WO2021139193A1

WO2021139193A1 - Sustained-release long-lasting antibacterial hand sanitizer and preparation method therefor

Info

Publication number: WO2021139193A1
Application number: PCT/CN2020/113972
Authority: WO
Inventors: 应光辉; 应宗效
Original assignee: 浙江神英科技股份有限公司
Priority date: 2020-01-06
Filing date: 2020-09-08
Publication date: 2021-07-15
Also published as: CN110960444A; CN110960444B

Abstract

A sustained-release long-lasting antibacterial hand sanitizer and a preparation method therefor. The method comprises: dispersing an antibacterial in a cross-linked polyvinyl alcohol which has water resistance and is easy to form a gel film to obtain polyvinyl alcohol antibacterial gel particles; and uniformly dispersing 3-5 parts of a polyvinyl alcohol antibacterial gel particle, 0.05-0.1 part of an antibacterial, 10-15 parts of cocamidopropyl betaine, 0.2-0.5 part of sodium chloride, 2-3 parts of polyglycerol-10, 0.5-1.5 parts of citric acid, 0.2-1 part of an esterifying agent, 0.1-0.2 part of a hard water-resistant agent, and 30-35 parts of deionized water to obtain a sustained-release long-lasting antibacterial hand sanitizer. The polyvinyl alcohol antibacterial gel particles disperse the hand sanitizer, which forms the gel film when rubbing and washing hands, thereby achieving a sustained-release and long-lasting antibacterial effect.

Description

Slow-release and durable antibacterial hand sanitizer and preparation method

Technical field

The invention relates to the field of daily chemicals, in particular to a slow-release and durable antibacterial hand sanitizer and a preparation method.

Background technique

In people's life and work, their hands will inevitably come into contact with bacteria, which may cause diseases. There has been an old saying in China since ancient times: "Illness comes from the mouth", which is enough to show that since ancient times, Chinese people have attached great importance to hand hygiene. At present, in terms of hygiene, frequent hand washing has become the norm. In particular, the antibacterial hand sanitizer can kill most of the bacteria and has been widely used. Antibacterial hand sanitizer is accepted by more and more consumers as a daily cleaning product. It is used in hospitals, schools and other public places, and has a good instant sterilization effect. Initially, restricted by living conditions and the market, people usually wash their hands with soap, soap, and washing powder. Although they can achieve a certain cleaning effect, they have a stimulating effect on the skin and have poor antibacterial effects.

Due to the wide application of hand sanitizer, people also have higher requirements for hand sanitizer. While requiring excellent sterilization effect, it is hoped that after washing hands, it can maintain long-term antibacterial properties. However, most of the current antibacterial hand sanitizers are instant hand sanitizers, which can only kill bacteria that have adhered to the hands, and cannot achieve a long-lasting sterilization effect after washing the hands.

At present, there is a kind of no-wash hand sanitizer on the market, which mainly disperses silver ions in glycerin for skin care and sterilization, but its decontamination ability is poor.

Summary of the invention

At present, most antibacterial hand sanitizers are instant hand sanitizers, which can only kill bacteria that have adhered to the hands, and cannot achieve a long-lasting bactericidal effect after washing the hands. In response to this problem, the present invention proposes a sustained-release and durable antibacterial hand sanitizer. The hand sanitizer is dispersed with polyvinyl alcohol antibacterial gel particles capable of forming a film. Because the polyvinyl alcohol antibacterial gel particles have certain water resistance, The hand sanitizer is dispersed in the form of fine rubber particles. When washing hands, as the rubbing occurs, the polyvinyl alcohol antibacterial rubber particles will gradually form a film to form a micro gel film on the surface of the hand. The antibacterial particles dispersed in the film The slow-release agent has a long-lasting antibacterial and antibacterial effect. Further, the present invention proposes a method for preparing the sustained-release and durable antibacterial hand sanitizer.

