A refreshing oil-control composition and its preparation process

Abstract

The invention discloses a refreshing oil-controlling composition and a preparation method thereof, and belongs to the technical field of cosmetics. The refreshing oil-controlling composition provided by the invention comprises the following components by weight: 1-10 parts of grape seed extract, 1-10 parts of Centella asiatica extract, 5-15 parts of sweet tea extract, 1-5 parts of Polygonum cuspidatum extract, 1-5 parts of White Willow bark extract, 5-30 parts of malic acid tripeptide, 2-4 parts of emulsifier, 4-15 parts of moisturizer, 0.5-2 parts of antioxidant, 10-20 parts of butylene glycol, and 50-100 parts of pure water. The malic acid tripeptide provided by the invention can enhance the stability of the tripeptide and improve the solubility of the tripeptide; the malic acid functional group can effectively remove oil esters on the skin surface; the tripeptide functional group can promote collagen synthesis, anti-oxidation and anti-aging, keep the skin moist, fundamentally adjust the water-oil balance, and achieve the refreshing oil-control effect.

Description

Technical Field

[0001] The invention relates to the technical field of cosmetics, in particular to a refreshing oil-controlling composition and a preparation process thereof. Background Art

[0002] For a long time, the skin care / cosmetics market has been dominated by big brands in European and American countries and has been sought after by many consumers. Generally speaking, Caucasians have lighter skin, are sensitive to ultraviolet rays, have thinner skin, and have relatively less oil secretion. Therefore, the research and development and formulation of European and American brands are often designed based on the skin quality and needs of their local populations. However, China has a vast territory and diverse climates, and Chinese skin also has its own uniqueness in terms of oil secretion and stratum corneum thickness. Especially for people in the hot and humid climate in the south, the body's own metabolism speeds up in summer, the skin's oil secretion increases, and too much sebum is distributed on the surface of the skin, which not only causes shiny skin, poor appearance and uncomfortable touch, but also easily absorbs dust. If it accumulates, sebum will clog the deep pores, causing thick keratin, and then form acne.

[0003] There are two views on the existing solutions. One is to use cleansing products with strong cleaning power, astringent water with high alcohol concentration or toner containing mint ingredients, etc., to instantly refresh and shrink pores to control oil secretion. However, this method is not only short-lived, but also causes side effects such as skin tingling, peeling and redness when used for a long time, turning it into an oily skin with dry skin inside. Another view is that the oily skin is caused by dryness and lack of water in the human skin, which causes skin damage. The human body's self-repair and protection system will secrete oil to protect the skin. Therefore, the oily face is a hydration signal sent by the skin. Sufficient water must be injected into the skin in time to maintain the balance of water and oil. In essence, it is still to solve the oil problem by hydrating. However, this hydration method is not suitable for healthy oily skin. On the contrary, it may cause acne due to blockage of the hair follicle sebaceous gland duct due to excessive hydration. In addition, for mixed skin, single oil control skin care products and hydrating skin care products cannot meet their use needs. Therefore, it is still necessary to develop a composition that can control the production of excess oil, moisturize the skin, and maintain the water-oil balance of the skin. Summary of the invention

[0004] In order to overcome the deficiencies of the above-mentioned prior art, the object of the present invention is to provide a refreshing oil-controlling composition and a preparation process thereof, which has the technical effects of low irritation, refreshing oil-controlling and moisturizing.

[0005] The present invention is achieved through the following technical scheme: a refreshing oil control composition, characterized in that it comprises the following components by weight: 1 to 10 parts of grape seed extract, 1 to 10 parts of Centella asiatica extract, 5 to 15 parts of sweet tea extract, 1 to 5 parts of knotweed extract, 1 to 5 parts of white willow bark extract, 5 to 30 parts of malic acid tripeptide, 2 to 4 parts of emulsifier, 4 to 15 parts of moisturizer, 0.5 to 2 parts of antioxidant, 10 to 20 parts of butylene glycol, and 50 to 100 parts of purified water. The molecular structure of the malic acid tripeptide is as follows:

[0006]

[0007] The preparation method of the malic acid tripeptide comprises the following steps:

[0008] S1. Place the solid resin in a peptide synthesis tube, pre-treat the resin, take 4 to 5 times the equivalent of Fmoc-Lys(Boc)-OH, 3 to 4 times the equivalent of condensing agent and 7 to 10 times the equivalent of acid binding agent of the resin capacity and dissolve them in N, N-dimethylformamide solvent, shake at room temperature, and then add them to the peptide synthesis tube for coupling. After the reaction, wash the resin with N, N-dimethylformamide and dichloromethane solvent to obtain Fmoc-Lys(Boc)-OR, where R is the resin;

