CN113018215B - Alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer and preparation method thereof - Google Patents
Alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer and preparation method thereof Download PDFInfo
- Publication number
- CN113018215B CN113018215B CN202110265747.XA CN202110265747A CN113018215B CN 113018215 B CN113018215 B CN 113018215B CN 202110265747 A CN202110265747 A CN 202110265747A CN 113018215 B CN113018215 B CN 113018215B
- Authority
- CN
- China
- Prior art keywords
- free
- hand sanitizer
- self
- aerosol
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/736—Chitin; Chitosan; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/046—Aerosols; Foams
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions 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
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/87—Polyurethanes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier 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
- A61Q17/005—Antimicrobial preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/30—Characterized by the absence of a particular group of ingredients
Abstract
The invention belongs to the technical field of antibacterial and bacteriostatic daily chemical articles, and particularly relates to an alcohol-free wash-free self-conjunctival antibacterial aerosol hand sanitizer and a preparation method thereof. The composite self-filming agent is formed by aqueous polyurethane liquid and konjac gum powder, and the composite antibacterial agent and the composite self-filming agent are dispersed by a spreader to prepare a liquid material; the propellant is utilized to enable the liquid material to form aerosol type hand sanitizer; the hand sanitizer is free of alcohol and is free of washing, after the hand sanitizer is sprayed to use, the composite antibacterial agent is uniformly dispersed due to the pressure dispersion effect of the aerosol, meanwhile, a smooth protective film is formed on the hand by glue liquid formed by the composite self-filming agent, and the antibacterial agent dispersed in the protective film can generate lasting sterilization and antibacterial effects. Is very suitable for public transport drivers, outdoor workers, people who have difficulty in washing hands such as long-distance traveling and business trips, and the like.
Description
Technical Field
The invention belongs to the technical field of antibacterial and bacteriostatic daily chemical articles, and particularly relates to an alcohol-free wash-free self-conjunctival antibacterial aerosol hand sanitizer and a preparation method thereof.
Background
Along with the demand of people for health and hygiene, antibacterial and bacteriostatic products are in great demand. The hand is the most likely to be exposed to germs as a part frequently exposed to the outside. People often touch door handles, elevator buttons and the like in daily trips, and bacteria are very easy to carry. Therefore, people are required to take care of washing hands in places where the hands can be washed after shopping, riding in vehicles, going to toilets and going out, and as long as the people are in public places, a lot of bacteria exist on the hands, and if the people rub eyes, touch noses and touch faces with hands, the bacteria can quickly enter the bodies. After the person goes home, the hand is thoroughly washed clean for the first thing.
The hand sanitizer is a conventional daily chemical product, is commonly used at present, but how to better and more durably maintain the antibacterial effect of hands becomes a problem of intensive research of technicians. The first type of the existing hand washing products is a common liquid type hand washing liquid containing a cleaning active agent and an antibacterial agent, the main purpose of the hand washing liquid is to wash hand bacteria, but the hand washing liquid does not have a later-stage antibacterial effect, so that the hand washing liquid needs to be washed again after contacting with articles, and particularly the hand washing liquid cannot be used under outdoor waterless washing conditions, and the hand washing liquid is extremely inconvenient; the second type is gel type hand sanitizer which can be free of washing, does not need to be washed with water, is convenient to clean and is suitable for being carried outside.
The aerosol has good spraying and dispersing effects, and is applied to fine chemical engineering, pharmacy, cosmetics, daily chemicals and the like at present, such as aerosol insecticides, aerosol disinfectants and the like. If be used for the disinfection of disinfecting of hand with aerosol, because aerial fog dispersion effect, can the at utmost be the hand and the germicide contact, play better bactericidal effect, can realize exempting from to wash simultaneously, become the novel hand disinfectant that can replace the liquid soap that develops in recent years. However, due to the rapid volatilization characteristics of the aerosol, the germicide contained therein, such as alcohol, high chlorine disinfectant, rapidly volatilizes and has a long-lasting bacteriostatic effect, so that it is also necessary to spray hands again for sterilization after contacting the article.
Disclosure of Invention
The invention discloses an alcohol-free washing-free self-conjunctiva antibacterial aerosol hand sanitizer, which is a novel hand sanitizer and has excellent effects in the aspects of realizing washing-free, alcohol-free, high efficiency and long-acting performance. Furthermore, a preparation method of the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer is provided.
