Anti-dandruff agent, preparation method of anti-dandruff agent and daily chemical product

Abstract

The invention belongs to the technical field of anti-dandruff daily chemical products, and discloses an anti-dandruff agent, a preparation method of the anti-dandruff agent and a daily chemical product. The anti-dandruff agent is a water-soluble cyclodextrin; the hydrophobic inner cavity of the water-soluble cyclodextrin is loaded with selenium disulfide; the surface of the water-soluble cyclodextrin is grafted with a quaternary ammonium salt; the content of the anti-dandruff agent in the daily chemical product is 0.5-2%; the daily chemical product is one or more of shampoo, shampoo, shampoo cream, conditioner, water-free shampoo gel and water-free shampoo spray.

Description

Technical Field

[0001] The invention relates to the technical field of anti-dandruff daily chemical products, and in particular to an anti-dandruff agent, a preparation method of the anti-dandruff agent and a daily chemical product. Background Art

[0002] Dandruff is a common skin disease that causes itching and flaking of the skin, and is even accompanied by a mild inflammatory reaction. Dandruff has affected the normal work and life of many people. Dandruff is a metabolic product of epidermal cells on the head, which can easily greatly accelerate the shedding rate of epidermal cells and deviate from the normal situation. Studies have shown that the presence of dandruff is closely related to the imbalance of the scalp's microecology. Generally speaking, the main fungal and bacterial genera on the skin surface are Malassezia and Staphylococcus, respectively.

[0003] At present, common anti-dandruff agents on the market include zinc pyrithione and piroctone olamine salt. As an efficient anti-dandruff ingredient, zinc pyrithione has been used in the field of daily chemical products for decades, and its application scenarios are very wide. It achieves the purpose of sterilization by increasing the metal content inside fungal cells and causing mitochondrial dysfunction. In addition, piroctone olamine salt can decompose peroxides, reduce the irritation caused by them to the scalp, and then effectively prevent dandruff and itching. However, zinc pyrithione is environmentally harmful, and the European Union officially included it in the list of banned substances in cosmetics on March 1, 2022; piroctone olamine salt has a high cost and is currently only used in some mid-to-high-end anti-dandruff products. Therefore, the development of safe, low-cost and efficient new anti-dandruff agents has become a current hot topic.

[0004] In recent years, selenium disulfide, as a new antidandruff agent, has a certain antifungal effect and good anti-seborrhea effect; therefore, it can control oil secretion, ensure the health of the scalp environment and inhibit bacteria and kill bacteria. It is more effective for stubborn dandruff caused by seborrheic dermatitis, tinea versicolor, pityriasis capitis, etc.; nano antidandruff agents, due to their small size and large specific surface area, will help improve the antidandruff efficiency of antidandruff agents and reduce the amount of antidandruff agents used.

[0005] However, due to the low water solubility of selenium disulfide and its easy agglomeration, the cost-effectiveness of its application will be reduced.

[0006] Based on the above problems, Chinese patent 202210497457.2 discloses a selenium disulfide encapsulation technology and a selenium disulfide shampoo. The surface of the selenium disulfide powder is treated with a silane coupling agent to form a surface structure with an external organic chain end, and then further cross-linked with silicone oil to form a package, which can effectively prevent selenium disulfide from contacting the outside world during storage and transportation, and effectively prevent its oxidation and discoloration. At the same time, the system can also show good dispersion and suspension effects in the subsequent formula development process; the use of a pretreated selenium disulfide system not only solves the technical problems of uneven dispersion, poor stability and easy discoloration of selenium disulfide particles, but also because selenium disulfide is encapsulated in the composite structure of the coupling agent and silicone oil, the lotion is non-irritating, and the hair is easy to comb, smooth and shiny.

[0007] The above patent can effectively solve the problem of local agglomeration of selenium disulfide particles by cross-linking and coating selenium disulfide with silicone oil. However, in the field of daily chemicals, the safety of silicone oil is not very high, and silicone oil is not soluble in water. It does not actually improve the water solubility of selenium disulfide and can only partially solve the problem of selenium disulfide particle agglomeration. Therefore, it is necessary to develop a new water-soluble selenium disulfide structure that has high safety while having high water solubility. Summary of the invention

[0008] One of the purposes of the present invention is to provide an anti-dandruff agent, which can prevent the agglomeration of nano-selenium disulfide by loading selenium disulfide on the surface of water-soluble cyclodextrin grafted with quaternary ammonium groups. It can be used as an anti-dandruff agent in daily chemical products to effectively increase the antibacterial and bactericidal effects and has high safety.

[0009] Another object of the present invention is to provide a method for preparing an anti-dandruff agent, wherein the prepared anti-dandruff agent has excellent water solubility, avoids the occurrence of nano-selenium disulfide agglomeration, and has high commercial application prospects.

[0010] In addition, the invention also provides a daily chemical product.

[0011] To achieve the above object, the present invention provides an anti-dandruff agent, which is a water-soluble cyclodextrin; the hydrophobic inner cavity of the water-soluble cyclodextrin is loaded with selenium disulfide; and the surface of the water-soluble cyclodextrin is grafted with a quaternary ammonium salt.

[0012] In the above anti-dandruff agent, the quaternary ammonium salt on the surface of the water-soluble cyclodextrin is obtained by grafting an unsaturated monomer containing a quaternary ammonium group onto the surface of the water-soluble cyclodextrin.

[0013] In the above anti-dandruff agent, the unsaturated monomer is grafted with the unsaturated group on the surface of the water-soluble cyclodextrin.

[0014] As the optional unsaturated monomers in the art, specific examples include: one or more of methacryloyloxyethyl trimethylammonium chloride, diallyldimethylammonium chloride, acryloyloxyethyl trimethylammonium chloride, allyltrimethylammonium chloride, allyltrimethylammonium bromide, and N,N,N-trimethyl-3-(2-methylallylamide)-1-chloropropylamine; in the present invention, methacryloyloxyethyl trimethylammonium chloride is preferred.

[0015] In the above anti-dandruff agent, the unsaturated group is connected to the surface of water-soluble cyclodextrin by esterification reaction of one or more of acrylic acid, methacrylic acid, crotonic acid, butenedioic acid (maleic anhydride is also acceptable).

[0016] In the above anti-dandruff agent, the water-soluble cyclodextrin is β-cyclodextrin.

[0017] More preferably, 0.1 g to 0.2 g of selenium disulfide is loaded per 10 g of water-soluble cyclodextrin.

[0018] At the same time, the present invention also discloses a preparation method of the above anti-dandruff agent, comprising the following steps:

[0019] Step 1: Grafting unsaturated groups onto the surface of water-soluble cyclodextrin;

[0020] Step 2: Grafting an unsaturated monomer onto the surface of the product of step 1;

[0021] Step 3: adding a soluble sulfide to a solution containing the product of step 2;

[0022] Step 4: Add selenious acid and glacial acetic acid to the solution in step 3, and react to obtain the product.

[0023] In the above-mentioned method for preparing the anti-dandruff agent, the mass ratio of the water-soluble cyclodextrin grafted with unsaturated groups to the unsaturated monomer in step 2 is 1:2-4;

[0024] The initiator used in step 2 is a water-soluble initiator; the initiation temperature is 40-70°C;

[0025] As a water-soluble initiator that can be selected in the art, a redox initiator is generally selected; the initiation temperature is determined by the type of initiator selected;

[0026] The step 4 is added dropwise;

[0027] The molar ratio of sulfide, selenous acid, and glacial acetic acid is 2:1:4;

[0028] The sulfide is one or more combinations of sodium sulfide and potassium sulfide.

[0029] Meanwhile, the present invention also discloses a daily chemical product containing any one of the above anti-dandruff agents.

[0030] In the above-mentioned daily chemical product, the content of the anti-dandruff agent is 0.5-2%; the daily chemical product is one or more of shampoo, shampoo gel, shampoo cream, conditioner, waterless shampoo gel, and waterless shampoo spray.

[0031] Beneficial Effects

[0032] Compared with the prior art, the present invention has the following advantages:

[0033] (1) The present invention provides an anti-dandruff agent, which encapsulates selenium disulfide by grafting a quaternary ammonium salt on the surface of a water-soluble cyclodextrin, so that the selenium disulfide is water-soluble and not easy to agglomerate. In addition, the water-soluble cyclodextrin of this structure and the nano-selenium disulfide produce a synergistic effect, further improving the antibacterial and bactericidal effect of selenium disulfide;

[0034] (2) The present invention provides a method for preparing an anti-dandruff agent, wherein step 3 comprises dissolving sodium sulfide in a solution containing a water-soluble cyclodextrin with a quaternary ammonium salt grafted on the surface, so that the sulfide ions and the nitrogen ions on the quaternary ammonium salt grafted on the surface of the water-soluble cyclodextrin generate an electrostatic attraction, and the sulfide ions gather at the periphery of the water-soluble cyclodextrin, and then dripping a mixed solution containing selenious acid and glacial acetic acid to react, so that the obtained selenium disulfide enters the hydrophobic inner ring cavity of the water-soluble cyclodextrin more quickly, avoiding the agglomeration of selenium disulfide, thereby better controlling the size and distribution of selenium disulfide and improving the antibacterial and bactericidal effect of selenium disulfide;

[0035] (3) The present invention provides a composition with strong antibacterial and bactericidal effects, which is formed by grafting a specific ratio of quaternary ammonium salt and water-soluble cyclodextrin and then coating nano-selenium disulfide. The specific ratio of quaternary ammonium salt and water-soluble cyclodextrin has the best synergistic antibacterial and bactericidal effect on nano-selenium disulfide.

[0036] (4) The present invention also provides a daily chemical product, which has excellent anti-dandruff ability by adding a specific content of an anti-dandruff agent. DETAILED DESCRIPTION

[0037] The present invention will be further described below in conjunction with the embodiments, but it does not constitute any limitation to the present invention. Any limited number of modifications made within the scope of the claims of the present invention are still within the scope of the claims of the present invention.

[0038] In order to explain the technical content of the present invention in detail, further description is given below in conjunction with the implementation modes.

[0039] Example 1

[0040] An anti-dandruff agent is prepared by the following steps:

[0041] Step 1: Refer to CN114736424A for an asymmetric nano-TiO 2 In the particle-filled bionic super-slippery surface and its preparation method and application, in the described Example 1 (1), a functionalized cyclodextrin derivative is prepared to obtain alkenyl β-cyclodextrin.

[0042] Step 2: 10 g of alkenyl β-cyclodextrin and 25 g of methacryloyloxyethyl trimethylammonium chloride were dissolved in 200 ml of deionized water, and 0.175 g of ammonium persulfate / sodium bisulfite mixture (the molar ratio of ammonium persulfate / sodium bisulfite was 1:1) was added under nitrogen protection, and the reaction was carried out at 60° C. for 8 h, cooled to room temperature, poured into acetone, precipitated, filtered, washed, dried in a vacuum drying oven at 50° C. for 24 h, and taken out to obtain substance A;

[0043] Step 3: Dissolve 10 g of substance A and 0.2 g of sodium sulfide in 200 mL of deionized water to obtain solution A;

[0044] Step 4: Add 0.16 g H 2 SeO 3 and 0.3gCH 3 The aqueous solution of COOH was added dropwise, and the reaction was continued with stirring for 30 minutes. After the reaction was completed, the reaction was centrifuged for 15 minutes, and the resulting precipitate was freeze-dried at -20°C to obtain anti-dandruff agent A.

[0045] Example 2

[0046] An anti-dandruff agent is prepared by the following steps:

[0047] Step 1: Refer to CN114736424A for an asymmetric nano-TiO 2 In the particle-filled bionic super-slippery surface and its preparation method and application, the functionalized cyclodextrin derivative is prepared in (1) of Example 1.

[0048] Step 2: 10 g of alkenyl β-cyclodextrin and 25 g of methacryloyloxyethyl trimethylammonium chloride were dissolved in 200 ml of deionized water, and 0.175 g of ammonium persulfate / sodium bisulfite mixture (the molar ratio of ammonium persulfate / sodium bisulfite was 1:1) was added under nitrogen protection, and the reaction was carried out at 60° C. for 8 h, cooled to room temperature, poured into acetone, precipitated, filtered, washed, dried in a vacuum drying oven at 50° C. for 24 h, and taken out to obtain substance A;

[0049] Step 3: Dissolve 10 g of substance A and 0.15 g of sodium sulfide in 200 mL of deionized water to obtain solution A;

[0050] Step 4: Add 0.12 g H2 SeO 3 and 0.23gCH 3 The aqueous solution of COOH was added dropwise, and the reaction was continued with stirring for 30 minutes. After the reaction was completed, the reaction was centrifuged for 15 minutes, and the resulting precipitate was freeze-dried at -20°C to obtain anti-dandruff agent A.

[0051] Example 3

[0052] An anti-dandruff agent is prepared by the following steps:

[0053] Step 1: Refer to CN114736424A for an asymmetric nano-TiO 2 In the particle-filled bionic super-slippery surface and its preparation method and application, the functionalized cyclodextrin derivative is prepared in (1) of Example 1.

[0054] Step 2: 10 g of alkenyl β-cyclodextrin and 25 g of methacryloyloxyethyl trimethylammonium chloride were dissolved in 200 ml of deionized water, and 0.175 g of ammonium persulfate / sodium bisulfite mixture (the molar ratio of ammonium persulfate / sodium bisulfite was 1:1) was added under nitrogen protection, and the reaction was carried out at 60° C. for 8 h, cooled to room temperature, poured into acetone, precipitated, filtered, washed, dried in a vacuum drying oven at 50° C. for 24 h, and taken out to obtain substance A;

[0055] Step 3: Dissolve 10 g of substance A and 0.12 g of sodium sulfide in 200 mL of deionized water to obtain solution A;

[0056] Step 4: Add 0.1 g H 2 SeO 3 and 0.19gCH 3 The aqueous solution of COOH was added dropwise, and the reaction was continued with stirring for 30 minutes. After the reaction was completed, the reaction was centrifuged for 15 minutes, and the resulting precipitate was freeze-dried at -20°C to obtain anti-dandruff agent A.

[0057] Example 4

[0058] An anti-dandruff agent is prepared by the following steps:

[0059] Step 1: Refer to CN114736424A for an asymmetric nano-TiO 2 In the particle-filled bionic super-slippery surface and its preparation method and application, the functionalized cyclodextrin derivative is prepared in (1) of Example 1.

[0060] Step 2: 10 g of alkenyl β-cyclodextrin and 20 g of methacryloyloxyethyl trimethylammonium chloride were dissolved in 200 ml of deionized water, and 0.175 g of ammonium persulfate / sodium bisulfite mixture (the molar ratio of ammonium persulfate / sodium bisulfite was 1:1) was added under nitrogen protection, and the reaction was carried out at 60° C. for 8 h, cooled to room temperature, poured into acetone, precipitated, filtered, washed, dried in a vacuum drying oven at 50° C. for 24 h, and taken out to obtain substance A;

[0061] Step 3: Dissolve 10 g of substance A and 0.2 g of sodium sulfide in 200 mL of deionized water to obtain solution A;

[0062] Step 4: Add 0.16 g H 2 SeO 3 and 0.3gCH 3 The aqueous solution of COOH was added dropwise, and the reaction was continued with stirring for 30 minutes. After the reaction was completed, the reaction was centrifuged for 15 minutes, and the resulting precipitate was freeze-dried at -20°C to obtain anti-dandruff agent A.

[0063] Example 5

[0064] An anti-dandruff agent is prepared by the following steps:

[0065] Step 1: Refer to CN114736424A for an asymmetric nano-TiO 2 In the particle-filled bionic super-slippery surface and its preparation method and application, the functionalized cyclodextrin derivative is prepared in (1) of Example 1.

[0066] Step 2: Dissolve 10 g of alkenyl β-cyclodextrin and 30 g of methacryloyloxyethyl trimethylammonium chloride in 200 ml of deionized water, add 0.2 g of ammonium persulfate / sodium bisulfite mixture (the molar ratio of ammonium persulfate / sodium bisulfite is 1:1) under nitrogen protection, react at 60°C for 8 h, cool to room temperature, pour into acetone, precipitate, filter, wash, dry in a vacuum drying oven at 50°C for 24 h, take out, and obtain substance A;

[0067] Step 3: Dissolve 10 g of substance A and 0.2 g of sodium sulfide in 200 mL of deionized water to obtain solution A;

[0068] Step 4: Add 0.16 g H 2 SeO 3 and 0.3gCH 3 The aqueous solution of COOH was added dropwise, and the reaction was continued with stirring for 30 minutes. After the reaction was completed, the reaction was centrifuged for 15 minutes, and the resulting precipitate was freeze-dried at -20°C to obtain anti-dandruff agent A.

[0069] Example 6

[0070] An anti-dandruff agent is prepared by the following steps:

[0071] Step 1: Refer to CN114736424A for an asymmetric nano-TiO 2 In the particle-filled bionic super-slippery surface and its preparation method and application, the functionalized cyclodextrin derivative is prepared in (1) of Example 1.

[0072] Step 2: Dissolve 10 g of alkenyl β-cyclodextrin and 40 g of methacryloyloxyethyl trimethylammonium chloride in 300 ml of deionized water, add 0.25 g of ammonium persulfate / sodium bisulfite mixture (the molar ratio of ammonium persulfate / sodium bisulfite is 1:1) under nitrogen protection, react at 60°C for 8 h, cool to room temperature, pour into acetone, precipitate, filter, wash, dry in a vacuum drying oven at 50°C for 24 h, take out, and obtain substance A;

[0073] Step 3: Dissolve 10 g of substance A and 0.2 g of sodium sulfide in 200 mL of deionized water to obtain solution A;

[0074] Step 4: Add 0.16 g H 2 SeO 3 and 0.3gCH 3 The aqueous solution of COOH was added dropwise, and the reaction was continued with stirring for 30 minutes. After the reaction was completed, the reaction was centrifuged for 15 minutes, and the resulting precipitate was freeze-dried at -20°C to obtain anti-dandruff agent A.

[0075] Comparative Example 1

[0076] Substance A as shown in Example 1.

[0077] Comparative Example 2

[0078] An anti-dandruff agent is prepared by the following steps:

[0079] Step 1: Refer to CN114736424A for an asymmetric nano-TiO 2 In the particle-filled bionic super-slippery surface and its preparation method and application, in the embodiment 1 described above, (1) a functionalized cyclodextrin derivative is prepared to obtain substance B;

[0080] Step 2: Dissolve 10 g of substance B and 0.2 g mol sodium sulfide in 200 mL of deionized water to obtain solution B;

[0081] Step 3: Add 0.16 g H 2 SeO 3 and 0.3gCH 3The aqueous solution of COOH was added dropwise, and the reaction was continued with stirring for 30 minutes. After the reaction was completed, the reaction was centrifuged for 15 minutes, and the resulting precipitate was freeze-dried at -20°C to obtain anti-dandruff agent B.

[0082] Comparative Example 3

[0083] The substance A shown in Example 1 and the anti-dandruff agent B of Comparative Example 2 were mixed in a weight ratio of 1:1.

[0084] Sample preparation

[0085] Shampoo was prepared according to the formula in Table 1 below to obtain samples 1-6 and comparative samples 1-2;

[0086] Table 1 Shampoo formula

[0087]

[0088]

[0089] Prepare shampoo with reference to the formula in Table 2 below to obtain comparative sample 3;

[0090] Table 2 Shampoo formula

[0091]

[0092] Process flow:

[0093] 1. Add the components of phase A in sequence, heat to 80-85°C, and stir slowly to dissolve;

[0094] 2. Add the components of phase B one by one and stir until completely dissolved.

[0095] 3. Cool down to 70℃, slowly add phase C components, stir and dissolve;

[0096] 4. Cool down to 40℃, add phase D components, stir and dissolve;

[0097] 5. Add phase E, adjust pH value and viscosity, continue stirring for 30 minutes, stop stirring, send for inspection, and discharge the material.

[0098] Performance Testing

[0099] Test Item 1 Minimum Inhibitory Concentration Test of the Antidandruff Agent Prepared in Example and the Antidandruff Agent Prepared in Comparative Example

[0100] The test method is as follows: the samples obtained from different embodiments and comparative examples are serially diluted with Leeming & Notman liquid culture medium to form test solutions of different concentrations, and 0.1 mL 10 6CFU / mL Malassezia suspension was inoculated into 1 mL of the above test solution of different concentrations and cultured at 37°C for 48 h. When no bacterial growth was observed in the test sample with the lowest concentration, the minimum inhibitory concentration of the corresponding sample was obtained.

[0101] The antibacterial and bactericidal effects can be found in Table 3 below.

[0102] Table 3 Antibacterial effect test results

[0103] Serial number Minimum inhibitory concentration (μg / mL) Example 1 0.52 Example 2 0.55 Example 3 0.63 Example 4 0.50 Example 5 0.57 Example 6 0.65 Comparative Example 1 3.50 Comparative Example 2 1.89 Comparative Example 3 2.14

[0104] Test Item 2 Shampoo Anti-dandruff Test

[0105] The test method is: according to the group standard "Test Method for Anti-dandruff Efficacy of Cosmetics" (standard number: T / ZHCA019-2022), the anti-dandruff effect of the obtained shampoo is tested. Among them, the scalp and hair roots of the subjects are evaluated for dandruff, and the scoring level is recorded (level 0: no dandruff; level 1-2: small pieces of powdery grayish-white rough scales; level 3-4: small to medium scales; level 5-6: large and thin scales loosely connected to the scalp; level 7-8: adhesive scales; level 9-10: thick white to yellow scales tightly attached to the scalp).

[0106] The test results can be found in Table 4;

[0107] Table 4 Anti-dandruff test results

[0108]

[0109]

[0110] It can be seen from the data in Table 3 that the present invention produces a synergistic antibacterial and bactericidal effect by coating selenium disulfide with a water-soluble cyclodextrin grafted with a quaternary ammonium salt on the surface. Compared with the water-soluble cyclodextrin grafted with a quaternary ammonium salt on the surface in Comparative Example 1 and the selenium disulfide coated with a water-soluble cyclodextrin without a quaternary ammonium salt grafted on the surface in Comparative Example 2, the present invention has a stronger antibacterial and bactericidal effect. Compared with the technical solution of combining a quaternary ammonium salt and a water-soluble cyclodextrin coated with selenium disulfide in Comparative Example 3, the antibacterial and bactericidal effect of the present invention is also significantly improved.

[0111] It can be seen from the data in Table 4 that the technical solution of the present invention using water-soluble cyclodextrin with quaternary ammonium salt grafted on the surface to coat selenium disulfide has an excellent anti-dandruff effect when used as an anti-dandruff agent in daily chemical products.

[0112] The embodiments presented herein are only embodiments selected according to the combination of all possible embodiments. The appended claims should not be limited by the embodiments describing the present invention. Some numerical ranges used in the claims include sub-ranges therein, and the changes in these ranges should also be covered by the appended claims.

Claims

1. An anti-dandruff agent, characterized in that The anti-dandruff agent is a water-soluble cyclodextrin; the hydrophobic inner cavity of the water-soluble cyclodextrin is loaded with selenium disulfide; the surface of the water-soluble cyclodextrin is grafted with a quaternary ammonium salt; The preparation method of the anti-dandruff agent comprises the following steps: Step 1: Grafting unsaturated groups on the surface of β-cyclodextrin; Step 2: Grafting an unsaturated monomer onto the surface of the product of step 1; Step 3: adding a soluble sulfide to a solution containing the product of step 2; Step 4: adding selenious acid and glacial acetic acid to the solution of step 3, and reacting to obtain; The unsaturated groups are connected to the surface of β-cyclodextrin by one or more of acrylic acid, methacrylic acid, crotonic acid and butenedioic acid through an esterification reaction; The unsaturated monomer is methacryloyloxyethyl trimethylammonium chloride; In the step 2, the mass ratio of the product of step 1 to the unsaturated monomer is 1:2-4.

2. The anti-dandruff agent according to claim 1, characterized in that Every 10g of water-soluble cyclodextrin is loaded with 0.1g-0.2g of selenium disulfide.

3. The anti-dandruff agent according to claim 1, characterized in that In step 2, a water-soluble initiator is used to initiate the reaction; the initiation temperature is 40-70° C.; The step 4 is added dropwise; The molar ratio of soluble sulfide, selenous acid, and glacial acetic acid is 2:1:4; The soluble sulfide is one or more combinations of sodium sulfide and potassium sulfide.

4. A daily chemical product, characterized in that: Contains the anti-dandruff agent as described in any one of claims 1 to 3.

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