing and repairing toner prepared in the following examples are as follows:

[0026] Skin and eye irritation test: The polypeptide moisturizing and repairing toners prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to acute skin irritation test and acute eye irritation test respectively. The specific experimental methods, scoring criteria and irritation reaction classification are all in accordance with the 2007 edition of the Hygiene Standards for Cosmetics.

[0027] Product moisturizing and hydrating performance experiment: The peptide moisturizing and repairing toners prepared in Examples 1-3 and Comparative Examples 1-5 were respectively subjected to product moisturizing and hydrating performance experiments. The same batch of volunteers were divided into 1 to 14 groups, with 3 people in each group. After cleaning the facial skin every morning and evening, each experimental group used the corresponding toner. No other moisturizing and hydrating products were used during the experiment. Before use, 14 days after use, and 28 days after use, the water loss test probe Tewameter TM300 produced by Courage+Kahazaka of Germany was used to measure the water loss of facial skin;

[0028] Anti-ultraviolet performance experiment: The polypeptide moisturizing and refreshing skin care water prepared in Examples 1-3 and Comparative Examples 1-5 were respectively tested for sun protection index;

[0029] Sun protection index testing instrument: LABSPHERE UV TRANSMITTANCEANALYZER-UV 2000;

[0030] SPF test method: COLIPA 2011.

[0031] Product whitening performance experiment: The polypeptide moisturizing and repairing toner prepared in Examples 1-3 and Comparative Examples 1-5 were respectively subjected to product whitening performance experiments. 33 subjects with dull facial skin color and ITA° values ​​below 55 were randomly selected, with an age range of 18 to 60 years old. The subjects were tested for skin brightness, skin glossiness, and skin melanin values ​​before using the test product, 14 days after continuous use, and 28 days after continuous use. A doctor also conducted a safety assessment on the subjects' skin after using the product. The evaluation results before and after product use were compared by statistical test methods to determine whether there were statistical differences. The statistical analysis software was SPSS. The measured values ​​at different time points were compared with the baseline values, and before and after use were compared. If the values ​​were normally distributed, the t-test method was used for statistical analysis; if the values ​​were not normally distributed, the rank sum test method was used for statistical analysis; the statistical methods all used two-tailed tests, and the test level α=0.05;

[0032] Skin brightness ITA° value test: Use the skin color test probe Colorimeter CL400 to measure three times on the subject's cheek;

[0033] Skin gloss test: Use the skin gloss test probe Glossymeter GL200 to measure the subject's cheek three times and record the skin gloss;

[0034] Skin melanin test: Use the skin melanin and hemoglobin tester Mexameter MX18 to measure the subject's cheek three times and record the skin melanin.

[0035] Example 1

[0036] (1) 20 parts of dithiopropanol, 20 parts of amino acid moisturizing agent NMF-50, and 5 parts of sulfuric acid with a mass fraction of 60% are added to 60 parts of anhydrous ethanol, and stirred at a speed of 500 r / min for 18 hours in an oil bath at 45°C and a nitrogen atmosphere, and then cooled to room temperature. The clear liquid after the reaction is subjected to rotary evaporation to remove the solvent, and then a crude product is obtained. The crude product is redissolved in tetrahydrofuran to obtain solution A, and then solution A is added to n-hexane at a speed of 0.5 drops / s through a glass dropper. The volume ratio of n-hexane to solution A is 3:1. The mixture is allowed to stand for 18 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally needle-shaped crystals are obtained. The upper solvent is then poured off, the mixture is dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization is repeated 5 times to finally obtain an amino acid moisturizing factor.

[0037] (2) 10 parts of L-glutamic acid were added to a clean Shrek bottle, and vacuum was drawn with an oil pump for 50 minutes. 100 parts of tetrahydrofuran and 60 parts of triphosgene were added under a nitrogen atmosphere, and the mixture was placed in an oil bath at 45°C and stirred at a speed of 300 r / min for 8 hours. The clear water after the reaction was completed was subjected to rotary evaporation to remove the solvent and part of the generated HCl. The crude product was then introduced into a glove box, and the crude product was redissolved in tetrahydrofuran to obtain solution B. Solution B was then added to n-hexane at a speed of 1 drop / s using a glass dropper. In the solution, the volume ratio of n-hexane to solution B is 3:1. After the solution is completely added, the solution is placed in a -20°C refrigerator and allowed to stand for 30 hours to allow the solution to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. The upper solvent is then poured off, the solution is dried with a vacuum pump, and then the solution is dissolved with tetrahydrofuran. The crystallization is repeated 4 times to obtain carboxylated anhydride L-glutamic acid. D-amino acid, L-proline and L-arginine are prepared according to the above method to obtain carboxylated anhydride D-amino acid, carboxylated anhydride L-proline and carboxylated anhydride L-arginine.

