Antibacterial acarus-killing shampoo and preparation method thereof

Abstract

The invention discloses antibacterial acarus-killing shampoo and a preparation method thereof, and relates to the technical field of daily chemicals. When the antibacterial mite-killing shampoo is prepared, firstly, long-carbon-chain alkyl acid reacts with 3-dimethylaminopropylamine to prepare long-carbon-chain amidated tertiary amine; reacting the long-carbon-chain amidated tertiary amine with ethylene 2-(methacryloyloxy) ethyl phosphate to obtain a phosphatidylated quaternary ammonium monomer; the preparation method comprises the following steps: copolymerizing a phosphatidylated quaternary ammonium monomer and N-vinyl pyrrolidone to prepare a modified phosphatidylated quaternary ammonium random copolymer; and mixing the modified phosphatidylated quaternary ammonium random copolymer with an auxiliary agent and water to prepare the antibacterial acarus-killing shampoo. The antibacterial and acarus-killing shampoo prepared by the invention has the advantages of being antibacterial, acarus-killing, hair-repairing and long-acting in adsorption.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of daily chemicals, in particular to an antibacterial and anti-mite shampoo and a preparation method thereof. BACKGROUND

[0002] Shampoo, also known as hair shampoo, hair wash, hair conditioner or hair cream, is the most widely used hair care product and one of the most commonly used hair cosmetics. With the change of times and the change of people's requirements, shampoo as a necessary product for hair is also changing. At first, people's requirement for shampoo is to remove oil on the scalp and hair to avoid sticky hair and scalp itching. However, over-washing will remove the oil on the surface of the hair, resulting in dry and unmanageable hair. At the same time, external environment such as ultraviolet rays, air and environmental pollution, and hair perming and dyeing will also cause damage to the hair, making the hair frizzy, split ends, lack of luster and poor combing. People gradually realize that hair is one of the important factors that determine a person's image, so people yearn for healthy and natural hair and start to pay attention to daily care of hair, and the emphasis on effectiveness is shifted from "the cleaning power required to keep the hair clean" to "the protection and repair effect required to keep the hair beautiful".

[0003] Mites belong to a class of small animals in the arthropod phylum arachnida and the order of acarina. Mites are widely distributed and have many species. The main ones that are harmful to human body are dust mites living in the home environment and Demodex mites parasitizing in the human body. The former is an important inducement of allergic diseases, and the latter parasitizing in the human body will cause clogged pores, imbalance of oil secretion, dull skin, large pores, rough skin, and even cause diseases such as acne, hair loss, dandruff, and seborrheic dermatitis. The imbalance of oil secretion caused by Demodex mite parasitic worms will destroy the balance of the bacterial flora on the skin surface, which will further aggravate the production of dandruff. Therefore, mite removal and antibacterial properties are crucial to control dandruff and maintain the health of the scalp. The existing mite removal products are not ideal, the mite removal speed is slow, the mite removal effect is not long-lasting, and it is easy to cause repeated infection of mites. In addition, the ingredients are complex and have low safety.

[0004] In addition, the charged polymer has better hydration lubrication performance than ordinary cationic surfactants, and the cationic surfactant has strong irritation. Therefore, a polymer that can stay on the surface of the hair and has good hydration capacity is added to the shampoo to better improve the combing performance of the hair and play the role of antibacterial and anti-mite. SUMMARY

[0005] The present application aims to provide an antibacterial and anti-mite shampoo and a preparation method thereof to solve the problems in the prior art.

[0006] To solve the above technical problems, the present application provides the following technical solutions: an antibacterial and acaricidal shampoo, which is prepared by mixing modified phosphatidylated quaternary ammonium random copolymer with additives and water; the modified phosphatidylated quaternary ammonium random copolymer is prepared by copolymerizing phosphatidylated quaternary ammonium monomer and N-vinyl pyrrolidone; the phosphatidylated quaternary ammonium monomer is prepared by reacting long-chain carbon chain amidated tertiary amine with ethylene 2-(methacryloyloxy)ethyl phosphate; and the long-chain carbon chain amidated tertiary amine is prepared by reacting long-chain alkyl acid with 3-dimethylaminopropylamine.

[0007] As optimization, the additives include sodium laureth sulfate, coconut monoethanolamide, ethylene glycol distearate, cetylstearyl alcohol, PEG-120 methyl glucose trioleate, cocamidopropyl betaine, preservatives, fragrances, citric acid, and sodium chloride.

[0008] As optimization, the long-chain alkyl acid is one of n-decanoic acid, n-undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, and palmitic acid.

