Anticorrosive composition and application thereof in cosmetics

Abstract

The invention relates to the technical field of anti-corrosion of cosmetics, in particular to an anti-corrosion composition and application thereof in cosmetics. The anti-corrosion composition is prepared from sodium dehydroacetate, capryloyl hydroximic acid, a solvent and D-sodium erythorbate. The D-sodium erythorbate, the sodium dehydroacetate and the capryloyl hydroximic acid are mixed for use, the D-sodium erythorbate is coordinated with the sodium dehydroacetate to reduce the activity of the sodium dehydroacetate, and the coordination product is competitive with a metal ion chelating agent, so that the effect of reducing the irritation to the skin is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of cosmetics preservation, and in particular to an antiseptic composition and application thereof in cosmetics. Background Art

[0002] Cosmetics contain abundant nutrients, such as water, oils, various functional extracts and additives, which provide an environment for the growth and reproduction of microorganisms. Once the product is contaminated by microorganisms, it will affect the quality of the cosmetics and even harm the health of consumers. Therefore, in order to kill and inhibit the microorganisms in cosmetics and maintain the quality of cosmetics for a long time, some preservatives must be added.

[0003] Common preservatives, such as kasonite preservatives: methylisothiazolinone (MIT) and methylchloroisothiazolinone (MCI), are easy to cause allergies, and long-term use can easily lead to irritant dermatitis. Another example is formaldehyde releasers: bis (hydroxymethyl) imidazolidinyl urea. This type of preservative can cause dermatitis, so pregnant women and people with sensitive skin should use it with caution. Another example is long-chain parabens: butyl hydroxybenzoate and propyl hydroxybenzoate. Long-term use can easily cause allergies, so people with sensitive skin should use it with caution. Another example is aromatic alcohols: phenoxyethanol. The main concern is liver toxicity, because phenoxyethanol is mainly metabolized in the body through the liver, so long-term use will be risky. It can be seen that most preservatives added to cosmetics currently have the defect of being highly irritating, and the safety aspect is not very satisfactory.

[0004] There are also some prior arts that use a combination of multiple preservatives, such as a cosmetic composition disclosed in the patent document with publication number CN112165931A, which includes a cosmetically acceptable carrier and a preservative system, wherein the preservative system includes: (i) an antimicrobial agent, including potassium sorbate, and further including chlorhexidine or its salt, chlorphenesin, benzoic acid or its salt or ester, sorbic acid or its salt, 4-hydroxybenzoic acid or its salt or ester, dehydroacetic acid or its salt, bromopol, benzyl alcohol, polyaminopropyl biguanide, phenoxyethanol or a combination thereof; (ii) a chelating agent; (iii) an antimicrobial enhancer selected from the group consisting of ethylhexylglycerin, caprylyl glycol, hydroxyacetophenone, caprylhydroxamic acid, phenethyl alcohol, p-anisic acid, glyceryl caprylate, levulinic acid, sodium levulinate, propylene glycol, hexylene glycol, pentylene glycol, capryloyl glycine, methylpropanediol, phenylpropanol, sodium anisate and a combination thereof. In the prior art, dehydroacetic acid or its salt, octanoylhydroxamic acid and the like are compounded, but the problem of skin irritation is still not solved. Summary of the invention

[0005] The present invention aims to solve the above problems and provides a preservative composition with low irritation to skin and its application in cosmetics.

[0006] The technical solution to the problem of the present invention is to first provide an antiseptic composition comprising sodium dehydroacetate, caprylhydroxamic acid, a solvent, and sodium D-isoascorbate.

[0007] The inventors unexpectedly discovered that by adding sodium D-isoascorbate to a compound of sodium dehydroacetate and octanoylhydroxamic acid, the irritation of sodium dehydroacetate and octanoylhydroxamic acid to the skin can be reduced while ensuring the preservative effect.

[0008] The inventor speculates that the reason why sodium dehydroacetate is irritating to the skin may be that the β-diketone group in its chemical structure has high chemical activity, which may generate free radicals through photocatalysis, trigger lipid peroxidation, and damage the skin cell membrane; it may also combine with free amino or sulfhydryl groups in the stratum corneum of the skin, causing protein cross-linking or denaturation, reducing the skin barrier function, and causing dryness, desquamation or irritation. The reason why octanoylhydroxamic acid is irritating to the skin may be that the oxygen and nitrogen atoms in the hydroxamic acid group have lone pairs of electrons and can form stable five-membered ring chelates with metal ions; this chelation may interfere with the function of metal-dependent enzymes in the skin, destroy the skin barrier or trigger an inflammatory response.

