WO2023115446A1

WO2023115446A1 - Cleaning agent, and preparation method therefor and use thereof

Info

Publication number: WO2023115446A1
Application number: PCT/CN2021/140764
Authority: WO
Inventors: 刘峰
Original assignee: 泰波亚太有限公司; 气净达国际有限公司; 刘峰
Priority date: 2021-12-23
Filing date: 2021-12-23
Publication date: 2023-06-29
Also published as: CN118265768A

Abstract

A cleaning agent, comprising: a silver superatomic antimicrobial sol, a quaternary ammonium salt, a fat-soluble surfactant and water, wherein the silver superatomic antimicrobial sol comprises a carrier and silver superatoms doped in the carrier, the carrier being modified or unmodified titanium dioxide, the scale of the size of the silver superatoms being 100-3000 pm, and the mass concentration of the silver superatoms in the cleaning agent being 1-5 ppm.

Description

Detergent and its preparation method and application

technical field

The present application relates to the technical field of cleaning agents, and more specifically relates to a cleaning agent and its preparation method and application.

Background technique

The statements herein merely provide background information related to the present application and may not necessarily constitute prior art.

With the development of society and the improvement of material level, people's cleaning requirements in daily life are no longer limited to the removal of stains visible to the naked eye, but also the ability to disinfect bacteria and viruses. At present, many cleaning products on the market, such as antibacterial soap, antibacterial lotion, antibacterial gel, etc., use silver ions or nano-silver particles as additives to make cleaning products have a certain sterilization and disinfection function. However, in the traditional technology, to achieve a qualified sterilization and disinfection capability, the amount of silver ions added is usually 5 ppm to 20 ppm, and the amount of silver nanoparticles added is as high as 20 ppm to 90 ppm. A high amount of addition means toxicity to the environment and various side effects that may be caused, especially silver ions, which have poor thermal stability and high mobility. pollution; at the same time, migration also means that the sterilization and disinfection ability of the product is greatly weakened.

Contents of the invention

According to various embodiments of the present application, a cleaning agent and its preparation method and application are provided.

According to one aspect of the present application, a cleaning agent is provided, comprising the following components: silver superatom antibacterial sol, quaternary ammonium salt, fat-soluble surfactant and water;

The silver superatom antibacterial sol includes a carrier and silver superatoms doped on the carrier, the carrier is titanium dioxide, the silver superatoms have a scale of 100pm to 3000pm, and the silver superatoms in the cleaning agent The mass concentration is 1ppm～5ppm.

According to another aspect of the present application, a preparation method of a cleaning agent is provided, comprising the following steps:

The material preparation is carried out according to the components in the aforementioned cleaning agent, and the components are physically mixed.

According to still another aspect of the present application, there is provided an application of the aforementioned cleaning agent in cleaning floors, walls, windows or desktops.

The details of one or more implementations of the application are set forth in the description below. Other features, objects and advantages of the application will be apparent from the description and claims.

Detailed ways

In order to make the purpose, technical solution and advantages of the present application clearer, the present application will be further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application, and are not intended to limit the present application.

In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the application, "multiple" means at least two, such as two, three, etc., unless otherwise specifically defined. In the description of the present application, "several" means at least one, such as one, two, etc., unless otherwise specifically defined.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this application belongs. The terms used herein in the specification of the application are only for the purpose of describing specific embodiments, and are not intended to limit the application. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In this application, the technical features described in open form include closed technical solutions consisting of the listed features, and open technical solutions including the listed features.

In this application, when referring to a numerical range, unless otherwise specified, the above numerical range is considered continuous, and includes the minimum and maximum values of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum of the range is included. Furthermore, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.

The percentage concentration involved in this application, unless otherwise specified, refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the component is added.

The temperature parameters in this application, unless otherwise specified, are allowed to be treated at a constant temperature, and also allowed to be treated within a certain temperature range. The isothermal treatment allows the temperature to fluctuate within the precision of the instrument control.

One aspect of the present application provides a cleaning agent, comprising the following components: silver superatom antibacterial sol, quaternary ammonium salt, fat-soluble surfactant and water;

The silver superatom antibacterial sol includes a carrier and a silver superatom doped on the carrier. The carrier is modified or unmodified titanium dioxide. The scale of the silver superatom is 100pm-3000pm, and the mass concentration of the silver superatom in the cleaning agent is 1ppm. ~5ppm.

This application uses the antibacterial sol containing silver superatoms with a scale of 100pm to 3000pm to compound with quaternary ammonium salts and fat-soluble surfactants to provide a cleaning agent with a silver superatom content as low as 1ppm to 5ppm. 5ppm-20ppm silver ion cleaner or cleaning product, or 20ppm-90ppm nano-silver particle cleaner or cleaning product, the cleaner of this application has low metal concentration, fast and long-lasting sterilization and disinfection ability, and can be applied or sprayed on the surface to be cleaned After the surface, a layer of inorganic mineral film can be formed. The metal components in the inorganic mineral film are not easy to migrate, which greatly reduces the pollution to the environment and the potential side effects on the human body.

Please refer to PCT/CN2020/103148 for the relevant content of the silver superatom antibacterial sol used in this application, and its entire content is now incorporated into this application, as long as it does not contradict this application.

"Modified or unmodified titanium dioxide" means that titanium dioxide can be modified with modifiers to further improve performance. The modifying agent can be selected from any modifying agent available in the art, for example, silicon-based substances can be used to modify the surface of the carrier, improve the surface adhesion of the carrier, optimize the size of the antibacterial agent and increase the particle size of the product. Uniformity; can also be selected from nitrogen-containing substances to make nitrogen interstitial doped titanium dioxide, nitrogen interstitial doping can improve the efficiency of generating electron-hole pairs after titanium dioxide is activated by light, and photogenerated holes can be injected into silver superatoms to form In-situ transient high-valent silver ions for further performance enhancement. Among them, "silicon-based substances" refer to silicon-containing substances acceptable in the art for surface modification of supports, including but not limited to: silicon oxide and substances that can be hydrolyzed into silicon oxide such as alkoxysilane; further, Selected from tetramethoxysilane, tetraethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxy One or more of silane and trimethoxysilane. Nitrogen-containing substances can be selected from one or more of ammonia water, triethylamine and ammonium salts.