[0009] A preparation method of the antibacterial and acaricidal shampoo includes the following preparation steps: (1) 40-50 parts of long-chain alkyl acid are heated to 120°C under a nitrogen atmosphere, 3-dimethylaminopropylamine is added at a rate of 0.8-1 ml / min according to a molar ratio of long-chain alkyl acid to 3-dimethylaminopropylamine of 2: (2.5-3), water is removed by a water trap, reflux reaction is performed at 145-155°C and 200-300 r / min for 8-9 h, unreacted raw materials are removed by vacuum distillation, the long-chain carbon chain amidated tertiary amine is prepared by recrystallizing 3-4 times with petroleum ether and vacuum drying at 50-60°C for 20-24 h; (2) 2-3 parts of long-chain carbon chain amidated tertiary amine and 20-30 parts of chloroform are uniformly mixed, ethylene 2-(methacryloyloxy)ethyl phosphate is added at room temperature and 200-300 r / min according to a molar ratio of long-chain carbon chain amidated tertiary amine to ethylene 2-(methacryloyloxy)ethyl phosphate of 1:1, reflux reaction is performed at 90-95°C and 200-300 r / min for 20-24 h, chloroform is removed by rotary evaporation, and the phosphatidylated quaternary ammonium monomer is prepared by vacuum drying at 50-60°C for 10-12 h; (3) Under the atmosphere of nitrogen, 2-3 parts of N-vinyl pyrrolidone, 4.68-7.03 parts of phospholipidized quaternary ammonium monomer, 25-30 parts of isopropyl alcohol are mixed uniformly, 0.09-0.12 parts of azobisisobutyronitrile is added, sealed, stirred at 65-70℃, 300-400r / min for 3-4h, poured into 180-200 parts of petroleum ether for precipitation, filtered, washed with petroleum ether for 2-3 times, washed with anhydrous ethanol for 3-4 times, vacuum dried at 50-60℃ for 10-12h, to obtain the modified phospholipidized quaternary ammonium random copolymer; (4) According to the formula, the modified phospholipidized quaternary ammonium random copolymer is added into 50 times of water to dissolve, stirred at 60℃, 200-300r / min until completely dissolved, to obtain A liquid, sodium lauryl polyoxyethylene ether sulfate is added into water with the same mass, stirred at 75-85℃, 200-300r / min until completely dissolved, coconut oil monoethanolamide, ethylene glycol distearate, cetyl stearyl alcohol are added, continue to stir until completely dissolved, add A liquid, continue to stir, naturally cool to 50℃, add cocamide propyl betaine, stir until dissolved, then add PEG-120 methyl glucose trioleate, stir at 200-300r / min for 50-60min to disperse, keep stirring and naturally cool to 30℃, add sodium chloride, after cooling to room temperature, add preservative and essence, add water to make up the balance, add citric acid to adjust pH to 6.5, stir at 200-300r / min for 50-60min to disperse uniformly, to obtain the antibacterial and acarid-killing shampoo.

[0010] As an optimization, the reaction process of the long carbon chain amide tertiary amine in step (1) is as follows: R=8-14.

[0011] As an optimization, the reaction process of the phospholipidized quaternary ammonium monomer in step (2) is as follows: R=8-14.

[0012] As an optimization, the reaction process of the modified phospholipidized quaternary ammonium random copolymer in step (3) is as follows: R=8-14.

[0013] As optimization, the formula of step (4) is: 18-22wt% sodium laureth sulfate, 0.9-1.1wt% coconut monoethanolamide, 1.4-1.5wt% glycol stearate, 0.7-0.8wt% cetyl stearyl alcohol, 2.5-3wt% PEG-120 methyl glucose trioleate, 3.5-4wt% cocamidopropyl betaine, 1-1.2wt% modified phospholipidized quaternary ammonium random copolymer, 0.06-0.8wt% preservative, 0.1-0.2wt% essence, 0.02-0.2wt% citric acid, 0.8wt% sodium chloride, and the balance is water.

[0014] Compared with the prior art, the application has the beneficial effects that: in the preparation of the antibacterial and acaricidal shampoo, the long-chain alkyl acid is first reacted with 3-dimethylaminopropylamine to obtain a long-chain amide tertiary amine; the long-chain amide tertiary amine is reacted with ethylene 2-(methacryloyloxy)ethyl phosphate to obtain a phospholipidized quaternary ammonium monomer; the phospholipidized quaternary ammonium monomer is copolymerized with N-vinylpyrrolidone to obtain a modified phospholipidized quaternary ammonium random copolymer; and the modified phospholipidized quaternary ammonium random copolymer is mixed with an auxiliary and water to obtain the antibacterial and acaricidal shampoo.

[0015] First, the long-chain alkyl acid is subjected to an amidation reaction with 3-dimethylaminopropylamine to obtain a long-chain amide tertiary amine having an amide group and a long carbon chain; and then the long-chain amide tertiary amine is subjected to a ring-opening quaternization reaction with ethylene 2-(methacryloyloxy)ethyl phosphate, the phosphate ring of the ethylene 2-(methacryloyloxy)ethyl phosphate is opened, and a quaternization reaction occurs with the tertiary amine group, forming a structure similar to phosphocholine, which is similar to the phospholipid structure of the skin cell membrane, thereby improving the compatibility with the skin; the amide group, the quaternary ammonium group, and the phosphate group all have beneficial effects on the improvement of the compatibility, can reduce skin irritation, the existence of the amphoteric ion enables it to have good emulsifying ability, foaming ability, and foam stability, has good compatibility, can be well compatible with other shampoo ingredients, thereby improving the stability, and the carbon-carbon double bond is also introduced on the monomer, which can be used for participating in copolymerization.

[0016] Secondly, the phospholipidized quaternary ammonium monomer is randomly copolymerized with N-vinyl pyrrolidone to obtain a modified phospholipidized quaternary ammonium random copolymer, wherein the N-vinyl pyrrolidone is adsorbed on the scalp and hair through electrostatic and hydrophobic interactions in the wet state, and the phospholipidized quaternary ammonium monomer has good hydrophilic properties due to the presence of zwitterions, can effectively bind water molecules in the wet state to form a lubricating layer, improve the wet combing properties of the hair, and reduce the friction of the hair. At the same time, after the hair dries, due to the electrostatic effect of N-vinyl pyrrolidone and the compatibility of the phospholipidized quaternary ammonium monomer with the scalp and hair, and compared with small-molecule amphoteric surfactants, the polymer modified phospholipidized quaternary ammonium random copolymer has stronger adsorption capacity and can be more adsorbed on the scalp and hair surface after washing, providing sustained repair ability and improving dry combing properties and reducing dry combing friction coefficient; the modified phospholipidized quaternary ammonium random copolymer also has long carbon chains and quaternary ammonium cations, which have excellent antibacterial and acaricidal properties. In a weakly acidic pH environment, the modified phospholipidized quaternary ammonium random copolymer exhibits the characteristics of a cationic surfactant, and the quaternary ammonium cations can be adsorbed on the surface of bacteria through electrostatic interaction, while the hydrophobic chains are combined with the lipid bilayer of the bacterial cell membrane, destroying the integrity of the cell membrane, causing the contents of the cell to leak, and ultimately causing the bacteria to lyse and die. Combined with its excellent adsorption performance on the surface of the hair and scalp, it can provide long-term antibacterial performance, reduce the damage of bacteria to the scalp and hair, and drive or kill mites to reduce the damage from mites, providing sustained protection.