[0009] Then, in the present application, when sodium D-isoascorbate is compounded with sodium dehydroacetate and caprylhydroxamic acid, firstly, the hydroxyl group and carboxylic acid group of sodium D-isoascorbate can form hydrogen bonds or weak coordination bonds with the β-diketone group of sodium D-isoascorbate, thereby reducing the activity of the β-diketone group of sodium dehydroacetate and reducing its attack on skin cells; it can also repair the protein thiol or lipid barrier components damaged by free radical oxidation through reduction; thereby reducing the irritation of sodium dehydroacetate. Secondly, after sodium D-isoascorbate coordinates with sodium dehydroacetate, a bulky group is introduced into the sodium D-isoascorbate molecule, producing a steric hindrance effect, which will hinder the chelation of metal ions with sodium D-isoascorbate, that is, weaken the metal chelation ability of sodium D-isoascorbate; this weak metal chelation ability can not only compete with octanoylhydroxamic acid to bind free metal ions, reduce the irritation caused by excessive consumption of essential metals for the skin by octanoylhydroxamic acid, but also will not completely lock metal ions like octanoylhydroxamic acid, but form a dynamic balance to ensure that metal ions can still be used by the enzyme system to ensure the normal function of the skin. In addition, sodium D-isoascorbate itself has a certain antibacterial effect, which can make up for the problem of decreased antiseptic performance after its action on sodium dehydroacetate and competition with octanoylhydroxamic acid.

[0010] Based on this, while ensuring the antiseptic effect, the irritation of sodium dehydroacetate and caprylhydroxamic acid to the skin is reduced.

[0011] in, Sodium dehydroacetateThe amount used in the antiseptic composition is not limited, and it can be within an appropriate range. In some embodiments, considering that too little use may affect the antiseptic effect, too much use increases the cost on the one hand and causes excessive irritation on the other hand. As a preferred embodiment of the present invention, the antiseptic composition includes 0.4wt% to 2wt% of sodium dehydroacetate, for example, it can be 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 2wt%, and more preferably 0.5wt% to 1wt%.

[0012] Octanoylhydroxamic acid The amount used in the antiseptic composition is not limited, as long as it is within an appropriate range. In some embodiments, considering that too little use may affect the antiseptic effect, too much use will increase the cost on the one hand and cause excessive irritation on the other hand. As a preferred embodiment of the present invention, the antiseptic composition includes 0.5wt% to 10wt% octanoylhydroxamic acid. For example, it can be 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%, and more preferably 1wt% to 5wt%.

[0013] In principle Sodium D-isoascorbate The amount used in the antiseptic composition is not limited, but the appropriate ratio of sodium dehydroacetate and octanoyl hydroxamic acid can effectively balance the antiseptic and low irritation of the composition. For example, excessive use of sodium D-isoascorbate may lead to insufficient antiseptic properties of the composition, and too little use of sodium D-isoascorbate may have a poor inhibitory effect on irritation. As a preferred embodiment of the present invention, the mass ratio of sodium D-isoascorbate to sodium dehydroacetate and octanoyl hydroxamic acid is (2.5-7):1:(1-5). For example, when the mass ratio of sodium dehydroacetate is 1 part, octanoyl hydroxamic acid can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, and more preferably 1.5-2.5 parts. The amount of sodium D-erythorbate may be 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, or 7 parts, and more preferably 4 to 6 parts.

[0014] SolventsThe choice of is not limited and may include any one of the recognized solvents allowed in cosmetic products that allows stable dispersion of sodium D-isoascorbate, sodium dehydroacetate, and caprylhydroxamic acid. As a preferred embodiment of the present invention, the solvent includes ethylhexylglycerol, a diol having 3 to 8 carbon atoms, and water. On the one hand, the solubility of ethylhexylglycerol is utilized, supplemented by alcohols and water as solvents; on the other hand, the core advantage of sodium dehydroacetate and caprylhydroxamic acid is antifungal, and although they also have inhibitory effects on bacteria, their effectiveness is relatively weak, while ethylhexylglycerol has a good antibacterial effect on bacteria. The combination of the three can improve the broad spectrum of preservation.

[0015] Among them, as preferred in the present invention, the diol with 3 to 8 carbon atoms includes at least one of 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol and dipropylene glycol.

[0016] The ratio of ethylhexylglycerol, diol with 3 to 8 carbon atoms, and water in the solvent is not limited, but a suitable ratio has better solubility and dispersibility. As preferred of the present invention, the antiseptic composition includes 2wt% to 16wt% ethylhexylglycerol, for example, it can be 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%; including 30wt% to 50wt% diol with 3 to 8 carbon atoms, for example, it can be 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 45wt%, 50wt%.

[0017] Mixing method of sodium D-isoascorbate, sodium dehydroacetate and caprylhydroxamic acid in solvent Without limitation, in some embodiments, the three are dispersed in the solvent in parallel.