[0009] S2. Use 10-20% piperidine in N,N-dimethylformamide solution to remove the Fmoc group, add 2-3 times the resin capacity of Fmoc-His(Trt)-OH, 3-4 times the equivalent of condensing agent and 7-10 times the equivalent of acid binding agent in N,N-dimethylformamide solution for coupling, and after the reaction, wash the resin with N,N-dimethylformamide and dichloromethane solvent to obtain Fmoc-His(Trt)-Lys(Boc)-OR;

[0010] S3. Use 10-20% piperidine in N,N-dimethylformamide solution to remove the Fmoc group, add 2-3 times the resin capacity of Fmoc-Gly-OH, 3-4 times the equivalent of condensing agent and 7-10 times the equivalent of acid binding agent in N,N-dimethylformamide solution for coupling, and after the reaction, wash the resin with N,N-dimethylformamide and dichloromethane solvent to obtain Fmoc-Gly-His(Trt)-Lys(Boc)-OR;

[0011] S4. Use 10-20% piperidine in N,N-dimethylformamide solution to remove the Fmoc group, add 2-(2,2-dimethyl-5-oxo-1,3-dioxolane-4-yl)acetic acid in an amount of 2-3 times the resin loading capacity, 3-4 times the condensation agent and 7-10 times the acid binding agent in an N,N-dimethylformamide solution for coupling, after the reaction is completed, wash the resin with N,N-dimethylformamide and dichloromethane solvent, dry and add acid solution to shake to obtain the malic acid tripeptide, the malic acid tripeptide is further extracted, purified and freeze-dried to obtain malic acid tripeptide freeze-dried powder.

[0012] The resin is Rink Amide MBHA resin, and the unit capacity of the resin is 0.2-0.8 mmol / g.

[0013] The pretreatment is to use N,N-dimethylformamide solvent to soak the resin of the polypeptide synthesis tube for 10 to 30 minutes, then soak it in 10 to 20% piperidine N,N-dimethylformamide solution for 10 to 30 minutes, and then fully wash the resin with N,N-dimethylformamide and dichloromethane.

[0014] The condensing agent is at least one of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate (TBTU, CAS: 125700-67-6), benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU, CAS: 94790-37-1), and N,N,N',N'-tetramethyl-O-(7-azabenzotriazole-1-yl)uronium hexafluorophosphate (HATU, 148893-10-1), and the acid binding agent is at least one of N,N-diisopropylethylamine (DIEA) and triethylamine (TEA).

[0015] The coupling reaction temperature is 20-35° C. and the reaction time is 1-3 hours.

[0016] The acid solution in step S4 is a mixed solution of trifluoroacetic acid, 3,6-dioxo-1,8-octanedithiol and water in a volume ratio of (90-95):(2.5-5):(2.5-5); the shaking time is 1-2 hours.

[0017] The extraction in step S4 is to use ether extraction at 5-10°C to obtain a crude malic acid tripeptide precipitate, which is then centrifuged in a refrigerated centrifuge and then extracted with ether at 5-10°C. The purification and freeze-drying are performed using high performance liquid chromatography; the mobile phase of the high performance liquid chromatography is water and acetonitrile containing 0.1% trifluoroacetic acid; after purification, freeze-drying is performed to obtain malic acid tripeptide powder, which is washed at least three times with anhydrous ethanol to remove the residual mobile phase, and then freeze-dried again and stored in a -20°C refrigerator.

[0018] The 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid (cas: 114458-03-6) can be purchased from the market or homemade; preferably, the 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid is homemade, and the preparation method is as follows: 1 equivalent of malic acid is dissolved in N,N-dimethylformamide solvent, 1.2 to 1.5 equivalents of 2,2-dimethoxypropane and 3 Add 1-5 equivalents of p-toluenesulfonic acid and stir for 10-30 minutes, add 1-2 mol / L NaOH aqueous solution and stir, extract and remove the organic phase, distill to remove p-toluenesulfonic acid at 90-100°C, then add 1-2 mol / L HCl aqueous solution and N,N-dimethylformamide dropwise to adjust the pH to 2-3, and extract to obtain a solution of 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid in N,N-dimethylformamide.