[0017] Finally, the modified phospholipidized quaternary ammonium random copolymer is mixed with auxiliaries and water to obtain an antibacterial and acaricidal shampoo. The modified phospholipidized quaternary ammonium random copolymer has zwitterions and phosphatidylcholine-like structures, and has good compatibility with other auxiliaries, and the prepared antibacterial and acaricidal shampoo has good stability. At the same time, the phosphatidylcholine-like structure has excellent cell compatibility and low irritation, which can effectively reduce the damage of the shampoo to the scalp and hair. During the washing process, the modified phospholipidized quaternary ammonium random copolymer can be adsorbed on the hair scales to provide repair effect. The modified phospholipidized quaternary ammonium random copolymer also has antibacterial and acaricidal properties, which can provide long-term antibacterial and acaricidal properties. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0019] The following all examples and comparative examples used raw material information as follows: lauryl alcohol polyoxyethylene ether sodium sulfate: model llb75354, purchased from Wuhan Lanya Bai Medicine and Chemical Co., Ltd.; coconut oil monoethanolamide: purchased from Suzhou Kenin Polyol Co., Ltd.; cetyl stearyl alcohol: purchased from Suzhou Kenin Polyol Co., Ltd.; PEG-120 methyl glucose trioleate: purchased from Hubei Xingyan New Material Technology Co., Ltd.; cocamidopropyl betaine: model CAB-35, purchased from Haolong Chemical Co., Ltd. of Bobxing County in Shandong Province; preservative: phenoxyethanol is used; essence: lemon essence, purchased from Shandong Ruiyu Business and Trade Co., Ltd.; long-chain alkyl acid: lauric acid is used.

[0020] The following all examples and comparative examples used formula as follows: 20wt% lauryl alcohol polyoxyethylene ether sodium sulfate, 1wt% coconut oil monoethanolamide, 1.5wt% glycol stearate, 0.8wt% cetyl stearyl alcohol, 3wt% PEG-120 methyl glucose trioleate, 3.5wt% cocamidopropyl betaine, 1.1wt% modified phosphatidyl quaternary ammonium random copolymer, 0.4wt% preservative, 0.15wt% essence, 0.8wt% sodium chloride, and the balance is water, and citric acid is added according to pH.

[0021] Example 1 A preparation method of an antibacterial and acaricidal shampoo, the preparation method of the antibacterial and acaricidal shampoo comprising the following preparation steps: (1) 40 parts of long-chain alkyl acid are heated to 120°C under a nitrogen atmosphere, 3-dimethylaminopropylamine is added at a rate of 0.8 ml / min according to a molar ratio of long-chain alkyl acid to 3-dimethylaminopropylamine of 2:2.5, water is removed by a water trap, reflux reaction is carried out at 145°C and 200 r / min for 9h, unreacted raw materials are removed by vacuum distillation, long-chain amide tertiary amine is prepared by recrystallizing 3 times with petroleum ether and vacuum drying at 50°C for 24h according to parts by mass; (2) 2 parts of long-chain amide tertiary amine and 20 parts of chloroform are uniformly mixed, ethylene 2-(methacryloyloxy)ethyl phosphate is added at room temperature and 200 r / min according to a molar ratio of long-chain amide tertiary amine to ethylene 2-(methacryloyloxy)ethyl phosphate of 1:1, reflux reaction is carried out at 90°C and 200 r / min for 24h, chloroform is removed by rotary evaporation, and phosphatidyl quaternary ammonium monomer is prepared by vacuum drying at 50°C for 12h. (3) According to the mass fraction, 2 parts of N-vinyl pyrrolidone, 4.68 parts of phospholipidized quaternary ammonium monomer, 25 parts of isopropyl alcohol are mixed uniformly under nitrogen atmosphere, 0.09 parts of azobisisobutyronitrile is added, sealed, stirred at 65℃, 300r / min for 4h, precipitated into 180 parts of petroleum ether, filtered, washed twice with petroleum ether, then washed three times with anhydrous ethanol, dried at 50℃ under vacuum for 12h, to prepare modified phospholipidized quaternary ammonium random copolymer; (4) According to the formula, the modified phospholipidized quaternary ammonium random copolymer is dissolved in 50 times the mass of water, stirred at 60℃, 200r / min until completely dissolved to obtain A liquid, sodium lauryl polyoxyethylene ether sulfate is added to an equal mass of water, stirred at 75℃, 200r / min until completely dissolved, coconut oil monoethanolamide, ethylene glycol distearate, cetyl stearyl alcohol are added, continue to stir until completely dissolved, add A liquid, continue to stir, naturally cool to 50℃, add cocamide propyl betaine, stir until dissolved, then add PEG-120 methyl glucose trioleate, stir at 200r / min for 60min to disperse, keep stirring and naturally cool to 30℃, add sodium chloride, after cooling to room temperature, add preservatives and essence, make up the rest of the water, add citric acid to adjust the pH to 6.5, stir at 200r / min for 60min to disperse evenly, to prepare an antibacterial and acaricidal shampoo.