[0038] (3) taking 5 parts of nano titanium dioxide with a particle size of 80 nm and 5 parts of nano zinc dioxide with a particle size of 80 nm, placing them in 60 parts of a sodium hydroxide solution with a concentration of 0.3 mol / L, stirring at 80° C. and 300 / min for 2 h, cooling to room temperature, washing with deionized water until the pH is 7.0, filtering and drying at 100° C. for 3 h to obtain pretreated nano titanium dioxide and nano zinc dioxide;

[0039] (4) In a glove box, 10 parts of carboxylic anhydride amino acids were weighed, and the mass ratio of carboxylic anhydride L-glutamic acid, carboxylic anhydride D-amino acid, carboxylic anhydride L-proline and carboxylic anhydride L-arginine in the carboxylic anhydride amino acids was 1:1:1:1, and added to 50 parts of N,N-dimethylformamide. After dissolution, 1 part of pretreated nano-titanium dioxide and nano-zinc dioxide and 1 part of hexamethyldisilazane were added. After stirring at 300 r / min at room temperature for 10 hours, the mixture was poured into ether with a volume twice that of the reaction solution, allowed to stand for 20 minutes, filtered, and the filtrate was dried at 30°C for 8 hours to obtain a whitening repair factor;

[0040] (5) 1 part of amino acid moisturizing factor, 1 part of whitening repair factor, 2 parts of ethanol, 10 parts of hydrosol, and 70 parts of deionized water were stirred at a speed of 350 r / min for 60 min to obtain a polypeptide moisturizing repair toner.

[0041] Example 2

[0042] (1) 30 parts of dithiopropanol, 30 parts of amino acid moisturizing agent NMF-50, and 8 parts of sulfuric acid with a mass fraction of 60% are added to 75 parts of anhydrous ethanol, and stirred at a speed of 500 r / min for 18 hours in an oil bath at 45°C and a nitrogen atmosphere, and then cooled to room temperature. The clear liquid after the reaction is subjected to rotary evaporation to remove the solvent, and then a crude product is obtained. The crude product is redissolved in tetrahydrofuran to obtain solution A, and then solution A is added to n-hexane at a speed of 0.5 drops / s through a glass dropper. The volume ratio of n-hexane to solution A is 3:1. The mixture is allowed to stand for 18 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally needle-shaped crystals are obtained. The upper solvent is then poured off, the mixture is dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization is repeated 5 times to finally obtain an amino acid moisturizing factor.

[0043] (2) 15 parts of L-glutamic acid were added to a clean Shrek bottle, and vacuum was drawn with an oil pump for 50 minutes. 120 parts of tetrahydrofuran and 80 parts of triphosgene were added under a nitrogen atmosphere, and the mixture was placed in an oil bath at 45°C and stirred at a speed of 300 r / min for 8 hours. The clear water after the reaction was completed was subjected to rotary evaporation to remove the solvent and part of the generated HCl. The crude product was then introduced into a glove box, and the crude product was redissolved in tetrahydrofuran to obtain solution B. Solution B was then added to n-hexane via a glass dropper at a speed of 1 drop / s. In the solution, the volume ratio of n-hexane to solution B is 3:1. After the solution is completely added, the solution is placed in a -20°C refrigerator and allowed to stand for 30 hours to allow the solution to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. The upper solvent is then poured off, the solution is dried with a vacuum pump, and then the solution is dissolved with tetrahydrofuran. The crystallization is repeated 4 times to obtain carboxylated anhydride L-glutamic acid. D-amino acid, L-proline and L-arginine are prepared according to the above method to obtain carboxylated anhydride D-amino acid, carboxylated anhydride L-proline and carboxylated anhydride L-arginine.

