CN113693954A - Antibacterial hand sanitizer - Google Patents

Antibacterial hand sanitizer Download PDF

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Publication number
CN113693954A
CN113693954A CN202111035200.7A CN202111035200A CN113693954A CN 113693954 A CN113693954 A CN 113693954A CN 202111035200 A CN202111035200 A CN 202111035200A CN 113693954 A CN113693954 A CN 113693954A
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hand sanitizer
sodium
acid
tio2
solution
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CN113693954B (en
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梁莲芝
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Swashes Products Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20Halogens; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26Aluminium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42Amides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783Angiosperms [Magnoliophyta]
    • A61K8/9789Magnoliopsida [dicotyledons]
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005Antimicrobial preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/22Inorganic acids
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/24Halogens or compounds thereof
    • C25B1/26Chlorine; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48Thickener, Thickening system
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • A61K2800/592Mixtures of compounds complementing their respective functions
    • A61K2800/5922At least two compounds being classified in the same subclass of A61K8/18
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • A61K2800/596Mixtures of surface active compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/805Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95

Abstract

The invention provides an antibacterial hand sanitizer, which obtains high-efficiency foaming and decontamination performances by compounding an anionic surfactant, an amphoteric surfactant and a nonionic surfactant as a surfactant, takes hypochlorous acid as a sterilization raw material, has strong sterilization and decontamination capabilities of about 4.48 for 2 minutes of escherichia coli and staphylococcus aureus, and has the performances of skin care, skin moistening, antibacterial and bacteriostatic effects, allergy resistance, relaxation resistance and strong sterilization and decontamination capabilities.

Description

Antibacterial hand sanitizer
Technical Field
The invention belongs to the field of detergents, and particularly relates to an antibacterial hand sanitizer.
Background
The hand sanitizer is used as a novel hand cleaning product and replaces the soap which is commonly used in the past in public places such as hotels, catering departments, airports and the like. Compared with soap, the hand sanitizer has unique advantages, can avoid contacting hands, prevents secondary pollution sources caused by dirt, bacteria, viruses and the like after use or in the environment, is easy to store, and has less natural consumption. The soap has strong dependence on mechanical kneading in the smearing and using processes, is in a wet state for a long time when used in a public place, and is beneficial to breeding bacteria and viruses.
The hand sanitizer has the characteristics of flexible and changeable formula, strong plasticity, easiness in improvement, mild performance, no skin irritation, hard water resistance, rich foam, diversified components and easiness in processing, and hand sanitizer products on the market are various in types and can be roughly divided into the following components according to different purposes: (1) a common hand sanitizer: no special component is added, and the cleaning agent generally only has the function of removing dirt and grease on hands; (2) skin-care hand sanitizer: skin care ingredients such as pure glycerin and aloe are added into the hand sanitizer, so that the hand sanitizer has the function of moistening the skin while cleaning hands; (3) heavy oil stain type hand sanitizer: the soap is mainly suitable for workers engaged in industries such as machine repair, oil refining, automobile repair and the like, the hands of the workers are often stained with heavy oil stains, and common soap and liquid soap are difficult to clean; (4) disinfecting and sterilizing type hand sanitizer: in response to a plurality of public health problems at present, the effective sterilization components are added into the hand sanitizer, so that the disease transmission can be blocked; (5) water-free type
Liquid soap: alcohol is generally used as a main component, water washing is not needed, the use is simple and convenient, and the hand cleaning and disinfecting liquid is generally used for hand cleaning and disinfection under the condition of water shortage; (6) other functional hand washing solutions: the special function hand sanitizer is developed for different consumer groups, such as a lead-removing hand sanitizer, a compound function hand sanitizer and the like. The variety and functions of the hand sanitizer are so rich, and the hand sanitizer is proved to be easy to process, high in product plasticity and wide in market prospect again, and can play a more important role in preventing diseases.
Hypochlorous acid is the most effective disinfectant in a dilute solution containing chlorine, is prepared by an electrochemical method, is acidic electrolyzed water, is water with the pH of 5.0-6.5 and the effective chlorine concentration of 10-30mg/L, has strong oxidizing ability and the effect of quickly killing microorganisms, and is widely used in hand sanitizer.
For example, Shandong Shuda Biotechnology Co., Ltd CN 111481452A discloses a safety protection hand sanitizer and a preparation method thereof, which comprises the following components: the sodium hypochlorite aqueous solution is weakly acidic, 0-phenylphenol, polyhexamethylene guanidine hydrochloride, chloroxylenol, quaternary ammonium salt, chlorhexidine acetate, glycerol and a surfactant, wherein the weakly acidic sodium hypochlorite aqueous solution contains 50-100 mg/L of available chlorine, and the pH value ranges from 5-7. . The preparation method comprises the following specific steps: the method comprises the following steps: respectively diluting hydrochloric acid and sodium hypochlorite solution with water, and fully mixing; step two: fully reacting the solution in the step one in a reactor; step three: and D, adding the rest components into the weakly acidic sodium hypochlorite solution prepared in the step two, stirring and mixing uniformly by using a stirring device, and bottling and packaging. Compared with the prior art, the invention has the advantages that: the alcohol-free sterilization liquid is colorless and odorless, is safe and convenient to use, does not generate secondary biological pollution after sterilization, and has good sterilization and bacteriostasis effects.
Further, CN201110066196A, which is similar to the present invention, discloses a natural disinfecting detergent composition without preservatives, which has both disinfecting and cleaning functions, said composition comprising an electrolytic chloroxidizing agent, APG, for use in washing the offensive odor of tableware, kitchenware, vegetables, melons and fruits, textiles, or sweaty feet, sweat socks, the electrolytic chloroxidizing agent comprising hypochlorite ions and hypochlorous acid, obtained by electrolyzing a dilute solution of sodium chloride in a diaphragm-free electrolytic cell.
Disclosure of Invention
Based on the content, the invention provides the antibacterial hand sanitizer which takes hypochlorous acid as a sterilizing substance, has a very strong sterilizing effect on escherichia coli, staphylococcus aureus and candida albicans, is clean, environment-friendly, safe and good in decontamination effect, and is a safe and effective daily use article.
The invention also adopts a special anode to electrolyze sodium chloride to prepare the high-efficiency hypochlorous acid solution, the anode obviously improves the binding force between the base material and the active layer by designing the micro-arc oxidation intermediate layer, the metal oxide reinforced electrolysis has long service life, and the compounding of Ti-W-Ir-Nb-Rh is realized by preparing the (Ir-Nb-Rh) Ox active layer, so that the electrode with high catalytic activity, high corrosion resistance and high conductivity is obtained, the oxygen evolution and chlorine evolution potentials are reduced, the electrochemical conversion efficiency is improved, and the anode current efficiency is 85.3-94.2%.
An antibacterial hand sanitizer comprises an alpha-sodium olefin sulfonate AOS anionic surfactant, a cocamidopropyl betaine CAB-35 amphoteric surfactant, a cocofatty acid monoethanolamide CMEA nonionic surfactant, a glycerin humectant, sodium chloride inorganic salt, a polyacrylic acid PPA thickener, disodium ethylene diamine tetraacetate EDTA-2Na, a mica powder pearlescent additive, lemon essence and a hypochlorous acid deionized water solution, wherein the pH of the hand sanitizer is 5.75-6.75, and the viscosity is 2000-4000 mPa.S.
Further, the hand sanitizer comprises the following components:
alpha-sodium olefin sulfonate AOS anionic surfactant: 7-9 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6-7 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5-6 wt.%;
glycerin humectant: 1-3 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetic acid EDTA-2 Na: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution: and (4) the balance.
Furthermore, the effective chlorine component in the hand sanitizer is 50-70 ppm.
Further, the sodium hypochlorite aqueous solution is prepared by the following method:
(1) setting a reaction tank: the reaction tank at least comprises a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode, and a titanium alloy or stainless steel is used as a cathode:
(2) electrolyzing sodium chloride: introducing a mixed solution of saturated saline water and hydrochloric acid to the bottom of the reaction tank;
(3) diluting and collecting hypochlorous acid disinfectant: effluent liquid is collected from the top of the electrolytic bath and then used and diluted with deionized water to obtain hypochlorous acid disinfectant water.
The preparation method of the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode comprises the following steps:
(a) pretreating a titanium plate or a titanium mesh substrate;
(b) preparing a TiO2-WO3 composite intermediate layer on the surface of a substrate: placing the pretreated substrate serving as an anode in an electrolyte for micro-arc oxidation treatment, wherein the electrolyte consists of sodium tungstate trihydrate, sodium hydroxide, sodium fluoride, sodium hexametaphosphate and deionized water;
electrolysis parameters: the bidirectional pulse voltage is 400V at positive pressure of 350-;
(c) preparing an (Ir-Nb-Rh) Ox active layer: adding a certain amount of NbCl4Dissolving in isopropanol, dissolving a certain amount of ammonium chlororhodate and chloroiridic acid in a mixed solution of isopropanol and hydrochloric acid in a ratio of 1:1, mixing the chloroiridic acid, the ammonium chlororhodate and niobium tetrachloride according to a molar ratio of (10-25) to (15-20) to (5-10) to obtain a precursor solution, coating the precursor solution on the surface of the TiO2-WO3 composite interlayer by brushing, drying at 60-70 ℃ for 3-5min, converting a muffle furnace, raising the temperature of the muffle furnace to 500 ℃ at a temperature of 5 ℃/min, keeping the temperature for 20-30min, naturally cooling, repeating the brushing process until the required loading capacity is reached, and then annealing at 500 ℃ for 1-1.5h at 450 ℃ to obtain the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode.
Further, the pretreatment comprises oil removal, sand blasting and washing, wherein the oil removal comprises the following steps: placing the substrate in 3-5wt.% Na2CO3Keeping the solution for 5-10min, and then 60-80oC, performing ultrasonic treatment for 1-3 min; sand blasting and coarsening: 0.1-0.5mm quartz sand, the hardness is approximately equal to 400HV, and the air pressure is 0.1-0.15 MPa; the washing is deionized water washing.
Further, 13-17g/L of sodium tungstate trihydrate, 1.5-2.5g/L of sodium hydroxide, 2-3g/L of sodium fluoride, 4-5g/L of sodium hexametaphosphate and the balance of deionized water.
Further, the thickness of the TiO2-WO3 composite intermediate layer is 5-10 μm, and the thickness of the (Ir-Nb-Rh) Ox active layer is 12-15 μm.
Further, the loading amount in the step (c) is 2.2-2.5mg/cm2
The hand sanitizer is a cleaning product designed for removing stains and bacteria on hands, and comprises necessary active ingredients, a sterilization ingredient and auxiliary ingredients.
Surfactant (b): the basic function is cleaning function, the hand sanitizer mainly cleans oil stains on hands, the surfactant can generate abundant foam, the surfactant can be dissolved in water under lower concentration, the surface tension of a solution system can be greatly reduced, a large number of micelles can be formed in the solution along with the fact that the surfactant reaches critical micelle concentration, the micelles can play roles of wetting, solubilizing, emulsifying and dispersing, and the oil stains are cleaned.
Humectant: for the market demand, not only simple cleansing and decontamination, but also the human feeling after cleansing is very important to avoid dryness and roughness of hands, so that there is a need for a moisturizing agent for improving the physical feeling, which is defined as a substance capable of retaining water in the horny layer of the skin or delaying and preventing the volatilization of water in the horny layer, and especially showing such a characteristic at low humidity, and the present invention employs glycerin having low volatility, high boiling point and strong hygroscopicity as a moisturizing agent.
Thickening agent: when the hand sanitizer is used, if the viscosity is too low, the hand sanitizer is very easy to slip away from hands, waste is caused, the dirt removing capability is also influenced, and the hand sanitizer is not easy to squeeze and wash due to too high viscosity adjustment. The hand sanitizer has proper viscosity, can enhance the sensory effect of consumers, and adopts sodium chloride and PPA (polyacrylic acid) as a thickening agent.
Complexing agent: the ordinary water contains Ca2+、Mg2+Some surfactants have poor hard water resistance, and the hard metal ions can form precipitates with the metal ions in the water to influence the performance of the detergent. The invention adopts EDTA-2Na as complexing agent, which can form a soluble ring structure in water to bind metal ions in the ring, thereby preventing the metal ions from forming precipitates and ensuring that the solution has good appearance.
Essence and pearl powder are used for improving the touch effect of the hand sanitizer, and the taste and the appearance required by customers can be selected according to requirements.
And (3) bactericide: because hypochlorous acid is uncharged and has a relatively low molecular weight, it can penetrate cell walls more rapidly than other bactericides or bacteriostats, and can perform oxidation reaction with organic matters (namely key components of microbial cells) more rapidly, so that the disinfection effect is more efficient, and only under the condition of low concentration, the hypochlorous acid can penetrate cell membranes by attacking physiologically-related molecules (such as ammonia, thioether, mercaptan, nucleotide and the like) to oxidize proteins, thereby achieving the aim of killing bacterial propagules, viruses, fungi, tubercle bacillus and bacterial spores.
With respect to the electrolytic process of the invention and the anodes used:
firstly: the surface pretreatment is carried out on the titanium substrate, the surface treatment comprises degreasing and sand blasting, wherein the degreasing step is an unnecessary treatment process, mainly because micro-arc oxidation is carried out subsequently, the voltage in the micro-arc oxidation process is large, and an obvious anodic electrochemical degreasing process can occur, so degreasing is optional, but the degreasing can influence the binding force of the micro-arc oxidation layer and the substrate to a certain extent.
Secondly, the intermediate layer has the functions of increasing the binding force between the titanium substrate and the active coating, resisting gas scouring and preventing the premature peeling of the coating, simultaneously, the intermediate layer prevents oxygen from diffusing and permeating to the substrate, slows down the forming speed of the non-conductive titanium oxide film between the substrate and the active coating, delays the passivation and inactivation of the substrate, and improves the service life of the oxide anode
Its life is long. The intermediate layer in the prior art is mainly SnO2, Sn-Sb oxide, Ir-Co oxide, Sn-Sb-Mn oxide, Sn-Ru-Mn oxide, Ru-Sn-Sb oxide, Ru-Sb-Mn oxide, Nb-Sn oxide and the like, and certainly, part of the intermediate layer is a titanium-based anodic oxide film, a titanium-based micro-arc oxide film is rarely used as the intermediate layer, and the anodic oxidation or micro-arc oxide film is used as the intermediate layer, so that the bonding force between the base material and the intermediate layer can be effectively improved, mainly because the oxide film is generated in situ, no obvious interface exists between the intermediate layer on the surface of the titanium base material and the base material, the transition is good, and the coating, electroplating or other deposition methods have obvious interfaces, when the interface is subjected to subsequent heat treatment on an active layer, certain thermal peeling or thermal stress accumulation inevitably occurs, in addition, compared with an anodic oxide film, the micro-arc oxide film is far higher than the micro-arc oxide film in corrosion resistance (salt spray resistance), hardness and service life, but the micro-arc oxide film has lower porosity in morphology, so that the bonding force between an active coating and a base material is reduced, the surface of the single titanium oxide micro-arc oxide film is rough, discharge residual holes with different sizes exist, the range of the holes is greatly changed, the porosity ranges from 2 wt.% to 8wt.%, wherein the main contribution of the porosity is a surface porous layer, the physicochemical contribution mainly lies in a transition layer, the bonding force mainly lies in a bottom dense layer, the hole absorption rate of the dense layer is lower than 1%, and the specific surface area of the micro-arc oxide slip film is 10.32m2(ii) in terms of/g. In contrast, the W element is added in the micro-arc oxidation film, higher porosity is shown, and the specific surface area is increased to 13.9 m2(g), the improvement of porosity and surface area is obviously improvedThe contact area with the active layer improves the bonding force of the active layer and the active layer, more active sites are provided in the process of composite synergistic activation, and the obtained TiO in the middle layer2About 50-55wt.%, the mass fraction of W is about 25-30wt.%, and the composition of Ti is greater due to Ti4+Participate in at least two main reactions, and W participates in at least one main reaction, the reaction formula is as follows:
Ti4++2OH-+2H2O→TiO2+2H2O+
Ti4++2WO4 2-+TiO2+2WO3
namely, the TiO2-WO3 has the advantages of corrosion resistance, good conductivity and close combination with a titanium matrix.
Active layer: two or more components mixed in the electrode seek a synergistic effect to achieve close electronic connection between the components
The invention aims to improve the electrode activity, and is the main purpose of active layer research, the main active elements adopted by the invention are Ir, Nb and Rh, namely the main body of the coating is Ir, Nb and Rh elements, wherein Ir and Rh are main oxides and provide high catalytic activity and corrosion resistance, Nb is used for improving the particle morphology of the oxide on the surface of the coating, refining the crystal grains of the coating, increasing the microscopic area of the electrode, having larger roughness and improving the specific surface area of the surface activity, and further improving the catalytic activity of the coating.
The (Ir-Nb-Rh) Ox solid solution can not be completely dissolved, and part of the (Ir-Nb-Rh) Ox solid solution can be precipitated by IrOX and RuO2, so that the microcosmic specific surface area and active sites of the anode can be increased, the chlorine precipitation efficiency is improved, a large number of micropores and gaps are formed on the surface of the electrode, obvious crystal clusters are precipitated from the gaps, the microcosmic specific surface area is increased, the current density is small, the service life of the electrode is prolonged, and the coating has the advantages of flat surface, compact crystallization, shallow depth of the cracks, narrow width and fine cracks.
The process of electrolyzing hypochlorous acid adopts a diaphragm-free electrolytic bath, the reaction bath at least comprises a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode, a titanium alloy or stainless steel is used as a cathode, the anode is used for chlorine evolution reaction, namely the chlorine ions lose electrons to formForming chlorine molecules, and reacting the chlorine with water to generate hypochlorous acid, chloride ions and a small part of chlorate ions. Meanwhile, oxygen is separated out after water molecules at the anode are electrolyzed, the oxygen evolution reaction is a side reaction, the oxygen evolution reaction is avoided as much as possible, the chlorine evolution reaction is dominant in the competition of the chlorine evolution reaction and the oxygen evolution reaction, but when the concentration of the sodium chloride electrolyte is too low, ionized chloride ions cannot meet the electrolysis speed of an electrolytic cell, so that water electrolysis is started, oxygen is separated out, the oxygen precipitation of the oxygen can obviously reduce the oxygen defect of the anode active oxide, the catalytic layer is inactivated, and the current density is: the current density of the invention is 100-2The available chlorine increases with the increase of the current density, the pH value shifts slowly to neutral, the chlorine evolution potential decreases significantly, as in example 3, the chlorine evolution potential is 0.98V, which is lower than that of example 2, after the current density is increased, and in addition, the current efficiency decreases with the increase of the current density, mainly due to the decrease of the current efficiency caused by the oxygen evolution competition reaction.
The pH of the effluent of the invention is 2.5-4, within the range, the hypochlorous acid can not be stored almost, the available chlorine of the obtained effluent is almost zero within about 20-30 days, therefore, the newly obtained effluent must be diluted to 6.5-7, the effluent obtained in the example 2 is diluted to pH =6.75 by deionized water, the content of the available chlorine is tested under the conditions of light shielding and sealing for different time, the initial content of the available chlorine is 62mg/L, the storage rate of the available chlorine is 97% after 120 days, the storage effect is excellent, the sterilization effect of the available chlorine stored in the sealed light shielding on escherichia coli and staphylococcus aureus is tested, the ORP value is 1040mV, the available chlorine is about 60 mg/L, and the sterilization effect is almost 100% within 3 min.
The beneficial technical effects are as follows:
(1) the efficient foaming and decontamination performances are obtained by compounding anionic surfactant, amphoteric surfactant and nonionic surfactant into the surfactant.
(2) The hand sanitizer has the effects of skin care, skin moistening, antibiosis, bacteriostasis, allergy resistance, relaxation and strong sterilization and decontamination capability, the sterilization efficiency of escherichia coli and staphylococcus aureus in 1min is 99.99%, and the sterilization log value in 2min is 4.48 (99.99668%).
(3) The TiO2-WO3 intermediate layer is prepared on the surface of the titanium substrate through in-situ oxidation, the bonding force between the titanium substrate and the active layer is effectively improved, the specific surface area of the intermediate layer is high, the microcosmic contact specific surface area is provided for coating the active layer, and the stability between the intermediate layer and the active layer is further improved.
(4) By coating the solid solution active component mainly containing Ir, Nb and Rh on the surface of the intermediate layer, the catalytic activity of electrolysis is obviously improved, coating crystal grains are refined, the obtained coating has the advantages of smooth surface, compact crystallization, shallow depth and width of cracks, fine cracks, improved catalytic activity and stability and prolonged service life.
(5) The hypochlorous acid prepared by electrolyzing sodium chloride has low chlorine evolution potential, high current efficiency, high effective chlorine concentration and excellent sterilization effect.
The specific implementation mode is as follows:
all the hypochlorous acid preparation processes in the embodiments 1 to 3 of the invention are as follows:
a preparation method of a disinfectant is characterized in that hypochlorous acid is used as the disinfectant, and the preparation method comprises the following steps:
(1) setting a reaction tank: the reaction tank at least comprises a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode, a titanium alloy or stainless steel is used as a cathode, and the polar distance between the cathode and the anode is 3.5 mm.
(2) Electrolyzing sodium chloride: introducing a mixed solution of saturated saline water and hydrochloric acid into the bottom of the reaction tank, wherein the pH value of the mixed solution is 0.9, the mixed solution inlet speed is 1.5L/h, and the current density is 125mA/cm2
(3) Diluting and collecting hypochlorous acid disinfectant: the effluent was collected from the top of the cell and then used and diluted with deionized water.
The preparation method of the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode is as follows.
(a) Pre-treating a titanium plate or titanium mesh substrate: the pretreatment comprises oil removal, sand blasting and washing, wherein the oil removal comprises the following steps: placing the substrate in 4wt.% Na2CO3Keeping the solution for 7.5min,then 70oC, performing ultrasonic treatment for 2 min; sand blasting and coarsening: 0.1-0.5mm quartz sand, the hardness is approximately equal to 400HV, and the air pressure is 0.125 MPa; the washing is deionized water washing.
(b) Preparing a TiO2-WO3 composite intermediate layer on the surface of a substrate: the pretreated substrate is used as an anode and placed in electrolyte for micro-arc oxidation treatment, wherein the electrolyte consists of 15g/L sodium tungstate trihydrate, 2g/L sodium hydroxide, 2.5g/L sodium fluoride, 4.5g/L sodium hexametaphosphate and the balance of deionized water.
Electrolysis parameters: bidirectional pulse voltage, positive voltage 375V, negative voltage 40V, duty ratio 35%, frequency 750Hz, positive-negative pulse ratio 1:1, time 6 min.
(c) Preparing an (Ir-Nb-Rh) Ox active layer: adding a certain amount of NbCl4Dissolving in isopropanol, dissolving certain amounts of ammonium chlororhodate and chloroiridic acid in a mixed solution of isopropanol and hydrochloric acid in a ratio of 1:1, mixing the chloroiridic acid, the ammonium chlororhodate and niobium tetrachloride according to a molar ratio of (17.5) to (7.5) to obtain a precursor solution, coating the precursor solution on the surface of a TiO2-WO3 composite intermediate layer by brushing, drying at 70 ℃ for 5min, converting a muffle furnace, raising the temperature of the muffle furnace to 475 ℃ at 5 ℃/min, keeping the temperature for 25min, naturally cooling, and repeating the brushing process until the required temperature reaches 2.35mg/cm2Carrying out annealing at 475 ℃ for 1.25h to obtain the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode.
Example 1
Alpha-sodium olefin sulfonate AOS anionic surfactant: 7 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5 wt.%;
glycerin humectant: 1 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetate EDTA-2Na complexing agent: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution with 60ppm of available chlorine: and (4) the balance.
The pH was 5.75.
Example 2
Alpha-sodium olefin sulfonate AOS anionic surfactant: 7-9 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6-7 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5-6 wt.%;
glycerin humectant: 1-3 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetate EDTA-2Na complexing agent: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution with 60ppm of available chlorine: and (4) the balance.
The pH was 6.2.
Example 3
Alpha-sodium olefin sulfonate AOS anionic surfactant: 7-9 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6-7 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5-6 wt.%;
glycerin humectant: 1-3 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetate EDTA-2Na complexing agent: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution with 60ppm of available chlorine: and (4) the balance.
The pH was 6.75.
The hand sanitizer obtained in example 2 was tested for foamability, and the foam rate was 372% and the foam was reduced by 5 to 7% at 0 to 3min, and then was maintained stable, and the foam stability was reduced by 43% after 1 hour, according to GB/T13173.6 "determination of foaming power of detergent", and the viscosity was 3752 mPa · S. The sterilization efficiency for escherichia coli and staphylococcus aureus is 99.8% within 1min, and the sterilization log value within 5min is 4.48 (99.99668%).
While the invention has been described in conjunction with specific embodiments thereof, it will be understood by those skilled in the art that many modifications and variations may be made to the invention. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit and scope of the invention.

Claims (9)

1. An antibacterial hand sanitizer is characterized by comprising alpha-alkenyl sodium sulfonate AOS anionic surfactant, cocamidopropyl betaine CAB-35 amphoteric surfactant, cocofatty acid monoethanolamide CMEA nonionic surfactant, a glycerin humectant, sodium chloride inorganic salt, polyacrylic acid PPA thickener, disodium ethylene diamine tetraacetate EDTA-2Na complexing agent, mica powder pearlescent additive, lemon essence and hypochlorous acid deionized water solution, wherein the pH of the hand sanitizer is 5.75-6.75, and the viscosity is 2000-4000 mPa.S.
2. The antimicrobial hand sanitizer according to claim 1, wherein the hand sanitizer comprises the following composition:
alpha-sodium olefin sulfonate AOS anionic surfactant: 7-9 wt.%;
cocamide propyl betaine CAB-35 amphoteric surfactant: 6-7 wt.%;
coconut oil fatty acid monoethanolamide CMEA nonionic surfactant: 5-6 wt.%;
glycerin humectant: 1-3 wt.%;
sodium chloride inorganic salt: 0.01-0.12 wt.%;
polyacrylic acid PPA thickener: 1-4 wt.%;
disodium ethylenediaminetetraacetate EDTA-2Na complexing agent: 0.05-0.12 wt.%;
0.5-1wt of mica powder pearlescent additive;
lemon essence: 0.1 to 1.0 percent;
hypochlorous acid deionized water solution: and (4) the balance.
3. The antibacterial hand sanitizer according to claim 1, wherein the active chlorine component in the hand sanitizer is 50 to 70 ppm.
4. An antibacterial hand sanitizer according to claim 1 wherein said aqueous hypochlorous acid solution is prepared by:
(1) setting a reaction tank: the reaction tank at least comprises a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode, and a titanium alloy or stainless steel is used as a cathode:
(2) electrolyzing sodium chloride: introducing a mixed solution of saturated saline water and hydrochloric acid to the bottom of the reaction tank;
(3) diluting and collecting hypochlorous acid disinfectant: effluent liquid is collected from the top of the electrolytic bath and then used and diluted with deionized water to obtain hypochlorous acid disinfectant water.
5. The antibacterial hand sanitizer of claim 4, wherein the Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode is prepared by the following method:
(a) pretreating a titanium plate or a titanium mesh substrate;
(b) preparing a TiO2-WO3 composite intermediate layer on the surface of a substrate: placing the pretreated substrate serving as an anode in an electrolyte for micro-arc oxidation treatment, wherein the electrolyte consists of sodium tungstate trihydrate, sodium hydroxide, sodium fluoride, sodium hexametaphosphate and deionized water;
electrolysis parameters: the bidirectional pulse voltage is 400V at positive pressure of 350-;
(c) preparing an (Ir-Nb-Rh) Ox active layer: adding a certain amount of NbCl4Dissolving in isopropanol, and dissolving certain amounts of ammonium chlororhodate and chloroiridic acid inIn a mixed solution of isopropanol and hydrochloric acid with the ratio of 1:1, mixing chloroiridic acid, ammonium chlororhodate and niobium tetrachloride according to the molar ratio of (10-25) to (15-20) to (5-10) to obtain a precursor solution, coating the precursor solution on the surface of a TiO2-WO3 composite intermediate layer by brushing, drying at the temperature of 60-70 ℃ for 3-5min, converting a muffle furnace, raising the temperature of the muffle furnace to 500 ℃ at the temperature of 450 ℃ at the programmed temperature of 5 ℃/min, keeping the temperature for 20-30min, naturally cooling, repeatedly brushing until the required loading capacity is reached, annealing at the temperature of 500 ℃ for 1-1.5h at the temperature of 450 ℃ to obtain a Ti/TiO2-WO3/(Ir-Nb-Rh) Ox anode.
6. An antibacterial hand sanitizer according to claim 5 wherein said pretreatment comprises degreasing, blasting and rinsing, said degreasing: placing the substrate in 3-5wt.% Na2CO3Keeping the solution for 5-10min, and then 60-80oC, performing ultrasonic treatment for 1-3 min; sand blasting and coarsening: 0.1-0.5mm quartz sand, the hardness is approximately equal to 400HV, and the air pressure is 0.1-0.15 MPa; the washing is deionized water washing.
7. The antibacterial hand sanitizer of claim 5, wherein the sodium tungstate trihydrate is 13-17g/L, the sodium hydroxide is 1.5-2.5g/L, the sodium fluoride is 2-3g/L, the sodium hexametaphosphate is 4-5g/L, and the balance is deionized water.
8. The antibacterial hand sanitizer according to claim 5, wherein the TiO2-WO3 composite intermediate layer has a thickness of 5-10 μm, and the (Ir-Nb-Rh) Ox active layer has a thickness of 12-15 μm.
9. The antibacterial hand sanitizer of claim 5, wherein the loading in the step (c) is 2.2-2.5mg/cm2
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