[0018] In other embodiments, at least part of the sodium dehydroacetate and at least part of the octanoylhydroxamic acid form a shell-core structure with sodium dehydroacetate as the shell and octanoylhydroxamic acid as the core. By designing the shell-core structure, sodium dehydroacetate is rapidly released and octanoylhydroxamic acid is slowly released, and sodium D-isoascorbate is controlled to react with sodium dehydroacetate first, and its coordination product competes with octanoylhydroxamic acid, thereby producing a better irritation reduction effect and reducing the problem that sodium D-isoascorbate directly participates in chelating with metal ions and locks the essential metal ions for the skin.

[0019] The core-shell structure may be formed in any manner, such as an emulsion-solvent evaporation method, a spray drying method, a complex coacervation method, etc. In some embodiments, the sodium dehydroacetate and octanoylhydroxamic acid form an oil-in-water structure.

[0020] In other embodiments, the sodium dehydroacetate and octanoyl hydroxamic acid form the core-shell structure through a carrier with internal hydrophobic modification and surface cation modification. The sodium dehydroacetate is adsorbed by the surface positively charged groups and rapidly desorbed, and the internal hydrophobicity is used to hydrophobically bind to octanoyl hydroxamic acid (octanoyl hydroxamic acid contains hydrophobic groups and hydrophilic groups, the eight-carbon long chain of the octanoyl group is relatively hydrophobic, the hydrophilic part of the hydroxamic acid group is relatively weak, and the molecule as a whole is more hydrophobic), and slowly released by diffusion or swelling.

[0021] The choice of carrier is not limited. In some embodiments, the carrier is a porous carrier, including attapulgite, silica, cyclodextrin, ion exchange resin (such as IRA67) or at least one of the above.

[0022] The molding method is not limited. In some embodiments, the molding is obtained by the following steps: immersing the carrier in a hydrophobic modifier to form a hydrophobic layer, and then adsorbing octanoyl hydroxamic acid; coating the surface of the carrier adsorbing octanoyl hydroxamic acid with a cationic film, and then adsorbing sodium dehydroacetate.

[0023] Since sodium D-isoascorbate reduces skin irritation by reducing the electrophilicity of sodium dehydroacetate and competing with octanoyl hydroxamic acid, the effects of sodium dehydroacetate and octanoyl hydroxamic acid on microorganisms will also be reduced. Although sodium D-isoascorbate has an antibacterial effect that can make up for it, overall, it still affects the antiseptic effect of the antiseptic composition to a certain extent. Therefore, based on the differences between microbial cells and human skin cells: bacterial cells lack cholesterol and have a strong negative charge on the surface, fungal cells lack vitamin D receptors and have a relatively neutral or weakly negative charge on the surface, and human cells have cholesterol and vitamin D receptors and have a weakly negative charge on the surface; the antiseptic composition of the present application can be further designed.

[0024] For example, in some embodiments , the sodium D-isoascorbate is coated with liposomes modified with vitamin D3 and cholesterol. In cosmetics, sodium D-isoascorbate is coated with liposomes and cannot interact with sodium dehydroacetate and octanoyl hydroxamic acid, so that sodium dehydroacetate and octanoyl hydroxamic acid can act on microorganisms; when the cosmetics come into contact with the skin, based on the vitamin D3 receptors on the skin cells and the affinity for cholesterol, the liposomes modified with vitamin D3 and cholesterol lead sodium D-isoascorbate to form a barrier on the surface of the skin cells, reduce the irritation of sodium dehydroacetate and octanoyl hydroxamic acid, and prevent them from entering the skin cells.

[0025] Among them, the method of encapsulating sodium D-isoascorbate with liposomes modified with vitamin D3 and cholesterol is not limited, for example, ethanol injection method, thin film dispersion method, reverse evaporation method, etc. can be used.

[0026] The ratio of vitamin D3 and cholesterol is not limited, but a suitable ratio can improve the stability of liposomes, reduce the effect of sodium D-isoascorbate on sodium dehydroacetate and caprylhydroxamic acid in cosmetics, and improve the antiseptic effect. As a preferred embodiment of the present invention, the mixing mass ratio of vitamin D3 and cholesterol is 1: (0.6-1), for example, it can be 1: 0.6, 1: 0.7, 1: 0.8, 1: 0.9, 1: 1. The main membrane material of the liposome is not limited, and can be at least one of soybean lecithin and hydrogenated lecithin.

[0027] As a preferred embodiment of the present invention, the liposomes modified with vitamin D3 and cholesterol also include ceramide to further form a skin barrier and reduce the penetration of sodium dehydroacetate and octanoylhydroxamic acid into skin cells.