[0022] Example 2 A method for preparing an antibacterial and acaricidal shampoo, the method comprising the following preparation steps: (1) According to the mass fraction, 45 parts of long-chain alkyl acid is heated to 120℃ under nitrogen atmosphere, 3-dimethylaminopropylamine is added at a rate of 0.9ml / min with a molar ratio of long-chain alkyl acid to 3-dimethylaminopropylamine of 2:2.8, the water is removed by a water separator, and the reaction is carried out at 150℃, 250r / min for 8.5h, the unreacted raw materials are removed by vacuum distillation, and the long-chain amide tertiary amine is prepared by recrystallizing with petroleum ether for 3 times and drying at 55℃ under vacuum for 22h; (2) According to the mass fraction, 2.5 parts of long-chain amide tertiary amine, 25 parts of chloroform are mixed uniformly, at room temperature, 250r / min, ethylene 2-(methacryloyloxy)ethyl phosphate is added with a molar ratio of long-chain amide tertiary amine to ethylene 2-(methacryloyloxy)ethyl phosphate of 1:1, the reaction is carried out at 90℃, 250r / min for 22h, the chloroform is removed by rotary evaporation, and the phospholipidized quaternary ammonium monomer is prepared by drying at 55℃ under vacuum for 11h; (3) According to the mass fraction, 2.5 parts of N-vinyl pyrrolidone, 5.86 parts of phospholipidized quaternary ammonium monomer, 28 parts of isopropyl alcohol are mixed uniformly under nitrogen atmosphere, 0.105 parts of azobisisobutyronitrile is added, sealed, stirred at 65℃ and 350r / min for 3.5h, poured into 190 parts of petroleum ether for precipitation, filtered, washed twice with petroleum ether, then washed 4 times with anhydrous ethanol, vacuum dried at 55℃ for 11h to prepare the modified phospholipidized quaternary ammonium random copolymer; (4) According to the formula, the modified phospholipidized quaternary ammonium random copolymer is dissolved in 50 times the mass of water, stirred at 60℃ and 250r / min until completely dissolved to obtain A liquid. Sodium lauryl polyoxyethylene ether sulfate is added to an equal mass of water, stirred at 80℃ and 250r / min until completely dissolved. Coconut oil monoethanolamide, ethylene glycol distearate, and cetylstearyl alcohol are added, and the stirring is continued until completely dissolved. A liquid is added, and the stirring is continued. The temperature is naturally reduced to 50℃. Cocamidopropyl betaine is added and stirred until dissolved. PEG-120 methyl glucose trioleate is added, and the stirring is continued at 250r / min for 55min to disperse. The stirring is maintained, and the temperature is naturally reduced to 30℃. Sodium chloride is added. After the temperature is reduced to room temperature, preservatives and fragrances are added. The remaining water is added. Citric acid is added to adjust the pH to 6.5. The stirring is continued at 250r / min for 55min to disperse uniformly. An antibacterial and acaricidal shampoo is prepared.

[0023] Example 3 A method for preparing an antibacterial and acaricidal shampoo, the method comprising the following preparation steps: (1) According to the mass fraction, 50 parts of long-chain alkyl acid is heated to 120℃ under nitrogen atmosphere. 3-dimethylaminopropylamine is added at a rate of 1ml / min with a molar ratio of long-chain alkyl acid to 3-dimethylaminopropylamine of 2:3. The water is removed by a water separator. The reaction is carried out at 155℃ and 300r / min for 8h. The unreacted raw materials are removed by vacuum distillation. The long-chain amide tertiary amine is prepared by recrystallizing 4 times with petroleum ether and vacuum drying at 60℃ for 20h. (2) According to the mass fraction, 3 parts of long-chain amide tertiary amine and 30 parts of chloroform are mixed uniformly. Ethylene 2-(methacryloyloxy)ethyl phosphate is added at room temperature and 300r / min with a molar ratio of long-chain amide tertiary amine to ethylene 2-(methacryloyloxy)ethyl phosphate of 1:1. The reaction is carried out at 95℃ and 300r / min for 20h. The chloroform is removed by rotary evaporation. The phospholipidized quaternary ammonium monomer is prepared by vacuum drying at 60℃ for 10h. (3) Under the atmosphere of nitrogen, 3 parts of N-vinyl pyrrolidone, 7.03 parts of phospholipidized quaternary ammonium monomer, 30 parts of isopropyl alcohol were mixed uniformly, 0.12 parts of azobisisobutyronitrile was added, sealed, stirred at 70°C and 400 r / min for 3h, poured into 200 parts of petroleum ether for precipitation, filtered, washed with petroleum ether for 3 times, washed with anhydrous ethanol for 4 times, and dried at 60°C under vacuum for 10h to prepare the modified phospholipidized quaternary ammonium random copolymer; (4) According to the formula, the modified phospholipidized quaternary ammonium random copolymer was dissolved in 50 times the mass of water, stirred at 60°C and 300 r / min until completely dissolved to obtain liquid A. Sodium lauryl polyoxyethylene ether sulfate was added to an equal mass of water, stirred at 85°C and 300 r / min until completely dissolved, then coconut oil monoethanolamide, stearyl glycol distearate and cetyl stearyl alcohol were added, and the stirring was continued until completely dissolved. Liquid A was added, and the stirring was continued, and the temperature was naturally lowered to 50°C. Cocamidopropyl betaine was added and stirred until dissolved. PEG-120 methyl glucose trioleate was added, and the stirring was continued at 300 r / min for 50 min to disperse. The stirring was maintained, and the temperature was naturally lowered to 30°C. Sodium chloride was added, and the temperature was lowered to room temperature. Preservatives and fragrances were added, and the remaining water was added. Citric acid was added to adjust the pH to 6.5. The stirring was continued at 300 r / min for 50 min to disperse uniformly, and the antibacterial and acaricidal shampoo was prepared.

[0024] Comparative Example 1: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 1 is different from that of Example 2 in step (3). Step (3) was modified as follows: under the atmosphere of nitrogen, 2.5 parts of N-vinyl pyrrolidone, 2.93 parts of phospholipidized quaternary ammonium monomer, and 28 parts of isopropyl alcohol were mixed uniformly, 0.105 parts of azobisisobutyronitrile was added, sealed, stirred at 65°C and 350 r / min for 3.5h, poured into 190 parts of petroleum ether for precipitation, filtered, washed with petroleum ether for 2 times, washed with anhydrous ethanol for 4 times, and dried at 55°C under vacuum for 11h to prepare the modified phospholipidized quaternary ammonium random copolymer. The remaining steps were the same as those of Example 2.