"Superatom" refers to an atomic cluster composed of more than 2 atoms, a critical structure between nanoparticles and a single atom. Superatoms are not ions and have their unique properties. Compared with ions or complexes containing ions substances, the mobility is lower, and it is difficult to enter the environment, and because the superatoms of the antibacterial sol are doped in the carrier, the superatoms are fixed on the carrier with a larger size, so they will not enter the skin barrier, while the superatoms doped on the surface Atoms (clusters) can provide extremely high activity, so that the antibacterial sol can take into account safety and high performance, and can effectively avoid environmental pollution caused by metal elements entering the natural environment. Moreover, the service life of the antibacterial sol can also be effectively extended, and it has a longer-acting antibacterial function.

Furthermore, the above-mentioned superatoms have a stronger nano-size effect. Just from the specific surface area, the theoretical equivalent specific surface area of 2nm nano-silver is 286m ² /g, while the equivalent specific surface area of 15nm nano-silver on the market is 38m ² /g, which makes a huge difference in performance.

In this application, "dimension" refers to the particle size of superatoms. Further, the scale of superatoms is 100pm-2500pm; further, the scale of superatoms is 100pm-2300pm; further, the scale of superatoms is 100pm-2200pm; further, the scale of superatoms is 100pm-2100pm; further , the scale of superatoms is 100pm-2000pm; further, the scale of superatoms is less than 2000pm and greater than or equal to 100pm; further, the scale of superatoms is 100pm-1500pm; further, the scale of superatoms is 100pm-1200pm; Further, the scale of superatoms is 100pm～1000pm; further, the scale of superatoms is less than 1000pm and greater than or equal to 100pm; further, the scale of superatoms is less than or equal to 1000pm and greater than 100pm; further, the scale of superatoms is The scale is less than 1000pm and greater than 100pm; further, the scale of superatoms is 200pm-800pm; further, the scale of superatoms is 300pm-500pm.

Optionally, the mass concentration of silver superatoms in the cleaning agent can be, for example, any one of the following values or the interval formed by any two values: 1ppm, 1.2ppm, 1.4ppm, 1.6ppm, 1.8ppm, 2ppm, 2.2ppm, 2.4 ppm, 2.6ppm, 2.8ppm, 3ppm, 3.2ppm, 3.4ppm, 3.6ppm, 3.8ppm, 4ppm, 4.2ppm, 4.4ppm, 4.6ppm, 4.8ppm, 5ppm.

In some embodiments, the water is deionized water.

In some embodiments, by mass percentage, the proportion of each component in the cleaning agent is as follows:

Silver superatom antibacterial sol 1% to 5%;

Quaternary ammonium salt 0.002%～0.01%;

Fat-soluble surfactant 0.05% to 0.5%.

Optionally, the mass percent of the silver superatom antibacterial sol in the cleaning agent can be, for example, any one of the following values or the interval formed by any two values: 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% , 4.5%, 5%.

Optionally, the mass percentage of the quaternary ammonium salt in the cleaning agent can be, for example, any one of the following values or the interval formed by any two values: 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.01%.

Optionally, the mass percentage of the fat-soluble surfactant in the detergent can be, for example, any one of the following values or the interval formed by any two values: 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35% %, 0.4%, 0.45%, 0.5%.

In some embodiments, the cleaning agent only contains the following components: silver superatom antibacterial sol, quaternary ammonium salt, fat-soluble surfactant and water. Now, by mass percentage, the proportion of each component in the cleaning agent is as follows:

In some embodiments, the quaternary ammonium salt is a single-chain quaternary ammonium salt and/or a double-chain quaternary ammonium salt. Further, the use of a mixture of single-chain quaternary ammonium salts and double-chain quaternary ammonium salts can further enhance the ability of the cleaning agent to quickly kill bacteria and fungi.

In some embodiments, the single-chain quaternary ammonium salt is one or more of benzalkonium chloride, benzalkonium bromide, benzethonium chloride and cetylpyridine chloride, and the double-chain quaternary ammonium salt is didecyldimethyl Ammonium chloride, didecyldimethylammonium bromide, dioctyldimethylammonium chloride, dioctyldimethylammonium bromide, didecyldimethylammonium chloride and didecyldimethylammonium One or more of ammonium bromide. The above-mentioned single-chain quaternary ammonium salt or double-chain quaternary ammonium salt has good effect and high safety, and has more usage scenarios.

In some embodiments, in the mixture of the single-chain quaternary ammonium salt and the double-chain quaternary ammonium salt, the mass ratio of the single-chain quaternary ammonium salt to the double-chain quaternary ammonium salt is 1:(0.4˜2.4). Controlling the mass ratio of the single-chain quaternary ammonium salt to the double-chain quaternary ammonium salt within a certain range, the two can synergize and achieve better bactericidal effect. Optionally, the mass ratio of the single-chain quaternary ammonium salt to the double-chain quaternary ammonium salt can be, for example, 1:(0.4～2.2), 1:(0.4～2), 1:(0.4～1.8), 1:(0.4～ 1.6), 1:(0.4～1.4), 1:(0.4～1.2), 1:(0.4～1), 1:(0.4～0.8), 1:(0.4～0.6), or 1: (0.6～2.4), 1:(0.8～2.4), 1:(1～2.4), 1:(1.2～2.4), 1:(1.4～2.4), 1:(1.8～2.4), 1:(2 ～2.4), 1:(2.2～2.4), or 1:(0.6～2.2), 1:(0.8～2), 1:(1～1.8), 1:(1.2～1.6), 1 :1.4.