[0019] Small molecule active peptides are also called oligopeptides or low-molecular peptides. They are generally composed of 2 to 10 amino acids and have unique biological activity. They have the advantages of small relative molecular mass, strong tissue penetration, good solubility, high stability, and easy absorption. Among them, GHK tripeptide, as an endogenous collagen tripeptide, was first discovered in human plasma. It has the effects of promoting collagen synthesis, stimulating collagen production, and anti-oxidation and anti-aging. Malic acid is acidic and can dissolve and decompose oil and dirt on the surface of the skin. It has the effect of promoting keratinocyte metabolism and making the skin smoother and more energetic. However, malic acid is highly acidic and can easily cause skin irritation and allergies when applied directly to the skin. The invention first reacts malic acid with 2,2-dimethoxypropane to obtain a reaction intermediate, and then protects the carboxyl group at one end of the malic acid, or directly uses 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid as a precursor of malic acid, so that the carboxyl group at the other end of the malic acid can be point-connected with the N-terminus of GHK to obtain a target peptide molecule. The prepared malic acid tripeptide can enhance the stability of the tripeptide, making it less likely to decompose or deteriorate, and improve the solubility of the tripeptide. In addition, the acidity of the malic acid itself is greatly weakened after being combined with the tripeptide. When the malic acid is applied to skin care products or cosmetics, the tripeptide can promote collagen synthesis, resist oxidation and resist aging while removing oil esters on the skin surface, thereby keeping the skin moist, adjusting the water-oil balance and achieving a refreshing and oil-controlling effect.

[0020] The invention uses malic acid tripeptide as a main active ingredient, and further adds plant extract components such as grape seed extract, sweet tea extract, Centella asiatica extract, Polygonum cuspidatum extract, and white willow bark extract. The grape seed extract is rich in antioxidant components such as proanthocyanidins, can remove free radicals, slow down skin aging, and protect the skin from oxidative damage; the sweet tea extract has anti-allergic and moisturizing effects, can reduce skin allergic reactions, soothe the skin, and keep the skin moisturized; the Centella asiatica extract has wound healing and anti-inflammatory effects, is helpful in repairing damaged skin tissue, accelerating wound healing, reducing skin inflammation, relieving symptoms such as redness, swelling, itching, and is helpful in eliminating and relieving acne; the Polygonum cuspidatum extract contains resveratrol, can improve dull skin tone and anti-oxidation, and can improve the dullness of oily skin; the main component of the white willow bark extract, salicin, can regulate sebum secretion, reduce oil, and can also gently remove aged cuticles to make the skin smooth, and has a good oil control and acne removal effect on oily skin.

[0021] Preferably, the mass ratio of the sweet tea extract, the knotweed extract and the white willow bark extract is (5-8):(1-2):1.

[0022] Preferably, the malic acid tripeptide is 10 to 20 parts.

[0023] The emulsifier is selected from at least one of cetyl PEG / PPG-10 / 1 polydimethylsiloxane, PEG-60 glyceryl isostearate, and sorbitan sesquioleate.

[0024] The moisturizing agent is selected from at least one of ethylhexylglycerol, oligofructose, fructose, glucose, 1,2-hexanediol, butylene glycol, glycerol, 1,2-pentanediol, and sodium hyaluronate.

[0025] The antioxidant is selected from at least one of tocopherol acetate, phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben, potassium sorbate and sodium benzoate.

[0026] Another object of the present invention is to provide a method for preparing a refreshing oil-control composition, comprising the following steps: grinding grape seed extract, sweet tea extract, Centella asiatica extract, Polygonum cuspidatum extract, and white willow bark extract through a 100-500 mesh sieve, respectively, and then dissolving in a mixed solution of part of pure water and butanediol, and stirring at a speed of 100-200 rpm to obtain an extract solution; mixing malic acid tripeptide with an emulsifier, a moisturizer, an antioxidant and the remaining pure water, stirring at a speed of 100-200 rpm to obtain a homogeneous solution, mixing the homogeneous solution with the extract solution, and stirring at a speed of 500-800 rpm to obtain a homogeneous solution.

[0027] Another object of the present invention is to protect the use of the refreshing oil-control composition in toner, essence water, lotion, essence, face cream, BB cream, sunscreen, liquid foundation, and isolation milk, and is particularly suitable for use in toner, essence water, and lotion.

[0028] It should be noted that the formula of the refreshing oil-control composition provided by the present invention is a raw material concentrate formula, which can be used in toner, essence water, lotion, essence, face cream, BB cream, sunscreen, foundation, and isolation milk and can be diluted and added with other functional ingredients according to actual needs.

