CN111690469A - Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof - Google Patents

Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof Download PDF

Info

Publication number
CN111690469A
CN111690469A CN202010651379.8A CN202010651379A CN111690469A CN 111690469 A CN111690469 A CN 111690469A CN 202010651379 A CN202010651379 A CN 202010651379A CN 111690469 A CN111690469 A CN 111690469A
Authority
CN
China
Prior art keywords
antibacterial agent
zinc pyrithione
zinc
powder containing
sodium
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.)
Granted
Application number
CN202010651379.8A
Other languages
Chinese (zh)
Other versions
CN111690469B (en
Inventor
张庆利
杨艳
叶霞
薛念刚
高义祥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Best New Materials Co ltd
Original Assignee
Qingdao Best New Materials Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Qingdao Best New Materials Co ltd filed Critical Qingdao Best New Materials Co ltd
Priority to CN202010651379.8A priority Critical patent/CN111690469B/en
Publication of CN111690469A publication Critical patent/CN111690469A/en
Application granted granted Critical
Publication of CN111690469B publication Critical patent/CN111690469B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/168Organometallic compounds or orgometallic complexes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2093Esters; Carbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/221Mono, di- or trisaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/32Amides; Substituted amides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/349Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers

Abstract

The invention provides a degerming washing powder containing a zinc pyrithione antibacterial agent and a preparation method thereof, belonging to the technical field of antibiosis. The sterilizing washing powder containing the zinc pyrithione antibacterial agent is prepared by the following method: s01, preparing the guanidine salt polymer and the polyethylene glycol into the composite antibacterial agent by a physical mixing method according to the proportion; s02, mixing the guanidine salt polymer/polyethylene glycol antibacterial agent with a zinc-carrying antibacterial agent, zinc pyrithione and dioctyl sodium sulfosuccinate to prepare the composite antibacterial agent containing zinc pyrithione, wherein the composite antibacterial agent is added into washing powder, soap powder and other washing formula systems, is quickly dissolved and dispersed when clothes are washed, releases guanidine salt polymer, zinc ions and zinc pyrithione antibacterial components, is easily dispersed in the washing process, and plays a role in quick sterilization and degerming.