In some embodiments, the fat-soluble surfactant is ethoxylated-C12-14-secondary alcohol, poly(oxy-1,2-ethylene glycol), α-[3,5-dimethyl-1- (2-methylpropyl)hexyl]-ω-hydroxypoly(oxo-1,2-ethylenediyl) and polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-benzene One or more of base ethers). Adding the above fat-soluble surfactants to the detergent can make the detergent have a rapid inactivation effect on enveloped viruses.

In some embodiments, the carrier has a hydrodynamic diameter of less than 20 nm. Optionally, the hydrodynamic diameter of the carrier may be, for example, less than 15 nm, further, less than 10 nm, and further, less than 5 nm.

In some embodiments, the support has a crystallographic diameter of less than 10 nm. Optionally, the crystallographic diameter of the carrier may be, for example, less than 8 nm, further, less than 6 nm, and further, less than 4 nm.

The hydrodynamic diameter and crystallographic diameter of the carrier are directly related to the dispersion effect of the carrier in the sol and detergent. Only with an excellent dispersion effect can it still have high antibacterial properties at a very low silver superatom concentration .

In some embodiments, the mass concentration of the carrier in the detergent is 350 ppm˜500 ppm. Optionally, the mass concentration of the carrier in the detergent can be, for example, any one of the following values or an interval formed by any two values: 350 ppm, 380 ppm, 410 ppm, 440 ppm, 470 ppm, 500 ppm. The carrier has an appropriate mass concentration in the detergent, which can further improve the dispersion effect and have a better use experience.

In some embodiments, the support is modified or unmodified anatase titania nanocrystals. Anatase titanium dioxide nanocrystals are used as a carrier, using the characteristics of photoexcited electron-hole separation, hole injection can excite silver atoms in superatom clusters to become in-situ transient high-valent silver ions, which have stronger antibacterial and antiviral properties. And it will not produce silver ions that are easily soluble in water and have a high risk of entering the environment and the human body.

In some embodiments, the support is modified or is a modified nitrogen-interstitially doped titania. The carrier is nitrogen gap doped titanium oxide to form Ag/N/TiO ₂ composite doped antibacterial agent, nitrogen gap doping improves the efficiency of TiO ₂ to generate electron-hole pairs after photoactivation, photogenerated holes can be injected into Ag In situ transient hypervalent silver ions formed by superatoms lead to further performance enhancements.

In some embodiments, the XPS spectrum of the silver superatom antibacterial sol has peaks at 368.000±0.200eV and 374.000±0.200eV.

In some embodiments, the preparation method of silver superatom antibacterial sol comprises the following steps:

S100. mixing the silver salt, the carrier precursor and water to obtain a mixed solution;

Wherein, the carrier precursor is a titanium-containing inorganic acid or a titanium-containing inorganic acid complex.

In some embodiments, the silver salt is selected from one or more of silver acetate, silver nitrate or silver sulfate.

In some embodiments, the carrier precursor is selected from: one or more of peroxotitanic acid, orthotitanic acid, peroxotitanic acid complexes, and orthotitanic acid complexes; further, the carrier precursor includes at least There is one of peroxytitanic acid complex and orthotitanic acid complex. A sol with better physical properties can be formed by introducing a complexing agent into the mixed solution.

Among them, the titanium-containing inorganic acid complex can be prepared from commercially available raw materials, or can be prepared by an existing method, specifically by mixing the titanium-containing inorganic acid, complexing agent and solvent, stirring and reacting for a predetermined time, that is, . It should be noted that the prepared titanium-containing inorganic acid complex can be separated for the preparation of antibacterial sol, or the reaction solution can be directly used to prepare antibacterial sol without separation. In addition, it can also be used in the preparation of titanium-containing Preparation of antimicrobial sol mixed solution at the same time as inorganic acid complex, that is, mixing silver salt, titanium-containing inorganic acid, complexing agent and water to prepare mixed solution, should be understood as all within the protection scope of the present application.

Further, the complexing agent is preferably one or more of tartaric acid and citric acid. In the above mixed liquid system, the use of the complexing agent can promote the formation of an antibacterial sol with excellent physical properties, so as to facilitate subsequent processing and application.

In some embodiments, the silver salt, the carrier precursor and water are mixed, and the step of obtaining the mixed solution comprises the following steps:

S110. mixing the silver salt and water to obtain a first solution;

Further, mix at a temperature of 25°C-35°C to fully dissolve the silver salt; furthermore, it is preferable to heat the water to 25°C-35°C first, and then add the silver salt;

S120. mixing the carrier precursor with water to obtain a second solution;

Further, mixing at a temperature of 15°C-25°C to fully dissolve the carrier precursor; furthermore, preferably heating the water to 15°C-25°C first, and then adding the carrier precursor;

Understandably, there is no sequence between step S110 and step S120, step S110 can be performed first and then step S120 can be performed, or step S110 can be performed first and then step S120 can be performed.

Further, the concentration of the carrier precursor is 1%-30%.

S130. Drop the first solution into the second solution at a rate of 100 mL/min-200 mL/min, and stir to obtain a mixed solution.

By dropping the first solution into the second solution at a fixed speed, the silver ions can be uniformly dispersed in the solution, avoiding the coating of titanium-containing inorganic acid or titanium-containing inorganic acid complex, improving the uniformity of the mixed solution, and effectively conducive to the subsequent steps.

In some embodiments, step S100 also includes the step of adding silicon-based substances; further, the silicon-based substances are tetramethoxysilane, tetraethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, One or more of γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane or trimethoxysilane to modify the surface of the carrier to further improve Surface adhesion of the carrier.

In some embodiments, step S100 further includes the step of adding ammonia water, triethylamine or ammonium salt. Further, the amount of ammonia water or ammonium salt added is a small amount, and further, the amount of ammonia water or ammonium salt is 4%-6% of the oxygen element content in the carrier, so as to facilitate the preparation of nitrogen-doped antibacterial agent.

