Application of sodium polyglutamate and polyglutamic acid hydrogel with long-lasting moisturizing and skin-lightening effects

Abstract

The invention discloses a kind of sodium polyglutamate and the use of polyglutamic acid hydrogel with long-term moisturizing and skin-lightening, and belongs to the field of cosmetic technology. The preparation method of the sodium polyglutamate comprises the following steps: taking poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), 0.1mol / L MES / sodium chloride buffer solution, mixing, stirring for 3-4h, adding carbodiimide hydrochloride, continuing stirring for 1-2h, freezing at 0℃ for 6-8h, and obtaining the sodium polyglutamate; using the sodium polyglutamate to prepare a polyglutamic acid hydrogel with long-term moisturizing and skin-lightening effect.

Description

Technical Field

[0001] The invention belongs to the technical field of cosmetics, and particularly relates to uses of sodium polyglutamate and polyglutamic acid hydrogel with long-lasting moisturizing and skin-lightening effects. Background Art

[0002] Under the influence of external environmental pollutants, microbial invasion and sunlight and other stimuli, the skin may experience varying degrees of allergies, such as dryness, itching, tingling and tightness, as well as aging, wrinkles, discoloration and dull skin tone, which seriously affect the health of the skin. There are countless moisturizing and skin-lightening compositions on the market, but their effects are always unsatisfactory and difficult to meet people's needs. Summary of the invention

[0003] The purpose of the present invention is to provide a sodium polyglutamate and a polyglutamic acid hydrogel with long-lasting moisturizing and skin-lightening effects, so as to improve the moisturizing and skin-lightening effects of the polyglutamic acid hydrogel.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A sodium polyglutamate with long-lasting moisturizing and skin-lightening properties, the preparation method of the sodium polyglutamate comprising the following steps:

[0006] Take poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid) (purchased from Shaanxi Xinyan Bomei Biotechnology Co., Ltd.), and 0.1 mol / L MES / sodium chloride buffer (purchased from Zhejiang Lianshuo Biotechnology Co., Ltd.), mix, stir for 3-4 hours, add carbodiimide hydrochloride, continue stirring for 1-2 hours, and freeze at 0°C for 6-8 hours to obtain the sodium polyglutamate.

[0007] As a preferred technical solution of the present invention, the dosage ratio of the poly-L-glutamic acid, ε-polylysine, cyclic (glutamic acid-glutamic acid), 0.1 mol / L MES / sodium chloride buffer, and carbodiimide hydrochloride is 10-12g: 8-10g: 7-9g: 150mL: 1.5-2.5g.

[0008] The method for preparing the above-mentioned sodium polyglutamate with long-lasting moisturizing and skin-lightening properties for preparing polyglutamic acid hydrogel comprises the following steps:

[0009] S1, taking the sodium polyglutamate and deionized water, mixing, stirring for 1-2h, adding o-nitrobenzyl alcohol and potassium carbonate, stirring at room temperature for 12-18h, transferring to anhydrous ethanol for precipitation, filtering, taking the solid phase, dialyzing with distilled water for 20-30h, and freeze-drying at -20°C for 12-16h to obtain material A;

[0010] S2, taking the sodium polyglutamate and deionized water, mixing, stirring for 1-2h, adding glycidyl methacrylate in a 0°C ice water bath, adding sodium hydroxide solution, stirring for 18-20h to obtain a mixed solution, introducing the mixed solution into a dialysis bag, dialyzing with distilled water for 20-30h, and freeze-drying at -20°C for 12-16h to obtain material B;

[0011] S3, mixing the material A, material B and deionized water, stirring for 2-3 hours, and irradiating under ultraviolet light for 1-2 hours to obtain the polyglutamic acid hydrogel.

[0012] As a preferred technical solution of the present invention, in step S1, the mass ratio of sodium polyglutamate, deionized water, o-nitrobenzyl alcohol and potassium carbonate is 1-2:100:0.4-0.5:0.4-0.5.

[0013] As a preferred technical solution of the present invention, in step S2, the dosage ratio of the sodium polyglutamate, deionized water, glycidyl methacrylate, and sodium hydroxide solution is 1-2 g: 100 mL: 0.4-0.5 g: 5-6 mmol.

[0014] As a preferred technical solution of the present invention, in step S3, the mass ratio of material A, material B and deionized water is 1-2:2-3:100.

[0015] As a preferred technical solution of the present invention, in step S2, the concentration of the sodium hydroxide solution is 1-2 mol / L.

[0016] The use of the polyglutamic acid hydrogel is to be used for the preparation of long-lasting moisturizing and skin-lightening cosmetics.