Description

Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof
Technical Field
The invention relates to the technical field of antibiosis, in particular to sterilizing washing powder containing a zinc pyrithione antibacterial agent and a preparation method thereof, wherein the washing powder can be quickly dissolved in water and has the functions of sterilization and degerming.
Background
In recent years, with the increasing economic level of people, the requirement for sanitation in life is higher, and a certain amount of disinfectant is often added by consumers when clothes are washed. Common disinfectant in the market generally contains effective components such as sodium hypochlorite, hydrogen peroxide, but sodium hypochlorite, hydrogen peroxide etc. have strong oxidizing property, probably can cause the clothing to fade, if remain on the clothes, cause irritative pruritus to skin, easily cause the damage to domestic non professional washing personnel. Therefore, it is very necessary to develop a milder, highly efficient and broad-spectrum antibacterial compound for washing.
The guanidine salt polymer (polyguanidine) is a polymer based on a guanidine group, has the excellent performances of high safety, broad sterilization spectrum, low effective concentration, high action speed, stable property, easy water dissolution and the like, is harmless to human body temperature, is an environment-friendly antibacterial agent, and has extremely wide application in industry, agriculture, medical use and daily life. The currently available types of guanidine salt polymers include polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, or other inorganic and organic acid salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine, etc., and many new guanidine salt polymers are being developed.
Zinc pyrithione is an efficient and safe antibacterial agent, has good effect of killing bacteria and fungi, and is widely used in the fields of daily chemicals, washing, adhesives, coatings, paints and the like. Zinc pyrithione is white to yellow crystalline powder and is present in most products in the form of suspending agents, such as shampoo and hand sanitizer, but if it is added to a solid matrix carrier, it needs to solve the problems of dispersibility and hydrophilicity in the product, and ensure that the instant solubility of the whole detergent is not affected, it needs to be subjected to surface dispersion treatment and surfactant activation, but not all surfactants can be matched with zinc pyrithione, some surfactants cannot impart good hydrophilicity to zinc pyrithione, and some nonionic surfactants may reduce the activity of zinc pyrithione, and the sterilization effect is reduced.
According to a large number of formula tests, by optimizing a surfactant system, compounding various antibacterial agents and other methods, the invention provides the sterilizing washing powder containing zinc pyrithione and the preparation method thereof, the sterilizing washing powder with antibacterial agents such as guanidine salt polymer and zinc pyrithione as main components is prepared, the uniformity is good, the use is convenient, the zinc pyrithione is compounded with the guanidine salt polymer, the broad spectrum and the high efficiency of sterilization during washing are improved, and during washing, the components such as guanidine salt polymer, zinc ion antibacterial agent and zinc pyrithione can be quickly released, so that the effects of sterilization and degerming are achieved.
Disclosure of Invention
The invention provides a degerming washing powder containing a zinc pyrithione antibacterial agent and a preparation method thereof.
The sterilizing washing powder containing the zinc pyrithione antibacterial agent is prepared by the following method:
s01, preparing a guanidine salt polymer/polyethylene glycol composite antibacterial agent, and preparing the guanidine salt polymer/polyethylene glycol composite antibacterial agent by physically mixing the guanidine salt polymer and polyethylene glycol according to a proportion, wherein the weight ratio of the guanidine salt polymer to the polyethylene glycol is 90: 10-99: 1, and the preferable weight ratio is 95: 5-99: 1; the polyethylene glycol contains a large amount of hydroxyl groups, has good water solubility, is preferably polyethylene glycol with the molecular weight of 600-2000, is slow in water solubility when the molecular weight is too large, is relatively poor in compatibility with a guanidinium polymer, can be fully mixed with molecular chains of the polyethylene glycol after being fully physically mixed with the guanidinium polymer, increases the instant solubility of the guanidinium polymer, can be more fully used with clothing fibers, and plays a better sterilization effect, and in addition, the sterilization efficiency is obviously improved after the polyethylene glycol is introduced;
s02, preparing the zinc pyrithione-containing composite antibacterial agent, and mixing the guanidine salt polymer/polyethylene glycol composite antibacterial agent with the zinc-loaded antibacterial agent, the zinc pyrithione and the sodium dioctyl sulfosuccinate by a physical mixing method such as a blender to prepare the zinc pyrithione-containing composite antibacterial agent, wherein the weight ratio of the zinc-loaded antibacterial agent to the zinc pyrithione is preferably 50: 50-70: 30; the weight sum of the zinc-carrying antibacterial agent and the zinc pyrithione and the preferable weight sum of the dioctyl sodium sulfosuccinate are 70: 30-90: 10; the total weight ratio of the guanidine salt polymer/polyethylene glycol composite antibacterial agent to the zinc-carrying antibacterial agent, zinc pyrithione and dioctyl sodium sulfosuccinate is 50: 50-95: 5, and the preferable weight ratio is 60: 40-90: 10. By optimizing the proportion of the guanidine salt polymer, the polyethylene glycol, the zinc ion antibacterial agent, the zinc pyrithione and the sodium dioctyl sulfosuccinate and fully and uniformly stirring the mixture, the composite antibacterial agent with good uniform hydrophilicity can be formed. The guanidine salt polymer/polyethylene glycol composite antibacterial agent is compounded with the zinc ion antibacterial agent, and the zinc ion antibacterial agent with the inorganic carrier is introduced, so that the zinc ion and the guanidine salt polymer can be compounded, and the antibacterial effect is further improved; the guanidine salt polymer/polyethylene glycol composite antibacterial agent is compounded with the zinc ion antibacterial agent and zinc pyrithione, so that the antibacterial effect is further improved, the effect on fungi is particularly high, and the sterilization efficiency and broad spectrum are improved; the dioctyl sodium sulfosuccinate can effectively improve the hydrophilicity and the wettability of the whole antibacterial system, so that the dioctyl sodium sulfosuccinate can play a role more efficiently during washing.