S200. Use the following method to process the mixed solution to prepare silver superatom antibacterial sol:

Raise the temperature, raise the temperature of the mixture to 120°C-250°C and the pressure to 15bar-60bar within 200s;

Keep warm, reduce the pressure to 10bar~40bar, and control the temperature at 130℃~200℃, keep warm for 270s~330s;

Cool down, reduce the temperature to 5°C~50°C within 65s;

By adopting the critical hydrothermal heating process of rapid heating-avalanche cooling, superatoms with a scale between nanoparticles and ions can be generated, and the carrier can be rapidly crystallized, so that the carrier crystal can be maintained with strong uniformity and is not easy to agglomerate , small size, and thus make the obtained antibacterial sol have strong antibacterial property and long service life. Hydrothermal can form crystals such as titanium oxide, and can also reduce the precursor of silver to simple substance. However, the traditional hydrothermal process is long, resulting in a wide range of crystallized particle sizes and large particles. The inventor found through research that the high temperature point is the key to complete the crystallization, and the slower heating process will cause the particles to become larger. Therefore, the method of rapid heating and cooling can maximize the control on the basis of completing the crystallization and superatom synthesis. For the size of superatoms, if traditional methods are used, 1) it is difficult to obtain quantum-sized nano-titanium oxide carriers, and agglomeration and precipitation will occur; 2) superatoms will also grow into nano-metal particles without special properties; 3) The superatoms will be separated from the titanium oxide and precipitated, and the antibacterial agent in which the superatoms are doped in the carrier cannot be formed.

In addition, the above-mentioned critical hydrothermal heating process of rapid heating-avalanche cooling takes less time, and the whole process does not exceed 10 minutes, which can greatly improve production efficiency. Compared with the traditional high-temperature calcination method, the temperature is lower and can avoid high temperature Destroying the activity of superatoms can also prevent superatoms from condensing into nanoparticles, prevent quantum dot crystals from growing into nanoparticles with aggregates, and reduce energy consumption at the same time, which is suitable for industrial production applications.

Existing instruments and equipment can be used for heating, heat preservation and cooling, and there is no special limitation here.

Further, in the heating step, the temperature and pressure are raised to the target temperature in 200s; further, the temperature and pressure are raised to the target temperature in 195s; further, the temperature and pressure are raised to the target temperature in 190s; further, the temperature and pressure are raised to the target temperature in 188s Temperature; further, 185s increases the temperature and pressure to the target temperature; further, 180s increases the temperature and pressure to the target temperature; further, 170s increases the temperature and pressure to the target temperature;

Further, in the heating step, the target temperature is 130°C-220°C; further, the target temperature is 140°C-210°C; further, the target temperature is 145°C-200°C; further, the target temperature is 150°C ℃～180℃; further, the target temperature is 155℃～175℃; further, the target temperature is 157℃～170℃; further, the target temperature is 155℃～168℃; further, the target temperature is 156°C to 167°C; further, the target temperature is 157°C to 166°C; further, the target temperature is 158°C to 165°C; further, the target temperature is 159°C to 164°C; further, The target temperature is 162°C;

Further, in the heating step, the target pressure is 12bar-60bar; further, the target pressure is 15bar-50bar; further, the target pressure is 15bar-40bar; further, the target pressure is 15bar-30bar; further , the target pressure is 16bar-29bar; further, the target pressure is 17bar-25bar; further, the target pressure is 18bar-24bar; further, the target pressure is 19bar-22bar;

Further, in the heating step, the temperature of the mixed solution is raised to 130°C-220°C within 200s, and the pressure is raised to 12bar-50bar; further, in the heating step, the temperature of the mixed solution is raised to 135°C within 200s ℃～210℃, the pressure rises to 15bar～40bar; further, in the heating step, the temperature of the mixed solution is raised to 150℃～200℃ within 200s, and the pressure is raised to 18bar～22bar; further, within 180s, the The temperature of the mixed liquid is raised to 150°C-200°C, and the pressure is raised to 18bar-22bar; further, the temperature of the mixed liquid is raised to 150°C-180°C, and the pressure is raised to 18bar-22bar within 180s.

Further, in the heating step, the heating rate is 50°C/min to 51°C/min; further, the heating rate is 50.1°C/min to 50.9°C/min; further, the heating rate is 50.2°C/min min～50.8℃/min; further, the heating rate is 50.3℃/min～50.7℃/min;

Further, in the heat preservation step, the pressure is 10bar-40bar; further, the pressure is 10bar-30bar; further, the target pressure is 10bar-20bar; further, the target pressure is 12bar-18bar; further, the target The pressure is 13bar~17bar; further, the target pressure is 14bar~16bar;

Further, in the heat preservation step, the temperature is 150°C-180°C; further, the temperature is 155°C-170°C; further, the temperature is 155°C-166°C; further, the temperature is 156°C-165°C ; Further, the temperature is 157°C to 164°C; Further, the temperature is 158°C to 162°C; Further, the temperature is 160°C;

Further, in the heat preservation step, the heat preservation time is 270s-330s; further, the heat preservation time is 280s-320s; further, the heat preservation time is 290s-310s; further, the heat preservation time is 292s-308s;

Further, in the heat preservation step, reduce the pressure to 10bar to 40bar, and control the temperature at 150°C to 180°C, and hold the heat for 270s to 330s; further, in the heat preservation step, reduce the pressure to 15bar to 30bar, and control the temperature At 150°C-170°C, keep warm for 270s-330s. Further, in the heat preservation step, the pressure is reduced to 15 bar to 21 bar, the temperature is controlled at 150°C to 160°C, and the temperature is kept for 300s to 320s.