[0028] For example, in some embodiments , the sodium dehydroacetate and / or the octanoylhydroxamic acid are coated with chitosan. Since the negative charge density on the bacterial surface is 5 to 10 times that of skin cells, chitosan can be preferentially adsorbed on the surface of microorganisms through cationic groups, thereby destroying their membrane structures. In this embodiment, chitosan can be coated on the outside of sodium dehydroacetate alone, chitosan can be coated on the outside of octanoylhydroxamic acid alone, or chitosan can be coated on the outside of a shell-core structure with sodium dehydroacetate as the shell and octanoylhydroxamic acid as the core.

[0029] Preferably, the molecular weight of the chitosan is not less than 200 kDa, so that the chitosan has a strong film-forming property and can prevent sodium dehydroacetate and / or the caprylhydroxamic acid from penetrating deep into the skin.

[0030] For example, in some embodiments The sodium D-isoascorbate is coated with liposomes modified with vitamin D3 and cholesterol, and the sodium dehydroacetate and / or the caprylhydroxamic acid are coated with chitosan.

[0031] Secondly, another object of the present invention is to provide the use of the above-mentioned preservative composition in cosmetics.

[0032] As a preferred embodiment of the present invention, the amount of the preservative composition in the cosmetic is 0.1wt% to 0.5wt%, for example, it can be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, and more preferably 0.2wt% to 0.4wt%.

[0033] Beneficial effects of the present invention:

[0034] 1. The present application provides an antiseptic composition, which achieves the effect of reducing skin irritation by mixing sodium D-isoascorbate, sodium dehydroacetate, and caprylhydroxamic acid, utilizing sodium D-isoascorbate to coordinate sodium dehydroacetate to reduce its activity, and the competitiveness of the coordination product with the metal ion chelator.

[0035] 2. In some embodiments, sodium D-isoascorbate is coated with liposomes modified with vitamin D3 and cholesterol, so that sodium D-isoascorbate can react with sodium dehydroacetate and caprylhydroxamic acid on the skin to reduce irritation and ensure the preservative effect of sodium dehydroacetate and caprylhydroxamic acid in cosmetics.

[0036] 3. In some embodiments, sodium dehydroacetate and / or octanoyl hydroxamic acid are coated with macromolecular chitosan, so that sodium dehydroacetate and / or octanoyl hydroxamic acid are preferentially adsorbed on the surface of microorganisms, achieve an antiseptic effect, and reduce penetration into the skin.

[0037] 4. In some embodiments, ethylhexylglycerol is further compounded as a solvent to compensate for the weak antibacterial efficacy of sodium dehydroacetate and caprylhydroxamic acid, thereby improving the broad-spectrum of preservation.

[0038] 5. The present application also provides the use of the above-mentioned preservative composition in cosmetics, which has good preservative effect and low skin irritation. DETAILED DESCRIPTION

[0039] The following are specific embodiments of the present invention, and further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.

[0040] Example 1

[0041] A preservative composition comprises 4 parts of sodium D-isoascorbate, 1 part of sodium dehydroacetate, 2 parts of caprylhydroxamic acid, 2 parts of ethylhexylglycerol, 45 parts of 1,2-propylene glycol and 46 parts of water, a total of 100 parts, in parts by mass.

[0042] The antiseptic composition is prepared by the following steps:

[0043] Add caprylylhydroxamic acid and ethylhexylglycerol to 1,2-propylene glycol, stir and heat to 80°C to completely dissolve, stir and cool to 35°C, and filter the material to obtain a mixture. Stir and mix sodium D-isoascorbate and sodium dehydroacetate with deionized water to dissolve to obtain a mixture. Stir and mix the two mixtures, then heat to 35°C and stir for 35 minutes, and cool to room temperature to obtain a preservative composition.

[0044] Embodiments 2 to 5

[0045] Examples 2 to 5 are substantially the same as Example 1, except that the amounts of the components are different, as shown in Table 1 below (the unit of data in Table 1 is parts by mass).

[0046] Table 1.

[0047]

[0048] Example 6

[0049] A preservative composition comprises, by weight, 4 parts of sodium D-isoascorbate, 1 part of sodium dehydroacetate, 2 parts of caprylhydroxamic acid, 2 parts of ethylhexylglycerol, 45 parts of 1,2-propylene glycol, and 46 parts of water. At least part of the sodium dehydroacetate and part of the caprylhydroxamic acid form a shell-core structure A with the sodium dehydroacetate as the shell and the caprylhydroxamic acid as the core.

[0050] The antiseptic composition is prepared by the following steps:

[0051] The silica aerogel, octyltrimethoxysilane and ammonium carbonate were placed together in a vacuum heating furnace, heated and gasified, and hydrophobically modified for 2.5 hours to obtain hydrophobically modified silica.