Further, the guanidine salt polymer, the polyethylene glycol, the zinc-loaded antibacterial agent, the zinc pyrithione and the sodium dioctyl sulfosuccinate are mixed according to the proportion, and the temperature is not more than 40 ℃.
Further, S03: compounding a composite antibacterial agent containing zinc pyrithione with a surfactant, coconut oil fatty diethanolamide, lauryl glucoside, sodium citrate, water and sodium carboxymethylcellulose, and fully and uniformly mixing in a low-speed mixer to prepare the powdery bactericidal detergent powder, wherein the mixture ratio of the components is as follows (weight percentage):
composite antimicrobial agent containing zinc pyrithione: 0.5 to 5 percent
Surfactant (b): 3 to 5 percent
Coconut oil fatty diethanolamide: 24 to 50 percent
Lauryl glucoside: 10 to 30 percent
Sodium citrate: 1 to 3 percent
Water: 15 to 30 percent
Sodium carboxymethylcellulose: 1 to 3 percent.
Further, the guanidine salt polymer is at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, polyhexamethylene guanidine nitrate, polyhexamethylene biguanide nitrate, polyhexamethylene guanidine carbonate, polyhexamethylene biguanide carbonate, polyhexamethylene guanidine propionate, polyhexamethylene biguanide propionate, polyhexamethylene guanidine phosphate and polyhexamethylene biguanide phosphate.
Furthermore, the zinc ion antibacterial agent is an antibacterial agent with zinc ions as a main antibacterial component, the carrier is 4A zeolite, 5A zeolite, natural zeolite, diatomite, montmorillonite and kaolin, the content of the zinc ions is 10-50 wt%, the 4A zeolite is preferred, the content of the zinc ions is preferably 20-30 wt%, the proportion of the zinc ion antibacterial agent is too high, or the content of the zinc ions in the antibacterial agent is too high, so that the dissolved zinc ions are too fast, a complex compound can be formed with a guanidinium polymer, the activity of the molecular chain movement of the guanidinium polymer is reduced, the content of the zinc ion antibacterial agent is too low, or the content of the zinc ions in the antibacterial agent is too low, so that the antibacterial efficiency is too low. The zeolite-carried zinc has better effect and is possibly related to the cubic form, hardness, particle size and the like of the zeolite, and inorganic carriers such as the zeolite and the like can generate friction with fabrics in the washing process, so that the molecular chain of the guanidine salt polymer is driven to act on the fabrics, and the antibacterial effect is further improved.
Further, the particle size D90 of the zinc pyrithione is preferably 300nm to 2 μm, preferably 300nm to 1 μm.
Furthermore, the molecular weight of the polyethylene glycol is 600-20000, preferably 600-2000.
Further, the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium lauryl sulfate and fatty alcohol-polyoxyethylene ether sodium sulfate.
The invention also provides a preparation method of the sterilizing washing powder containing the zinc pyrithione antibacterial agent, which comprises the steps of uniformly mixing the composite antibacterial agent containing the zinc pyrithione with the surfactant, the coconut oil fatty diethanolamide, the lauryl glucoside, the sodium citrate, the water and the sodium carboxymethyl cellulose according to the sequence and the content, and fully and uniformly mixing in a low-speed mixer to prepare the powdery sterilizing washing powder.
The invention also provides application of the sterilizing washing powder containing the zinc pyrithione prepared by the preparation method of the sterilizing washing powder containing the zinc pyrithione antibacterial agent, and the sterilizing washing powder containing the zinc pyrithione can be quickly dissolved and dispersed when clothes are washed, and release guanidine salt polymer, zinc ions and zinc pyrithione components to play a role in quickly sterilizing and degerming.
The invention provides degerming washing powder containing a zinc pyrithione antibacterial agent and a preparation method thereof, which comprise active ingredients such as guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent/zinc pyrithione/dioctyl sodium sulfosuccinate and the like, and are added into formula systems such as clothes and soap powder, so that the degerming washing powder can quickly and continuously release antibacterial components such as guanidine salt polymer, zinc ions, zinc pyrithione and the like during washing, has the functions of quick sterilization and degerming, enables clothes to be cleaner and more sanitary, and has the advantages of high safety, convenience in use and high-efficiency degerming.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic view of a powdery complex antibacterial agent containing zinc pyrithione prepared according to the present invention.
FIG. 2 is a schematic diagram of a degerming washing powder containing a zinc pyrithione antibacterial agent prepared by the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete description of the present invention will be given below with reference to specific embodiments, and it is obvious that the described embodiments are some but not all embodiments of the present invention, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The raw materials and equipment involved in the embodiment of the invention are as follows:
polyhexamethylene guanidine hydrochloride: hubeidingchengjingshikai pharmaceutical chemical Co., Ltd, CAS No.57028-96-3, powder;
zinc-loaded antimicrobial agents: zinc content 30%, Z301, powder, commercially available;
polyethylene glycol: the molecular weight is 600-2000, the chemical purity is high, and the molecular weight is commercially available;
zinc pyrithione: d90<2 μm, commercially available;
sodium dioctyl sulfosuccinate: AEROSOLOT100, Cyanid Inc.;
sodium dodecylbenzenesulfonate: chemically pure, commercially available;
coconut oil fatty diethanolamide: is sold on the market;
lauryl glucoside: is sold on the market;
sodium citrate: chemically pure, commercially available;
sodium carboxymethylcellulose: fushan Ri Special chemical Co., Ltd, commercially available;
preparation method of composite antibacterial agent containing zinc pyrithione
1. Preparation of guanidine salt polymer/polyethylene glycol composite antibacterial agent
The water-soluble polyhexamethylene guanidine hydrochloride and polyethylene glycol (different molecular weights) are uniformly stirred in a stirrer according to the proportion shown in the table 1 to prepare the guanidine salt polymer/polyethylene glycol composite antibacterial agent.
Table 1.
Figure BDA0002574358370000061
Figure BDA0002574358370000071
2. Preparation of composite antibacterial agent containing zinc pyrithione
2.1 preparation of Zinc-loaded antimicrobial agent/Zinc pyrithione
The zinc-loaded antibacterial agent and the zinc pyrithione are mixed according to the proportion shown in the table 2 and are uniformly stirred.
Table 2.
Numbering Zinc-loaded antimicrobial agent/g Zinc pyrithione/g
Comparative example 17 450 550
Example 10 500 500
Example 11 600 400
Example 12 700 300
Comparative example 18 750 250
Comparative example 19 1000 0
2.2 preparation of Zinc-loaded antibacterial agent/Zinc pyrithione/sodium dioctyl sulfosuccinate composite antibacterial agent
The zinc-loaded antibacterial agent/zinc pyrithione and sodium dioctyl sulfosuccinate are mixed according to the proportion shown in the table 3 and stirred uniformly.
Table 3.
Numbering Zinc-loaded antimicrobial agent/zinc pyrithione/g Dioctyl succinate sodium sulfonate/g
Comparative example 20 Example 11/750 250
Example 13 Example 11/700 300
Example 14 Example 11/800 200
Example 15 Example 11/900 100
Comparative example 21 Example 11/950 50
Comparative example 22 Example 11/1000 0
Comparative example 23 Comparative example 19/800 200
2.3 preparation of Complex antibacterial Agents containing Zinc pyrithione
The prepared water-soluble polyhexamethylene guanidine hydrochloride and polyethylene glycol are uniformly stirred in a stirrer, then the zinc-loaded antibacterial agent, zinc pyrithione and sodium dioctyl sulfosuccinate shown in the table 4 are added and continuously stirred uniformly, and the powdery composite antibacterial agent containing zinc pyrithione is prepared by a physical mixing method such as a stirrer (shown in figure 1).
Table 4.
Numbering Guanidine salt polymer/polyethylene glycol/g Zinc-carrying antibacterial agent/zinc pyrithione/sodium dioctyl sulfosuccinate/g
Comparative example 24 Comparative example 12/850 Example 14/150
Comparative example 25 Example 5/450 Example 14/550
Example 16 Example 5/500 Example 14/500
Example 17 Example 5/600 Example 14/400
Example 18 Example 5/700 Example 14/300
Example 19 Example 5/800 Example 14/200
Example 20 Example 5/900 Example 14/100
Example 21 Example 5/950 Example 14/50
Comparative example 26 Example 5/970 Example 14/30
Comparative example 27 Example 5/700 Comparative example 22/300
Comparative example 28 Example 5/700 Comparative example 23/300
Preparation of degerming washing powder containing zinc pyrithione antibacterial agent
After the prepared compound antibacterial agent containing zinc pyrithione, water, sodium dodecyl benzene sulfonate, coconut oil fatty diethanolamide, lauryl glucoside, sodium citrate and sodium carboxymethylcellulose are preliminarily and uniformly mixed in a low-speed mixer according to the proportion designed in the table 5, the sterilizing washing powder (shown in figure 2) containing the zinc pyrithione antibacterial agent with good component dispersibility, high sterilizing efficiency and uniformity is prepared.
Table 5.
Figure BDA0002574358370000081
Figure BDA0002574358370000091
Thirdly, evaluating the sterilization effect of the sterilization washing powder containing zinc pyrithione in water
The sterilizing washing powder containing zinc pyrithione prepared in any one of comparative example 29, comparative example 30, comparative example 31 and examples 22-42, which is prepared in the present example, was used for evaluation of sterilizing effect in washing clothes, respectively, using example 29. Referring to the sterilization detection method of GB21551.5-2010 antibacterial, sterilization and purification functions of household and similar electric appliances-Special requirements of washing machines, standard washing materials are added into a common 10 kg washing machine without sterilization function: the bleaching medium plain cloth required by GB/T411 is characterized in that a kerchief of 330mm x 330mm is prepared by desizing treatment of 21 +/-2 counts of warp yarns and 21 +/-2 counts of weft yarns. Test sample cloth: the bleaching medium plain cloth required by GB/T411 is characterized in that 21 +/-2 counts of warp yarns and 21 +/-2 counts of weft yarns are subjected to desizing treatment to prepare square cloth with the thickness of 100mm multiplied by 100mm, and the total weight is 3 kilograms.
Uniformly coating 1mL of diluted bacterial liquid on each test sample block cloth with the thickness of 100mm × 100mm, preparing 2 washing machines with the same model according to appendix A in GB21551.5, adding the sterilizing washing powder during washing, not adding the sterilizing washing powder (reference sample), taking out the test cloth after the washing procedure is started, and testing the number of the residual viable bacteria on the test sample blocks by a viable bacteria counting method according to the operation method, wherein the concentration of the bacterial liquid is 1.0 × 109~9.0× 109CFU/mL. The experiment was repeated 3 times, and the respective sterilization rates were calculated, and the average values were taken, and the addition amounts and sterilization effects of the sterilization detergent powders are shown in table 7.
The calculation formula is as follows:
Figure BDA0002574358370000101
table 7.
Figure BDA0002574358370000102
The sterilizing washing powder containing the zinc pyrithione antibacterial agent can quickly and continuously release components such as guanidine salt polymer, zinc ions, zinc pyrithione and the like after meeting water, and is added when clothes are washed, so that the functions of quick sterilization and sterilization are achieved. The sterilizing effect is shown in table 7, when the addition amount of the sterilizing washing powder is more than 5g, the sterilizing rate of escherichia coli, staphylococcus aureus and candida albicans is as high as 99.9%, and a good antibacterial effect can be achieved, when the addition amount of the sterilizing washing powder is far more than 5g, the antibacterial effect achieved is basically the same as that achieved when the addition amount is slightly more than 5g, but in specific application, the dosage can be adjusted according to the degree of pollution of the washing clothes, the types of bacterial pollution are different, the dosage can be properly increased, for example, the dosage of the hospital-polluted clothes and the like, and the capacities, the rotating speeds and the powers of different washing machines are different, and the dosage of the sterilizing washing powder is also different. In the embodiment, when clothes are washed, the addition amount of the sterilizing washing powder is between 5g and 10g, so that the antibacterial washing powder not only has a good antibacterial effect, but also can effectively save resources. According to the preparation of the guanidine salt polymer/polyethylene glycol composite antibacterial agent, polyethylene glycol contains a large number of hydroxyl groups, the polyethylene glycol has good water solubility, the polyethylene glycol with the molecular weight of 600-2000 is preferable, the polyethylene glycol with the molecular weight of 60000 is slow to dissolve in comparative examples 1-16, and undissolved solid particles exist on the surface of clothes after washing in a washing machine of comparative example 29, so that the sterilization rate is reduced.
The guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent/zinc pyrithione/sodium dioctyl sulfosuccinate is prepared, the proportion of the zinc-loaded antibacterial agent in the comparative example 18 is too large, when the mixture is uniformly stirred, the formed composite antibacterial agent has poor hydrophilicity, insoluble particles are easy to remain after washing, and the sterilization effect after washing in the comparative example 34 shows that the sterilization rate of candida albicans (fungi) added with zinc pyrithione in the composite antibacterial agent is obviously superior to that of the composite antibacterial agent without zinc pyrithione. In comparative example 33, the degerming detergent powder without adding sodium dioctyl sulfosuccinate is added after the washing machine is started, and after the washing machine is started and the degerming detergent powder is added for washing for 20 minutes in a short time, residual granular substances, such as zinc pyrithione and the like with poor hydrophilicity, are found on clothes after washing, insoluble components are agglomerated, the washing time is short, and the agglomerated substances are remained on the surfaces of clothes fibers, so that the clothes are easily polluted. Meanwhile, the antibacterial rate of Candida albicans (fungi) is obviously better than that of the added sodium dioctyl sulfosuccinate. It follows that the weight ratio of zinc-loaded antimicrobial agent to zinc pyrithione is preferably 50: 50-70: 30; the weight sum of the zinc-carrying antibacterial agent and the zinc pyrithione and the preferable weight sum of the dioctyl sodium sulfosuccinate are 70: 30-90: 10; the total weight ratio of the guanidine salt polymer/polyethylene glycol composite antibacterial agent to the zinc-carrying antibacterial agent, zinc pyrithione and dioctyl sodium sulfosuccinate is 50: 50-95: 5, and the preferable weight ratio is 60: 40-90: 10.
In summary, the embodiments of the present invention can at least achieve the following beneficial effects:
1. the invention provides a compound antibacterial agent containing zinc pyrithione, which is added into washing formulas of washing powder or soap powder and the like, and 5-10 g of the compound antibacterial agent is added during washing of a washing machine, can be quickly dissolved, and has the effects of removing and killing pathogenic microorganisms such as bacteria, fungi and the like.
2. By compounding the guanidine salt polymer and the polyethylene glycol, the dissolving speed of the polyguanidine antibacterial agent added into water is improved, the polyguanidine antibacterial agent is compatible with fabrics and other detergents, and the permeability of the polyguanidine antibacterial agent to the fabrics is improved, so that a better antibacterial effect is achieved.
3. By using the guanidine salt polymer and the zinc-loaded antibacterial agent, the zinc pyrithione and the sodium dioctyl sulfosuccinate in a composite way, the broad spectrum and the antibacterial efficiency of the antibacterial are improved, the using amount is reduced, and the time for washing and sterilizing is shortened.
4. Preferably, the zeolite zinc-loaded antibacterial agent and the guanidine salt polymer are compounded, and when the fabric is washed, the water-soluble guanidine salt polymer antibacterial agent and zinc ions are released simultaneously by utilizing the friction between the zeolite and the fabric, and the antibacterial agent and the microorganisms such as bacteria on the surface of the fabric are contacted repeatedly by cooperating with the antibacterial effect, so that a better antibacterial effect is achieved.
5. The zinc pyrithione has more efficient effect on fungi, and the antibacterial efficiency and broad spectrum are improved; the sodium dioctyl sulfosuccinate can effectively improve the hydrophilicity and wettability of an antibacterial system and increase the sterilization rate of clothes during washing.
Finally, it is to be noted that: the above description is only a preferred embodiment of the present invention, and is only used to illustrate the technical solutions of the present invention, and not to limit the protection scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. The sterilizing washing powder containing the zinc pyrithione antibacterial agent is characterized by being prepared by the following method:
s01, preparing a guanidine salt polymer/polyethylene glycol composite antibacterial agent, and preparing the guanidine salt polymer/polyethylene glycol composite antibacterial agent by physically mixing the guanidine salt polymer and polyethylene glycol according to a proportion, wherein the weight ratio of the guanidine salt polymer to the polyethylene glycol is 90: 10-99: 1, and the preferable weight ratio is 95: 5-99: 1;
s02, preparing a zinc pyrithione-containing composite antibacterial agent, and mixing the guanidine salt polymer/polyethylene glycol composite antibacterial agent with a zinc-carrying antibacterial agent, zinc pyrithione and sodium dioctyl sulfosuccinate, wherein the weight ratio of the zinc-carrying antibacterial agent to the zinc pyrithione is preferably 50: 50-70: 30; the weight sum of the zinc-carrying antibacterial agent and the zinc pyrithione and the preferable weight sum of the dioctyl sodium sulfosuccinate are 70: 30-90: 10; the total weight ratio of the guanidine salt polymer/polyethylene glycol composite antibacterial agent to the zinc-carrying antibacterial agent, zinc pyrithione and dioctyl sodium sulfosuccinate is 50: 50-95: 5, and the preferable weight ratio is 60: 40-90: 10.
2. The sterilizing detergent powder containing zinc pyrithione antimicrobial agent according to claim 1, wherein the temperature of said guanidine salt polymer, polyethylene glycol, zinc-loaded antimicrobial agent, zinc pyrithione, sodium dioctyl sulfosuccinate when mixed in proportion does not exceed 40 ℃.
3. The bactericidal detergent powder containing a zinc pyrithione antibacterial agent according to claim 2, wherein the ratio of S03: the compound antibacterial agent containing zinc pyrithione is compounded with a surfactant, coconut oil fatty diethanolamide, lauryl glucoside, sodium citrate, water and sodium carboxymethylcellulose, and the mixture is fully and uniformly mixed in a low-speed mixer to prepare the sterilizing washing powder containing the zinc pyrithione antibacterial agent, wherein the mixture ratio of the components is as follows (weight percentage):
composite antimicrobial agent containing zinc pyrithione: 0.5 to 5 percent
Surfactant (b): 3 to 5 percent
Coconut oil fatty diethanolamide: 24 to 50 percent
Lauryl glucoside: 10 to 30 percent
Sodium citrate: 1 to 3 percent
Water: 15 to 30 percent
Sodium carboxymethylcellulose: 1 to 3 percent.
4. The bactericidal detergent powder containing a zinc pyrithione antibacterial agent according to claim 3, wherein the guanidine salt polymer is at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, polyhexamethylene guanidine nitrate, polyhexamethylene biguanide nitrate, polyhexamethylene guanidine carbonate, polyhexamethylene biguanide carbonate, polyhexamethylene guanidine propionate, polyhexamethylene biguanide propionate, polyhexamethylene guanidine phosphate, and polyhexamethylene biguanide phosphate.
5. The sterilizing washing powder containing the zinc pyrithione antibacterial agent according to claim 4, wherein the zinc ion antibacterial agent is an antibacterial agent with zinc ions as a main antibacterial component, the carrier is 4A zeolite, 5A zeolite, natural zeolite, diatomite, montmorillonite and kaolin, and the content of zinc ions is 10-50 wt%, wherein the 4A zeolite is preferred, and the content of zinc ions is preferably 20-30 wt%.
6. The sterilizing washing powder containing the zinc pyrithione antibacterial agent according to claim 5, wherein the particle size D90 of the zinc pyrithione is 300nm to 2 μm, preferably 300nm to 1 μm.
7. The sterilizing washing powder containing the zinc pyrithione antibacterial agent according to claim 6, wherein the molecular weight of the polyethylene glycol is 600-20000, preferably 600-2000.
8. The bactericidal detergent powder containing a zinc pyrithione antibacterial agent according to claim 3, wherein the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium lauryl sulfate and sodium fatty alcohol-polyoxyethylene ether sulfate.
9. The method for preparing the sterilizing washing powder containing the zinc pyrithione antibacterial agent according to any one of claims 3 to 8, characterized in that the compound antibacterial agent containing the zinc pyrithione is uniformly mixed with the surfactant, the coconut oil fatty diethanolamide, the lauryl glucoside, the sodium citrate, the water and the sodium carboxymethyl cellulose according to the sequence and the content, and the mixture is fully and uniformly mixed in a low-speed mixer to prepare the powdery sterilizing washing powder.
10. The use of the bactericidal detergent powder containing zinc pyrithione prepared by the method of claim 9, wherein the detergent powder is rapidly dissolved and dispersed to release the guanidine salt polymer, zinc ions and zinc pyrithione components for rapid sterilization and disinfection.
CN202010651379.8A 2020-07-08 2020-07-08 Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof Active CN111690469B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010651379.8A CN111690469B (en) 2020-07-08 2020-07-08 Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010651379.8A CN111690469B (en) 2020-07-08 2020-07-08 Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111690469A true CN111690469A (en) 2020-09-22
CN111690469B CN111690469B (en) 2022-03-11

Family

ID=72485057

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010651379.8A Active CN111690469B (en) 2020-07-08 2020-07-08 Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111690469B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111607469A (en) * 2020-07-08 2020-09-01 青岛拜士特新材料有限公司 Instant antibacterial masterbatch and preparation method thereof
CN111733021A (en) * 2020-07-08 2020-10-02 青岛拜士特新材料有限公司 Sterilizing washing powder containing PCMX and preparation method thereof
CN111733027A (en) * 2020-07-08 2020-10-02 青岛拜士特新材料有限公司 Instant washing antibacterial master batch and preparation method thereof
WO2022198049A1 (en) * 2021-03-19 2022-09-22 Arxada, LLC Biocidal composition and method

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1109501A (en) * 1994-03-30 1995-10-04 北京丹侬-霍兰德日用化工有限公司 Sterilizing washing powder without phosphorous and its preparing method
US6251844B1 (en) * 1999-05-21 2001-06-26 Colgate-Palmolive Co. Hydroxy aliphatic acidic microemulsion liquid cleaning compositions
JP2002038373A (en) * 2000-07-26 2002-02-06 Daiwa Kagaku Kogyo Kk Antimicrobial fiber
CN101270232A (en) * 2008-04-22 2008-09-24 浙江时代金科过氧化物有限公司 Method for preparing particle type coating sodium percarbonate
CN101720785A (en) * 2008-10-31 2010-06-09 中国石油化工股份有限公司 Compound antimicrobial and preparation method thereof
WO2011135577A1 (en) * 2010-04-29 2011-11-03 Bios Agricorp Pvt. Ltd. Polyhexamethyleneguanidine and its salts based disinfectant.
CN102499259A (en) * 2011-11-18 2012-06-20 北京崇高纳米科技有限公司 Clothing degerming liquid and preparation method thereof
CN104920426A (en) * 2015-05-27 2015-09-23 武汉桀升生物科技有限公司 Powder bactericide based on guanidine salt polymer and preparation method for powder bactericide
CN105754753A (en) * 2016-05-11 2016-07-13 于文 Antibacterial fabric detergent and preparation method thereof
CN106075577A (en) * 2016-07-21 2016-11-09 南京工业大学 Based on organic guanidinesalt and the antimicrobial coating of Polyethylene Glycol
CN106689126A (en) * 2016-12-14 2017-05-24 广州泰晟生物科技有限公司 Polyhexamethylene guanidine effervescent preparation and preparing method thereof
CN110066459A (en) * 2019-04-18 2019-07-30 青岛拜士特新材料有限公司 A kind of antibacterial matrices and preparation method of sustained-release antibacterial
CN110583681A (en) * 2019-08-22 2019-12-20 芜湖广济医院 Chlorine-containing disinfectant and preparation method thereof
CN110903918A (en) * 2019-11-25 2020-03-24 广州立白企业集团有限公司 Antibacterial fabric detergent composition
CN111032060A (en) * 2017-06-28 2020-04-17 科利迪恩公司 Compositions, methods and uses for cleaning, disinfecting and/or sterilizing
CN111607469A (en) * 2020-07-08 2020-09-01 青岛拜士特新材料有限公司 Instant antibacterial masterbatch and preparation method thereof
CN111733027A (en) * 2020-07-08 2020-10-02 青岛拜士特新材料有限公司 Instant washing antibacterial master batch and preparation method thereof
CN111733021A (en) * 2020-07-08 2020-10-02 青岛拜士特新材料有限公司 Sterilizing washing powder containing PCMX and preparation method thereof
CN111748416A (en) * 2020-07-08 2020-10-09 青岛拜士特新材料有限公司 Instant degerming and virus-removing master batch and preparation method thereof

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1109501A (en) * 1994-03-30 1995-10-04 北京丹侬-霍兰德日用化工有限公司 Sterilizing washing powder without phosphorous and its preparing method
US6251844B1 (en) * 1999-05-21 2001-06-26 Colgate-Palmolive Co. Hydroxy aliphatic acidic microemulsion liquid cleaning compositions
JP2002038373A (en) * 2000-07-26 2002-02-06 Daiwa Kagaku Kogyo Kk Antimicrobial fiber
CN101270232A (en) * 2008-04-22 2008-09-24 浙江时代金科过氧化物有限公司 Method for preparing particle type coating sodium percarbonate
CN101720785A (en) * 2008-10-31 2010-06-09 中国石油化工股份有限公司 Compound antimicrobial and preparation method thereof
WO2011135577A1 (en) * 2010-04-29 2011-11-03 Bios Agricorp Pvt. Ltd. Polyhexamethyleneguanidine and its salts based disinfectant.
CN102499259A (en) * 2011-11-18 2012-06-20 北京崇高纳米科技有限公司 Clothing degerming liquid and preparation method thereof
CN104920426A (en) * 2015-05-27 2015-09-23 武汉桀升生物科技有限公司 Powder bactericide based on guanidine salt polymer and preparation method for powder bactericide
CN105754753A (en) * 2016-05-11 2016-07-13 于文 Antibacterial fabric detergent and preparation method thereof
CN106075577A (en) * 2016-07-21 2016-11-09 南京工业大学 Based on organic guanidinesalt and the antimicrobial coating of Polyethylene Glycol
CN106689126A (en) * 2016-12-14 2017-05-24 广州泰晟生物科技有限公司 Polyhexamethylene guanidine effervescent preparation and preparing method thereof
CN111032060A (en) * 2017-06-28 2020-04-17 科利迪恩公司 Compositions, methods and uses for cleaning, disinfecting and/or sterilizing
CN110066459A (en) * 2019-04-18 2019-07-30 青岛拜士特新材料有限公司 A kind of antibacterial matrices and preparation method of sustained-release antibacterial
CN110583681A (en) * 2019-08-22 2019-12-20 芜湖广济医院 Chlorine-containing disinfectant and preparation method thereof
CN110903918A (en) * 2019-11-25 2020-03-24 广州立白企业集团有限公司 Antibacterial fabric detergent composition
CN111607469A (en) * 2020-07-08 2020-09-01 青岛拜士特新材料有限公司 Instant antibacterial masterbatch and preparation method thereof
CN111733027A (en) * 2020-07-08 2020-10-02 青岛拜士特新材料有限公司 Instant washing antibacterial master batch and preparation method thereof
CN111733021A (en) * 2020-07-08 2020-10-02 青岛拜士特新材料有限公司 Sterilizing washing powder containing PCMX and preparation method thereof
CN111748416A (en) * 2020-07-08 2020-10-09 青岛拜士特新材料有限公司 Instant degerming and virus-removing master batch and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李妮妮,于文: "聚六亚甲基胍类消毒剂性能及应用研究进展", 《日用化学品科学》 *
柳峰,刘学: "The Synthesis of Polyhexamethyleneguanidine", 《SCIENCE & TECHNOLOGY INFORMATION》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111607469A (en) * 2020-07-08 2020-09-01 青岛拜士特新材料有限公司 Instant antibacterial masterbatch and preparation method thereof
CN111733021A (en) * 2020-07-08 2020-10-02 青岛拜士特新材料有限公司 Sterilizing washing powder containing PCMX and preparation method thereof
CN111733027A (en) * 2020-07-08 2020-10-02 青岛拜士特新材料有限公司 Instant washing antibacterial master batch and preparation method thereof
WO2022198049A1 (en) * 2021-03-19 2022-09-22 Arxada, LLC Biocidal composition and method

Also Published As

Publication number Publication date
CN111690469B (en) 2022-03-11

Similar Documents

Publication Publication Date Title
CN111690469B (en) Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof
CN111733021B (en) Sterilizing washing powder containing PCMX and preparation method thereof
CN111748416B (en) Instant degerming and virus-removing master batch and preparation method thereof
CN102499259B (en) Clothing degerming liquid and preparation method thereof
CN111733027B (en) Instant washing antibacterial master batch and preparation method thereof
EP2440702B1 (en) Antimicrobial textiles comprising peroxide
CN111607469B (en) Instant antibacterial masterbatch and preparation method thereof
WO1992019555A1 (en) Divalent silver alkaline bactericide compositions
CN102382728A (en) Special underwear laundry detergent and preparation method for same
CN104082287A (en) Preparation method of cellulose based bactericidal emulsion
CN111500127A (en) Broad-spectrum long-acting antibacterial coating spray and preparation method thereof
CN100552011C (en) A kind of disinfectant detergent powder and preparation method thereof
CN109718130A (en) A kind of preparation method of nano silver/chitosan composite antibiotic hand cleanser
EP2792244B1 (en) Active-powder biocidal composition comprising at least one copper salt and at least one zinc salt and the method for the production thereof
CN107641416A (en) A kind of antibacterial powder paint
CN111944616A (en) Disinfecting and antibacterial laundry detergent
CN105112174B (en) A kind of fungus and mildew resistance liquid detergent
CN111876273A (en) Sterilization laundry detergent based on hydrophilic zinc oxide, preparation method and application thereof
CN1030227C (en) Multipurpose sterilizing detergent
CN115262227B (en) Antibacterial finishing agent and preparation method and application thereof
US20100136077A1 (en) Biocidic household cleansing materials
CN114437878A (en) Silver ion antibacterial laundry detergent
CN106520403A (en) Silver carboxymethyl chitosan anti-microbial brightening laundry detergent and preparation method thereof
CN103875666A (en) Degerming composition and application thereof
CN102824298A (en) Sanitary wet tissue for women

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