Further, in the cooling step, reduce the temperature to 5°C-50°C within 65s; further, in the cooling step, reduce the temperature to 5°C-50°C within 60s; further, in the cooling step, reduce the temperature to 5°C-50°C within 60s; Lower the temperature to 5°C to 40°C. Further, in the cooling step, the temperature is lowered to 10°C-30°C within 60s.

Further, in the cooling step, the cooling rate °C is 120 °C/min～140 °C/min; further, the cooling rate is 122 °C/min～138 °C/min; further, the cooling rate is 123 °C/min～ 137°C/min; further, the cooling rate is 124°C/min～136°C/min; further, the cooling rate is 125°C/min～135°C/min;

Furthermore, in the heating step, the heating rate is 50°C/min-51°C/min; in the holding step, the pressure is 15bar-21bar, the temperature is 154°C-160°C, and the time is 300s-312s; in the cooling step, The cooling rate is 125°C/min～135°C/min.

The preparation method of the above-mentioned antibacterial sol can form a monodisperse antibacterial sol through the rapid crystallization technology directly synthesized in the liquid, so that the surface of the antibacterial sol is maintained stable by the electric double layer without surfactant. After the surface of the object, the evaporation of water will cause the double layer to disappear, and the first contact will occur between the particles. Because the carrier nanoparticles are <10nm, they have a strong surface effect, and there are a large number of active-broken chemical bonds on the surface, so the particles will Chemical bridging occurs to form an inorganic mineral film, and the entire process does not require film-forming substances, so it will not wrap active substances and affect performance.

Another aspect of the present application provides a preparation method of a cleaning agent, comprising the following steps:

The components in the cleaning agent according to any of the foregoing embodiments are prepared, and the components are physically mixed.

Another aspect of the present application also provides the application of the cleaning agent of any of the aforementioned embodiments in the cleaning of the ground, wall, window or desktop, that is, it provides the use of the cleaning agent of any of the aforementioned embodiments to clean the ground, wall, etc. methods for cleaning surfaces, windows or tabletops.

In some embodiments, the following steps are included: applying or spraying the cleaning agent to the ground, wall, window or desktop; or after diluting the cleaning agent with water, applying or spraying the diluted solution to the ground, wall, window surface or desktop. For example, when used to clean the floor, the mop can be immersed in diluted or undiluted detergent, and then mop the floor. While removing the dirt visible to the naked eye, it can also quickly disinfect bacteria on the floor with the detergent attached. Virus and long-lasting antibacterial ability.

In some embodiments, the cleaning agent can be added to the automatic cleaning robot, and the robot will apply the cleaning agent on the floor, wall, window or tabletop for cleaning and disinfection.

In some embodiments, the amount of diluted water is 1-5 times the mass of the detergent.

Specific examples are listed below to illustrate the present application.

Preparation of silver superatom antibacterial sol:

Preparation Example 1

(1) Take 2g of silver acetate and add it to 500ml of water for stirring, heat to 40°C and stir for about 1 hour to fully dissolve, then cool down to room temperature, and obtain the first solution after filtering;

(2) Take 5 kg (2% wt) of peroxotitanic acid aqueous solution, add water and dilute to 10 kg (1% wt) to obtain the second solution;

(3) At a rate of 150ml/min, drop the above-mentioned first solution into the second solution and fully stir to obtain a mixed solution;

(4) The above-mentioned mixed solution is processed in the following manner by using a nano-supercritical segmented program-controlled hydrothermal reactor with an avalanche refrigeration module (commercial model Nano Hydrosynthesis SH5UC): the pressure is increased to 20bar (heating rate 50.6°C/min), The maximum temperature is 162°C. After reaching the maximum temperature, the pressure is reduced to 15bar and the temperature is maintained at 160°C for 300 seconds. After that, pressurize 12bar and enter the avalanche refrigeration program to reduce the solution temperature to 30°C within 60 seconds (the program cooling rate is 130°C/ min) to obtain the desired nano-titanium dioxide-doped silver superatom sol.

Preparation example 2

(4) Take 10 g of tetramethoxysilane and slowly drop it into the above mixture and stir for 30 minutes.

(5) The above-mentioned mixed solution is treated in the following manner by using a nano-supercritical stage-controlled hydrothermal reactor with an avalanche refrigeration module (commercial model Nano Hydrosynthesis SH5UC): the pressure is increased to 20bar (heating rate 50.6°C/min), The highest temperature is 162°C, reaching the highest temperature after about 192 seconds, then the pressure is reduced to 15bar and the temperature is maintained at 160°C for 300 seconds, and then the pressure is increased to 12bar to enter the avalanche refrigeration program, and the solution temperature is reduced to 30°C within 60 seconds (programmed cooling rate of 130° C./min) to obtain the desired silicon-surface-modified nano-titanium dioxide-doped silver superatom sol.

Preparation of detergent:

Example 1

Take 250 g of the sol obtained in the above Preparation Example 1, 4238 g of deionized water, 500 g of benzalkonium chloride (0.1%) aqueous solution, polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl Ether 12g, after fully shearing, stirring and mixing, 5kg of cleaning agent product was obtained.

Apply the above-mentioned cleaning agent product on the glass sheet after it dries and leave it for more than 6 months, then rinse the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of the antibacterial activity against Staphylococcus aureus on the surface is 5.1, and the antibacterial activity of Staphylococcus aureus is 5.1. The number of cocci decreased by 10 ^{to 5.1} times, and the number of bacteria killed was >99.999%, which proved that the product had strong long-term antibacterial activity.

According to EN14476, the above-mentioned cleaning agent product is tested for the effect on MVA (varicella virus) within 60 minutes, its inactivation logarithm value is 4.62, the quantity of MVA is reduced by ^104.62 times, and the quantity of killing virus>99.99%, proves that this product has a strong and rapid Virus-killing activity.