[0029] Beneficial Effects

[0030] The invention provides a refreshing oil-controlling composition. The composition comprises the following steps: firstly reacting malic acid with 2,2-dimethoxypropane to obtain a reaction intermediate, protecting the carboxyl group at one end of the malic acid, or directly using 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid as a precursor of the malic acid, so that the carboxyl group at the other end of the malic acid can be point-connected with the N-terminus of GHK to obtain a malic acid tripeptide. The malic acid tripeptide can enhance the stability of the tripeptide and improve the solubility of the tripeptide. In addition, the malic acid functional group can effectively remove oil esters on the surface of the skin, and the tripeptide functional group can promote collagen synthesis, anti-oxidation and anti-aging, keep the skin moist, fundamentally adjust the water-oil balance, and achieve a refreshing oil-controlling effect. The present invention also adds plant extract components such as grape seed extract, sweet tea extract, Centella asiatica extract, Polygonum cuspidatum extract, and white willow bark extract, which can regulate sebum secretion, improve oily and dull skin and clogged pores, while soothing the skin and keeping the skin moisturized. It has a good refreshing and oil-control effect for people in the rainy southern climate or oily skin. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is the synthetic route of malic acid tripeptide;

[0032] Figure 2 The reaction formula for synthesizing 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid;

[0033] Figure 3 This is the H NMR spectrum of malic acid tripeptide. DETAILED DESCRIPTION

[0034] 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.

[0035] In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0036] The raw materials used in the embodiments and comparative examples are described below:

[0037] Grape seed extract: purchased from Morning Light Biotechnology

[0038] Sweet tea extract: Hunan Huacheng Biological

[0039] Centella asiatica extract: Xi'an Tianyi Biological

[0040] Polygonum cuspidatum extract: Shaanxi Jiahe Biological

[0041] White willow bark extract: Shaanxi Jiahe Biological

[0042] Emulsifier: sorbitan sesquioleate, purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.;

[0043] Moisturizer: glycerin, purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.;

[0044] Antioxidant: Tocopherol acetate, purchased from Tianjin Xiensi Biochemical Technology Co., Ltd.;

[0045] Fmoc-Lys(Boc)-OH, Fmoc-His(Trt)-OH, Fmoc-Gly-OH, and 2-(1H-benzotriazol-L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate were all from Shanghai Jier Biochemical Company;

[0046] Malic acid was DL-malic acid, and 2,2-dimethoxypropane was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.

[0047] 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid: homemade, the preparation method is as follows: take 1 equivalent of malic acid and dissolve it in N,N-dimethylformamide solvent, add 1.5 equivalents of 2,2-dimethoxypropane and 5 equivalents of p-toluenesulfonic acid and stir for 10 to 30 minutes, add 1.5 mol / L NaOH aqueous solution and stir, extract and remove the organic phase, distill to remove p-toluenesulfonic acid at 95°C, then add 2 mol / L HCl aqueous solution to adjust the pH to 2 to 3, extract twice with N,N-dimethylformamide to obtain 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid in N,N-dimethylformamide, the reaction formula is as follows Figure 2 shown.

[0048] Malic acid tripeptide: Homemade, preparation method is as follows:

[0049] S1. Place RinkAmide MBHA resin in a peptide synthesis tube. The unit capacity of the resin is measured to be 0.68 mmol / g. Pre-treat the resin by soaking it in N,N-dimethylformamide solvent for 10 minutes. After the resin is swollen, soak it in 20% piperidine in N,N-dimethylformamide solution for 20 minutes. Wash it three times with N,N-dimethylformamide, three times with dichloromethane, and three times with N,N-dimethylformamide before use. Take 2.72 equivalents of Fmoc-Lys(Boc)-OH, 2.5 equivalents of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate and 5.44 equivalents of N,N-diisopropylethylamine and dissolve them in N,N-dimethylformamide solvent. First shake at room temperature for 2 minutes, then add them into the peptide synthesis tube for coupling for 2 hours. After the reaction, wash with N,N-dimethylformamide three times, dichloromethane three times, and N,N-dimethylformamide three times to obtain Fmoc-Lys(Boc)-OR, where R is resin;

[0050] S2. Add 20% piperidine in N,N-dimethylformamide solution to the peptide synthesis tube, shake for 10 minutes, pour out the solution, re-add 20% piperidine in N,N-dimethylformamide solution, shake again for 10 minutes and pour out to remove the Fmoc group of Fmoc-Lys(Boc)-OR, then add 2.04 equivalents of Fmoc-His(Trt)-OH with a resin loading capacity, 2.5 equivalents of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate and 5.44 equivalents of N,N-diisopropylethylamine in N,N-dimethylformamide solution for coupling for 2 hours. After the reaction, wash three times with N,N-dimethylformamide, three times with dichloromethane and three times with N,N-dimethylformamide to obtain Fmoc-His(Trt)-Lys(Boc)-OR;