[0052] Caprylhydroxamic acid is added to part of 1,2-propylene glycol, stirred and heated to 80°C, and then cooled to 35°C to obtain a mixture. Hydrophobically modified silica is added to the mixture, magnetically stirred and adsorbed for 3 hours, and then centrifuged to obtain silica adsorbing caprylhydroxamic acid and residual liquid a. The more the amount of hydrophobically modified silica is used, the more caprylhydroxamic acid is adsorbed.

[0053] Chitosan and chitosan quaternary ammonium salt are mixed in a mass ratio of 3:1 and dissolved in a 1% v / v acetic acid solution to prepare a 2% w / v solution. Silica adsorbed with octanoyl hydroxamic acid is added to the solution and stirred evenly. Then 0.1% v / v glutaraldehyde solution is added and stirred evenly. After the mixed system is centrifuged at low temperature to remove the supernatant, the precipitate is taken out and freeze-dried to obtain silica with a cationic film coated on the surface.

[0054] Sodium dehydroacetate is added to a portion of water to obtain a mixture. Silicon dioxide with a surface coated with a cationic film is added to the mixture, and adsorbed under magnetic stirring for 5 hours to obtain a mixed system containing a core-shell structure A.

[0055] The mixed system, the residual liquid a, the remaining 1,2-propylene glycol and water are mixed with sodium D-isoascorbate and ethylhexylglycerin and homogenized to obtain a preservative composition.

[0056] Example 7

[0057] A preservative composition comprises, by weight, 4 parts of sodium D-isoascorbate, 1 part of sodium dehydroacetate, 2 parts of caprylhydroxamic acid, 2 parts of ethylhexylglycerol, 45 parts of 1,2-propylene glycol, and 46 parts of water. The sodium D-isoascorbate forms a coating structure A in which a liposome co-modified with vitamin D3 and cholesterol encapsulates the sodium D-isoascorbate.

[0058] The antiseptic composition is prepared by the following steps:

[0059] According to the mass ratio, 15 parts of vitamin D3, 12 parts of cholesterol, 24 parts of phospholipids, and 0.1 parts of Tween-80 were mixed and ultrasonically dissolved in anhydrous ethanol to obtain an organic phase. 4 parts of sodium D-isoascorbate were dissolved in 4 parts of PBS buffer and magnetically stirred to form a uniform vortex as the aqueous phase. The organic phase was slowly and evenly injected into the aqueous phase, stirred and hydrated at 50°C for 4 hours, and ultrasonicated for 10 minutes to obtain a coating structure A.

[0060] Caprylylhydroxamic acid and ethylhexylglycerol are added to 1,2-propylene glycol, stirred and heated to 80°C for complete dissolution, stirred and cooled to 35°C, and then filtered to obtain a mixture. Coating structure A, sodium dehydroacetate, the mixture and water are mixed and homogenized to obtain an antiseptic composition.

[0061] Embodiments 8 to 11

[0062] Examples 8 to 11 are substantially the same as Example 7, the only difference being that the mass ratios of vitamin D3 and cholesterol are different as shown in Table 2 (the unit of data in Table 2 is parts by mass).

[0063] Table 2.

[0064] Example Vitamin D3 cholesterol Phospholipids Example 8 16.9 10.1 24 Example 9 13.5 13.5 24 Example 10 22.5 4.5 24 Embodiment 11 9 18 24

[0065] Example 12

[0066] A preservative composition comprises, by mass, 4 parts of sodium D-isoascorbate, 1 part of sodium dehydroacetate, 2 parts of caprylhydroxamic acid, 2 parts of ethylhexylglycerol, 45 parts of 1,2-propylene glycol, and 46 parts of water. Among them, at least part of sodium dehydroacetate and part of caprylhydroxamic acid form a shell-core structure A with sodium dehydroacetate as a shell and caprylhydroxamic acid as a core, and sodium D-isoascorbate forms a coating structure A in which sodium D-isoascorbate is coated with liposomes modified with vitamin D3 and cholesterol.

[0067] The antiseptic composition is prepared by the following steps:

[0068] The mixed system including the core-shell structure A obtained in Example 6, the residual liquid a, the remaining 1,2-propylene glycol and water, the coating structure A obtained in Example 7, and ethylhexylglycerin were mixed and homogenized to obtain an antiseptic composition.

[0069] Embodiment 13

[0070] A preservative composition comprises, by weight, 4 parts of sodium D-isoascorbate, 1 part of sodium dehydroacetate, 2 parts of caprylhydroxamic acid, 2 parts of ethylhexylglycerol, 45 parts of 1,2-propylene glycol, and 46 parts of water. At least part of the sodium dehydroacetate and part of the caprylhydroxamic acid form a multilayer core-shell structure A of chitosan-coated sodium dehydroacetate and caprylhydroxamic acid.