The aerosol technology is a conventional technology, and the basic instantaneous hand sterilization can be realized by utilizing the technical principle of the aerosol technology to atomize alcohol, high-chlorine disinfectant and the like with sterilization effect. However, it is rapidly volatile and does not have long-lasting effect.
Based on the problems, the invention firstly provides an alcohol-free washing-free self-conjunctival antibacterial aerosol hand sanitizer which is characterized by comprising a liquid material A and a propellant B; wherein the mass ratio of the liquid material A to the propellant B is 3: 1;
the liquid material A comprises the following raw materials in parts by weight:
0.1 to 0.5 portion of composite antibacterial agent,
3-5 parts of a composite self-filming agent,
0.5 to 1.0 portion of glycerol polyacrylate,
0.1 to 0.3 portion of spreading agent,
3-5 parts of glycerol, namely,
0.05 to 0.1 portion of octyl glycol
0.01 to 0.02 portion of defoaming agent,
60-70 parts of deionized water, namely,
0-0.01 part of edible essence;
the propellant B is prepared by mixing propane and butane in a volume ratio of 2: 1;
the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer is prepared by the following method:
(1) adding the composite antibacterial agent, the composite self-filming agent and the spreading agent into deionized water, and stirring and dispersing at a high speed to obtain a dispersion liquid;
(2) adding the glycerol polyacrylate, the glycerol, the caprylyl glycol, the defoaming agent and the essence into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, and filling the propellant B to ensure that the feed liquid A and the propellant B are statically and uniformly mixed in a spray can body;
(4) after filling, the spray head is arranged on the aerosol can and packaged to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
The composite antibacterial agent is prepared from silver-loaded particles, chitin micropowder and an organosilicon quaternary ammonium salt antibacterial agent in a mass ratio of 1: 3: 2, mixing the components. The ratio is determined by comprehensively considering the cost and the antibacterial effect, on one hand, the instant sterilization and the long-acting sterilization are considered, and on the other hand, the hand sanitizer is generally cleaned and removed within one day after being used, so that the high-cost silver-loaded particles are less used. The silver-carrying particles are commercially available D90 fine particles with the particle size of 1 μm, and one of zeolite silver-carrying particles and silica gel silver-carrying particles is particularly preferable. Wherein the chitin micropowder is micropowder with particle size less than 5 μm. The composite antibacterial agent has quick antibacterial performance and excellent antibacterial effect on escherichia coli, staphylococcus aureus and the like. When the composite antibacterial agent is used in the aerosol, the composite antibacterial agent is sprayed on the hands, a micro-film is formed on the hands under the action of the composite self-filming agent, the composite antibacterial agent is dispersed in the micro-film, and the organosilicon quaternary ammonium salt antibacterial agent has a good instant sterilization effect and can sterilize the hands in a scientific and timely manner; the silver-carrying particles and the chitin micropowder are not easy to run off and have long-acting sterilization and bacteriostasis effects.
The composite self-filming agent is a complex of aqueous polyurethane liquid and konjac powder according to a mass ratio of 2: 1; the aqueous polyurethane solution is not only easy to form a micro-membrane in a hand self-conjunctiva to fix an antibacterial agent in the membrane so as to realize a long-acting antibacterial and bacteriostatic effect, but also has a smooth and non-greasy formed membrane so as to effectively prevent the adhesion of hand bacteria, preferably, the mass concentration of the aqueous polyurethane solution is 40%, and the C1000 aqueous polyurethane solution provided by Guangzhou oil science and technology Co., Ltd is used in pilot scale production; the konjac gum powder has good film forming property, can form a transparent and high-density protective film on hands, contains natural antibiotics, and prevents bacteria from adhering and propagating.
The spreader is one of glyceryl monostearate and diisostearyl malate, and is beneficial to effectively dispersing the composite antibacterial agent in the feed liquid.
The glycerin polyacrylate is used, not only has certain moisture retention and film forming properties, but also has moisture retention and water retention capacity, and the formed water-soluble transparent gel can increase the texture and the lubricity of the skin.
The caprylyl glycol is a common additive of cosmetics, has a humectant and also has a corrosion resistance.
The defoaming agent is silicone oil.
The edible essence can be added according to needs, and preferably is one of lavender essential oil, rose essential oil and tea tree essential oil.