[0025] Comparative Example 2: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 2 is different from that of Example 2 in step (3). Step (3) was modified as follows: under the atmosphere of nitrogen, 2.5 parts of N-vinyl pyrrolidone, 4.39 parts of phospholipidized quaternary ammonium monomer, and 28 parts of isopropyl alcohol were mixed uniformly, 0.105 parts of azobisisobutyronitrile was added, sealed, stirred at 65°C and 350 r / min for 3.5h, poured into 190 parts of petroleum ether for precipitation, filtered, washed with petroleum ether for 2 times, washed with anhydrous ethanol for 4 times, and dried at 55°C under vacuum for 11h to prepare the modified phospholipidized quaternary ammonium random copolymer. The remaining steps were the same as those of Example 2.

[0026] Comparative Example 3: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 3 is different from that of Example 2 in that step (3) is modified. In step (3), 2.5 parts of N-vinylpyrrolidone, 7.32 parts of phospholipidized quaternary ammonium monomer, and 28 parts of isopropyl alcohol are mixed uniformly under a nitrogen atmosphere, 0.105 parts of azobisisobutyronitrile is added, and the mixture is stirred at 65°C and 350 r / min for 3.5 h. The reaction product is precipitated in 190 parts of petroleum ether, filtered, washed with petroleum ether twice, washed with anhydrous ethanol four times, and dried at 55°C under vacuum for 11 h to obtain a modified phospholipidized quaternary ammonium random copolymer. The remaining steps are the same as those of Example 2.

[0027] Comparative Example 4: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 4 is different from that of Example 2 in that step (3) is modified. In step (3), 2.5 parts of N-vinylpyrrolidone, 8.78 parts of phospholipidized quaternary ammonium monomer, and 28 parts of isopropyl alcohol are mixed uniformly under a nitrogen atmosphere, 0.105 parts of azobisisobutyronitrile is added, and the mixture is stirred at 65°C and 350 r / min for 3.5 h. The reaction product is precipitated in 190 parts of petroleum ether, filtered, washed with petroleum ether twice, washed with anhydrous ethanol four times, and dried at 55°C under vacuum for 11 h to obtain a modified phospholipidized quaternary ammonium random copolymer. The remaining steps are the same as those of Example 2.

[0028] Comparative Example 5: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 5 is different from that of Example 2 in that the amount of the modified phospholipidized quaternary ammonium random copolymer added in the formula is modified to 0 wt%. The remaining steps are the same as those of Example 2.

[0029] Comparative Example 6: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 6 is different from that of Example 2 in that the amount of the modified phospholipidized quaternary ammonium random copolymer added in the formula is modified to 0.5 wt%. The remaining steps are the same as those of Example 2.

[0030] Comparative Example 7: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 7 is different from that of Example 2 in that the amount of the modified phospholipidized quaternary ammonium random copolymer added in the formula is modified to 0.8 wt%. The remaining steps are the same as those of Example 2.

[0031] Comparative Example 8: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 8 is different from that of Example 2 in that the amount of the modified phospholipidized quaternary ammonium random copolymer added in the formula is modified to 1.5 wt%. The remaining steps are the same as those of Example 2.

[0032] Comparative Example 9: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 9 is different from that of Example 2 in that the amount of the modified phosphatidylated quaternary ammonium random copolymer added in the formula is different, and the amount is modified to 1.8 wt%. The remaining steps are the same as those of Example 2.

[0033] Comparative Example 10: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 10 is different from that of Example 2 in that step (1) is not performed, and step (2) is modified as follows: 2.5 parts of lauryl dimethyl tertiary amine and 25 parts of chloroform are uniformly mixed, at room temperature and at 250 r / min, ethylene 2-(methacryloyloxy)ethyl phosphate is added at a molar ratio of lauryl dimethyl tertiary amine to ethylene 2-(methacryloyloxy)ethyl phosphate of 1:1, and refluxed at 90°C and at 250 r / min for 22 h, chloroform is removed by rotary evaporation, and dried at 55°C under vacuum for 11 h to obtain a phosphatidylated quaternary ammonium monomer. The remaining steps are the same as those of Example 2.

[0034] Comparative Example 11: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 11 is different from that of Example 2 in that step (2) is different, and step (2) is modified as follows: 2.5 parts of long-chain carbon amide tertiary amine and 25 parts of chloroform are uniformly mixed, at room temperature and at 250 r / min, 2-chloromethyl acrylate is added at a molar ratio of long-chain carbon amide tertiary amine to 2-chloromethyl acrylate of 1:1, and refluxed at 90°C and at 250 r / min for 22 h, chloroform is removed by rotary evaporation, and dried at 55°C under vacuum for 11 h to obtain a phosphatidylated quaternary ammonium monomer. The remaining steps are the same as those of Example 2.

[0035] Comparative Example 12: The preparation method of the antibacterial and acaricidal shampoo of Comparative Example 12 is different from that of Example 2 in that steps (1) and (2) are not performed, and step (3) is modified as follows: 2.5 parts of N-vinyl pyrrolidone, 5.86 parts of 2-methyl-2-acrylic acid-2-(phosphoryl oxy) ethyl ester, and 28 parts of isopropyl alcohol are uniformly mixed under a nitrogen atmosphere, 0.105 parts of azobisisobutyronitrile is added, sealed, stirred at 65°C and at 350 r / min for 3.5 h, poured into 190 parts of petroleum ether to precipitate, filtered, washed twice with petroleum ether, and then washed four times with anhydrous ethanol, and dried at 55°C under vacuum for 11 h to obtain a modified phosphatidylated quaternary ammonium random copolymer. The remaining steps are the same as those of Example 2.