As the technical core concept of the present invention, the key to the invention is to obtain polyvinyl alcohol antibacterial colloidal particles. The purpose is to disperse the antibacterial agent in polyvinyl alcohol and form colloidal particles with fine morphology. This colloidal particle is called polyvinyl alcohol. Vinyl alcohol antibacterial rubber particles. This rubber particle has the characteristics of being uniformly dispersed in liquid hand sanitizer for a long time, and has a certain degree of water resistance. It will not be dissolved by liquid hand sanitizer and destroy the shape of the gel particle, so as to meet the storage and application of hand sanitizer. Use; Further, the rubber particles will gradually form a glue film when rubbed strongly to form a layer of micro glue film on the surface of the hand, and the antibacterial agent dispersed in the glue film is slowly released to meet the lasting antibacterial and antibacterial effect.

In order to achieve the above technical objectives, the following technical solutions are adopted:

A preparation method of sustained-release and durable antibacterial hand sanitizer, its key feature is: the specific preparation method is as follows:

(1) Stir and mix the polyvinyl alcohol, glycerin and water evenly, and leave it in a sealed bag for 24 hours;

(2) The aged materials in step (1) are stirred for cross-linking reaction with organic acid, ammonium persulfate, and glutaraldehyde at 50-60°C to obtain a cross-linked polyvinyl alcohol liquid;

(3) Add the antibacterial agent to the cross-linked polyvinyl alcohol solution, stir for 3-5 min at 60-70°C, and then high-pressure atomization and drying to obtain polyvinyl alcohol antibacterial gel particles dispersed with antibacterial agents;

(4) According to parts by weight, combine 3-5 parts of polyvinyl alcohol antibacterial granules, 0.05-0.1 parts of antibacterial agent, 10-15 parts of cocamidopropyl betaine, 0.2-0.5 parts of sodium chloride, 2-3 parts of poly Glycerin-10, 0.5-1.5 parts of citric acid, 0.2-1 part of esterification agent, 0.1-0.2 part of anti-hardening agent, and 30-35 parts of deionized water are dispersed and evenly filled to obtain a sustained-release and lasting antibacterial hand sanitizer.

Preferably, the polyvinyl alcohol, glycerin, and water described in step (1) are mixed and sealed uniformly in a mass ratio of 50:15:100-200. The purpose is to make the small molecules of glycerin and water fully penetrate the plasticized polyvinyl alcohol to make The hydroxyl groups of polyvinyl alcohol are fully exposed.

Further, as a preference, the polyvinyl alcohol described in step (1) is 1788 polyvinyl alcohol. Its remarkable advantage is that it is water-soluble and has good water resistance after cross-linking treatment, so as to meet the requirements of the polyethylene prepared by the present invention. The alcohol antibacterial rubber particles can be dispersed in the hand sanitizer, and the rubber particles become film-like when rubbed.

Preferably, the materials aged in step (2), organic acid, ammonium persulfate, and glutaraldehyde are mixed in a mass ratio of 100:1-2:0.1-0.3:1 to 3, the purpose of which is to make polyvinyl alcohol cross-linked Water resistance. More preferably, the organic acid is acetic acid.

Preferably, the cross-linking reaction in step (2) controls the cross-linking time within 1-2 hours.

Preferably, in step (3), the antibacterial agent and the cross-linked polyvinyl alcohol liquid are dispersed in a mass ratio of 5:100, and the antibacterial agent is uniformly dispersed in the cross-linked polyvinyl alcohol liquid by stirring treatment at 60-70° C. for 3-5 minutes. The antibacterial agent is selected from at least one of 2,4,4'-trichloro-2'-hydroxydiphenyl ether, p-chloro-m-xylenol, and hexamidine diisethionate. Among them, 2,4,4'-trichloro-2'-hydroxydiphenyl ether is a white crystalline powder with a melting point of 56-58°C. It is slightly soluble in water and has a bactericidal effect on intestinal pathogens and pyogenic cocci; Chloro-m-xylenol is a white crystalline powder, which can kill most Gram-positive and negative bacteria, fungi and molds without irritation; hexamidine diisethionate is a white crystalline powder, white powder, It is soluble in water, ethanol and propylene glycol, has broad-spectrum antibacterial activity, has significant resistance and killing effect to Gram-positive and negative bacteria, yeast, mold, dermatophytes, etc., and has a high skin affinity.