The invention further provides a preparation method of the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer, which is characterized by comprising the following steps:
(1) adding the composite antibacterial agent, the composite self-filming agent and the spreading agent into deionized water, and stirring and dispersing at a high speed to obtain a dispersion liquid;
(2) adding the glycerol polyacrylate, the glycerol, the caprylyl glycol, the defoaming agent and the essence into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, and filling the propellant B to ensure that the feed liquid A and the propellant B are statically and uniformly mixed in a spray can body;
(4) after filling, the spray head is arranged on the aerosol can and packaged to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
The high-speed stirring dispersion is carried out at the temperature of 60-80 ℃ by adopting the rotation speed of 1200-1500rpm, the stirring time is controlled for 30-45min, and the composite antibacterial agent and the composite self-filming agent are dispersed in deionized water under the action of the spreader to obtain dispersion liquid.
Preferably, the pressure of the spray tank body after being filled is 0.7-0.8 MPa.
Aiming at the problem that the existing common antibacterial hand sanitizer and gel type no-clean hand sanitizer have poor antibacterial and bacteriostatic durability, the invention provides the alcohol-free no-clean self-conjunctiva antibacterial aerosol hand sanitizer and a preparation method thereof in order to realize the antibacterial and bacteriostatic effects of no-clean, no alcohol, high efficiency and long-acting performance. The composite antibacterial agent and the composite self-filming agent are designed in the aerosol, the composite antibacterial agent and the composite self-filming agent are dispersed through the spreader, after the aerosol is sprayed on hands, the composite antibacterial agent is uniformly dispersed due to the pressure dispersion effect of the aerosol, meanwhile, a smooth protective film is formed on the hands by glue liquid formed by the composite self-filming agent, and the antibacterial agent dispersed on the protective film can generate lasting sterilization and antibacterial effects. It is similar to a micro-film protective glove containing an antibacterial agent for hands. Therefore, after the hand is sprayed for one time, the protection of the whole day can be ensured, and the inconvenience of repeated washing of hands is avoided. Is very suitable for public transport drivers, outdoor workers, people who have difficulty in washing hands such as long-distance traveling and business trips, and the like.
The invention relates to an alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer and a preparation method thereof, and the beneficial effects are as follows:
1. the prepared aerosol is sprayed on the hands to form a micro-membrane from a conjunctiva to fix the antibacterial agent in the membrane, so that the long-acting antibacterial and bacteriostatic effects are realized, and the problem of poor antibacterial durability of the existing hand sanitizer is solved.
2. The film is smooth and not greasy, so that the adhesion and propagation of bacteria on hands can be effectively prevented.
3. The selected composite antibacterial agent has the instant sterilizing effect, can achieve the long-acting antibacterial and bacteriostatic effects, has excellent antibacterial and bactericidal effects on escherichia coli, staphylococcus aureus and the like, has reasonable cost, and is suitable for being used in hand sanitizer.
4. The aerosol hand sanitizer prepared by the invention is free of alcohol and free of washing, is suitable for being used in occasions where hand washing is inconvenient for long-time outdoor work, and avoids inconvenience of repeated hand washing.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention will be clearly and completely described below with reference to the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art without any inventive step based on the technical idea of the present invention shall fall within the scope of protection of the present invention.
Weighing commercially available zeolite silver-loaded particles with the particle size of 1 mu m of D90 0.6kg, chitin micropowder 1.8kg and organosilicon quaternary ammonium salt antibacterial agent 1.2kg, and mixing to obtain a composite antibacterial agent for later use;
20kg of C1000 aqueous polyurethane solution (with the mass concentration of 40%) provided by Guangzhou daily oil science and technology Limited and 10kg of 500-mesh konjac gum powder are weighed and mixed to serve as a composite self-filming agent for standby.