According to EN1276, the above-mentioned detergent product was tested for its effect on Staphylococcus aureus within 60 minutes. The inactivation logarithm value was 4.71, the number of Staphylococcus aureus was reduced by ^10-4.71 times, and the sterilizing quantity was >99.99%, which proved that the product had a strong antibacterial effect. Rapid sterilizing activity.

Example 2

Get the sol 250g that obtains in the above-mentioned preparation example 2, deionized water 4238g, didecyl dimethyl ammonium chloride (0.1%) aqueous solution 300g, benzalkonium chloride (0.1%) aqueous solution 200g, polyethylene glycol to (1 , 12g of 1,3,3-tetramethylbutyl)-phenyl ether, and fully sheared and stirred to obtain 5kg of cleaning agent products.

Apply the above-mentioned cleaner product on the glass sheet after it dries and leave it for more than 6 months, then rinse the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of the antibacterial activity against Staphylococcus aureus on the surface is 5.7, and the antibacterial activity of Staphylococcus aureus is 5.7. The number of cocci decreased by 10 ^{to 5.7} times, and the number of bacteria killed was >99.999%, which proved that the product had strong long-term antibacterial activity.

According to OCSPP810.2200, the above-mentioned cleaning agent product was tested for its effect on the new coronavirus within 10 minutes. The inactivation logarithm value was >4, the number of new coronaviruses was reduced by more than ¹⁰⁴ times, and the number of virus kills was >99.99%, which proved that the product had Strong and rapid antiviral activity.

According to EN14476, the above-mentioned cleaning agent product was tested for its effect on the new coronavirus within 10 minutes. The inactivation logarithm value was >3, the number of new coronaviruses was reduced by more than ¹⁰³ times, and the number of virus kills was >99.9%, which proved that the product has strong and fast Virus-killing activity.

According to EN1276, the above detergent product was tested for its effect on Escherichia coli within 10 minutes. The inactivation logarithm value was 5.05, the number of Staphylococcus aureus was reduced by ^105.05 times, and the bactericidal quantity was >99.999%, which proved that this product has a strong rapid killing effect bacterial activity.

Example 3

Get the sol 50g that obtains in the above-mentioned preparation example 1, deionized water 4438g, didecyl dimethyl ammonium chloride (0.1%) aqueous solution 300g, benzalkonium chloride (0.1%) aqueous solution 200g, polyethylene glycol to (1 , 12g of 1,3,3-tetramethylbutyl)-phenyl ether, and fully sheared and stirred to obtain 5kg of cleaning agent products.

Apply the above-mentioned cleaning agent product on the glass sheet after drying and leave it for more than 3 months, then rinse the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of the antibacterial activity against Staphylococcus aureus on the surface is 4.5, and the golden yellow grape The number of cocci decreased by 10 ^{to 4.5} times, and the number of bacteria killed was >99.99%, which proved that the product had strong long-term antibacterial activity.

According to EN14476, the above-mentioned cleaning agent product was tested for its effect on TGEV coronavirus within 60 minutes. The inactivation logarithm value was >4.1, the number of TGEV coronavirus was reduced by more than ^104.1 times, and the number of killed viruses was >99.99%, which proved that the product had Strong and rapid antiviral activity.

According to EN1276, the above-mentioned detergent product was tested for its effect on Staphylococcus aureus within 10 minutes. The inactivation logarithm value was 5.18, the number of Staphylococcus aureus was reduced by ^10-5.18 times, and the number of sterilization was >99.999%, which proved that the product had a strong Rapid sterilizing activity.

Example 4

Get 250g of the sol obtained in the above Preparation Example 2, 4438g of deionized water, 500g of didecyldimethylammonium chloride (0.1%) aqueous solution, polyethylene glycol p-(1,1,3,3-tetramethylbutyl base)-phenyl ether 12g, obtain cleaning product 5kg after fully shearing, stirring and mixing.

Apply the above-mentioned cleaning agent product on the glass sheet and leave it for more than 6 months after drying, then wash the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of antibacterial activity against Staphylococcus aureus on the surface is 5.6, and the antibacterial activity of Staphylococcus aureus on the surface is 5.6. The number of cocci decreased by 10 ^{to 5.6} times, and the number of bacteria killed was >99.999%, which proved that the product had strong long-term antibacterial activity.

Apply the above-mentioned cleaning agent product on the stainless steel sheet after drying, then wipe the surface with alcohol for more than 100 times, and then conduct an anti-virus test. According to the ASTM-E1053 standard, the anti-viral activity against human coronavirus 229E on the surface is >99.9%, which proves that the The product has strong long-term antiviral activity.

According to EN14476, the above-mentioned cleaning agent product was tested for the effect on MVA (varicella virus) within 60 minutes, its inactivation logarithm value>4.99, the number of MVA dropped by more than ^104.99 times, and the number of killed virus>99.99%, which proves that the product has Strong and rapid antiviral activity.

According to EN1276, the above-mentioned detergent product was tested for its effect on Staphylococcus aureus within 10 minutes. The inactivation logarithm value was 5.17, the number of Staphylococcus aureus was reduced by ^10-5.17 times, and the sterilizing quantity was >99.999%, which proved that the product had a strong Rapid sterilizing activity.

According to EN1650, the above cleaning agent product was tested for its effect on Candida albicans within 60 minutes. The logarithmic value of its inactivation was 4.33, the number of Candida albicans decreased by ^10-4.33 times, and the sterilizing quantity was >99.99%, which proved that the product had a strong rapid killing effect. fungal activity.

Example 5

Get 250g of the sol obtained in the above Preparation Example 2, 4238g of deionized water, 300g of didecyldimethylammonium chloride (0.1%) aqueous solution, 200g of benzalkonium chloride (0.1%) aqueous solution, poly(oxygen-1,2 -ethylene glycol), α-[3,5-dimethyl-1-(2-methylpropyl)60828-78-6hexyl]-ω-hydroxypoly(oxo-1,2-ethylenediyl ) 11.5g, polyoxyethylene 0.5g, and after fully shearing, stirring and mixing, 5kg of detergent product was obtained.