[0044] (3) 8 parts of nano titanium dioxide with a particle size of 80 nm and 8 parts of nano zinc dioxide with a particle size of 80 nm were placed in 80 parts of a sodium hydroxide solution with a concentration of 0.3 mol / L, stirred at 80° C. and 300 min for 2 h, cooled to room temperature, washed with deionized water until the pH value was 7.0, filtered, and dried at 100° C. for 3 h to obtain pretreated nano titanium dioxide and nano zinc dioxide;

[0045] (4) In a glove box, 15 parts of carboxylic anhydride amino acids were weighed, and the mass ratio of carboxylic anhydride L-glutamic acid, carboxylic anhydride D-amino acid, carboxylic anhydride L-proline and carboxylic anhydride L-arginine in the carboxylic anhydride amino acids was 1:1:1:1, and added to 80 parts of N,N-dimethylformamide. After dissolution, 3 parts of pretreated nano-titanium dioxide and nano-zinc dioxide and 3 parts of hexamethyldisilazane were added. After stirring at 300 r / min at room temperature for 10 hours, the mixture was poured into ether with a volume twice that of the reaction solution, allowed to stand for 20 minutes, filtered, and the filtrate was dried at 30°C for 8 hours to obtain a whitening repair factor;

[0046] (5) 1.5 parts of amino acid moisturizing factor, 1.5 parts of whitening repair factor, 3 parts of ethanol, 15 parts of hydrosol, and 80 parts of deionized water were stirred at a speed of 350 r / min for 60 min to obtain a polypeptide moisturizing repair toner.

[0047] Example 3

[0048] (1) 40 parts of dithiopropanol, 40 parts of amino acid moisturizing agent NMF-50, and 10 parts of sulfuric acid with a mass fraction of 60% were added to 90 parts of anhydrous ethanol, and stirred at a speed of 500 r / min for 18 hours in an oil bath at 45°C and a nitrogen atmosphere, and then cooled to room temperature. The clear liquid after the reaction was evaporated to remove the solvent, and then a crude product was obtained. The crude product was redissolved in tetrahydrofuran to obtain solution A, and then solution A was added to n-hexane at a speed of 0.5 drops / s through a glass dropper. The volume ratio of n-hexane to solution A was 3:1. The mixture was allowed to stand for 18 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally needle-shaped crystals were obtained. The upper solvent was then poured off, the mixture was dried with a vacuum pump, and then dissolved in tetrahydrofuran. The crystallization was repeated 5 times to finally obtain an amino acid moisturizing factor.

[0049] (2) Add 20 parts of L-glutamic acid to a clean Shrek bottle, evacuate with an oil pump for 50 minutes, add 150 parts of tetrahydrofuran and 100 parts of triphosgene under nitrogen atmosphere, place in an oil bath at 45°C, and stir at a speed of 300 r / min for 8 hours. After the reaction is completed, the clear water is evaporated to remove the solvent and part of the generated HCl, and then the crude product is introduced into a glove box, and the crude product is redissolved in tetrahydrofuran to obtain solution B, and then solution B is added to n-hexane at a speed of 1 drop / s through a glass dropper. In the solution, the volume ratio of n-hexane to solution B is 3:1. After the solution is completely added, the solution is placed in a -20°C refrigerator and allowed to stand for 30 hours to allow the solution to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. The upper solvent is then poured off, the solution is dried with a vacuum pump, and then the solution is dissolved with tetrahydrofuran. The crystallization is repeated 4 times to obtain carboxylated anhydride L-glutamic acid. D-amino acid, L-proline and L-arginine are prepared according to the above method to obtain carboxylated anhydride D-amino acid, carboxylated anhydride L-proline and carboxylated anhydride L-arginine.

[0050] (3) taking 10 parts of nano titanium dioxide with a particle size of 80 nm and 10 parts of nano zinc dioxide with a particle size of 80 nm, placing them in 100 parts of a sodium hydroxide solution with a concentration of 0.3 mol / L, stirring at 80° C. and 300 / min for 2 h, cooling to room temperature, washing with deionized water until the pH is 7.0, filtering and drying at 100° C. for 3 h, to obtain pretreated nano titanium dioxide and nano zinc dioxide;

[0051] (4) In a glove box, 20 parts of carboxylic anhydride amino acids were weighed, and the mass ratio of carboxylic anhydride L-glutamic acid, carboxylic anhydride D-amino acid, carboxylic anhydride L-proline and carboxylic anhydride L-arginine in the carboxylic anhydride amino acids was 1:1:1:1, and added to 100 parts of N,N-dimethylformamide. After dissolution, 5 parts of pretreated nano-titanium dioxide and nano-zinc dioxide and 5 parts of hexamethyldisilazane were added. After stirring at 300 r / min at room temperature for 10 hours, the mixture was poured into ether with a volume twice that of the reaction solution, allowed to stand for 20 minutes, filtered, and the filtrate was dried at 30°C for 8 hours to obtain a whitening repair factor;

[0052] (5) 2 parts of amino acid moisturizing factor, 2 parts of whitening repair factor, 4 parts of ethanol, 20 parts of hydrosol, and 90 parts of deionized water were stirred at a speed of 350 r / min for 60 min to obtain a polypeptide moisturizing repair toner.