[0071] The antiseptic composition is prepared by the following steps:

[0072] The silica aerogel, octyltrimethoxysilane and ammonium carbonate were placed together in a vacuum heating furnace, heated and gasified, and hydrophobically modified for 2.5 hours to obtain hydrophobically modified silica.

[0073] Caprylhydroxamic acid was added to part of 1,2-propylene glycol, stirred and heated to 80°C, and then cooled to 35°C to obtain a mixture. Hydrophobically modified silica was added to the mixture, magnetically stirred and adsorbed for 3 hours, and then centrifuged to obtain silica adsorbing caprylhydroxamic acid and residual liquid a.

[0074] Chitosan and chitosan quaternary ammonium salt are mixed in a mass ratio of 3:1 and dissolved in a 1% v / v acetic acid solution to prepare a 2% w / v solution. Silica adsorbed with octanoyl hydroxamic acid is added to the solution and stirred evenly. Then 0.1% v / v glutaraldehyde solution is added and stirred evenly. After the mixed system is centrifuged at low temperature to remove the supernatant, the precipitate is taken out and freeze-dried to obtain silica with a cationic film coated on the surface.

[0075] Sodium dehydroacetate is added to part of the water to obtain a mixture. Silicon dioxide with a surface coated with a cationic film is added to the mixture, and adsorbed under magnetic stirring for 5 hours and then centrifuged to obtain a core-shell structure A and a residual liquid b.

[0076] 200 kDa chitosan was dissolved in 1% v / v acetic acid solution to prepare a 2% w / v solution. Shell-core structure A was added to the solution, and then 0.1% v / v glutaraldehyde solution was added and stirred evenly. The mixed system was centrifuged at low temperature to remove the supernatant, and the precipitate was removed and freeze-dried to obtain a multilayer shell-core structure A.

[0077] The multilayer core-shell structure A, the residual liquid a, the residual liquid b, the remaining 1,2-propylene glycol and water are mixed with sodium D-isoascorbate and ethylhexylglycerin and homogenized to obtain a preservative composition.

[0078] Embodiment 14

[0079] A preservative composition comprises, by mass, 4 parts of sodium D-isoascorbate, 1 part of sodium dehydroacetate, 2 parts of caprylhydroxamic acid, 2 parts of ethylhexylglycerol, 45 parts of 1,2-propylene glycol, and 46 parts of water. At least part of sodium dehydroacetate and part of caprylhydroxamic acid form a multilayer core-shell structure A of chitosan-coated sodium dehydroacetate-coated caprylhydroxamic acid, and sodium D-isoascorbate forms a coating structure A of liposomes co-modified with vitamin D3 and cholesterol-coated sodium D-isoascorbate.

[0080] The antiseptic composition is prepared by the following steps:

[0081] The multilayer core-shell structure A, residual liquid a, residual liquid b, remaining 1,2-propylene glycol and water obtained in Example 13, the coating structure A obtained in Example 7, and ethylhexylglycerin were mixed and homogenized to obtain an antiseptic composition.

[0082] Blank example

[0083] A composition comprises, by weight, 49 parts of 1,2-propylene glycol and 51 parts of water.

[0084] Comparative Example 1

[0085] Comparative Example 1 is substantially the same as Example 1, except that caprylhydroxamic acid is not contained and is replaced by an equal amount of 1,2-propylene glycol, that is, in parts by mass, it includes 4 parts of sodium D-isoascorbate, 1 part of sodium dehydroacetate, 2 parts of ethylhexylglycerol, 47 parts of 1,2-propylene glycol, and 46 parts of water.

[0086] Comparative Example 2

[0087] Comparative Example 1 is substantially the same as Example 1, except that it does not contain sodium dehydroacetate and is replaced by water of equal mass, that is, in parts by mass, it includes 4 parts of sodium D-isoascorbate, 2 parts of caprylhydroxamic acid, 2 parts of ethylhexylglycerol, 45 parts of 1,2-propylene glycol, and 47 parts of water.

[0088] Comparative Example 3

[0089] Comparative Example 1 is substantially the same as Example 1, except that it does not contain sodium D-isoascorbate and is replaced by water of equal mass, that is, in parts by mass, it includes 1 part of sodium dehydroacetate, 2 parts of caprylhydroxamic acid, 2 parts of ethylhexylglycerol, 45 parts of 1,2-propylene glycol, and 50 parts of water.