Apply the above-mentioned cleaning agent product on the stainless steel sheet and dry it, then conduct an anti-virus test. According to the ISO21702 standard, the anti-virus activity against the new coronavirus on the surface is >99.9%, which proves that the product has strong long-term anti-virus activity.

According to EN14476, the above-mentioned detergent product was tested for its effect on BCV coronavirus within 120 minutes. The inactivation log value was >3.28, the number of MVA was reduced by more than ^103.28 times, and the number of virus killing was >99.9%, which proved that the product had strong and fast Virus-killing activity.

According to EN1276, the above-mentioned detergent product was tested for its effect on Staphylococcus aureus within 30 minutes. The inactivation logarithm value was 5.08, the number of Staphylococcus aureus was reduced by ^105.08 times, and the number of sterilization was >99.999%, which proved that the product had a strong Rapid sterilizing activity.

According to EN1650, the above-mentioned cleaning agent product was tested for its effect on Candida albicans within 30 minutes. The logarithmic value of inactivation was 4.11, the number of Staphylococcus aureus was reduced by ^10-4.11 times, and the bactericidal quantity was >99.99%, which proved that this product has a strong rapid fungicidal activity.

Comparative example 1

Take 250 g of the sol obtained in the above preparation example 1, 4750 g of deionized water, and fully shear and stir to obtain 5 kg of the cleaning agent product.

Apply the above-mentioned cleaning agent product on the glass sheet after drying and leave it for more than 6 months, then rinse the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of the antibacterial activity against Staphylococcus aureus on the surface is 4.1, and the antibacterial activity of Staphylococcus aureus is 4.1. The number of cocci decreased by 10 ^{to 4.1} times, and the number of bacteria killed was >99.99%, which proved that the product had strong long-term antibacterial activity.

According to EN14476, the above cleaning agent product is tested for the effect of MVA (varicella virus) within 10 minutes, its inactivation logarithm value is 0.61, the quantity of MVA is reduced by ^100.61 times, and the quantity of killing virus<90%, proves that this product does not have rapid Virus-killing activity.

According to EN1276, the above-mentioned cleaning agent product is tested for its effect on Staphylococcus aureus within 10 minutes. The inactivation logarithm value is <4, the number of Staphylococcus aureus is reduced by less than ¹⁰⁴ times, and the bactericidal quantity is <99.99%, which proves that the product does not have Rapid sterilizing activity.

Comparative example 2

Take 250g of the sol obtained in the above Preparation Example 1, 4250g of deionized water, 500g of benzalkonium chloride (0.1%) aqueous solution, and fully shear and stir to obtain 5kg of detergent product.

Apply the above-mentioned cleaning agent product on the glass sheet after drying and leave it for more than 6 months, then wash the surface with water and alcohol, and then conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of the antibacterial activity against Staphylococcus aureus on the surface is 3.1, and the golden yellow grape The number of cocci decreased by 10 ³ times, and the number of bacteria killed was >99.9%, which proved that the product had strong long-term antibacterial activity.

According to EN1276, the above-mentioned cleaning agent product is tested for its effect on Staphylococcus aureus within 30 minutes. The inactivation logarithm value is <4, the number of Staphylococcus aureus is reduced by less than ¹⁰⁴ times, and the bactericidal quantity is <99.99%, which proves that the product does not have Rapid sterilizing activity.

According to EN14476, the above-mentioned cleaning agent product is tested for the effect of MVA (varicella virus) within 60 minutes, its inactivation logarithm value is 1.13, the quantity of MVA is reduced by ^101.13 times, and the quantity of killing virus <99%, proves that this product does not have rapid Virus-killing activity.

Comparative example 3

Take 250g of the sol obtained in the above Preparation Example 1, 4738g of deionized water, 12g of polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether, fully shear and stir to obtain a clean Agent product 5kg.

Apply the above-mentioned cleaning agent product on the glass sheet and leave it for more than 6 months after drying, then wash the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of the antibacterial activity against Staphylococcus aureus on the surface is 5.2, and the golden yellow grape The number of cocci decreased by 10 ^{to 5.2} times, and the number of bacteria killed was >99.999%, which proved that the product had strong long-term antibacterial activity.

According to EN14476, the above-mentioned cleaning agent product is tested for the effect on MVA (varicella virus) within 60 minutes. The inactivation logarithm value is 4.15, the number of MVA is reduced by ^10-4.15 times, and the number of killing viruses>99.99%, which proves that this product has strong and rapid Virus-killing activity.

Comparative example 4

500 g of benzalkonium chloride (0.1%) aqueous solution and deionized water (4500 g) were fully sheared and mixed to obtain 5 kg of the product.

Apply the above product on the glass sheet and let it dry for more than 6 months, then rinse the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of the antibacterial activity against Staphylococcus aureus on the surface is 0.8, and the antibacterial activity of Staphylococcus aureus is 0.8. Quantity drops 10 ^0.8 times, and bactericidal quantity＜99%, proves that this product does not possess long-term antibacterial activity.

Comparative example 5

300g of didecyldimethylammonium chloride (0.1%) aqueous solution, 200g of benzalkonium chloride (0.1%) aqueous solution, and deionized water (4500g) were fully sheared and mixed to obtain 5kg of product.

Apply the above product on the glass sheet after it dries and leave it for more than 6 months, then wash the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of the antibacterial activity against Staphylococcus aureus on the surface is 0.9, and the antibacterial activity of Staphylococcus aureus is 0.9. Quantity drops 10 ^0.9 times, and bactericidal quantity＜99%, proves that this product does not possess long-term antibacterial activity.

Comparative example 6

Didecyldimethylammonium chloride (0.1%) aqueous solution 500g, deionized water (4500g) fully shear and mix to obtain product 5kg.

Apply the above product on the glass sheet after it dries and leave it for more than 6 months, then wash the surface with water and alcohol and conduct an antibacterial test. According to the ISO22196 standard test, the logarithm value of antibacterial activity against Staphylococcus aureus on the surface is 1.2, and the antibacterial activity of Staphylococcus aureus is 1.2. Quantity drops 10 ^1.2 times, and sterilizing quantity <99%, proves that this product does not possess long-term antibacterial activity.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present application, and the description thereof is relatively specific and detailed, but should not be construed as limiting the scope of the patent. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application should be determined by the appended claims.

Claims

A cleaning agent comprising the following components: silver superatom antibacterial sol, quaternary ammonium salt, fat-soluble surfactant and water;

The silver superatom antibacterial sol includes a carrier and silver superatoms doped on the carrier, the carrier is modified or unmodified titanium dioxide, the scale of the silver superatoms is 100pm to 3000pm, and the silver superatoms The mass concentration of atoms in the cleaning agent is 1ppm-5ppm.
The cleaning agent according to claim 1, wherein, in terms of mass percentage, the proportion of each component in the cleaning agent is as follows:

Silver superatom antibacterial sol 1% to 5%;

Quaternary ammonium salt 0.002%～0.01%;

Fat-soluble surfactant 0.05% to 0.5%.
The cleaning agent according to claim 1 or 2, wherein the quaternary ammonium salt is a single-chain quaternary ammonium salt and/or a double-chain quaternary ammonium salt.
Cleaning agent according to claim 3, it is characterized in that, described single-chain quaternary ammonium salt is one or more in benzalkonium chloride, benzalkonium bromide, benzethonium chloride and cetyl chloride, so The double-chain quaternary ammonium salt is didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium bromide, dioctyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, didecyl dimethyl ammonium bromide, One or more of dimethylammonium chloride and didecyldimethylammonium bromide.
The cleaning agent according to claim 3 or 4, wherein the quaternary ammonium salt is a mixture of a single-chain quaternary ammonium salt and a double-chain quaternary ammonium salt, wherein the single-chain quaternary ammonium salt and the double-chain quaternary ammonium salt The mass ratio of quaternary ammonium salt is 1:(0.4～2.4).
The cleaning agent according to any one of claims 1 to 5, wherein the fat-soluble surfactant is ethoxylated-C12-14-secondary alcohol, poly(oxygen-1,2-ethylene glycol) ), α-[3,5-dimethyl-1-(2-methylpropyl)hexyl]-ω-hydroxypoly(oxo-1,2-ethylenediyl) and polyethylene glycol for (1 , one or more of 1,3,3-tetramethylbutyl)-phenyl ether).
The cleaning agent according to any one of claims 1-6, characterized in that, the hydrodynamic diameter of the carrier is less than 20 nm.
The cleaning agent according to any one of claims 1-6, characterized in that, the crystallographic diameter of the carrier is less than 10 nm.
The cleaning agent according to any one of claims 1-8, characterized in that, the mass concentration of the carrier in the cleaning agent is 350ppm-500ppm.
The cleaning agent according to any one of claims 1 to 9, wherein the carrier is modified or unmodified anatase titanium dioxide nanocrystals.
The cleaning agent according to any one of claims 1-9, characterized in that the carrier is modified or unmodified nitrogen-interstitially doped titanium dioxide.
The cleaning agent according to any one of claims 1-11, characterized in that, the XPS spectrum of the silver superatom antibacterial sol has peaks at 368.000±0.200eV and 374.000±0.200eV.
The cleaning agent according to any one of claims 1 to 12, wherein the preparation method of the silver superatom antibacterial sol comprises the following steps:

Mixing the silver salt, the carrier precursor and water to obtain a mixed solution;

Adopt the following method to process described mixed solution, prepare described silver superatom antibacterial sol:

Raise the temperature, raise the temperature of the mixture to 120°C-250°C and the pressure to 15bar-60bar within 200s;

Keep warm, reduce the pressure to 10bar~40bar, and control the temperature at 130℃~200℃, keep warm for 270s~330s;

Cool down, reduce the temperature to 5°C~50°C within 65s;

Wherein, the carrier precursor is a titanium-containing inorganic acid or a titanium-containing inorganic acid complex.
The cleaning agent according to claim 13, characterized in that, in the heating step, the heating rate is 50°C/min-51°C/min; and/or

In the heat preservation step, the pressure is 15bar-21bar, the temperature is 154°C-160°C, and the time is 300s-312s; and/or

In the cooling step, the cooling rate is 125° C./min˜135° C./min.
Cleaning agent according to claim 13 or 14, it is characterized in that, described silver salt, carrier precursor and water are mixed, and the step of obtaining mixed solution comprises the following steps:

mixing silver salt and water to obtain a first solution;

mixing the carrier precursor with water to obtain a second solution;

Drop the first solution into the second solution at a rate of 100 mL/min-200 mL/min, and stir to obtain a mixed solution.
The cleaning agent according to any one of claims 13 to 15, characterized in that the step of mixing the silver salt, carrier precursor and water also includes the step of adding silicon-based substances; and/or

The step of mixing the silver salt, the carrier precursor and water also includes the step of adding ammonia water, triethylamine or ammonium salt.
A preparation method of cleaning agent, is characterized in that, comprises the following steps:

Prepare materials according to each component in the cleaning agent described in any one of claims 1 to 16, and physically mix the components.
Application of the cleaning agent according to any one of claims 1 to 16 in floor, wall, window or desktop cleaning.
The application according to claim 18, characterized in that it comprises the following steps: applying or spraying the cleaning agent to the ground, wall, window or desktop; or diluting the cleaning agent with water, diluting the Apply or spray to floors, walls, windows or tabletops.
The application according to claim 19, characterized in that the amount of the diluted water is 1 to 5 times the mass of the cleaning agent.