[0053] Comparative Example 1

[0054] (1) 15 parts of L-glutamic acid were added to a clean Shrek bottle, and vacuum was drawn with an oil pump for 50 minutes. 120 parts of tetrahydrofuran and 80 parts of triphosgene were added under a nitrogen atmosphere, and the mixture was placed in an oil bath at 45°C and stirred at a speed of 300 r / min for 8 hours. The solvent and part of the generated HCl were removed by rotary evaporation at night after the reaction was completed. The crude product was then introduced into a glove box, and the crude product was redissolved in tetrahydrofuran to obtain solution B. Solution B was then added to n-hexane at a speed of 1 drop / s using a glass dropper. In the solution, the volume ratio of n-hexane to solution B is 3:1. After the solution is completely added, the solution is placed in a -20°C refrigerator and allowed to stand for 30 hours to allow the solution to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. The upper solvent is then poured off, the solution is dried with a vacuum pump, and then the solution is dissolved with tetrahydrofuran. The crystallization is repeated 4 times to obtain carboxylated anhydride L-glutamic acid. D-amino acid, L-proline and L-arginine are prepared according to the above method to obtain carboxylated anhydride D-amino acid, carboxylated anhydride L-proline and carboxylated anhydride L-arginine.

[0055] (2) 8 parts of nano titanium dioxide with a particle size of 80 nm and 8 parts of nano zinc dioxide with a particle size of 80 nm were placed in 80 parts of a sodium hydroxide solution with a concentration of 0.3 mol / L, stirred at 80° C. and 300 min for 2 h, cooled to room temperature, washed with deionized water until the pH value was 7.0, filtered, and dried at 100° C. for 3 h to obtain pretreated nano titanium dioxide and nano zinc dioxide;

[0056] (3) In a glove box, 15 parts of carboxylic anhydride amino acids were weighed, and the mass ratio of carboxylic anhydride L-glutamic acid, carboxylic anhydride D-amino acid, carboxylic anhydride L-proline and carboxylic anhydride L-arginine in the carboxylic anhydride amino acids was 1:1:1:1, and added to 80 parts of N,N-dimethylformamide. After dissolution, 3 parts of pretreated nano-titanium dioxide and nano-zinc dioxide and 3 parts of hexamethyldisilazane were added. After stirring at 300 r / min at room temperature for 10 hours, the mixture was poured into ether with a volume twice that of the reaction solution, allowed to stand for 20 minutes, filtered, and the filtrate was dried at 30°C for 8 hours to obtain a whitening repair factor;

[0057] (4) 1.5 parts of whitening repair factor, 3 parts of ethanol, 15 parts of hydrosol, and 80 parts of deionized water were stirred at a speed of 350 r / min for 60 minutes to obtain a polypeptide moisturizing and repairing toner.

[0058] Comparative Example 2

[0059] (1) 30 parts of dithiopropanol, 30 parts of amino acid moisturizing agent NMF-50, and 8 parts of sulfuric acid with a mass fraction of 60% are added to 75 parts of anhydrous ethanol, and stirred at a speed of 500 r / min for 18 hours in an oil bath at 45°C and a nitrogen atmosphere, and then cooled to room temperature. The clear liquid after the reaction is subjected to rotary evaporation to remove the solvent, and then a crude product is obtained. The crude product is redissolved in tetrahydrofuran to obtain solution A, and then solution A is added to n-hexane at a speed of 0.5 drops / s through a glass dropper. The volume ratio of n-hexane to solution A is 3:1. The mixture is allowed to stand for 18 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally needle-shaped crystals are obtained. The upper solvent is then poured off, the mixture is dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization is repeated 5 times to finally obtain an amino acid moisturizing factor.

[0060] (2) 1.5 parts of amino acid moisturizing factor, 3 parts of ethanol, 15 parts of hydrosol, and 80 parts of deionized water were stirred at a speed of 350 r / min for 60 min to obtain a polypeptide moisturizing and repairing toner.