[0017] Beneficial effects of the present invention:

[0018] The invention discloses a sodium polyglutamate and polyglutamic acid hydrogel with long-lasting moisturizing and skin-lightening effects. The polyglutamate salt is prepared by the synergistic effect of poly-L-glutamic acid, ε-polylysine and cyclo(glutamic acid-glutamic acid), and then the polyglutamic acid hydrogel is prepared, thereby improving the long-lasting moisturizing and skin-lightening effects. DETAILED DESCRIPTION

[0019] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0020] Example 1

[0021] A method for preparing a polyglutamic acid hydrosol having long-lasting moisturizing and skin-lightening properties comprises the following steps:

[0022] 1) Mix poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), and 0.1 mol / L MES / sodium chloride buffer, stir for 3 h, add carbodiimide hydrochloride, continue stirring for 1 h, and freeze at 0°C for 6 h to obtain sodium polyglutamate; the dosage ratio of the poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), 0.1 mol / L MES / sodium chloride buffer, and carbodiimide hydrochloride is 10 g: 8 g: 7 g: 150 mL: 1.5 g;

[0023] 2) Mix the sodium polyglutamate and deionized water, stir for 1 hour, add o-nitrobenzyl alcohol and potassium carbonate, stir at room temperature for 12 hours, transfer to anhydrous ethanol for precipitation, filter, dialyze the solid phase with distilled water for 20 hours, and freeze-dry at -20°C for 12 hours to obtain material A; the mass ratio of the sodium polyglutamate, deionized water, o-nitrobenzyl alcohol, and potassium carbonate is 1:100:0.4:0.4;

[0024] 3) Mix the sodium polyglutamate and deionized water, stir for 1 hour, add glycidyl methacrylate in a 0°C ice water bath, add sodium hydroxide solution, stir for 18 hours to obtain a mixed solution, introduce the mixed solution into a dialysis bag, dialyze with distilled water for 20 hours, and freeze-dry at -20°C for 12 hours to obtain material B; the dosage ratio of the sodium polyglutamate, deionized water, glycidyl methacrylate, and sodium hydroxide solution is 1g:100mL:0.4g:5mmol; the concentration of the sodium hydroxide solution is 1mol / L;

[0025] 4) Mix the material A, material B and deionized water, stir for 2 hours, and irradiate under ultraviolet light for 1 hour to obtain the polyglutamic acid hydrogel; the mass ratio of the material A, material B and deionized water is 1:2:100.

[0026] Example 2

[0027] A method for preparing a polyglutamic acid hydrosol having long-lasting moisturizing and skin-lightening properties comprises the following steps:

[0028] 1) Mix poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), and 0.1 mol / L MES / sodium chloride buffer, stir for 3.5 hours, add carbodiimide hydrochloride, continue stirring for 1.5 hours, and freeze at 0°C for 7 hours to obtain sodium polyglutamate; the dosage ratio of the poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), 0.1 mol / L MES / sodium chloride buffer, and carbodiimide hydrochloride is 11 g: 9 g: 8 g: 150 mL: 2 g;

[0029] 2) Mix the sodium polyglutamate and deionized water, stir for 1.5 hours, add o-nitrobenzyl alcohol and potassium carbonate, stir at room temperature for 16 hours, transfer to anhydrous ethanol for precipitation, filter, dialyze the solid phase with distilled water for 25 hours, and freeze-dry at -20°C for 14 hours to obtain material A; the mass ratio of the sodium polyglutamate, deionized water, o-nitrobenzyl alcohol, and potassium carbonate is 1.5:100:0.45:0.45;

[0030] 3) Mix the sodium polyglutamate and deionized water, stir for 1.5 hours, add glycidyl methacrylate in a 0°C ice water bath, add sodium hydroxide solution, stir for 19 hours to obtain a mixed solution, introduce the mixed solution into a dialysis bag, dialyze with distilled water for 25 hours, and freeze-dry at -20°C for 14 hours to obtain material B; the dosage ratio of the sodium polyglutamate, deionized water, glycidyl methacrylate, and sodium hydroxide solution is 1.5g:100mL:0.45g:5.5mmol; the concentration of the sodium hydroxide solution is 1.5mol / L;

[0031] 4) Mix the material A, material B and deionized water, stir for 2.5 hours, and irradiate under ultraviolet light for 1.5 hours to obtain the polyglutamic acid hydrogel; the mass ratio of the material A, material B and deionized water is 1.5:2.5:100.

[0032] Example 3

[0033] A method for preparing a polyglutamic acid hydrosol having long-lasting moisturizing and skin-lightening properties comprises the following steps:

[0034] 1) poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), and 0.1 mol / L MES / sodium chloride buffer were mixed, stirred for 4 hours, carbodiimide hydrochloride was added, stirred for 2 hours, and frozen at 0°C for 8 hours to obtain sodium polyglutamate; the dosage ratio of the poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), 0.1 mol / L MES / sodium chloride buffer, and carbodiimide hydrochloride was 12 g: 10 g: 9 g: 150 mL: 2.5 g;

[0035] 2) Mix the sodium polyglutamate and deionized water, stir for 2 hours, add o-nitrobenzyl alcohol and potassium carbonate, stir at room temperature for 18 hours, transfer to anhydrous ethanol for precipitation, filter, dialyze the solid phase with distilled water for 30 hours, and freeze-dry at -20°C for 16 hours to obtain material A; the mass ratio of the sodium polyglutamate, deionized water, o-nitrobenzyl alcohol and potassium carbonate is 2:100:0.5:0.5;

[0036] 3) Mix the sodium polyglutamate and deionized water, stir for 2 hours, add glycidyl methacrylate in a 0°C ice water bath, add sodium hydroxide solution, stir for 20 hours to obtain a mixed solution, introduce the mixed solution into a dialysis bag, dialyze with distilled water for 30 hours, and freeze-dry at -20°C for 16 hours to obtain material B; the dosage ratio of the sodium polyglutamate, deionized water, glycidyl methacrylate, and sodium hydroxide solution is 2g:100mL:0.5g:6mmol; the concentration of the sodium hydroxide solution is 2mol / L;

[0037] 4) Mix the material A, material B and deionized water, stir for 3 hours, and irradiate under ultraviolet light for 2 hours to obtain the polyglutamic acid hydrogel; the mass ratio of the material A, material B and deionized water is 2:3:100.

[0038] Comparative Example 1

[0039] The difference from Example 1 is that the dosage ratio of poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), 0.1 mol / L MES / sodium chloride buffer, and carbodiimide hydrochloride in step 1) is 0g:18g:7g:150mL:1.5g.

[0040] Comparative Example 2

[0041] The difference from Example 1 is that the dosage ratio of poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), 0.1 mol / L MES / sodium chloride buffer, and carbodiimide hydrochloride in step 1) is 18 g: 0 g: 7 g: 150 mL: 1.5 g.

[0042] Comparative Example 3

[0043] The difference from Example 1 is that in step 1), the dosage ratio of poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), 0.1 mol / L MES / sodium chloride buffer, and carbodiimide hydrochloride is 10 g:15 g:0 g:150 mL:1.5 g.

[0044] Comparative Example 4

[0045] The difference from Example 1 is that in step 4), the mass ratio of material A, material B and deionized water is 0:3:100.

[0046] Comparative Example 5

[0047] The difference from Example 1 is that in step 4), the mass ratio of material A, material B and deionized water is 3:0:100.

[0048] Performance Testing

[0049] Test Example 1

[0050] Human patch test

[0051] 1. Test substance: product of Example 1.

[0052] 2. Negative control: blank control.

[0053] 3. Subjects: A total of 30 subjects, including 3 males and 27 females, aged 18-59 years old, with an average age of 37.2±10.6 years old, who met the voluntary inclusion criteria.

[0054] 4. Patch test method: Select qualified patch test equipment and use the closed patch test method. Place about 0.020g-0.025g of the test substance in the patch tester and apply it to the back of the subject with low-allergenic 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 standards in the current valid technical specifications.

[0055] 5. Experimental results:

[0056]

[0057]

[0058] 6. Skin reaction grading standards:

[0059]

[0060] The polyglutamic acid hydrosol of the present application has no adverse reaction to human skin; the inventors of the present application repeated the above test using samples prepared in other embodiments and comparative examples, and the test results were the same as above, showing no adverse reaction to human skin.

[0061] Test Example 2

[0062] 40 volunteers with healthy skin were randomly selected (with a male-female ratio of 20:20) and randomly divided into 8 groups, with 5 people in each group, and each group corresponded to a polyglutamic acid hydrosol in the embodiment and the comparative example;

[0063] Each volunteer cleansed his / her facial skin with a facial cleanser, wiped it dry, and then cleaned his / her facial skin with clean water and wiped it dry. 12 test groups respectively took 1 g of the polyglutamic acid hydrosol prepared in the above Examples 1-3 and Comparative Examples 1-5 and dissolved it in 100 mL of deionized water to make a slurry and evenly applied it on the face, and patted the facial skin for 30 seconds for testing, and took the average value;

[0064] After the moisture on the face dries naturally, use a skin detector to measure the moisture content A of the facial skin at room temperature of 25°C and humidity of 60%; sit still indoors for 1 hour, and measure the moisture content B of the facial skin again under the same conditions to calculate the moisture retention rate. The higher the moisture retention rate, the better the water-locking performance;

[0065] After comparison, statistical analysis was performed, and the comparison results of each group showed that P<0.05, the difference was statistically significant;

[0066] Water retention rate = B ÷ A × 100%

[0067] The test results are shown in Table 1 below;

[0068] Table 1

[0069] Water retention rate (%) Example 1 85.4 Example 2 86.6 Example 3 85.7 Comparative Example 1 77.3 Comparative Example 2 76.6 Comparative Example 3 78.4 Comparative Example 4 80.9 Comparative Example 5 81.1

[0070] It can be seen from Table 1 that the polyglutamic acid hydrosols prepared in Examples 1-3 of the present application have long-lasting moisturizing effects.

[0071] Test Example 3

[0072] 80 female volunteers aged between 30 and 35 were selected and randomly divided into 8 groups. A control test was conducted on a 3 cm × 3 cm area of ​​the inner skin of the left and right arms. 0.5 g of the polyglutamic acid hydrosol of Examples 1-3 and Comparative Examples 1-5 was applied to the inner side of the left arm, and 0.5 g of glycerol was applied to the inner side of the right arm. The application was performed twice a day for 6 weeks.

[0073] The skin brightness of the test area on the left hand and the control area on the right hand was measured before use and six weeks after use. The skin brightness was measured using a skin colorimetry probe + MPA 9 tester. The test results are shown in Table 2 below.

[0074] Table 2

[0075]

[0076]

[0077] It can be seen from Table 2 that the polyglutamic acid hydrogels prepared in Examples 1-3 of the present application have good skin lightening effects.

[0078] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A sodium polyglutamate with long-lasting moisturizing and skin-lightening properties, characterized in that: The preparation method of sodium polyglutamate comprises the following steps: Take poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), and 0.1 mol / L MES / sodium chloride buffer, mix, stir for 3-4 hours, add carbodiimide hydrochloride, continue stirring for 1-2 hours, and freeze at 0°C for 6-8 hours to obtain the sodium polyglutamate; The dosage ratio of the poly-L-glutamic acid, ε-polylysine, cyclo(glutamic acid-glutamic acid), 0.1 mol / L MES / sodium chloride buffer, and carbodiimide hydrochloride is 10-12 g: 8-10 g: 7-9 g: 150 mL: 1.5-2.5 g.

2. A method for preparing polyglutamate hydrogel using the sodium polyglutamate with long-lasting moisturizing and skin-lightening properties as claimed in claim 1, characterized in that: The following steps are involved: S1, taking the sodium polyglutamate and deionized water, mixing, stirring for 1-2h, adding o-nitrobenzyl alcohol and potassium carbonate, stirring at room temperature for 12-18h, transferring to anhydrous ethanol for precipitation, filtering, taking the solid phase, dialyzing with distilled water for 20-30h, and freeze-drying at -20°C for 12-16h to obtain material A; S2, taking the sodium polyglutamate and deionized water, mixing, stirring for 1-2h, adding glycidyl methacrylate in a 0°C ice water bath, adding sodium hydroxide solution, stirring for 18-20h to obtain a mixed solution, introducing the mixed solution into a dialysis bag, dialyzing with distilled water for 20-30h, and freeze-drying at -20°C for 12-16h to obtain material B; S3, mixing the material A, material B and deionized water, stirring for 2-3 hours, and irradiating under ultraviolet light for 1-2 hours to obtain the polyglutamic acid hydrogel.

3. The method for preparing polyglutamate hydrogel using sodium polyglutamate having long-lasting moisturizing and skin-lightening properties according to claim 2, characterized in that: In step S1, the mass ratio of sodium polyglutamate, deionized water, o-nitrobenzyl alcohol and potassium carbonate is 1-2:100:0.4-0.5:0.4-0.

5.

4. The method for preparing polyglutamate hydrogel using sodium polyglutamate having long-lasting moisturizing and skin-lightening properties according to claim 2, characterized in that: In step S2, the dosage ratio of the sodium polyglutamate, deionized water, glycidyl methacrylate, and sodium hydroxide solution is 1-2 g: 100 mL: 0.4-0.5 g: 5-6 mmol.

5. The method for preparing polyglutamate hydrogel using sodium polyglutamate having long-lasting moisturizing and skin-lightening properties according to claim 2, characterized in that: In step S3, the mass ratio of material A, material B and deionized water is 1-2:2-3:

100.

6. The method for preparing polyglutamate hydrogel using sodium polyglutamate having long-lasting moisturizing and skin-lightening properties according to claim 2, characterized in that: In step S2, the concentration of the sodium hydroxide solution is 1-2 mol / L.

7. Use of the polyglutamic acid hydrogel according to any one of claims 2 to 6, characterized in that: The use refers to the preparation of long-lasting moisturizing and skin-lightening cosmetics.

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