Preferably, high-pressure atomization drying is adopted in step (3), the pressure of the atomization gun is controlled at 1.2-1.5 MPa, the gun caliber is controlled at 0.5-1 mm, and the drying temperature is controlled at 70-80°C. By controlling the pressure and caliber of the atomizing gun, the particle size of the dried polyvinyl alcohol antibacterial colloidal particles is 50-100μm. Too coarse particle size affects the dispersion in the hand sanitizer and the hand-washing feel; too fine particle size, because it is delicate, it is difficult to form a film by the rubber particles during kneading.

Preferably, the antibacterial agent in step (4) is selected from 2,4,4'-trichloro-2'-hydroxydiphenyl ether, p-chloro-m-xylenol, and hexamidine diisethionate At least one. The purpose is to achieve immediate sterilization when washing hands, which is a conventional choice for conventional antibacterial hand sanitizers.

In step (4), cocamidopropyl betaine is the main surface active ingredient in the hand sanitizer formula. Its basic function is to remove oily dirt and dirt on the hands, and produce a certain amount of foam. It is both acidic and alkaline. It has excellent stability, good compatibility, low irritation, easily soluble in water, and excellent flexibility.

When the surface active agent is used to clean the dirt on the hands, it will remove the protective oils of the skin at the same time. Long-term use will cause the hand skin to be chapped, rough and lose elasticity. The esterification agent used in the present invention prevents the skin from degreasing and drying. Preferably, in step (4), the esterifying agent is selected from at least one of isopropyl myristate, glycerol coco-based polyethylene glycol ester, and octyl hydroxystearate.

In step (4), polyglycerol-10 has oil and water commonality. It associates through hydrogen bonds, locks water in a cage, and has good moisture retention; at the same time, it can continuously form a film on the skin to assist polyvinyl alcohol antibacterial colloidal particles in the After washing the hands, a film is formed on the surface of the hand to improve the texture discomfort that occurs on the surface of the hand after the polyvinyl alcohol antibacterial colloidal particle is formed into the film.

In step (4), EDTA-2Na is selected as the anti-hard water agent, in order to ensure that the hand sanitizer has a better washing effect in hard water.

Human skin has a pH value of 5-6, which is acidic. In step (4), citric acid is selected to adjust the hand sanitizer to be weakly acidic.

In addition, the present invention provides a slow-release and durable antibacterial hand sanitizer prepared by the above method. It is characterized by containing a polyvinyl alcohol antibacterial colloidal particle capable of slow-release antibacterial agent. By dispersing the antibacterial agent in the cross-linked polyvinyl alcohol, the obtained polyvinyl alcohol antibacterial rubber particles have good water resistance and can be dispersed in the hand sanitizer. When the hands are washed, the polyvinyl alcohol antibacterial glue is rubbed under the action of rubbing. The particles disperse to form a microfilm, and the antibacterial agent dispersed in the glue microfilm will be continuously released to have a long-lasting antibacterial and antibacterial effect.

It is well-known that conventional antibacterial hand sanitizers are obtained by adding antibacterial agents to the hand sanitizer to disperse them. They are basically instant hand sanitizers that kill bacteria that have adhered to the hands. After washing the hands, the antibacterial agents are then rinsed and removed, which cannot achieve long-lasting Sterilization effect. The present invention is based on this problem and proposes a sustained-release and durable antibacterial hand sanitizer. After washing the hands, the hand sanitizer will form a micro-film on the surface of the hand, and the micro-film is dispersed with antibacterial agents to maintain long-lasting Antibacterial and antibacterial properties. In particular, the hand sanitizer has great application prospects for long-term antibacterial and antibacterial hand sanitizers for people who enter and exit public places for a long time, such as hospitals, public transportation, office buildings, etc.