[0061] Comparative Example 3

[0062] (1) 15 parts of L-glutamic acid were added to a clean Shrek bottle, and vacuum was drawn with an oil pump for 50 minutes. 120 parts of tetrahydrofuran and 80 parts of triphosgene were added under a nitrogen atmosphere, and the mixture was placed in an oil bath at 45°C and stirred at a speed of 300 r / min for 8 hours. The solvent and part of the generated HCl were removed by rotary evaporation at night after the reaction was completed. The crude product was then introduced into a glove box, and the crude product was redissolved in tetrahydrofuran to obtain solution B. Solution B was then added to n-hexane at a speed of 1 drop / s using a glass dropper. In the solution, the volume ratio of n-hexane to solution B is 3:1. After the solution is completely added, the solution is placed in a -20°C refrigerator and allowed to stand for 30 hours to allow the solution to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. The upper solvent is then poured off, the solution is dried with a vacuum pump, and then the solution is dissolved with tetrahydrofuran. The crystallization is repeated 4 times to obtain carboxylated anhydride L-glutamic acid. D-amino acid, L-proline and L-arginine are prepared according to the above method to obtain carboxylated anhydride D-amino acid, carboxylated anhydride L-proline and carboxylated anhydride L-arginine.

[0063] (2) 8 parts of nano titanium dioxide with a particle size of 80 nm and 8 parts of nano zinc dioxide with a particle size of 80 nm were placed in 80 parts of a sodium hydroxide solution with a concentration of 0.3 mol / L, stirred at 80° C. and 300 min for 2 h, cooled to room temperature, washed with deionized water until the pH value was 7.0, filtered, and dried at 100° C. for 3 h to obtain pretreated nano titanium dioxide and nano zinc dioxide;

[0064] (3) In a glove box, 15 parts of carboxylic anhydride amino acids were weighed, and the mass ratio of carboxylic anhydride L-glutamic acid, carboxylic anhydride D-amino acid, carboxylic anhydride L-proline and carboxylic anhydride L-arginine in the carboxylic anhydride amino acids was 1:1:1:1, and added to 80 parts of N,N-dimethylformamide. After dissolution, 3 parts of pretreated nano-titanium dioxide and nano-zinc dioxide and 3 parts of hexamethyldisilazane were added. After stirring at 300 r / min at room temperature for 10 hours, the mixture was poured into ether with a volume twice that of the reaction solution, allowed to stand for 20 minutes, filtered, and the filtrate was dried at 30°C for 8 hours to obtain a whitening repair factor;

[0065] (4) 1.5 parts of amino acid moisturizer NMF-50, 1.5 parts of whitening repair factor, 3 parts of ethanol, 15 parts of hydrosol, and 80 parts of deionized water were stirred at a speed of 350 r / min for 60 min to obtain a polypeptide moisturizing and repairing toner.

[0066] Comparative Example 4

[0067] (1) 30 parts of dithiopropanol, 30 parts of amino acid moisturizing agent NMF-50, and 8 parts of sulfuric acid with a mass fraction of 60% are added to 75 parts of anhydrous ethanol, and stirred at a speed of 500 r / min for 18 hours in an oil bath at 45°C and a nitrogen atmosphere, and then cooled to room temperature. The clear liquid after the reaction is subjected to rotary evaporation to remove the solvent, and then a crude product is obtained. The crude product is redissolved in tetrahydrofuran to obtain solution A, and then solution A is added to n-hexane at a speed of 0.5 drops / s through a glass dropper. The volume ratio of n-hexane to solution A is 3:1. The mixture is allowed to stand for 18 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally needle-shaped crystals are obtained. The upper solvent is then poured off, the mixture is dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization is repeated 5 times to finally obtain an amino acid moisturizing factor.

[0068] (2) 15 parts of L-glutamic acid were added to a clean Shrek bottle, and vacuum was drawn with an oil pump for 50 minutes. 120 parts of tetrahydrofuran and 80 parts of triphosgene were added under a nitrogen atmosphere, and the mixture was placed in an oil bath at 45°C and stirred at a speed of 300 r / min for 8 hours. The clear water after the reaction was completed was subjected to rotary evaporation to remove the solvent and part of the generated HCl. The crude product was then introduced into a glove box, and the crude product was redissolved in tetrahydrofuran to obtain solution B. Solution B was then added to n-hexane via a glass dropper at a speed of 1 drop / s. In the solution, the volume ratio of n-hexane to solution B is 3:1. After the solution is completely added, the solution is placed in a -20°C refrigerator and allowed to stand for 30 hours to allow the solution to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. The upper solvent is then poured off, the solution is dried with a vacuum pump, and then the solution is dissolved with tetrahydrofuran. The crystallization is repeated 4 times to obtain carboxylated anhydride L-glutamic acid. D-amino acid, L-proline and L-arginine are prepared according to the above method to obtain carboxylated anhydride D-amino acid, carboxylated anhydride L-proline and carboxylated anhydride L-arginine.