[0090] Application Examples 1 to 14, Application Blank Examples, Application Comparative Examples 1 to 3

[0091] A cosmetic has the following formula: 0.05wt% disodium EDTA, 7wt% glycerol, 0.15wt% xanthan gum, 2wt% cetearyl glucoside, 1wt% glyceryl stearate, 1wt% cetearyl alcohol, 5wt% ethylhexyl palmitate, 3wt% caprylic triglyceride, 2wt% polydimethylsiloxane, 1.6wt% sodium acrylate / sodium acryloyldimethyl taurate copolymer, 0.1wt% essence, 0.1wt% citric acid, and 0.2wt% preservative composition, with the remainder being water.

[0092] The antiseptic compositions are respectively the antiseptic compositions prepared in Examples 1 to 14, the blank examples, and the comparative examples 1 to 3.

[0093] This cosmetic is prepared by the following steps:

[0094] Premix glycerin and xanthan gum at room temperature and disperse them evenly for use. Add water to the main pot, start stirring, add disodium EDTA, stir evenly, then add the premix of glycerin and xanthan gum, stir evenly and start heating to 80°C as the water phase. Add cetearyl glucoside, glyceryl stearate, cetearyl alcohol, ethylhexyl palmitate, caprylic triglyceride, and polydimethylsiloxane to the auxiliary pot in turn, and slowly heat to 80°C until dissolved evenly as the oil phase. At a temperature of 80°C, start homogenization, add the oil phase to the water phase for emulsification to form a milky white appearance, and start cooling to 60°C after homogenization for 5 minutes. At 60°C, start homogenization, add sodium acrylate / sodium acryloyldimethyl taurate copolymer, and homogenize for another 5 minutes. Cool down to 30°C, add flavors and preservative compositions in turn at 30°C, stir evenly, adjust the pH to 5.0-5.5 with citric acid, and discharge after stirring evenly.

[0095] Irritation testing

[0096] Test method: 50 women were selected as subjects, and about 0.025g of sample was weighed and placed in the small chamber of the patch tester. The patch tester with sample was immediately applied longitudinally to the inner side of the right forearm of the subject from the bottom with hypoallergenic tape, and lightly pressed with the palm to evenly apply it to the skin. The test site was marked for observation. The patch was applied once every 24 hours, and the test patch was removed for 30 minutes (after the indentation disappeared), and then checked according to the terminology of the "Technical Specifications for Safety of Cosmetics" (2015 Edition). A total of 6 patch tests were conducted. Identification was carried out according to the following Table 3.

[0097] Table 3.

[0098]

[0099] The samples are the cosmetics prepared in Application Examples 1 to 14, Application Blank Example, and Application Comparative Examples 1 to 3, and the irritation test results after 6 patch applications are shown in Table 4 below.

[0100] Table 4.

[0101]

[0102] Corrosion resistance testing

[0103] Detection method: Add strains to the sample: mixed bacteria (Staphylococcus aureus ATCC 6538, Escherichia coli ATCC8739 and Pseudomonas aeruginosa ATCC9027 mixed inoculation) 6.0×10 6 CFU / g; mixed fungi (mixed inoculation of Aspergillus niger ATCC16404 and Candida albicans ATCC10231) 3.0×10 5 CFU / g. The samples inoculated with the strain were cultured under the same conditions for 28 days, and the bacterial count was tested at regular intervals.

[0104] The samples are the cosmetics prepared in Application Examples 1 to 14, Application Blank Example, and Application Comparative Examples 1 to 3, and the bacterial content detection results are shown in Table 5 below.

[0105] Table 5.

[0106]

[0107] As shown in Table 4 and Table 5, by comparing the application examples, blank examples and application comparison examples, it can be seen that in the present application, sodium D-isoascorbate, sodium dehydroacetate and caprylhydroxamic acid are mixed and used to achieve the effect of improving the antiseptic effect and reducing the irritation to the skin: in application comparison example 1, caprylhydroxamic acid is not contained, which obviously reduces the antiseptic effect; in application comparison example 2, sodium dehydroacetate is not contained, which on the one hand also significantly reduces the antiseptic effect, and on the other hand, it may be due to the lack of sodium dehydroacetate to coordinate with sodium D-isoascorbate to reduce the metal chelating ability of sodium D-isoascorbate, so that sodium D-isoascorbate may form a stable chelate with metal ions like caprylhydroxamic acid and interfere with the function of metal-dependent enzymes in the skin, destroy the skin barrier or induce an inflammatory response. In application comparison example 3, sodium D-isoascorbate is not contained, and it is impossible to act on sodium dehydroacetate and caprylhydroxamic acid to reduce irritation.