Example 1
(1) Weighing 0.35kg of composite antibacterial agent, 3kg of composite self-filming agent and 0.1kg of spreading agent glyceryl monostearate, adding 60kg of deionized water, placing in a stirring kettle, heating to 80 ℃, stirring at a high speed of 1500rpm for dispersing for 30min, and uniformly dispersing the composite antibacterial agent and the composite self-filming agent in the deionized water under the action of the spreading agent to obtain a dispersion liquid;
(2) weighing 0.5kg of glycerol polyacrylate, 3kg of glycerol, 0.05kg of caprylyl glycol, 0.01 kg of defoaming agent silicone oil and 0.01 kg of lavender essential oil, adding the mixture into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, mixing propane and butane according to the volume of 2:1 to obtain a propellant B, filling the propellant B according to the mass ratio of the feed liquid A to the propellant B of 3:1, and statically and uniformly mixing the feed liquid A and the propellant B in a spray can body under the pressure of 0.7MPa after the can body is filled;
(4) after filling, the spray head is arranged on the aerosol can, and plastic package is carried out to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
Example 2
(1) Weighing 0.4kg of composite antibacterial agent, 4kg of composite self-film forming agent and 0.3kg of spreading agent diisostearyl malate, adding 65kg of deionized water, placing in a stirring kettle, heating to 60 ℃, stirring at a high speed of 1200rpm for dispersing for 45min, and uniformly dispersing the composite antibacterial agent and the composite self-film forming agent in the deionized water under the action of the spreading agent to obtain a dispersion liquid;
(2) weighing 0.5kg of glycerol polyacrylate, 3kg of glycerol, 0.05kg of caprylyl glycol, 0.02 kg of defoaming agent silicone oil and 0.01 kg of rose essential oil, adding the above components into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, mixing propane and butane according to the volume of 2:1 to obtain a propellant B, filling the propellant B according to the mass ratio of the feed liquid A to the propellant B of 3:1, and statically and uniformly mixing the feed liquid A and the propellant B in a spray can body under the pressure of 0.7MPa after the can body is filled;
(4) after filling, the spray head is arranged on the aerosol can, and plastic package is carried out to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
Example 3
(1) Weighing 0.5kg of composite antibacterial agent, 5kg of composite self-filming agent and 0.3kg of spreading agent glyceryl monostearate, adding 70kg of deionized water, placing in a stirring kettle, heating to 80 ℃, stirring at a high speed of 1500rpm for dispersing for 45min, and uniformly dispersing the composite antibacterial agent and the composite self-filming agent in the deionized water under the action of the spreading agent to obtain a dispersion liquid;
(2) weighing 1.0kg of glycerol polyacrylate, 5kg of glycerol, 0.1kg of caprylyl glycol, 0.01 kg of defoaming agent silicone oil and 0.01 kg of tea tree essential oil, adding the mixture into the dispersion, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, mixing propane and butane according to the volume of 2:1 to obtain a propellant B, filling the propellant B according to the mass ratio of the feed liquid A to the propellant B of 3:1, and statically and uniformly mixing the feed liquid A and the propellant B in a spraying agent can body under the pressure of 0.7-0.8MPa after the can body is filled;
(4) after filling, the spray head is arranged on the aerosol can, and plastic package is carried out to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
Comparative example 1
Weighing 0.6kg of commercially available zeolite silver-loaded particles with the particle size of 1 mu m D90 and 1.2kg of organosilicon quaternary ammonium salt antibacterial agent, and mixing to obtain a composite antibacterial agent for later use;
20kg of C1000 aqueous polyurethane solution (with the mass concentration of 40%) provided by Guangzhou daily oil science and technology Limited and 10kg of 500-mesh konjac gum powder are weighed and mixed to serve as a composite self-filming agent for standby.
(1) Weighing 0.35kg of composite antibacterial agent, 3kg of composite self-filming agent and 0.1kg of spreading agent glyceryl monostearate, adding 60kg of deionized water, placing in a stirring kettle, heating to 80 ℃, stirring at a high speed of 1500rpm for dispersing for 30min, and uniformly dispersing the composite antibacterial agent and the composite self-filming agent in the deionized water under the action of the spreading agent to obtain a dispersion liquid;
(2) weighing 0.5kg of glycerol polyacrylate, 3kg of glycerol, 0.05kg of caprylyl glycol, 0.01 kg of defoaming agent silicone oil and 0.01 kg of lavender essential oil, adding the mixture into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, mixing propane and butane according to the volume of 2:1 to obtain a propellant B, filling the propellant B according to the mass ratio of the feed liquid A to the propellant B of 3:1, and statically and uniformly mixing the feed liquid A and the propellant B in a spray can body under the pressure of 0.7MPa after the can body is filled;
(4) after filling, the spray head is arranged on the aerosol can, and plastic package is carried out to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
Comparative example 2
Weighing commercially available silver-loaded zeolite particles with the particle size of 1 mu m of D90 0.6kg and chitin micropowder 1.8kg, and mixing to obtain a composite antibacterial agent for later use;
20kg of C1000 aqueous polyurethane solution (with the mass concentration of 40%) provided by Guangzhou daily oil science and technology Limited and 10kg of 500-mesh konjac gum powder are weighed and mixed to serve as a composite self-filming agent for standby.