[0036] Test Example 1: Antibacterial and anti-mite performance test: the modified phosphatidylated quaternary ammonium random copolymer prepared in step (3) of examples 1-3 and comparative examples 5-12 and the antibacterial and anti-mite shampoo prepared in step (4) were evaluated for their antibacterial and anti-mite performance by testing their antibacterial properties and mite removal rates. The specific testing method is as follows: copolymer test sample preparation: the modified phosphatidylated quaternary ammonium random copolymer prepared in step (3) of each example and comparative example was dissolved in water to prepare a 2wt% solution, obtaining a copolymer test sample; antibacterial property test: the antibacterial performance was tested according to QB / T2738-2012, the bacteria were Staphylococcus aureus, Escherichia coli and Candida albicans, and the suspension quantitative method was used for the test, wherein 5ml of the copolymer test sample or the antibacterial and anti-mite shampoo was added, the time was 1h, each group was tested in parallel for 5 times, and the average value was recorded; mite removal performance test: (1) human Demodex acquisition: the Demodex was acquired by using transparent tape sticking method, the specific steps were as follows: after the subjects washed their faces with water before sleeping, a transparent tape with a length of 6cm and a width of 1.5cm was pasted on the forehead, cheek, nose and chin, etc., the next morning the tape was removed and stuck on the glass slide, and then the Demodex was observed under a microscope and sealed on the glass slide; (2) test grouping: the antibacterial and anti-mite shampoo and the copolymer test sample prepared in each example and comparative example were added dropwise on the glass slide, the amount of addition was 0.1mg / cm 2 The sample was evenly spread to ensure that the sample was in full contact with the insect. The sample was placed in an environment with 60%RH and 25℃, and after 1h, the survival of the Demodex was observed under a microscope. The insect was observed under a microscope for 3min, and the insect was determined to be dead if the claws or feet were not moving.

[0037] The data recorded in Table 1, the left is the copolymer test sample data, and the right is the antibacterial and anti-mite shampoo data.

[0038] The results are shown in Table 1.

[0039]

[0040] From the experimental data of examples 1-3 and comparative examples 5-12 in Table 1, it can be found that the antibacterial and anti-mite shampoo prepared by the present application has good antibacterial and anti-mite performance.

[0041] Through comparison of the data in the table, the data of comparative example 5 shows that when the modified phosphatidylated quaternary ammonium random copolymer is not added to the antibacterial and anti-mite shampoo, the antibacterial and anti-mite performance of the original system is insufficient, and it is difficult to provide higher antibacterial performance by adding a small amount of preservative and other surfactants.

[0042] Through comparison of the data in the table, the data of comparative examples 6-7 shows that when the amount of the modified phosphatidylated quaternary ammonium random copolymer is small, the improvement of the antibacterial and anti-mite performance is small, and it is difficult to improve the antibacterial and anti-mite performance to the highest.

[0043] The data of the comparative example 10 in the table show that the introduction of the amide bond in the modified phospholipidized quaternary ammonium random copolymer improves the adsorption performance, so that the acaricidal component can be better adsorbed on the mites, thereby killing the mites.

[0044] The data of the comparative example 11 in the table show that the introduction of the phosphate group in the modified phospholipidized quaternary ammonium random copolymer improves the acaricidal performance, and the phosphate group has a similar phospholipid structure on the cell surface, which can be effectively adsorbed to improve the acaricidal efficiency of the quaternary ammonium structure.

[0045] The data of the comparative example 12 in the table show that the quaternary ammonium structure in the modified phospholipidized quaternary ammonium random copolymer is the main active component for antibiosis and acaricidal performance, and the structure of the cation and the long carbon chain enable it to have good antibacterial and acaricidal performance.

[0046] Test example 2: Hair care performance test: the modified phospholipidized quaternary ammonium random copolymer prepared in step (3) of test examples 1-3 and comparative examples 5-12 and the antibacterial and acaricidal shampoo prepared in step (4) are evaluated in terms of the change rate of the friction force of wet combing and dry combing of the hair sample, and the specific test method is as follows: copolymer test sample preparation: the modified phospholipidized quaternary ammonium random copolymer prepared in step (3) of each example and comparative example is dissolved in water to prepare a 2wt% solution, to obtain a copolymer test sample; shampoo sample preparation: the antibacterial and acaricidal shampoo prepared in each example and comparative example is diluted 10 times to obtain a shampoo sample; pretreatment of hair sample: the hair sample is selected from natural black Chinese hair, which is washed by ultrasonic treatment with acetone, anhydrous ethanol and deionized water in sequence for 15 min, the hair sample is washed with deionized water and then dried in air, the relative humidity is kept at 50% RH and the temperature is kept at 20℃; wet combing hair sample preparation: 1g of the pretreated hair sample is soaked in 50ml of the copolymer test sample or the shampoo sample, and is shaken in a constant temperature water bath shaker for 30min, and then is washed with pure water to obtain a wet combing hair sample; dry combing hair sample preparation: the wet combing hair sample is naturally dried at 20℃ and 50% RH for 4h to obtain a dry combing hair sample; friction coefficient test method: the change rate K of the friction force of the hair sample is tested according to T / GDCA 025-2023 “Hair Product Head Hair Nourishing Efficacy Evaluation Method”, the change rate K is calculated according to the calculation formula in the standard document, each group of samples is tested in parallel for 20 times, and the average value is recorded; the results are shown in table 2.

[0047]

[0048] From the experimental data of examples 1-3 and comparative examples 5-12 in table 2, it can be found that the antibacterial and acaricidal shampoo prepared in the present application has good hair care performance.

[0049] By comparing the data in the table, the data of Comparative Example 5 shows that when the modified phosphatidylated quaternary ammonium random copolymer is not added in the antibacterial and acarid-killing shampoo, other surfactant products are difficult to remain on the hair surface due to the lack of adsorption performance, and thus the repair performance is low.

[0050] By comparing the data in the table, the data of Comparative Examples 6-7 shows that when the amount of the modified phosphatidylated quaternary ammonium random copolymer added in the antibacterial and acarid-killing shampoo is small, the adsorption amount is low, and the repair effect is poor.

[0051] By comparing the data in the table, the data of Comparative Example 10 shows that the amide groups introduced in the modified phosphatidylated quaternary ammonium random copolymer improve the adsorption amount of the modified phosphatidylated quaternary ammonium random copolymer on the hair surface through hydrogen bonds and the like, thereby improving the repair effect.