A slow-release and long-lasting antibacterial hand sanitizer and a preparation method thereof have the following beneficial effects compared with the prior art:

(1) The present invention obtains polyvinyl alcohol antibacterial colloidal particles by dispersing the antibacterial agent in cross-linked polyvinyl alcohol with water resistance and easy to form a gel film. The rubber particles are used in hand sanitizers and form glue when rubbing and washing hands. Membrane to achieve a sustained-release and lasting antibacterial effect.

(2) Polyglycerol-10 is added to the hand sanitizer of the present invention to take advantage of its oil and water commonality. It associates through hydrogen bonds, locks water in a cage, and has good moisture retention; at the same time, it can continuously form a film on the skin to assist polyethylene Alcohol antibacterial rubber particles form a film on the surface of the hands after washing hands, which can improve the texture and discomfort that occurs on the surface of the hands after the polyvinyl alcohol antibacterial rubber particles are filmed.

(3) The present invention achieves long-lasting bacteriostasis, and can effectively reduce the number of times that people in and out of public places and staff wash their hands. It is especially suitable for the hands of people in hospitals, schools, hotels, banks, transportation, aviation, homes, and public places. Ministry of cleaning and sterilization to protect people's health and hygiene.

In summary, the present invention has many of the above advantages and practical value, and there is no related publicly published technology in the prior art products, and it has significant progress compared with the existing technology, so it is more suitable for practical use, and has Extensively promote production value on a large scale.

Description of the drawings

In order to more clearly illustrate the technical core concept and technical solution of the present invention, the technical idea of the present invention will be shown in a schematic diagram below.

Figure 1 is a simplified flow chart of the preparation of the present invention.

Detailed ways

In order to make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention. At the same time, on the basis of the concept of the present invention, a hand sanitizer with a certain fragrance prepared by adding various flavors and the like is also within the protection scope of the present invention.

Example 1

(1) Mix 1788 polyvinyl alcohol with glycerin and water at a mass ratio of 50:15:200 and stir evenly, then seal and place for 24 hours to make the small molecules of glycerin and water fully penetrate the plasticized polyvinyl alcohol;

(2) Mix the aged materials in step (1) with acetic acid, ammonium persulfate, and glutaraldehyde in a mass ratio of 100:2:0.1:1, and stir the cross-linking reaction at 60°C for 1 hour to obtain a cross-linked polyvinyl alcohol liquid;

(3) Disperse the antibacterial agent 2,4,4'-trichloro-2'-hydroxydiphenyl ether and the cross-linked polyvinyl alcohol solution at a mass ratio of 5:100, and stir at 60°C for 5 minutes to make the antibacterial agent uniformly dispersed. The cross-linked polyvinyl alcohol liquid is then dried by high-pressure atomization, the pressure of the atomizing gun is controlled at 1.5MPa, the gun caliber is controlled at 1mm, and the drying temperature is controlled at 80°C. By controlling the pressure and caliber of the atomizing gun, the particle size of the dried polyvinyl alcohol antibacterial rubber particles is maintained at 50-100 μm, and the antibacterial agent dispersed polyvinyl alcohol antibacterial rubber particles are obtained.

Example 2

Using the polyvinyl alcohol antibacterial rubber particles obtained in Example 1 as the core additive, 3 parts of polyvinyl alcohol antibacterial rubber particles, 0.1 parts of the antibacterial agent hexamidine diisethionate, and 15 parts of cocamidopropyl betaine , 0.2 parts of sodium chloride, 2 parts of polyglycerol-10, 1.0 part of citric acid, 0.5 part of isopropyl myristate, 0.1 part of EDTA-2Na, 30 parts of deionized water, dispersed evenly to obtain a sustained-release and durable antibacterial hand sanitizer .

Example 3

Using the polyvinyl alcohol antibacterial rubber particles obtained in Example 1 as the core additive, 5 parts of polyvinyl alcohol antibacterial rubber particles, 0.1 parts of the antibacterial agent hexamidine diisethionate, and 15 parts of cocamidopropyl betaine , 0.5 parts of sodium chloride, 3 parts of polyglycerol-10, 1.5 parts of citric acid, 0.2 parts of isopropyl myristate, 0.1 parts of EDTA-2Na, 30 parts of deionized water, dispersed evenly to obtain a sustained-release and lasting antibacterial hand sanitizer .

Comparative example 1

Combine 0.5 parts of polyvinyl alcohol antibacterial granules, 0.1 parts of antibacterial agent hexamidine diisethionate, 15 parts of cocamidopropyl betaine, 0.2 parts of sodium chloride, 2 parts of polyglycerol-10, 1.0 parts Citric acid, 0.5 parts of isopropyl myristate, 0.1 parts of EDTA-2Na, and 30 parts of deionized water are evenly dispersed to obtain a bacteriostatic hand sanitizer.

Comparative example 1 greatly reduces the amount of polyvinyl alcohol antibacterial rubber particles. Due to the reduction of the amount of antibacterial rubber particles, after washing hands, there are fewer antibacterial films on the hands, which will affect the continuous antibacterial performance.

Comparative example 2

Combine 5 parts of polyvinyl alcohol antibacterial pellets, 0.5 parts of antibacterial agent hexamidine diisethionate, 15 parts of cocamidopropyl betaine, 0.2 parts of sodium chloride, 1.0 part of citric acid, 0.5 part of nutmeg Isopropyl acid, 0.1 part of EDTA-2Na, and 30 parts of deionized water are evenly dispersed to obtain a sustained-release and durable antibacterial hand sanitizer.

Comparative Example 2 did not use polyglycerol-10. Due to the lack of auxiliary polyvinyl alcohol antibacterial colloidal particles to form a film on the surface of the hands after washing hands, the antibacterial durability was reduced to a certain extent.

Comparative example 3

0.1 parts of antibacterial agent hexamidine diisethionate, 15 parts of cocamidopropyl betaine, 0.2 parts of sodium chloride, 2 parts of polyglycerol-10, 1.0 part of citric acid, 0.5 part of myristic acid isocyanate Propyl ester, 0.1 part of EDTA-2Na, and 30 parts of deionized water are evenly dispersed to obtain a bacteriostatic hand sanitizer.

Comparative Example 3 did not use polyvinyl alcohol antibacterial gel particles, and only relied on the antibacterial agent hexamidine diisethionate. Therefore, the hand sanitizer only has instant sterilization properties, while the lasting antibacterial properties after hand washing are relatively poor. .

In order to qualitatively compare and verify the long-lasting antibacterial effect of the present invention, part of QB/T 2738-2005 "Evaluation Method of Antibacterial and Antibacterial Effects of Daily Chemical Products" was used for antibacterial tests. details as follows:

1. Put the silicone gloves on the hands, and use the hand sanitizers obtained in Examples 2-3 and 1-3 to simulate the hand washing method to rub and wash the silicone gloves, so that the silicone gloves can ensure the same scrubbing strength and time. Use washed silicone gloves as simulated washed hands;

2. The test bacteria used Staphylococcus aureus ATCC6538. After the third generation of culture, it was diluted with tryptone soy broth to prepare an average concentration of 1×10 ⁴ cfu/mL.

3. Drop 20 μL of bacterial solution in the area of the silicone glove with a diameter of 3 cm, and test the concentration of Staphylococcus aureus colonies after 60 minutes to measure the antibacterial performance. The test results are shown in Table 1.

Table 1:

Through testing, the antibacterial hand sanitizer of the present invention has a continuous antibacterial effect after washing hands, not only can effectively inhibit the reproduction of Staphylococcus aureus, but also has a good sterilization effect. Comparative Example 1 reduces the amount of polyvinyl alcohol antibacterial colloidal particles. Due to the reduction of the amount of antibacterial colloidal particles, after washing, less antibacterial film-forming material is formed, which will affect the continuous antibacterial performance. Comparative Example 2 did not use polyglycerol-10, due to the lack of auxiliary polyvinyl alcohol antibacterial colloidal particles for surface film formation, the antibacterial durability was reduced to a certain extent. Comparative Example 3 did not use polyvinyl alcohol antibacterial pellets, and only relied on the antibacterial agent hexamidine diisethionate. Therefore, it was difficult to form an antibacterial film after washing, and the lasting antibacterial performance was extremely poor. Poor, Staphylococcus aureus will multiply, so the number of colonies will increase.

Claims

A preparation method of sustained-release and long-lasting antibacterial hand sanitizer is characterized in that: the specific preparation method is as follows:

(1) Stir and mix the polyvinyl alcohol, glycerin and water evenly, and leave it in a sealed bag for 24 hours;

(2) The aged materials in step (1) are stirred for cross-linking reaction with organic acid, ammonium persulfate, and glutaraldehyde at 50-60°C to obtain a cross-linked polyvinyl alcohol liquid;

(3) Add the antibacterial agent to the cross-linked polyvinyl alcohol solution, stir for 3-5 min at 60-70°C, and then high-pressure atomization and drying to obtain polyvinyl alcohol antibacterial gel particles dispersed with antibacterial agents;

(4) According to parts by weight, combine 3-5 parts of polyvinyl alcohol antibacterial granules, 0.05-0.1 parts of antibacterial agent, 10-15 parts of cocamidopropyl betaine, 0.2-0.5 parts of sodium chloride, 2-3 parts of poly Glycerin-10, 0.5-1.5 parts of citric acid, 0.2-1 part of esterification agent, 0.1-0.2 part of anti-hardening agent, and 30-35 parts of deionized water are dispersed and evenly filled to obtain a sustained-release and lasting antibacterial hand sanitizer.
The method for preparing a sustained-release and durable antibacterial hand sanitizer according to claim 1, wherein the polyvinyl alcohol, glycerin, and water in step (1) are mixed uniformly in a mass ratio of 50:15:100-200 Sealed and placed.
The method for preparing a sustained-release and long-lasting antibacterial hand sanitizer according to claim 1, wherein the polyvinyl alcohol in step (1) is 1788 polyvinyl alcohol.
The preparation method of a sustained-release and long-lasting antibacterial hand sanitizer according to claim 1, characterized in that the materials, organic acid, ammonium persulfate, and glutaraldehyde aged in step (2) are in a mass ratio of 100:1 2:0.1-0.3:1-3 mixed; the organic acid is acetic acid.
The method for preparing a sustained-release and durable bacteriostatic hand sanitizer according to claim 1, wherein the cross-linking reaction in step (2) controls the cross-linking time within 1-2 hours.
The method for preparing a sustained-release and durable antibacterial hand sanitizer according to claim 1, characterized in that in step (3), the antibacterial agent and the cross-linked polyvinyl alcohol liquid are dispersed in a mass ratio of 5:100.
The method for preparing a sustained-release and durable bacteriostatic hand sanitizer according to claim 1, wherein the antibacterial agent in step (3) is 2,4,4'-trichloro-2'-hydroxydiphenyl At least one of ether, p-chloro-m-xylenol, and hexamidine diisethionate.
The method for preparing a sustained-release and durable antibacterial hand sanitizer according to claim 1, characterized in that: in step (3), high-pressure atomization is used for drying, the pressure of the atomizing gun is controlled at 1.2-1.5MPa, and the gun caliber is controlled At 0.5-1mm, the drying temperature is controlled at 70-80℃.
The preparation method of a sustained-release and durable antibacterial hand sanitizer according to claim 1, wherein the antibacterial agent in step (4) is 2,4,4'-trichloro-2'-hydroxydiphenyl At least one of ether, p-chloro-m-xylenol, and hexamidine diisethionate; the esterifying agent is selected from isopropyl myristate, glycerol coco-based polyethylene glycol ester, and octyl At least one of hydroxystearate; the anti-hardening agent is EDTA-2Na.
A sustained-release and durable antibacterial hand sanitizer prepared by the method according to any one of claims 1-9 is characterized by containing polyvinyl alcohol antibacterial colloidal particles.