(1) Weighing 0.35kg of composite antibacterial agent, 3kg of composite self-filming agent and 0.1kg of spreading agent glyceryl monostearate, adding 60kg of deionized water, placing in a stirring kettle, heating to 80 ℃, stirring at a high speed of 1500rpm for dispersing for 30min, and uniformly dispersing the composite antibacterial agent and the composite self-filming agent in the deionized water under the action of the spreading agent to obtain a dispersion liquid;
(2) weighing 0.5kg of glycerol polyacrylate, 3kg of glycerol, 0.05kg of caprylyl glycol, 0.01 kg of defoaming agent silicone oil and 0.01 kg of lavender essential oil, adding the mixture into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, mixing propane and butane according to the volume of 2:1 to obtain a propellant B, filling the propellant B according to the mass ratio of the feed liquid A to the propellant B of 3:1, and statically and uniformly mixing the feed liquid A and the propellant B in a spray can body under the pressure of 0.7MPa after the can body is filled;
(4) after filling, the spray head is arranged on the aerosol can, and plastic package is carried out to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
Comparative example 3
Weighing commercially available zeolite silver-loaded particles with the particle size of 1 mu m of D90 0.6kg, chitin micropowder 1.8kg and organosilicon quaternary ammonium salt antibacterial agent 1.2kg, and mixing to obtain a composite antibacterial agent for later use;
a C1000 aqueous polyurethane solution (with the mass concentration of 40%) provided by Guangzhou daily oil science and technology Limited is weighed as a self-filming agent for later use.
(1) Weighing 0.35kg of composite antibacterial agent, 3kg of self-film forming agent and 0.1kg of spreading agent glyceryl monostearate, adding 60kg of deionized water, placing in a stirring kettle, heating to 80 ℃, stirring at a high speed of 1500rpm for dispersing for 30min, and uniformly dispersing the composite antibacterial agent and the self-film forming agent in the deionized water under the action of the spreading agent to obtain a dispersion liquid;
(2) weighing 0.5kg of glycerol polyacrylate, 3kg of glycerol, 0.05kg of caprylyl glycol, 0.01 kg of defoaming agent silicone oil and 0.01 kg of lavender essential oil, adding the mixture into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, mixing propane and butane according to the volume of 2:1 to obtain a propellant B, filling the propellant B according to the mass ratio of the feed liquid A to the propellant B of 3:1, and statically and uniformly mixing the feed liquid A and the propellant B in a spray can body under the pressure of 0.7MPa after the can body is filled;
(4) after filling, the spray head is arranged on the aerosol can, and plastic package is carried out to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
Comparative example 4
Weighing commercially available zeolite silver-loaded particles with the particle size of 1 mu m of D90 0.6kg, chitin micropowder 1.8kg and organosilicon quaternary ammonium salt antibacterial agent 1.2kg, and mixing to obtain a composite antibacterial agent for later use;
10kg of konjac gum powder of 500 meshes is weighed and mixed to be used as a self-filming agent for standby.
(1) Weighing 0.35kg of composite antibacterial agent, 3kg of self-film forming agent and 0.1kg of spreading agent glyceryl monostearate, adding 60kg of deionized water, placing in a stirring kettle, heating to 80 ℃, stirring at a high speed of 1500rpm for dispersing for 30min, and uniformly dispersing the composite antibacterial agent and the self-film forming agent in the deionized water under the action of the spreading agent to obtain a dispersion liquid;
(2) weighing 0.5kg of glycerol polyacrylate, 3kg of glycerol, 0.05kg of caprylyl glycol, 0.01 kg of defoaming agent silicone oil and 0.01 kg of lavender essential oil, adding the mixture into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, mixing propane and butane according to the volume of 2:1 to obtain a propellant B, filling the propellant B according to the mass ratio of the feed liquid A to the propellant B of 3:1, and statically and uniformly mixing the feed liquid A and the propellant B in a spray can body under the pressure of 0.7MPa after the can body is filled;
(4) after filling, the spray head is arranged on the aerosol can, and plastic package is carried out to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
Comparative example 5
Weighing commercially available zeolite silver-loaded particles with the particle size of 1 mu m of D90 0.6kg, chitin micropowder 1.8kg and organosilicon quaternary ammonium salt antibacterial agent 1.2kg, and mixing to obtain a composite antibacterial agent for later use;