[0108] In addition, it can be seen from the comparison within the application examples that by adjusting the ratio of each component in the antiseptic composition, the existence form of each component, etc., the antiseptic effect can be further improved and the skin irritation can be reduced:

[0109] Compared with Application Example 1, Application Example 6 uses a shell-core structure A of octanoylhydroxamic acid coated with sodium dehydroacetate, which may strengthen the mechanism that sodium D-isoascorbate first reacts with sodium dehydroacetate and its coordination product then competes with octanoylhydroxamic acid, further reducing the irritation; however, due to the formation of the shell-core structure, the effect on microorganisms is slower, but the antiseptic effect can still be achieved in the end.

[0110] Application Example 7 is compared with Application Example 1, and Application Example 12 is compared with Application Example 6. Both of them use the coating structure A of liposomes modified with vitamin D3 and cholesterol to encapsulate sodium D-isoascorbate, which may reduce the problem that sodium D-isoascorbate in cosmetics affects the effects of sodium dehydroacetate and octanoyl hydroxamic acid on microorganisms, thereby improving the antiseptic effect. Among them, Application Example 12 uses the core-shell structure A compared with Application Example 7, strengthening the mechanism of reducing irritation to further reduce irritation.

[0111] In Application Example 13, compared with Application Example 6, the core-shell structure A is coated with chitosan to form a multilayer core-shell structure A. It is possible that chitosan enhances the effects of sodium dehydroacetate and octanoylhydroxamic acid on microorganisms, further improving the antiseptic effect.

[0112] Compared with Application Example 13, Application Example 14 adopts the coating structure A of liposomes modified with vitamin D3 and cholesterol to encapsulate sodium D-isoascorbate while using the multi-layer core-shell structure A. Based on the coating of the outer shell polysaccharide of the multi-layer core-shell structure A, sodium D-isoascorbate is not easy to affect the effects of sodium dehydroacetate and caprylhydroxamic acid on microorganisms in cosmetics. At this time, coating sodium D-isoascorbate can reduce the skin irritation problem that may be caused by sodium D-isoascorbate itself.

[0113] Compared with Application Example 1, Application Examples 2 to 5 adjusted the dosage of sodium D-isoascorbate. It can be seen that when the dosage of sodium D-isoascorbate is too much, the inhibition of sodium dehydroacetate and caprylhydroxamic acid will be too high, affecting the preservative effect; when the dosage of sodium D-isoascorbate is too little, there may be a problem of insufficient effect in reducing irritation.

[0114] Compared with Application Example 7, Application Examples 8 to 11 adjusted the dosage of vitamin D3 and cholesterol. It can be seen that too little cholesterol affects the stability of liposomes, and the coating structure A may release sodium D-isoascorbate in the cosmetics to act on sodium dehydroacetate and octanoyl hydroxamic acid, affecting the preservative effect. Too little vitamin D3 may affect the affinity of the coating structure A to the skin, which may cause the skin to contact sodium dehydroacetate and octanoyl hydroxamic acid before forming a barrier on the skin, causing irritation.

[0115] The specific embodiments described herein are merely examples of the spirit of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in similar ways, but they will not deviate from the spirit of the present invention or exceed the scope defined by the appended claims.

Claims

1. An antiseptic composition, characterized in that: It includes sodium dehydroacetate, caprylhydroxamic acid, solvent, and sodium D-isoascorbate.

2. An antiseptic composition according to claim 1, characterized in that: The mass ratio of the sodium D-isoascorbate to sodium dehydroacetate and octanoylhydroxamic acid is (2.5-7):1:(1-5).

3. An antiseptic composition according to claim 1, characterized in that: At least part of the sodium dehydroacetate and at least part of the octanoylhydroxamic acid form a core-shell structure with the sodium dehydroacetate as a shell and the octanoylhydroxamic acid as a core.

4. An antiseptic composition according to claim 3, characterized in that: The sodium dehydroacetate and octanoyl hydroxamic acid form the core-shell structure through a carrier with internal hydrophobic modification and surface cation modification.

5. An antiseptic composition according to claim 1, 3 or 4, characterized in that: The D-sodium isoascorbate is coated with liposomes modified with vitamin D3 and cholesterol.

6. An antiseptic composition according to claim 5, characterized in that: The mass ratio of vitamin D3 to cholesterol is 1:(0.6-1).

7. An antiseptic composition according to claim 1, 3 or 4, characterized in that: The sodium dehydroacetate and / or the caprylhydroxamic acid are coated with chitosan.

8. An antiseptic composition according to claim 1, characterized in that: The solvent includes ethylhexylglycerin, a glycol having 3 to 8 carbon atoms, and water.

9. Use of the antiseptic composition according to any one of claims 1 to 8 in cosmetics.

10. Use of the antiseptic composition according to claim 9 in cosmetics, characterized in that: The amount of the antiseptic composition used in the cosmetics is 0.1 wt% to 0.5 wt%.

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