[0052] By comparing the data in the table, the data of Comparative Example 11 shows that the phosphatidyl groups introduced in the modified phosphatidylated quaternary ammonium random copolymer have good hydration effect, can effectively reduce the friction, and improve the repair effect.

[0053] By comparing the data in the table, the data of Comparative Example 12 shows that the quaternary ammonium groups introduced in the modified phosphatidylated quaternary ammonium random copolymer have good hydration effect, can effectively reduce the friction, and improve the repair effect.

[0054] Test Example 3: Adsorption performance test: the modified phosphatidylated quaternary ammonium random copolymer prepared in step (3) of Test Examples 1-3 and Comparative Examples 5-12 and the antibacterial and acarid-killing shampoo prepared in step (4) are used to test the antibacterial and acarid-killing performance of the hair sample after washing for 8h, and the data are compared with those in Test Example 2 to evaluate the adsorption performance. The specific test method is as follows: copolymer test sample preparation: the modified phosphatidylated quaternary ammonium random copolymer prepared in step (3) of each example and comparative example is dissolved in water to prepare a 2wt% solution, and a copolymer test sample is obtained.

[0055] Shampoo sample preparation: the antibacterial and acarid-killing shampoo prepared in each example and comparative example is diluted 5 times to obtain a shampoo sample.

[0056] Hair sample preparation: natural black Chinese hair is selected as the hair sample, and the hair sample is sequentially washed with acetone, anhydrous ethanol and deionized water by ultrasonic treatment for 15min. The hair sample is washed with deionized water, dried in air, kept at a relative humidity of 50%RH and a temperature of 20℃, then 1g of the hair sample is soaked in 50ml of the copolymer test sample or the shampoo test sample, oscillated in a constant temperature water bath oscillator for 30min, washed with pure water, and naturally dried at 20℃ and 50%RH for 8h to obtain the hair sample.

[0057] Antibacterial test: refer to the antibacterial test method in appendix C of GB / T 15979-2002, the bacteria are staphylococcus aureus, escherichia coli and candida albicans, refer to C5 non-dissolved antibacterial product antibacterial performance test method, wherein the sample piece is replaced by 0.75g of hair sample, each group is tested in parallel for 5 times, and the average value is recorded.

[0058] Mite repellency test: refer to the mite repellency test in GB / T 24253-2009, the mite species is selected to be dust mites, and the sample is selected to be hair sample, and the test is performed in parallel for 5 times, and the average value is recorded.

[0059] The data recorded in Table 3, the left is the copolymer test sample data, and the right is the antibacterial and mite repellent shampoo data.

[0060] The results are shown in Table 3.

[0061]

[0062] From the experimental data comparison of examples 1~3 and comparative examples 1~12 in Table 3, it can be found that the antibacterial and mite repellent shampoo prepared by the present application has good adsorption performance and long-acting antibacterial and mite repellent performance.

[0063] Through the comparison of the data in the table, the data of comparative examples 1~2 show that reducing the addition of phosphatidylated quaternary ammonium monomer in the copolymerization of step (3) leads to the decrease of the content of antibacterial and mite repellent groups on the copolymer, resulting in the decrease of the antibacterial and mite repellent performance.

[0064] Through the comparison of the data in the table, the data of comparative examples 3~4 show that increasing the addition of phosphatidylated quaternary ammonium monomer in the copolymerization of step (3) leads to the decrease of the molecular weight of the polymer chain segment and the content of N-vinyl pyrrolidone groups due to the presence of more bulky groups on the copolymer chain, resulting in the decrease of the adsorption performance, and thus the residual effective antibacterial and mite repellent molecules decrease after long-time air drying, leading to the decrease of the long-acting antibacterial and mite repellent performance.

[0065] Through the comparison of the data in the table, the data of comparative example 5 show that when the modified phosphatidylated quaternary ammonium random copolymer is not added to the antibacterial and mite repellent shampoo, it basically does not have long-acting antibacterial and mite repellent performance.

[0066] Through the comparison of the data in the table, the data of comparative examples 6~7 show that when the amount of the modified phosphatidylated quaternary ammonium random copolymer added to the antibacterial and mite repellent shampoo is small, the adsorption amount also decreases accordingly, the residual amount after long-time air drying also decreases, and the long-acting antibacterial and mite repellent performance decreases.

[0067] Through the comparison of the data in the table, the data of comparative example 10 show that the introduction of amide groups on the modified phosphatidylated quaternary ammonium random copolymer improves the adsorption amount through hydrogen bonds and the like, thereby improving the long-acting antibacterial and mite repellent effect.

[0068] By comparing the data in the table, the data of Comparative Example 11 shows that the introduction of phospholipid groups on the modified phospholipidized quaternary ammonium random copolymer has higher cell compatibility, can better adsorb on the hair surface, and improves the adsorption amount, thereby improving the long-acting antibacterial and acarid removal performance.

[0069] By comparing the data in the table, the data of Comparative Example 12 shows that the quaternary ammonium groups on the modified phospholipidized quaternary ammonium random copolymer are the main antibacterial and acarid removal active groups, which provide the main antibacterial and acarid removal performance.

[0070] The above specific embodiments further specifically describe the purposes, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. An antibacterial and anti-mite shampoo, characterized in that, The antibacterial and anti-mite shampoo is prepared by mixing a modified phospholipidated quaternary ammonium random copolymer with additives and water; the modified phospholipidated quaternary ammonium random copolymer is prepared by copolymerizing a phospholipidated quaternary ammonium monomer with N-vinylpyrrolidone; the phospholipidated quaternary ammonium monomer is prepared by reacting a long-chain amidated tertiary amine with ethylene 2-(methacryloyloxy)ethyl phosphate; the long-chain amidated tertiary amine is prepared by reacting a long-chain alkyl acid with 3-dimethylaminopropylamine.

2. The antibacterial and anti-mite shampoo according to claim 1, characterized in that, The additives include sodium lauryl ether sulfate, coconut oil monoethanolamide, ethylene glycol stearate diester, cetearyl alcohol, PEG-120 methyl glucotrioleate, cocamidopropyl betaine, preservatives, flavorings, citric acid, and sodium chloride.

3. The antibacterial and anti-mite shampoo according to claim 1, characterized in that, The long-chain alkyl acid is one of n-decanoic acid, n-undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, and palmitic acid.

4. A method for preparing an antibacterial and anti-mite shampoo, characterized in that, The preparation steps include the following: (1) Under a nitrogen atmosphere, the long-chain alkyl acid was heated and 3-dimethylaminopropylamine was added dropwise. Water was separated by a water separator, and the reaction was carried out under reflux. The reaction was carried out under reduced pressure, recrystallized, and dried to obtain a long-chain amidated tertiary amine. (2) Mix long-chain amidated tertiary amine and chloroform, stir at room temperature, add ethylene 2-(methacryloyloxy)ethyl phosphate, heat under reflux, evaporate by rotary evaporation, and dry to obtain phospholipidated quaternary ammonium monomer; (3) Under a nitrogen atmosphere, N-vinylpyrrolidone, phospholipidated quaternary ammonium monomer and isopropanol were mixed, azobisisobutyronitrile was added, the mixture was sealed, heated and stirred to react, and then poured into petroleum ether to precipitate. The mixture was filtered, washed and dried to obtain the modified phospholipidated quaternary ammonium random copolymer. (4) According to the formula, add the modified phospholipidated quaternary ammonium random copolymer to water and dissolve it. Heat and stir until completely dissolved to obtain solution A. Add sodium lauryl polyoxyethylene ether sulfate to water and heat and stir until completely dissolved. Add coconut oil monoethanolamide, ethylene glycol stearate diester and cetearyl alcohol. Continue stirring until completely dissolved. Add solution A and continue stirring. Allow to cool naturally to 50°C. Add cocamidopropyl betaine and stir until dissolved. Add PEG-120 methyl glucotrioleate and stir to disperse. Keep stirring and allow to cool naturally. Add sodium chloride. After cooling to room temperature, add preservatives and fragrance. Add the remaining water. Add citric acid to adjust the pH. Stir until evenly dispersed to obtain antibacterial and anti-mite shampoo.

5. The method for preparing an antibacterial and anti-mite shampoo according to claim 4, characterized in that, The long-chain amidated tertiary amine described in step (1) is prepared by heating 40-50 parts of long-chain alkyl acid to 120°C under a nitrogen atmosphere, adding 3-dimethylaminopropylamine dropwise at a rate of 0.8-1 ml / min according to a molar ratio of long-chain alkyl acid to 3-dimethylaminopropylamine of 2:(2.5-3), separating water with a water separator, stirring and refluxing at 145-155°C for 8-9 h, removing unreacted raw materials by vacuum distillation, recrystallizing with petroleum ether, and then vacuum drying at 50-60°C for 20-24 h.

6. The method for preparing an antibacterial and anti-mite shampoo according to claim 4, characterized in that, The phospholipidated quaternary ammonium monomer in step (2) is prepared by mixing 2-3 parts of long-chain amidated tertiary amine and 20-30 parts of chloroform by mass, stirring at room temperature, adding ethylene 2-(methacryloyloxy)ethyl phosphate at a molar ratio of 1:1, reacting under stirring and reflux at 90-95°C for 20-24 hours, removing chloroform by rotary evaporation, and drying under vacuum at 50-60°C for 10-12 hours.

7. The method for preparing an antibacterial and anti-mite shampoo according to claim 4, characterized in that, The modified phospholipidated quaternary ammonium random copolymer described in step (3) is prepared by mixing 2-3 parts of N-vinylpyrrolidone, 4.68-7.03 parts of phospholipidated quaternary ammonium monomer, and 25-30 parts of isopropanol by mass under a nitrogen atmosphere, adding 0.09-0.12 parts of azobisisobutyronitrile, sealing, stirring and reacting at 65-70°C for 3-4 hours, pouring into 180-200 parts of petroleum ether to precipitate, filtering, washing with petroleum ether, then washing with anhydrous ethanol, and vacuum drying at 50-60°C for 10-12 hours.

8. The method for preparing an antibacterial and anti-mite shampoo according to claim 4, characterized in that, The formula described in step (4) is as follows: 18~22wt% sodium lauryl ether sulfate, 0.9~1.1wt% coconut oil monoethanolamide, 1.4~1.5wt% ethylene glycol stearate diester, 0.7~0.8wt% cetearyl alcohol, 2.5~3wt% PEG-120 methyl glucotrioleate, 3.5~4wt% cocamidopropyl betaine, 1~1.2wt% modified phospholipidated quaternary ammonium random copolymer, 0.06~0.8wt% preservative, 0.1~0.2wt% fragrance, 0.02~0.2wt% citric acid, 0.8wt% sodium chloride, and the balance being water.

9. The method for preparing an antibacterial and anti-mite shampoo according to claim 4, characterized in that, The antibacterial and anti-mite shampoo in step (4) is prepared by dissolving the modified phospholipidated quaternary ammonium random copolymer in 50 times its mass of water according to the formula, stirring at 60°C until completely dissolved to obtain solution A, adding sodium lauryl ether sulfate to an equal mass of water, stirring at 75~85°C until completely dissolved, adding coconut oil monoethanolamide, ethylene glycol stearate diester, and cetearyl alcohol, continuing to stir until completely dissolved, adding solution A, continuing to stir, naturally cooling to 50°C, adding cocamidopropyl betaine, stirring until dissolved, then adding PEG-120 methyl glucotrioleate, stirring for 50~60 minutes to disperse, maintaining stirring and naturally cooling to 30°C, adding sodium chloride, cooling to room temperature, adding preservatives and fragrance, adding the remaining water, adding citric acid to adjust the pH to 6.5, stirring for 50~60 minutes until evenly dispersed to obtain the product.

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