(1) weighing 0.35kg of composite antibacterial agent and 0.1kg of spreading agent glyceryl monostearate, adding 60kg of deionized water, placing in a stirring kettle, heating to 80 ℃, stirring at a high speed of 1500rpm for dispersing for 30min, and uniformly dispersing the composite antibacterial agent in the deionized water under the action of the spreading agent to obtain a dispersion solution;
(2) weighing 0.5kg of glycerol polyacrylate, 3kg of glycerol, 0.05kg of caprylyl glycol, 0.01 kg of defoaming agent silicone oil and 0.01 kg of lavender essential oil, adding the mixture into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, mixing propane and butane according to the volume of 2:1 to obtain a propellant B, filling the propellant B according to the mass ratio of the feed liquid A to the propellant B of 3:1, and statically and uniformly mixing the feed liquid A and the propellant B in a spray can body under the pressure of 0.7MPa after the can body is filled;
(4) after filling, the spray head is arranged on the aerosol can, and plastic package is carried out to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
Testing the instant spray sterilization effect:
cultivating Escherichia coli (ATCC8099) bacterial liquid with the concentration of 1000 cfu/ml; the concentration of the staphylococcus aureus (ATCC6538) is 200 cfu/ml; soaking 8 pieces of filter paper in the Escherichia coli solution for 30s, taking out, and naturally drying for 1 h; soaking 8 pieces of filter paper in the golden yellow staphylococcus liquid for 30s, and naturally drying for 1h after taking out; with the aerosol as a sterilization object, 8 aerosol samples obtained in examples 1 to 3 and comparative examples 1 to 5 were sprayed on the surface of filter paper for 2 seconds, and the sterilization efficiency of the spray for 5min and 1h was tested. As shown in table 1.
And (3) testing the bacterial inhibition effect:
cultivating Escherichia coli (ATCC8099) bacterial liquid with the concentration of 1000 cfu/ml; the concentration of the staphylococcus aureus (ATCC6538) is 200 cfu/ml; 8 pieces of filter paper are sprayed on 8 aerosol samples obtained in examples 1-3 and comparative examples 1-5, and the surface of the paper is sprayed for 2 s; 8 pieces of filter paper are sprayed on 8 aerosol samples obtained in examples 1-3 and comparative examples 1-5, and the surface of the paper is sprayed for 2 s; naturally drying for 10min, soaking 8 pieces of treated filter paper in the Escherichia coli solution for 30s, taking out, and naturally drying for 1 h; soaking 8 pieces of treated filter paper in the golden yellow grape bacterial liquid for 30s, taking out and naturally drying for 1 h; the number of bacteria per unit area on 6h, 12h filter paper was tested. As shown in table 2.
Table 1: immediate spray sterilization effect test
Table 2: test for inhibitory Effect on bacteria
Through tests, the aerosol absorption liquid has good instant sterilization effect, and the microfilm formed after spraying can well inhibit the reproduction and killing of adsorbed bacteria, and has lasting sterilization and bacteriostasis.
Comparative example 1 chitin micropowder was not added to the composite antibacterial agent in the trial production, but only zeolite silver-carrying particles and organosilicon quaternary ammonium salt antibacterial agent, and the obtained hand sanitizer had an obvious instant bactericidal effect at the initial stage of spraying, but had a poor bacteria inhibition effect at the later stage. The reason for this is that chitin micropowder has a significant bacteriostatic effect in the hand microfilm, and the chitin powder is absent, so that the persistence of hand bacteriostatic action is influenced to a certain extent, but the influence is not obvious.
Comparative example 2 in the test production, the composite antibacterial agent was not added with the organosilicon quaternary ammonium salt antibacterial agent, and its immediate antibacterial effect was affected, which is represented by incomplete sterilization at the initial stage of aerosol spraying, but the antibacterial effects of the silver-carrying zeolite particles and the chitin micropowder gradually appeared with the time.
In the comparative example 3, no konjac gum powder is used in the self-filming agent, a compact protective film is difficult to form due to no film formation assistance of the konjac gum powder, the smoothness of the microfilm is general, bacteria are adhered and propagated, and the antibacterial effect is influenced to a certain extent.
In the comparative example 4, the self-conjunctival agent does not use aqueous polyurethane solution, the micro-film formed by the aerosol has poor antibacterial agent fixing effect, the micro-film has poor film forming property and is easy to fall off, and the durability of the antibacterial micro-film is influenced.