[0069] (3) 8 parts of nano titanium dioxide with a particle size of 80 nm and 8 parts of nano zinc dioxide with a particle size of 80 nm were placed in 80 parts of a sodium hydroxide solution with a concentration of 0.3 mol / L, stirred at 80° C. and 300 min for 2 h, cooled to room temperature, washed with deionized water until the pH value was 7.0, filtered, and dried at 100° C. for 3 h to obtain pretreated nano titanium dioxide and nano zinc dioxide;

[0070] (4) In a glove box, 15 parts of carboxylic anhydride amino acids were weighed, and the mass ratio of carboxylic anhydride L-glutamic acid, carboxylic anhydride D-amino acid, carboxylic anhydride L-proline and carboxylic anhydride L-arginine in the carboxylic anhydride amino acids was 1:1:1:1, and added to 80 parts of N,N-dimethylformamide. After dissolution, 3 parts of hexamethyldisilazane were added, and the mixture was stirred at 300 r / min at room temperature for 10 hours. Then, the mixture was poured into ether with a volume twice that of the reaction solution, allowed to stand for 20 minutes, filtered, and the filtrate was dried at 30° C. for 8 hours to obtain a whitening repair factor;

[0071] (5) 1.5 parts of amino acid moisturizing factor, 1.5 parts of whitening repair factor, 0.5 parts of pretreated nano titanium dioxide and nano zinc dioxide, 3 parts of ethanol, 15 parts of hydrosol, and 80 parts of deionized water were stirred at a speed of 350 r / min for 60 min to obtain a polypeptide moisturizing repair toner.

[0072] Comparative Example 5

[0073] (1) 15 parts of L-glutamic acid were added to a clean Shrek bottle, and vacuum was drawn with an oil pump for 50 minutes. 120 parts of tetrahydrofuran and 80 parts of triphosgene were added under a nitrogen atmosphere, and the mixture was placed in an oil bath at 45°C and stirred at a speed of 300 r / min for 8 hours. The solvent and part of the generated HCl were removed by rotary evaporation at night after the reaction was completed. The crude product was then introduced into a glove box, and the crude product was redissolved in tetrahydrofuran to obtain solution B. Solution B was then added to n-hexane at a speed of 1 drop / s using a glass dropper. In the solution, the volume ratio of n-hexane to solution B is 3:1. After the solution is completely added, the solution is placed in a -20°C refrigerator and allowed to stand for 30 hours to allow the solution to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. The upper solvent is then poured off, the solution is dried with a vacuum pump, and then the solution is dissolved with tetrahydrofuran. The crystallization is repeated 4 times to obtain carboxylated anhydride L-glutamic acid. D-amino acid, L-proline and L-arginine are prepared according to the above method to obtain carboxylated anhydride D-amino acid, carboxylated anhydride L-proline and carboxylated anhydride L-arginine.

[0074] (2) 8 parts of nano titanium dioxide with a particle size of 80 nm and 8 parts of nano zinc dioxide with a particle size of 80 nm were placed in 80 parts of a sodium hydroxide solution with a concentration of 0.3 mol / L, stirred at 80° C. and 300 min for 2 h, cooled to room temperature, washed with deionized water until the pH value was 7.0, filtered, and dried at 100° C. for 3 h to obtain pretreated nano titanium dioxide and nano zinc dioxide;

[0075] (3) 1.5 parts of amino acid moisturizer NMF-50, 1.5 parts of carboxylic anhydride amino acid, 0.5 parts of pretreated nano titanium dioxide and nano zinc dioxide, 3 parts of ethanol, 15 parts of hydrosol, and 80 parts of deionized water were stirred at a speed of 350 r / min for 60 min to obtain a polypeptide moisturizing and repairing toner.

[0076] Effect example

[0077] Tables 1 to 6 below show the performance analysis results of skin and eye irritation, moisturizing and UV resistance of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0078] Table 1 Results of skin irritation and eye irritation reactions of subjects in Examples 1-3 and Comparative Examples 1-5

[0079]

[0080]

[0081] Table 2 Water loss results of facial skin of subjects in Examples 1-3 and Comparative Examples 1-5

[0082]

[0083] Table 3 Sunscreen performance results of polypeptide moisturizing and repairing toners of Examples 1-3 and Comparative Examples 1-5

[0084]

[0085] Table 4 Test results of skin brightness ITA° value of subjects in Examples 1-3 and Comparative Examples 1-5

[0086] Group Baseline Use the product for 14 days (D14) Use the product for 28 days (D28) Example 1 39.2778±0.3377 41.3201±0.1728 43.6699±0.3168 Example 2 39.5726±0.1358 41.9765±0.2215 43.9943±0.1334 Example 3 39.4357±0.2074 41.1655±0.2126 43.5357±0.2017 Comparative Example 1 39.1867±0.1337 39.9988±0.2017 39.7897±0.5130 Comparative Example 2 39.2677±0.1453 40.4435±0.1043 41.2766±0.1022 Comparative Example 3 39.4253±0.2110 39.1132±0.2516 39.0077±0.3366 Comparative Example 4 39.5330±0.3311 40.2513±0.1537 41.3207±0.4115 Comparative Example 5 39.3688±0.2064 39.9947±0.1122 39.8966±0.2136

[0087] Table 5 Test results of skin glossiness of subjects in Examples 1-3 and Comparative Examples 1-5

[0088] Group Baseline Use the product for 14 days (D14) Use the product for 28 days (D28) Example 1 8.4453±0.5123 9.1732±0.0439 10.0317±0.2100 Example 2 8.6234±0.1144 9.3866±0.0518 10.6528±0.0913 Example 3 8.5172±0.0153 9.2507±0.2017 10.2735±0.1412 Comparative Example 1 8.3561±0.0273 8.2699±0.1344 8.7366±0.0207 Comparative Example 2 8.7208±0.1336 8.9799±0.1627 9.6374±0.3024 Comparative Example 3 8.4093±0.2108 8.5733±0.0722 8.9988±0.1519 Comparative Example 4 8.4187±0.0457 9.0366±0.3301 9.9657±0.0978 Comparative Example 5 8.3679±0.1399 8.1165±0.0615 8.2577±0.1017

[0089] Table 6 Melanin test results of subjects' skin of Examples 1-3 and Comparative Examples 1-5

[0090] Group Baseline Use the product for 14 days (D14) Use the product for 28 days (D28) Example 1 165.3799±0.1762 162.3177±0.3215 158.3457±0.1773 Example 2 165.5731±0.3211 161.9966±0.1153 157.9586±0.2498 Example 3 165.2587±0.2733 162.0057±0.2417 158.1231±0.3152 Comparative Example 1 165.3461±0.1547 164.7934±0.4366 163.2121±0.1733 Comparative Example 2 165.5429±0.0287 163.2819±0.3744 160.3737±0.2043 Comparative Example 3 165.1768±0.2787 164.2178±0.2057 163.7725±0.2566 Comparative Example 4 165.7367±0.3746 163.0027±0.1144 160.1754±0.3407 Comparative Example 5 165.2643±0.0478 164.1337±0.3357 163.0017±0.1537

[0091] From the results of Tables 1 to 3, it is found that the amino acid moisturizing factor and whitening repair factor prepared by the present application are added to the toner, which is friendly to the user's skin and eyes, non-irritating, and has high anti-ultraviolet performance. However, if we add nano titanium dioxide and nano zinc dioxide directly to the toner, there will be certain irritation to the skin and eyes. Therefore, after the nano titanium dioxide and nano zinc dioxide are grafted onto the amino acid anhydride-modified amino acid, the damage caused to the skin and eyes by these two additives can be effectively reduced. From the results of Tables 4 to 6, it can be seen that the amino acid moisturizing factor prepared by using dimercaprol modified amino acid moisturizer can effectively improve the brightness and glossiness of the skin and reduce the formation of melanin. And from the results of Comparative Examples 2 and 4, it is found that due to the addition of nano titanium dioxide and nano zinc dioxide, the damage to the skin by ultraviolet rays is effectively blocked, and the whitening effect is achieved to a certain extent. From the results of Examples 1-3, Comparative Examples 2 and Comparative Examples 4 in Tables 4-6, we find that the synergistic effect between nano titanium dioxide, nano zinc dioxide and dimercaprol makes the whitening effect more prominent.

[0092] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A polypeptide moisturizing and repairing toner, characterized in that: The polypeptide moisturizing and repairing toner contains amino acid moisturizing factor, whitening and repairing factor, ethanol, hydrosol and deionized water.

2. A polypeptide moisturizing and repairing toner according to claim 1, characterized in that: The amino acid moisturizing factor is prepared by dehydration condensation of dimercaprol and amino acid moisturizing agent NMF-50.

3. The polypeptide moisturizing and repairing toner according to claim 1, characterized in that: The whitening and repairing factor is prepared by anhydrifying amino acids through carboxylation, further polymerizing to form small molecular weight oligopeptides, and then modifying nano titanium dioxide and nano zinc dioxide with the small molecular weight oligopeptides.

4. A polypeptide moisturizing and repairing toner according to claim 3, characterized in that: The amino acid is one or more of L-glutamic acid, D-amino acid, L-proline and L-arginine.

5. The polypeptide moisturizing and repairing toner according to claim 1, characterized in that: The hydrosol is one or more of lavender hydrosol, tea tree hydrosol, jasmine hydrosol and rose hydrosol.

6. A method for preparing a polypeptide moisturizing and repairing toner, characterized in that: The method comprises the following preparation steps: (1) Add dithiopropanol, amino acid moisturizing agent NMF-50, and 60% sulfuric acid by mass into anhydrous ethanol, place in an oil bath at 40-50°C, stir at a speed of 300-600 r / min for 12-24 hours under a nitrogen atmosphere, cool to room temperature, and remove the solvent from the clear liquid after the reaction by rotary evaporation to obtain a crude product. The crude product is redissolved in tetrahydrofuran to obtain solution A, and then solution A is added to n-hexane at a speed of 0.5-1 drop / s through a glass dropper. The volume ratio of n-hexane to solution A is 3:

1. Let stand for 15-20 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran to obtain crystals. Then, the upper solvent is poured off, the product is dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization is repeated 4-6 times to finally obtain an amino acid moisturizing factor. (2) Add the amino acid to a clean Shrek bottle, evacuate with an oil pump for 20 to 60 minutes, add tetrahydrofuran and triphosgene under a nitrogen atmosphere, place in an oil bath at 40 to 50°C, stir at a speed of 200 to 400 r / min for 5 to 10 hours, and perform rotary evaporation to remove the solvent and part of the generated HCl after the reaction. Then, introduce the crude product into a glove box, redissolve the crude product with tetrahydrofuran to obtain solution B, and then add solution B to n-hexane at a speed of 1 to 2 drops / s through a glass dropper. The volume ratio of n-hexane to solution B is 3:

1. After complete addition, place in a -20°C refrigerator and stand for 24 to 36 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran to obtain crystals. Then, pour off the upper solvent, evacuate with a vacuum pump, and then dissolve with tetrahydrofuran. Repeat the crystallization 2 to 5 times to obtain carboxylic anhydride amino acids. (3) taking 5 to 10 parts of nano titanium dioxide with a particle size of 50 to 100 nm and 5 to 10 parts of nano zinc dioxide with a particle size of 50 to 100 nm, placing them in 60 to 100 parts of a sodium hydroxide solution with a concentration of 0.1 to 0.4 mol / L, stirring them at 60 to 90° C. and 200 to 400 r / min for 1 to 3 hours, cooling them to room temperature, washing them with deionized water until the pH value is 6.8 to 7.2, filtering them, and drying them at 90 to 120° C. for 1 to 4 hours to obtain pretreated nano titanium dioxide and nano zinc dioxide; (4) In a glove box, weigh the carboxylic anhydride amino acid obtained in step (2) and add it to N,N-dimethylformamide. After dissolving, add the pretreated nano-titanium dioxide, nano-zinc dioxide and hexamethyldisilazane. Stir the mixture at a rate of 200 to 400 r / min at room temperature for 8 to 12 hours, pour it into ether twice the volume of the reaction solution, let it stand for 10 to 30 minutes, filter it, and dry the filtrate at 25 to 40° C. for 6 to 8 hours to obtain a whitening repair factor; (5) Stir the amino acid moisturizing factor, whitening repair factor, ethanol, hydrosol, and deionized water at a speed of 200 to 400 r / min for 30 to 60 minutes to obtain a polypeptide moisturizing repair toner.

7. The method for preparing a polypeptide moisturizing and repairing toner according to claim 6, characterized in that: In the step (1), the mass ratio of dimercaprol, amino acid moisturizer NMF-50, sulfuric acid and anhydrous ethanol is 20-40:20-40:5-10:60-90.

8. The method for preparing a polypeptide moisturizing and repairing toner according to claim 6, characterized in that: In the step (2), the mass ratio of amino acid, tetrahydrofuran and triphosgene is 10-20:100-150:60-100.

9. The method for preparing a polypeptide moisturizing and repairing toner according to claim 6, characterized in that: In the step (4), the mass ratio of carboxylic anhydride amino acid, N,N-dimethylformamide, pretreated nano titanium dioxide and nano zinc dioxide, and hexamethyldisilazane is 10-20:50-100:1-5:1-5.

10. The method for preparing a polypeptide moisturizing and repairing toner according to claim 6, characterized in that: In the step (5), the mass ratio of the amino acid moisturizing factor, the whitening and repairing factor, ethanol, the polysaccharide compound, the hydrosol and the deionized water is 1-2:1-2:2-4:2-4:10-20:70-90.

Images