[0051] S3. Add 20% piperidine in N,N-dimethylformamide solution to the peptide synthesis tube, shake for 10 minutes, pour out the solution, add 20% piperidine in N,N-dimethylformamide solution again, shake for 10 minutes and pour out, remove the Fmoc group in Fmoc-His(Trt)-Lys(Boc)-OR, add 2.04 equivalents of Fmoc-Gly-OH, 2.5 equivalents of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate and 5.44 equivalents of N,N-diisopropylethylamine in N,N-dimethylformamide solution for coupling for 2 hours, wash with N,N-dimethylformamide three times, dichloromethane three times and N,N-dimethylformamide three times after the reaction is completed to obtain Fmoc-Gly-His(Trt)-Lys(Boc)-OR;

[0052] S4. Add 20% piperidine in N,N-dimethylformamide solution to the peptide synthesis tube, shake for 10 minutes, pour out the solution, add 20% piperidine in N,N-dimethylformamide solution again, shake for another 10 minutes and pour out, remove the Fmoc group of Fmoc-Gly-His(Trt)-Lys(Boc)-OR, add 2.04 equivalents of 2-(2,2-dimethyl-5-oxo-1,3-dioxolane-4-yl)acetic acid, 2.5 equivalents of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate and 5.44 equivalents of N,N-diisopropylethylamine in N,N-dimethylformamide solution for coupling. 2 hours, after the reaction is completed, wash three times with N, N-dimethylformamide, three times with dichloromethane, and three times with N, N-dimethylformamide, and after drying, add a mixed solution of trifluoroacetic acid, 3,6-dioxy-1,8-octanedithiol and water in a volume ratio of 95:2.5:2.5 and shake for 2 hours to obtain the malic acid tripeptide, remove most of the reagents by rotary evaporation, add 5°C ether and shake and extract the malic acid tripeptide twice, and then centrifuge in a refrigerated centrifuge to obtain a crude malic acid tripeptide precipitate, and then extract it with 5°C ether twice, and purify the crude malic acid tripeptide precipitate by high performance liquid chromatography; the mobile phase of the high performance liquid chromatography is water and acetonitrile containing 0.1% trifluoroacetic acid; the chromatographic column is peptide BEH C18 OBDTM Prep column, 5μm, 10×250mm, the crude peptide was purified at a flow rate of 4.7mL / min, and the malic acid tripeptide powder was obtained by freeze drying after purification. The residual mobile phase was fully washed with anhydrous ethanol at least three times, and then freeze dried again and stored in a -20℃ refrigerator. Figure 1 shown.

[0053] Tripeptide: Homemade, preparation method is as follows:

[0054] S1. Place RinkAmide MBHA resin in a peptide synthesis tube. The unit capacity of the resin is measured to be 0.68 mmol / g. Pre-treat the resin by soaking it in N,N-dimethylformamide solvent for 10 minutes. After the resin is swollen, soak it in 20% piperidine in N,N-dimethylformamide solution for 20 minutes. Wash it three times with N,N-dimethylformamide, three times with dichloromethane, and three times with N,N-dimethylformamide before use. Take 2.72 equivalents of Fmoc-Lys(Boc)-OH, 2.5 equivalents of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate and 5.44 equivalents of N,N-diisopropylethylamine and dissolve them in N,N-dimethylformamide solvent. First shake at room temperature for 2 minutes, then add them into the peptide synthesis tube for coupling for 2 hours. After the reaction, wash with N,N-dimethylformamide three times, dichloromethane three times, and N,N-dimethylformamide three times to obtain Fmoc-Lys(Boc)-OR, where R is resin;

[0055] S2. Add 20% piperidine in N,N-dimethylformamide solution to the peptide synthesis tube, shake for 10 minutes, pour out the solution, re-add 20% piperidine in N,N-dimethylformamide solution, shake again for 10 minutes and pour out to remove the Fmoc group of Fmoc-Lys(Boc)-OR, then add 2.04 equivalents of Fmoc-His(Trt)-OH with a resin loading capacity, 2.5 equivalents of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate and 5.44 equivalents of N,N-diisopropylethylamine in N,N-dimethylformamide solution for coupling for 2 hours. After the reaction, wash three times with N,N-dimethylformamide, three times with dichloromethane and three times with N,N-dimethylformamide to obtain Fmoc-His(Trt)-Lys(Boc)-OR;

[0056] S3. Add 20% piperidine in N,N-dimethylformamide solution to the peptide synthesis tube, shake for 10 minutes, pour out the solution, add 20% piperidine in N,N-dimethylformamide solution again, shake for 10 minutes and pour out, remove the Fmoc group in Fmoc-His(Trt)-Lys(Boc)-OR, add 2.04 equivalents of Fmoc-Gly-OH, 2.5 equivalents of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate and 5.44 equivalents of N,N-diisopropylethylamine in N,N-dimethylformamide solution for coupling for 2 hours, wash with N,N-dimethylformamide three times, dichloromethane three times and N,N-dimethylformamide three times after the reaction is completed to obtain Fmoc-Gly-His(Trt)-Lys(Boc)-OR;

[0057] S4. Add 20% piperidine in N,N-dimethylformamide solution to the peptide synthesis tube, shake for 10 minutes, pour out the solution, add 20% piperidine in N,N-dimethylformamide solution again, shake for 10 minutes and pour out, remove the Fmoc group of Fmoc-Gly-His(Trt)-Lys(Boc)-OR, add 2.04 equivalents of acetic anhydride in N,N-dimethylformamide solution for coupling for 2 hours, and after the reaction, wash three times with N,N-dimethylformamide, three times with dichloromethane, and three times with N,N- The product was washed three times with dimethylformamide, dried, added with a mixed solution of trifluoroacetic acid, 3,6-dioxo-1,8-octanedithiol and water in a volume ratio of 95:2.5:2.5 and shaken for 2 hours to obtain the tripeptide, most of the reagents were removed by rotary evaporation, 5°C ether was added and shaken to extract the tripeptide twice, and then centrifuged in a refrigerated centrifuge to obtain a crude tripeptide precipitate, which was then extracted twice with 5°C ether, and the crude tripeptide precipitate was purified by high performance liquid chromatography; the mobile phase of the high performance liquid chromatography was water and acetonitrile containing 0.1% trifluoroacetic acid; the chromatographic column was peptide BEH C18OBDTM Prep column, 5μm, 10×250mm, the crude peptide was purified at a flow rate of 4.7mL / min, and the tripeptide powder was obtained by freeze-drying after purification. The powder was washed with anhydrous ethanol at least three times to remove the residual mobile phase, and then freeze-dried again and stored in a -20°C refrigerator.

[0058] The prepared malic acid tripeptide was tested by nuclear magnetic resonance hydrogen spectrum, and the results were as follows Figure 3 shown.

[0059] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0060] Examples 1 to 9

[0061] Grape seed extract, sweet tea extract, Centella asiatica extract, Polygonum cuspidatum extract, and white willow bark extract were respectively ground through a 200-mesh sieve, and then dissolved in a mixed solution of part of purified water and butylene glycol, and stirred at 200 rpm to obtain an extract solution; malic acid tripeptide, an emulsifier, a moisturizer, an antioxidant, and the remaining purified water were mixed, and stirred at 200 rpm to obtain a homogeneous solution, the homogeneous solution was mixed with the extract solution, and stirred at 800 rpm to obtain a homogeneous solution, and the obtained homogeneous solution was diluted with butylene glycol and purified water to prepare a refreshing oil-control essence water. The specific components and their weight parts formula are shown in Table 1.

[0062] Table 1 Components and weight parts of Examples 1 to 9

[0063]

[0064] Comparative Examples 1 to 6

[0065] The preparation method is the same as that of Examples 1 to 9, except that the specific components and their weight fractions are different, as shown in Table 2.

[0066] Table 2 Components and weight parts of comparative examples 1 to 6

[0067] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Grape Seed Extract 5 5 5 5 5 5 Centella Asiatica Extract 5 5 5 5 5 5 Sweet Tea Extract 11 11 11 11 11 Polygonum cuspidatum extract 3 3 3 3 3 White Willow Bark Extract 2 2 2 2 2 Malate Tripeptide 15 15 15 Tripeptide 15 15 Malic Acid 15 Emulsifier 3 3 3 3 3 3 Moisturizer 10 10 10 10 10 10 Antioxidants 1 1 1 1 1 1 Butanediol 50 50 50 50 50 50 Purified water 950 950 950 950 950 950

[0068] The refreshing oil-controlling essence water prepared in Examples 1-9 and Comparative Examples 1-6 was subjected to the following performance tests, and the results are shown in Table 3, respectively.

[0069] (1) Skin irritation test: The refreshing oil-control compositions of the embodiments and comparative examples were subjected to skin irritation tests. The subjects were adults aged 25 to 50 years old, with 10 people for each sample. After the forehead of the subjects was cleaned, the left and right parts were marked as the test area and the blank area. After applying the sample (20 μL) on the test area of ​​the subjects for 24 hours, the scores were scored according to the following criteria. The final score was the arithmetic mean of the sample scores:

[0070] User experience Rating / points No stimulation 5 Mild irritation 4 Redness of the skin 3 Rash and edema 2 Rash, edema, blisters 0～1

[0071] (2) Oil control test: The test subjects were healthy East Asian consumers aged 18 and above, including 66 females (average age 35.2±9.9 years old); Test method: (1) Test site: face; (2) Usage cycle: 14 days (at least 3 times a week); (3) Evaluation method: A questionnaire survey was conducted on consumers’ skin condition and product satisfaction; (4) Judgment basis: A comparison was made between the skin condition perceived by consumers before use of the product and 7 and 14 days after use of the product, and the self-evaluation results of consumers’ perception of the degree to which skin oiliness was not obvious were analyzed; Scoring was performed according to the following criteria:

[0072]

[0073] (3) Moisturizing test: The test subjects were 10 female adult volunteers, with an average age of 63 years old, ranging from 56 to 70 years old, with dry skin on their legs. When they used the product, the moisture content measured by the skin moisture tester was less than or equal to 50%. The moisture content of the skin was measured 1 hour, 2 hours, and 3 hours after applying the product.

[0074] Table 3 Performance tests of embodiments and comparative examples

[0075]

[0076]

[0077] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A refreshing oil control composition, characterized in that: The composition includes the following components by weight: 1-10 parts of grape seed extract, 1-10 parts of Centella asiatica extract, 5-15 parts of sweet tea extract, 1-5 parts of Polygonum cuspidatum extract, 1-5 parts of white willow bark extract, 5-30 parts of malic acid tripeptide, 2-4 parts of emulsifier, 4-15 parts of moisturizer, 0.5-2 parts of antioxidant, 10-20 parts of butylene glycol, 50-100 parts of purified water. The molecular structure of the malic acid tripeptide is as follows:

2. The refreshing oil control composition according to claim 1, characterized in that: The preparation method of the malic acid tripeptide comprises the following steps: S1. Place the solid resin in a peptide synthesis tube, pre-treat the resin, take 4 to 5 times the equivalent of Fmoc-Lys(Boc)-OH, 3 to 4 times the equivalent of condensing agent and 7 to 10 times the equivalent of acid binding agent of the resin capacity and dissolve them in N, N-dimethylformamide solvent, shake at room temperature, and then add them to the peptide synthesis tube for coupling. After the reaction, wash the resin with N, N-dimethylformamide and dichloromethane solvent to obtain Fmoc-Lys(Boc)-OR, where R is the resin; S2. Use 10-20% piperidine in N,N-dimethylformamide solution to remove the Fmoc group, add 2-3 times the resin capacity of Fmoc-His(Trt)-OH, 3-4 times the equivalent of condensing agent and 7-10 times the equivalent of acid binding agent in N,N-dimethylformamide solution for coupling, and after the reaction, wash the resin with N,N-dimethylformamide and dichloromethane solvent to obtain Fmoc-His(Trt)-Lys(Boc)-OR; S3. Use 10-20% piperidine in N,N-dimethylformamide solution to remove the Fmoc group, add 2-3 times the resin capacity of Fmoc-Gly-OH, 3-4 times the equivalent of condensing agent and 7-10 times the equivalent of acid binding agent in N,N-dimethylformamide solution for coupling, and after the reaction, wash the resin with N,N-dimethylformamide and dichloromethane solvent to obtain Fmoc-Gly-His(Trt)-Lys(Boc)-OR; S4. Use 10-20% piperidine in N,N-dimethylformamide solution to remove the Fmoc group, add 2-(2,2-dimethyl-5-oxo-1,3-dioxolane-4-yl)acetic acid in an amount of 2-3 times the resin loading capacity, 3-4 times the condensation agent and 7-10 times the acid binding agent in an N,N-dimethylformamide solution for coupling, after the reaction is completed, wash the resin with N,N-dimethylformamide and dichloromethane solvent, dry and add acid solution to shake to obtain the malic acid tripeptide, the malic acid tripeptide is further extracted, purified and freeze-dried to obtain malic acid tripeptide freeze-dried powder.

3. The refreshing oil-control composition according to claim 2, characterized in that: Any of the following (1) to (6): (1) The resin is Rink Amide MBHA resin, and the unit loading capacity of the resin is 0.2 to 0.8 mmol / g; (2) The pretreatment is to soak the resin of the peptide synthesis tube with N,N-dimethylformamide solvent for 10 to 30 minutes, then soak it in 10 to 20% piperidine in N,N-dimethylformamide solution for 10 to 30 minutes, and then fully wash the resin with N,N-dimethylformamide and dichloromethane; (3) The condensing agent is at least one of 2-(1H-benzotriazol L-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate, benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate, and N,N,N',N'-tetramethyl-O-(7-azabenzotriazole-1-yl)uronium hexafluorophosphate, and the acid binding agent is at least one of N,N-diisopropylethylamine and triethylamine; (4) The coupling reaction temperature is 20 to 35° C. and the reaction time is 1 to 3 hours; (5) The acid solution in step S4 is a mixed solution of trifluoroacetic acid, 3,6-dioxo-1,8-octanedithiol and water in a volume ratio of (90-95):(2.5-5):(2.5-5); the shaking time is 1-2 hours; (6) The extraction in step S4 is performed by using ether extraction at 5 to 10° C. to obtain a crude malic acid tripeptide precipitate, which is then centrifuged in a refrigerated centrifuge and then extracted with ether at 5 to 10° C. The purification and freeze-drying are performed by using high performance liquid chromatography; the mobile phase of the high performance liquid chromatography is water and acetonitrile containing 0.1% trifluoroacetic acid; after purification, the malic acid tripeptide powder is freeze-dried to obtain the powder, which is washed at least three times with anhydrous ethanol to remove the residual mobile phase, and then freeze-dried again and stored in a -20° C. refrigerator.

4. The refreshing oil-control composition according to claim 2, characterized in that: The preparation method of 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid is as follows: 1 equivalent of malic acid is dissolved in an N,N-dimethylformamide solvent, 1.2-1.5 equivalents of 2,2-dimethoxypropane and 3-5 equivalents of p-toluenesulfonic acid are added, and the mixture is stirred for 10-30 minutes, 1-2 mol / L of a NaOH aqueous solution is added, and the mixture is stirred, and an organic phase is removed by extraction, and p-toluenesulfonic acid is removed by distillation at 90-100° C., and a 1-2 mol / L HCl aqueous solution is added dropwise to adjust the pH to 2-3, and an N,N-dimethylformamide solution of 2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl)acetic acid is obtained by extraction with N,N-dimethylformamide.

5. The refreshing oil control composition according to claim 1, characterized in that: The mass ratio of the sweet tea extract, the knotweed extract and the white willow bark extract is (5-8):(1-2):

1.

6. The refreshing oil-control composition according to claim 1, characterized in that: The emulsifier is selected from at least one of cetyl PEG / PPG-10 / 1 polydimethylsiloxane, PEG-60 glyceryl isostearate, and sorbitan sesquioleate.

7. The refreshing oil-control composition according to claim 1, characterized in that: The moisturizing agent is selected from at least one of ethylhexylglycerol, oligofructose, fructose, glucose, 1,2-hexanediol, glycerol, 1,2-pentanediol, and sodium hyaluronate.

8. The refreshing oil-control composition according to claim 1, characterized in that: The antioxidant is selected from at least one of tocopherol acetate, phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben, potassium sorbate and sodium benzoate.

9. The method for preparing the refreshing oil-controlling composition according to claim 1, characterized in that: The following steps are involved: Grape seed extract, sweet tea extract, Centella asiatica extract, Polygonum cuspidatum extract and white willow bark extract are respectively ground through 100-500 mesh sieves, then dissolved in a mixed solution of partly purified water and butylene glycol, and stirred at a speed of 100-200 rpm to obtain an extract solution; malic acid tripeptide, an emulsifier, a moisturizer, an antioxidant and the remaining purified water are mixed, and stirred at a speed of 100-200 rpm to obtain a homogeneous solution; the homogeneous solution is mixed with the extract solution, and stirred at a speed of 500-800 rpm to obtain a homogeneous solution.

10. Use of the refreshing oil-controlling composition according to claim 1 in toner, essence water, lotion, essence, face cream, BB cream, sunscreen, liquid foundation and isolation milk.

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