In comparative example 5, no self-filming agent was used, and the obtained aerosol could not form a microfilm after spray coating, and the antibacterial agent was easily peeled off, and had a bactericidal antibacterial effect at the initial stage of spray, but the antibacterial effect at the later stage was greatly lowered.
Claims (10)
1. An alcohol-free wash-free self-conjunctiva antibacterial aerosol hand sanitizer is characterized by comprising a liquid material A and a propellant B; wherein the mass ratio of the liquid material A to the propellant B is 3: 1;
the liquid material A comprises the following raw materials in parts by weight:
0.1 to 0.5 portion of composite antibacterial agent,
3-5 parts of a composite self-filming agent,
0.5 to 1.0 portion of glycerol polyacrylate,
0.1 to 0.3 portion of spreading agent,
3-5 parts of glycerol, namely,
0.05 to 0.1 portion of octyl glycol
0.01 to 0.02 portion of defoaming agent,
60-70 parts of deionized water, namely,
0-0.01 part of edible essence;
the composite antibacterial agent is prepared from silver-loaded particles, chitin micropowder and an organosilicon quaternary ammonium salt antibacterial agent in a mass ratio of 1: 3: 2, mixing; the composite self-filming agent is a complex of aqueous polyurethane liquid and konjac powder according to a mass ratio of 2: 1;
the propellant B is prepared by mixing propane and butane in a volume ratio of 2: 1;
the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer is prepared by the following method:
(1) adding the composite antibacterial agent, the composite self-filming agent and the spreading agent into deionized water, and stirring and dispersing at a high speed to obtain a dispersion liquid;
(2) adding the glycerol polyacrylate, the glycerol, the caprylyl glycol, the defoaming agent and the essence into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, and filling the propellant B to ensure that the feed liquid A and the propellant B are statically and uniformly mixed in a spray can body;
(4) after filling, the spray head is arranged on the aerosol can and packaged to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
2. The alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to claim 1, wherein the hand sanitizer comprises: the silver-carrying particles are commercially available D90 particles with the particle size of 1 mu m, and one of zeolite silver-carrying particles and silica gel silver-carrying particles is selected.
3. The alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to claim 1, wherein the hand sanitizer comprises: the chitin micropowder is micropowder with particle size less than 5 μm.
4. The alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to claim 1, wherein the hand sanitizer comprises: the mass concentration of the aqueous polyurethane solution is 40%.
5. The alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to claim 1, wherein the hand sanitizer comprises: the spreader is one of glyceryl monostearate and diisostearyl malate.
6. The alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to claim 1, wherein the hand sanitizer comprises: the defoaming agent is silicone oil.
7. The alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to claim 1, wherein the hand sanitizer comprises: the edible essence is selected from one of lavender essential oil, rose essential oil and tea tree essential oil.
8. A method for preparing the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to any one of claims 1 to 7, which is characterized by comprising the following steps of:
(1) adding the composite antibacterial agent, the composite self-filming agent and the spreading agent into deionized water, and stirring and dispersing at a high speed to obtain a dispersion liquid;
(2) adding the glycerol polyacrylate, the glycerol, the caprylyl glycol, the defoaming agent and the essence into the dispersion liquid, and uniformly stirring to obtain a feed liquid A;
(3) subpackaging the prepared feed liquid A into aluminum cans, assembling valves for sealing, and filling the propellant B to ensure that the feed liquid A and the propellant B are statically and uniformly mixed in a spray can body;
(4) after filling, the spray head is arranged on the aerosol can and packaged to obtain the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer.
9. The method for preparing the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to claim 8, wherein the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer comprises the following steps: the high-speed stirring dispersion is carried out at the temperature of 60-80 ℃ at the rotating speed of 1200-1500rpm, and the stirring time is controlled for 30-45 min.
10. The method for preparing the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer according to claim 8, wherein the alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer comprises the following steps: the pressure of the spray tank body after being filled is 0.7-0.8 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110265747.XA CN113018215B (en) | 2021-03-11 | 2021-03-11 | Alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110265747.XA CN113018215B (en) | 2021-03-11 | 2021-03-11 | Alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113018215A CN113018215A (en) | 2021-06-25 |
| CN113018215B true CN113018215B (en) | 2022-04-22 |
Family
ID=76469895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110265747.XA Active CN113018215B (en) | 2021-03-11 | 2021-03-11 | Alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113018215B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114568429A (en) * | 2022-03-29 | 2022-06-03 | 浙江绿岛科技有限公司 | Bacteriostatic and mildewproof aerosol based on self-film forming and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014133149A1 (en) * | 2013-02-28 | 2014-09-04 | 株式会社タイキ | Process for producing silver-ion antibacterial liquid, silver-ion antibacterial liquid produced by said process, and silver-ion-containing product containing said antibacterial liquid |
| CN104798809A (en) * | 2015-03-12 | 2015-07-29 | 江西领行药业有限公司 | Organosilicon quaternary ammonium long-acting antibacterial product and preparation method thereof |
| JP2015137268A (en) * | 2014-01-24 | 2015-07-30 | 英昌化学工業株式会社 | Foamed hand cream having excellent antibacterial/moisture retention property |
| CN109330944A (en) * | 2018-11-27 | 2019-02-15 | 东莞市润孚医药科技有限公司 | A kind of external sterilizing antiallergic skin care agent |
| CN110664623A (en) * | 2019-11-18 | 2020-01-10 | 浙江绿岛科技有限公司 | Aerosol type alcohol-free wash-free antibacterial hand sanitizer and preparation method thereof |
-
2021
- 2021-03-11 CN CN202110265747.XA patent/CN113018215B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014133149A1 (en) * | 2013-02-28 | 2014-09-04 | 株式会社タイキ | Process for producing silver-ion antibacterial liquid, silver-ion antibacterial liquid produced by said process, and silver-ion-containing product containing said antibacterial liquid |
| JP2015137268A (en) * | 2014-01-24 | 2015-07-30 | 英昌化学工業株式会社 | Foamed hand cream having excellent antibacterial/moisture retention property |
| CN104798809A (en) * | 2015-03-12 | 2015-07-29 | 江西领行药业有限公司 | Organosilicon quaternary ammonium long-acting antibacterial product and preparation method thereof |
| CN109330944A (en) * | 2018-11-27 | 2019-02-15 | 东莞市润孚医药科技有限公司 | A kind of external sterilizing antiallergic skin care agent |
| CN110664623A (en) * | 2019-11-18 | 2020-01-10 | 浙江绿岛科技有限公司 | Aerosol type alcohol-free wash-free antibacterial hand sanitizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113018215A (en) | 2021-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9913476B2 (en) | Antimicrobial articles of manufacture produced from masterbatches | |
| US10034478B2 (en) | Antimicrobial articles of manufacture | |
| US5403587A (en) | Disinfectant and sanitizing compositions based on essential oils | |
| CN103190442B (en) | A kind of composite antibacterial anion air cleanser and preparation method thereof | |
| CN111449093A (en) | Natural essential oil composition with antibacterial and disinfecting effects and application thereof | |
| US5767163A (en) | Lubricating and/or germicidal composition | |
| CN102552072B (en) | Hand wash for children | |
| WO2006109898A8 (en) | Antimicrobial composition containing natural extract, nano silver and natural essential oil | |
| CN106634553B (en) | A kind of environment-friendly water-based woodcare paint of water dispersible and preparation method with desinsection and release anionic property | |
| CA2549307C (en) | Essential oils based disinfecting compositions having tuberculocidal and fungicidal efficacies | |
| CN109135946B (en) | Edible detergent and preparation method thereof | |
| CN113018215B (en) | Alcohol-free wash-free self-conjunctival bacteriostatic aerosol hand sanitizer and preparation method thereof | |
| CN106085627A (en) | A kind of natural environmental-protective cleaning agent | |
| CN104382807A (en) | Alcohol-free washing-free antibacterial hand sanitizer and preparation method thereof | |
| WO2015124943A1 (en) | Cleaning composition | |
| KR20060117875A (en) | Antimicrobial detergent compositions | |
| JP3130262B2 (en) | Bath additive | |
| CN102846717A (en) | Disposable hand disinfection wet wipe | |
| CN114532352B (en) | Composite quaternary ammonium salt long-acting disinfectant and preparation method and application thereof | |
| US5028458A (en) | Antiseptic polish | |
| CN100553609C (en) | A kind of skin superficies insulation protecting film and preparation method thereof | |
| WO2015076840A1 (en) | Antimicrobial compositions for use in products for petroleum extraction, personal care, wound care and other applications | |
| AU2011100933A4 (en) | Sanitising antimicrobial compositions | |
| CN106577807A (en) | Fragrant bactericide | |
| CN105581936A (en) | Traditional Chinese medicinal hand sanitizer containing flos genkwa and production method of hand sanitizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |